Kinetic study on effect of novel cationic dimeric surfactants for the cleavage of carboxylate ester

Kinetic study has been performed to understand the reactivity of novel cationic gemini surfactants viz. alkanediyl‐α,ω‐bis(hydroxyethylmethylhexadecylammonium bromide) C₁₆‐s‐C₁₆ MEA, 2Br^? (where s = 4, 6) in the cleavage of p‐nitrophenyl benzoate (PNPB). Novel cationic gemini C₁₆‐s‐C₁₆ MEA, 2Br^? surfactants are efficient in promoting PNPB cleavage in presence of butane 2,3‐dione monoximate and N‐phenylbenzohydroxamate ions. Model calculation revealed that the higher catalytic effect of ethanol moiety of gemini surfactants (C₁₆H₃₃N⁺ C₂H₄OH CH₃ (CH₂)_S N⁺ C₂H₄OH CH₃C₁₆H₃₃, 2Br^?, s = 4, 6) is due to their higher binding capacity toward substrate. This is in line with finding that binding constants for novel series of cationic gemini surfactants are higher than conventional cationic gemini (C₁₆H₃₃N⁺(CH₃)₂(CH₂)_SN⁺(CH₃)₂C₁₆H₃₃, 2Br^?, s = 10, 12), cetyldimethylethanolammonium bromide and zwitterionic surfactants, i.e. C_nH_2n+1N⁺Me₂ (CH₂)₃ SO₃^? (n = 10; SB3‐10). The fitting of kinetic data was analyzed by the pseudophase model. Copyright © 2013 John Wiley & Sons, Ltd.     

Comparative nucleophilic reactivities in carboxylate,phosphinate, and thiophosphate esters cleavage

Nucleophilic substitution reaction of p‐nitrophenyl acetate (PNPA), p‐nitrophenyldiphenyl phosphinate, and pesticide parathion with different α‐nucleophiles [I] have been studied at 27 °C in different pH in the presence of a novel cationic surfactant. The kinetic study was performed spectrophotometrically under pseudo‐first order conditions with the α‐nucleophile in excess. The pK_a of nucleophiles have also been determined by kinetic method. In the presence of surfactant, the rate constant increased with increasing surfactant concentration up to a limiting value. This behavior has been analyzed in quantitative terms on the basis of pseudo‐phase model of micellar catalysis. Finally the nucleophilic reactivity of hydroxamate ions has been compared with other α‐nucleophiles, like oxime, hydroxybenzotriazole, and 2‐iodosobenzoic acid (IBA). The order of cleavage of electrophilic centers, that is, C?O, P?O, and P?S have also been discussed. Copyright © 2008 John Wiley & Sons, Ltd.     

The lamellar and sponge phases of dilute surfactant systems: Structures and defects at equilibrium and under shear

We report on the physical properties of swollen solutions of the amphiphilic molecules of cetylpyridinium chloride and hexanol in brine. A remarkable characteristic of this system is the existence of a crossover between dilute and less dilute solutions, in the lamellar phase and the sponge phase, with some interesting consequences for the theory of membranes.     

Theoretical studies on the hydrogen abstraction reactions of methyl esters with HO2 radical and the following β‐scission reactions

Unsaturated fatty acid methyl esters are ubiquitous in biodiesel fuels. The C = C double bond greatly affects the combustion characteristics of biodiesel, especially its ignition behavior at low temperatures. In this work, we report detailed theoretical study on the mechanism and kinetics of the hydrogen abstraction reactions of linear unsaturated C6 methyl esters with hydroperoxy radical (HO₂), which play a critical role in the low‐temperature combustion of biodiesel. Reaction profiles are obtained via intrinsic reaction coordinate (IRC) analysis including the formation of reactant complexes and product complexes at the entrance and exit channels, respectively. The potential energy surfaces are explored at the CBS‐QB3 level. The following β‐scission reactions of the forming radicals are also investigated at the same level of theory. The high‐pressure limit rate constants for all the reactions in the temperature range from 500 to 2000 K are calculated via conventional transition‐state theory with quantum tunneling effect and fitted to the modified Arrhenius expression.     

Interplay of surface morphology, strain relief, and surface stress during surfactant mediated epitaxy of Ge on Si

Lattice-mismatch-induced surface or film stress has significant influence on the morphology of heteroepitaxial films. This is demonstrated using Sb surfactant-mediated epitaxy of Ge on Si(111). The surfactant forces a two-dimensional growth of a continous Ge film instead of islanding. Two qualitatively different growth regimes are observed. Elastic relaxation: Prior to the generation of strain-relieving defects the Ge film grows pseudomorphically with the Si lattice constant and is under strong compressive stress. The Ge film relieves strain by forming a rough surface on a nm scale which allows partial elastic relaxation towards the Ge bulk lattice constant. The unfavorable increase of surface area is outbalanced by the large decrease of strain energy. The change of film stress and surface morphology is monitored in situ during deposition at elevated temperature with surface stress-induced optical deflection and high-resolution spot profile analysis low-energy electron diffraction. Plastic relaxation: After a critical thickness the generation of dislocations is initiated. The rough phase acts as a nucleation center for dislocations. On Si(111) those misfit dislocations are arranged in a threefold quasi periodic array at the interface that accommodate exactly the different lattice constants of Ge and Si. Received: 1 April 1999 / Accepted: 17 August 1999 / Published online: 6 October 1999     

Kinetics,mechanism and thermodynamics of reactions of CH3NHNH2 with OOH

Reactions between CH₃NHNH₂ and OOH radical were studied using computational methods. The activation energies (E_a) and Gibbs free energies of activation (ΔG^#) were calculated at the MP2 and B3LYP levels of theory. The calculated activation energies of the hydrogen abstraction reactions were less than 100 kJ/mol and those for the substitution reactions were about 150–250 kJ/mol. The calculated activation energies for the intra-molecular hydrogen transfer reactions in CH₃NHNH, CH₂NNH₂ and CH₃NN molecules were 210–250 kJ/mol. Catalytic effect of the water molecule on the intra-molecular hydrogen transfer reactions was studied. It was found that the water molecule decreases the activation energies by about 70–100 kJ/mol. Rate constants of the reactions were calculated using transition state theory in the temperature range of 298–2000 K. Consecutive hydrogen abstraction reactions from CH₃NHNH₂ led to the formation of CH₂NN, which was a very stable molecule.     

Ultrasonication assisted and surfactant mediated synergistic approach for synthesis of calcium sulfate nano-dendrites

Calcium sulfate (CaSO₄) nano-dendrimers were fabricated successfully via ultrasonic irradiation method using calcium chloride [CaCl₂] and ammonium per sulfate [(NH₄)₂SO₄] as precursors in aqueous solution by using cetyl trimethyl ammonium bromide (CTAB) as chemical surfactants. Diffusion-induced branching growth mechanism (DIBGM), influenced with the action of head-group and hydrocarbon chain effect of cationic surfactants, was the backbone in the formation of CaSO₄ nano-dendrites. Fourier Transform Infra-red Spectroscopy (FTIR), X-Ray powder Diffraction (XRD), Atomic Emission Spectroscopy (AES), Selected Area Electron Diffraction (SAED), Field-Emission Scanning Electron Microscopy (FE-SEM), Energy-Dispersive Spectroscopy (EDS), Dynamic Light Spectroscopy (DLS) and BET surface area analyzer were used to characterize the products. Results obtained were compared with conventional stirring method that proved the superiority of sonication method to obtain well-crystalline nanostructures. Also, surfactant concentration, sonication frequency and time were noticed as the critical factors to generate such absolute morphologies at nano-crystalline size.     

Preparation of onium salts of a reduced anthracenone crown ether macrocycle: a reactivity series involving pyridine,phosphine, thiophene,nitrile and primary amide nucleophiles

Reaction of mineral acids with a cyclic macromolecule containing a secondary alcohol produces ammonium, phosphonium, thiophene, and amide adducts via a carbocation intermediate. X‐ray crystallography confirms the structures of the products, including those when two competing nucleophiles are present. A reactivity series that mirrors the nucleophilicity index, where reactivity decreases in the order thiophene > pyridine > primary amides > alkyl nitriles >> aromatic nitriles (unreactive), results. Addition of metal ions to ammonium adducts dissolved in acetonitrile produces secondary amides via the Ritter amide synthesis. Copyright © 2012 John Wiley & Sons, Ltd.     

Microstructural and electrochromic properties of tungsten oxide thin films produced by surfactant mediated electrodeposition

By electrochemically controlling the structure of the surface aggregates, the grain microstructure has been optimized to yield mesoporous thin films of tungsten oxide (WO₃) at the electrode-electrolyte interface in a peroxotungstate sol in the presence of a structure-directing agent (Triton) at room temperature. Apart from the dominant ultrafine nanocrystallites and pores (5-10 nm), well-developed abutting grains (25-100 nm) and nanofibrils also constitute an integral part of the film matrix. X-ray photoemission spectra reveal the as-deposited film (WO_3−x) to be constituted by a high proportion of W⁶⁺ states with a low oxygen deficiency (x = 0.02). A relatively high W⁵⁺ content in the film, upon intercalation of 18 mC cm⁻² charge translates into a large coloring efficiency (η_VIS ∼ 70 cm² C⁻¹) and transmission modulation. At a lithium intercalation level of 22 mC cm⁻², in addition to W⁵⁺ and W⁶⁺ states, the film also comprises of W⁴⁺ states. The extremely fast color-bleach kinetics (3 and 2 s, respectively, for a 50% change in transmittance) shown by the as-deposited WO₃ film are repercussions of the mesopore morphology, the multiple nanostructures and the sixfold channels of its hexagonal modification. The film shows a high cycling stability as the switching times do not show any significant decline even after 3500 repetitive cycles. Coloration efficiency over the solar and photopic regions and current density for lithium intercalation for the as-deposited film are superior to that observed for the films annealed at 100, 250 and 500 °C. The abysmal electrochromic response of the annealed films is a consequence of surface defects like cracks and uncontrolled densification and pore shrinkage.     

Diastereoselectivity and kinetics of hetero diels-alder reactions under high pressure

Abstract

The Hetero Diels-Alder reaction of enamino ketones and ethyl vinyl ether to give dihydropyrans is studied in different solutions under pressure up to 7 kbar. The kinetics is measured via on-line FT IR spectroscopy. The cycloaddition shows a remarkable pressure dependent increase in diastereo-selectivity. For the difference in activation volumes referring to the reaction to the two diastereomers, values up to 5.9 ± 0.5 cm³/mol are observed. The ratio of cis and trans diastereomers can be improved by almost one order of magnitude by changing pressure and temperature from 1 bar and 90 °C to 6 kbar and 0.5 °C.     

On the preparation, microscopic investigation and application of ISCOMs

ISCOM matrices constitute colloidal structures formed from Quillaja saponins, cholesterol and phospholipid. Addition of protein antigens to these matrices leads to the formation of ISCOMs. In this review we report on microscopic investigations of ISCOM matrices and ISCOMs as well as related colloidal structures, such as helices, worm-like micelles, ring-like micelles, and lamellae structures. We briefly outline the immunologic basis for the use of ISCOMs as vaccine delivery systems, and describe the various methods to form ISCOMs. Negative staining transmission electron micrographs of all colloidal structures are presented and described. On the basis of our microscopic investigations, different formation mechanisms of ISCOMS are discussed.     

Preparation and characterisation of CoS2 nanomaterial in aqueous cationic surfactant medium of cetyltrimethylammonium bromide (CTAB)

Cobalt disulfide is an important nanomaterial in the field of material chemistry due to its interesting catalytic and electromagnetic properties. We herein report the simple solution phase preparation of nanoparticles of cobalt disulfide in micellar medium of cationic surfactant cetyltrimethylammonium bromide (CTAB) and also by way of capping with thiophenol. The product has been characterized using spectroscopic and electron microscopic and magnetic moment measurements. The presence of disulfide bond is clearly evident from the 480 cm⁻¹ peak in the infrared spectrum. The thiol passivated particles prepared in aqueous and ethanol medium has been found to have different compositions as observed from the ESIMS study.     

Structure and reactivity in the hydrolyses of aliphatic carboxylic acid esters and chlorides

For hexanoic acid and its seven isomers, relative rates have been determined for acid catalysed esterification with methanol, and compared with those for saponification of the methyl esters. A good correlation between logarithms of relative rates for the two reactions is obtained, and it is suggested that the eight isomers provide a test set of compounds in which steric effects alone act on reactivity at the acyl carbon. A full set of steric parameters ( values) are presented. Rates of solvolyses of the acid chlorides of the isomers have been determined conductometrically in 3:1 wt:wt acetonitrile water. Logarithms of relative rates show a poor correlation with , and, taking into account the solvent dependence of the rates, the pattern excludes both rate‐limiting formation of a tetrahedral intermediate and rate‐limiting dissociation of chloride to form acylium ions. The remaining possibilities, a concerted process (A_ND) and rapid reversible formation of a hydrate followed by rate‐limiting dissociation of chloride (A_N + D) are considered. Copyright © 2007 John Wiley & Sons, Ltd.     

Quantum chemical and RRKM calculations of reactions in the H/S/O system

Quantum chemical calculations at the MRCI/aug-cc-pV5Z level are used to describe the conversions between HSO, HOS, H + SO, S + OH and O + SH on the doublet H/S/O potential energy surface. An RRKM analysis of this multiple-well system was carried out in the temperature range 300-2000 K between 0.1 and 10 atm. At these pressures, the stabilization reaction H + SO → HSO or HOS is at the low pressure limit, and stabilization from S + OH and O + SH was not detected. The reactions S + OH → H + SO and O + SH → H + SO were found to be barrierless and very fast at room temperature (4 × 10¹⁴ and 1.5 × 10¹⁴ cm³ mol⁻¹ s⁻¹, respectively). The reaction channel O + SH → S + OH is two orders of magnitude slower than the more exothermic O + SH → H + SO reaction, although a second pathway involving direct H-abstraction (O + SH → S + OH) on the quartet surface appears as a minor channel at high temperatures.     

From Bulk to Nanoparticles: An Overview of Antiviral Materials,Its Mechanisms,and Applications

Infectious diseases caused by viruses are a global health concern and have become prominent in light of the recent COVID-19 pandemic. Considering the limitations of drugs and prophylactic methods used in current medicine, antiviral materials are a useful strategy in preventing the spread of viruses and enhancing treatment efficiency. Thus, this review highlights the state-of-the-art antiviral materials, describes the scientific landscape of the primary antiviral materials used based on bibliometric analysis, presents their mechanisms of action, and discusses their clinical applications. The mechanisms of action underlying the broad-spectrum antiviral properties of metals, ceramics, polymers, and composites are also discussed. Polyanions, polycations, oxides, and metal-based materials, from bulk to nanoparticles, have good potential in antiviral applications that may help prepare the world for future viral breakouts.     

Physical properties,thermal stability,and glass transition temperature of multi-walled carbon nanotube/polypyrrole nanocomposites

Polypyrrole (PPy) was synthesized and doped with 1, 2, 4, and 8?wt.% of functionalized multi-wall carbon nanotubes (MWCNTs) by in situ polymerization. TGA/DTA analysis of nanocomposites revealed an increase in thermal stability by increasing the CNTs wt.%. Measurement of electrical resistivity showed a reduction in the resistivity of the composites at all temperatures. The glass transition temperature (T_g) of the samples was measured using electrical resistivity measurements and showed that by increasing the amount of functionalized MWCNTs in PPy, its T_g was increased. Temperature dependence of resistivity of pressed pure PPy showed that by increasing the pelletization pressure, the T_g increased. Also the hardness of nanocomposites was increased by increasing the MWCNTs wt.%.     

Network structure of molybdenum lead phosphate glasses: Infrared spectra and constants of elasticity

Molybdenum lead phosphate glasses doped with La₂O₃ of the system xMoO₃-5La₂O₃-50P₂O₅-(45−x)PbO, with 0≤x≤25 mol%, have been synthesized and studied by FTIR, ultrasonic and differential scanning calorimetry (DSC) in order to investigate the role of MoO₃ content on their atomic structure. The constants of elasticity and Debye temperatures of the glasses have been investigated using sound velocity measurements at 4 MHz. According to the IR analysis, the vibrations of the phosphate structural units are shifted towards higher wavenumbers associated with the formation of bridging oxygens. The change in density with MoO₃ content reveals that the molybdate units are less dense than the lead units. The observed compositional dependence of the constants of elasticity is interpreted in terms of the effect of MoO₃ on the different phosphate bonds. It is assumed that MoO₃ plays the role of a former by increasing the ultrasonic velocity and the constants of elasticity of the phosphate glasses.     

Spectral-Kinetic Characteristics of Pyrene Fluorescence in Model Systems and Membranes of Etioplasts

The decay kinetics parameters of monomer and excimer fluorescence of pyrene in artificial galactolipid protein-free micelles and membranes of prolamellar bodies (PLB) of etioplasts have been determined. A complex law of probe fluorescence decay in artificial and native membranes has been discovered. It has been found that the addition of protochlorophyllide (Pd) to lipid micelles led to a considerable reduction in the lifetime of the long-lived component of the fluorescence-decay kinetics of the monomer form of pyrene (₂) and to the appearance of luminescence in the region of 640 nm in the stationary spectra of fluorescence at excitation of the pyrene molecules present in the bilayer. In native membranes of etioplasts, the monomer duration ₂ did not depend on the pigment content and the Pd fluorescence upon excitation through pyrene was absent. The membranes of etioplasts and the pigment-containing artificial micelles did not differ in the ₂ value of the excimer. They only differed in the contribution of the long-lived component to the total fluorescence (low in native membranes). The pigment-protein interaction in the etioplast membranes and the absence from them of pigment directly associated with lipids are discussed.     

Substituent effect on structure and surface activity of N‐methylpyridinium salts studied by FT‐IR,FT‐RS,SERS and DFT calculations

The substituent effect on structure and surface activity of mono‐ and disubstituted N‐methylpyridinium salts was investigated by means of Raman, infrared and surface‐enhanced Raman spectroscopy (SERS). The significant differences observed in Raman and infrared spectra have been correlated with marker bands assigned to in‐plane and out‐of‐plane vibrations, respectively. This vibrational analysis, complemented by quantum chemical calculations (B3LYP/6‐311++G(d,p)) was a basis for investigation of the surface activity of the studied compounds. Significant differences in their SERS spectra related to the enhancement mechanism and adsorbate orientation have been observed and analyzed. Copyright © 2012 John Wiley & Sons, Ltd.     

A novel probe for determination of electrical surface potential of surfactant micelles: N,N'‐di‐n‐octadecylrhodamine

The peculiarities of the structure of the fluorescent dye N,N'‐di‐n‐octadecylrhodamine advantage its using as an interfacial acid–base probe in aqueous micellar solution of colloidal surfactants. Two long hydrocarbon tails of the dye provide similar orientation of both cation and zwitterion on the micelle/water interface, with the ionizing group COOH exposed to the Stern region in all the systems studied. Further, the charge type of the acid–base couple, A⁺B^±, ensures similar values of the ‘intrinsic’ contribution, pK, to the ‘apparent’ pK value in micelles of different surfactants. This makes the indicator suitable for determination of electrical surface potentials, Ψ. The pKs have been obtained in cationic, anionic, zwitterionic, and nonionic surfactant systems, at various salt background. In total 17 systems were studied. At bulk counterion concentration of ca. 0.05 M, the pK values vary from 2.14 ± 0.07 in n–C₁₈H₃₇N(CH₃)Cl^– micelles to 5.48 ± 0.06 in n–C₁₆H₃₃OSONa⁺ micelles. The Ψ values, corresponding to the Stern region of micelles, have been evaluated as Ψ = 59.16 pK–pK for T = 298.15 K. The pK parameter was equated to the average value of 4.23 in nonionic surfactants (4.12–4.32, depending on the surfactant type). For cetyltrimethylammonium bromide and sodium n‐dodecylsulfate micelles, the Ψ values (±(7–11) mV) appeared to be +118 mV and at bulk Br^? concentration 0.019 M and ?76 mV at bulk Na⁺ concentration 0.020 M, respectively. This satisfactorily agrees with the theoretical values +111 and ?84 mV, estimated using the Oshima, Healy, and White equation for these well‐defined colloidal systems. Finally, not only absorption, but also fluorescence spectra display the same response to changes in bulk pH. Copyright © 2007 John Wiley & Sons, Ltd.