Advances in Heterogemini Surfactants

Transcription

1 PROGRESS IN CHEMISTRY Vol. 17 No. 6 Nov., ( ) gemini,, gemini (,heterogemini surfactant) heterogeminis,,, 2, 2, heterogemini : O ; TQ423 : A : X(2005) Advances in Heterogemini Surfactants Zhao Jianxi 3 3 (Department of Applied Chemistry, College of Chemistry and Chemical Engineering, Fuzhou University, Fuzhou , China) Abstract Symmetrical gemini surfactants are made up of two identical amphiphilic moieties covalently connected at the level of the headgroups by a spacer chain. The gemini surfactants have been attracting increasing attention owing to their novel and complicated self2assembly behaviour. Up to now, however, only a few works have been focused on unsymmetrical gemini surfactants ( also called heterogeminis) because of the difficulty for synthesis. The initial investigations showed that the heterogeminis have more molecular structure factors that can be regulated and governed during the process of the molecular self2assembly than symmetrical geminis. Some novel results had been obtained, for example, enhanced driving force of enthalpy factor, constructed counterions2free systems by the heterogeminis containing cationic2anionic head groups and bound vesicles formed by heterogeminis making use of its different length of alkyl chains, etc. The advances in investigating heterogemini surfactants are reviewed and the potential significance in study of heterogeminis is pointed out. Key words heterogemini surfactants ; self2assembly ; regulation [3 ] 10,gemini, [1,2 ] [4,5 gemini ], gemini,, gemini : , : (No ) 3 3 e2mail : jxzhao. edu. cn Tsinghua Tongfang Optical Disc Co., Ltd. All rights reserved.

2 [6 ], geminis, heterogeminis,?? heterogeminis,gemini,,, gemini heterogeminis, Heterogeminis,,, gemini 1 heteroge2 gemini minis, heterogeminis (, heterogemini surfactant) Jaeger [7 ] Renouf [8 ],, heterogemini,, cmc cmc 1 heterogemini Table 1 The heterogemini surfactants synthesized so far Tsinghua Tongfang Optical Disc Co., Ltd. All rights reserved.

3 6 989,, ( G mic < 0) ( ), Π, 5 % ( ) Π [9,10 ] 011molΠL, ( ),, [17 ],, Zemb [18 ] C 13 H 27 COO H + C 16 H 33 N + (CH 3 ) 3 OH, H + ( H mic ) : OH Π van der Waals, ;, [11 geminis ] Π, [19,20, ], heterogeminis H mic, 1 1, [12 14 ] geminis H mic,,, 12 Peresypkin Menger [21 ] gemini, 308K H mic G mic (cryo2hrsem) C m 2P2N2C n ( 84 % [15 ] 1C) Bai [16 ] C m H 2 m + 1 (CH 3 ) 2 N (CH 2 ) 6 N(CH 3 ) 2 C n H 2 n + 1 (heterogeminis) C 8 2P2N2C 10 C 8 2P2N2C 14 (sponge2like) (coacervate) ( 2) ( ) H mic, mπn 1 3, H mic 3167kJΠmol 14118kJΠmol H mic G mic,,,,, ( ),, (tubules) ( 1), heterogeminis [21 ] 1 geminis, Fig. 1 Various morphologies of the aggregates : ( a) tubular H mic structures, (b) 20 30nm vesicles, (c) 20 50nm geminis vesicles, (d) giant vesicles [21 ] Tsinghua Tongfang Optical Disc Co., Ltd. All rights reserved.

4 [21 ] 2 C 8 2P2N2C 10 Fig. 2 Coacervate structure formed by C 8 2P2N2C 10 [21 ] [24 ], 4 42 C m 2P2N2C n, Fig. 4 Structural phase diagram of 42 series compounds (second aqueous layer) [22 ] [24 ], 3 of C m 2P2N2C n,, heterogeminis :, ; [24 [22 ] 3, ] 5 Fig. 3 Schematic representation of the coacervates formed by, self2assembly of amphiphilic molecules [22 ] C 8 2P2N2C 10 Menger [23 ], C m 2P2N2C n,, D E( 1,, ) 1wt % 5 wt % (gel) (coacervate), F ( E 1 ) 10wt %,, 4,,,, C 8 2P2N2C 10 C 10 2P2N2C 8,,, C 10 2P2N2C 8 Heterogeminis Menger [24 ] 42 C m 2P2N2C n [24 ] 5 C, 8 2P2N2C 10 ( ) C 10 2P2N2C 8 ( ) Fig. 5 Molecular models of C ( 4), 8 2P2N2C 10 (left) and C 10 2P2N2C 8 (right), [24 ] Tsinghua Tongfang Optical Disc Co., Ltd. All rights reserved.

5 6 991,,, ( lamellar ),, Menger Peresypkin [25 ] C m 2P2N2C n, m > n, cryo2hrsem, (pearls on a string) m = n,, 6 [25 ],Oda [26 ] _ CH 2 β 2, Fig. 6 Proposed mechanism of vesicles cohesion [25 ] heterogeminis, ( elongated aggregates), Menger Peresypkin,? heterogeminis Π,, C m 2P2N2C n,menger [27,28 ] (strings of micelles) Π A min (cohesive bilayers),, 2 heterogeminis [25 ] 6 [ 27,28] 2 C m 2P2N2C n Π max A min Table 2 The maximum adsorption amount max and the minimum molecular area A min of C m 2P2N2C n at airπwater interface surfactant systems C 10 H 21 PO 4 _ CH 2 β 2 N + (CH 3 ) 2 C 12 H 25 C 10 H 21 PO 4 _ CH 2 β 2 N + (CH 3 ) 2 C 12 H 25 + NaBr (1 1mol) C 10 H 21 PO 4 Na + C 12 H 25 N + (CH 3 ) 3 Br C 12 H 25 N + (CH 3 ) 3 Br ΠC 10 H 21 PO 4 Na + (1 1mol) C 8 H 17 PO 4 _ CH 2 β 2 2N + (CH 3 ) 2 C 14 H 29 C 8 H 17 PO 4 _ CH 2 β 2 2N + (CH 3 ) 2 C 14 H 29 + NaBr (1 1mol) C 14 H 29 PO 4 C 14 H 29 PO 4 C 14 H 29 PO 4 _ CH 2 β 2 2N + (CH 3 ) 2 C 8 H 17 + NaBr (1 1mol) _ CH 2 β 2 2N + (CH 3 ) 2 C 8 H 17 + NaBr (1 2mol) _ CH 2 β 2 2N + (CH 3 ) 2 C 8 H 17 + NaBr (1 4mol) max Πmol m 2 A min Πnm ,C 10 2P2N2C 12 ( C 10 6 molπl)? A min, 1 1, C 8 2P2N2C 14 C 14 2P2N2C 8, A min gemini heterogeminis, Π gemini,nmr gemini,, A min [27 ] Menger, Tsinghua Tongfang Optical Disc Co., Ltd. All rights reserved.

6 992 17, 14, heterogeminis Π A min (monolayer),, (bilayer), gemini,, (interdigitated bilayer),, heterogeminis, A min,,,, Heterogeminis Π heterogeminis Kumar [33 ] heterogeminis SDS, Π, Kumar heterogeminis 1 1 heterogeminis ( 1 D E F) SDS Alami [29 ] SO 4 SDS ( ) heterogeminis heterogeminis, heterogeminis, SDS, Π 1 1,heterogeminis, heterogeminis,,,, ( SO 4 NH + 3 ) heterogeminis Π Alami Holmberg [30 ] (align) phosphatidylcholines ( PCs,, heterogeminis [29,31 ] Heterogeminis ) heterogeminis gemini [4,5 ],,, gemini Eastoe [34 ] PCs heterogeminis Alami Holmberg [31 ], heterogeminis, [32 ], cmc A min, (122s214, s = ) Sikiric [32 ] XRD 122s214,, DSC Tsinghua Tongfang Optical Disc Co., Ltd. All rights reserved. heterogemini ( 1 C),

7 6 993, gemini,heterogeminis heterogeminis gemini,,,,, [ 1 ] Zana R. Advances in Colloid and Interface Science, 2002, 97 : [ 2 ] Menger F M, Keiper J S. Angew. Chem. Int. Ed., 2000, 39 : [ 3 ] Rosen M J. Chemtech, 1993, [ 4 ] De S, Aswal V K, Goyal P S, Bhattacharya S. J. Phys. Chem., 1996, 100 : [ 5 ] Zana R. J. Colloid Interface Sci., 2002, 248 : [ 6 ] Israelachvili J. Intermolecular & Surface Forces. San Diego : Academic Press, 1992 [ 7 ] Jaeger D A, Li B, Clark T. Langmuir, 1996, 12 : [ 8 ] Renouf P, Mioskowski C, Lebeau L, Hebrault D, Desmurs J R. Tetrahedron Letters, 1998, 39 : [ 9 ] Lee D J. Colloid Polym. Sci., 1995, 273 : [10] Tanford C. The Hydrophobic Effect : Formation of Micelles and Biological Membranes, 2nd ed. Krieger Publishing Company, [11] Diamant H, Andelman D. Langmuir, 1995, 11 : [12] Bai G Y, Wang YJ, Yan H K, Tnomas R K. J. Colloid Interface Sci., 2001, 240 : [13] Bai G Y, Wang J B, Yan H K, Li Z X, Thomas R K. J. Phys. Chem. B, 2001, 105 : [14] Bai G Y, Wang J B, Yan H K, Li Z X, Thomas R K. J. Phys. Chem. B, 2001, 105 : [15] Bai G Y, Yan H K, Thomas R K. Langmuir, 2001, 17 : [16] Bai G Y, Wang J B, Wang Y J, Yan H K, Thomas R K. J. Phys. Chem. B, 2002, 106 : [17] Soderman O, Herrington K L, Kaler E W, Miller D D. Langmuir, 1997, 13 : [18] Zemb T, Dubois M, Deme B, Gulik2Krzywicki T. Science, 1999, 283 : [19] Jung H T, Coldren B, Zasadzinski J A, Iampietro D J, Kaler E W. PNAS, 2001, 98 : [30] Jung H T, Lee S Y, Kaler E W, Coldren B, Zasadzinski J A. PNAS, 2002, 99 : [21] Peresypkin A V, Menger F M. Org. Lett., 1999, 1 : [22] Menger F M, Sykes B M. Langmuir, 1998, 14 : [23] Menger F M, Seredyuk V A, Apkarian R P, Wright E R. J. Am. Chem. Soc., 2002, 124 : [24] Menger F M, Peresypkin A V. J. Am. Chem. Soc., 2001, 123 : [25] Menger F M, Peresypkin A V. J. Am. Chem. Soc., 2003, 125 : [26] Oda R, Huc I, Homo J C, Heinrich B, Schmutz M, Candau S. Langmuir, 1999, 15 : [27] Seredyuk V, Alami E, Nyden M, Holmberg K, Peresypkin A V, Menger F M. Colloids Surfaces A, 2002, 203 : [28] Seredyuk V, Alami E, Nyden M, Holmberg K, Peresypkin A V, Menger F M. Langmuir, 2001, 17 : [29] Alami E, Holmberg K, Eastoe J. J. Colloid Interface Sci., 2002, 247 : [30] Alami E, Holmberg K. J. Colloid Interface Sci., 2001, 239 : [31] Alami E O, Holmberg K. Advances in Colloid Interface Sci., 2003, 100Π102 : [32] Sikiric M, Smit I, Tusek2Bozic L, Tomasic V, Pucic I, Primozic I, Filipovic2Vincekovic F. Langmuir, 2003, 19 : [33] Kumar A, Alami E, Holmberg K, Seredyuk V, Menger F M. Colloids Surfaces A, 2003, 228 : [34] Eastoe J, Dalton J S, Heenan R K. Langmuir, 1998, 14 : [35] Seredyuk V, Holmberg K. J. Colloid Interface Sci., 2001, 241 : [36] Alami E, Abrahmsen2Alami S, Eastoe J, Heenan R K. Langmuir, 2003, 19 : [37] Abrahmsen2Alami S, Alami E, Eastoe J, Cosgrove T. J. Colloid Interface Sci., 2002, 246 : [38] Alami E, Abrahmsen2Alami S, Eastoe J, Grillo I, Heenan R K. J. Colloid Interface Sci., 2002, 255 : [39] Pinazo A, Seguer J, Infante M R, Park S Y, Franses E I. Colloids Surfaces A, 1997, 126 : [40] Fischer P, Rehage H, Gruning B. J. Phys. Chem. B, 2002, 106 : [41] Gouzy M F, Guidetti B, Andre2Barres C, Rico2Lattes I, Lattes A, Vidal C. J. Colloid Interface Sci., 2001, 239 : Tsinghua Tongfang Optical Disc Co., Ltd. All rights reserved.