Probing the Site-Specific Reactivity and Catalytic Activity of Ag n (n = 15-20) Silver Clusters.

Density functional theory calculations within the framework of generalized gradient approximation (GGA), meta-GGA, and local functionals were carried out to investigate the reactivity and catalytic activity of Ag n (n = 15-20) clusters. Our results reveal that all the Ag n clusters in this size range, except Ag20, adsorb O2 preferably in the bridged mode with enhanced binding energy as compared to the atop mode. The O2 binding energies range from 0.77 to 0.29 in the bridged mode and from 0.36 to 0.15 eV in the atop mode of O2 adsorption. The strong binding in the case of the bridged mode of O2 adsorption is also reflected in the increase in O-O bond distance. Natural bond orbital charge analysis and vibrational frequency calculations reveal that enhanced charge transfer occurs to the O2 molecule and there is significant red shift in the stretching frequency of O-O bond in the case of the bridged mode of O2 adsorption on the clusters, thereby confirming the above results. Moreover, the simulated CO oxidation reaction pathways show that the oxidation of the CO molecule is highly facile on Ag16 and Ag18 clusters involving small kinetic barriers and higher heats toward CO2 formation.

Transforming micelles into mixed micelles: a promising approach to tune the catalytic performance of imidazolium-based surface active ionic liquids toward degradation of rhodamine B.

Herein, we demonstrate that the catalytic performance of imidazolium-based surface-active ionic liquid (SAIL) micelles can be significantly enhanced through the addition of an appropriate type and amount of intelligently conceived amphiphile to form mixed micelles. Specifically, we show that the catalytic performance of 1-dodecyl-3-methyl imidazolium chloride (DDMIMCl) micelles toward the reductive degradation of rhodamine B (RhB), a carcinogenic dye extensively used in multiple industrial applications, can be appreciably boosted through addition of Brij56, a nonionic surfactant. Detailed kinetic investigations on the catalytic performance of pre- and post-micellar concentrations of DDMIMCl and its mixed micelles with Brij56 over various mole fractions, toward the reductive degradation of RhB, are presented. The data analyzed in light of Berezin's kinetic model suggest that the addition of Brij56 to DDMIMCl micelles significantly enhances their catalytic performance. The catalytic activity exhibited by the DDMIMCl-Brij56 (XBrij56 = 0.2) mixed micellar system is better than that reported for many state-of-the-art nanoparticle/homogenous catalysts. The results explained in light of Berezin's kinetic model are well supported by physico-chemical studies like conductometry, fluorimetry and dynamic light scattering. The presented results anticipate stimulation of extensive research activity for exploiting the mixed micellization approach as a novel avenue for modulating the catalytic performance of SAILs.

Structural-functional integrity of lysozyme in imidazolium based surface active ionic liquids.

The present study was designed to explore the hydrophobicity and concentration dependence of imidazolium based surface active ionic liquids (SAILs) effects on the structural-functional integrity of proteins. Specifically, we investigated the impact of SAILs viz. 1-octyl-3-methylimidazolium dodecylbenzenesulfonate ([OMIM][DBS]) and 1-dodecyl-3-methylimidazolium dodecylbenzenesulfonate ([DDMIM][DBS]) on activity, structure and stability of lysozyme. Activity measurements revealed that, in contrast to [DDMIM][DBS] that renders lysozyme either feebly active or inactive, [OMIM][DBS] significantly enhances the lysozyme activity in the concentration range of critical aggregation concentrations (CAC) to Cs (SAIL saturation concentration of protein backbone) i.e., 0.5 mM-1.35 mM. Tensiometric results in agreement with turbidity measurements inferred significant composition and concentration dependence of the lysozyme-SAIL interactions. Spectroscopic investigations revealed that compared to destabilizing behaviour of [DDMIM][DBS], [OMIM][DBS] significantly enhances both conformational as well as thermal stability of lysozyme in the CAC to Cs concentration regime. Altogether, results obtained do indicate that [OMIM][DBS], in the concentration regime of CAC to Cs, serves as an efficient stabiliser with an ability to appreciably enhance the activity, thermal stability and overall conformational stability of lysozyme. We firmly believe that [OMIM][DBS], at least in the CAC to Cs concentration ranges, can be exploited as a promising stabiliser and activity enhancer for numerous industrially important enzymes.

PdAg Bimetallic Nanoalloy-Decorated Graphene: A Nanohybrid with Unprecedented Electrocatalytic, Catalytic, and Sensing Activities.

Recent reports about the promising and tunable electrocatalytic activity and stability of nanoalloys have stimulated an intense research activity toward the design and synthesis of homogeneously alloyed novel bimetallic nanoelectrocatalysts. We herein present a simple one-pot facile wet-chemical approach for the deposition of high-quality bimetallic palladium-silver (PdAg) homogeneous nanoalloy crystals on reduced graphene (Gr) oxide sheets. Morphological, structural, and chemical characterizations of the so-crafted nanohybrids establish a homogeneous distribution of 1:1 PdAg nanoalloy crystals supported over reduced graphene oxide (PdAg-Gr). The PdAg-Gr nanohybrids exhibit outstanding electrocatalytic, catalytic, and electroanalytical performances. The PdAg-Gr samples were found to exhibit exceptional durability when subjected to repeated potential cycles or long-term electrolysis. In the CVs recorded for fuel cell reactions, viz. methanol oxidation reaction and oxygen reduction reaction, and for detoxification of environmental pollutants, viz. electroreduction of methyl iodide and chloroacetonitrile over PdAg-Gr with potential sweep rate of 25 mVs-1, the peak potentials were observed to be just -0.221, -0.297, (vs Ag/AgCl, 3 M KCl) -1.508, and -1.189 V (vs Fc+/Fc), respectively. The potential of PdAg-Gr nanohybrid for simultaneous and sensitive electrochemical sensing and estimation of hydroxybenzene isomers with very low detection limits (0.05 µM for hydroquinone, 0.06 µM for catechol, 6.7 nM for 4-aminophenol, and 13.7 nM for 2-aminophenol) is demonstrated. Additionally, PdAg-Gr was observed to offer excellent solution-phase catalytic performance in bringing about the reduction of notorious environmental pollutant 4-nitrophenol to pharmaceutically important 4-aminophenol with an apparent rate constant ( kapp) of 3.106 × 10-2 s-1 and a normalized rate constant ( knor) of 6.21 × 102 s-1 g-1. The presented synthetic scheme besides being high yielding, low cost, and easy to carry out results in the production of PdAg-Gr nanohybrids with stability and activity significantly better than most of the nanomaterials purposefully designed and testified so far by various groups.

Rheological response of methylcellulose toward alkanediyl-α,ω-bis(dimethylcetylammonium bromide) surfactants with varying spacer length.

The modulation of properties of methylcellulose (MC) by cationic gemini surfactants with varying spacer lengths was studied employing tensiometry, rheometry and turbidimetry. Surface tension measurements anticipate that the gemini surfactant with longer spacer chain length saturates MC at lower concentrations owing to its greater hydrophobicity compared to shorter spacer analogues. Rheometric and turbidimetric measurements suggest that at very low concentrations of gemini surfactants, ion-dipole type of interactions between MC and gemini surfactants promote the extension of polymer chains which is manifested by an initial increase in the low shear viscosity and gelation temperature of MC-gemini surfactant systems, and lowering of turbidity. Such interactions were found to be stronger in case of 16-4-16 than 16-5-16, and almost absent in case of 16-6-16 surfactant system. However at concentrations above CAC, hydrophobic forces operative between MC and gemini surfactants were found to be more for 16-6-16 than that of 16-5-16 and 16-4-16. The final levelling of MC viscosity in presence of all the three gemini surfactants and the variation of gelation temperature suggests the solubilization of network junctions in the surfactant micelles. Moreover, the presence of gemini surfactant strongly affects the interaction of MC with a model hydrophobic drug rifampicin.The results highlight the importance of gemini surfactants and their spacer length in controlling the structural dynamics of MC and its effective use in pharmaceutical and food industry.

Rheological behavior and Ibuprofen delivery applications of pH responsive composite alginate hydrogels.

Synthesis and structural characterization of hydrogels composed of sodium alginate, polyethylene oxide and acrylic acid with cyclodextrin as the hydrocolloid prepared at different pH values is presented. The hydrogels synthesized show significant variations in rheological properties, drug encapsulation capability and release kinetics. The hydrogels prepared at lower pH (pH 1) are more elastic, have high tensile strength and remain almost unaffected by varying temperature or frequency. Further, their Ibuprofen encapsulation capacity is low and releases it slowly. The hydrogel prepared at neutral pH (pH 7) is viscoelastic, thermo-reversible and also exhibits sol-gel transition on applying frequency and changing temperature. It shows highest Ibuprofen encapsulation capacity and also optimum drug release kinetics. The hydrogel prepared at higher pH (pH 12) is more viscous, has low tensile strength, is unstable to change in temperature and has fast drug release rate. The study highlights the pH responsiveness of three composite alginate hydrogels prepared under different conditions to be employed in drug delivery applications.

Hydrogels of sodium alginate in cationic surfactants: Surfactant dependent modulation of encapsulation/release toward Ibuprofen.

The interaction of cetyltrimethylammoium bromide (CTAB) and its gemini homologue (butanediyl-1,4-bis (dimethylcetylammonium bromide), 16-4-16 with biocompatible polymer sodium alginate (SA) has been investigated in aqueous medium. Addition of K2CO3 influences viscoelastic properties of surfactant impregnated SA via competition between electrostatic and hydrophobic interactions. Viscosity of these polymer-surfactant systems increases with increase in concentration of K2CO3, and a cryogel is formed at about 0.5M K2CO3 concentration. The thermal stability of gel (5% SA+0.5M K2CO3) decreases with increase in surfactant concentration, a minimum is observed with increase in 16-4-16 concentration. The impact of surfactant addition on the alginate structure vis-à-vis its drug loading capability and release thereof was studied using Ibuprofen (IBU) as the model drug. The hydrogel with 16-4-16 exhibits higher IBU encapsulation and faster release in comparison to the one containing CTAB. This higher encapsulation-cum-faster release capability has been related to micelle mediated solubilization and greater porosity of the hydrogel with gemini surfactant.

Determination of cmc of imidazolium based surface active ionic liquids through probe-less UV-vis spectrophotometry.

In the first of its kind we herein report the results of our studies undertaken on the micellization behaviour of imidazolium based surface active ionic liquids (SAILs) to prove that their critical micelle concentration (cmc) can be estimated through ultraviolet-visible (UV-vis) spectroscopy without using any external probe. Tensiometric and spectrophotometric investigations of a series of freshly prepared SAILs viz. 1-octyl-3-methylimidazolium chloride ([OMIM][Cl]), 1-octyl-3-methylimidazolium dodecylsulphate ([OMIM][DS]), 1-octyl-3-methylimidazolium benzoate ([OMIM][Bz]), 1-octyl-3-methylimidazolium salicylate ([OMIM][Sc]), 1-octyl-3-methylimidazolium acetate ([OMIM][Ac]) are presented as a case study in support of the said claim. The cmcs estimated through spectrophotometric method were found to be close to the values estimated through tensiometry for the said SAILs. The cmcs for the investigated SAILS were found to vary in order of [OMIM][Cl]>[OMIM][Ac]>[OMIM][Bz]>[OMIM][Sc]>[OMIM][DS]. To the best of our knowledge the present communication will be the first report about the synthesis, characterization and micellization behaviour of [OMIM][Bz] and [OMIM][Sc].

Interaction of cetyltrimethylammonium bromide and its gemini homologue bis(cetyldimethylammonium)butane dibromide with xanthine oxidase.

The interaction of xanthine oxidase (XO), a key enzyme in purine metabolism, with cetyltrimethylammonium bromide (CTAB) and bis(cetyldimethylammonium)butane dibromide (C16C4C16Br2) has been studied using tensiometry, spectrofluorometry, spectrophotometry, and circular dichroism at pH 7.4 and 25 °C. The tensiometric profiles of CTAB and C16C4C16Br2 in the presence of XO exhibit a single break at a lower surfactant concentration termed as C1 compared to their CMC in the buffered solution and show the existence of interaction between the surfactants and the enzyme. The results of the multitechnique approach showed that, although both CTAB as well as C16C4C16Br2 interact with the XO, C16C4C16Br2 interacts more strongly than its conventional single chain counterpart. Fluorescence and absorption measurements revealed that, compared to CTAB, C16C4C16Br2 is more effective in unfolding the enzyme. Change in XO activity by the surfactants was in concurrence with the structural alterations monitored by circular dichroism and showed structural stabilization of XO at higher surfactant concentrations, consistent with the aggregation results. This stabilization has been explained in light of strong tendency of C16C4C16Br2 for micellar growth and membrane/water stabilization of proteins by membrane-like fragments provided by higher concentrations of C16C4C16Br2 . The results are related to the stronger electrostatic and hydrophobic forces in C16C4C16Br2, owing to the presence of two charged headgroups and two hydrophobic tails.

Solubilization of triphenylamine, triphenylphosphine, triphenylphosphineoxide and triphenylmethanol in single and binary surfactant systems.

Solubilization and co-solubilization of triphenyls (TPs) viz., triphenylphosphine (TPP), triphenylphosphineoxide (TPPO), triphenylamine (TPA) and triphenylmethanol (TPM) were studied in various single and binary surfactant systems at 25 °C using UV-visible spectroscopy and HPLC. The solubilization capacities of different micelles towards TPs were found to be a function of the nature and structure of solubilizates, locus of solubilization, size of micelles and the nature of interactions between the solubilizate and micelles. The effect of surfactant mixing on the solubilization of TPs was evaluated using the Regular Solution Approach (RSA). The solubility enhancement of TPs within mixed micelles relative to that observed in single surfactant systems was explained in light of the structural micellar changes associated with the mixing of ionic and non-ionic surfactants. Moreover, kinetics of oxidation of TPP by hydrogen peroxide investigated in these surfactant systems was found to be sensitive to the nature of micelle and the locus of solubilization of TPP within the micelles.

Refolding of bovine serum albumin via artificial chaperone protocol using gemini surfactants.

Surfactants prevent the irreversible aggregation of partially refolded proteins, and they are also known to assist in protein refolding. A novel approach to protein refolding that utilizes a pair of low molecular weight folding assistants, a detergent and cyclodextrin, was proposed by Rozema and Gellman (D. Rozema, S.H. Gellman, J. Am. Chem. Soc. 117 (1995) 2373). We report the refolding of bovine serum albumin (BSA) assisted by these artificial chaperones, utilizing gemini surfactants for the first time. A combination of cationic gemini surfactants, bis(cetyldimethylammonium)pentane dibromide (C(16)H(33)(CH(3))(2)N(+)-(CH(2))(5)-N(+)(CH(3))(2)C(16)H(33)·2Br(-) designated as G5 and bis(cetyldimethylammonium)hexane dibromide (C(16)H(33)(CH(3))(2)N(+)-(CH(2))(6)-N(+)(CH(3))(2)C(16)H(33)·2Br(-) designated as G6 and cyclodextrins, was used to refold guanidinium chloride (GdCl) denatured BSA in the artificial chaperone assisted two step method. The single chain cationic surfactant cetyltrimethylammonium bromide (CTAB) was used for comparative studies. The studies were carried out in an aqueous medium at pH 7.0 using circular dichroism, dynamic light scattering and ANS binding studies. The denatured BSA was found to get refolded by very small concentrations of gemini surfactant at which the single chain counterpart was found to be ineffective. Different from the single chain surfactant, the gemini surfactants exhibit much stronger electrostatic and hydrophobic interactions with the protein and are thus effective at much lower concentrations. Based on the present study it is expected that gemini surfactants may prove useful in the protein refolding operations and may thus be effectively employed to circumvent the problem of misfolding and aggregation.

Effects of surfactant micelles on solubilization and DPPH radical scavenging activity of Rutin.

The interaction of the antioxidant Rutin with the radical DPPH (2,2-diphenyl-1-picrylhydrazyl) in presence of cationic (CTAB, TTAB, DTAB), non-ionic (Brij78, Brij58, Brij35), anionic (SDS) and mixed surfactant systems (CTAB-Brij58, DTAB-Brij35, SDS-Brij35) has been followed by spectrophotometric and tensiometric methods to evaluate the DPPH radical scavenging activity (RSA) of Rutin in these model self-assembled structures. The results show that the solubilization capacity of various single surfactant systems for both DPPH as well as Rutin followed the order cationics > non-ionics > anionic. The radical scavenging activity of Rutin in the solubilized form was higher within ionic micelles than in non-ionic micelles. However, the antioxidant exhibited enhanced activity for the radical in mixed cationic-non-ionic micelles compared with any of the single component micelles. In contrast, anionic-non-ionic mixed micelles modulated the activity of Rutin in-between that seen for pure anionic and non-ionic micelles only.

Effect of spacer length of alkanediyl-alpha,omega-bis(dimethylcetylammonium bromide) gemini homologues on the interfacial and physicochemical properties of BSA.

The interactions of bovine serum albumin (BSA) with cationic gemini surfactants alkanediyl-alpha,omega-bis(dimethylcetylammonium bromide) (designated as C(16)C(s)C(16)Br(2), s=4, 5, and 6) and single chain surfactant cetyltrimethylammonium bromide (CTAB) have been investigated with tensiometry, Rayleigh's scattering, fluorescence spectroscopy, and circular dichroism at physiological pH and 25 degrees C. The results of the multi-technique approach showed that the gemini surfactants interact more efficiently with the proteins than their conventional single chain counterparts and their efficiency increases with decrease in the length of the spacer. The saturation in interfacial tension occurred at a lower concentration in presence of BSA compared to CMC of the surfactants in absence of BSA and the concentration of gemini surfactants corresponding to interfacial saturation decreases with decrease in the spacer length. Fluorescence and circular dichroism spectroscopy results revealed increase in unfolding of BSA with decrease in spacer length of gemini surfactants.

Interaction of bovine serum albumin with cationic single chain+nonionic and cationic gemini+nonionic binary surfactant mixtures.

The interaction of bovine serum albumin (BSA) with cetyltrimethylammonium bromide (CTAB), C(16)C(4)C(16)Br(2), Brij58, and their binary mixtures has been studied using tensiometry, spectrofluorometry, and circular dichroism at physiological pH and 25 degrees C. The tensiometric profiles of CTAB and C(16)C(4)C(16)Br(2) in the presence of BSA exhibit a single break at a lower surfactant concentration termed as C(1) (concentration corresponding to saturation of the interface) compared to their critical micelle concentration (CMC) in the buffered solution. However, for Brij58, CTAB+Brij58, and C(16)C(4)C(16)Br(2)+Brij58, two breaks were observed, first at the critical aggregation concentration (CAC), corresponding to onset of interaction with BSA and the second at C(1) corresponding to saturation of the interface. The interaction of CTAB+Brij58 and C(16)C(4)C(16)Br(2)+Brij58 mixtures with the BSA solution is discussed in terms of competition between surfactant-surfactant and surfactant-BSA interactions. CTAB+Brij58 and C(16)C(4)C(16)Br(2)+Brij58 mixtures show nonideality with respect to mixed micelle formation, which is reflected in their interaction with the BSA. The interaction of CTAB+Brij58 with BSA decreases with increase in the mole fraction of CTAB in the mixture, whereas in C(16)C(4)C(16)Br(2)+Brij58 the reverse is the case. The results of the present study may prove fruitful in optimizing the properties of surfactant-protein mixtures relevant for many formulations.

Effect of surfactant mixing on partitioning of model hydrophobic drug, naproxen, between aqueous and micellar phases.

Mixed surfactants may improve the performance of surfactant-enhanced solubilization of drugs and thus can serve as the tool for increased bioavalaibility, controlled drug release, and targeted delivery. Solubilization of Naproxen by micellar solutions at 25 degrees C using single and mixed surfactant systems was measured and compared. Solubilization capacity determined with spectrophotometry and tensiometry has been quantified in terms of molar solubilization ratio, micelle-water partition coefficient, and locus of solubilization. Cationic surfactants exhibited higher solubilization capacity than nonionics and anionics, the efficiency increasing with chain length. Mixing effect of surfactants on mixed micelle formation and solubilization efficiency has been discussed in light of regular solution approximation (RSA). Equimolar cationic-nonionic surfactant combinations showed better solubilization capacity than pure cationics or nonionics, which, in general, increased with increase in hydrophobic chain length. Equimolar cationic-nonionic-nonionic ternary surfactant systems exhibited intermediate solubilization efficiency between their single and binary counterparts. Use of RSA has been extended, with fair success, to predict the partition coefficient of ternary surfactant systems using data from binary mixtures. The theoretical micelle-water partition coefficients calculated from the geometric mean equation compared well with experimental values. Locus of solubilization of NAP in different micellar solutions was probed by UV-visible spectroscopy.

Micellization and interfacial behavior of binary and ternary mixtures of model cationic and nonionic surfactants in aqueous NaCl medium.

Mixed micelle formation and interfacial properties of aqueous binary and ternary combinations of hexadecyltrimethylammonium bromide (C(16)Br), hexadecylbenzyldimethylammonium chloride (C(16)BzCl) and polyoxyethylene (20) cetyl ether (Brij58) at 25 degrees C in 30 mM aqueous NaCl have been studied in detail employing tensiometric and fluorimetric techniques. The micellar and adsorption characteristics like composition, activity coefficients, mutual interaction parameters and free energy of micellization have been estimated using the theoretical approaches of Clint, Rosen, Rubingh, Blankschtein et al., Rubingh-Holland and Maeda. A comprehensive account of the comparative performance of these models on the selected cationic-cationic-nonionic surfactant mixtures at constant ionic strength has been presented. The Blankschtein model predicted lower synergism than from Rubingh's method because it neglects the contribution due to steric interaction between surfactant head groups of different sizes and charges. Free energy of micellization calculated using Maeda's approach, which employs interaction parameter and micellar mole fraction from Rubingh's model as inputs, shows good correlation with that calculated from commonly used phase separation model. The present study also reveals that the modified Rubingh-Holland method along with the Rosen's model can be applied to analyze the interfacial characteristics of ternary surfactant mixtures with a fair degree of success thereby widening the domain of applicability of this model.

Mixed micelle formation and solubilization behavior toward polycyclic aromatic hydrocarbons of binary and ternary cationic-nonionic surfactant mixtures.

Water solubility enhancements of polycyclic aromatic hydrocarbons (PAHs), viz., naphthalene, anthracene and pyrene, by micellar solutions at 25 degrees C using two series of surfactants, each involving two cationic and one nonionic surfactant in their single as well as equimolar binary and ternary mixed states, were measured and compared. The first series was composed of three surfactants, benzylhexadecyldimethylammonium chloride (C16BzCl), hexadecyltrimethylammonium bromide (C16Br), and polyoxyethylene(20)mono-n-hexadecyl ether (Brij-58) with a 16-carbon (C16) hydrophobic chain; the second series consisted of dodecyltrimethylammonium bromide (C12Br), dodecylethyldimethylammonium bromide (C12EBr), and polyoxyethylene(4)mono-n-dodecyl ether (Brij-30) with a 12-carbon (C12) chain. Solubilization capacity has been quantified in terms of the molar solubilization ratio, the micelle-water partition coefficient, the first stepwise association constant between solubilizate monomer and vacant micelle, and the average number of solubilizate molecules per micelle, determined employing spectrophoto-, tensio-, and flourimetric techniques. Cationic surfactants exhibited lesser solubilization capacity than nonionics in each series of surfactants with higher efficiency in the C16 series compared to the C12 series. Increase in hydrophobicity of head groups of cationics by incorporation of ethyl or benzyl groups enhanced their solubilization capacity. The mixing effect of surfactants on mixed micelle formation and solubilization efficiency has been discussed in light of the regular solution approximation (RSA). Cationic-nonionic binary combinations showed better solubilization capacity than pure cationics, nonionics, or cationic-cationic mixtures, which, in general, showed increase with increased hydrophobicity of PAHs. Equimolar cationic-cationic-nonionic ternary surfactant systems showed lower solubilization efficiency than their binary cationic-nonionic counterparts but higher than cationic-cationic ones. In addition, use of RSA has been extended, with fair success, to predict partition coefficients of ternary surfactant systems using data of binary surfactants systems. Mixed surfactants may improve the performance of surfactant-enhanced remediation of soils and sediments by decreasing the applied surfactant level and thus remediation cost.