We greatly thank all the sponsors of the - Unistra · Strasbourg has hosted famous scientists such...

We greatly thank all the sponsors of the IVth French-Chinese Workshop on Polymers and Soft Matter

Bouquey

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Bouquey

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4th Sino-French workshop on macromolecules and soft matter

Dear Participant,

We are very happy to welcome you for this 4th edition of the Sino-French workshop on

macromolecules and soft matter. This workshop was initiated in 2009 by the ESPCI and the

University of Fudan. After three successful editions in Shanghai (May 2009), Paris (October

2010) and Hefei (May 2012), we decided to organize the workshop in Strasbourg. Located at

the border between France and Germany, Strasbourg is famous for its single-tower cathedral,

its old historical center and, of course, its wine and food culture!

However, Strasbourg is also one of the main historical spots for Chemistry and Physics in

Europe. Having changed back and forth between France and Germany through History,

Strasbourg has hosted famous scientists such as Hermann Staudinger, Pierre Weiss, Emil

Fischer, Wilhelm Röntgen and Jean-Marie Lehn. In this exciting scientific context, we are

happy to welcome this year 32 invited speakers from China and France. This year workshop

will be a part of the “Institut Charles Sadron Conference Series”, a label created four years ago

and given each year to a conference organized by members of the Institut Charles Sadron.

We hope that this exciting program will permit to establish strong ties and collaborations

between France and China and wish you three days of excellent science in Strasbourg.

Michel Bouquey Costantino Creton Jean-François Lutz Carlos Marques Pierre Muller

3

4th Sino-French Workshop on Macromolecules and Soft Matter 2015

Program

Monday October 12th morning

8:30 Opening Ceremony. ICS and ESPCI-PSL welcome

9:00 TANG Benzhong (Hong Kong Univ. of Sci. and Tech.)

AIE-Active Macromolecules

9:25 CHARLEUX Bernadette (Saint Gobain)

Global R&D at Saint-Gobain and focus on the polymer activities in China

9:50 TANG Chuanbing (Univ. of South Carolina)

Metallocene Polyelectrolytes: from Chemoselective Synthesis to Biomedical Applications

10:15 Coffee Break

10:45 LI Min-Hui (Chimie ParisTech – PSL)

Towards biocompatible and biodegradable stimuli-responsive polymersomes

11:10 ZHOU Yongfeng (Shanghai Jiaotong Univ.)

Facile Functionalization of polymeric self-assemblies

11:35 CHASSENIEUX Christophe (Univ. of le Mans)

Amphiphilic Block Copolymers : Search for Tunable dynamics

12:00 WANG Feng (Univ. Sci. & Technol. China, Hefei)

Controlled Supramolecular Polymerization Based on the π-Conjugated Organometallic Building Blocks

12:25 Lunch Break

Chairman: Jean-François Lutz

Monday October 12th afternoon

13:30 OBERDISSE Julian (Univ. of Montpellier)

Contrast-matching gone wrong? A study of chain conformation in polymer nanocomposites

13:55 CHEN Hongzheng (Zhejiang Univ.)

Enhanced Efficiency of Polymer and Perovskite Solar Cells Via Interface Engineering

14:20 TRIBET Christophe (ENS Paris – PSL)

Dynamic surface switches based on adlayers of stimuli-responsive poly(Lysine) comb-like copolymers

14:45 Coffee Break and poster session

15:45 WOISEL Patrice (Univ. of Lille)

Supramolecular chemistry: a powerful tool to elaborate “colourful” multi-stimuli responsive

macromolecular assemblies

16:10 XU Huaping (Tsinghua Univ.)

ROS Responsive Selenium-containing Polymers

16:35 THOMAS Christophe (Chimie ParisTech – PSL)

Polymerization of Heterocycles: a Simple Approach to Sequence Control in Polymer Synthesis

17:00 LI Yuesheng (Tianjin Univ.)

Development of Facile and Efficient Strategy to Chemical Modified Isotactic Polypropylene with Well-

defined Structure

Chairman: Jacques Lalevée

Tuesday October 13th

8:30 LECOMMANDOUX Sébastien (Univ. of Bordeaux)

Self-assembled polymersomes as virus and cell mimics

8:55 LIU Shiyong (Univ. Sci. & Technol. China, Hefei)

Hyperbranched Self-Immolative Polymers (hSIPs) for Programmed Payload Delivery and Ultrasensitive

Detection

9:20 DESTARAC Mathias (Univ. of Toulouse)

Some new trends in aqueous RAFT/MADIX polymerization

9:45 NICOLAY Renaud (ESPCI Paristech – PSL)

Exploring old and new dynamic covalent chemistries for formulation and material science

10:10 THALMANN Fabrice (Univ. of Strasbourg)

Investigating lipid membrane dynamics at a nanoscale with excimer fluorescence: lessons from

molecular dynamics simulations

10:35 Coffee Break

11:05 LI Zichen (Peking Univ.)

Importance of Monomer Sequence in Controlling the Properties of Polymers

11:30 PONSINET Virginie (Univ. of Bordeaux)

Polymer self-assembly: towards materials with novel optical properties

11:55 XU Chunye (Univ. Sci. & Technol. China, Hefei)

Self-polarized piezoelectric thin films: preparation, formation mechanism and application

12:20 DUCHET Jannick (Univ. of Lyon)

Ionic liquids: new additives for the polymer materials

Afternoon: Free afternoon

Chairman: Carlos Marques

Wednesday October 14th

8:30 GRANDE Daniel (CNRS – Thiais)

Crossing porosity scales in functional polymer materials: From design to application

8:55 Zhu Jintao (Huazhong Univ. of Sci. and Tech.) Assembly of Block Copolymers in 3D Confined Geometry

9:20 HEUX Laurent (Univ. of Grenoble)

Man-made and bioinspired materials from nanocellulose : challenges and opportunities

9:45 BOUQUEY Michel (Univ. of Strasbourg)

Using intensified polymerization processes to elaborate novel polymeric materials

10:10 SANSON Nicolas (ESPCI ParisTech – PSL)

Cold Welding or How Polymer/Surfactant Interactions Promote the Welding of Colloidal Gold

Nanoparticles

10:35 Coffee Break

11:05 WANG Changchun (Fudan Univ.)

Stimuli-responsive biodegradable polymer nanoparticles for triggered drug delivery system

11:30 BASCHNAGEL Joerg (Univ. of Strasbourg)

Modeling of solvent evaporation from thin glass-forming polymer films: Molecular-

dynamics simulations and diffusion equation approach

11:55 WU Zongquan (Hefei Univ. of Tech.)

Facile Synthesis of Stereoregular Helical Polyisocyanide and Its Copolymers

12:20 Closing Ceremony

Chairman: Costantino Creton

1982: BS, Department of Polymer Science &

Engineering, South China University of Technology

1988 : PhD, Department of Polymer Chemistry,

Kyoto University, Kyoto, Japan

1989-1994 : Postdoctoral Research Associate,

University of Toronto, Toronto, Ontario, Canada

1994: Assistant Professor, Department of

Chemistry, HKUST

2008: Chair Professor, Department of Chemistry, ,

Division of Biomedical Engineering , Division of

Life Science , HKUST

TANG Ben Zhong

Chair Professor, , HKUST

Tel: +33 4 72 43 85 48

Email: [email protected]

Web : http://ihome.ust.hk/~tangbenz/

Current Research interests:

Exploration of new polymerization reactions

Synthesis of new functional (macro)molecules

Deciphering of new luminescent processes

Creation of new advanced materials

Development of new fluorescent biosensors

Selected Recent Publications

Multichannel Conductance of Folded Single-Molecule Wires Aided by

Through-Space Conjugation Angew. Chem. Int. Ed. 2015, 54, 4231.

Single Molecule with Dual Function on Nanogold: Biofunctionalized Construct for

In Vivo Photoacoustic Imaging and SERS Biosensing Adv. Funct. Mater. 2015, 25,

2316.

High-order Nonlinear Optical Effects in Organic Luminogens with

Aggregation-Induced Emission Adv. Mater. 2015, 27, 2332.

An Aggregation-Induced-Emission Platform for Direct Visualization of Interfacial

Dynamic Self-Assembly Angew. Chem. Int. Ed. 2014, 53, 13518.

Two-Dimensional Metal-Organic Framework with Wide Channels and Responsive

Turn-On Fluorescence for the Chemical Sensing of Volatile Organic Compounds J.

Am. Chem. Soc. 2014, 136, 7241.

8

http://ihome.ust.hk/~tangbenz/

AIE-Active Macromolecules

Ben Zhong Tang

Department of Chemistry, The Hong Kong University of Science and Technology

Clear Water Bay, Kowloon, Hong Kong

E-mail: [email protected]

Abstract: Polymers with aggregation-induced emission (AIE) are widely studied

recently because of their good solubility, processability, and high emission efficiency

in the aggregated states. A large variety of AIE-active macromolecules have been

developed. In this talk, the research efforts directed to AIE-active macromolecules

including the designs and syntheses, structures and topologies, as well as

functionalities and applications will be introduced with an emphasis on the most up to

date progress. The synthetic approaches for the construction of AIE macromolecules

include chain polymerizations such as free-radical polymerization and metathesis

polymerizations, step polymerizations such as transition-metal catalyzed

carbon-carbon coupling reactions and polycycloadditions, as well as

post-modification of polymers. Through such versatile polymerization approaches, a

vast array of AIE macromolecules with various chemical and topological structures

can be easily accessed such as linear or zigzag shaped oligomers and polymers,

star-shaped oligomers, dendrimers and hyperbranched polymers, conjugated

microporous polymers, as well as crystalline supramolecular polymers. Combining

the AIE characteristics with the desired traits of the polymeric materials will endow

the resulting macromolecules with fascinating functionalities and they have found

applications in fluorescent sensors, stimuli-responsive materials, biological probes,

cell imaging, electroluminescence devices, optical nonlinearities, circular polarized

luminescence, photopatterning, light refractive materials, liquid crystalline, gas

adsorption, etc. AIE-active macromolecule is still a young research area with

numerous possibilities and it is a fast-growing promising field.[1],[2]

Key Words: aggregation-induced emission, macromolecules

Reference:

[1] Rongrong Hu, Nelson L. C. Leung and Ben Zhong Tang. Chem. Soc. Rev. 2014,

43, 4494-4562.

[2] Anjun Qin, Jacky W. Y. Lam and Ben Zhong Tang. Prog. Polym. Sci. 2012, 37,

182-209.

9

mailto:[email protected]

1987: School of Chemistry, Physics & Engineering, Lyon, France

1991: Ph.D. University Claude Bernard Lyon 1

1993: CNRS researcher, Laboratory of Macromolecular Chemistry, University Pierre & Marie Curie, Paris 6

2001: Professor at the University Pierre & Marie Curie, Paris 6

2009: Professor at the University Claude Bernard, Lyon 1 ; senior member of the Institut Universitaire de France ; director of the Laboratory of Chemistry, Catalysis, Polymers & Processes

2013: Deputy Director for R&D at Saint-Gobain

CHARLEUX Bernadette Deputy Director for R&D at Saint-Gobain Tel: +33 1 47 62 32 09 Email: [email protected]

Past Research Area

The former research activity developed in academic laboratories was devoted to polymer

chemistry with a focus on kinetic and mechanistic studies of ionic polymerizations and

conventional and controlled radical polymerizations. A special attention was given to reactions

in aqueous and non-aqueous dispersed media, with the synthesis of well-defined polymer

architectures, their self-assemblies (in particular the development of polymerization-induced

self-assembly) and the synthesis of organic-inorganic hybrid nanostructured colloids.


Core-Shell Nanoreactors for Efficient Aqueous Biphasic Catalysis X.W. Zhang, A.F. Cardozo, S. Chen, W.J. Zhang, C. Julcour, M. Lansalot, J.F. Blanco, F. Gayet, H. Delmas, B. Charleux, E. Manoury, F. D'Agosto, R. Poli, Chemistry-A European Journal 20 (47), 15505-15517 (2014) Synthesis of Amphiphilic Poly(acrylic acid)-b-poly(n-butyl acrylate-co-acrylic acid) Block Copolymers with Various Microstructures via RAFT Polymerization in Water/Ethanol Heterogeneous Media X. Zhang, F. Boisson, O. Colombani, C. Chassenieux, B. Charleux Macromolecules 47(1), 51-60 (2014) Dynamic behavior of crosslinked amphiphilic block copolymer nanofibers dispersed in liquid poly(ethylene oxide) below and above their glass transition temperature W. Zhang, B. Charleux, P. Cassagnau Soft Matter 9 (7), 2197-2205 (2013) Polymerization-induced self-assembly: From soluble macromolecules to block copolymer nano-objects in one step B. Charleux, G. Delaittre, J. Rieger, F. D’Agosto Macromolecules 45 (17), 6753–6765 (2012) – Perspective Article Toward a better understanding of the parameters that lead to the formation of non-spherical polystyrene particles via RAFT-mediated one-pot aqueous emulsion polymerization. W. Zhang, F. D’Agosto, O. Boyron, J. Rieger, B. Charleux Macromolecules 45 (10), 4075–4084 (2012)

10

Abstract Research and Development at Saint-Gobain: Global overview and Research in China in

the domain of Performance Plastics

Yiwei Fu,1 Jing Dai,

1 Yue Dong,

1 Eric Yin,

1 Muthu Jeevanantham,

1 Bernadette Charleux

2*

1- Saint-Gobain Research Shanghai, 55 Wenjing Rd, Minhang, Shanghai, China

2- Saint-Gobain Headquarters, Les Miroirs – 18 Avenue d’Alsace, 92096 La Défense

Cedex - France

The Research and Development organization and strategy of Saint-Gobain at the global level

will first be presented: R&D centers, open-innovation, university collaborations and

transversal programs. A special attention will then be given to the R&D activities in China with

a highlight on the Performance Plastics business and the foams & tapes products. A particular

example regarding the development of a new foamed bonding tape will be given, as a

technical illustration.

11

Dr. Chuanbing Tang, Associate Professor

College of Arts and Sciences Distinguished Professor

Department of Chemistry & Biochemistry

University of South Carolina

631 Sumter Street, Columbia, South Carolina 29208, USA

Email: [email protected]; Tel: 1-803-777-3628

Group Research URL: http://www.chem.sc.edu/faculty/tang/index.htm

Dr. Chuanbing Tang received B.S. from Nanjing University and Ph.D. from Carnegie Mellon University with Profs. Krzysztof Matyjaszewski and Tomasz Kowalewski. He was a postdoctoral scholar at the University of California Santa Barbara with Profs. Edward J. Kramer and Craig J. Hawker. Since August 2009, he has been an Assistant, Associate and College of Arts and Sciences Distinguished Professor in Department of Chemistry and Biochemistry at the University of South Carolina. His research interests focus on organic polymer synthesis, sustainable polymers from renewable natural resources, metal-containing polymers, and polymers for biomedical application and nanophase-separated copolymers for energy storage. He has been recognized with a few awards including NSF Career Award, Thieme Chemistry Journal Award and USC Distinguished Undergraduate Research Mentor Award. He has also been named an ACS PMSE Young Investigator and a Rising Star at the University of South Carolina. He has published about 90 papers and 10 patent applications.


1. Tang C.; Lennon E. M.; Fredrickson G. H.; Kramer E. J.; Hawker C. J. Evolution of Block Copolymer Lithography to Highly Ordered Square Arrays. Science, 2008, 322, 429-432.

2. Ren L.; Hardy C. G.; Tang C. Synthesis and Solution Self-Assembly of Side-Chain Cobaltocenium-Containing Block Copolymers, J. Am. Chem. Soc. 2010, 132, 8874-8875.

3. Tang C.; Wu W.; Smilgies D-M.; Matyjaszewski K.; Kowalewski T. Robust Control of Long-Range Order in Thin Films of Block Copolymers by Zone Casting. J. Am. Chem. Soc. 2011, 130, 11802-11809.

4. Qiao Y.; Islam M. D.; Han G.; Leonhardt E.; Zhang J.; Wang Q.; Ploehn H. J.; Tang C. Polymers Containing Highly Polarizable Conjugated Side Chains as High Performance All-Organic Nanodielectric Materials, Adv. Funct. Mater., 2013, 23, 5638–5646.

5. Yao K.; Tang C. Controlled Polymerization of Next-Generation Renewable Monomers and Beyond. Macromolecules 2013, 46, 1689-1712.

6. Ganewatta M. S.; Chen Y.-P.; Wang J.; Zhou J.; Ebalunde J.; Nagarkatti M.; Decho A. W.; Tang C. Bio-inspired Resin Acid-Derived Materials as Anti-Bacterial Resistance Agents with Unexpected Activities. Chem. Sci., 2014, 5, 2011 - 2016.

12


http://www.chem.sc.edu/faculty/tang/index.htm

Metallocene Polyelectrolytes: from Chemoselective Synthesis to Biomedical Applications

Chuanbing Tang

Department of Chemistry & Biochemistry, University of South Carolina

Metallopolymers combine synthetic efficiency and versatility of an organic polymer framework with unique properties of inorganic metals. Cationic metallocene-containing polymers have recently garnered attention with their emerging electrolyte chemistry and niche applications in biomedical fields. Advances in polymerization techniques have provided opportunities to prepare polymers with tunable chemistry and compositions, controlled topologies, predetermined molecular weight and narrow molecular weight distribution. In this presentation, I will talk about the latest development from chemoselective synthesis of cationic metallocene derivatives to the use of controlled and living polymerization for the preparation of well-defined polyelectrolytes. These cationic polyelectrolytes have shown surprising promise as novel antimicrobial agents that could kill some of most malicious bacteria. I will also discuss a new strategy to addressing bacteria resistance via revitalizing conventional β-lactam antibiotics.

References:

(1) Ren L.; Zhang J.; Bai X.; Hardy C. G.; Shimizu K. D.; Tang C. Preparation of Cationic Cobaltocenium Polymers and Block Copolymers by “Living” Ring-Opening Metathesis Polymerization. Chem. Sci. 2012, 3, 580-583. (2) Zhang J.; Yan Y.; Chance W. M.; Chen J.; Hayat J.; Ma S.; Tang C. Charged Metallopolymers as Universal Precursors for Versatile Cobalt Materials, Angew. Chem. Int. Ed. 2013, 52, 13387 –133. (3) Zhang J.; Chen Y.-P.; Miller K. P.; Ganewatta M. S. Bam M.; Yan Y.; Nagarkatti M.; Decho A. W.; Tang C. Antimicrobial Metallopolymers and Their Bioconjugates with Antibiotics against Multidrug Resistant Bacteria, J. Am. Chem. Soc. 2014, 136, 4873-4876.

13

Degrees :

1986 Bachelor of Engineering, Tsinghua University,

Beijing, China

1988 Master of Polymer Science, Tsinghua University,

Beijing, China

1993 Ph. D., Pierre & Marie Curie Univerity, working in the

Laboratoire Léon Brillouin in CEA

2005 Habilitation (HDR 博导证书)

Research :

1993-1994 Post-doc, French Institute of Petroleum (IFP)

1994-1997 CNRS Research Scientist (Assistant Professor),

Paul Pascal Research Center (CRPP), Bordeaux

1997-2011 CNRS Senior Research Scientist (Associate

Professor), Institut Curie, Paris

2011-2014 CNRS Research Director (Professor), Institut Curie,

Paris

2014- CNRS Research Director (Professor), Chimie

ParisTech, Paris

LI Min-Hui 李敏慧

Research Director at CNRS

Institut de Recherche de Chimie Paris

CNRS – Chimie ParisTech

5 rue Pierre et Marie Curie, 75231 Paris

Tel: +33 1 44 27 60 70


Web : http://www.chimie-

paristech.fr/fr/min-hui-li/

Current Research Area

- Polymersomes

- Soft actuators by liquid crystal polymers

- Polymer self-assembly

- Nanotechnology for drug delivery and bioimaging

Selected Publications

1. Jia L., Li M.-H. “Liquid crystalline polymer vesicles: thermotropic phases in lyotropic

structures” Liquid Crystals, 2014, 41, 368-384. Also in arXiv:1503.00904 [cond-mat.soft].

2. Xing X., Shin H., Bowick M. J., Yao Z., Jia L., and Li M.-H., “Morphology of Nematic and

Smectic Vesicles”, Proc. Natl. Acad. Sci. USA, 2012, 109, 5202-5206.

3. Mabrouk E., Cuvelier D., Brochard-Wyart F., Nassoy P., Li M.-H., “Bursting of sensitive

polymersomes induced by curling”, Proc. Natl. Acad. Sci. USA, 2009, 106, 7294-7298.

4. Li M.-H. & Keller P. “Stimuli-responsive polymer vesicles”. Soft Matter, 2009, 5, 927-937.

5. Li M.-H., Keller P., “Artificial muscles based on liquid crystal elastomers”, Phil. Trans. A.

2006, 364, 2763-2777.

14


http://www.chimie-paristech.fr/fr/min-hui-li/

http://www.chimie-paristech.fr/fr/min-hui-li/

http://arxiv.org/abs/1503.00904

Towards biocompatible and biodegradable stimuli-responsive

polymersomes

Min-Hui Li

Institut de Recherche de Chimie Paris, CNRS UMR8247, Chimie ParisTech, Paris, France

Synthetic amphiphilic polymers have been largely developed since last decades for the purpose of

forming self-assembled polymer vesicles (polymersomes) which mimick lipid vesicles (liposomes).

Polymersomes are much more stable, more robust and less permeable than liposomes due to the high

molecular weight of polymers. Another interesting feature of polymersomes is that their properties can

be tuned extensively by chemical design of the amphiphilic building blocks. These nanostructures are

currently studied as a means of drug delivery and biomedical imaging for their ability to entrap

hydrophobic molecules in the membrane and encapsulate hydrophilic ones in the inner aqueous

compartment. The tailor-design of smart polymersomes, i.e., polymersomes bearing a protective coat,

site-specific targeting ligands and stimuli-responsive release function, is state-of-the-art research in

this field. The research of our group has focussed, since several years, on the development of stealth

and stimuli-responsive polymersomes made from amphiphilic block copolymers. We develop robust

and responsive nanostructures by combining the properties of two kinds of soft materials, polymers

and liquid crystals (LC). In this talk I will describe our recent effort on developing biocompatible and

biodegradable stimuli-responsive polymersomes.

My talk consists of two parts. In the first part I will describe a reduction-sensitive polymersomes,

which can release encapsulated molecules under the action of glutathione, an intracellular trigger.1 In

the second part, I will discuss polysarcosine-containing block copolymers and their thermo-responsive

self-assemblies, especially polymersomes.2

References:

1. Jia, L.; Cui, D.; Bignon, J.; Di-Cicco, A.; Wdzieczak-Bakala, J.; Liu, J.; Li, M.-H.

“Reduction-Responsive Cholesterol-Based Block Copolymer Vesicles for Drug

Delivery”, Biomacromolecules 2014, 15, 2206–2217.

2. Deng, Y.; Zou, T.; Tao, X.; Semetey, V.; Trepout, S.; Marco, S.; Ling, J. and Li, M.-

H. “Polysarcosine-block-Poly(ε-Caprolactone) by Ring-Opening Polymerization of

Sarcosine N-Thiocarboxyanhydride: Synthesis and Thermo-responsive Self-

Assembly”, 2015, submitted.

15

1999: Materials Science & Engineering

B.S. degree, Haerbin Institute of Technology,

P.R. China

2001: Master of Material Science, Haerbin

Institute of Technology, P.R. China

2005: Ph. D. Shanghai Jiao Tong university,

P. R. China

2005-now: Lecturer, associate professor and

full professor, School of Chemistry and

Chemical Engineering, Shanghai Jiao Tong

university, P. R. China.

Yongfeng Zhou

School of Chemistry and Chemical

Engineering

Shanghai Jiao Tong University

800 Dongchuan Road, Shanghai 200240

People’s republic of China


Tel: +86-21-54742665


Supramolecular self-assembly of hyperbranched polymers and hybrid nanomaterials

Cytomimetic chemistry by using the polymer vesicles as the model membranes

Controllable synthesis of functional block copolymers with various topologies


Chen, J. X.; Yu, C. Y.; Shi, Z. Q.; Yu, S. R.;Lu, Z. Y.; Jiang, W. F.;Zhang, M.; He, W.*;

Zhou, Y. F. *; Yan, D. Y. Ultrathin Alternating Copolymer Nanotubes with Readily Tunable

Surface Functionalities, Angew. Chem. Int. Ed. 2015, 54, 3621–3625.

Jiang,W. F.; Zhou, Y. F.*; Yan, D. Y. Hyperbranched polymer vesicles: from self-assembly,

characterization, mechanisms, and properties to applications, Chem. Soc. Rev. 2015, 44,

3874–3889.

Liu, Y.; Yu, C. Y.; Jin, H. B.; Jiang, B. B.; Zhu, X. Y.; Zhou, Y. F.*; Lu, Z. Y.*; Yan, D. Y.,

A Supramolecular Janus Hyperbranched Polymer and Its Photoresponsive Self-Assembly of

Vesicles with Narrow Size Distribution, J. Am. Chem. Soc. 2013, 135, 4765–4770.

Jin, H. B.; Huang, W.; Zhu, X. Y.; Zhou, Y. F.*; Yan, D. Y., Biocompatible or

biodegradable hyperbranched polymers: from self-assembly to cytomimetic applications,

Chem. Soc. Rev. 2012, 41, 5986–5997.

Tao, W.; Liu, Y.; Jiang, B. B.; Yu, S. R.; Huang, W.; Zhou, Y. F.*; Yan, D.Y.; A

Linear-Hyperbranched Supramolecular Amphiphile and Its Self-Assembly into Vesicles with

Great Ductility, J. Am. Chem. Soc. 2012, 134, 762−764.

Dong, R. J.; Zhu, B. S.; Zhou, Y. F.*; Yan, D. Y.; Zhu, X. Y.*. “Breathing” Vesicles with

Jellyfish-like On-Off Switchable Fluorescence Behavior, Angew. Chem. Int. Ed. 2012, 51,

11633–11637.

Awards and Honors

2012, The Winner of the China National Funds for Distinguished Young Scholar

2009, The State Natural Science Award (the second prize)

2008, The National Excellent Doctoral Dissertation of China

16

Facile Functionalization of polymeric self-assemblies

Yongfeng Zhou*, Deyue Yan

School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University,

800 Dongchuan Road, Shanghai, 200240, P. R. China. (0086-21-54742664;

[email protected])

Hyperbranched polymers (HBPs), comprising of dendritic units, linear units and terminal

units, are highly branched macromolecules with three-dimensional dendritic globular architecture.

In recent years, we have synthesized many amphiphilic HBPs in a covalent or noncovalent way,

and found these polymers can be used as the excellent precursors in solution self-assembly,

interfacial self-assembly, or hybrid self-assembly self-assembly, and many impressive

supramolecular aggregates at all scales and dimemsions, such as macroscopic tubes, micro- or

nano-vesicles, fibers, spherical micelles, honeycomb films, large compound vesicles and physical

gels, have been obtained.

In this presentation, selected examples on the self-assembly and functionalization of

hyperbranched polymer vesicles will be introduced. Although, it was firstly invented in year 2004

and was denoted as “branched-polymersome” (BP), there have been many kinds of HBP vesicles

reported up to now, for example, pH-responsive BPs, peptide-coated BPs, protein-coated BPs,

DNA-conjugated BPs, nanoparticle-coated BPs. In addition, some recent work in our lab on the

functional nanotubes and micelles as well as the applications will be also discussed.

References

1. Zhou, Y. F.; Yan, D. Y. Chem. Commun. 2009, 1172.

2. Zhou, Y. F.; Huang, W.; Liu, J. Y.; Zhu, X. Y.; Yan, D. Y. Adv. Mater. 2010, 22, 4567.

3. Jin, H. B.; Huang, w.; Zhu, X. Y.; Zhou, Y. F.; Yan, D. Y. Chem. Soc. Rev. 2012, 41,

5986.

4. Jiang, W.F.; Zhou, Y. F.;Yan, D. Y. Chem. Soc. Rev. Chem. Soc. Rev., 2015, 44, 3874.

5. Chen, J. X.; Yu, C. Y.; Shi, Z. Q.; Yu, S. R.;Lu, Z. Y.; Jiang, W. F.;Zhang, M.;He, W.;

Zhou, Y. F.; Yan, D. Y. Angew. Chem. Int. Ed. 2015, 54, 3621-3625.

6. Wang, J.; Ni, Y. Z.; Jiang, W. F.; Li, H.M.; Liu, Y. N.; Lin, S. L.; Zhou, Y. F.; Yan, D. Y.

small 2015, DOI: 10.1002/smll.201500699..

17

1994 : Polymer Science Master Degree Université

du Maine, Le Mans, France

1997 : Ph. D. Université du Maine, Le Mans,

France

1998: Research Fellow, University of Toronto,

Canada within Pr. M. Winnik’group

1998-2005: Assistant Professor, Laboratory of

Physical Chemistry of Polymers, Paris, Université

Pierre et Maris Curie, Paris France

2005- : Professor, Institut des Molécules et

des Matériaux, Université du maine, Le mans,

France

CHASSENIEUX Christophe

Professor at Université du Maine, Le Mans,

France.

Tel: +33 2 43 83 39 12


Web : http://immm.univ-lemans.fr


Self-assembly in solution and stimuli-responsive systems are research domains of prior

importance for me and my main goal is to elaboration of functional nanostructured

macromolecular assemblies. The fine control of their formation allows the

development of several properties (rheological, transport,…) for various application

fields (EOR, medicine, home and personal care,…). Since a clear image of these

systems must be gained at several levels, I investigate them through a multiscale

approach. Nevertheless, the first step for each study consists in synthesizing in large

amount macromolecules with a perfect control of their structures, composition and

molar mass distributions. Most of the time, controlled radical polymerization

techniques and grafting reactions are processed. Recently, I have developed

amphiphilic block copolymers whose dynamics of self assembly can be finely

controlled through external triggers such as pH. I also use biomacromolecules (such as

proteins and polysaccharides) in order generating nanostructured matrices for food

industry.


1) Patterson, J.P., M.P. Robin, C. Chassenieux, O. Colombani, and R.K. O'Reilly, The

analysis of solution self-assembled polymeric nanomaterials. Chemical Society Reviews,

2014. 43(8): p. 2412-2425.

2) Shedge, A., O. Colombani, T. Nicolai, and C. Chassenieux, Charge Dependent Dynamics

of Transient Networks and Hydrogels Formed by Self-Assembled pH-Sensitive Triblock

Copolyelectrolytes. Macromolecules, 2014. 47(7): p. 2439-2444.

3) Klymenko, A., T. Nicolai, L. Benyahia, C. Chassenieux, O. Colombani, and E. Nicol,

Multiresponsive Hydrogels Formed by Interpenetrated Self-Assembled Polymer Networks.

Macromolecules, 2014. 47(23): p. 8386-8393.

4) Shahin, A., T. Nicolai, L. Benyahia, J.F. Tassin, and C. Chassenieux, Evidence for the

Coexistence of Interpenetrating Permanent and Transient Networks of Hydroxypropyl Methyl

Cellulose. Biomacromolecules, 2014. 15(1): p. 311-318.

18

Amphiphilic Block Copolymers : Search for Tunable dynamics.

A. Shedge, C. Charbonneau O. Colombani, T. Nicolai, C. Chassenieux

LUNAM Université, Université du Maine, IMMM UMR CNRS 6283, Dept PCI,

Avenue O. Messiaen, 72085 Le Mans cedex 05, France

Amphiphilic block copolymers are macromolecules composed of at least one hydrophilic block

chemically linked to one or several hydrophobic blocks. In water, these macromolecules

self-assemble to form micelles composed of a hydrophobic core surrounded by a hydrated

hydrophilic corona. The majority of amphiphilic block copolymers form “frozen” micelles in

aqueous solution. This means that there is no dynamic exchange of chains between micelles

because the energy necessary to extract a hydrophobic block from the core of micelles is too high.

Consequently, the characteristics of the micelles are controlled kinetically and not

thermodynamically. In order to decrease this energy, we have incorporated acrylic acid units (AA)

in the hydrophobic block of poly(n-butyl acrylate) (PnBA). It was previously shown that the

incorporation of 50% molar of AA units in the hydrophobic block led to generation of

pH-sensitive micelles in the case of PAA-b-P(AA0.5-stat-nBA0.5) diblocks.

We will present a quantitative analysis of the dynamics of self-assembled amphiphilic diblock and

triblock copolymer based on acrylic acid units and n-butyl acrylate units. The hydrophobic blocks

contained 50% of acrylic acids units incorporated randomly. The block copolymers were

synthesized by controlled radical polymerization (ATRP). The influence of the concentration, pH,

temperature and the ionic strength on the structure and the mechanical properties of the resulting

self-assembled hydrogels was systematically studied. At low concentrations, static light scattering

measurements showed the formation of star-like micelles (diblock) or flower-like micelles

(triblock) above a critical aggregation concentration (CAC). At higher concentrations, purely

repulsive excluded volume interactions between micelles appeared in the case of diblock

copolymers. In the case of triblock copolymers bridging of flower-like micelles induced in

addition attractive interactions leading to network formation above the percolation concentration.

At high ionic strength and low pH, we showed that the attraction between flower-like micelles

became sufficiently strong to induce phase separation. The formation of the network and the

exchange dynamic of chains were studied by rheology. The viscosity of solutions increased

sharply at the percolation concentration. The terminal visco-elastic relaxation time of the

network is related to the lifetime of bridges. It could be controlled and tuned over several decades

by varying of pH, temperature and the ionic strength.

19

2006: Master of Medicinal Chemistry from

College of Pharmaceutical Sciences, Zhejiang

University, Hangzhou, China.

2009: PhD of Supramolecular Chemistry from

Department of Chemistry, Zhejiang University,

Hangzhou, China.

2009-2011: Postdoc from Institute for Complex

Molecular Systems, Eindhoven University of

Technology, Eindhoven, Netherlands.

2011-present: Associate Professor,

CAS Key Laboratory of Soft Matter Chemistry

University of Science and Technology of China,

Hefei, China

Feng WANG

Associate Professor

Tel: +86-551-3606095



My current research is focused on the fabrication and mechanism investigation of

supramolecular π-conjugated polymers, which are driven by the combination of multiple

non-covalent bonds such as donor-acceptor, hydrogen bonding and metal-metal interactions.

The responsiveness of the resulting supramolecular polymers to external stimuli is also under

investigation. The current study is expected to provide a range of potential applications such

as smart/adaptive materials and supramolecular electronics.


1. Shi, Y.; Yang, Z.; Liu, H.; Li, Z.; Tian, Y.; Wang, F. ACS Macro Lett. 2015, 4, 6.

2. Shi, E.; Gao, Z.; Yuan, M.; Wang, X.; Wang, F. Polym. Chem. 2015, 6, 5575.

3. Tian, Y.-K.; Yang, Z.-S.; Lv, X.-Q.; Yao, R.-S.; Wang, F. Chem. Commun. 2014, 50,

9477.

4. Tian, Y.-K.; Shi, Y.-G.; Yang, Z.-S.; Wang, F. Angew. Chem., Int. Ed. 2014, 53,

6090.

5. Tian, Y.-J.; Shi, E.-T.; Tian, Y.-K.; Yao, R.-S.; Wang, F. Org. Lett. 2014, 16, 3180.

6. Tian, Y.-J.; Meijer, E. W.; Wang, F. Chem. Commun. 2013, 49, 9197.

7. Ding, Y.; Wang, P.; Tian, Y.-K.; Tian, Y.-J.; Wang, F. Chem. Commun. 2013, 49,

5951.

20

Controlled Supramolecular Polymerization Based on the

π-Conjugated Organometallic Building Blocks

Feng Wang

Department of Polymer Science and Engineering, CAS Key Laboratory of Soft Matter

Chemistry, University of Science and Technology of China

Metallo-supramolecular polymers are considered as ideal candidates for the development of

intelligent soft materials. Platinum(ІІ) acetylide complex is an appealing metallo-building block

due to its unique properties. Specifically, square planar geometry of the d8 transition metal ion,

Pt(ІІ), facilitates the combination with other non-covalent bonds, which potentially imparts

cooperativity to the resulting self-assembly systems. Moreover, platinum(ІІ) acetylide

chromophore, due to its intriguing optical property, demonstrates promising applications in

electronics and photonics fields. Herein, we have demonstrated that rod-like platinum(ІІ) acetylide

complex could self-assemble into ordered one-dimensional supramolecular architectures in a

cooperative manner. Detailed mechanistic studies illustrate that both intermolecular hydrogen

bonding and π–π stacking exert significant effects on the supramolecular polymerization

process.1-2

On the other hand, we have successfully constructed novel supramolecular polymers based on

the bis-alkynylplatinum(ІІ) terpyridine molecular tweezer/arene recognition motif, which expands

the host–guest toolboxes and represents a more versatile strategy for the fabrication of

supramolecular polymeric assemblies. Furthermore, stimuli-responsive properties were assigned to

the resulting supramolecular polymers, by taking advantage of the unique tweezer/arene

recognition behavior. With the employment of anthracene derivatives and cyano-functionalized

dienophile as the stimuli-responsive auxiliaries, supramolecular polymerization/depolymerization

process could be precisely regulated in a facile manner. Such protocol advances the concept of

utilizing Diels–Alder chemistry to achieve stimuli-responsive materials in compartmentalized

systems.3

References

[1] Tian, Y.-J.; Meijer, E. W.; Wang, F. Chem. Commun. 2013, 49, 9197.

[2] Tian, Y.-J.; Shi, E.-T.; Tian, Y.-K.; Yao, R.-S.; Wang, F. Org. Lett. 2014, 16, 3180.

[3] Tian, Y.-K.; Shi, Y.-G.; Yang, Z.-S.; Wang, F. Angew. Chem., Int. Ed. 2014, 53, 6090.

21

1994: Physics degree at Ecole Normale

Supérieure de Lyon (France).

1997: Ph. D. University of Montpellier (G. Porte),

France.

1997-1999: CNRS Researcher (Assistant

Professor) at Laboratoire Léon Brillouin, Saclay,

France.

1999-2000: Post-doc at Università Federico II

di Napoli (G. Marrucci), Italy.

2001-2003: CNRS, Laboratoire Léon Brillouin.

Since 2003: Laboratoire Charles Coulomb,

University of Montpellier.

Since 2010: CNRS research director (Professor)

at Laboratoire Charles Coulomb, University of

Montpellier.

OBERDISSE Julian

Directeur de Recherche at CNRS

Tel: +33 4 67 14 35 23



The general topics of the soft matter group of Laboratoire Charles Coulomb (Montpellier)

encompass many fundamental research areas of soft matter science: liquid crystals, physics of

biological systems, polymers, colloids, and surfactants, as well as any composite system. We

are particularly interested in correlating structure, dynamics, and rheological properties of

polymer nanocomposites. Starting from original formulations of model or simplified industrial

nanocomposite systems, we focus on the analysis of microstructure of filler and chains by small

angle scattering (neutrons and x-rays), and quantitatively coupled structural models based on

electron microscopy and scattering. Recently, we have also turned to investigations of

dynamics mainly using dielectric spectroscopy.


1. Aggregation of colloidal nanoparticles in polymer matrices, J. Oberdisse, Soft Matter 2006,

1, 29-36

2. Hard colloids in a soft elastomer matrix: impact of colloid dispersion and polymer mobility

modification on the mechanical properties, Aurélie Papon, Hélène Montès, François Lequeux,

Julian Oberdisse, Kay Saalwächter, Laurent Guy, Soft Matter 2012, 8 (15), 4090-4096

3. Multiscale Filler Structure in Simplified Industrial Nanocomposite Silica/SBR Systems

Studied by SAXS and TEM, Guilhem P. Baeza, Anne-Caroline Genix, Christophe

Degrandcourt, Laurent Petitjean, Jeremie Gummel, Marc Couty, Julian Oberdisse,

Macromolecules 2013, 46, 317−329

4. Studying twin-samples provides evidence for a unique structure-determining parameter in

simplied industrial nanocomposites, Guilhem P. Baeza, Anne-Caroline Genix, Christophe

Degrandcourt, Jérémie Gummel, Anas Mujtaba, Kay Saalwächter, Thomas Thurn-Albrecht,

Marc Couty, and Julian Oberdisse, ACS MacroLetters, 2014, 3 (5), pp 448–452

5. Impact of grafting of phosphonic acids on nanoparticle interactions and stability in aqueous

suspensions, C. Schmitt, A.-C. Genix, J. Alauzun, M. Sztucki, J. Oberdisse, H. Mutin, Physical

Chemistry Chemical Physics 2015, 17, 19173-19182

22

Contrast-matching gone wrong? A study of chain conformation in

polymer nanocomposites

Anne-Caroline Genix1, Amélie Banc

1, Christelle Dupas

1, Ralf Schweins

2,

Marie-Sousai Appavou3, Julian Oberdisse

1

1 Laboratoire Charles Coulomb, UMR 5221 CNRS-Université de Montpellier,

F-34095 Montpellier, France

2 Institut Laue-Langevin, 6 rue Jules Horowitz, F-38042 Grenoble, France

3JCNS, FZ Jülich, Outstation at MLZ, D-85747 Garching, Germany

The structure of polymer nanocomposites has important consequences on final

properties, like for instance mechanical reinforcement. While the structure of the hard

filler phase is usually characterized by electron microscopy and small-angle X-ray

scattering, the chain conformation can only be measured by small-angle neutron

scattering (SANS). Continuous efforts over the past 15 years have produced a body of

sometimes contradictory, because system-dependent, results, see e.g. [1,2]. In

virtually all studies, however, a mismatch ruining the polymer form factor at

low-angles has been observed, in spite of careful contrast-matching.

In this study, the conformation of polymer chains in silica-latex-nanocomposites has

been studied under zero-average contrast conditions using SANS. Samples have been

prepared by drying colloidal suspensions of silica and polymer nanoparticles (NPs)

for two different silica NPs (radius of 5 and 15 nm) and two chain molecular weights

(17 and 100 kg/mol). By appropriate mixing of hydrogenated and deuterated polymer,

chain scattering contrast is introduced, and in principle silica scattering suppressed.

The silica structure consisting mostly of small fractal aggregates is characterized by

transmission electron microscopy (TEM) and small angle X-ray scattering (SAXS) on

the same samples. The measurement of the chain structure by SANS, however, is

perturbed by unwanted silica contributions, as often reported in the literature. Here,

the contribution of contrast-matched silica is evidenced as a function of system

parameters, namely chain mass, silica size, and volume fraction, and a model

rationalizing these contributions for the first time is proposed. Via a statistical model,

a nanometer-thick polymer shell surrounding silica NPs is shown to create contrast,

which is presumably maintained by the reduced mobility of polymer close to

interfaces or attractive polymer-silica interactions. This shell is proven to be

quantitatively important only for the smallest silica NPs. As a consequence, the pure

polymer scattering can be isolated, and the polymer radius of gyration is found to be

independent of filler content and NP size [3].

[1] A. Botti et al, Polymer, 44, 7505–7512(2003)

[2] K. Nusser et al, Macromolecules, 43, 9837–9847 (2010)

[3] A. Banc et al, submitted

23

1988 : Chemistry degree, Zhejiang University,

China

1994 : Ph. D. Zhejiang University, China

1994-1996 : Assistant Professor at Zhejiang

University, China

1996-1999: Associated Professor at Zhejiang

University, China

1999- : Full Professor at Zhejiang University,

China

1999: Visiting Scholar for 3 months at Hong

Kong University of Science & Technology, Hong

Kong, China

1999-2001: Visiting Scholar at Antwerpen

University and Interuniversities MicroElectronic

Center (IMEC), Belgium

2005: Visiting Professor for half year at Stanford

University, USA

CHEN Hongzheng

Professor at Zhejiang University, China

Tel: + 86 571 87952557


Web : http://polymer.zju.edu.cn/osl/english/


The focus of the research done in my group is the organic (organic/inorganic) optoelectronic

materials for photovoltaics, photodetectors and biosensors applications. The objective is to

develop advanced organic (organic/inorganic) optoelectronic materials by tailoring molecular

structures and aggregations, to construct new optoelectronic devices, and to achieve a

fundamental understanding of optical and electronic processes in organic semiconductors.

We are particularly interested in organic solar cell applications.


1. L. Zuo, Z. Gu, T. Ye , W. Fu , G. Wu , H. Li, H. Chen, Enhanced Photovoltaic

Performance of CH3NH3PbI3 Perovskite Solar Cells through Interfacial Engineering Using

Self-Assembling Monolayer, J Am Chem Soc 2015, 137, 2674-2679.

2. L. Zuo, C.-Y. Chang, C.-C. Chueh, S. Zhang, H. Li, A. K.-Y. Jen, H. Chen, Design of a

Versatile Interconnecting Layer for Highly Efficient Series-Connected Polymer Tandem Solar

Cells, Energy & Environmental Science 2015, 8, 1712-1718

3. H. Li, C. Fan, W. Fu, H. Xin, H. Chen, Solution-grown organic single-crystalline

donor-acceptor heterojunctions for photovoltaics, Angew. Chem. Int. Ed. 2015, 54, 956-960.

4. W. Fu, L. Wang, J. Ling, H. Y. Li, M. M. Shi, J. Xue, H. Chen, High Efficient Hybrid

Solar Cells with Tunable Dipole at the Donor/Acceptor Interface, Nanoscale 2014, 6,

10545-10550.

5. S.-Y. Liu, H. Li, M.-M. Shi, H. Jiang, X.-L. Hu, W.-Q. Li, L. Fu, and H. Chen, Pd/C as a

Clean and Effective Heterogeneous Catalyst for C-C Couplings toward Highly Pure

Semiconducting Polymers, Macromolecules, 2012, 45, 9004-9009.

24

Enhanced Efficiency of Polymer and Perovskite Solar Cells Via

Interface Engineering

Hongzheng Chen

Department of Polymer Science and Engineering, Zhejiang University, Hangzhou

310027, China. Email: [email protected]

Polymer and hybrid solar cells have been the subject of extensive study for energy

issues due to their potential applicability in low-cost, lightweight, flexible,

solution-process ability and/or transparent large-area devices. Although the efficiency

of both polymer and small molecule solar cells has already been reached to 10% for

single junction device, there is one important hindrance for further efficiency

improvement. Organic semiconductors usually have much lower charge transport and

shorter exciton diffusion length compared to their inorganic counterpart. The low

mobility and the short exciton diffusion length strongly limit the thickness of the

photoactive layers in devices, leading to insufficient light absorption in the active

layer due to the narrower absorption of the organics. In this presentation, I will talk

about the design and the fabrication of highly efficient polymer and hybrid solar cells

by enhancing light absorption, improving charge carrier mobility, interface

engineering and so on. As a result, polymer solar cells and perovskite hybrid solar

cells with high efficiencies over 10% were fabricated.

1. Yang X, Chueh CC, Li CZ, Yip HL, Yin PP, Chen H, Chen WC, Jen AKY. High-Efficiency Polymer

Solar Cells Achieved by Doping Plasmonic Metallic Nanoparticles into Dual Charge Selecting

Interfacial Layers to Enhance Light Trapping, Adv. Energy Mater. 2013, 3, 666-673.

2. Zuo L, Chueh CC, Xu YX, Chen KS, Zang Y, Li CZ, Chen H, Jen AKY. Microcavity-driven

Enhanced Light-trapping for Highly Efficient Organic Parallel Tandem Solar Cells, Adv. Mater. 2014,

26, 6778–6784.

3. Zuo, L; Chang, CY; Chueh, CC; Zhang, S; Li, H; Jen, AKY; Chen, H., Design of a Versatile

Interconnecting Layer for Highly Efficient Series-Connected Polymer Tandem Solar Cells, Energy &

Environmental Science 2015, 8, 1712-1718.

4. Zuo, L; Gu, Z.; Ye, T.; Fu, W.; Wu, G.; Li, H.; Chen, H., Enhanced Photovoltaic Performance of

CH3NH3PbI3 Perovskite Solar Cells through Interfacial Engineering Using Self-Assembling

Monolayer, J Am Chem Soc 2015, 137, 2674-2679.

25


1989 : Master of Science in Electrochemistry,

Univ. Paris 6, France

1993 : Ph. D. Univ. Paris 6 (UPMC)

1992-1993 : Research Fellow, ULB, Bruxelles

Belgium


Professor) at ESPCI, Laboratory of Physical

Chemistry of Polymers, Paris

2007- 2010 : CNRS Research Director

(Professor) at ESPCI

2010- : CNRS Research Director (Professor) at

Ecole Normale Supérieure, Paris

Tribet Christophe

Directeur de Recherche at CNRS

Tel: +33 1 44 32 24 03


Web : http://www.chimie.ens.fr/?q=node/3166


The group of Biophysical Chemistry at ENS Paris is interested in manipulating and

understanding biological systems in new ways using the knowledge of chemistry. We develop

in particular (macro)molecules and methods enabling observation, and remote control of

biological targets, including living cells. Current research projects involving polymers include

optically controlled cell permeabilization, switchable polymer layers that display biological

ligands, artificial chaperons and microcapsules for protein protection.


Martin, N.; Ma, D.; Herbet, A.; Boquet, D.; Winnik, F. M.; Tribet,C. Biomacromolecules

2014, 15 (8), 2952-2962, Prevention of Thermally Induced Aggregation of IgG Antibodies by

Noncovalent Interaction with Poly(acrylate) Derivatives.

Marie, E.; Sagan, S.; Cribier, S.; Tribet, C., J. Membrane Biol., 2014, 10.1007/

s00232-014-9679-3 , Amphiphilic Macromolecules on Cell Membranes: From Protective

Layers to Controlled Permeabilization

Stijn F. M. van Dongen, P. Maiuri, E. Marie, C. Tribet and M. Piel, Adv. Mater. 2013,

25(12):1687-91, Triggering Cell Adhesion, Migration or Shape Change with a Dynamic

Surface Coating

S. Sebai, et al. Angewandte Chemie Int Ed., (2012), 51, 2132-2136, Photo-control by

copolymers of molecules, peptides and quantum dots translocation through cell plasma

membranes and lipid bilayer.

Jing Sun, J. Ruchmann, A. Pallier, L. Jullien, M. Desmadril, and C. Tribet,

Biomacromolecules (2012), 13(11), 3736-3746, Unfolding of Cytochrome c upon

Interaction with Azobenzene-modified Copolymers

E. Chevallier, C. Monteux, F. Lequeux, C. Tribet, Langmuir (2012), 28(5), 2308-2312.

Photofoamers : Remote Control of Foam Destabilization by Exposure to Light Using an

Azobenzene Surfactant

26

Dynamic surface switches based on robust adlayers of light-, or

temperature-responsive poly(Lysine) comb-like copolymers.

Fabrice Dalier, Emmanuelle Marie, Christophe Tribet

Ecole Normale Supérieure-PSL Research University, Dpt Chemistry, Sorbonne

Universités - UPMC, CNRS UMR 8640, 24 rue Lhomond, 75005 Paris, France.

E-mail : christophe.tribet @ens.fr

Polymer hydrogels and polymer-coated surfaces are ubiquitous substrates for cell

culture. Passive, static substrates are however limited compared to natural matrices

that can dynamically affect cell migration, proliferation or cell fate by spatial and

temporal modulation of presentation / sequestration of guidance cues.

We design systems that switch on demand the macromolecule-cell membrane

association in cell culture conditions. Two “toolboxes” will be described: (1) soluble

azobenzene-containing polyamphiphiles that bind to lipid bilayers and to cells under

blue light, phototriggering mild cytosolic penetration of peptides. (2) Comb-like

poly(Lysine)-g-PEO and PLL-g-(PNIPAM-co-ligand) derivatives that adsorb

spontaneously on many substrates, and form cell-repellant layers. These layers

become activated (displaying ligands, and triggering specific binding) by external

stimulations including temperature shifts, exposure to light, or copper-free click

reaction with an adhesion peptide. In addition to cell responses (triggering cell

adhesion and migration on surface micropatterns), the switch of surfaces properties

was assessed by AFM and by observation of the capture of Streptavidin-conjugated

particles. It is correlated with switching between collapsed and extended

conformations of surface-attached polymer strands.

.

1. F. Dalier et al., submitted ; and Stijn F. M. van Dongen, P. Maiuri, E. Marie, C. Tribet and M.

Piel, Adv. Mater. 2013, 25(12):1687-91.

2. S. Sebai, et al., Angewandte Chemie Int Ed., 2012, 51, 2132-2136.

27

1996 : Ph. D. in Organic

Chemistry, Lille University,

France

1997-2006: Lecturer in Organic

Chemistry at the University of

Dunkerque, France

2006 : Research Fellow,

Edinburgh University, Scotland

2007- : Professor at ENSCL

of the University of Lille,

Laboratory of “ Matériaux et

Transformation”, UMR-CNRS

8207, France.

WOISEL Patrice

Professor at the University of Lille

Tel: +33 3 20 43 49 54


Web:

http://umet.univ-lille1.fr/detailscomplets.php?id=119&lang=en


Research within our research group focuses upon the design, synthesis and characterisation

of functional macromolecules and nanoparticles and their assemblies. Current themes

includes multi-stimuli responsive micelles, hydrogels, surfaces and smart supramolecular

sensors.


1. L. Sambe, V. R. De la rosa, K. Belal, F. Stoffelbach, J. Lyskawa, F. Delattre, M. Bria,

G. Cooke, R. Hoogenboom, P. Woisel, Programmable Polymer-Based

Supramolecular Temperature Sensor with a Memory Function, 2014, Angewandte

Chemie, 53, 5044–5048. COVER PICTURE

2. M. Arslan, T. N. Gevrek, J. Lyskawa, S. Szunerits, R. Boukherroub, R. Sanyal, P.

Woisel, A. Sanyal, Bioinspired Anchorable Thiol-Reactive Polymers: Synthesis and

Applications Toward Surface Functionalization of Magnetic Nanoparticles, 2014,

Macromolecules, 47, 5124-513.

3. W. Laure, P. Woisel, J. Lyskawa, Switching the Wettability of Titanium Surfaces

through Diels-Alder Chemistry, 2014, Chemistry of Materials, 26, 3771-3780

4. L. Sambe, k. Belal, F. Stoffelbach, J. Lyskawa, F. Delattre, M. Bria, F. X. Sauvage, M.

Sliwa, V. Homblot, B. Charleux, G. Cooke, P. Woisel, Multi-stimuli responsive

supramolecular diblock copolymers, 2014, Polym. Chem., 5, 1031-1036

5. S. T. Caldwell, C. Maclean, M. Riehle, A. Cooper, M. Nutley, G. Rabani, B.

Fitzpatrick, V. M. Rotello, B. O. Smith, K. Belal, P. Woisel, G. Cooke,

Protein-mediated dethreading of a biotin-functionalised pseudorotaxane, 2014,

Org.Biomol. Chem. 12 pp. 511-516.

28

http://umet.univ-lille1.fr/detailscomplets.php?id=339&lang=fr

http://umet.univ-lille1.fr/detailscomplets.php?id=119&lang=fr

Supramolecular chemistry: a powerful tool to elaborate “colourful”

multi-stimuli responsive macromolecular assemblies

P. Woisel, Pr ENSCL

USTL, ENSCL, UNITÉ DES MATÉRIAUX ET TRANSFORMATIONS (UMET, ISP, UMR

8207), F-59655 VILLENEUVE D’ASCQ CEDEX (FRANCE)– EMAIL:

[email protected]

The development and application of multi-stimuli responsive materials is a burgeoning field

of study in leading research groups in the USA, Asia and mainland Europe. There is no doubt that

the creation of such high performance materials relies directly on our ability to manipulate these

“smart” materials in a controllable, predictable and orchestrated fashion from nano-to

macro-scale.

Complexes fabricated from the electron deficient cyclophane

cyclobis(paraquat-p-phenylene) (CBPQT4+

) and electron rich guests have become one of the

most important building blocks for the synthesis of coloured self-assembled architectures. Here, I

will report the successful engineering of new multi-stimuli responsive macromolecular assemblies

based on well-defined functionalized polymer building blocks incorporating both

electro-deficient (CBPQT4+

) and electron-rich units (tetrathiafulvalene, naphthalene) moieties.

The architectures of these materials have been constructed by specifically holding together

complementary well-defined polymer building blocks (prepared by Controlled Radical

Polymerisation) with specially designed host/guest motifs attached in specific locations on

polymer backbones. The inherent reversibility of supramolecular architectures has allowed “on

demand” modular and tunable modification of structures and properties of materials. More

particularly, we have exploited the presence of coloured CBPQT4+

based interactions to create i)

“smart” micelles and hydrogels and ii) (re)programmable supramolecular temperature and pH

sensors with memory function. An important practical aspect of these new functional materials is

that all relevant phenomena (self-assembly and disassembly processes, reading/reprogramming

of temperature, memory function) have an associated visible readout, thereby affording

convenient and quantifiable systems with applications spanning the physical and biological

sciences.

References

1. L. Sambe, V. R. De la rosa, K. Belal, F. Stoffelbach, J. Lyskawa, F. Delattre, M. Bria, G. Cooke, R.

Hoogenboom, P. Woisel, Programmable Polymer-Based Supramolecular Temperature Sensor

with a Memory Function Angewandte Chemie, 2014, 53, 5044–5048. COVER PICTURE.

2. L.Sambe, F. Stoffelbach, K. Poltorak, J. Lyskawa, A. Malfait, M. Bria, G. Cooke, P. Woisel,

Elaboration of Thermoresponsive Supramolecular Diblock Copolymers in Water from

Complementary CBPQT4+

and TTF End-Functionalized Polymers, Macromol. Rapid Comm., 2014,

35, 498-504. SPECIAL ISSUE.

3.L. Sambe, k. Belal, F. Stoffelbach, J. Lyskawa, F. Delattre, M. Bria, F. X. Sauvage, M. Sliwa, V.

Homblot, B. Charleux, G. Cooke, P. Woisel, Multi-stimuli responsive supramolecular diblock

copolymers, Polym. Chem., 2014, 5, 1031-1036

29

2001: Bachelor, College of Chemistry, Jilin

University, China

2006: PhD with X. Zhang, College of Chemistry,

Jilin University, China

2004-2005: Exchange student, University of

Leuven, Belgium

2006-2008: Post-doc with D. N. Reinhoudt and J.

Huskens, University of Twente, the Netherlands

2008- 2014: Assistant and Associate professor,

Department of Chemistry, Tsinghua University

2014 till now: Professor, Department of Chemistry

Tsinghua University

Huaping Xu

Deputy Chair, Department of Chemistry,

Tsinghua University

Tel: +86 10 62773672


Web: http://xuslab.com


Selenium-containing Polymers: Redox responsive polymers have attracted wide interest for

their promising applications in controllable encapsulation and delivery in physiological

environments, where the redox process is constantly and widely present. We are aiming at

designing and synthesizing all kinds of selenium-containing polymers, including main chain

and side chain block copolymers, dendrimers and hyperbranched polymers for controlled

self-assembly and disassembly under various responsive stimuli, leading to new biomaterials

for controlled drug delivery and gene therapy.


1. Xu, H.; Cao, W.; Zhang, X.: Selenium-containing Polymers: Promising Biomaterials for

Controlled Release and Enzyme Mimics. Acc. Chem. Res., 2013, 46, 1647.

2. Ji, S.; Cao, W.; Yu, Y.; Xu, H.: Dynamic Diselenide Bonds: Exchange Reaction Induced

by Visible Light without Catalysis. Angew. Chem. Int. Ed., 2014, 53, 6781.

3. Cao, W.; Gu, Y.; Meineck, M.; Li, T.; Xu, H.: Tellurium-containing Polymer Micelles:

Competitive-Ligand-Regulated Coordination Responsive Systems. J. Am. Chem. Soc.,

2014, 136, 5132.

4. Cao, W.; Zhang, X.; Miao, X.; Yang, Z.; Xu, H.: Gamma-ray Responsive Supramolecular

Hydrogel Based on Diselenide-containing Polymer and Peptide. Angew. Chem. Int. Ed.,

2013, 52, 6233.

5. Cao, W.; Li, Y.; Yi, Y.; Ji, S.; Zeng, L.; Sun, Z.; Xu, H.: Coordination-Responsive

Selenium-Containing Polymer Micelles for Controlled Drug Release. Chem. Sci., 2012, 3,

3403.

6. Ma, N.; Li, Y.; Xu, H.; Wang, Z.; Zhang, X.: Dual Redox Responsive Assemblies Formed

from Diselenide Block Copolymers J. Am. Chem. Soc., 2010, 132, 442.

30

ROS Responsive Selenium-containing Polymers

Huaping Xu*

Department of Chemistry, Tsinghua University, Beijing 100084, China


Selenium, an essential element for animals and humans, possesses unique chemical and

biological properties. As reactive oxygen species (ROS) are natural by-products of oxygen

metabolism that may cause chronic diseases such as cancer and heart disease to human beings,

great effort has been put to synthesize numerous antioxidant compounds based on

selenium-containing small molecules. However, literatures on selenium-containing polymers

are rather scarce. Here we are going to highlight the most recent advances on

selenium-containing polymers and their potential bio-applications as ROS-responsive drug

delivery vehicles in physiological conditions. Take the linear polymer for example,

diselenide-containing amphiphilic block copolymer micelles exhibited unique dual redox

triggered disassembly behavior in response to a very dilute concentration of ROS or reductant.

The diselenide bonds could also be cleaved by ROS generated by photosensitizer under light

radiation. As gamma rays is one of the most widely used radiation in clinical application and

that gamma radiation on water could also produce ROS, selenium-containing polymers were

also used for the combination of chemotherapy and radiotherapy.

Scheme 1 Selenium-containing Polymers

References

1. Xu, H.; Cao, W.; Zhang, X. Acc. Chem. Res. 2013, 46, 1647.

2. Ma, N.; Li, Y.; Xu, H.; Wang, Z.; Zhang, X. J. Am. Chem. Soc. 2010, 132, 442.

3. Cao, W.; Zhang, X.; Miao, X.; Yang, Z.; Xu, H. Angew. Chem., Int. Ed. 2013, 52, 6233.

4. Ji, S.; Cao, W.; Yu, Y.; Xu, H. Angew. Chem., Int. Ed. 2014, 53, 6781-6785

5. Cao, W.; Gu, Y.; Meineck, M.; Li, T.; Xu, H. J. Am. Chem. Soc. 2014, 136, 5132.

6. Cao, W.; Gu, Y.; Li, T.; Xu, H. Chem. Commun. 2015, 51, 7069.

31


1996 M.S. in Chemistry, University of Strasbourg

(France)

2002 Ph.D. in Chemistry, University of Neuchâtel

(Switzerland)

2003 Postdoctoral Research Associate, Cornell

University (NY, USA)

2004 Postdoctoral Research Associate, University

of Neuchâtel (Switzerland)

2004 Assistant Professor, University of Rennes 1

(France)

2008 Professor, Chimie ParisTech (France)

THOMAS Christophe

Professor

Tel: +33 1 44 27 67 21

Email:

[email protected]

Web : http://www.chimie-paristech.fr


Development of new methods for polymer synthesis, with an emphasis on catalytic

transformations and the control of stereochemistry

Development of new strategies for tandem catalysis

Use of inorganic oxides as supports for metal-based catalysts


J. W. Kramer, D. S. Treitler, E. W. Dunn, P. M. Castro, T. Roisnel, C. M. Thomas, G. W.

Coates: Polymerization of Enantiopure Monomers Using Syndiospecific Catalysts: A

New Approach To Sequence Control in Polymer Synthesis. Journal of the American

Chemical Society, 2009, 131, 16042-16044.

N. Ajellal, G. Durieux, L. Delevoye, G. Tricot, C. Dujardin, C. M. Thomas, R. M. Gauvin:

Polymerization of Racemic -Butyrolactone using Supported Catalysts: a Simple Access

to Isotactic Polymers. Chemical Communications 2010, 46, 1032-1034.

C. Robert, F. de Montigny, C. M. Thomas: Tandem Synthesis of Alternating Polyesters

from Renewable Resources. Nature Communications 2011, 2:586 doi: 10.1038 /

ncomms1596.

J. Guo, P. Haquette, J. Martin, K. Salim, C. M. Thomas: Replacing Tin in Lactide

Polymerization: Design of Highly Active Germanium-Based Catalysts. Angewandte

Chemie International Edition 2013, 52, 13584-13587.

C. Robert, C. M. Thomas: Tandem Catalysis: A New Approach to Polymers. Chemical

Society Reviews 2013, 42, 9392-9402.

J. Fang, M. J.-L. Tschan, T. Roisnel, X. Trivelli, R. M. Gauvin, C. M. Thomas, L. Maron:

Yttrium catalysts for syndioselective β-butyrolactone polymerization: On the origin of

ligand-induced stereoselectivity. Polymer Chemistry 2013, 4, 360-367.

32

Polymerization of Heterocycles: a Simple Approach to Sequence

Control in Polymer Synthesis

Carine Robert1, Frédéric de Montigny

1, Pierre Haquette

1, Christophe M. Thomas

1

1 PSL Research University, CNRS-Chimie ParisTech, Institut de Recherche de Chimie

Paris, 75005 Paris, France ([email protected])

Given the growing need for inexpensive biodegradable plastics for use in various

applications, the development of synthetic methods for the polymerization of a wide

range of monomers with control over the stereochemistry, molecular weight, and

comonomer incorporation is of particular importance1. In this context aliphatic

polyesters have emerged as biodegradable materials with huge potential.

Figure 1. Synthetic approaches to aliphatic polyesters

Recently we have synthesized new biodegradable poly(β-hydroxyalkanoate)s (PHAs)

with controlled primary structures2. By using highly efficient yttrium complexes as

initiators, we were able to synthesize highly alternating copolymers by ring-opening

polymerization of a mixture of enantiomerically-pure but different monomers (Fig. 1).

This efficient catalytic system makes copolymers that would be very difficult to make

through any other method. Also we have reported a new strategy to obtain

biodegradable polyesters3. This was achieved by tandem catalysis, which confers

great interest to this approach4. Commercially available complexes were used as

efficient catalysts for cyclization of dicarboxylic acids followed by alternating

copolymerization of the resulting anhydrides with epoxides (Fig. 1). Given an

operationally simple method, this tandem catalysis is an attractive strategy for the

production of new renewable materials.

1. C. M. Thomas, Chem. Soc. Rev. 2010, 39, 165-173.

2. J. W. Kramer, D. S. Treitler, E. W. Dunn, P. M. Castro, T. Roisnel, C. M. Thomas G. W. Coates, J.

Am. Chem. Soc. 2009, 131, 16042-16044.

3. a) C. Robert, F. De Montigny, C. M. Thomas, Nat. Commun. 2011, 2:586, doi:

10.1038/ncomms1596. b) C. Robert, F. De Montigny, C. M. Thomas, ACS. Catal. 2014, 4, 3586-3589.

4. C. Robert, C. M. Thomas, Chem. Soc. Rev. 2013, 42, 9392-9402.

33

1983: Bachelor of Science, Northeast University, China

1992: Changchun Institute of Applied Chemistry

(CIAC), Chinese Academy of Sciences (CAS)

1992-1994: Postdoctoral Fellow, Zhejiang

University, China

1994-1996: Associate Professor, CIAC, CAS

1997-1999: Research fellow of Humboldt,

Institute of Technique and Macromolecular

Chemistry, Hamburger University

1997-2014: Professor, State Key Lab of Polymer

Physics and Chemistry, CIAC, CAS

2014- : Professor, Institute for Advanced

Polymer Materials, Tianjin University, China

LI Yuesheng

Director of Institute for Advanced

Polymer Materials

Tel: +86-22-2740-3774



The focus of the research done in our group is the coordination polymerization of olefin

catalyzed by well-defined transition metal complexes. Present research work includes

syntheses and characterization of new transition metal catalysts, copolymerization of olefin

with polar/functional monomer, selective (co)polymerization of polyene monomers. In

addition, we is also engaged into various aspects of polymer syntheses including various

living polymerization and branched/hyperbranched polymer syntheses.


1. Dong, Z.M.; Liu, X.H.; Lin,Y.; Li, Y.S., Synthesis of novel star polymers with vinyl-

functionalized hyperbranched core via “arm-first” strategy, Macromolecules, 2010, 43,

7985-7992.

2. Shi, X.C.; Wang, Y.X.; Liu, J.Y.; Cui, D.M.; Men, Y.F.; Li, Y.S., Stereospecific

cyclopolymerization of α,ω-diolefins by pyridylamidohafnium catalyst with the highest

activity, Macromolecules, 2011, 44, 1062-1065.

3. Hong, M.; Cui, L.; Liu, S.R.; Li, Y.S., Synthesis of novel cyclic olefin copolymer (COC)

with high performance via effective copolymerization of ethylene with bulky cyclic olefin,

Macromolecules, 2012, 45, 5397-5402.

4. Bao, Y.M.; Shen, G.R.; He, J.; Li, Y.S., Water-soluble hyperbranched poly(ester urethane)s

based on D,L-alanine: isocyanate-free synthesis, post-functionalization and application,

Green Chem., 2012, 14, 2243-2250.

5. Tao, P.; Mu, H L. Liu, J. Y. Li, Y.S.; New half-sandwich chromium(III) complexes bearing

phenoxy-phosphine (oxide) [O,P(= O)] ligands: synthesis, structures, and catalytic

properties for ethylene (co)polymerization, Organometallics, 2013, 32, 4805-4812.

6. Wang, B.; Wang, Y.X.; Cui, J.; Long, Y.Y.; Li, Y.G.; Yuan, X.Y.; Li, Y.S., Cyclopoly-

merization of Si-containing alpha,omega-diolefins by a pyridylamidohafnium catalyst with

high cyclization selectivity and stereoselectivity, Macromolecules, 2014, 47, 6627-6634.

34

Development of Facile and Efficient Strategy to Chemical Modified

Isotactic Polypropylene with Well-defined Structure

Yuesheng Li, Xiaoyan Wang, Li Pan

Institute for Advanced Polymer Materials, Tianjin University, Tianjin 300072.

[email protected]

Catalyzed by (pyridylamido)hafnium, a series of halogen-functionalized isotactic

polypropylenes (iPP) were synthesized via the stereospecific copolymerization of

propylene with ω-halo-α-alkenes. The high molecular weight (MW) functional iPPs

possessing abundant iodoalkene units and high isotacticity were easily obtained under

mild conditions with excellent catalytic activity. Detailed in situ NMR analysis, DFT

calculations and the copolymerization of propylene with a series of ω-halo-α-alkenes

suggest that the ω-iodine group has very weak interaction with the active Hf center,

and ω- halo-α-alkenes with long chain show a better possibility to be copolymerized

with propylene. The thiol-halogen click chemistry between halogenated iPPs and

thiols was systematically investigated, based on which, various polar groups including

hydroxyl, ester, aryl, thiazolyl and amino have been successfully introduced into iPP

in a quantitative way, by employing iodinated iPP as the highly reactive intermediate.

The regio-/stereo-selective coordination copolymerization of propylene with

p-(3-butenyl) styrene (BSt) was also conducted by using the Hf catalyst that produces

exclusively high MW iPPs with abundant ethenyl benzene (styrene) groups.

Remarkably, the current Hf catalyst, which exhibits overwhelmingly favorable

reactivity toward α-olefin over styrene moieties, effectively promoted the copoly-

merization of propylene with BSt under judiciously chosen reaction conditions, in

which catalytic activity (1.35 kg polymer/mmolHfh), MW, styrene group content

and tacticity reached a satisfying level simultaneously. Various side- and graft-

functionalized iPPs were synthesized via the UV-light initiated thiol-ene click

chemistry and iodine- catalyzed hydroalkylation as well as controllable radical

polymerization of the resultant propylene/BSt copolymer with commercially available

materials.

The authors are grateful for financial support by the National Natural Science

Foundation of China (No. 21234006).

1. Wang, X.Y.; Wang, Y.X.; Shi, X.C.; Chen, C.L.; Li, Y.S., Macromolecules, 2014, 47, 552-559.

2. Wang, X.Y.; Wang, Y.X.; Pan, L.; Li, Y.S., Macromolecules, 2015, 48, 1991-1998.

3. Wang, X.Y.; Li, Y.G.; Mu, H.L.; Pan, L.; Li, Y.S., Polym. Chem. 2015, 6, 1150-1158.

35

1996: PhD at the University of Bordeaux in the

Centre de Recherche Paul Pascal (CRPP-CNRS)

1998: Postdoctoral Fellowship at the University

of Illinois at Urbana-Champaign in the group of

Professor S.I. Stupp, UIUC-USA

1998: Assistant Professor at the Ecole Nationale

Supérieure de Chimie et de Physique de

Bordeaux (ENSCPB) and Laboratoire de Chimie

des Polymères Organiques (LCPO-CNRS)

Since 2005: Professor, ENSCBP Bordeaux INP

LECOMMANDOUX Sebastien

Professor, Bordeaux-INP

Tel: +33 540 00 22 41


Web : www.lcpo.fr


SL is currently leading the group “Polymer Self-Assembly and Life Sciences” at the LCPO. His

research interests include polypeptide and polysaccharide based block copolymers

self-assembly, biomimetic approaches toward design of synthetic viruses and cells as well as

the design of polymersomes for drug-delivery and theranostic. He is especially worldwide

recognized for the design of original polymeric nanoparticles, “bioactive by design” and stimuli

responsive, able to load and release “on demand” molecular and biomacromolecular drugs

(anti-cancer, peptide,…). He is deputy director of the LCPO and will become director in

January 2016. He is also currently chairing the ESF Research Network Programme on

“Precision Polymer materials” P2M and in the board of the French Society of Nanomedicine

(SFNano). He is Associate Editor for Biomacromolecules (ACS) and in the Editorial Advisory

Board of several international journals, including Bioconjugate Chemistry (ACS), Polymer

Chemistry and Biomaterials Science (RSC).


1) R. J. R. W. Peters, M. Marguet, S. Marais, M. W. Fraaije, J. C. M. Van Hest, S.

Lecommandoux. “Cascade Reactions in Multicompartmentalized Polymersomes”. Angew.

Chem. Int. Ed. 53, 146-150 (2014) (highlighted in Nature Chemistry)

2) R. Salva, J.-F. Le Meins, O. Sandre, A. Brulet, M. Schmutz, P. Guenoun, S.

Lecommandoux. “Polymersome Shape Transformation at the Nanoscale”. ACS Nano 7,

9298-9311 (2013)

3) H. Oliveira, E. Pérez-Andrés, J. Thevenot, O. Sandre, E. Berra, S. Lecommandoux.

“Magnetic field triggered drug release from polymersomes for cancer therapeutics”.

Journal of Controlled Release 169, 165-170 (2013)

4) E. Garanger, S. Lecommandoux. “Towards Bioactive Nanovehicles Based on Protein

Polymers”. Angew. Chem. Int. Ed., 51, 3060-3062 (2012)

5) J. Huang, C. Bonduelle, J. Thevenot, S. Lecommandoux, A. Heise. “Biologically Active

Polymersomes from Amphiphilic Glycopeptides”. J. Am. Chem. Soc. 134 (1), 119-122

(2012)

36


http://www.lcpo.fr/

Biomimetic polymersomes for virus and cell mimicry

Sebastien Lecommandoux

Univ. Bordeaux, LCPO, Bordeaux-INP, UMR CNRS 5629, 33600, Pessac, France


Polymersomes are among the most attractive systems for drug delivery applications.

We report here an overview on the self-assembly in water of amphiphilic block

copolymers into polymersomes, and their applications in loading and controlled

release of both hydrophilic and hydrophobic molecules and biomolecules. We pay

special attention to polysaccharide and polypeptide-based block copolymer vesicles

(1). These copolymers that mimic the structure and function of glycoproteins

represent an example of the effectiveness of a biomimetic strategy in implementing

materials design. In addition, magnetic polymersomes, -Fe2O3

nanoparticles are currently investigated, together with their potential applications as

contrast agent for imaging and as therapeutic nanoparticles using hyperthermia (2). In

vitro and in vivo efficacy results on different cancer models will be presented. Finally

our recent advances in using “biomimicry approaches” to design complex,

compartmentalized materials will be proposed. Such a system constitutes a first step

towards the challenge of structural cell mimicry and functionality (3).

1. (a) Upadhyay, KK.; Bhatt, A.N.; Mishra, A.N.; Dwarakanath, B. S.; Jain, S.; Schatz, C.; Le Meins,

JF.; Farooque, A.; Chandraiah, G.; Jain, AK.; Misra, AK.; Lecommandoux, S. Biomaterials 2010, 31,

2882. (b) C. Bonduelle, S. Lecommandoux. Biomacromolecules 2013, 14, 2976-2983. (c) Bonduelle,

C. ; Huang, J. ; Ibarboure, E. ; Heise, A. ; Lecommandoux, S. Chem. Commun. 2012, 48, 8353. (d)

Huang, J. ; Bonduelle, C. ; Thévenot, J.; Lecommandoux, S. ; Heise, A. J. Am. Chem. Soc. 2012, 134,

119.

2. (a) Sanson, C. ; Diou, O. ; Thevenot, J. ; Ibarboure, E. ; Soum, A. ; Brulet, A. ; Miraux, S. ;

Thiaudiere, E. ;Tan, S. ; Brisson, A. ; Dupuis, V. ; Sandre, O. ; Lecommandoux, S. ACS Nano 2011, 5,

1122. (b) Oliveira, H. ; Pérez-Andrés, E. ; Thevenot, J. ; Sandre, O. ; Berra, E. ; Lecommandoux, S. J.

Control. Release 2013, 169, 165. (c) Pourtau, L. ; Oliveira, H. ; Thevenot, J. ; Wan, Y. ; Brisson, A. ;

Sandre, O. ; Miraux, S. ; Thiaudiere, E. ; Lecommandoux, S. Advanced Healthcare Materials 2013, 2,

1420-1424.

3. (a) Marguet, M.; Edembe, L.; Lecommandoux, S. Angew. Chem. Int. Ed. 2012, 51, 1173. (b)

Marguet, M.; Sandre, O.; Lecommandoux, S. Langmuir 2012, 28, 2035. (c) Marguet, M. ; Bonduelle,

C. ; Lecommandoux, S. Chem. Soc. Rev. 2013, 42, 512-529. (d) R. J. R. W. Peters, M. Marguet, S.

Marais, M. W. Fraaije, J. C. M. Van Hest, S. Lecommandoux. Angew. Chem. Int. Ed. 2014, 53,

146-150.

37


2000: Ph.D, Department of Macromolecular Science,

Fudan University, China

1996: MS, Department of Chemistry, Wuhan

University, China

1993: BS, Department of Environmental Science,

Wuhan University, China

2000-2002: Postdoc, School of Life Science,

University of Sussex, England

2002-2003: Postdoc, Department of Chemical

Engineering, University of Delaware, USA

2004~: Professor at Department of Polymer Science

and Engineering, University of Science and

Technology of China

2010~: Director, CAS Key Laboratory of Soft Matter

Chemistry

Prof. Dr. Shiyong LIU

University of Science and Technology of

China, Hefei, Anhui Province, China

Tel: +86-551-63607348


Web: http://staff.ustc.edu.cn/~sliu


Current research interests include the design and synthesis of functional polymeric materials,

colloids, and stimuli-responsive polymeric assemblies with controlled properties for applications

in imaging, sensing, diagnostics, and nanomedicines.


(1) Hu, J. M.; Zhang, G. Y.; Ge, Z. S.; Liu, S. Y. Stimuli-responsive tertiary amine methacrylate-based

block copolymers: Synthesis, supramolecular self-assembly and functional applications. Prog. Polym. Sci.

2014, 39, 1096-1143.

(2) Hu, J. M.; Liu, S. Y. Engineering Responsive Polymer Building Blocks with Host-Guest Molecular

Recognition for Functional Applications. Acc. Chem. Res. 2014, 47, 2084-2095.

(3) Hu, X. L.; Liu, G. H.; Li, Y.; Wang, X. R.; Liu, S. Y. Cell-Penetrating Hyperbranched Polyprodrug

Amphiphiles for Synergistic Reductive Milieu-Triggered Drug Release and Enhanced Magnetic

Resonance Signals. J. Am. Chem. Soc. 2015, 137, 362-368.

(4) Wang, X. R.; Hu, J. M.; Zhang, G. Y.; Liu, S. Y. Highly Selective Fluorogenic Multianalyte

Biosensors Constructed via Enzyme-Catalyzed Coupling and Aggregation-Induced Emission. J. Am.

Chem. Soc. 2014, 136, 9890-9893.

(5) Liu, G. H.; Wang, X. R.; Hu, J. M.; Zhang, G. Y.; Liu, S. Y. Self-Immolative Polymersonnes for

High-Efficiency Triggered Release and Programmed Enzymatic Reactions. J. Am. Chem. Soc. 2014, 136,

7492-7497.

(6) Wang, X. R.; Liu, G. H.; Hu, J. M.; Zhang, G. Y.; Liu, S. Y. Concurrent Block Copolymer

Polymersome Stabilization and Bilayer Permeabilization by Stimuli-Regulated "Traceless" Crosslinking.

Angew. Chem. Int. Ed. 2014, 53, 3138-3142.

(7) Li, Y. M.; Yu, H. S.; Qian, Y. F.; Hu, J. M.; Liu, S. Y. Amphiphilic Star Copolymer-Based Bimodal

Fluorogenic/Magnetic Resonance Probes for Concomitant Bacteria Detection and Inhibition. Adv. Mater.

2014, 26, 6734-6741.

(8) Hu, X. L.; Hu, J. M.; Tian, J.; Ge, Z. S.; Zhang, G. Y.; Luo, K. F.; Liu, S. Y. Polyprodrug

Amphiphiles: Hierarchical Assemblies for Shape-Regulated Cellular Internalization, Trafficking, and

Drug Delivery. J. Am. Chem. Soc. 2013, 135, 17617-17629.

38

Hyperbranched Self-Immolative Polymers (hSIPs) for Programmed

Payload Delivery and Ultrasensitive Detection

Guhuan Liu and Shiyong Liu*

CAS Key Laboratory of Soft Matter Chemistry, Department of Polymer Science and

Engineering,, University of Science and Technology of China, Hefei, Anhui 230026,

China; [email protected]

Upon stimuli-triggered single cleavage of capping moieties at the focal point and chain

terminal, self-immolative dendrimers (SIDs) and linear self-immolative polymers

(l-SIPs) undergo spontaneous domino-like radial fragmentation and cascade head-to-tail

depolymerization, respectively. The nature of response selectivity and signal

amplification has rendered them an unique type of stimuli-responsive materials.

However, SIDs involve tedious multistep synthesis, and steric congestion at the

periphery dictates that the SID generation is limited to the third, with a maximum

amplification factor of 8. Although the signal amplification capability of l-SIPs can be

modulated by chain lengths, they typically possess less design modularity and poor

water solubility, and those equipped with side chain release motifs are also synthetically

challenging; accordingly, core functions of l-SIPs in aqueous media (e.g., amplified

drug delivery and sensing) have been far less explored as compared to those of SIDs.

Thus, further advancement in the field of self-immolative polymers (SIPs) requires

novel design criteria and a paradigm shift. Herein, we report the facile fabrication of

water-dispersible SIPs with a novel chain topology, hyperbranched self-immolative

polymers (hSIPs), by utilizing one-pot AB2 polycondensation methodology and

sequential post-functionalization. The modular engineering of three categories of

branching scaffolds, three types of stimuli-cleavable capping moieties at the focal point,

and seven different types of peripheral functional groups and polymeric building blocks

affords both structurally and functionally diverse hSIPs with chemically tunable

amplified release features (up to 20 per hSIP molecule). Based on the hSIP platform, we

demonstrate myriad functions including visible light-triggered intracellular release of

peripheral conjugated drugs in a targeted and spatiotemporally controlled fashion,

intracellular delivery and cytoplasmic reductive milieu-triggered plasmid DNA release

via on/off multivalency switching, mitochondria-targeted fluorescent sensing of H2O2

with a detection limit down to ~20 nM, and colorimetric H2O2 assay via triggered

dispersion of gold nanoparticle aggregates. To further demonstrate the potency and

generality of hSIP platform, we further configure it into biosensor design for the

ultrasensitive detection of pathologically relevant antigens (e.g. human

carcinoembryonic antigen) by integrating with enzyme-mediated positive feedback

cycle amplification and enzyme-linked immunosorbent assay (ELISA).

39


1993 : Materials Science degree, Montpellier 2

University, France

1997 : Ph. D. Montpellier 2 University, France

1997-1998 : Research Fellow, Carnegie

Mellon University, Pittsburgh, USA

1998-2007: Project Manager then Scientific

Expert at Rhodia, Aubervilliers R&D Center,

Paris, France

2007- : Professor of Chemistry, University

Paul Sabatier Toulouse 3 University, Toulouse,

France

DESTARAC Mathias

Professor, Paul Sabatier Toulouse 3 University

Tel: +33 5 61 55 69 68


Web : http://imrcp.ups-tlse.fr/


The activities of the Precision Polymers by Radical Processes (P3R) team revolve around

controlled radical polymerization using RAFT technology. We study the structure-reactivity

relationships of new RAFT agents, and the synthesis and physical chemistry of RAFT

polymers, using the green solvents water and supercritical carbon dioxide wherever possible.

Our chief field of activity is the synthesis of functional polymers with complex architecture

and microstructure (amphiphilic and double hydrophilic block, comb and gradient copolymers)

which possess targeted interfacial properties such as adhesion, stabilization of emulsions,

dispersion of inorganic nanoparticles and rheology modification.


1. Kulai, I.; Brusylovets, O.; Voitenko, Z.; Harrisson, S.; Mazières, S.; Destarac; M.; RAFT

Polymerization with triphenylstannylcarbodithioates (Sn-RAFT). ACS Macrolett. 2015, 4, (8),

809-813.

2. Read, E.; Guinaudeau, A.; Wilson, D.J.; Cadix, A.; Violleau, F.; Destarac, M.; Low

temperature RAFT/MADIX gel polymerization: access to controlled ultra-high molar mass

polyacrylamides. Polym. Chem. 2014, 5, (7), 2202-2207.

3. Guinaudeau, A.; Coutelier, O.; Sandeau, A.; Mazières, S. Nguyen Thi, H-D.; Le Drogo, V.;

Wilson, D. J.; Destarac, M.; Facile access to poly(N-vinylpyrrolidone)-based double

hydrophilic block copolymers by aqueous RAFT/MADIX polymerization. Macromolecules

2014, 47, (1), 41-50.

4. Girard, E.; Tassaing, T.; Camy, S.; Condoret, J-S.; Marty, J-D.; Destarac, M.; Enhancement

of Poly(vinyl ester) Solubility in Supercritical CO2 by Partial Fluorination: The Key Role of

Polymer-Polymer Interactions. J. Am. Chem. Soc. 2012, 134, 29, 11920-11923.

40


http://imrcp.ups-tlse.fr/

Some new trends in aqueous RAFT/MADIX polymerization

Aymeric Guinaudeau1, Emmanuelle Read

1, Laurie Despax

1, Olivier Coutelier

1, Simon

Harrisson1, Stéphane Mazières

1, James Wilson

2 and Mathias Destarac

1

1

Université Toulouse 3 Paul Sabatier, Laboratoire IMRCP, UMR-CNRS 5069, 118

route de Narbonne, 31062 Toulouse Cedex 9, France 2

Solvay Novecare, Research and Innovation Centre - Paris, 52 rue de la Haie coq,

93308 Aubervilliers Cedex, France

[email protected]

Nowadays, there is a substantial need for new water soluble polymers with original

properties. Reversible-deactivation radical polymerization (RDRP) is one of the most

convenient approaches for tailor-making various kinds of hydrophilic polymers with

complex architectures. Among the RDRP options available, xanthate-mediated RAFT

(also known as RAFT/MADIX) polymerization is a method of choice because of its

high tolerance to water and ionic monomers. In contrast with most of other classes of

RAFT agents, xanthates allow the synthesis of block copolymers based on monomers

of highly disparate reactivities (e.g. acrylamides and N-vinyl monomers). We recently

reported the first example of RDRP of N-vinyl pyrrolidone (NVP) in water by means

of a RAFT/MADIX redox-initiated process at room temperature in the presence of a

O-ethyl xanthate (refs. 1-2). Consequently, several original P(NVP)-based double

hydrophilic block copolymers were prepared in pure water (2). We also pushed back

the limits of molar mass control in aqueous RAFT/MADIX polymerisation through a

fast and quantitative gel polymerisation of a series of acrylamido monomers (3).

Unprecedentedly high Mn up to 106 g.mol

-1 with low dispersities (Ð < 1.2) were

achieved. The reasons for access to abnormally high kinetic chain length in the

presence of a RAFT/MADIX agent are discussed. Access to ultra-high molar mass

thermoresponsive block copolymers and their physicochemical properties in water is

presented. These findings can open up avenues for fast precision polymer synthesis in

environmentally friendly conditions, and above all in ranges of molar masses that

were not attainable before.

References

1. A. Guinaudeau, S. Mazières, D. J. Wilson, M. Destarac, Polym. Chem. 2012, 3,

81-84.

2. A. Guinaudeau, S. Sandeau, S. Mazières, O. Coutelier, H. D. Nguyen Thi, V. Le

Drogo, D. J. Wilson, M. Destarac, Macromolecules 2014, 47, 41-50.

3. E. Read, A. Guinaudeau, D. J. Wilson, A. Cadix, F. Violleau, M. Destarac, Polym.

Chem. 2014, 5, 2202-2207

41


2003 M.S. in Chemistry & Chemical Engineering, ESCOM,

France

2003-2004 M.S. in Chemistry and Physico-Chemistry of

Polymers, Pierre et Marie Curie University, Paris, France

2004-2008 Ph.D. on Polymer Chemistry, Polymer Chemistry

Lab, Pierre et Marie Curie University, Paris, France

2005-2009 Ph.D. on Living Radical Polymerization,

Matyjaszewski Lab, Carnegie Mellon, Pittsburgh, USA

2010 Postdoctoral Researcher in E.W. (Bert) Meijer’s Group at

the Eindhoven University of Technology (TU/e), the

Netherlands

2010- Assistant Professor at ESPCI-ParisTech, Soft Matter and

Chemistry Lab, Paris, France

Renaud NICOLAŸ

Assistant Professor at ESPCI-ParisTech

Tel: +33 1 40 79 51 21


Web : http://www.mmc.espci.fr


Our research focuses on the development of new methodologies to prepare multifunctional

polymeric architectures as well as on the conception of materials and formulations relying on

dynamic covalent chemistry.


Denissen, W.; Rivero, G.; Nicolaÿ, R.; Leibler, L.; Winne, J. M.; Du Prez F. E., “Vinylogous

Urethane Vitrimers” Adv. Funct. Mater. 2015, 25, 2451

Le Neindre, M.; Nicolaÿ, R., "Polythiol copolymers with precise architectures: a platform for

functional materials" Polym. Chem. 2014, 5, 4601

Le Neindre, M.; Nicolaÿ, R., "One-pot deprotection and functionalization of polythiol

copolymers via 6 different thiol-X reactions" Polym. Int. 2014, 63, 887

Le Neindre, M.; Magny, B.; Nicolaÿ, R., "Evaluation of thiocarbonyl and thioester moieties as

thiol protecting groups for controlled radical polymerization" Polym. Chem. 2013, 4, 5577

Stals, P. J. M.; Gillissen, M. A. J.; Nicolaÿ, R.; Palmans, A. R. A.; Meijer, E. W., "The balance

between intramolecular hydrogen bonding, polymer solubility and rigidity in single-chain

polymeric nanoparticles" Polym. Chem. 2013, 4, 2584

Stals, P. J. M.; Li, Y.; Burdynska, J.; Nicolaÿ, R.; Nese, A.; Palmans, A. R. A.; Meijer, E. W.;

Matyjaszewski, K.; Sheiko. S. S., "How Far Can We Push Polymer Architectures?" J. Am.

Chem. Soc. 2013, 135, 11421

Nicolaÿ, R., “Synthesis of Well-Defined Polythiol Copolymers by RAFT Polymerization”

Macromolecules 2012, 45, 821

R. Nicolaÿ, K. Matyjaszewski. “Synthesis of Cyclic (Co)polymers by Atom Transfer Radical

Cross-Coupling and Ring Expansion by Nitroxide-Mediated Polymerization” Macromolecules

2011, 44, 240

Nicolaÿ, R.; Kamada, J.; Van Wassen, A.; Matyjaszewski, K., “Responsive Gels Based on a

Dynamic Covalent Trithiocarbonate Cross-Linker” Macromolecules 2010, 43, 4355

Nicolaÿ, R.; Kwak, Y.; Matyjaszewski, K., “A Green Route to Well-Defined High-Molecular-

Weight (Co)polymers Using ARGET ATRP with Alkyl Pseudohalides and Copper Catalysis”

Angew. Chem., Int. Ed. 2010, 49, 541

42

Dynamic covalent chemistry as a tool for formulation

and material science

Renaud Nicolaÿ and Ludwik Leibler

Matière Molle et Chimie, ESPCI-CNRS (UMR 7167) 10 rue Vauquelin, 75005 Paris, France.

[email protected]

Vitrimers are a new class of permanently cross-linked networks that can undergo associative

exchange reactions through dynamic covalent bonds. As a result, the topology of these networks can

be dynamic under certain conditions, which allow these materials to relax stress or to be reshaped and

recycled like thermoplastics, while being insoluble like thermosets [1-3]. Extending this concept to

various exchange reactions and polymer matrices, as well as tuning the dynamics of the exchange

reactions, to adapt to different processing routes, are examples of remaining challenges that are

currently being addressed. In addition, some of the systems explored can be advantageously used in

solvent formulations, to control their rheological properties for example.

[1] D. Montarnal, M. Capelot, F. Tournilhac, L. Leibler, Science 2011, 334, 965

[2] M. Capelot, M. M. Unterlass, F. Tournilhac, L. Leibler, ACS Macro Letters 2012, 1, 789

[3] M. Capelot, D. Montarnal, F. Tournilhac, L. Leibler, J. Am. Chem. Soc. 2012, 134, 7664

43


1994 : M.Sc. Physics, Univ. Claude

Bernard Lyon and ENS Lyon

1998 : Ph. D., University J. Fourier,

Grenoble, France

1999-2001 : Research Associate,

Department of Physics and Astronomy,

Manchester UK.

2001-2004: Assistant Professor

University of Strasbourg, Laboratory of

Complex Fluids Dynamics, Strasbourg

France

2005- : Institut Charles Sadron,

Strasbourg, France

THALMANN Fabrice Assistant Professor, University of Strasbourg Tel: +33 3 88 41 41 49 Email: [email protected] Web : http://www.ics-cnrs.unistra.fr/Mcube/ http://www-ics.u-strasbg.fr


My interest is in statistical and soft matter physics. I currently belong to the M3 (Membrane

and Microforces) team in Institut Charles Sadron, which gathers several researchers and

postgraduate students on both theoretical and experimental aspects of model lipid bilayers

physics. One of our main current focus lies on the oxidative alteration of membranes,

including their phase coexistences and permeation properties. The other focus is on the

interaction and translocation of nanoparticles of size commensurate to the bilayer thickness.

Finally, I am interested in lipid membrane dynamics and work on some aspects of colloidal

physics such as the drying of waterborne latex suspensions.

Selected Recent Publications 1. F. Thalmann, A schematic model for molecular affinity and binding with Ising variables.

European Journal of Physics E 2010 (31) 441.

2. F. Thalmann, V. Billot and C.M. Marques, Lipid bilayer adhesion on sparse DNA

carpets: Theoretical analysis of membrane deformations induced by single-end-grafted

polymers. Phys. Rev. E 2011 (83) 061922

3. C.I. Mendoza, C.M. Marques and F. Thalmann, Enhanced shear separation for chiral

magnetic colloidal aggregates, Phys. Rev. E (Rapid. Comm.) 2010 (82) 060401

4. J. Wolff, C.M. Marques and F. Thalmann. Thermodynamic Approach to Phase

Coexistence in Ternary Phospholipid-Cholesterol Mixtures, Physical Review Letters 2011,

106, (12), 128104.

5. O.Mertins, I.O.L. Bacellar, F. Thalmann, C.M. Marques, M.S. Baptista, R.Itri, Physical Damage on Giant Vesicles Membrane as a Result of Methylene Blue Photoirradiation,

Biophysical Journal 2014, 106, 162

44

Investigating lipid membrane dynamics at a nanoscale with excimer

fluorescence: lessons from molecular dynamics simulations

Fabrice Thalmann, Pierre Ayoub

Institut Charles Sadron, CNRS and UniStra, 23 rue du Loess, 67034 Strasbourg

Cedex France, [email protected]

Excimer formation of pyrene conjugated phospholipid molecules is sensitive to self-

diffusion dynamics in lipid bilayers. Measures of the diffusion coefficient D based on

this phenomenon have been proposed as early as 1974 (Galla, Sackmann). Using

coarse-grained lipids (Martini) molecular dynamics simulation, we revisit these

results and attempt to improve the determination of the diffusion coefficient D. This

method opens a window on lipid molecular motions at the nanometer scale.

45

1987 : B.Sc. Shandong Univ., China

1990 : M.Sc. Institute of Chemistry, Chinese

Academy of Sciences (CAS), China

1995: D. Sci. Peking Univ (PKU). China.

1993-1994: Exchanging doctor course student,

Waseda Univ. Japan

1995-1996: Post doctor, PKU; JSPS and JST

fellow, Waseda Univ. Japan.

1997-: College of Chemistry, PKU.

Zi-Chen Li

Professor at Peking University

Tel: +86 10 62755543



The research interest of our group is polymer chemistry. In particular, we focused on

developing new polymerization methods, controlling over the composition, sequence,

topology as well as functional groups of polymers, with an aim to obtain polymers with

precise structure and advanced properties like biomacromolecules. Most recently, we are

interested in developing new polymerization methods based on multicomponent reactions for

functional polymer synthesis, such polymerization methods are atom-economic, functional

group tolerance and can be conducted under ambient reaction conditions, and therefore, may

find many applications in constructing more complex polymer architectures and functions.


1. Lv, A.; Li, Z.-L.; Du, F.-S.; Li, Z.-C. Synthesis, Functionalization, and Controlled

Degradation of High Molecular Weight Polyester from Itaconic Acid via ADMET

Polymerization, Macromolecules 2014, 47, 7707-7716.

2. Li, Z.-L.; Lv, A.; Du, F.-S.; Li, Z.-C. Intrachain Cyclization via Postmodification of the

Internal Alkenes of Periodic ADMET Copolymers: The Sequence Matters, Macromolecules

2014, 47, 5942-5951.

3. Li, L.; Deng, X.-X.; Li, Z.-L.; Du, F.-S.; Li, Z.-C. Multifunctional Photodegradable Polymers

for Reactive Micropatterns, Macromolecules 2014, 47, 4660-4667.

4. C.-H. Wang, Z.-Y. Song, X.-X. Deng, L.-J. Zhang, F.-S. Du, Z.-C. Li, Combination of ATRA

and ATRC for the Synthesis of Periodic Vinyl Copolymers, Macromol. Rapid Commun. 2014,

35, 474-478.

5. Zhang, L.-J.; Deng, X.-X.; Du, F.-S.; Li, Z.-C. Chemical Synthesis of Functional

Poly(4-hydroxybutyrate) with Controlled Degradation via Intramolecular Cyclization,

Macromolecules 2013, 46, 9554-9562.

6. Song, C.-C.; Ji, R.; Du, F.-S.; Li, Z.-C. Oxidation-Responsive Poly(amino ester)s Containing

Arylboronic Ester and Self-Immolative Motif: Synthesis and Degradation Study,

Macromolecules 2013, 46, 8416-8425.

7. Qiao, Z.-Y.; Ji, R.; Huang, X.-N.; Du, F.-S.; Zhang, R.; Liang, D.-H.; Li, Z.-C. Polymersomes

from Dual Responsive Block Copolymers: Drug Encapsulation by Heating and

Acid-Triggered Release, Biomacromolecules 2013, 14, 1555-1563.

8. Song, C.-C.; Su, C.-C.; Cheng, J.; Du, F.-S.; Liang, D.-H.; Li, Z.-C. Toward Tertiary

Amine-Modulated Acid-Triggered Hydrolysis of Copolymers Containing Pendent Ortho

Ester Groups, Macromolecules 2013, 46, 1093-1100.

46

Importance of Monomer Sequence in Controlling the Properties of

Polymers

Zi-Chen Li

Key Laboratory of Polymer Chemistry & Physics of Ministry of Education,

Department of Polymer Science & Engineering, College of Chemistry,

Peking University, Beijing 100871, China.

Phone: +86-10-6275-5543; Fax: +86-10-6275-1708, E-mail: [email protected]

Microstructure control in polymer chain including sequence regulation has attracted

much attention and is definitely a significant parameter in polymer design that leads

to polymers with complex structures and sophisticated functions. Many types of

polymers with controlled microstructure have been designed and synthesized in recent

years. Then, the next question is how these microstructure variations can affect the

polymer properties. In this talk, I will present some examples to show you the

importance of specific monomer sequence in controlling the properties of polymers.

It contains: (1) Three types of periodic vinyl copolymers were synthesized and the

relationship between the monomer sequences and the thermal properties of these

copolymers was elucidated. (2) The tandem reaction between the adjacent monomer

units within a single polymer chain was realized upon post-modification of the

internal alkenes of periodic vinyl copolymers. Those formed cyclic structure by the

tandem reaction could increase the rigidity of the polymer chain and thus greatly

increase the Tg of the final polymer. (3) Passerini multicomponent polymerization was

developed as a new method to synthesize functional poly(4-hydroxybutyrate)s. These

polyesters exhibited unique degradation behavior in solution. The degradation was

driven by the consecutive intramolecular cyclization to form stable a neutral

γ-butyrolactone compound.

47


1994 : Ph. D. Paris 6, Collège de France

1994-1995 : Post-doc Fellow, Technion, Haifa,

Israel


Professor) at the Collège de France, Condensed

Matter Laboratory, Paris, France

1999-2004: CNRS Researcher at the

Rhodia-CNRS research center, Complex Fluids

Laboratory, Cranbury, NJ, USA

2004-present: CNRS Researcher at the Centre

de Recherche Paul Pascal, Bordeaux, France

2012-2013 : Visiting professor at the State Key

Laboratory of Chemical Engineering, East

China University of Science and Technology,

Shanghai, China

Collab : Honglai Liu, Jun Hu, Xia Han

PONSINET Virginie

Chargée de Recherche at the CNRS

Tel: +33(0)5 56 84 56 25


Web :

www.crpp-bordeaux.cnrs.fr/PONSINET-Virginie


Hybrid materials composed of polymers and plasmonic nanoparticles ; study of the

relation between nanostructure and optical properties

Ordered phases of block copolymers : application to nanoparticle structuration

Self-assembled nanoresonators and hybrid materials for metamaterial fabrication

Structure and alignment of thin films of block copolymers

Structure of complex fluids


1- Controlled Assembly of Plasmonic Nanoparticles Using Neutral-Charged Diblock

Copolymers, Quanyi Yin, Xia Han, Virginie Ponsinet, Honglai Liu, J. Coll. Interf.

Sci. 431, 97–104 (2014)

2- Microfluidic-Induced Growth and Shape-Up of Three-Dimensional Extended Arrays

of Densely Packed Nanoparticles, J. Angly, A. Iazzolino, J.-B. Salmon, J. Leng, S. P.

Chandran, V. Ponsinet, A. Désert, A. Le Beulze, S. Mornet, M. Tréguer-Delapierre,

M. A. Correa-Duarte, ACS Nano 7, 6465–6477 (2013)

3- Polymorphism of natural fatty acid liquid crystalline phases, H. Fay, S. Meeker, J.

Cayer-Barrioz, D. Mazuyer, I. Ly, F. Nallet, B. Desbat, J.-P. Douliez, V. Ponsinet, O.

Mondain-Monval, Langmuir 28, 272–282 (2012)

4- Facile formulation of high density well-ordered nanoparticle-copolymer

nanocomposites, Benoit Maxit, Denis Bendejacq, Virginie Ponsinet, Soft Matter 8,

1317-1320 (2012)

5- Double-Polyelectrolyte, Like-Charged Amphiphilic Diblock Copolymers : Swollen

Structures and pH- and Salt-Dependent Lyotropic Behavior, D. Bendejacq, V. Ponsinet

J. Phys. Chem. B 112, 7996–8009 (2008)

48

http://www.crpp-bordeaux.cnrs.fr/PONSINET-Virginie

Polymer-based nanomaterials with novel optical properties

Xuan Wang1, Kevin Ehrhardt

1, Remy Robertson

1, Ashod Aradian

1, Philippe Barois

1,

Virginie Ponsinet1, Sergio Gomez-Graña

2, Mona Tréguer-Delapierre

2

1 Centre de Recherche Paul Pascal, Univ. Bordeaux - CNRS, Pessac, France

2 Institut

de Chimie de la Matière Condensée de Bordeaux, Univ. Bordeaux - CNRS, Pessac,

France ([email protected])

The interest for nanostructures has exploded in the recent years, with many

applications in view, which has led to the search for new and versatile fabrication

methodologies, among which nanochemistry and self-assembly have become

promising routes. The versatility of chemical synthesis offers an almost unlimited

range of achievable nanoparticles of controlled composition, size, shape, and surface

coating. Self-assembly induces spontaneous structures, possibly presenting

characteristic sizes at the nanoscale and variable degrees of order, using in particular

liquid crystals, surfactants (or more generally amphiphiles) and block copolymers in

the solid or dispersion states. Other types of controlled assembly phenomena, using

polymer properties, can also be used to engineer complex colloidal assemblies, on

which are based functional nanomaterials.

Among the exciting emerging functional nanomaterials, metamaterials are artificial

composites presenting unusual properties of light propagation thanks to a specific

structure at a lengthscale smaller than the operational wavelength. The search for

meta-properties in the visible domain, which could open the way to technical

breakthrough in optics such as hyperlenses and cloaking, is mostly focused on

nanostructured plasmonic systems. In this context, chemistry and controlled assembly

of metallic nanoparticles can lead to interesting dense organized structures, in which

the localized surface plasmon resonances (LSPR) of the metallic nanoparticles at

visible or near infrared wavelengths, provide large amplitude variations of the optical

responses. Several experimental systems will be discussed here, with the goal of

relating the controlled structures and the obtained unusual optical properties.

49

1994-1998: Sc.D. Nara Women’s University,

Japan

1998-2000: JSPS Postdoctoral Fellowship,

Japan

2000-2002: Research Associate, University

of Washington, USA

2002-2009: Research Assistant Professor and

Research Associate Professor,

University of Washington

2009-present: Professor, University of

Science and Technology of China

Chunye Xu

Professor, University of Science and Technology

of China

Tel: +86-551-6360-3459


Web: http://en.hfnl.ustc.edu.cn/Faculty/Facultys/20

1107/t20110715_116167.html


Her group research has focused on electroactive and conjugated polymers for sensor, artificial

muscle and smart window applications (Boeing smart window and 3M project). She initiated

her interest in smart materials and structures since 1998. Her team has focused on the design of

soft/hard polymer network architectures ranging from conventional PVAs, PVDF materials all

the way to soft swollen hydrogel electrode and flexible tactile sensor. They have particularly

committed themselves into regulating solubility in aqueous/organic solvent for inkjet

processable electrochromic applications and into tuning electron density of main chain for

polymer film of different color and transmittance.


1. Li, B.; Xu, C.; Zhang, F.; Zheng, J.; Xu, C., Self-polarized piezoelectric thin films:

preparation, formation mechanism and application. J. Mater. Chem. C 2015, 3 (34),

8926-8931.

2. Wei, Y.; Zhou, J.; Zheng, J.; Xu, C., Improved stability of electrochromic devices using

Ti-doped V2O5 film. Electrochimica Acta 2015, 166, 277-284.

3. Mi, S.; Wu, J.; Liu, J.; Zheng, J.; Xu, C., Donor-pi-bridge-acceptor fluorescent polymers

based on thiophene and triphenylamine derivatives as solution processable electrochromic

materials. Organic Electronics 2015, 23, 116-123.

4. Xu C.; Li B.; Xu C.; Zheng J., A novel dielectric elastomer actuator based on compliant

polyvinyl alcohol hydrogel electrodes, Journal of Materials Science: Materials in

Electronics, 2015, DOI: 10.1007/s10854-015-3614-y.

5. Yang, S.; Zheng, J.; Li, M.; Xu, C., A novel photoelectrochromic device based on

poly(3,4-(2,2-dimethylpropylenedioxy)thiophene) thin film and dye-sensitized solar cell.

Solar Energy Materials and Solar Cells 2012, 97, 186-190.

50


http://en.hfnl.ustc.edu.cn/Faculty/Facultys/201107/t20110715_116167.html

http://en.hfnl.ustc.edu.cn/Faculty/Facultys/201107/t20110715_116167.html

Self-polarized piezoelectric thin films: preparation, formation

mechanism and application

Baozhang Li, Chengyi Xu, Feifei Zhang, Jianming Zheng, Chunye Xu*

CAS Key Laboratory of Soft Matter Chemistry, Department of Polymer Science and

Engineering, Hefei National Laboratory for Physical Sciences at the Microscale,

University of Science and Technology of China, Hefei, China. [email protected]

A facile method is introduced for preparation of porous self-polarized piezoelectric

thin films (100–300 nm) by depositing polyvinylidene fluoride solution onto the

surface of an aqueous solution1. Polar β crystalline phase enhancement is realized

with the addition of sodium chloride into the aqueous solution. Fully saturated

piezoresponse hysteresis loops and out-of-plane piezoresponse phase images reveal

that the PVDF films show good piezoelectricity and present a self-polarized feature

with the C–F dipoles aligned vertically to the surface. Also, the film deposited on 15%

salt aqueous solution shows the highest content of β crystalline phase. In addition, the

device based on prepared multi-layer PVDF film is fabricated and characterized using

homemade equipment. Notably, the device based on 50 layers of film deposited on the

surface of a 15% salt aqueous solution shows the outstanding sensitivity of 52.2 pC

N-1

and electrical output of 24 V and 16 mA. It suggests that the facile method for

preparation of self-polarized film has promising potential for assembling wearable

devices. Compared with previous researches on electrospinning and electrical poling,

our preparation of PVDF film is more convenient and costs less. The polar β

crystalline phase in PVDF film is higher and its performance is better. Therefore, we

provide a facile and costless approach to obtain self-polarized piezoelectric films with

an enhanced polar β crystalline phase and create a dual functional device for pressure

sensing and electricity generation.

1. Li, B.; Xu, C.; Zhang, F.; Zheng, J.; Xu, C., Self-polarized piezoelectric thin films: preparation,

formation mechanism and application. Journal of Materials Chemistry C 2015, 3 (34), 8926-8931.

51


1993 : Materials Science & Engineering

degree, INSA de Lyon, FRance

1996 : Ph. D. University of Lyon, France

1997-1998 : Postdoctoral position in Louvain

la Neuve, Belgium

1998-2010: Assistant Professor at INSA,

Laboratory of Engineering Polymer Materials,

Lyon, France

2010-: Professor at INSA, Laboratory of

Engineering Polymer Materials, Lyon, France

2013 : Head of National Network “Polymers

and Ionic Liquids” GDR CNRS #3585.

DUCHET-RUMEAU Jannick

Professor

Tel: +33 4 72 43 85 48


Web : http://www.imp.cnrs.fr/

GDR LIPs http://www.gdr-lips.fr


Her research topics are related to i/Processing of nanocomposites materials where fillers dispersion

(NTC, silica, clays, oxides) is tailored from physicochemical interactions between fillers and matrix

(surface modification, compatibilizer agents) and from processing ways (melt intercalation, solvent cast

method, in situ polymerization). A fine characterization of morphologies during processing and in the

final state of material (electronic microscopy, x-rays scattering, rheological analysis) were developed to

establish the relationships between structuration and physical properties (crystallinity, mechanical,

barrier, dielectrical properties,etc.); ii/Processing of mesoporous materials with the use of carbon dioxide

in supercritical medium as a foaming agent; iii/Processing of self assembled materials onto inorganic

surfaces with the use of phase separation phenomena in polymer blends and of self organization

phenomena into di or triblock copolymers to achieve a specific application (nanolithography, optical

properties, etc.); iv/Processing of nanomaterials from Ionic Liquids where a wide variety of Ionic Liquids

Salts can be used as an efficient compatibilizer, nanobuilding block agent or plasticizer and v/Tailoring of

interfaces/interphases in the heterogeneous materials : polymer blends and fiber based composites where

the physicochemical modification of interfaces/interphases and the understanding of adhesion

mechanisms in composites are investigated.


1-Livi, S.; Gérard, J.F.; Duchet-Rumeau, J. “Ionic Liquids : structuration agents in a fluorinated

matrix” Chemical Communications, (2011) 47, 3589-3591

2-NGuyen, T.K.L., Livi, S., Pruvost, Soares, B. G., Duchet-Rumeau, J “Ionic Liquids as reactive

additives for the preparation and modification of epoxy networks” Journal of Polymer Science Part A:

Polymer Chemistry (2014),52 (24), 3463-3471.

3-S. Livi, V. Bugatti, Bluma G. Soares, J. Duchet-Rumeau, "Structuration of ionic liquids in a

poly(butylene-adipate-co-terephtalate) matrix: Influence on the water vapour permeability and

mechanical properties” , Green chemistry (2014) 16 (8), 3

52

http://www.imp.cnrs.fr/

http://www.gdr-lips.fr/

Ionic Liquids/Polymer : a new promising combination

J.Duchet-Rumeau, S. Livi, S. Pruvost, B.G. Soares, J.F. Gérard

Université de Lyon, F-69003 Lyon, France INSA Lyon, F-69621 Villeurbanne, France

CNRS, UMR 5223, Ingénierie des Matériaux Polymères, France [email protected]

In the last decade, ionic liquids have moved from relative obscurity to something that

most chemists are now very aware of. At present, the interest in ionic liquids shows a continuous increase. They are being examined as new components for designing polymer materials as novel electrolytes in batteries, templates for porous polymers, plasticizers, surfactants in the preparation of functional polymers. The unique set of physico-chemical properties of ionic liquids finely tuned from their chemical structure makes them as ideal components for processing of advanced materials. As shown in Figure 1, ionic liquids can be both i) interfacial agents for tailoring the dispersion state of fillers in nanocomposites [1] and the pore size in the foams [2] or still for enhancing the compatibilization of polymer blends [3]; ii) chemically reactive agents able to initiate the polycondensation of epoxy networks [4]; iii) structuring agents leading to the formation of three-dimensional networks of anions and cations inducing strongly enhanced physical properties [5]. This talk will give a wide overview of the use of ILs in polymer science and will tend to deepen the understanding of specific properties of ionic liquids so that the true potential of ionic liquids in polymer science can be highlighted.

a) b) c)

Figure 1. Highlights of ionic liquid role : as a structuring agent (a), compatibilizer (b) and interfacial agent (c)

[1] S. Livi, J.F. Gérard, J. Duchet-Rumeau Eur. Polym. J. 2011, 1361-1369 [2] S. Livi, T.N. Pham, J.F. Gérard, J. Duchet Chem. Eng. J. 2014, 240, 534-540 [3] M. Yousfi , S. Livi, J. Duchet-Rumeau, Chem. Eng. J. 2014, 255, 513-524 [4] B.G. Soares, S. Livi, J. Duchet-Rumeau, J.F. Gérard, Polymer 2012 53(1) 60-66 [5] S. Livi, J.F. Gérard, J. Duchet-Rumeau, Chem. Comm 2011 47, 3589-3591

53

1994 M.S., Polymer Chemistry, Université de

Pau et des Pays de l'Adour (France)

1998 Ph.D., Polymer Chemistry, Université

Bordeaux-I (France) and Universidad Autónoma

de Coahuila (Mexico)

1998-2001 NIH Post-Doctoral Fellow, Emory

University, Atlanta (USA)

2001-2014 CNRS Researcher, ICMPE, Thiais

(France)

2014-date CNRS Senior Researcher, ICMPE,

Thiais (France)

GRANDE Daniel

Directeur de Recherche au CNRS

Tel: +33 (0)1 49 78 11 77


Web : http://www.icmpe.cnrs.fr/spip.php?article43


The main focus of interest in my research group lies in the development of functional polymer

materials with a broad range of porosity scales, and the whole spectrum from their design to their

potential applications is investigated. More specifically, original nanoporous materials with

controlled morphology and pore functionality are engineered from newly synthesized block

copolymers or polymer networks (IPNs, hybrid systems). Such nanoreactors are further used as

efficient catalytic supports. More recently, doubly porous polymeric materials are tailored from a

double porogen templating approach in order to tune two porosity levels within such novel systems,

i.e. nano- and macro-porosity. Electrospun nanofibrous materials are also produced as 3-D

biocompatible scaffolds meant for tissue engineering applications.


1. “Porous polystyrene-based monolithic materials templated by semi-Interpenetrating Polymer

Networks for capillary electrochromatography”, T.-X. Lav, B. Carbonnier, M. Guerrouache, D.

GRANDE, Polymer, 51, 5890-5894 (2010)

2. “Functionalized ordered nanoporous polymeric materials: From the synthesis of diblock

copolymers to their nanostructuration and their selective degradation”, D. GRANDE, J. Penelle, P.

Davidson, I. Beurroies, R. Denoyel, Microporous and Mesoporous Materials, 140, 34-39 (2011)

3. “Novel mesoporous high-performance films derived from polycyanurate networks containing

high-boiling temperature liquids”, D. GRANDE, O. Grigoryeva, A. Fainleib, K. Gusakova,

European Polymer Journal, 49, 2162-2171 (2013)

4. “Engineering functional doubly porous PHEMA-based materials”, B. Le Droumaguet, R.

Lacombe, H.-B. Ly, M. Guerrouache, B. Carbonnier, D. GRANDE, Polymer, 55, 373-379 (2014)

5. “Biocomposite scaffolds based on electrospun poly(3-hydroxybutyrate) nanofibers and

electrosprayed hydroxyapatite nanoparticles for bone tissue engineering applications”, J. Ramier, T.

Bouderlique, O. Stoilova, N. Manolova, I. Rashkov, V. Langlois, E. Renard, P. Albanese, D.

GRANDE, Materials Science and Engineering C, 38, 161-169 (2014)

54


http://www.icmpe.cnrs.fr/spip.php?article43

Crossing porosity scales in functional polymer materials:

From design to application

Daniel Grande

Institut de Chimie et des Matériaux Paris-Est, UMR 7182 CNRS – Université Paris-Est

Créteil Val-de-Marne, 2, rue Henri Dunant, 94320 Thiais, France


Over the last decade, the generation of organic porous materials with tunable pore sizes and

desired functionalities has been the subject of increasing attention in materials science.

Interest in such porous frameworks originates from the large variety of applications in

which they are involved, e.g. size/shape-selective nanoreactors, monoliths for advanced

chromatographic techniques, nanofiltration membranes, high specific area catalytic

supports, as well as 3-D scaffolds for tissue engineering.

This lecture examines the scope and limitations of three different approaches to nano- to

macro-porous polymers with controlled porosity and functionality. The first approach

relies on the synthesis of polystyrene-block-poly(D,L-lactide) diblock copolymers with

functional groups at the junction between both blocks (e.g., COOH, SO3H, SH), followed

by their macroscopic orientation, and the subsequent selective hydrolysis of the polyester

block.1,2

The second strategy entails the preparation of biocompatible doubly porous

crosslinked polymer materials through the use two distinct types of porogen templates,

namely a macroporogen in combination with a nanoporogen. To generate the

macroporosity, either CaCO3 or NaCl particles or fused PMMA beads are used, while the

second porosity is obtained by using either hydroxyapatite nanoparticles or a porogenic

solvent.3 Finally, 3-D macroporous scaffolds based on biodegradable polyesters have

been engineered by electrospinning to generate nanofibrous biomaterials that mimic the

extracellular matrix.4,5

The potentialities afforded by these approaches will be addressed,

and some typical applications of the resulting porous materials will be illustrated.

References

[1] Grande, D.; Penelle, J.; Davidson, P.; Beurroies, I.; Denoyel, R. Microporous

Mesoporous Mater. 2011, 140, 34-39.

[2] Majdoub, R.; Antoun, T.; Le Droumaguet, B.; Benzina, M.; Grande, D. React. Funct.

Polym. 2012, 72, 495-502.

[3] Le Droumaguet, B.; Lacombe, R.; Ly, H.-B.; Guerrouache, M.; Carbonnier, B.; Grande,

D. Polymer 2014, 55, 373-379.

[4] Ramier, J.; Bouderlique, T.; Stoilova, O.; Manolova, N.; Rashkov, I.; Langlois, V.;

Renard, E.; Albanese, P.; Grande, D. Mater. Sci. Eng. C 2014, 38, 161-169.

[5] Ramier, J.; Grande, D.; Bouderlique, T.; Stoilova, O.; Manolova, N.; Rashkov, I.;

Langlois, V.; Albanese, P.; Renard, E. J. Mater. Sci.: Mater. Med. 2014, 25, 1563-1575.

55


2000 : Chemistry, B. S., Hunan University, China

2002 : Applied Chemistry, M. S., Hunan

University, China

2005 : Polymer Chemistry and Physics, Ph.D.,

Changchun Institute of Applied Chemistry,

Chinese Academy of Science, China

2005-2006 : Postdoctoral Fellow, University of

Alberta, Canada

2006-2009 : Postdoctoral Researcher,

University of Massachusetts Amherst, USA

2009 - : Professor, School of Chemistry and

Chemical Engineering, Huazhong University of

Science and Technology, China

Jintao Zhu

Professor of Huazhong University

of Science and Technology

Tel: +86 27 8779 3240


Web : http://www.jintaozhu.polymer.cn


The focus of the research done in our group is the design, synthesis of polymer particles with

well-defined sizes, shapes, and functionalities. Several strategies and techniques, including

microfluidics processing, supramolecular assembly, and nanoprecipitation have been

employed to tune the morphology and size of the polymer microstructured materials. We are

interested in exploring the applications of the polymer particles with built-in functionalities in

the area of optics, diagnostics, delivery and release, and imaging.


1. Deng, R. H.; Liang, F. X.; Zhou, P.; Zhang, C. L.; Qu, X. Z.; Wang, Q.; Li, J. L.; Zhu, J. T.;

Yang, Z. Z. Janus nano-disc of diblock copolymer. Advanced Materials 2014, 26, 4469-4472.

2. Deng, R. H.; Liu, S. Q.; Li, J. Y.; Liao, Y. G.; Tao, J.; Zhu, J. T. Mesoporous block

copolymer nanoparticles with tailored structures by hydrogen-bonding-assisted

self-assembly. Advanced Materials 2012, 24, 1889-1893.

3. Liu, S. Q.; Deng, R. H.; Li, W. K.; Zhu, J. T. Polymer microparticles with controllable

surface-textures generated through interfacial instabilities of emulsion droplets. Advanced

Functional Materials 2012, 22, 1692-1697.

4. Bar, J.; Lawrence, J.; Miesch, C.; Ribbe, A.; Li, W. K.; Emrick, T.; Zhu, J. T.; Hayward,

R., Multifunctional nanoparticles-loaded spherical and wormlike micelles formed by

interfacial instabilities. Advanced Materials 2012, 24, 2735-2742.

5. Li, W. K.; Liu, S. Q.; Deng, R. H.; Zhu, J. T. Encapsulation of nanoparticles in block

copolymer micellar aggregates by directed supramolecular assembly. Angewandte

Chemie International Edition 2011, 50, 5865-5868.

56

http://www.jintaozhu.polymer.cn/

Assembly of Block Copolymers in 3D Confined Geometry

Renhua Deng, Jiangping Xu, and Jintao Zhu

School of Chemistry and Chemical Engineering, Huazhong University of Science and

Technology, Wuhan 430074, China, [email protected]

Block copolymer nano-objects have attracted great attention due to their potential

applications in the fields of drug delivery, targeting therapy, medical diagnosing and

imaging. 3 dimensional (3D) confinement, which can break the symmetry of a

structure, has proven to be a powerful route to tailor the morphologies of block

copolymer particles. Particle shape and internal structure can thus be tuned by using

the supramoelcular strategy or tailoring the interfacial interaction of the particles with

the dispersed medium.1,2

We will introduce the generation of the nano-objects with

well tunable shapes by taking advantage of 3D confined assembly and supramolecular

chemistry. Particles with various internal structures can be obtained due to the 3D soft

confinement in emulsion droplets. Moreover, we will show that selective disassembly

of the structured particles will give rise to mesoporous particles or nano-objects with

unique shapes.

Acknowledgement

We gratefully acknowledge funding for this work provided by the National Natural

Science Foundation of China (51173056 and 91127046).

1. Deng, R. H.; Liang, F. X.; Zhou, P.; Zhang, C. L.; Qu, X. Z.; Wang, Q.; Li, J. L.;

Zhu, J. T.; Yang, Z. Z. Janus nano-disc of diblock copolymer. Advanced Materials

2014, 26, 4469-4472.

2. Deng, R. H.; Liu, S. Q.; Li, J. Y.; Liao, Y. G.; Tao, J.; Zhu, J. T. Mesoporous

block copolymer nanoparticles with tailored structures by

hydrogen-bonding-assisted self-assembly. Advanced Materials 2012, 24,

1889-1893.

57


1992 : Physical Chemistry of Polymers, ESPCI

and Paris VI, France

1995 : Ph. D. Paris VI, France

1995-1996 : Assistant ESPCI, Paris, France


Professor) at CERMAV, Grenoble, France

2004-2005 : Post-Doc Utrecht University

2009- : CNRS Research Director (Professor)

at CERMAV, Grenoble, France

HEUX Laurent

Directeur de Recherche at the CNRS

Tel: +33 4 76 03 76 14


Web :http://www.cermav.cnrs.fr/en/user/1403

http://www.cermav.cnrs.fr/en/node/123n


The research team "Structure and Properties of Glycomaterials" is interested in natural

polysaccharides from a Polymer and Material Science point of view. This class of polymer is

very diversified in terms of structure and represent a great part of the biomass and an almost

inexhaustable resource of materials, that can be used to replace oil based materials. In Nature,

they are arranged in complex hierarchical structures that exhibit remarkable properties and are

elaborated at low energy cost. My scientific interests are focused on the characterization of the

ultrastructure of polysaccharides (especially cellulose which is the most abundant) and

understand how their specificity (strong anisotropic properties, chirality, lightness…) can be

used to design new innovative and sustainable materials, combining classical polymer or soft

matter science approaches and bioinspired pathways for applications as different as mechanical

reinforcement or optical devices.


1.S. Elazzouzi-Hafraoui, J.-L. Putaux and L. Heux Self-assembling and Chiral Nematic Properties

of Organophilic Cellulose Nanocrystals J. Phys. Chem. B, 113, 11069-11075 (2009).

2. M. Wada, L. Heux, Y. Nishiyama & P. Langan, Crystallographic, scanning microprobe X-ray

diffraction, and cross-polarized/magic angle spinning 13

C NMR studies of the structure of

cellulose IIIII, Biomacromolecules, 10(2), 302-309 2009

Muller, Francois; Jean, Bruno; Perrin, Patrick; Heux, Laurent; Boue, Francois; Cousin, Fabrice

3. “Mechanism of Associations of Neutral Semiflexible Biopolymers in Water: The Xyloglucan

Case Reveals Inherent Links", Macromolecular Chemistry and Physics, 2312-2323, 2013.

4. Bruno Frka-Petesic, Bruno Jean and Laurent Heux First experimental evidence of a giant

permanent electric-dipole moment in cellulose nanocrystals EPL 107 28006 2014

5. N.Guigo, K. Mazeau, J.-L. Putaux, L. Heux Surface modification of cellulose microfibrils by

periodate oxidation and subsequent reductive amination with benzylamine: a topochemical study

Cellulose 21, 4119-4133 2014

58

https://scifinder.cas.org/scifinder/references/answers/B8AC7C47X86F35098X4676E1D91F86EA41FC:B8B6DB76X86F35098X1CD7ED0461CAE29123/3.html?nav=eNpb85aBtYSBMbGEQcXJwsnMxcncLMLCzM3Y1MDSIsLQ2cXc1cXAxMzQ2dHVyNLQyBioNKm4iEEwK7EsUS8nMS9dzzOvJDU9tUjo0YIl3xvbLZgYGD0ZWMsSc0pTK4oYBBDq_Epzk1KL2tZMleWe8qCbiYGhooCBgYEbaGBGCYO0Y2iIh39QvKdfmKtfCJDh5x_vHuQfGuDp517CwJmZW5BfVAI0obiQoY6BGaiPASianVsQlFqIJspUlI_qPqf8_JzUxLyzCkUNV-f8egd0XxTMfQUg9cXFQPXa-UXpesmJxXr5xcmJRXrFqUVlqUV6Kfm5iZl5esn5ubn5eXrBQCcEF6Qm20xYvUB2-oNTTAxMPgw8uZX-RSmZeYk53qmVJQwaPkCD9IEG6YMN0ocYpA8xSB9ikD5QpbUPA3tuJcjE4hIGSR-Qa_VLSzJz9H0y87JTUzwSizOCU0usKwoKgI4TB3sGJK2HIn0j53rU1LtacqCwhHkZrAoqv8uldeq0HdtNmEFhXc4DDB4BewcGMKgAAKRio4A&key=caplus_2013:1178032&title=TWVjaGFuaXNtIG9mIEFzc29jaWF0aW9ucyBvZiBOZXV0cmFsIFNlbWlmbGV4aWJsZSBCaW9wb2x5bWVycyBpbiBXYXRlcjogVGhlIFh5bG9nbHVjYW4gQ2FzZSBSZXZlYWxzIEluaGVyZW50IExpbmtz&launchSrc=reflist&pageNum=1&sortKey=ACCESSION_NUMBER&sortOrder=DESCENDING

https://scifinder.cas.org/scifinder/references/answers/B8AC7C47X86F35098X4676E1D91F86EA41FC:B8B6DB76X86F35098X1CD7ED0461CAE29123/3.html?nav=eNpb85aBtYSBMbGEQcXJwsnMxcncLMLCzM3Y1MDSIsLQ2cXc1cXAxMzQ2dHVyNLQyBioNKm4iEEwK7EsUS8nMS9dzzOvJDU9tUjo0YIl3xvbLZgYGD0ZWMsSc0pTK4oYBBDq_Epzk1KL2tZMleWe8qCbiYGhooCBgYEbaGBGCYO0Y2iIh39QvKdfmKtfCJDh5x_vHuQfGuDp517CwJmZW5BfVAI0obiQoY6BGaiPASianVsQlFqIJspUlI_qPqf8_JzUxLyzCkUNV-f8egd0XxTMfQUg9cXFQPXa-UXpesmJxXr5xcmJRXrFqUVlqUV6Kfm5iZl5esn5ubn5eXrBQCcEF6Qm20xYvUB2-oNTTAxMPgw8uZX-RSmZeYk53qmVJQwaPkCD9IEG6YMN0ocYpA8xSB9ikD5QpbUPA3tuJcjE4hIGSR-Qa_VLSzJz9H0y87JTUzwSizOCU0usKwoKgI4TB3sGJK2HIn0j53rU1LtacqCwhHkZrAoqv8uldeq0HdtNmEFhXc4DDB4BewcGMKgAAKRio4A&key=caplus_2013:1178032&title=TWVjaGFuaXNtIG9mIEFzc29jaWF0aW9ucyBvZiBOZXV0cmFsIFNlbWlmbGV4aWJsZSBCaW9wb2x5bWVycyBpbiBXYXRlcjogVGhlIFh5bG9nbHVjYW4gQ2FzZSBSZXZlYWxzIEluaGVyZW50IExpbmtz&launchSrc=reflist&pageNum=1&sortKey=ACCESSION_NUMBER&sortOrder=DESCENDING

http://iopscience.iop.org/0295-5075/107/2/28006

http://iopscience.iop.org/0295-5075/107/2/28006

http://link.springer.com/search?facet-author=%22Nathana%C3%ABl+Guigo%22

http://link.springer.com/search?facet-author=%22Karim+Mazeau%22

http://link.springer.com/search?facet-author=%22Jean-Luc+Putaux%22

http://link.springer.com/search?facet-author=%22Laurent+Heux%22

Man-made and bioinspired materials from nanocellulose : challenges and opportunities

Laurent HEUX. CERMAV-CNRS, Structure and Properties of Glycomaterials, CNRS and

Grenoble Alpes University, France, [email protected]

Natural structures exhibit spectacular properties like, for instance, the toughness of wood, the

elasticity of primary walls or in the animal kingdom the iridescence of beetle shells. All those

properties rely on hierarchical assemblies made of fibrillar nano-elements that fulfill their function

at a very reasonable energy cost and a light weight. Among the different possible sources,

cellulose is the most abundant polymer produced in Nature. Two types of the so-called

“nanocelluloses” are nowadays exploited for their properties i.e. cellulose micro/nanofibrils

(MFC/NFC) with almost infinite longitudinal sizes obtained by a mechanical disruption of the

original fibers (Figure 1a) or cellulose nanocrystals (CNC) recovered after acid hydrolysis that are

rodlike shaped (Figure 2a).

The applications that are considered often requires the modification of their dispersability and

hence some kind of surface modification. Nanocelluloses can be prepared as cellulose aerogel

(Figure 1b) that can be further hydrophobized [1, 2]. Those aerogels can be directly used after

chemical modification for elastomer reinforcement [3] or cellulose can be directly transformed in

all cellulose composite [4]. In colloidal suspension, CNCs can be physically covered by

surfactants to give stable suspensions in organic solvents that exhibit nice self-organizing

properties in organic solvents (Figure 2b) and oriented in external fields. Recently, we also

demonstrated that these nanorods bear a permanent dipole moment that allows their orientation

under relatively modest electric fields allowing the control of designed helicoidal structures.

Références :

[1] M. Fumagalli ; D. Ouhab; S. Boisseau; L. Heux, Biomacromolecules , 3246-3255 (2013)

[2] M. Fumagalli,. ; F. Sanchez, F.; S. Boisseau; L. Heux, Soft Matter 9, 11309-11317,(2013)

[3] B. DE Gdemaris, J. Berriot, A. Veyland, N. Seeboth, L. Heux, S. Boisseau & M. Fumagalli

Rubber composition comprising cellulose , WO2014096188 (2012)

[4] A. Codou ,N. Guigo, L. Heux N. Sbirrazzuoli- Composites Science and Technology 117 (2015)

200 nm

20 µm

Figure 1a Figure 1b

Figure 2bFigure 2a

59


1996: Ph. D. LCPO/University of Bordeaux I

(A. Soum), France.

1996-1997: Post-doc LCPO/University of

Bordeaux I (A. Deffieux), France.

1997-2014: Assistant Professor at University of

Strasbourg – ECPM, Department of polymer

science (LPMP, LIPHT and ICPEES)

2011: Accreditation to condute research

University of Strasbourg

Thesis : Synthesis and elaboration of polyfonctionnal

polymeric materials using intensified process

Since 2015: Assistant Professor at University of

Strasbourg – ECPM, Charles Sadron Institute -

CMP (CNRS).

BOUQUEY Michel

Assistant Professor

Tel: +33 3 88 41 40 54


Web : http:// www-ics.u-strasbg.fr


The main objectives of the research group “Precision Macromolecular Chemistry” at Charles

Sadron Institute is to control the molecular structure (i.e. architecture, microstructure and

functionality) and, as well, polymer morphology with the aim of developing new polymeric

materials. In this perspective, we are particularly interested in correlating the key aspects of

polymer synthesis (building-blocks for polymerizations, preparation of tailored

macromolecules, …) and the polymerization processing technology. Starting from well-known

reactive systems or formulations, we focus on the influence of the process parameters on the

final properties of materials. That is why we develop specific intensified reactors i.e

microfluidics types in order to improve or control some fundamental parameters in polymer

synthesis like the efficiency of mixing or the thermal exchange. Recently, we have interested to

produce emulsions in water with a controllable size in range of 30-100nm.


1. Souilem I., C.A. Serra, R. Muller, Y. Holl and M. Bouquey, Dimensional analysis of a

novel low pressure device for the production of size-tunable, AIChE J. 2015, 61, (1), 23-30.

2. Ibarra R., R. Muller, M. Bouquey, C. Serra, J. Rondin, F. Hassouna, Y. Mouedden and V.

Toniazzo, Processing of nanocomposites PLA/graphite using a novel elongational mixing

device, Polym. Eng. Sci. 2015, 55, (1), 214-222.

3. Souilem I., M. Bouquey, R. Muller, Y. Holl, C.A. Serra, T. Vandamme, N. Anton, A novel

low-pressure device for production of nano emulsion, Chem. Eng. Technol 2012, 35, (9),

1692-1698.

4. Bouquey M., R. Muller, G. Bouchet and C. Loux, Morphological study of two-phase

polymer blends during compounding in a novel compounder on the basis of elongational flow,

J. Appl. Polym Sci., 2011, 119, (1), 482-490.

5. Chang Z., C. Serra, M. Bouquey, L. Prat and G. Hadziioannou, Co-axial capillaries

microfluidic device for synthesizing size- and morphology-controlled polymer- polymer

core-shell particles, Lab. Chip. 2009, 9, 3007-3011.

60


Using intensified polymerization processes to elaborate novel polymeric

materials

Michel Bouquey, Christophe A. Serra, René Muller, Yves Holl

Université de Strasbourg (UdS), École Européenne de Chimie, Polymères et Matériaux

(ECPM), 25 rue Becquerel, F-67087 Strasbourg Cedex 2, France.

Institut Charles Sadron (ICS) – UPR 22 CNRS, 23 rue du Loess, F-67034 Strasbourg

Cedex 2, France, [email protected].

Properties of polymeric materials not only depend upon the chemical nature of

the macromolecules but also of their arrangement at different scales from nano to

mesoscale. Moreover these morphologies are strongly affected by the type of

polymerization process and by its operating parameters. To assess this affect, our

group has developed in the last decade intensified polymerization reactors which,

under specific conditions, allowed elaborating new polymeric materials. Two main

results in this area will be detailed and discussed during the presentation. The first

deals with the use of microfluidic devices to produce size-, composition- and

morphology-controlled polymer micro and nanoparticles in the size range 10-600 µm

and 40-500 nm respectively1 (low viscosity systems). The second concerns a new

reactor/mixer2 (so-called RMX®) for the synthesis of polymers in highly viscous

media (high viscosity systems). It consists in an in situ polymerization conducted

within a melted polymer matrix which induces uncommon morphologies and

properties.

References

1- Chang Z., C. Serra, M. Bouquey, L. Prat and G. Hadziioannou, Co-axial capillaries

microfluidic device for synthesizing size- and morphology-controlled polymer-

polymer core-shell particles, Lab. Chip. 2009, 9, 3007-3011.

2- Bouquey M., R. Muller, G. Bouchet and C. Loux, Morphological study of two-phase

polymer blends during compounding in a novel compounder on the basis of

elongational flow, J. Appl. Polym Sci., 2011, 119, (1), 482-490.

61

2005 Ph. D. University Montpellier,

FRANCE

2005 Postdoctorate Fellow, University

of Toronto, CANADA

2006 Postdoctorate Fellow, Centre de

Recherche Paul Pascal, Bordeaux,

FRANCE

2007 Associate Professor at University

Pierre et Marie Curie (UPMC), Soft

Matter Sciences and Engineering,

Paris, FRANCE

SANSON Nicolas Associate Professor at UPMC

Tel: +33 1 40 79 44 17


Web:

https://www.ppmd.espci.fr/spip.php?article167&lang=

en


My research interests are focused on the fundamental and practical aspects involved

in the synthesis of smart colloidal materials with special emphasis on

stimuli-responsive polymers grafted inorganic nanoparticles. My research also

includes activities on the synthesis of microgels for the elaboration of hybrid materials

or using as stabilizers of emulsions.

Selected Recent Publications Signal enhancement of electrochemical biosensors via direct electrochemical oxidation of

silver nanoparticle labels coated with zwitterionic polymer, R. Geagea, P.-H. Aubert, P. Banet,

N. Sanson, Chemical Communications, 2015, 51, 402. Colloidal stability of zwitterionic polymer-grafted gold nanoparticles in water, C.

Durand-Gasselin, R. Koerin, J. Rieger, N. Lequeux, N. Sanson, Journal of Colloid and Interface Science, 2014, 434, 188. Selective Cold Welding of Colloidal Gold Nanorods, S. Laza, N. Sanson, C. Sicard-Roselli,

A. Aghedu, B. Palpant, Particle and Particle Systems Characterization, 2013, 7, 584. Tunable and reversible aggregation of poly(ethylene oxide-st-propylene oxide) grafted

gold nanoparticles C. Durand-Gasselin, M. Capelot, N. Sanson, N. Lequeux, Langmuir, 2010,

26, 12321.

Synthesis of nanogels/microgels by conventional and controlled radical crosslinking

copolymerization, N. Sanson, J. Rieger, Polymer Chemistry, 2010, 1, 965. Microgels loaded with gold nanorods: Photothermally triggered volume transition under

physiological conditions, M. Das, N. Sanson, D. Fava, E. Kumacheva, Langmuir, 2007, 23,

196.

Highly stable metal hydrous oxide colloids by inorganic polycondensation in suspension C.

Gérardin, N. Sanson, F. Bouyer, F. Fajula, J-L. Putaux, M. Joanicot, T. Chopin, Angewandte Chemie Int. Ed., 2003, 42, 3681.

62

Cold Welding or How Soft Interactions Promote the Welding of

Colloidal Gold Nanorods

Sen Li,a Julien Smith,

a Simona Laza,

b Nicolas Sanson

a

aSoft Matter Sciences and Engineering, PSL Research University, ESPCI ParisTech, Sorbonne

Universités, UPMC Univ Paris 06, CNRS UMR 7615, 10 rue Vauquelin, 75231 Paris, Cedex

05,France. bEcole Centrale Paris, Laboratoire de Photonique Quantique et Moléculaire, UMR 8537 –

CNRS, Ecole Normale Supérieure de Cachan, Grande Voie des Vignes, 92295 Châtenay-

Malabry cedex, France.

[email protected]

The increasing interest for the self-organization of metallic nanoparticles is due to its

potential use in the construction of functional nano/micro-systems for sensing,

photonics and biomolecular electronics. For these reasons, self-organization has

become for the last years a major research theme in nanotechnology. One of the main

factors determining the final geometry of the resulting assembly is the nanoparticle

shape. At present, among anisotropic metallic nanoparticles, there is considerable

interest for gold nanorods (GNR) due to their aptitude for bidirectional ordering.

Here we demonstrate a new, soft, fast and simple way to produce long gold nanowires

(up to 6µm) based on the end-to-end self-organization and cold-nanowelding of

colloidal gold nanorods in water at room temperature and without any external force.

The welding of colloidal gold nanorods in water is promoted by polymer/surfactant

interactions between CTAB surfactants located on the GNR surface and polymers

added in solution. The GNRs self-organization process can be stopped at any time in

order to control the length of the gold nanowires. The nature, functionality,

concentration and the average molar mass of the polymer added in solution were

investigated on the reaction rate. The kinetics of the gold nanowires formation is

modelled by a oriented attachment mechanism mimicking a step-growth

polymerization in which colloidal gold nanorods act as multifunctional monomer units.

This cold nanowelding technique, based on polymer/surfactants interactions,

represents an attractive strategy to the bottom-up production of metallic nanowires

and anticipates to be a possible future microfabrication technique with a strong

analogy with polymer chemistry.

63

1987: BS degree from Fudan University,

majoring in Chemistry, China

1990: MS degree from Fudan University,

majoring in Physical Chemistry, I China

1996: PhD degree from Fudan University,

majoring in Polymer Chemistry and Physics

1996-1998: Visiting Scientist at Eastern

Michigan University, USA

1996-2002: Associate Professor, at Fudan

University, China

2002- : Professor, at Department of

mactomolecular Sciece , Fudan University,

China

2013- : Dean of Department of

mactomolecular Sciece , Fudan University,

China

Wang Changchun

Dean of Department of mactomolecular Sciece

Tel: +86-21-65642385


Web: http://www.polymer.fudan.edu.cn/

polymer/research/wangcc/index.html


The focus of the research done in my group is design and synthesis of various

functional polymeric composite microspheres with controlled properties for

biomedical applications in imaging, sensing, enrichment, diagnostics and drug

delivery.


1. Li D, Zhang YT, Li RM, Guo J, Wang CC, Tang CB, Selective Capture and Quick Detection

of Targeting Cells with the Technique of Liquid Suspension Chips, Small, 2015, 11(18),

2200-2208.

2. Zhang YT , Ma WF, Li D, Yu M, Guo J, Wang CC, Benzoboroxole-functionalized magnetic

core/shell microspheres for highly specific enrichment of glycoproteins under physiological

conditions, Small, 2014, 10(7), 1379–1386.

3. Yang P, Li D, Jin S,Ding J, Guo J, Shi WB, Wang CC, Stimuli-responsive biodegradable

poly(methacrylic acid) based nanocapsules for ultrasound traced and triggered drug delivery

system, Biomaterials, 2014, 35, 2079-2088.

4. Guo J, Yang WL, Wang CC, Magnetic colloidal supraparticles: Design, fabrication and

biomedical applications, Adv. Mater., 2013, 25, 5196-5214 (IF=14.829)

5. Ma WF, Zhang Y, Li LL, Zhang YT, Yu M, Guo J, Lu HJ, Wang CC, Ti4+

-immobilized

magnetic composite microspheres for highly selective enrichment of phosphopeptides, Adv.

Funct. Mater., 2013, 23, 107-115.

6. Li D, Zhang YT, Yu M, Guo J, Chaudhary D, Wang CC, Cancer therapy and fluorescence

imaging using the active release of doxorubicin from MSPs/Ni-LDH folate targeting

nanoparticles, Biomaterials, 2013, 34, 7913-7922

7. Shen XY, Viney C, Johnson ER, Wang CC, Lu Q, Large negative thermal expansion of a

polymer driven by a submolecular conformational change, Nature Chemistry, 2013, 5,

1035-1041.

64

http://www.polymer.fudan.edu.cn/

Stimuli-responsive biodegradable polymer nanoparticles for

triggered drug delivery system

Peng Yang, Sha Jin, Yuanjia Pang, Jia Guo and Chang-Chun Wang

State Key Laboratory of Molecular Engineering of Polymers, and Department of

Macromolecular Science, Laboratory of Advanced Materials, Fudan University,

Shanghai 200433, China. E-mail: [email protected]

Cancer can affect various organs and occur in nearly every tissue in the body,

which is one of the most challenging medical issues for handling1. The modern

personal healthcare and pharmaceutical industries have raised some new concepts and

requirements for the therapy of cancer2,3

, that is, it can be found at the early stages

before the cancer metastasizes through the lymph systems and then the abnormal cells

can be efficiently killed by chemotherapeutic agents. In this abstract, we have

successfully developed a US traced and triggered drug delivery system using a new

preparation method, the superiority of their US contrast efficiency and excellent

drug-delivery capacity has been confirmed. In comparison with previous reported

ultrasound targeted drug release systems, our system has four advantages as following:

(1) the PMAA-PFH nanocapsules are very uniform, soft and small (300 nm), which

can easily enter the tumor tissues via EPR effect; (2) the PMAA shell has high

DOX-loading content (36 wt%) and great drug loading efficiency (93.5 %) by strong

electrostatic interactions between carboxyl groups and amino groups, and the loading

drug can be quickly released (< 5 min.) under US conditions; (3) the PFH filled can

effectively enhance US imaging signal through acoustic droplet vaporization (ADV),

ensuring diagnostic and image-guided therapeutic applications; (4) what is more, the

disulfide-crosslinked PMAA shell is biodegradable and thus safe for normal

organisms. All these merits enabled us attain the final goal for optimizing the balance

of diagnostic, therapeutic and biodegradable functionalities in a three-in-one

theranostic nanoplatform.

References

(1) Varmus, H. Science 2006, 312, 1162-1165.

(2) Minchinton, A. I.; Tannock, I. F. Cancer 2006, 6, 583-592.

(3) Schroeder, A., Heller, D. A.; Winslow, M. M.; Dahlman, J. E;, Pratt, G. W.; Langer, R.; et al. Nat.

Rev. Cancer 2012, 12, 39-50.

65

1984-1990 : Chemistry major,

University of Mainz, Germany

1993 : PhD in Theoretical Physics,


1995-1997 : Post-doc, Institut Charles

Sadron, Strasbourg, France

1999 : Habilitation in Physics,


As of 1999 : Professor for Physics at the

University of Strasbourg, France BASCHNAGEL Jörg Professor at the University of Strasbourg

Tel: +33 3 88 41 40 56


Web: http://www-ics.u-

strasbg.fr/spip.php?article128&lang=en


My research activity is focused on the physics of polymers. Over the last years, I have worked

on the conformation and dynamics of bulk polymer melts and thin films, both in the liquid

phase and in the glass phase. More specifically, my research has been concerned with the

following topics: the corrections to chain ideality in the melt due to residual excluded volume

interactions [1], the subdiffusive motion of the center of mass of a polymer in a nonentangled

melt [2], the conformation and structure of two-dimensional polymer solutions and melts [3],

the structural relaxation of polymer melts and films on cooling toward the glass transition

[4,5], the mechanical properties (shear and bulk moduli) of (polymer) glasses [6], the

correlation between chain conformation and shear forces when two brush-bearing surfaces are

in contact with one another [7], and the tribological properties of glassy polymer films in

contact with a nanoindenting tip [8].

Selected Recent Publications [1] J.P. Wittmer, A. Cavallo, H. Xu, J. E. Zabel, P. Polińska, N. Schulmann, H. Meyer, J. Farago, A. Johner, S. P. Obukhov, J. Baschnagel, Scale-Free Static and Dynamical Correlations

in Melts of Monodisperse and Flory-Distributed Homopolymers, J. Stat. Phys. 145, 1017 (2011).

[2] J. Farago, H. Meyer, J. Baschnagel, A. N. Semenov, Mode-coupling approach to polymer

diffusion in an unentangled melt: I. The effect of viscoelastic hydrodynamic interactions, Phys.

Rev. E 85, 051807 (2012).

[3] H. Meyer, J. P. Wittmer, T. Kreer, A. Johner, J. Baschnagel, Static Properties of Polymer

Melts in Two Dimensions, J. Chem. Phys. 132, 184904 (2010).

[4] J.-L. Barrat, J. Baschnagel, A. Lyulin, Molecular dynamics simulations of glassy polymers

Soft Matter 6, 3430 (2010).

[5] S. Peter, H. Meyer, J. Baschnagel, MD Simulations of Concentrated Polymer Solutions

in Thin Film Geometry: II. Solvent Evaporation near the Glass Transition, J. Chem. Phys.

131, 014903 (2009).

[6] J. Wittmer, H. Xu, J. Baschnagel, Shear stress relaxation and ensemble transformation of

shear-stress auto-correlation functions revisited, Phys. Rev. E 91, 022107 (2015).

[7] A. Galuschko, L. Spirin, T. Kreer, A. Johner, C. Pastorino, J. Wittmer, J. Baschnagel, Frictional Forces between Strongly Compressed, Nonentangled Polymer Brushes: Molecular

Dynamics Simulations and Scaling Theory, Langmuir 26, 6418 (2010).

[8] M. Solar, H. Meyer, C. Gauthier, O. Benzerara, H. Pelletier, R. Schirrer, J. Baschnagel,

Molecular dynamics simulations as a way to investigate the local physics of contact mechanics: a

comparison between experimental data and numerical results, J. Phys. D: Appl. Phys. 43,

455406 (2010).

66

http://ccreton.ppmd.espci.fr/

http://ccreton.ppmd.espci.fr/

Modeling of solvent evaporation from glass-forming polymer films:

Molecular-dynamics simulations and diffusion equation approach

Jörg Baschnagel1, Hendrik Meyer

1, Simone Peter

1

1 Institut Charles Sadron, Université de Strasbourg, Strasbourg, France

[email protected]

We perform molecular dynamics simulations of a coarse-grained model of a polymer-

solvent mixture to study solvent evaporation from supported and free-standing

polymer films near the bulk glass transition temperature Tg. We find that the

evaporation process is characterized by three time (t) regimes: an early regime where

the initially large surplus of solvent at the film-vapor interface evaporates and the film

thickness h varies little with t, an intermediate regime where h decreases strongly, and

a final regime where h slowly converges toward the asymptotic value of the dry film.

In the intermediate regime the decrease of h goes along with an increase of the

monomer density at the retracting interface. This polymer-rich “crust” is a non-

equilibrium effect caused by the fast evaporation rate in our simulation. The

interfacial excess of polymer gradually vanishes as the film approaches the dry state.

In the intermediate and final time regimes it is possible to describe the simulation data

for h(t) and the solvent density profile by the numerical solution of a one-dimensional

diffusion model depending only on the y direction perpendicular to the interface. The

key parameter of this model is the mutual diffusion coefficient D of the solvent in the

film. Above Tg we find that a constant D allows to describe the simulation data,

whereas near Tg agreement between simulation and modeling can only be obtained if

the diffusion coefficient depends on y through two factors: a factor describing the

slowing down of the dynamics with decreasing solvent concentration and a factor

parametrizing the smooth gradient toward enhanced dynamics as the film-vapor

interface is approached.

1. S. Peter, H. Meyer, J. Baschnagel, MD Simulation of Concentrated Polymer Solutions: Structural

Relaxation near the Glass Transition, Eur. Phys. J. E 28, 147 (2009).

2. S. Peter, H. Meyer, J. Baschnagel, MD Simulations of Concentrated Polymer Solutions in Thin

Film Geometry: I. Equilibrium Properties near the Glass Transition, J. Chem. Phys. 131, 014902

(2009).

3. S. Peter, H. Meyer, J. Baschnagel, MD Simulations of Concentrated Polymer Solutions in Thin

Film Geometry: II. Solvent Evaporation near the Glass Transition, J. Chem. Phys. 131, 014903 (2009).

67


2001: B.S degree of Chemistry, Anhui Normal

University, Wuhu, China

2006: Ph. D degree of Organic Chemistry,

Shanghai Institute of Organic Chemistry, Chinese

Academy of Science.

2006-2009: Postdoctoral Research Fellow,

Nagoya University, Japan

2010-2011: Research Associate, University of

Texas at Austin, USA

2011- : Professor at Department of Polymer

Science and Engineering, Hefei University of

Technology, Hefei, China

Zong-Quan Wu

Tel: +86-551-6290-2931


Web : http://www.gngfz.hfut.edu.cn


The research in our group is focus on design and synthesis of optically active helical polymers

and exploring theirs applications in chiral recognition, asymmetric reaction, and enantiomer

separation. We focus on developing new catalyst or initiator for facile synthesis of stereoregular

helical polyisocyanide and polyallene under living/controlled manner. We are interested in

facile synthesis of well-defined hybrid block copolymers and polymer brushes containing

helical polymer segments, and explore their self-assembly and the related optical properties.

We particularly interested in the applications of chiral materials based on the helical polymers

in asymmetric reactions and enantiomer separation with in high efficient.


1. Xue, Y.-X.; Zhu, Y.-Y.; Gao, L.-M.; He, X.-Y.; Liu, N.; Zhang, W.-Y.; Yin, J.; Ding, Y.;

Zhou, H.; Wu, Z.-Q., Air-Stable (Phenylbuta-1,3-diynyl)palladium(II) Complexes: Highly

Active Initiators for Living Polymerization of Isocyanides. J. Am. Chem. Soc. 2014, 136,

4706–4713.

2. Zhu, Y.-Y.; Yin, T.-T.; Li, X.-L.; Su, M.; Xue, Y.-X.; Yu, Z.-P.; Liu, N.; Yin J.; Wu, Z.-Q.,

Synthesis and Chiroptical Properties of Helical Polyallenes Bearing Chiral Amide Pendants,

Macromolecules 2014, 47, 7021–7029.

3. Gao, L.-M.; Hu, Y.-Y.; Yu, Z.-P.; Liu, N.; Yin, J.; Zhu, Y.-Y.; Ding, Y.; Wu, Z.-Q., Facile

Preparation of Regioregular Poly(3-hexylthiophene) and Its Block Copolymers with

π-Allylnickel Complex as External Initiator. Macromolecules 2014, 47, 5010−5018.

4. Jiang, Z.-Q.; Xue, Y.-X.; Chen, J.-L.; Yu, Z.-P.; Liu, N.; Yin, J.; Zhu, Y.-Y.; Wu, Z.-Q.,

One-Pot Synthesis of Brush Copolymers Bearing Stereoregular Helical Polyisocyanides as

Side Chains through Tandem Catalysis. Macromolecules 2015, 48, 81–89.

68

Facile Synthesis of Stereoregular Helical Polyisocyanide and Its

Copolymers

Zhi-Qiang Jiang, Jia-Li Chen, Ya-Xin Xue, Zong-Quan Wu

Department of Polymer Science and Engineering, School of Chemistry and Chemical

Engineering, Hefei University of Technology and Anhui Key Laboratory of Advanced

Functional Materials and Devices, Anhui Province, Hefei 230009, China.

[email protected]

Inspired by the helical structures of natural occurring biomacromolecules, researches

on optically active helical polyisocyanides have attracted considerable attentions in

recently decades.1 Well-defined helical polyisocyanides are usually prepared by the

polymerization of appropriate isocyanide monomers by using transition metal

complexes as initiator or catalyst. However, the living/controlled synthetic method is

limited. Here, we report a series of new palladium complexes which can initiate the

polymerization of various isocyanide monomer under living/controlled manners,

afforded well-defined polyisocyanides in high yields with controlled molecular

weights (Mns), narrow molecular weight distributions (Mw/Mns), and interestingly,

high stereoregularity.2 We revealed that the substituents and ligands on the Pd(II)

initiator affect the polymerization activity. Additionally, modifications on this Pd(II)

complexes, such polymerization can be further applied in the synthesis of copolymer

containing helical poisocyanide segments. For example, incorporated norborene unit

onto the Pd(II) complex, this Pd(II) initiator can be used to readily synthesis of

polymer brushes containing polynorborene as main chain and helical polyisocyanide

as side chains.3 Moreover, introduced a hydroxyl (OH) group onto the Pd(II) initiator,

a series of block copolymers compose of stereoregular polyisocyanide and

poly(L-lactic acide) can be facilely prepared in one-pot. Given the modification on the

Pd(II) initiator and isocyanide monomers, various optically active functional materials

can be readily obtained.4

This work is financially supported by the National Natural Science Foundation of

China (Nos. 21104015, 21172050) and Thousand Young Talents Program

1. Yashima, E.; Maeda, K.; Iida, H.; Furusho, Y.; Nagai, K. Chem. Rev. 2009, 109, 6102.

2. Xue, Y.-X.; Zhu, Y.-Y.; Gao, L.-M.; He, X.-Y.; Liu, N.; Zhang, W.-Y.; Yin, J.; Ding, Y.; Zhou, H.;

Wu, Z.-Q., J. Am. Chem. Soc. 2014, 136, 4706–4713.

3. Jiang, Z.-Q.; Xue, Y.-X.; Chen, J.-L.; Yu, Z.-P.; Liu, N.; Yin, J.; Zhu, Y.-Y.; Wu, Z.-Q.,

Macromolecules 2015, 48, 81–89.

4. Jia-Li Chen, Ming Su, Zhi-Qiang Jiang, Na Liu, Jun Yin, Yuan-Yuan Zhu and Zong-Quan Wu*,

Polym. Chem. 2015, 6, 4784–4793.

69

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