A Comprehensive Study on the Synthesis and Micellization of Disymmetric Gemini Imidazolium Surfactants

Two groups of disymmetric Gemini imidazolium surfactants, [C₁₄C₄C _m im]Br₂ (m = 10, 12, 14) and [C _m C₄C _n im]Br₂ (m + n = 24, m = 12, 14, 16, 18) surfactants, were synthesized and their structures were confirmed by ¹H NMR and ESI–MS spectroscopy. Their adsorption at the air/water interface, thermodynamic parameters and aggregation behavior were explored by means of surface tension, electrical conductivity and steady-state fluorescence. A series of surface activity parameters, including cmc, γ _cmc, π _cmc, pC ₂₀, cmc/C ₂₀, Γ _max and A _min, were obtained from surface tension measurements. The results revealed that the overall hydrophobic chain length (N _c) for [C₁₄C₄C _m im]Br₂ and the disymmetry (m/n) for [C _m C₄C _n im]Br₂ had a significant effect on the surface activity. The cmc values decreased with an increase of N _c or m/n. The thermodynamic parameters of micellization (ΔG _m ^θ , ΔH _m ^θ , ΔS _m ^θ ) derived from the electrical conductivity indicated that the micellization process of [C₁₄C₄C _m im]Br₂ and [C _m C₄C _n im]Br₂ was entropy-driven at different temperatures, but the contribution of ΔH _m ^θ to ΔG _m ^θ was enhanced by increasing N _c or m/n. The micropolarity and micellar aggregation number (N _agg) were estimated by steady-state fluorescence measurements. The results showed that the surfactant with higher N _c or m/n can form larger micelles, due to a tighter micellar structure.     

Mixed Micellization Study of Alkyltrimethylammonium and Alkyltriphenylphosphonium Bromides in Aqueous Solution

Mixed micellization study of cationic surfactants viz. alkyltrimethylammonium bromides (C_nTAB) and alkyltriphenylphosphonium bromides (C_nTPPB) with similar hydrophobic groups (C₁₂-, C₁₄-, and C₁₆-) was performed using tensiometry and UV–visible light spectrophotometry techniques. Critical micelle concentration (CMC) values of the single and binary surfactant mixtures were obtained from a plot of surface tension versus the logarithm of surfactant concentration (C _s). The degree of synergy and various mixed micelle parameters like interaction parameter (β), activity coefficients (f ^m ) and interfacial parameters like surface pressure (π _CMC), packing parameter (P), surface excess concentration (Г _max), surface tension at the CMC (γ _CMC), and minimum area per molecule (A _min) were evaluated using the regular solution theory (RST). Thermodynamic parameters were calculated using several proposed models which suggest the mixed micellar system to be more thermodynamically stable than their respective individual components. In addition, a dye solubilization study was performed using a spectrophotometric method to validate the CMC data obtained from tensiometric method. Conductometric measurements were also carried out for the mixture of C₁₂TAB + C₁₂TPPB only as it showed a more negative β, indicating a higher degree of synergism.     

Ion conducting nano-composite polymer electrolytes: synthesis and ion transport characterization

Synthesis and ion transport characterization of a new K⁺-ion conducting nano-composite polymer electrolytes (NCPEs): (1?x) [70PEO:30KBr] + x SiO₂, where 0 < x < 20 wt%, are reported. The present NCPEs have been cast using a novel hot-press technique in place of the traditional solution cast method. The conventional solid polymer electrolyte (SPE) composition: (70PEO:30KBr), identified as the highest conducting composition at room temperature, has been used as first-phase host matrix and nano-size (~8 nm) particles of SiO₂ as second-phase dispersoid. As a consequence of dispersal of SiO₂ in SPE host, two orders of conductivity enhancement have been observed in NCPE composition: [95(70PEO:30KBr) + 5SiO₂] and this has been referred to as optimum conducting composition (OCC). The polymer-salt/nano-filler SiO₂ complexation and thermal properties characterization were done with the help of XRD, FTIR, SEM, DSC and TGA studies. The ion transport behavior in NCPEs have been discussed on the basis of experimental measurements on some basic ionic parameters, viz. conductivity (σ), ionic mobility (μ), mobile ion concentration (n), ionic transference number (t _ion), etc. The temperature-dependent conductivity studies of NCPE OCC have been done and activation energy (E _a) value was determined using log σ?1/T Arrhenius plot.     

Mixed Micellization of Polyoxyethylene (20) Oleyl Ether with Cetylpyridinium Chloride at the Air–Water Interface

Adsorption and micellization behaviour of binary surfactant mixtures containing a nonionic surfactant, polyoxyethylene (20) oleyl ether (C_18-1E₂₀), and a cationic surfactant, cetylpyridinium chloride (CPC), was studied at the air–water interface using the Wilhelmy plate method. A pseudo-phase separation model was used to analyse mixed micellization. A Margules equation with one constant (interaction parameter, β) was fitted to the nonideal behaviour of the mixed surfactant system. This system shows synergism (β = ?6.0) for micellization. The dynamic behaviour and foamability of binary mixtures at the same bulk concentration and at different mole fractions were also studied using drop volume and horizontal impinging jet methods, respectively. It was found that with an increase in the mole fraction of C_18-1E₂₀, the foamability of a mixture increases and t* value decreases.     

Esterification of acrylic acid with ethanol using pervaporation membrane reactor

Esterification of acrylic acid with ethanol was carried out using an in-situ reactor with an integrated pervaporation assembly (IPAE) made of polyvinyl alcohol (PVA) membrane and was compared with a non-integrated (NIE) system. Effect of reaction temperature (T _r ), catalyst loading (C _C ), molar ratios of reactants (MR) and ratio of effective membrane area to unit volume of reaction mixture (S/V _o ) on kinetics of esterification reaction were studied. Conversions achieved in IPAE were found to be distinctly higher than the NIE. The highest conversion of acrylic acid was obtained as 83.3% at T _r =60 °C, M _R =3 : 1, C _C =2% and S/V _o =14.1 m^?1. Equilibrium conversion of acrylic acid in NIE was obtained as 55.1% at 60 °C, 1 : 1 in 7 h, while using IPAE conversion enhances to 67.6%. Esterification of acrylic acid and ethanol with presently studied operating parameters provides a new approach to existing literature reported esterification-pervaporation system.     

Synthesis and Characterization of pH-Responsive Organic–Inorganic Hybrid Material with Excellent Catalytic Activity

Poly(N-isopropylmethacrylamide-co-methacrylic acid) [p(NipAam-Mac)] microgels were synthesized and used as microreactors to fabricate silver nanoparticles. Pure and hybrid microgels were characterized using Ultraviolet–Visible (UV/Vis) spectroscopy, Fourier transform infra-red (FTIR) spectroscopy and transmission electron microscopy (TEM). Catalytic activity of hybrid microgels and mechanism of catalysis by this system was explored using different reaction conditions. At the same temperature, apparent rate constant (k_app) was found to be varied from 0.0414 to 0.7852 min^?1 by increasing the concentration of NaBH₄ from 2.49 to 22.41 mM at constant concentration of substrate and catalyst. However upon extra increase in concentration of NaBH₄ from 22.41 to 37.35 mM reduced the value of k_app to 0.2178 min^?1. Likewise, the value of k_app was found to be increased from 0.1242 to 0.5495 min^?1 with increasing the concentration of 4-nitrophenol [Para-nitrophenol (p-Np)] from 0.063 to 0.079 mM keeping other parameters constant. Further increase in concentration of p-Np caused decline in the value of k_app. Kinetic data reveals that catalytic reduction of p-Np obeys Langmuir–Hinshelwood mechanism and p-Np is converted to p-Ap on the surface of the silver nanoparticles passing through various reaction intermediates.     

Dielectric study of side-chain liquid crystalline polyazomethine/fullerene C<Subscript>60</Subscript> nanocomposite

For side-chain liquid crystalline polyazomethine/fullerene C₆₀ nanocomposite (C₆₀ loading is 0.25 wt%), both real and imaginary components of the dielectric permittivity were investigated in wide regions of temperature and frequency. Analysis of frequency dependent permittivity allowed finding three relaxations (α, β ₁ and β ₂) in the nanocomposite. They were attributed to specific modes of molecular mobility. β-relaxations were described with the Arrhenius equation, whereas α-relaxation was described with the Vogel-Fulcher-Tammann equation. Anti-plasticization effect of the C₆₀ doping was shown to be manifested as an increase of the glass transition temperature of the nanocomposite as compared with that of the neat polymer.     

Mixed Stability and Antimicrobial Properties of Gluconamide-Type Cationic Surfactants

The stability of anionic-cationic surfactant solutions and the antimicrobial properties of novel N,N-dimethyl-N-[3-(gluconamide/lactobionamide)]propyl-N-alkylammonium bromides (CnDGPB and CnDLPB), N-methyl-N-hydroxyethyl group-N-[3-(gluconamide)-propyl]-N-alkylammonium bromide (CnMHGPB) and star-shaped gluconamide-type cationic surfactants N-dodecyl-N,N-bis[(3-d-gluconylamido)propyl]-N-alkylammonium bromide (CnDBGB) were investigated. Mixed stability in combination with sodium n-alkylbenzenesulfonate (LAS) was determined via transmittance; stability is achieved when percent transmittance was greater than 90 %. Transmittance results suggest that these cationic surfactants can form stable solutions with anionic surfactants over a broad concentration range. The inhibition activity of C _n DBGB is the best among the three kinds of glucocationic surfactants. Antimicrobial activity of C₁₂ surfactants was the best, C₁₄ was the second and C₁₀ was the worst. Moreover, antibacterial activity of glucose-based cationic surfactants was greater than lactose-based cationic surfactants.     

Novel amphiphilic temperature responsive graft copolymers PCL-<Emphasis Type="Italic">g</Emphasis>-P(MEO<Subscript>2</Subscript>MA-<Emphasis Type="Italic">co</Emphasis>-OEGMA) via a combination of ROP and ATRP: synthesis,characterization, and sol-gel transition

A series of well-defined novel amphiphilic temperature-responsive graft copolymers containing PCL analogues P(αClεCL-co-εCL) as the hydrophobic backbone, and the hydrophilic side-chain PEG analogues P(MEO₂MA-co-OEGMA), designated as P(αClεCL-co-εCL)-g-P(MEO₂MA-co-OEGMA) have been prepared via a combination of ring-opening polymerization (ROP) and atom transfer radical polymerization (ATRP). The composition and structure of these copolymers were characterized by ¹H NMR and GPC analyses. The self-assembly behaviors of these amphiphilic graft copolymers were investigated by UV transmittance, a fluorescence probe method, dynamic light scattering (DLS) and transmission electron microscopy (TEM) analyses. The results showed that the graft copolymers exhibited the good solubility in water, and was given the low critical temperature (LCST) at 35(±1) °C, which closed to human physiological temperature. The critical micelle concentrations (CMC) of P(αClεCL-co-εCL)-g-P(MEO₂MA-co-OEGMA) in aqueous solution were investigated to be 2.0 × 10^?3, 9.1 × 10^?4 and 1.5 × 10^?3 mg·mL^?1, respectively. The copolymer could self-assemble into sphere-like aggregates in aqueous solution with diverse sizes when changing the environmental temperature. The vial inversion test demonstrated that the graft copolymers could trigger the sol-gel transition which also depended on the temperature.     

Effect of Sodium Carbonate on the Cloud Point in Alkyl Ether/Brine Systems: Apparent Relation with Dynamic Interfacial Tension Minimum

The effect of Na₂CO₃ on the cloud point in Na₂CO₃/surfactant/brine was investigated using two series of nonionic surfactants, C₁₃EO _x and C₁₇EO _x . The cloud point, T _cp, was found to decrease linearly with increasing Na₂CO₃ concentration. This was attributed to Na⁺ and particularly to CO₃ ^2?salting-out effect. The slope a = dTcp/d[Na₂CO₃] became more and more negative as the degree of ethoxylation is increased, suggesting that the higher the number of ethylene oxide (EO) groups the stronger is the cloud point depression for a given increment in Na⁺and CO₃ ^2?ions in solution. This was also illustrated by the linear variation of ΔT _cp = T _cp,0 ? T _cp,[Na2CO3] with the surfactant degree of ethoxylation.     

Enzyme-Catalyzed Synthesis of Monoacylglycerols Citrate: Kinetics and Thermodynamics

The kinetics and thermodynamics of the esterification of citric acid (CA) and monoglycerides (MGs) for citrate esters of monoacylglycerols catalyzed by Novozym 435 in tert-butyl alcohol system was studied in this work. The relationship between initial reaction rate and temperature was established, based on the Arrhenius law. A linear relationship was established between the initial reaction rate and enzyme load up to 3 g/L, which demonstrated that the influence of external mass transfer limitations on the reaction could be eliminated. The reaction kinetics agreed with the Ping-Pong Bi–Bi mechanism with CA inhibition characterized by V _max, K _B, K _A, and K _iA , values of 0.7092 mmol/(min g), 0.0553, 0.0136 and 0.1948 mol/L, respectively. The model was used to simulate the reaction process. The values calculated from the kinetic mode agreed well with the experimental rate data under the different MG and CA concentrations.     

The Effect of Aniline Hydrochloride Hydrotrope on the Phase Behavior of SDS/Water System

The aim of this work was to determine the detailed phase behavior of the sodium dodecyl sulfate/aniline hydrochloride/water system as a function of concentration of sodium dodecyl sulfate (SDS), aniline hydrochloride (AHC) to sodium dodecyl sulfate molar ratio (R = [AHC]/[SDS]) and temperature. Phase behavior information was obtained via polarizing microscopy, differential scanning calorimetry (DSC), cryo-scanning electron microscopy (Cryo-SEM) and oscillatory linear rheological measurements with good agreement among these techniques. It is well known that SDS in water forms spherical micelles at concentrations lower than 40 wt% and temperatures above its Krafft temperature (T _k = 16–21 °C). In this region, the SDS/water system exhibits Newtonian rheological behavior, which is characteristic of spherical micellar solutions. The addition of the hydrotrope, aniline hydrochloride, to SDS aqueous solutions produces a viscosity increase in this system as R augments, and a maximum of about five orders of magnitude was found at R = 0.47 for 5 wt% SDS at 20 °C. Moreover, the system shows a transition from viscous to strong viscoelastic behavior. These changes in the rheological behavior are produced by the transitions from sphere to rodlike micelles, which are induced by the hydrophobicity of AHC causing it to be absorbed into the core and the hydrophilic interface of the micelles, which screens the repulsions between the charged head groups.     

Microbial Conversion of Arachidonic Acid to Arachidonyl Alcohol by a New <Emphasis Type="Italic">Acinetobacter</Emphasis> Species

Arachidonyl alcohol rarely occurs in natural oils. It can be used as a substrate for production of several ether lipids possessing beneficial functions. Although arachidonyl alcohol has been produced on a laboratory scale by the chemical reduction of arachidonic acid, it will be difficult to scale up this process for industrial application. The aim of this study was to develop a new bioprocess for converting arachidonic acid to arachidonyl alcohol. Screening was conducted using 11 wax ester- (esters of fatty acids and fatty alcohols) producing strains reported in our previous study, and a single-cell oil containing arachidonic acid. A new strain, Acinetobacter species N-476-2, most effectively converted arachidonic acid to arachidonyl alcohol, which accumulated inside the cells as a wax ester. GC–MS, FT–IR, and NMR analyses showed that this strain reduced the carboxyl group of 5-cis,8-cis,11-cis,14-cis-arachidonic acid to a hydroxyl group without altering the position or configuration of the double bonds; the product was identified as 5-cis,8-cis,11-cis,14-cis-arachidonyl alcohol. A time-course study of cultivation showed that the amount of arachidonyl alcohol produced by the strain after 4 days was 2.2 mg/mL culture. The bioprocess using Acinetobacter sp. N-476-2 can be applied to the large-scale production of arachidonyl alcohol.     

Purification,Surface Tensions,and Miscibility Gaps of Alkyldimethyl and Alkyldiethylphosphine Oxides

Alkyldimethyl (C _n DMPO) with chain lengths of n = 8 (octyl), 10 (decyl), 12 (dodecyl), and 14 (tetradecyl) as well as alkyldiethyl (C _n DEPO) phosphine oxides with chain lengths of n = 10, 12, and 14 were synthesized and purified to study how the adsorption properties and the location of the miscibility gap of these surfactants depend on the size of the head group and on the length of the alkyl chain. After surfactant purification, the surface tension isotherms were determined from which the cmc, the minimum surface tension σ_cmc, the maximum surface concentration Γ_max, and the minimum surface area A _min were obtained. As expected, for one homologous series, a decrease in the cmc and an increase in Γ_max was observed with increasing alkyl chain length. For two surfactants of the same alkyl chain length, the cmc values of the C _n DEPO surfactants are approximately two times lower than those of the C _n DMPO surfactants. However, the Γ_max values of C _n DEPO are lower than those of C _n DMPO as two ethyl chains are sterically more demanding than two methyl chains. In addition to the adsorption properties, the location of the miscibility gap as a function of the alkyl chain length and the head group size was studied. Its location depends on the total number of carbon atoms and not primarily on the length of the main alkyl chain. This observation reflects the decreasing water solubility which can be tuned by increasing the length of either the main alkyl chain or of the shorter head group chains.     

Optimization of controlled ring-opening polymerization of <Emphasis Type="SmallCaps">l</Emphasis>-lactide to hydroxyl terminated polylactides using zinc acetate catalyst

Hydroxyl terminated polylactide polymers with number of average molecular weights (M _n ) varying from 1625 to 3459 g mol^?1 were synthesized by ring opening bulk polymerization of lactide in the presence of zinc acetate being a potent catalyst. The use of 1,4 butanediol (BDO) initiator leads to hydroxyl terminated polylactides, thus excellent precursors for shape-memory biodegradable polyurethanes. Different reaction conditions employed for the synthesis of hydroxyl terminated polylactide polymers via activated monomer mechanism may result in differences in M _n , percentage mass conversion and percentage degree of crystallinity (%χ _c ) of the product. Influence of process parameters, i.e. catalyst concentration, initiator concentration, reaction temperature and time on characteristics of hydroxyl terminated polylactides was studied. These polymers were characterized by Nuclear Magnetic Resonance (¹H-NMR) spectroscopy, Fourier transforms infrared (FTIR) spectroscopy, gel permeation chromatography (GPC) and X-ray diffraction (XRD) techniques. FTIR and ¹H-NMR confirmed the formation of hydroxyl terminated polylactides. M _n was determined by ¹H-NMR, GPC and end group analysis. %χ _c was calculated from XRD spectra. Maximum mass conversion, M _n and %χ _c were observed at 5 mol% SnOct₂ and 5 mol% BDO concentration. At optimum temperature of 145 °C, these characteristics improved linearly with polymerization time up to 6 h and declined thereafter.     

Synthesis,Surface Activities and Toluene Solubilization by Amine-oxide Gemini Surfactants

A series of amine-oxide gemini surfactants featuring amide groups [N, N’-dimethyl-N, N’-bis(2-alkylamideethyl)-ethylenediamine oxide (alkyl = C₁₁H₂₃, C₁₃H₂₇, C₁₅H₃₁, C₁₇H₃₅)] have been synthesized via a three-step synthetic route, and their chemical structures were confirmed by mass spectra, FTIR and ¹H-NMR spectra. The surface activities of these compounds have been measured. The results show that these synthesized amine-oxide gemini surfactants reduced the surface tension of water to a minimum value of approximately 26.91 mN m^?1 at a concentration of 2.92 × 10^?5mol L^?1. Furthermore, their critical micelle concentration (CMC) values and solubilization of toluene decrease with an increase of the hydrophobic chain length from 12 to 18. Isoelectric point measurements revealed that their pI values range from 4.0 to 10.5.     

Synthesis and properties of amphiphilic thermo-sensitive block copolymers

Octadecyl acrylate (ODA) as hydrophobic monomer and N-isopropylacryamide (NIPAAm) as hydrophilic monomer were chosen to synthetize the thermo-sensitive block copolymers PODA_x-PNIPAAm_y-PODA_x (BAB-type) via reversible-addition-fragmentation chain transfer (RAFT) polymerization, the block copolymers could self-assemble to flower-like micelles in aqueous solution with hydrophobic PODA as the inner core and stabilized by hydrophilic PNIPAAm as the outer shell. The characterizations of the micelles such as surfactivity, thermo-sensitivity, micelle hydrodynamic radius (R _h ) and polydispersity index (PdI) were demonstrated by surface tension technique, UV-Vis, and dynamic light scattering (DLS) measurements, respectively. The longer the hydrophilic chain was, the higher the critical micellization concentration (CMC) would be, and the higher content of the PODA was, the lower the lower critical solution temperature (LCST) would be. The average R _h remained at about 100 nm below LCST, but decreased sharply to about 42 nm and kept constant when reaching and above LCST, which meant the non-aggregation of BAB type block copolymers. The micelle was homogeneous with the small PdI within the range of research. B_0.5mA_24mB_0.5m had the largest capacity to encapsulate lipophilic Sudan Red IV model drugs and the drug loading efficiency was 9.76%.     

Change of the thermal behavior of 55Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> ⋅ 45B<Subscript>2</Subscript>O<Subscript>3</Subscript> glass at annealing close to the vitrification temperature

The characteristic properties of relaxation processes for 55Bi₂O₃ ? 45B₂O₃ glass were described. The pattern of changes of the vitrification temperature (T _g ) is found to be quasi-periodic; the value of the endothermic effect near T _g (ΔC’ _p ) and the difference between the softening point and the vitrification temperature (T _m –T _g ) were determined. The temperature-time parameters of the transition from quasi-periodic to the continuous change of the properties were determined and an explanation of such behavior of the system was offered.     

Synthesis and Characterization of Novel Aryl Alkyl Sulfonates Based on Nonylphenol

A series of nonylphenol-substituted alkyl sulfonates (C _x NPAS, x = 8, 10, 12, 14, 16) with two hydrocarbon chains and two different hydrophilic groups has been synthesized from α-olefins and nonylphenol. The respective products have a “pseudo-gemini” surfactant structure. The structures of the C _x NPAS have been characterized by IR, UV, ¹H nuclear magnetic resonance, electrospray ionization mass spectrometry, and elemental analysis. The effects of carbon chain length of the obtained surfactants on properties such as the critical micelle concentrations (CMC) in aqueous solutions, surface tension at the CMC (γ _CMC), and efficiency of adsorption at the water/air interface (pC ₂₀) have been determined. The γ _CMC of the surfactants first decreased and then increased with increasing length of the carbon chain x, and reached a minimum of 29.25 mN/m at x = 10, which is much lower than that of α-olefin sulfonate (AOS) (33.52 mN/m). The CMC decreased and pC ₂₀ increased with increasing x. The introduction of the hydroxyl group is responsible for multiple molecular conformations at the water/air interface and leads to a greater molecular area A _min and smaller Γ_max than those of AOS.     

Impact of Chain Length on the Catalytic Performance in Hydroisomerization of <Emphasis Type="Italic">n</Emphasis>-Alkanes Over Commercial and Alkaline Treated *BEA Zeolites

The present paper highlights the influence of desilication of nanocrystal *BEA zeolites (CP811 and CP814E) by different alkaline treatments in presence of NaOH alone, NaOH?+?TPABr and NaOH?+?TBAOH, on the catalytic performance in the hydroisomerization reactions of n-alkanes (n-C₁₀, n-C₁₂ and n-C₁₄). The well-balanced catalyst was reached after impregnation of 1.5 wt% of Pt, where the activity and isomers selectivity was seen to be the maximum, knowing that the Pt content effect was studied on the CP811 zeolite catalyst. All the other catalysts were after impregnated by approximately 1.5 wt% of Pt. The improvement of the textural properties by means of desilication was not always accounting for the influence of the catalytic performance of the catalysts, but rather it may be the bifunctional characteristics in charge. The impact of chain length was investigated on the catalysts to study if the presence of the inter- and intracrystalline mesopores would account for better diffusion of larger molecules as, n-C₁₂ and n-C₁₄. It was found on the majority of the catalysts that the activity was high whether the chain length was, but the isomers selectivity was decreasing with chain length except on one catalyst that possesses high textural and bifunctional characteristics. Among the three n-alkanes studied, n-C₁₂ have marked the highest TOF values and lowest selectivity to isomers, a phenomenon attributed to the confinement effect that seems to increase the interaction of n-C₁₂ molecules with the acidic sites of the zeolites, apparently causing their strength to be higher. This effect was pronounced more with n-C₁₂ than the other two n-alkanes.

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