J. Flow Injection Anal., Vol.9, No.2 (1992)

Flow Chemiluminescence Sensing

in Microheterogeneous systems as Reaction Media

Junjiro Hayashi, Masaaki Yarnada

Faculty of Technology, Tokyo Metropolitan University, Hachioji,

Minami-ohsawa, Tokyo 192-03

Fig. 2-1 A first order cherniluminescent reaction. It=<I>c~ki[A]oexp(-kit), Iatx=$c~k~[A]o

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Table 4-1 Summary of CL analyses using microheterogeneous systems as reaction media

Reaction Medium CL reaction Anal yte Detection ref, limit

-

[Normal micelles] CTAB Luminol/oxidase

SDS Luminol/Fe2+ TDBAC FMNIH202 CTAOH Lucigeninl

catecholamines CTAB Lurninol/(H202)

glucose oxidse CTAB 6 -nitrostirenel

NaOH/fluorescein [Reversed micelles]

CTAC Luminoll (CHCt3h-octane) glucose oxidae

CTAC Luminol/H~Oz (CHClsICoHii)

CTAC Luminol/iodine (CHCldC6H 12)

CTAC Luminoll ( C H C ~ ~ / C ~ H I ~ ) chloroauric acid SDS ,CTAB,Brij 96, CPPO/H2Q2 Triton x-100 (B uOH */toluene) (peroxyoxalate CL)

AOT Schiff base/ (heptane) Fenton' s reagent

[vesicle] DODAC Mn2+/adrenaline DODAC Co2*/

phenylpyruvic acid DDAB eosin Y/NaOH DDAB TCNQIOH-Ieosin Y DODAC(CH3CN) TCNQIOH-/

rhodamine B DDAB uranine

[CDI 6 -CD AB MI(isolumino1)

u , I S , Y -CD LucigenineM202 8 -CD Lucigenine/I-LOZ

[Polymer] BSA,PEI AB MI(isolumino1) hemin1VP H202/buffer(pH7) ion exchange resin Mn2+'adrenarine

glucose, 5.4x104M 10 L-amino acids 4x1O"M lipid hydroperoxides - 11 C ? + , C P 5x108M 12 catecholamines 1 -SOX 1 O-8M 13

Hz02 2 . 4 ~ l O . ~ M 14 glucose 3~10% cu2+ I X ~ O - ~ M 15

glucose, 16 oxidase activity Hz02 6.4x107M 17

iodine 50pg/ml 18

gold lopglml 19

primary amines, 1 . 5 ~ lO^M 2 1 amino acids 1 . 4 ~ 1 0 . ~ M

adrenaline 1x10-'M 22 phenylpyruvic acid 23

I x i 0 - 7 ~ H+ 2x106M 24 Mn2+ 1x10-'M 25 S2- 5x10-'M 26

CN- ~ x ~ o - ~ M 27

31 32

adrenaline 3~10--M 33

Fig.4-l?L-%?J: 5 L <L%%%&BIÂ¥LH?SE(S%%( p H . *@ ~ T ' ~ ~ % f e W l O - l l ~ ~ C T L T , C T A B 3 ; I 4 Â ¤ % W 7 . 7 5

dp^WC97 }à LTVao pH7.25K;^j-5 C T A B < ±7VWT<r> ~ j  £ g \ & ] / ; ¤SO <^74%& < f~^-W6~ $k8 Fig.4-2fcSt-j; 5 K $

pHIL-&'5CL^W^ffcL, P H ) C T < ~ ^ K E V ~ ~ W B < & ~ Z ~ ~ ~ ~ ~ S

Fig.4-1 Effect of pH on the luminescence intensity: (a) in micellar CTAB solution;

(b) in aqueous buffer solution.

Fig.4-2 Dependence of the decay of the luminescence signal on pH: (a) phosphate

buffer (pH8.1); (b) borax buffer (pH9.05); (c) borax buffer (pH9.9); (d) borax buffer (pH 10.9).

Fig. 4-3

0 60 120 180 Time ( s e c )

Second-order kinetic plots of the oxidation of Fe2" by peroxides in SDS rnicelles Ao, At, Bo,and Bi represent the concentrations of peroxides and FeS04, respectively, at times zero and t.

Fig.4-4 Diagram of localization of chemilumines~ence reactants, CLA, Linoleic acid

hydroperoxide and ~ e ~ * , in the surface region of SDS rnicelles.

Fig.4-5 Dependence of the CL intensity upon the R value (i.e., [H20]/[CTAC]).

Conditions were [luminol]= l.96xlo5M, [ ~ 2 0 2 ] = 6 . 4 0 ~ 1 0 ~ ~ , pHw9.00 (0.10M borate), delay time 5 s, and run time 30 s (for integrated signal).

* 0 0

ABMI 0 Intermediate Emitter 0

Scheme of AB MI CL reaction.

Fig.4-6 Relationship between the cherniluminescence intensity (IcL), the fluorescence

intensity (IFL) and p -CD concentration. A : a -CD, D : y -CD

Fig.4-7 Relationship between the' product ifi es N, ifi fi and -CD concentration, A : a -CD, : y -CD

CO-UH Luminol Isoluminol

CO-NH

A B I derivative

compound xi---- A B M I A B E I A B P I A B B I

Fig. 4-8 Chemical structures of luminol and its analogs

- 152 -

BSAsystem

PE I system

0 I I I

1 2 3 0 4 -

WSP Concentration/wt%

Fig. 4-9 Effects of BSA and P H on the initial Chemiluminescence intensity -5 - [Lumi1~01]=8xlO M m 0. l M NaCCB. [H202]=0.1M, [K2~208]=2. ~ x ~ o - ~ M , (BSA]=O. lwt%.

[PEI]=0. l wt%

Table4-2 Effect of BSA on Oni and on CL intensity(1). <I>D.ns~-&n, and <I>~.BsA, and initial I ratio compound" + n . n ~ ~ - f r e t ~ B S A ' " IBSA/~BSA-~~~~ 0

Luminol 0.16 0.17 66.7 Isolumiriol 0.034 0.030 40.3 ABI 0.040 0.050 5.3 ABM1 0.053 0.045 10.3 ABEI 0.044 0.043 9.7 ABPI 0.038 0.043 4.5 ABBI 0.039 0.040 5.5

a) [Compo~~n<^]= 1.6X 10-s~iiol ilin-3 in 0.1 inol i l ~ n - ~ Ni12C03. b) [BSA]=0.10 \vt%. c) I in t h e prcscnce of BSA [o I in the absence of BSAiit 10safter the i n i t i i i l i o n of [lie reaction.

4 v/l^ / -11 7 5 / ~ % ^ ; ~ s ~ A ~ 6 2 < ffi L 2 1 ?). B S A=- : B S AMi^w ~ S % S C * / c

(Ol 5 7 -/me% 0fi5 C~E~L(chemical l~ induced electron exchange

luminescence) #4#;Wff1 k$t -5 f r A 2 f%t% L-TV*.

Fig.4-10 Diagram of the cyclic flow-injection system with chemiluminescence detection

Fig. 4-1 1 Effect of age of reagent solution on the relative signal for copper. [NaOH] : ( 0 ) l x 1 0 " ~ . (@)lxl~^M, (x)~x~o"M. Other conditions as in Fig. 4-10

Table4-3 Effect of cationic micelles on the signal for Cr(V1) and Cu(I1) in the FMN chemilu~escence systems

Surfactant Concentration Relative signal * Signal ratio * Relative (lo-' M) Cr(V1) ' Cu(I1) e Cr(VI)/Cu(II) fluorescence

intensity of FMN

None 100 (110) 2500 (1900) 0.04 (0.06) 1.3 TTAB 5.0 (0.35) 51 90 0.6 - 0.36 (1.2) ' TDBAC 0.4 (0.037) 130 (85) 110 (70) 13. (1.2) 0.70 HTAB 2.0 (0.09) 56 71 0.8 0.44 (0.94) ' HEDAB 2.0 43 86 0.5 0.43 HPC 0.9 (0.09) 47 54 0.9 0.81 (0.53)

* Flow system and conditions as in previous work [9]. T A B = tetradecyltrimethylamrnonium bromide; TDBAC - tetradecyldimethylbenzylamonium chloride; HTAB = hexadecyltriinethylanunonium bromide; HEDAB hexadecylethyldimethyl- ammonium bromide; HPC = hexadecylpyridinium chloride. Values in parentheses are critical rnicelle concentrations. * Values in parentheses are in the absence of phosphate buffer. ' 20-pl injection of lo-' M solution. ' For chloride counter ion. ' For bromide counter ion.

Fig. 4-12 Schematic flow diagram of the flavin mononucleotide chemiluminescence system

Fig. 4-13 Schematic diagram of the flow system for hydrogen ion determination

Table 4-4 Effect of Surfactants on the CL intensities of hydrogen ion

Surfactant Re'ative molar CL

(3X 103 '1 ) intensity, YO

~ None 0

Relative Surfactant molar ,-,, ( 3 X lo-' M, intensity, YO

Cationic DDAB=) 100 M T A B ~ ) 13 STAG" 13 CTAB^ 7

a) didodecyldimethylammoniun~ bromide (bilayer vesicle); b) tetradecyltrimethylammonium bromide (micelle); c) octadecylammonium chloride (micelle); d ) hexadecyl- trimethylammonium bromide (micelle); e) hexadecyl- trimethylammonium chloride (micelle); f ) hexadecylethyl- dimethylammonium bromide (micelle); g) sodium dodecylsulfate, h) 0. 1% solution. Condition : as in Fig. I except for concentration of surfactant.

Anionic S D S ~ ) 0

Non-ionic Brij-35 20 Tween Soh' 0

medium

water methanol acetonitrile acetone dodecyltrimethylammonium bromide (DTAB) didodecyldimethylammonium bromide (DDDAB) tetradecyltrimethylarnmonium bromide (TTAB) tetradecyldimethylbenzylammonium chloride (TDBAC) hexadecyltrimethylammonium chloride (HTAC) hesadecylpyridinium chloride (HPC) hexadecylethyldimethylammonium bromide (HEDAB) octadecyltrimethylammonium chloride (OTAC) dioctadecyldimethylammonium chloride (DODAC) sodium dodecyl sulfate (SDS) polyoxyethylene(23)dodecanol (Brij 35)

"Mixing order: 1 x lO-'-M PPA+ 1x lO-'M NaOH+meclium+ lx W M Co(I1). IlO-'M (values in parentheses show critical micelle concentration). 'Normalized with respect to the signal (=I. 0) when the reaction medium is acetonitrile. 'Not detected.

Table4-6 Effects of DODAC bilayer membranous aggregates and Co(I1) catalyst on the present CL reaction

CL parameter CL systemb k.8-I aCLC IBc

PPA + H20 + t-BuO-/DMSO<* 1 1 1 PPA + Co(I1) + t-BuO-/DMSO 0.02 70 1.4 PPA + Co(1I) + OH-/DODAC 0.03 840 25 PPA + Co(I1) + OH-/OTAC 0.03 210 6.3

Â¥Base on batch experiments. CL decay curve: I, = h k - [PPAIo exp(+t), 1- = *cik[PPA]e ^MSO was used as the homogeneous medium because of no light emission in aqueous medium. Each of the reagent solutions M PPA, lo4 M Co- (a), M alkali, M surfactant) was mixed in that order, as PPA emitted light without Co(I1) in the t-BuO'/DMSO medium. 'Normalized with respect to the value (=I) for the CL system, PPA + H20 + t-BuO"/DMSO. dPotassium tert-butoxide/di- methyl sulfoxide.

^ $ - f e l l ^

( 5 ) 3t>9^)%Ek[181 9#<r>Zg&k LT/I^ /-/PC L&As%E&;h/W60 L+

Lm:?,, T K @ B % W p H M R K b T 3 $'$#@12, IOH, 1, 13-%$c^??k % Her^ V ft@Â¥%~TTRfB 3 9%Vs.&MEt^E(D^a^TA~fe-50 4?

.T. 3 9% (12) ^^^4^%aL^<^&^'W^ 7 -/^OC L^

- ' Reversed micellar luminol reagent

Cyclohexane: PI @ , 100 u1 Detector

Waste

Fig.4-14 Flow diagram for the determinationof iodine with CL detection

W O v a l u e

Fig. 4-15 Rate constants, k2 and k-2, as a function of Wo

Table4-7 Effects of Schiff base formation media

Amino Concentration Relative CL intensity compound (MI ' Methanol Normal micelle Reverse micelle:

(lo-' M) (lo-' M) (lo-' M) (ID + M)

n-Hexylamine 1.00 x 100.0 n.d. ' 0.9 n.d. 3.2 Isopropylamine 9.95 X lo-' 138.2 n.d. n.d. 6.0 1.8 Alanine 1.03 X lom4 n.d. n.d. n.d. 0.9 11.4 Phenylalanine 1.01 x n.d. n.d. 0.9 36.9 137.3

a Each Schiff base was prepared by incubating each amino compound and 0.01 M PAA for 60 min at 60°C Intensities compared with that of n-hexylamine in methanol (¥ 100). ' Based on final concentration of amino compounds accounting for all dilutions. " Polyoxyeihylene (23) lauryl ether. ' Sodium dodecyl sulphate. ' Hexadecyltrimethylammonium chloride. ' [HiO]/IAOT] ratio (wo) - 5.6. N o detectable intensity.

Fig.4-16 Schematic digam of flow ysytem - RI: H20. R2: H20 or 1M NaOH, P: peristaltic pump, S: sample injector(20pl) C: Pyrex tube (5x26 rnm) packed with ion-exchange resin, PMT: photomultiplier tube

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