Effect of Confinement on the Properties of Sequestered Mixed Polar Solvents: Enzymatic Catalysis in Nonaqueous 1,4-Bis-2-ethylhexylsulfosuccinate Reverse Micelles.

The influence of different glycerol, N,N-dimethylformamide (DMF) and water mixtures encapsulated in 1,4-bis-2-ethylhexylsulfosuccinate (AOT)/n-heptane reverse micelles (RMs) on the enzymatic hydrolysis of 2-naphthyl acetate by α-chymotrypsin is demonstrated. In the case of the mixtures with DMF and protic solvents it has been previously shown, using absorption, emission and dynamic light-scattering techniques, that solvents are segregated inside the polar core of the RMs. Protic solvents anchor to the AOT, whereas DMF locates to the polar core of the aggregate. Thus, DMF not only helps to solubilize the hydrophobic substrate, increasing its effective concentrations but surprisingly, it does not affect the enzyme activity. The importance of ensuring the presence of RMs, encapsulation of the polar solvents and the corrections by substrate partitioning in order to obtain reliable conclusions is highlighted. Moreover, the effect of a constrained environment on solvent-solvent interactions in homogenous media and its impact on the use of RMs as nanoreactors is stressed.

[1]  J. Coutinho,et al.  Superactivity induced by micellar systems as the key for boosting the yield of enzymatic reactions , 2014 .

[2]  A. Wand,et al.  High-resolution NMR spectroscopy of encapsulated proteins dissolved in low-viscosity fluids. , 2014, Journal of magnetic resonance.

[3]  F. Moyano,et al.  Enzymatic hydrolysis of N-benzoyl-L-tyrosine p-nitroanilide by α-chymotrypsin in DMSO-water/AOT/n-heptane reverse micelles. A unique interfacial effect on the enzymatic activity. , 2013, Langmuir : the ACS journal of surfaces and colloids.

[4]  N. M. Correa,et al.  More evidence on the control of reverse micelles sizes. Combination of different techniques as a powerful tool to monitor AOT reversed micelles properties. , 2013, The journal of physical chemistry. B.

[5]  F. Zaera Nanostructured materials for applications in heterogeneous catalysis. , 2013, Chemical Society reviews.

[6]  N. M. Correa,et al.  Nonaqueous polar solvents in reverse micelle systems. , 2012, Chemical reviews.

[7]  Awanish Kumar,et al.  Overview of the stability of α-chymotrypsin in different solvent media. , 2012, Chemical reviews.

[8]  N. M. Correa,et al.  Inhibited phenol ionization in reverse micelles: confinement effect at the nanometer scale. , 2012, Chemphyschem : a European journal of chemical physics and physical chemistry.

[9]  E. Lissi,et al.  KINETICS OF P - NITROPHENYL ACETATE HYDROLYSIS CATALYZED BY α- CHYMOTRYPSIN IN PRESENCE OF POLYETHYLENE GLYCOL , 2011 .

[10]  N. M. Correa,et al.  A new organized media: glycerol:N,N-dimethylformamide mixtures/AOT/n-heptane reversed micelles. The effect of confinement on preferential solvation. , 2011, The journal of physical chemistry. B.

[11]  N. Levinger,et al.  Coexisting aggregates in mixed aerosol OT and cholesterol microemulsions. , 2011, Langmuir : the ACS journal of surfaces and colloids.

[12]  F. Moyano,et al.  Cationic reverse micelles create water with super hydrogen-bond-donor capacity for enzymatic catalysis: hydrolysis of 2-naphthyl acetate by alpha-chymotrypsin. , 2010, Chemistry.

[13]  N. M. Correa,et al.  What are the factors that control non-aqueous/AOT/n-heptane reverse micelle sizes? A dynamic light scattering study. , 2009, Physical chemistry chemical physics : PCCP.

[14]  N. M. Correa,et al.  Effect of the constrained environment on the interactions between the surfactant and different polar solvents encapsulated within AOT reverse micelles. , 2009, Chemphyschem : a European journal of chemical physics and physical chemistry.

[15]  R. J. Sengwa,et al.  Dielectric properties and hydrogen bonding interaction behaviour in binary mixtures of glycerol with amides and amines , 2008 .

[16]  K. Mutch,et al.  Tuning aggregation of microemulsion droplets and silica nanoparticles using solvent mixtures. , 2008, Journal of colloid and interface science.

[17]  E. Lissi,et al.  Kinetics of reactions catalyzed by enzymes in solutions of surfactants. , 2008, Advances in colloid and interface science.

[18]  E. Lissi,et al.  Kinetics of p-nitrophenyl Acetate Hydrolysis Catalyzed by Mucor javanicus Lipase in AOT Reverse Micellar Solutions Formulated in Different Organic Solvents , 2007, The protein journal.

[19]  N. M. Correa,et al.  When is water not water? Exploring water confined in large reverse micelles using a highly charged inorganic molecular probe. , 2006, Journal of the American Chemical Society.

[20]  Xin-gen Hu,et al.  Enthalpies of Interaction of N,N-Dimethylformamide with Polyalcohols in Aqueous Solutions at 298.15 K , 2006 .

[21]  A. Wand,et al.  Novel surfactant mixtures for NMR spectroscopy of encapsulated proteins dissolved in low‐viscosity fluids , 2005, Protein science : a publication of the Protein Society.

[22]  E. Lissi,et al.  Effect of the addition of a nonaqueous polar solvent (glycerol) on enzymatic catalysis in reverse micelles. Hydrolysis of 2-naphthyl acetate by alpha-chymotrypsin. , 2004, Langmuir : the ACS journal of surfaces and colloids.

[23]  Rui-sen Lin,et al.  Volumetic Properties of Glycerol with N,N-Dimethylformamide and with Water at 25 and 35°C , 2003 .

[24]  E. Lissi,et al.  Solubilization in AOT-water reverse micelles. Effect of the external solvent , 2002 .

[25]  Nilmoni Sarkar,et al.  Intramolecular Charge Transfer and Solvation Dynamics of Coumarin 152 in Aerosol-OT, Water-Solubilizing Reverse Micelles, and Polar Organic Solvent Solubilizing Reverse Micelles , 2002 .

[26]  E. Lissi,et al.  A procedure for the joint evaluation of substrate partitioning and kinetic parameters for reactions catalyzed by enzymes in reverse micellar solutions. I. Hydrolysis of 2-naphthyl acetate catalyzed by lipase in sodium 1,4-bis(2-ethylhexyl) sulphosuccinate (AOT)/buffer/heptane. , 2001, Archives of biochemistry and biophysics.

[27]  H. Bohidar,et al.  Characterization of reverse micelles by dynamic light scattering , 2001 .

[28]  E. Lissi,et al.  A General Treatment for Meaningful Comparison of Rate Parameters of Enzyme-Catalyzed Reactions in Aqueous and Reverse Micellar Solutions , 2000 .

[29]  H. Bohidar,et al.  Solubilization of gelatin by water–AOT–iso-octane reverse micelles studied by dynamic laser light scattering , 2000 .

[30]  E. Lissi,et al.  INTERACTIONS OF SMALL MOLECULES WITH REVERSE MICELLES , 1999 .

[31]  A. Deshpande,et al.  Reactivity of trypsin in reverse micelles: pH-effects on the W0 versus enzyme activity profiles. , 1998, Biochimie.

[32]  S. P. Moulik,et al.  Structure, dynamics and transport properties of microemulsions , 1998 .

[33]  N. Levinger,et al.  Novel Reverse Micelles Partitioning Nonaqueous Polar Solvents in a Hydrocarbon Continuous Phase , 1997 .

[34]  H. Piekarski,et al.  Enthalpies of solution of glycine in aqueous solutions of 1,2-diols and glycerol at 25°C , 1997 .

[35]  D. Birch,et al.  The fluorescence and circular dichroism of proteins in reverse micelles: application to the photophysics of human serum albumin and N-acetyl-L-tryptophanamide. , 1996, Biophysical chemistry.

[36]  Shinji Yamamoto,et al.  Study on tryptophan fluorescence and catalytic activity of α-chymotrypsin in aqueous-organic media , 1996 .

[37]  M. Hoppert,et al.  Functional compartmentalization in bacteria and archaea. A hypothetical interface between cytoplasmic membrane and cytoplasm. , 1996, Die Naturwissenschaften.

[38]  A. Maitra,et al.  Solution behaviour of Aerosol OT in non-polar solvents , 1995 .

[39]  N. M. Correa,et al.  Micropolarity of Reverse Micelles of Aerosol-OT in n-Hexane , 1995 .

[40]  Kozo Nakamura,et al.  Structure and reactivity of aerosol-OT reversed micelles containing α-chymotrypsin , 1995 .

[41]  M. Teramoto,et al.  Enzymatic reaction in water-in-oil microemulsions. Part 2.—Rate of hydrolysis of a hydrophobic substrate, 2-naphthyl acetate , 1994 .

[42]  J. Sinisterra,et al.  Structure—activity relationship in the hydrolysis of N-benzoylphenylalanine esters catalysed by α-chymotrypsin , 1993 .

[43]  E. Lissi,et al.  Incorporation of n-alkanols in reverse micelles in the AOT/n-heptane/water system , 1992 .

[44]  E. Ruckenstein,et al.  On the enzymatic superactivity in ionic reverse micelles , 1990 .

[45]  K. Martínek,et al.  Micellar enzymology: Potentialities in applied areas (biotechnology) , 1988 .

[46]  E. Lissi,et al.  Solubilization of neutral molecules in AOT inverse micelles in n-heptane , 1986 .

[47]  R. Freedman,et al.  Reactivity of α-chymotrypsin in water-in-oil microemulsions , 1984 .

[48]  B. Robinson,et al.  Structural study of aerosol-OT-stabilised microemulsions of glycerol dispersed in n-heptane , 1984 .

[49]  B. Belleau,et al.  Polyol–Water interactions. Apparent molal heat capacities and volumes of aqueous polyol solutions , 1977 .