Mass Detection for the Cosmetics Industry

©2015 Waters Corporation 1

Mass Detection for the Cosmetics Industry

Jane Cooper

Senior Applications Scientist

Chemical Materials Business Operations

Wilmslow, UK


Introduction

Background

–Analytical challenges

Mass detection

–Ease of Use

–Advantages

Application examples

Questions


An Ecosystem Focused on Innovation

Contract Research

Organizations (CRO)

Contract Manufacturing Organizations

(CMO)

Active Ingredient Suppliers

(Botanicals/ Synthetic Molecules)

Raw Materials Suppliers

Cosmetics & Personal Care

Company


Analytical Solutions for Cosmetics & Personal Care


Analytical Challenges

Raw Materials Testing

– Establishing Action and Safety

o Verification liability on manufacturers

o Testing materials from certain geographical regions

o Heavy metals in raw materials

o What is the cost to you of non-conforming goods?

Active Ingredients

o What is it?

o How much?

o What else is in the plant extraction?



Formulation

– Ensuring Performance and Characterisation

o Chemical Diversity

o Impurities, Allergens, Pesticides

o How many components in a cosmetic formulation?

Quality Control

– Delivering Optimum Production Volume

o Ensuring batch-to-batch conformity

o How much does losing a batch of cosmetic cost?

o Time delay in bringing product to market?



Safety and Regulatory Compliance

– Making Compliance Routine

o Protecting customers is Number 1 goal

o Different requirements for FDA and Europe

o Understanding the impact of packaging on product safety

• Non Intentionally Added Substances

o Allergens

• Utilising LC not just GC

• 0.001% leave on and 0.01% rinse off

o Pesticides

o Heavy metals in raw materials

o How much is the fine for getting this wrong?



Counterfeit Detection

– Protecting brand identity

o How much does it cost the cosmetic industry?

Data Management

– Leveraging the Power of Information

o What cost failing an FDA audit?

Phytochemistry

– Rise of botanical ingredients

o Profile and understand composition

o Do we understand metabolite activity?


• DISPOSABLE APERATURE • ONE PIECE PROBE • AUTOMATIC CALIBRATION • REDUCED MAINTENANCE AND PROVEN ROBUSTNESS

Purposely innovated to eliminate downtime...

Adjustment free single piece electrospray probe

Protected detector orifice


Simply switch off after use....

READY TO USE IN UNDER TEN MINUTES

Integrated calibration can be automatically performed upon start up


Complementary & compatible….

Providing information-rich mass spectral data

Detector concept

Built to consider …

- Samples

- Separations

- Scientists

• 30-1250 DA • PRE-OPTIMIZED ES± • 20 HZ FS • 100 HZ SIR • 4 ORDERS • INTUITIVE •


Return on investment....

Streamlined workflows and improved lab

efficiency via accessible mass detection

Significant measurable return on investment

– Low running costs

o Power consumption

o Service plan costs

o Simply turn off after use

o Laboratory space savings

Standardise on QDa and achieve substantial

savings over typical ownership duration

• LOW RUNNING COSTS • 110 – 240 V • PUSH BUTTON USAGE •


Provides mass data to separation scientists

Compact, intuitive and simple to use

Improving workflows and efficiency in every laboratory – giving

a guaranteed return on investment!


Benefits of Mass Detection for the Cosmetics Industry

Method development

– Aim: One peak = one compound

o Detect coelutions and peaks missed by optical detection

o Track peaks more effectively

Sample profiling

– Aim: Identify components and quantify

o Process complex matrices and low level target compounds

o Improved selectivity, more sensitivity

Synthetic chemistry

– Aim: Confirm product identity

o Improve turnaround of results

o Improve information available on impurities

Purification

– Aim: Isolate pure compound

o Collect fewer fractions with increased confidence


The power of mass detection….

D

Identify co-elutions

Detect non-chromophoric analytes


For all your separations….


Track peaks, see

coelutions, see more

peaks

One peak, one component

Coelutions and missed peaks

Method Development….

• RISK MANAGEMENT • WORKFLOW STREAMLINING • PRODUCTIVITY •


Identify and quantify

Complex matrices & low levels

More selectivity, more sensitivity

Sample Profiling….

• QUALITY • WORKFLOW INTEGRATION • PRODUCTIVITY •


Results now

Confirm product

Delay to analysis

Synthetic Chemistry….

• WORKFLOW INTEGRATION • RESOURCE MANAGEMENT • DEADLINES •


Single fraction

Isolate compound

Purification….

• WORKFLOW INTEGRATION • RESOURCE MANAGEMENT • PRODUCTIVITY •

Multiple fractions


Improving sensitivity and selectivity for primary aromatic amines....

Highly legislated Inks and Dyes industry

– PAA’s suspected carcinogens

Added benefits:

– Improved Signal-to-noise over UV

– Increased Selectivity – distinguishes components masked in UV

METHOD DEVELOPMENT


Time-0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00

AU

-2.5e-3

0.0

2.5e-3

5.0e-3

7.5e-3

1.0e-2

1.25e-2

1.5e-2

1.75e-2

2.0e-2

2.25e-2

2.5e-2

2.75e-2

3.0e-2

3.25e-2

3.5e-2

3.75e-2

-0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00

AU

-1.5e-2

-1.0e-2

-5.0e-3

0.0

5.0e-3

1.0e-2

1.5e-2

2.0e-2

2.5e-2

3.0e-2

3.5e-2

4.0e-2

4.5e-2

5.0e-2

5.5e-2

5.865.03

4.73

4.53

3.61

0.33

0.30

0.98

0.540.70

0.83

2.09

1.492.78

2.90

3.47

3.88

4.33

3.96

5.42

7.53

6.37

6.11 7.00

7.88

8.42

9.30

5.29

3.80

1.27

0.54

0.26

0.73

0.98

2.37

2.183.44

4.94

4.624.22

4.46

5.19

5.07

6.74

5.41

6.00

8.02

7.37

7.13

7.51

8.07

9.28

Peak tracking with Primary Aromatic Amines....

PAA

letter Primary Aromatic Amines

A Aniline

B o-Toluidine

C 1,3-Phenylenediamine

D 2,4-Dimethylaniline

E 2,6-Dimethylaniline

F 2,4-Toluenediamine

G 2,6-Toluenediamine

H o-Anisidine

I 2-Methoxy-5-methylaniline

J 4-Methoxy-m-phenylenediamine

K 2-Naphtylamine

L 3-Amino-4-methylbenzamide

M 1,5-Diaminonaphtalene

N 4-Aminobiphenyl

O 2-Aminobiphenyl

P Benzidine

Q 4-Chloro-2,5-dimethoxyaniline

R 4-Aminoazobenzol

S 4,4'-Methylenedianiline

T 3,3'-Dimethylbenzidine

U 4,4'-Thioaniline

V o-Aminoazotoluene

W 4,4'- Diamino-3,3'-dimethylbiphenylmethane

X o-Dianisidine

ACQUITY UPLC BEH Phenyl , 1.7 µm, 2.1 x 50 mm

ACQUITY BEH C18, 1.7 µm, 2.1 x 50mm

A

U

J

I

H

G/L

F

D/E

C

B

M

R

V

P

N

W

K/T/X

S

O

Q

A

G/L

J

F

H

T

D/E

C

U

M W

V

P

N

X/Q

S/I

R

B

K

Reducing method development times


Time-0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00

AU

-2.5e-3

0.0

2.5e-3

5.0e-3

7.5e-3

1.0e-2

1.25e-2

1.5e-2

1.75e-2

2.0e-2

2.25e-2

2.5e-2

2.75e-2

3.0e-2

3.25e-2

3.5e-2

3.75e-2

-0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00

AU

-1.5e-2

-1.0e-2

-5.0e-3

0.0

5.0e-3

1.0e-2

1.5e-2

2.0e-2

2.5e-2

3.0e-2

3.5e-2

4.0e-2

4.5e-2

5.0e-2

5.5e-2

5.865.03

4.73

4.53

3.61

0.33

0.30

0.98

0.540.70

0.83

2.09

1.492.78

2.90

3.47

3.88

4.33

3.96

5.42

7.53

6.37

6.11 7.00

7.88

8.42

9.30

5.29

3.80

1.27

0.54

0.26

0.73

0.98

2.37

2.183.44

4.94

4.624.22

4.46

5.19

5.07

6.74

5.41

6.00

8.02

7.37

7.13

7.51

8.07

9.28

Peak tracking with Primary Aromatic Amines....

ACQUITY UPLC BEH Phenyl , 1.7 µm, 2.1 x 50 mm

ACQUITY BEH C18, 1.7 µm, 2.1 x 50mm

A

U

J

I

H

G/L

F

D/E

C

B

M

R

V

P

N

W

K/T/X

S

O

Q

A

G/L

J

F

H

T

D/E

C

U

M W

V

P

N

X/Q

S/I

R

B

K

Reducing method development times

Time4.10 4.15 4.20 4.25 4.30 4.35 4.40 4.45 4.50 4.55 4.60 4.65 4.70 4.75 4.80 4.85 4.90 4.95 5.00 5.05 5.10 5.15 5.20

AU

0.0

5.0e-3

1.0e-2

1.5e-2

2.0e-2

2.5e-2

4.10 4.15 4.20 4.25 4.30 4.35 4.40 4.45 4.50 4.55 4.60 4.65 4.70 4.75 4.80 4.85 4.90 4.95 5.00 5.05 5.10 5.15 5.20

%

16

4.10 4.15 4.20 4.25 4.30 4.35 4.40 4.45 4.50 4.55 4.60 4.65 4.70 4.75 4.80 4.85 4.90 4.95 5.00 5.05 5.10 5.15 5.20

%

0

4.62

4.64

4.094.23 4.37

5.154.81

4.94

4.624.22

4.46

4.81

5.19

5.07

I

S 4,4'-Methylenedianiline

UV chromatogram (260 nm)

QDa chromatogram (m/z = 199)

QDa chromatogram (m/z = 138)

2-Methoxy-5-methylaniline

nm200 220 240 260 280 300 320 340

AU

0.0

2.0e-2

4.0e-2

6.0e-2

8.0e-2

1.0e-1

1.2e-1

1.4e-1

1.6e-1

1.8e-1

nm200 220 240 260 280 300 320 340

AU

0.0

2.0e-2

4.0e-2

6.0e-2

8.0e-2

1.0e-1

1.2e-1

1.4e-1

1.6e-1

206

290

202

244

2-Methoxy-5-methylaniline

4,4'-Methylenedianiline

I

S


UPC2 – Convergence Chromatography

Simplify the analytical workflow

– Access robust normal phase separations

– Eliminate solvent exchange steps for organic extracts

Deal with compound Similarity challenges

– Positional isomers (differ in location of functional groups)

– Chiral Separations (enantiomers & diastereomers)

Deliver Orthogonal separations

– Different relative retention ensures full characterization

– Check method specificity by comparison to a second procedure

– Reveal “hidden” impurity or degradation peaks

– Increase confidence in characterization of complex samples


UPC2/QDa – Enhancing already powerful and orthogonal separations


Chiral purity of propiconazole using UPC2/QDa....

Rapid separation of diasteroisomers

AU

0.00

0.05

0.10

0.15

0.20

0.25

AU

0.00

0.02

0.04

0.06

0.08

Minutes

0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00

AU

-0.005

0.000

0.005

0.010

0.015

0.020

0.025

0.030

0.035

AU

-0.002

0.000

0.002

0.004

0.006

0.008

0.010

Minutes

4.00 4.50 5.00

AU

-0.005

0.000

0.005

0.010

0.015

0.020

0.025

0.030

0.035

AU

-0.002

0.000

0.002

0.004

0.006

0.008

0.010

Minutes

4.00 4.50 5.00

12

3 Formulation sample

UV at 220 nm

Propiconazolestandard

4

5 86 7

1 2

3 4

5 86

7

SAMPLE PROFILING


Chiral purity using UPC2/QDa.... Linking mass detection to PDA data

Empower Mass Analysis window

1 2

3 4

5 6 7 8UV

TIC

XIC

1 2 3

UV and MS spectra

4

UV spectra

Mass spectra


Chiral purity using UPC2/QDa.... Improved selectivity and sensitivity

PDA and mass chromatograms

AU

0.00

0.05

0.10

0.15

0.20

0.25

Inte

ns

ity

0.0

2.0x108

4.0x108

6.0x108

8.0x108

1.0x109

1.2x109

1.4x109

1.6x109

Minutes

0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50

PDA 220 nm

XIC m/z 342

12

3 4

58

6 7

12

3 4

5 86 7

AU

-0.010

0.000

0.010

0.020

0.030

0.040

Inte

nsity

-5.0x107

0.0

5.0x107

1.0x108

1.5x108

2.0x108

2.5x108

Minutes

4.00 5.00

AU

-0.010

0.000

0.010

0.020

0.030

0.040

Inte

nsity

-5.0x107

0.0

5.0x107

1.0x108

1.5x108

2.0x108

2.5x108

Minutes

4.00 5.00

AU

-0.010

0.000

0.010

0.020

0.030

0.040

Inte

nsity

-5.0x107

0.0

5.0x107

1.0x108

1.5x108

2.0x108

2.5x108

Minutes

4.00 5.00

PDA 220 nm

XIC m/z 342

5 86 7

AU

-0.010

0.000

0.010

0.020

0.030

0.040

Inte

nsity

-5.0x107

0.0

5.0x107

1.0x108

1.5x108

2.0x108

2.5x108

Minutes

4.00 5.00


Is my peak pure….?

“My peak looked pure,

but the core MS lab

found otherwise”

Apex

Trailing

Check peak purity using both mass

and PDA data in Empower®

Leading


ACQUITY QDa Detector application notes....


– Direct Analysis in Real Time

o DART is a desorption APCI ionisation

technique where a heated ionised gas is

directed at a target between the DART

interface and the QDa

o Ionises molecules from the surface of a

solid (e.g. tablet, food stuff, powder) or a

liquid (e.g. beverage)

o If the molecule can be ionized by ESI or

APCI it will work using DART

o Produces simple mass spectra as no

adducts are formed

DART/QDa

2005 Editors’ Gold Award for Best Product

Compatible with MassLynx software


Sample introduction options for QDa/DART interface....

Direct manual analysis Direct analysis of solid or liquid samples

DART-OS Sample applied to OpenSpot card which is aligned in the DART-OS source for analysis


Automated sample introduction on DART/QDa...

DART-SVP Allows analysis of multiple samples using single axis automation

Sample holding options for DART-SVP • Multiple tablet holder • TLC plate holder • Tweezer module • Adapter for solid phase micro extraction (SPME) tips • Adapter for up to 12 DIP-it tips


4 species of cinnamon

– Ceylon or true cinnamon

– Indonesian cinnamon

– Saigon cinnamon

– Chinese cinnamon

Ceylon is the only species that does not

contact high concentration of coumarin

Coumarin is linked to liver damage

True cinnamon is more expensive and other

cinnamons are commonly used as

alternatives

Labelling often does not disclose species of

cinnamon

Example DART/QDa Applications: Analysis of Cinnamons for Adulteration


Direct analysis of Cinnamon Sticks…

“True Cinnamon”

Indonesian cinnamon


Direct analysis of Cinnamon Sticks…

“True Cinnamon”

Indonesian cinnamon

147 Coumarin

133 Cinnamaldehyde

133 Cinnamaldehyde

147 Coumarin


Analysis of ground cinnamons using DART-SVP/QDa…

Cinnamaldehyde 133 m/z

Coumarin 147 m/z

Methyl Cinnamate 163 m/z


Analysis of ground cinnamons using DART-SVP/QDa…

True cinnamon

Indonesian cinnamon

Saigon cinnamon

Cinnamaldehyde 133 m/z

Coumarin 147 m/z

Methyl Cinnamate 163 m/z


Cosmetics formulations are complex:

– Creams

– Lotions

– Powders

Each formulation has a wide chemical diversity:

– Functional polymers

– Detergents

– Fungicides

– Colourants

– Fragrance

– Conditioning agents

Important to screen for presence of:

– Impurities

– Allergens

– Pesticides

Ensuring Product Performance and Characterisation

Five commercial sources of Goldenseal acquired for characterization


Separation of five different

sources of Goldenseal

2 main component peaks (A and

B) were identified as hydrastine

and berberine, respectively

– 5 other compounds also identified

Characterizing Goldenseal using ACQUITY QDa Detection

Zoomed in UV chromatograms


No two samples show exactly the

same compounds at the same

concentrations :

– Easily fingerprint each sample

– Compare formulations from

different manufacturers as well as

different sources of plant

Rapid separation of complex

sample enabled by high efficiency

CORTECS columns

Combining UV with mass data

gives a full characterization of

each sample with minimal effort

Characterizing Goldenseal using ACQUITY QDa Detection

Identification of UV peaks in the liquid sample by m/z value

A

B


Accessible MS-directed purification....

PURIFICATION

Analytical screening User defines criteria to determine whether purification is needed

AUTOMATED PURIFICATION USING AUTOPURIFY



PURIFICATION

Preparative Isolation MS-directed purification collects target analyte only



PURIFICATION

Analytical Purity Confirmation Fraction tested to confirm higher purity


Simple, accurate purification....

2.00 4.00 6.00

m/z250 500

%

0

100145.2

m/z250 500

%

0

100242.3

m/z250 500

%

0

100

m/z250 500

%

0

100279.4


Simple, accurate purification....

2.00 4.00 6.00


Benefits of Mass Detection for the Cosmetics Industry

Method development

– Aim: One peak = one compound

o Detect coelutions and peaks missed by optical detection

o Track peaks more effectively

Sample profiling

– Aim: Identify components and quantify

o Process complex matrices and low level target compounds

o Improved selectivity, more sensitivity

Synthetic chemistry

– Aim: Confirm product identity

o Improve turnaround of results

o Improve information available on impurities

Purification

– Aim: Isolate pure compound

o Collect fewer fractions with increased confidence


Any Questions?

Mass Detection for the Cosmetics Industry

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