Evaluation of methods for measuring amino acid hydrophobicities and interactions

The concept of hydrophobicity has been addressed by researchers in all aspects of science, particularly in the fields of biology and chemistry. Over the past several decades, the study of the hydrophobicity of biomolecules, particularly amino acids has resulted in the development of a variety of hydrophobicity scales. In this review, we discuss the various methods of measuring amino acid hydrophobicity and provide explanations for the wide range of rankings that exist among these published scales. A discussion of the literature on amino acid interactions is also presented. Only a surprisingly small number of papers exist in this rather important area of research; measuring pairwise amino acid interactions will aid in understanding structural aspects of proteins.     

Kinetic studies on the acid catalyzed reaction of hydroxamic acids in β-cyclodextrin/surfactant mixed systems

The acid catalyzed hydrolysis of two N-substituted hydroxamic acids (C₆H₅CON(OH)R, R = C₆H₅ (PBHA), R = C₆H₅CH₂(BBHA)) in mixed systems containing -cyclodextrin (—CD) and a surfactant (sodium dodecyl sulfate, SDS) has been studied. The reactions are inhibited by —CD. The inhibition is attributed to the formation of inclusion complex and competition between the micellization and complexation processes.This revised version was published online in December 2005 with corrections to the Cover Date.     

Nucleophilic dephosphorylation of p-nitrophenyl diphenyl phosphate in cationic micellar media

The kinetics of nucleophilic dephosphorylation of p-nitrophenyl diphenyl phosphate by hydroxamate ions (R'(C=O)N(RO-)) have been investigated in aqueous cationic micellar media at pH 9.12 and 27 degrees C. The pseudo-first-order rate constant-surfactant profiles show micelle-assisted bimolecular reactions involving interfacial ion exchange between bulk aqueous media and micellar pseudophase. N-Substituted hydroxamate ion shows higher reactivity over the unsubstituted hydroxamate ions in cationic micellar media. The kinetic data are discussed in terms of the pseudophase ion exchange model.     

Molecular and electronic structure of four- and five-coordinate cobalt complexes containing two o-phenylenediamine- or two o-aminophenol-type ligands at various oxidation levels: an experimental, density functional, and correlated ab initio study

The bidentate ligands N-phenyl-o-phenylenediamine, H(2)((2)L(N)IP), or its analogue 2-(2-trifluoromethyl)anilino-4,6-di-tert-butylphenol, ((4)L(N)IP), react with [Co(II)(CH(3)CO(2))(2)]4H(2)O and triethylamine in acetonitrile in the presence of air yielding the square-planar, four-coordinate species [Co((2)L(N))(2)] (1) and [Co((4)L(O))(2)] (4) with an S=1/2 ground state. The corresponding nickel complexes [Ni((4)L(O))(2)] (8) and its cobaltocene reduced form [Co(III)(Cp)(2)][Ni((4)L(O))(2)] (9) have also been synthesized. The five-coordinate species [Co((2)L(N))(2)(tBu-py)] (2) (S=1/2) and its one-electron oxidized forms [Co((2)L(N))(2)(tBu-py)](O(2)CCH(3)) (2 a) or [Co((2)L(N))(2)I] (3) with diamagnetic ground states (S=0) have been prepared, as has the species [Co((4)L(O))(2)(CH(2)CN)] (7). The one-electron reduced form of 4, namely [Co(Cp)(2)][Co((4)L(O))(2)] (5) has been generated through the reduction of 4 with [Co(Cp)(2)]. Complexes 1, 2, 2 a, 3, 4, 5, 7, 8, and 9 have been characterized by X-ray crystallography (100 K). The ligands are non-innocent and may exist as catecholate-like dianions ((2)L(N)IP)(2-), ((4)L(N)IP)(2-) or pi-radical semiquinonate monoanions ((2)L(N)ISQ)(*) (-), ((4)L(N)ISQ)(*) (-) or as neutral benzoquinones ((2) L(N)IBQ)(0), ((4) L(N)IBQ)(0); the spectroscopic oxidation states of the central metal ions vary accordingly. Electronic absorption, magnetic circular dichroism, and EPR spectroscopy, as well as variable temperature magnetic susceptibility measurements have been used to experimentally determine the electronic structures of these complexes. Density functional theoretical (DFT) and correlated ab initio calculation have been performed on the neutral and monoanionic species [Co((1)L(N))(2)](0,-) in order to understand the structural and spectroscopic properties of complexes. It is shown that the corresponding nickel complexes 8 and 9 contain a low-spin nickel(II) ion regardless of the oxidation level of the ligand, whereas for the corresponding cobalt complexes the situation is more complicated. Spectroscopic oxidation states describing a d(6) (Co(III)) or d(7) (Co(II)) electron configuration cannot be unambiguously assigned.     

Catalytic hydrolysis of phosphodiesters by nucleophilic ions in gemini micellar media

The catalytic hydrolysis of bis(4‐nitrophenyl)phosphate (BNPP) and bis(2,4‐dinitrophenyl)phosphate (BDNPP) catalyzed by α‐nucleophiles in gemini micellar media was investigated at 27 °C. The cationic gemini surfactants, i.e., alkanediyl‐α‐ω‐bis(hydroxyethylmethylhexadecylammonium bromide) (16‐s‐16 MEA 2Br^?, where s = 4 and 6) were used. Nucleophilic reactivity of α‐nucleophiles such as hydroperoxide (HOO^?), acetohydroxamate (AHA^?), and butane 2,3‐dione monoximate ions (BDMO^?) were compared. The kinetic rate data were treated by applying the pseudophase model. The cationic gemini surfactants show unusual rate acceleration toward the cleavage of phosphodiesters with nucleophiles. These studies reveal that the hydroperoxide ion shows the highest catalytic activity reported so far with an unprecedented acceleration rate, 10⁷ times faster than that of the uncatalyzed reaction. The possible mechanism for the BNPP and BDNPP cleavage promoted by α‐nucleophiles is proposed on the basis of kinetic analysis. Copyright © 2014 John Wiley & Sons, Ltd.     

Studies of Nucleophilic Substitution Reactions of p‐Nitrophenyl Acetate with Some Dihydroxamate Ions in Cationic Micellar Media

Pseudo‐first‐order rate constants have been determined for the nucleophilic substitution reactions of p‐nitrophenyl acetate with oxalo, malono, and succinodihydroxamate ions (^?ONHC(O)(CH₂)_nC(O)NHO^?) in phosphate buffer (pH=7.9) at 27°C. The rate data of the reaction revealed that the nucleophilic reactivity sequence of these hydroxamate ions is generally ODHA>MDHA>SDHA. The k_obs value increases upon addition of cationic surfactants to the reaction medium which is typical behavior of micelle‐assisted bimolecular reactions. The pseudo‐phase ion exchange model has been successfully applied to determine binding constant.     

Preparation of Ag Nanoparticles in Surfactant Solution

The physicochemical properties of Ag nanoparticles have been determined by the nature of the used chemical reductors. The reported procedures describe the reduction of silver ions using N‐Phenylbenzohydroxamic acid (PBHA) and ascorbic acid individually. The influencing factors including cationic, anionic, zwitterionic and nonionic surfactants and pH have also been investigated in detail.     

Hydrolysis of carboxylate and phosphate esters using monopyridinium oximes in cationic micellar media

The reactions of p‐nitrophenyl acetate (PNPA) with a series of monopyridinium oximes, viz. 2‐PAM (2‐hydroxyiminomethyl‐1‐methylpyridinium iodide), 3‐PAM (3‐hydroxyiminomethyl‐1‐methylpyridinium iodide), and 4‐PAM (4‐hydroxyiminomethyl‐1‐methylpyridinium iodide) have been studied in the presence of cationic surfactants of same hydrophobic chain length (C₁₆) within the concentration range of 0.5–6.0 mM at pH 8.0 under the pseudo‐first‐order condition. The observed rate constant (k_obs) increases with increasing surfactant concentration culminating into a maximum, and this has been analyzed in detail following the concepts of micellar catalysis. The structure–activity relationship of the investigated oximes has been discussed, and 2‐PAM was found to be the most reactive among all the three investigated oximes for the cleavage of PNPA. Esterolytic decomposition of p‐nitrophenyldiphenyl phosphate with oximate ions (? CH?NO^?) was followed in cetyltrimethylammonium bromide micelles at pH 9.0, and 4‐PAM was the most reactive oxime for the micellar hydrolysis of phosphate ester. The apparent acid dissociation constants (pK_a) of the investigated oximes have been determined spectrophotometrically. © 2011 Wiley Periodicals, Inc. Int J Chem Kinet 43: 569–578, 2011     

Reactivity studies of carbon,phosphorus and sulfur‐based acyl sites with tertiary oximes in gemini surfactants

Kinetic studies of the reactions of tertiary oximes (monoisonitroso acetone; MINA and butane 2,3 dione monooxime; BDMO) with some carboxylate (p‐nitrophenyl acetate and p‐nitrophenyl benzoate), phosphate (p‐nitrophenyl diphenyl phosphate and bis (2,4‐dinitrophenyl) phosphate) and sulfonate (p‐nitrophenyl p‐toluene sulphonate) esters in gemini surfactants have been conducted. The observed first‐order rate constant versus surfactant profiles show micelle‐assisted bimolecular reactions involving interfacial ion exchange between bulk aqueous media and micellar pseudophase. Experimental results showed that MINA exhibited better nucleophilic activity towards ester cleavage than BDMO. Pseudophase model has been applied in order to determine micellar second‐order rate constants and binding constants. Copyright © 2013 John Wiley & Sons, Ltd.     

Kinetics of the reaction of methyl 4‐nitrobenzenesul‐fonate + Br− in ethanol amine based surfactants

The kinetics of the reaction of methyl 4‐nitrobenzenesulfonate + Br^? ions has been studied in ethanol amine based (alkyldimethylethanolammonium bromide and alkyldiethylethanolammonium bromide) surfactant solutions. The observed first‐order rate constants increase monotonically with surfactant concentration, with hydrophobic chain length and with head group bulk in a manner similar to other quaternary ammonium surfactants. The results were analyzed using the pseudophase model of micellar rate effects in conjunction with a Langmuir form to describe micellar binding of bromide ion. An attempt to estimate activation parameters of the reaction from temperature variance of micellar pseudophase rate constants has also been made. © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 38: 303–308, 2006