TP CH PHT TRIN KH&CN, TP 12, S 03 - 2009

KHO ST S TO MIXEL CA MT S COPOLYME PLURONIC

Nguyn Quc Hng(1), Sren Hvidt(2), Walther Batsberg(3), Hong Ngc Cng(1) (1)Trng i hc Khoa Hc T Nhin, HQG-HCM (2)i hc Roskilde, an Mch (3)Trung tm th nghim Quc gia Ris, an Mch
(Bi nhn ngy 17 thng 12 nm 2007, c chp nhn ngy 11 thng 04 nm 2008)

TM TT: Qu trnh to mixel ca Pluronic L81 v L121 (copolyme tam khi PEO PPOPEO i xng) c kho st bng phng php phn tch nhit vi sai (DSC). T l thnh phn ca cc mt xch polypropylen oxit (PPO) v polyetylen oxit (PEO) trong copolyme c xc nh bng phng php ph cng hng t ht nhn (1H-NMR). T kt qu cc th nghim DSC ca cc copolyme L81 v L121 cho thy xut hin mi vai (shoulder) pha nhit thp trn ng cong nhit dung theo nhit . Bn cht cc mi vai trong ng cong DSC l do cc thnh phn k nc nht trong copolyme, nn to mixel nhit thp hn. Cu t k nc ny c th c tch bng cch chit vi hexan. Cc copolyme c PTL thp c tch bng sc k lng hiu nng cao (HPLC) v chng khng tham gia vo qu trnh to mixel ca copolyme. 1. M U Copolyme tam khi i xng c cu to t polyetylen oxit (PEO) v polypropylen oxit (PPO), thng c vit tt PEO-PPO-PEO hay (EO)x(PO)y(EO)x l nhng cht hot ng b mt (HBM) cao phn t khng ion thng mi c sn trn th trng. Tn thng mi ca cc cht HBM ny l Poloxamer (cng ty ICI) hay Pluronic (cng ty BASF) [1]. Bng vic thay i thnh phn copolyme (t l PO/EO) v phn t lng (chiu di khi PEO v PPO) trong qu trnh tng hp dn n vic to ra cc phn t c tnh cht ph hp vi cc yu cu khc nhau trong nhiu lnh vc p dng trong cng nghip nh ty ra, to bt bn, nh ho, du bi trn, m phm, mc v mt s ng dng c bit nh trong dc phm, cha vt thng Bn cht lng i (amphiphilic) ca copolyme tam khi trong dung dch nc l chng c kh nng t kt hp li to thnh mt trng thi vi cu trc ging nh mixel c to thnh bi cc cht HBM phn t lng thp, ph thuc vo nng , thnh phn copolyme v nhit [2]. nhit thp hoc (v) nng thp copolyme Pluronic khi c ho tan trong nc l nhng mch polyme ring l (unime). Khi nhit hoc (v) nng tng, do s khc bit v tng tc ca khi PPO v PEO vi nc, cc on PPO k nc c xu hng tin li gn nhau v to thnh mixel bn nhit ng [3]. Trong m hnh kt hp n gin, s to mixel ca copolyme Pluronic l mt qu trnh cn bng ng gia cc unime v mixel:

nUnime

Mixel n (1)

trong n l s unime trn 1 mixel. Chuyn pha unime-mixel khng xy ra tc thi nhng tri rng trong vng nng cch nhau 1 gi tr thp phn hay 10K. Nng mixel ti hn (CMC) v nhit mixel ti hn (CMT) l nhng thng s c bn nht ca qu trnh to mixel. CMC l nng ti mixel (tp hp cc mch bn nhit ng hc) bt u to thnh. CMT l nhit ti mixel to thnh ti mt nng cho trc. Gi tr CMC v CMT gim khi tng t l PPO trong copolyme hoc khi tng phn t lng.

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Science & Technology Development, Vol 12, No.03 - 2009 DSC l mt k thut quan trng kho st s to mixel ca copolyme khi, nghin cu nhit chuyn pha ca copolyme tam khi trong dung dch nc. Hvidt kho st qu trnh to mixel ca mt s copolyme Pluronic trong dung dch nc bng DSC [4]. T ng cong biu din nhit dung theo nhit ca dung dch copolyme P84 v F88, thy xut hin cc mi chuyn pha thu nhit. S chuyn pha c cho l s to thnh cc mixel cu. Gi tr Hm (entalpy ca s to mixel), Tm (nhit chuyn pha) v Ton (nhit bt u s mixel ho) c th c tnh ton t cc ng cong nhit. Kt qu cho thy c s ph hp rt tt gia nhit bt u thu nhit v CMT xc nh t cc phng php o khc [1]. Entalpy chun cho s to mixel c gi tr dng nn bt li v mt nhit ng. Trong khi s to thnh mixel bn nhit ng phi c nng lng t do G m. Nh vy ch cn yu t entropy phi dng v y l ng lc chnh cho s to thnh mixel. S hin din ca cc phn t hydrocacbon trong nc lm gim ng k entropy ca nc. Khi phn hydrocacbon tp hp li trong pha nc to thnh mixel, cu trc lin kt hydro trong pha nc c ti lp v entropy ca nc tng vt qu gim entropy do cc mch hydrocacbon nh v trong mixel. Mitchard v cng s cng nghin cu s chuyn pha ca mt s pluronic bng phn tch nhit vi sai nhy cao (HSDSC) [4]. Kt qu cho thy cc thng s nhit ng ca qu trnh chuyn pha xc nh t DSC u ph thuc vo hm lng PPO ca polyme v khng ph thuc vo hm lng PEO hay phn t lng ca copolyme. 2.PHN THC NGHIM 2.1.Ho cht Pluronic L81 v L121 l nhng copolyme thng mi t cng ty BASF c phn t lng trung bnh tng ng l 2790 v 4678 g/mol. Trong mi tn thng mi ca copolyme pluronic, ch s cui cng nhn vi 10 l phn trm etylen oxit (PEO) trong copolyme. Ch s cn li c m ho cho phn t lng ca khi PPO v chng cng ln th khi lng PPO trong copolyme cng cao. Cng thc v phn t lng ca cc copolyme ny theo nh sn xut c tm tt trong Bng 1. Bng 1.Phn t lng v thnh phn ca cc Pluronic c kho st Polyme L81 L121 Phn t lng trung bnh (g/mol) 2790 4678 (EO)x(PO)y(EO)x (EO)6(PO)39(EO)6 (EO)9(PO)67(EO)9

2.1.Cc phng php thc nghim 2.1.1.Phn tch nhit vi sai Phng php phn tch nhit vi sai c thc hin bng my phn tch vi nhit SCAL-1 vi th tch ng ng mu l 0,34 mL. Mu o l dung dch copolyme c pha trong nc nng 2 mg/mL. Thit b c gia nhit tc 0,25/pht t 5 n 80C. Ch s dng cch gia nhit nghin cu qu trnh to mixel. S liu c x l bng chng trnh ORIGIN ca cng ty MicroCal (Northampton, MA). Gi tr nhit chuyn pha to mixel c lp li trong khong 0,1C v sai s v gi tr entalpy vo khong 2%. 2.1.2.Phng php cng hng t ht nhn (NMR) Thnh phn tng i EO/PO ca tt c cc mu copolyme c xc nh bng ph NMR vi cht chun TMS. Mu polyme c ho tan trong CDCl3 vi nng 2% khi lng. Ph

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proton c o trn my Bruker 250 MHz. Thnh phn tng i ca EO v PO trong copolyme c xc nh t din tch di nhng mi cng hng 1H (CH3 1,1 ppm, CH2 v CH 3,4-3,7 ppm) [5]. 2.1.3.Sc k lng hiu nng cao Sc k tng tc c s dng loi b nhng polyme phn t lng thp ca L81 v L121. Trong phng php ny, s dng ct sc k Nucleosil 500 CN (25 cm 10 mm). Tc bm 4 mL/min nhit phng. Th tch bm 1 mL. Pha ng (% khi lng) L81 L121 45% MeOH + 55% H2O 50% MeOH + 50% H2O Nng 50 mg/mL 100 mg/mL

2.1.4.Khi ph MALDI-TOF Phn t lng ca copolyme c phn tch bng khi ph MALDI-TOF (BRUKER). Cht nn l 2,5-dihydroxybenzoic acid (DHB). Hn hp gm etanol, mu cn o, DHB v NaCl c nh ln a cha mu v kh t nhin. 2.1.5.Phng php chit bng hexan Qu trnh chit bng hexan c thc hin nh sau: 25 g mi loi copolyme Pluronic c ho tan trong 150 mL n-hexan, sau dung dch c lc mnh trong 30 pht 40C v 20C qua m cho n khi dung dch c tch thnh 2 lp. Pha hexan c gn ra. Phn polyme khng ho tan trong hexan tip tc c chit 2 ln na vi mi ln 150 mL n-hexan. Gom li lng dung dch hexan sau 3 ln chit v loi hexan bng h thng c quay. Cui cng c polyme trong pha hexan (HE) v polyme kt ta (HP) c sy kh trong chn khng v em cn. Cc th nghim chit bng hexan 4C v 18C c thc hin tng t, ch khc l dung dch c lc mnh nhit phng trc khi nhit thp. 3.KT QU V BIN LUN S to mixel ca cc Pluronic L81 v L121 c kho st trong khong nhit t 0 n 80C bng phng php DSC. Cc ng cong trn Hnh 1 cho thy nhit dung ng p (Cp) theo nhit ca dung dch L81 v L121 trong nc. th cho thy tng ng vi mi loi polyme c mt mi chuyn pha thu nhit. Entalpy ca s to mixel (Hm) c tnh bng cch ly tch phn ca mi so vi ng nn. Cc gi tr ca Hm, Ton, Tm, v T1/2 (khong b rng nhit na cao chuyn pha) c trnh by trong Bng 2. Bng 2.Cc gi tr Hm, Ton, Tm, T1/2 ca L81 v L121 Polyme Hm (kJ/mol) Ton (C) Tm (C) T1/2 (C) L81 214 23,2 31,5 10,9 L121 539 14,8 19,1 4,8

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Science & Technology Development, Vol 12, No.03 - 2009

Hnh 1. ng cong DSC ca cc dung dch L81 v L121.

Gi tr Hm thu c c gi tr kh gn vi kt qu theo Alexandridis cng cng s [6] (253 kJ/mol cho khong nng 0,25 mg/mL n 49,6 mg/mL) v theo Bohorquez [7] (312 kJ/mol cho khong nng di 50 mg/mL, v 136 kJ/mol cho nng trn 50 mg/mL). Mu L121 c phn t lng gn nh gp i ca L81 nn Hm thu c cng gn nh gp i. Pluronic vi cc thnh phn khc nhau (t l PO/EO) cho cc tnh cht nhit khc nhau. Do polyme L121 c khi PPO di hn so vi polyme L81, cc gi tr Ton, Tm v T1/2 ca L121 thp hn L81 tng ng. iu ny kh ph hp v s to mixel ca copolyme tam khi ph thuc ch yu vo khi PPO, trong khi khi PEO ch ng vai tr th yu [6]. iu th v trn cc ng cong nhit l ch trn mi mi thu nhit ca tng loi copolyme c mt mi vai ti mt khong nhit nh hn nhit chuyn pha (Hnh 1). Nh vy c th d on mi vai ny tng ng vi s chuyn pha sm ca mt s cu t polyme, tc l c kh nng to mixel nhit thp hn. nghin cu tnh cht ny, phng php chit bng hexan c thc hin vi L81 v L121 20C. Hexan l mt dung mi khng phn cc nn d dng ho tan nhng thnh phn khng phn cc (tnh k nc nhiu). Vi Pluronic tam khi PEO-PPOPEO, polyme tr nn km phn cc nu chiu di khi PPO cng di v/hoc chiu di khi PEO cng ngn (t l PO/EO cng ln). Do mch PPO trong copolyme L121 di hn L81 nn s tan nhiu hn trong hexan (70,8% khi lng L121 tan trong hexan so vi 27,1% polyme L81). Phng php ph NMR c s dng xc nh t l PO/EO tng i ca copolyme (y/x). Vi x v y l cc gi tr trong cng thc tng qut (EO)x(PO)y(EO)x. Cc kt qu c trnh by trong Bng 3 cho thy vi polyme ho tan trong hexan c t l y/x ln v polyme kt ta trong hexan c t l y/x nh. Bng 3. T l PO/EO t ph 1H-NMR ca cc mu L81 v L121
Mu L81 S PO/EO (y/x) 5,06 4,36 12,94 7,21 5,29 9,16

L81

L81HP (72,9%) L81HE (27,1%) L121

L121

L121HP (29,2%) L121HE (70,8%)

Ghi ch: HP:kt ta trong hexan; HE: tan trong hexan

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3.1.nh hng ca t l PO/EO ln qu trnh to mixel Cc copolyme sau khi chit bng hexan c tip tc nghin cu bng DSC. Kt qu c trnh by trong Hnh 3 v Hnh 4. Trong cc ng cong DSC tng ng vi cc polyme ca L81 (Hnh 3), s hin din ca mi vai trong ng cong Cp theo nhit ca copolyme ban u khng cn sau khi chit bng hexan. Gi tr Tm gim khi t l PO/EO trong copolyme tng (L81HP<L81<L81HE). Bi v mi vai c nhn thy ti nhit thp hn nhit Tm ca L81, c th kt lun rng mi vai l do cc thnh phn trong L81HE to thnh, tc l thnh phn tan trong hexan hay cc thnh phn k nc nhiu trong copolyme. Kt qu trong Hnh 3 cho thy Tm ca dung dch L81HE rt gn vi nhit xut hin mi vai.

Hnh 3. ng cong DSC ca polyme L81 trc v sau chit bng hexan.

Hnh 4. ng cong DSC ca polyme L121 trc v sau chit bng hexan.

Tng t, trong cc gin nhit ca cc copolyme L121 (Hnh 4) sau khi chit bng hexan, khng thy xut hin mi vai trn ng cong nhit ca L121HP, trong khi phn L121HE li xut hin mt mi vai ln. Hn na, gi tr Cp ca mi vai ca L121HE c gi tr cao hn so vi L121 bi v trong L121HE nng cc thnh phn k nc to thnh mi vai cao hn khi cng nng kho st so vi L121. Cc kt qu trn cho thy phng php DSC rt nhy vi s thay i t l PO/EO trong copolyme. Do hiu r hn bn cht ca mi vai, phng php chit bng hexan c tip tc thc hin vi L121HE nhng nhit thp hn (4 v 18C). Cc kt qu c trnh by trong Hnh 5 v Hnh 6.

Hnh 5. ng cong DSC cc thnh phn ca L121HE sau khi chit bng hexan 4C.

Hnh 6. ng cong DSC cc thnh phn ca L121HE sau khi chit bng hexan 18C

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Science & Technology Development, Vol 12, No.03 - 2009 Tht vy, phng php chit bng hexan rt hiu qu loi b mi vai trong cc gin nhit ca dung dch polyme L81 v L121. Vi phn polyme kt ta ca L121HE trong hexan ti 4C, ng cong nhit khng xut hin mi vai, trong khi polyme tan trong hexan to ra mi vai ln hn ca polyme L121HE. Khi polyme L121HE c chit bng hexan 18C, ng cong ca polyme kt ta ca L121HE c quan st vi mt mi vai nh (Hnh 6), iu ny cho thy rng mt lng t thnh phn k nc c t l PO/EO ln ca L121HE c th kt ta trong hexan do nhit th nghim qu thp. Vi cc thnh phn ca polyme L121HE c kh nng ho tan trong hexan 18C, ng cong nhit trong Hnh 6 cho thy cc mi thu nhit chnh khng cn xut hin mi vai v cc gi tr Tm v Ton cng thp hn hn so vi cc polyme cn li. Hn na, gi tr Tm xp x nhit ti xut hin mi vai, cho thy thnh phn polyme tan trong hexan 18C l thnh phn ch yu to nn mi vai ca L121. Polyme tam khi c tng hp t homopolyme PPO a phn tn cho phn ng vi EO to thnh khi PEO cng a phn tn. Do hn hp copolyme thu c c t l EO/PO rt khc nhau. T l s mt xch EO/PO (x/y) t 1H NMR c trnh by trong Bng 4. Cc kt qu tnh ton cho thy phn polyme tan trong hexan c s mt xch PEO thp nht (t l x/y thp nht) v cc polyme kt ta trong hexan c s mt xch PEO cao nht (t l x/y cao nht). Nh vy, th nghim chit bng hexan tch cc thnh phn trong copolyme theo di mch PEO hn l theo mch PPO, tc l thnh phn no c mch PEO di hn th d kt ta trong hexan hn. Bng 4. T l x/y ca cc mu polyme
Mu L81HP L81 L81HE L121HP Kt ta ca L121HE 4C x/y 0,229 0,197 0,077 0,189 0,145 Mu L121 Kt ta ca L121HE 18C L121HE Phn tan trong hexan ca L121HE 4C Phn tan trong hexan ca L121HE 18C x/y 0,139 0,123 0,109 0,079 0,035

hiu r bn cht ca mi vai trong ng cong DSC, khi ph MALDI-TOF c s dng xc nh PTL ca L81HE v phn tan trong hexan ca L121HE 18C (Hnh 7). Hai mu ny c gi tr x (phn PEO) nh nht. Nh mu L81HE x/y = 0,077, tc l c 100 mt xch PPO mi c khong 7,7 mt xch PEO hoc trong L121HE 18C x/y = 0,035, tc l c 100 mt xch PPO mi c khong 3,5 mt xch PEO. Do s mt xch PEO thp nn c th b qua khi xc nh cng thc da trn MS. Cc mi ln trn MS u cch nhau 58 n v tng ng 1 mt xch PPO, do c th xem nh y l cc tn hiu ca PPO. PTL ca PPO c tnh M = m/z 23 6. Vi 23 l s khi ca Na, 6 l lch v s khi ca thit b o so vi mu chun. Cc kt qu c trnh by trong Bng 5.

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Hnh 7. Khi ph MALDI-TOF ca L81HE v phn tan t hexan ca L121HE 18C

Bng 5. Cng thc d on cho mt s mi c trng trong khi ph MALDI-TOF m/z (L81HE) 2076,52 2134,68 2192,77 2250,93 2309,01 2367,08 Cng thc d on H(PO)35OH H(PO)36OH H(PO)37OH H(PO)38OH H(PO)39OH H(PO)40OH m/z (phn tan L121HE 18C) 4281,53 4339,62 4397,65 4455,76 4513,77 4571,77 Cng thc d on H(PO)73OH H(PO)74OH H(PO)75OH H(PO)76OH H(PO)77OH H(PO)78OH

Kt qu cho thy mt s mi c trng ca cc polyme to thnh mi vai trong gin DSC (L81HE v phn tan t L121HE 18C) ch yu l cc homopolyme PO. y c th l phn PPO khng cho phn ng vi etylen oxit trong qu trnh iu ch copolyme khi. Cng thc ca L81HE tng i ph hp vi cng thc do nh sn xut a ra y = 39. Tuy nhin vi mu L121HE 18C cng thc c trng hp ln hn nhiu so vi ca nh sn xut y = 67. C th gii thch l khi phn t lng PPO cng tng kh nng phn ng vi EO cng gim nn cn li trong hn hp sn phm. Do , c th cho rng cc polyme to thnh mi vai c s mt xch PEO rt thp hoc thm ch khng c mt xch PEO. Cc kt qu ny cng ph hp vi cc nghin cu trc y. Nixon v cng s nghin cu s to mixen ca P94 bng DSC ti cc nng khc nhau v ch cho mt mi n trong gin [8]. Cc copolyme thuc nhm 80 cng c kho st bng DSC, trong cc Pluronic P84, P85, F87 v F88 vi chiu di mch PEO di cng ch cho mi n trong gin nhit nhng ch c L81 xut hin mi vai [3]. Do , c th kt lun rng s xut hin mi vai trong ng cong nhit ca cc copolyme Pluronic ch xy ra vi copolyme c chiu di mch PEO ngn. 3.2.nh hng ca phn PTL nh Qua phn tch sc k lng cho thy cc mu copolyme Pluronic u cha cc phn t copolyme c phn t lng thp hn so vi copolyme chnh. Cc phn t nh ca L81 v L121 c tch bng phng php sc k tng tc HPLC (Hnh 8).

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Hnh 8. Sc k ca qu trnh tch dung dch copolyme bng sc k tng tc.

Cc copolyme sau khi tinh ch c tip tc nghin cu bng DSC, kt qu c trnh by trong Hnh 9.

Hnh 9. nh hng ca polyme PTL thp ln s to mixel ca L81 v L121.

Kt qu cho thy khng c s khc bit ln v nhit chuyn pha vi tt c cc dung dch copolyme trc v sau khi loi b phn PTL nh. Cc gi tr entalpy ca cc copolyme chnh cao hn cc copolyme cha tinh ch vi cng mt loi copolyme cng mt nng kho st. V gi tr entalpy ph thuc vo nng nn c th kt lun rng nng cc copolyme to thnh mixel trong phn chnh ln hn trong copolyme ban u. Hay ni cch khc, cc phn PTL nh khng ng gp vo s to thnh mixel iu kin v nng v nhit kho st. Kt qu ny cng ph hp vi nghin cu trc y ca nhm tc gi khi nghin cu nh hng ca phn PTL nh ln s to mixel ca Pluronic P85 [3].

4.KT LUN
Cc mi vai xut hin trong cc gin nhit DSC ca dung dch L81 v L121 v cc mi vai ny c th c loi b bng cch chit vi hexan. K thut DSC rt nhy vi s thay i t l PO/EO, cho thy s thay i nhit dung ca mi vai t cc iu kin khc nhau ca th nghim. Th nghim chit bng hexan tch copolyme ch yu theo chiu di mch PEO hn l mch PPO. Thnh phn mch PEO cng di cng d kt ta trong hexan. Bn cht ca cc mi vai l nhng thnh phn c tnh k nc cao nht trong tng loi copolyme, vi s mt xch EO nh nht hoc khng c. Cc polyme PTL thp c th c tch bng sc k tng tc v chng khng ng gp vo qu trnh to mixel.

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THE MICELLIZATION OF PLURONICS (PEO-PPO-PEO TRIBLOCK COPOLYMERS)

Nguyen Quoc Hung(1), Sren Hvidt(2), Walther Batsberg(3), Hoang Ngoc Cuong(1) (1) University of Natural Sciences, VNU-HCM (2) Roskilde University, Denmark, (3) National Lab Ris, Denmark. ABSTRACT:The micellization of several Pluronics (PEO-PPO-PEO triblock copolymers) was investigated by Differential Scanning Calorimetry (DSC). These copolymers were also characterized and purified by liquid chromatography. The PEO/PPO compositions of Pluronics were determined by 1H-NMR. The thermograms from DSC showed a premicellization shoulder for L81 and L121 solutions. The effects of temperature, PO/EO ratios and impurities on the micellization of copolymers were investigated. The origin of the shoulders in DSC thermograms was shown to be due to the most hydrophobic components in the copolymers, which could be removed by hexane extraction. Low molecular weight fractions of the copolymers were separated by interaction chromatography. The low molecular weight fractions did not contribute to the micellization of the copolymers. Keywords: Pluronics, PEO-PPO-PEO triblock copolymers, micellization, hydrophobic components, DSC, NMR, HPLC. TI LIU THAM KHO [1]. P. Alexandridis, T. A. Hatton, Poly(ethylene oxide)-poly(propylene oxide)poly(ethylene oxide) block copolymer surfactants in aqueous solutions and at interfaces: thermodynamics, structure, dynamics, and modeling, Colloids and Surfaces A: Physicochemical and Engineering Aspects, 96, 1-46 (1995). [2]. M. Almgren, W. Brown, S. Hvidt, Self-aggregation and phase behavior of poly(ethylene oxide )-poly(propylene oxide)-poly(ethylene oxide) block copolymers in aqueous solution, Colloid Polym. Sci, 273, 215 (1995). [3]. W. Batsberg, S. Ndoni, C. Trandum, S. Hvidt, Effects of Poloxamer Inhomogeneities on Micellization in Water, Macromolecules, 37, 29652971 (2004). [4]. N. M. Mitchard, A. E. Beezer, J. C. Mitchell, J. K. Armstrong, B. Z. Chowdhry, S. Leharne, G. Bucktod. Thermodynamic analysis of scanning calorimetric transitions observed for dilute aqueous solutions of ABA block copolymers, J. Phys. Chem, 96, 95079512 (1992). [5]. S. Hvidt, S., E. B.Jrgensen, K.Schilln, W.Brown, Micellization and Gelation of Aqueous Solutions of a Triblock Copolymer Studied by Rheological Techniques and Scanning Calorimetry, J. Phys. Chem, 98, 1232012328 (1994) [6]. Alexandridis, P., Holzwarth J., Hatton T., Micellization of Poly(ethylene oxide)Poly(propylene oxide)-Poly(ethylene oxide) Triblock Copolymers in Aqueous Solutions: Thermodynamics of Copolymer Association, Macromolecules 27, 2414 (1994).

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Science & Technology Development, Vol 12, No.03 - 2009 [7]. Bohorquez M., Koch C., Trygstad T., Pandit N., A Study of the TemperatureDependent Micellization of Pluronic F127, Journal of Colloid and Interface Science 216, 3440 (1999) [8]. Nixon S. K., Hvidt S., Booth C., Micellization of block copolymer P94 in aqueous solution, Journal of Colloid and Interface Science, 280, 219223 (2004)

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