Interaction between two homologues of cationic surface active ionic liquids and the PEO-PPO-PEO triblock copolymers in aqueous solutions

The interaction of nonionic triblock copolymers of poly(ethyleneoxide) (PEO) and poly(propyleneoxide) (PPO) (PEO_nPPO_mPEO_n) with a series of cationic surface-active ionic liquids in aqueous solutions have been investigated. The cationic surface-active ionic liquids include 1-alkyl-3-methylimidazolium bromide (C_nmimBr, n?=?8, 10, 12, 14, 16) and N-alkyl-N-methylpyrrolidinium bromide (C_nMPB, n?=?12, 14, 16). For different polymer-surfactant systems, the critical aggregation surfactant concentration (cac), the surfactant concentration to form free micelles (C _m), and the saturation concentration of surfactant on the polymer chains (C ₂) were determined using isothermal titration microcalorimetry (ITC) and conductivity measurements. The structure of the formed aggregates depended strongly on the hydrophobicity of the surfactant and the ratio of polymer/surfactant concentration. For C₈mimBr, there were not any micelle-like surfactant?Cpolymer clusters detected in the solution, and only micelles appeared. For other surfactants, the polymer?Csurfactant aggregates were formed in the solution, which was verified by the appearance of a broad endothermic peak in the ITC thermograms. The intensity of polymer?Csurfactant interaction increased with the hydrophobicity of the surfactants and the polymers but was not affected by the surfactant headgroups.     

Surface adsorption and micelle formation of surface active ionic liquids in aqueous solution

Aqueous solutions of three kinds of surface active ionic liquids composed of the 1-alkyl-3-methylimidazolium cation have been investigated by means of surface tension and electrical conductivity measurements at room temperature (298 K). The surface tension measurements provided a series of parameters, including critical micelle concentration (cmc), surface tension at the cmc (gammacmc), adsorption efficiency (pC20), and effectiveness of surface tension reduction (Picmc). In addition, with application of the Gibbs adsorption isotherm, maximum surface excess concentration (Gammamax) and minimum surface area/molecule (Amin) at the air-water interface were estimated. The effect of sodium halides, NaCl, NaBr, and NaI, on the surface activity was also investigated. It was found that both the pC20 and the Picmc were rather larger than those reported for traditional ionic surfactants and the cmc values were somewhat lower than those for typical cationic surfactants, alkyltrimethylammonium bromides, and comparable to typical anionic surfactants, sodium alkyl sulfates. These results demonstrate that the surface activity of long-chained imidazolium IL is somewhat superior to that of conventional ionic surfactants.     

Microwave-assisted separation of ionic liquids from aqueous solution of ionic liquids

Microwave-assisted separation has been applied to recover ionic liquid (IL) from its aqueous solution as an efficient method with respect to time and energy compared to the conventional vacuum distillation. Hydrophilic ILs such as 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim][BF(4)]), 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([Bmim][TfO]) and 1-ethyl-3-methylimidazolium methylsulfate ([Emim][MS]) could be recovered in 6 min from the mixture of ILs and water (1:1, w/w) under microwave irradiation at constant power of 10 W while it took at least 240 min to obtain ILs containing same water content (less than 0.5 wt%) by conventional vacuum oven at 363.15 K with 90 kPa of vacuum pressure. Energy consumptions per gram of evaporated water from the homogeneous mixture of hydrophilic ILs and water (1:1, w/w) by microwave-assisted separation were at least 52 times more efficient than those in conventional vacuum oven. It demonstrated that microwave-assisted separation could be used for complete recovery of ILs in sense of time and energy as well as relevant purity.     

Interaction of cationic surfactants with carboxymethylcellulose in aqueous media

We have examined the polymer-surfactant interaction in mixed solutions of the cationic surfactants, i.e., dodecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide, tetradecyltriphenylphosphonium bromide, and tetradecylpyridinium bromide and a semiflexible anionic polyelectrolyte carboxymethylcellulose in water and aqueous salt solutions by various techniques: tensiometry, viscosimetry or ion-selective electrode method, and dynamic light scattering. We have investigated the effect of varying surfactant chain length, head group size, counterion, and ionic strength on the critical aggregation concentration (CAC) of mixed polymer surfactant systems and the collapse of the polymer molecule under different solution conditions. The CAC decreases with increasing alkyl chain length. Above a certain surfactant concentration, mixed aggregates start growing until their macroscopic phase separation. The growth is more rapid with greater surfactant tail length and with increasing head group size. This is attributed in both cases to the increasing hydrophobic interaction between polymer and surfactant. Among surfactants with monovalent halide counterions, iodide induces the strongest binding, reflected by the onset of growth of the mixed aggregates at low surfactant concentration. This is perhaps related to the decreasing hydration of the counterion from chloride to iodide. The surfactant concentration at which the viscosity of the solution starts to decrease sharply is smaller than the CAC, and probably reflects polymer chain shrinkage due to noncooperative binding.     

Salt-induced viscoelastic wormlike micelles formed in surface active ionic liquid aqueous solution

The growth and structure of the aqueous micellar solutions of a surface active ionic liquid, 1-hexadecyl-3-methylimidazolium bromide (C16mimBr), in the presence of an organic salt sodium tosylate (NaTos), were investigated by rheological measurements and freeze-fracture transmission electron microscopy at room temperature (298 K). As in some conventional ionic surfactant/salt aqueous systems, wormlike micelles and network structures could be formed in the C16mimBr/NaTos aqueous solutions, according to measurements of the zero-shear viscosity, the entanglement length, the average contour length, as well as application of the Cox-Merz empirical rule and Cole-Cole plots. FF-TEM images further confirmed that wormlike micelles were formed in these aqueous solutions. The wormlike micelles presented here would expand potential applications of ionic liquids in home care products, oilfield stimulation fluids, and nanobiotechnology.     

Effect of imidazolium-based ionic liquids on the aggregation behavior of twin-tailed cationic gemini surfactant in aqueous solution

Micellization behavior of the twin-tailed surfactants can be modulated by the addition of various modifiers. Ionic liquids (ILs) are one of them and are documented here. The beauty of these environmentally benign neoteric molecules lies in their structural versatility. Here, we have investigated the effect of three ILs: 1-butyl-3-methylimidazolium bromide ([C₄mim][Br]), 1-hexyl-3-methylimidazolium bromide ([C₆mim][Br]), and 1-octyl-3-methylimidazolium bromide ([C₈mim][Br]) on the aggregation and surface adsorption behavior of cationic gemini surfactant, bis(hexadecyldimethyl ammonium)propane dibromide (16-3-16) through experimentally measured electrical conductivities, surface tensions, and by spectral methods (UV-vis absorbance and fluorescence measurements). The main focus of the study is to observe the effect of added ILs on the critical micelle concentration (cmc), various surface parameters, aggregation number, and size of the aggregates of gemini surfactant. The results show that the more hydrophobic ILs, that is, [C₆mim][Br] and [C₈mim][Br] behave as electrolyte at lower concentration and cosurfactant at higher concentration, whereas moderately hydrophobic IL [C₄mim][Br] acts as an electrolyte at all concentration ranges studied. The modulating effects of ILs were also compared with conventional electrolyte (NaBr) at similar conditions.     

Aggregation and micelle formation of ionic liquids in aqueous solution

Association of ionic liquids possessing n-octyl moiety either in the cation or in the anion has been studied in aqueous solution with conductivity and turbidity measurements as well as using 2-hydroxy-substituted Nile Red solvatochromic probe. 1-Butyl-3-methylimidazolium octyl sulfate was found to act as a surfactant above 0.031 M critical micelle concentration. In contrast, 1-methyl-3-octylimidazolium chloride produced inhomogeneous solution of larger aggregates, which were dissolved on the addition of more than 2:1 molar excess of sodium dodecyl sulfate (SDS) due to mixed micelle formation. Even small amount (<10 mM) of ionic liquids could markedly reduce the polarity of the Stern layer of SDS micelle.     

Laser photolysis studies of quaternary ammonium ionic liquids aqueous solution

The reactions between quaternary ammonium ionic liquids ([Me₃NC₂H₄OH]⁺[Zn₂Cl₅]⁻, abbrev. Ch-Zn₂Cl₅) and one-electron oxidant (SO₄^•−), have been studied by nano-second laser photolysis techniques. The mechanism of monophotonic ionization by 266 nm laser excitation was suggested and the quantum yield was estimated to be 0.04. The second-order decay rate constant of SO₄^•− oxidation reactions at 460 nm, 1.3 × 10⁹ M⁻¹ s⁻¹, was almost equal to the product rate constant of 1.5 × 10⁹ M⁻¹ s⁻¹ at 320 nm in Ch-Zn₂Cl₅ aqueous solution showing that the decay and the product were synchronic. Comparison of Ch-Zn₂Cl₅ with chloride choline and ZnCl₂ showed that the anion Zn₂Cl₅ ⁻ played an important role in photoionization while choline cation had little function on its photolysis and radiolysis. The present study would be helpful for understanding the application of ionic liquids in the field of electrochemical deposition.     

Interactions and dynamics in ionic liquids

Precise dielectric spectra have been determined at 25 degrees C over the exceptionally broad frequency range of 0.1 相似文献   

Aggregate formation in aqueous solutions of carboxymethylcellulose and cationic surfactants

The addition of cationic surfactants to an aqueous solution of an anionic polymer, carboxymethylcellulose (carboxyMC), causes the spontaneous formation of aggregates in a certain range of concentrations. Here we studied two surfactants, dodecyl and hexadecyl trimethylammonium bromide (DTAB and CTAB, respectively). Using different techniques (light scattering, potentiometry, viscosimetry, and zetametry), we found that a simple lengthening of the surfactant tail length by four CH2 groups drastically changes the aggregate morphology, size, and charge. We explored in detail how the surfactant and polymer concentrations act on these systems.     

Laser flash photolysis of carboxymethylcellulose in an aqueous solution

Laser flash photolysis with excitation at 248 nm was used to study photochemically derived changes of carboxymethylcellulose (CMC) in aqueous solutions. Transient absorption spectra of solutions after photolysis revealed a broad band with a maximum of approximately 720 nm, which could be ascribed to the signal of the hydrated electron. The interaction of the hydrated electron with CMC was slow (<10⁷ dm³ mol^?1 s^?1), but the OH radical, formed by the decomposition of H₂O₂, reacted with CMC at a high rate constant (9.5–11.0 × 10⁸ dm³ mol^?1 s^?1). The rate constant of the reactions of CMC with hydroxyl radicals depended on the conformation of the macromolecules, which was determined by the pH of the solution. Transient absorption was recorded at a wavelength shorter than 370 nm for CMC solutions photolyzed in the presence of H₂O₂. As a result of OH attack, long‐lived radicals were formed on CMC. The recombination of macroradicals led to the formation of crosslinking bonds between side‐chain groups, and as a result of it an insoluble gel arose in low‐pH solutions. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 505–518, 2005     

Interactions between a surface active imidazolium ionic liquid and BSA

The interactions between a surface active imidazolium ionic liquid (IL), 1-tetradecyl-3-methylimidazolium bromide (C₁₄mimBr) and bovine serum albumin (BSA) were studied. To investigate the structure changes of BSA induced by addition of C₁₄mimBr, this system was studied by surface tension, isothermal titration microcalorimetry, far-UV circular dichroism (CD) and fluorescence spectra. The surface tension measurement shows the formation of C₁₄mimBr/BSA complex and the effect of the complex on surface tension. Furthermore, it reveals the interaction type. The enthalpy change in the whole interaction process between C₁₄mimBr and BSA was obtained by isothermal titration microcalorimetry, and the results prove the alteration of the BSA structure. To realize the structure alteration position more definitely, far-UV CD was used to obtain the contents of α-helix and random coil. Changes of these contents reveal that the secondary structure of BSA changes with addition of C₁₄mimBr. Fluorescence spectra are used to prove that the alteration of the secondary structure is due to the interactions of C₁₄mimBr molecules and amino acid residues. They show that tryptophan (Trp) residues, one of the intrinsic fluorophores in BSA, are exposed to a hydrophobic microenvironment with the addition of C₁₄mimBr.     

Self-aggregation and antimicrobial activity of imidazolium and pyridinium based ionic liquids in aqueous solution

Adsorbed cetyldimethylbenzylammonium chloride (CDBACl) or cetyltrimethylammonium bromide (CTAB) on mercury is used as template for the adsorption of CTAB, CDBACl, or their equimolar mixture at 20 °C. Adsorptive stripping voltammetry with the two step procedure is used. The results are compared with previously published results on the adsorption of CTAB and CDBACl on mercury and then transferred in base electrolyte. A surfactant is preadsorbed. The adsorption of the second does not remove away from the mercury the first one, as evidenced by the capacitance measurements and the repeated scans. The surfactants were maintained close to each other and in the vicinity of the electrode by the applied electric field. In all cases studied, there was a decrease in the capacitance in the potential range -0.8 to -1 V to very low capacitance values forming condensed film. Mixed films and synergy effects were observed. The already adsorbed CTAB on mercury did not permit the desorption-reorientation peaks of CDBACl. Shifts of the capacitance peaks were observed to more positive potentials and were attributed to the occurrence of a slow change in the organization of the monolayer. The electrical state of the preadsorbed surfactant would be of critical importance in the formation of the various structures. The results suggested that the ordering and arrangement of molecules could be controlled by appropriate selection of templates.     

Electrical conductivity study on micelle formation of long-chain imidazolium ionic liquids in aqueous solution

Electrical conductivity was measured for aqueous solutions of long-chain imidazolium ionic liquids (IL), 1-alkyl-3-methylimidazolium bromides with C(12)-C(16) alkyl chains. The break points appeared in specific conductivity (kappa) vs concentration (c) plot indicates that the molecular aggregates, i.e., micelles, are formed in aqueous solutions of these IL species. The critical micelle concentration (cmc) determined from the kappa vs c plot is somewhat lower than those for typical cationic surfactants, alkyltrimethylammonium bromides with the same hydrocarbon chain length. The electrical conductivity data were analyzed according to the mixed electrolyte model of micellar solution, and the aggregation number, n, and the degree of counter ion binding, beta, were estimated. The n values of the present ILs are somewhat smaller than those reported for alkyltrimethylammonium bromides, which may be attributed to bulkiness of the cationic head group of the IL species. The thermodynamic parameters for micelle formation of the present ILs were estimated using the values of cmc and beta as a function of temperature. The contribution of entropy term to the micelle formation is superior to that of enthalpy term below about 30 degrees C, and it becomes opposite at higher temperature. This coincides with the picture drawn for the micelle formation of conventional ionic surfactants.     

Peculiar surface behavior of some ionic liquids based on active pharmaceutical ingredients

The ionic liquids based on biologically active cations and anions, commonly designated by ionic liquids based on active pharmaceutical ingredients (ILs-APIs), are interesting compounds for use in pharmaceutical applications. Lidocaine docusate, ranitidine docusate, and didecyldimethylammonium ibuprofen are examples of promising ILs-APIs that were recently synthesized. They were submitted to biological testing and calorimetric measurements, but nothing is known about their surface properties. In this work, we measured the surface tension and the contact angles on both hydrophilic and hydrophobic surfaces in a temperature range as wide as possible. Based on the wettability data, the polarity fractions were estimated using the Fowkes theory. The peculiar surface behavior observed was tentatively attributed to the presence of mesophases.     

Interactions of cholesterol with cyclodextrins in aqueous solution

The interaction of cholesterol with several cyclodextrins (CDs) was investigated in water using solubility method. It was found that heptakis (2,6-di-O-methyl)-beta-CD (DOM-beta-CD) forms two types of soluble complex, with molar ratios of 1 : 1 and 1 : 2 (cholesterol : DOM-beta-CD), and neither a soluble nor insoluble complex is formed between cholesterol and alpha-CD, beta-CD, and gamma-CD, although a minor soluble complex formation was observed between cholesterol and 2-hydroxylpropyl-beta-CD. The thermodynamic parameters for 1 : 1 and 1 : 2 complex formation of cholesterol with DOM-beta-CD obtained from the changes in K with temperature are as follows: DeltaG degrees (1 : 1)=-11.6 kJ/mol at 25 degrees C (K(1 : 1)=1.09x10(2) M(-1)); DeltaH degrees (1 : 1)=-3.38 kJ/mol; TDeltaS degrees (1 : 1)=8.25 kJ/mol; DeltaG degrees (1 : 2)=-27.1 kJ/mol at 25 degrees C (K(1 : 2)=5.68x10(4) M(-1)); DeltaH degrees (1 : 2)=-3.96 kJ/mol; and TDeltaS degrees (1 : 2)=23.2 kJ/mol. The formation of the 1 : 2 complex occurred much more easily than that of the 1 : 1 complex. The driving force for 1 : 1 and 1 : 2 complex formation was considered to be mainly hydrophobic interaction. Also, based on the measurements of proton nuclear magnetic resonance spectra and studies with Corey-Pauling-Koltun atomic models, the probable structutures of the 1 : 2 complex were estimated.     

Interactions of ionic liquids with polysaccharides. VI. Pure cellulose nanoparticles from trimethylsilyl cellulose synthesized in ionic liquids

Trimethylsilyl cellulose (TMSC) can be efficiently synthesized with 1,1,1,3,3,3‐hexamethyldisilazane (HMDS) by applying the ionic liquids (ILs) 1‐ethyl‐3‐methylimidazolium acetate, 1‐ethyl‐3‐methylimidazolium chloride, and 1‐butyl‐3‐methylimidazolium chloride as reaction medium, yielding pure biopolymer derivatives with degrees of substitution (DS) up to 2.89. Cosolvents, for example, chloroform, could be used to adjust the viscosity of the system and to achieve the miscibility of the components. During the synthesis of highly functionalized derivatives precipitation of the TMSC occurred, which simplifies the recycling of the IL. The high tendency of TMSC toward the formation of supermolecular structures was exploited for the formation of nanoparticles studying a simple dialysis process. Amazingly, pure cellulose nanoparticles can be obtained by dissolving TMSC in tetrahydrofurane or N,N‐dimethyl acetamide and dialysis against water. FTIR spectroscopy confirmed the complete removal of the TMS functions during this process. Scanning electron microscopy, dynamic light scattering, atomic force microscopy, and particle size distribution analysis showed that cellulose particles down to a size of 170 nm are accessible in this simple manner. The nanoparticle suspensions exhibit viscosities in the range of water. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4070–4080, 2008     

Effect of ionic liquids on the aggregation behavior of PEO-PPO-PEO block copolymers in aqueous solution

Effect of 1-butyl-3-methyl-imidazolium bromide (BmimBr) on the aggregation behavior of PEO-PPO-PEO Pluronic P104 aqueous solution was studied by Fourier transform infrared (FTIR) spectroscopy, freeze fracture transmission electron microscopy (FF-TEM), dynamic light scattering (DLS), and NMR spectroscopy. When the BmimBr concentration was below 1.232 mol/L, the critical micelle temperature (CMT) of Pluronic P104 remained constant, while the size of micelles increased with increasing the BmimBr concentration; above this concentration, the CMT of Pluronic P104 decreased abruptly, and bigger clusters of BmimBr were formed. The selective nuclear Overhauser effect (NOE) spectrum indicates that the PO block of the P104 interacts with the butyl group of the Bmim+ cation by hydrophobic interaction. It suggests that when the concentration of BmimBr is below 1.232 mol/L, there are P104 micelles in the aqueous solution with BmimBr embedding to the micellar core, while above this concentration, P104 micelles and BmimBr clusters coexist in the system.