Abstract
The aqueous surfactant (Surf) solution at [Surf] > cmc (critical micelle concentration) contains flexible micelles/nanoparticles. These particles form a pseudophase of different shapes and sizes where the medium polarity decreases as the distance increases from the exterior region of the interface of the Surf/H2O particle towards its furthest interior region. Flexible nanoparticles (FNs) catalyse a variety of chemical and biochemical reactions. FN catalysis involves both positive catalysis (i.e. rate increase) and negative catalysis (i.e. rate decrease). This article describes the mechanistic details of these catalyses at the molecular level, which reveals the molecular origin of these catalyses. Effects of inert counterionic salts (MX) on the rates of bimolecular reactions (with one of the reactants as reactive counterion) in the presence of ionic FNs/micelles may result in either positive or negative catalysis. The kinetics of cationic FN (Surf/MX/H2O)-catalysed bimolecular reactions (with nonionic and anionic reactants) provide kinetic parameters which can be used to determine an ion exchange constant or the ratio of the binding constants of counterions.
Keywords
References
1.
Stang P.J.
(2012 ) J. Am. Chem. Soc. , 134 , 11829 –11830 .
2.
Menger F.M.
(1979 ) Acc. Chem. Res. , 12 , 111 –117 .
3.
Fendler J.H.
, and
Fendler E.J.
(1975 ) Catalysis in micellar and macromolecular systems. Academic Press , New York .
4.
Fendler J.H.
(1982 ) Membrane mimetic chemistry. Wiley-Interscience , New York .
5.
Khan M.N.
(2006 ) Micellar catalysis , Surfactant Science Series, Vol. 133 , Chap. 3. CRC Press, Taylor & Francis Group , Boca Raton, FL.
6.
Romsted L.S.
(2007 ) Langmuir , 23 , 414 –424 .
7.
Jungwirth P.
, and
Tobias D.J.
(2006 ) Chem. Rev. , 106 , 1259 –1281 .
8.
Parsons D.F.
,
Boström M.
,
Lo Nostro P.
, and
Ninham B.W.
(2011 ) Phys. Chem. Chem. Phys. , 13 , 12352 –12367 .
9.
Dunlap R.B.
, and
Cordes E.H.
(1968 ) J. Am. Chem. Soc. , 90 , 4395 –4404 .
10.
Romsted L.S.
, and
Cordes E.H.
(1968 ) J. Am. Chem. Soc. , 90 , 4404 –4409 .
11.
Romsted L.S.
(1984 ) In:
Mittal K.L.
, and
Lindman B.
(eds), Surfactants in solution , Vol. 2 , p. 1015 . Plenum , New York .
12.
Germani R.
,
Savelli G.
,
Romeo T.
,
Spreti N.
,
Cerichelli G.
, and
Bunton C.A.
(1993 ) Langmuir , 9 , 55 –60 .
13.
Khan M.N.
(2002 ) In:
Hubbard A.T.
(ed.), Encyclopedia of surface and colloid science , pp. 3178 –3191 . Marcel Dekker, Inc. , New York .
14.
Khan M.N.
(2010 ) Adv. Colloid Interface Sci. , 159 , 160 –179 .
15.
Davies D.M.
,
Gillitt N.D.
, and
Paradis P.M.
(1996 ) J. Chem. Soc., Perkin Trans. 2 , 659 –666 .
16.
Mishra A.
,
Behera R.K.
,
Behera P.K.
,
Mishra B.K.
, and
Behera G.B.
(2000 ) Chem. Rev. , 100 , 1973 –2011 .
17.
Khan M.N.
, and
Ismail E.
(2007 ) J. Mol. Liq. , 136 , 54 –63 .
18.
Laschewsky A.
(2003 ) Curr. Opin. Colloid Interface Sci. , 8 , 274 –281 .
19.
Sterpone F.
,
Pierleoni C.
,
Briganti G.
, and
Marchi M.
(2004 ) Langmuir , 20 , 4311 –4314 .
20.
Khan M.N.
, and
Ismail E.
(2004 ) J. Phys. Org. Chem. , 17 , 376 –386 .
21.
Cheong M.Y.
,
Ariffin A.
, and
Khan M.N.
(2007 ) J. Phys. Chem. B , 111 , 12185 –12194 .
22.
Khan M.N.
, and
Fui C.T.
(2009 ) J. Mol. Liq. , 147 , 170 –177 .
23.
Rao U.R.K.
,
Manohar C.
,
Valaulikar B.S.
, and
Iyer R.M.
(1987 ) J. Phys. Chem. , 91 , 3286 –3291 .
24.
Geng Y.
,
Romsted L.S.
,
Froehner S.
,
Zanette D.
,
Magid L.J.
,
Cuccovia I.M.
, and
Chaimovich H.
(2005 ) Langmuir , 21 , 562 –568 .
25.
Geng Y.
,
Romsted L.S.
, and
Menger F.M.
(2006 ) J. Am. Chem. Soc. , 128 , 492 –501 .
26.
Carver M.
,
Smith T.L.
,
Gee J.C.
,
Delichere A.
,
Caponetti E.
, and
Magid L.J.
(1996 ) Langmuir , 12 , 691 –698 .
27.
Vermathen M.
,
Stiles P.
,
Bachofer S.J.
, and
Simonis U.
(2002 ) Langmuir , 18 , 1030 –1042 .
28.
Zhang J.
,
Ge Z.
,
Jiang X.
,
Hassan P.A.
, and
Liu S.
(2007 ) J. Colloid Interface Sci. , 316 , 796 –802 .
29.
Davies T.S.
,
Ketner A.M.
, and
Raghavan S.R.
(2006 ) J. Am. Chem. Soc. , 128 , 6669 –6675 .
30.
Khan M.N.
,
Ismail E.
, and
Yusof N.S.M.
(2010 ) Colloids Surf., A , 361 , 150 –161 .
31.
Khan M.N.
, and
Ismail E.
(2009 ) J. Phys. Chem. A , 113 , 6484 –6488 .
32.
Bunton C.A.
(1979 ) Catal. Rev.: Sci. Eng. , 20 , 1 –56 .
33.
Bunton C.A.
(2006 ) Adv. Colloid Interface Sci. , 123–126 , 333 –343 .
34.
Cordes E.H.
, and
Gitler C.
(1973 ) Prog. Bioorg. Chem. , 2 , 1 –53 .
35.
Duynstee E.F.J.
, and
Grunwald E.
(1959 ) J. Am. Chem. Soc. , 81 , 4540 –4542 .
36.
Duynstee E.F.J.
, and
Grunwald E.
(1959 ) J. Am. Chem. Soc. , 81 , 4542 –4548 .
37.
Yusof N.S.M.
, and
Khan M.N.
(2012 ) J. Phys. Chem. B , 116 , 2065 –2074 .
38.
Kunitake T.
,
Okahata Y.
,
Ando R.
,
Shinkai S.
, and
Hirakawa S.
(1980 ) J. Am. Chem. Soc. , 102 , 7877 –7881 .
39.
Brinchi L.
,
Di Profio P.
,
Geramani R.
,
Goracci L.
,
Savelli G.
,
Gilliff N.D.
, and
Bunton C.A.
(2007 ) Langmuir , 23 , 436 –442 .
40.
Khan M.N.
, and
Gambo S.K.
(1985 ) Int. J. Chem. Kinet. , 17 , 419 –428 .
41.
Khan M.N.
(1989 ) J. Chem. Soc., Perkin Trans. 2 , 199 –208 .
42.
Khan M.N.
(1983 ) J. Org. Chem. , 48 , 2046 –2052 .
43.
Khan M.N.
(1990 ) J. Chem. Soc., Perkin Trans. 2 , 445 –457 .
44.
Khan M.N.
,
Arifin Z.
,
Lasidek M.N.
,
Hanifiah M.A.M.
, and
Alex G.
(1997 ) Langmuir , 13 , 3959 –3964 .
45.
Khan M.N.
,
Arifin Z.
,
Ismail E.
, and
Ali S.F.M.
(2000 ) J. Org. Chem. , 65 , 1331 –1334 .
46.
Khan M.N.
, and
Ismail E.
(2001 ) Int. J. Chem. Kinet. , 33 , 288 –294 .
47.
Bunton C.A.
, and
Savelli G.
(1986 ) Adv. Phys. Org. Chem. , 22 , 213 –309 .
48.
Bunton C.A.
(1991 ) In:
Mittal K.L.
, and
Shah D.O.
(eds), Surfactants in solution , Vol. 11 , pp. 17 –40 . Plenum Press , New York .
49.
Yusof N.S.M.
, and
Khan M.N.
(2010 ) Langmuir , 26 , 10627 –10635 .
50.
Khan M.N.
,
Cheong M-Y.
, and
Ariffin A.
(2008 ) Nano-SciTech, International Conference on Nanoscience and Nanotechnology , Organised by Universiti Teknologi MARA, Abstract No. O-137, pp. 129 –130 .
51.
Narayanan J.
,
Manohar C.
,
Kern F.
,
Lequeux F.
, and
Candau S.J.
(1997 ) Langmuir , 13 , 5235 –5243 .
52.
Chen X.
,
Flores S.C.
,
Lim S.-M.
,
Zhang Y.
,
Yang T.
,
Kherb J.
, and
Cremer P.S.
(2010 ) Langmuir , 26 , 16447 –16454 .
53.
Cheong M.-Y.
,
Ariffin A.
, and
Khan M.N.
(2007 ) Bull. Korean Chem. Soc. , 28 , 1135 –1140 .
54.
Khan M.N.
(1997 ) J. Org. Chem. , 62 , 3190 –3193 .
55.
Magid L.J.
(2008 ) J. Phys. Chem. B , 102 , 4064 –4074 .
56.
Abdel-Rahem R.
(2008 ) Adv. Colloid Interface Sci. , 141 , 24 –36 .
57.
Qi Y.
, and
Zakin J.L.
(2002 ) Ind. Eng. Chem. Res. , 41 , 6326 –6336 .
58.
Zhang Y.
,
Schmidt J.
,
Talmon Y.
, and
Zakin J.L.
(2005 ) J. Colloid Interface Sci. , 286 , 696 –709 .
59.
Shikata T.
,
Hirata H.
, and
Kotaka T.
(1988 ) Langmuir , 4 , 354 –359 .
60.
Muijselaar P.G.H.M.
,
Claessens H.A.
, and
Cramers C.A.
(1996 ) J. Chromatogr. A , 696 , 273 –284 .
61.
Nielsen K.R.
, and
Foley J.P.
(1993 ) J. Microcolumn Sep. , 5 , 347 –360 .
62.
Ahuja E.S.
, and
Foley J.P.
(1995 ) Anal. Chem. , 67 , 2315 –2324 .
63.
Trone M.D.
,
Mack J.P.
,
Goodell H.P.
, and
Khaledi M.G.
(2000 ) J. Chromatogr. A , 888 , 229 –240 .
64.
Lu B.
,
Zheng Y.
,
Davis H.T.
,
Scriven L.E.
,
Talmon Y.
, and
Zakin J.L.
(1998 ) Rheol. Acta , 37 , 528 –548 .
65.
Hoffmann H.
,
Platz G.
,
Rehage H.
, and
Schorr W.
(1982 ) Adv. Colloid Interface Sci. , 17 , 275 –298 .
66.
Yusof N.S.M.
, and
Khan M.N.
(2013 ) Adv. Colloid Interface Sci. , 193–194 , 12 –23 .
67.
Khan M.N.
, and
Sinasamy S.
(2011 ) Int. J. Chem. Kinet. , 43 , 9 –20 .
68.
Magid L.J.
,
Han Z.
,
Warr G.G.
,
Cassidy M.A.
,
Butler P.D.
, and
Hamilton W.A.
(1997 ) J. Phys. Chem. B , 101 , 7919 –7927 .
69.
Cuccovia I.M.
,
da Silva I.N.
,
Chaimovich H.
, and
Romsted L.S.
(1997 ) Langmuir , 13 , 647 –652 .
70.
Bartet D.
,
Gamboa C.
, and
Sepulveda L.
(1980 ) J. Phys. Chem. , 84 , 272 –275 .
71.
Khan M.N.
,
Yusof N.S.M.
, and
Razak N.A.
(2013 ) J. Oleo Sci. , 62 , 695 –708 .
72.
Morgan J.D.
,
Napper D.H.
, and
Warr G.G.
(1995 ) J. Phys. Chem. , 99 , 9458 –9465 .
73.
Abuin E.
,
Lissi E.
,
Bianchi N.
,
Miola L.
, and
Quina F.H.
(1983 ) J. Phys. Chem. , 87 , 5166 –5172 .
74.
Drummond C.J.
, and
Grieser F.
(1989 ) J. Colloid Interface Sci. , 127 , 281 –291 .