The self-assembly of an imidazolium surfactant in an aprotic ionic liquid. 1. Comparison in aprotic and protic ionic liquids.

The aggregation behaviour of a cationic surfactant in an aprotic ionic liquid has been explored. Prolate micelles are formed at low surfactant concentrations, while a lamellar lyotropic liquid crystal phase is formed at high surfactant concentrations.

Effects of a Spacer on the Phase Behavior of Gemini Surfactants in Ethanolammonium Nitrate.

The aggregation behavior of quaternary ammonium gemini surfactants (12-s-12) in a protic ionic liquid, ethanolammonium nitrate (EOAN), was investigated by small-angle X-ray scattering, freeze-fracture transmission electron microscopy, polarized optical microscopy, and rheological measurements. The rarely reported nonaqueous two phases in the ionic liquid were observed at lower 12-s-12 concentrations. The upper phase was composed of micelles, whereas only the surfactant unimers or multimers were detected in the low phase. At higher 12-s-12 concentrations, different aggregates were formed. The lamellar phase was observed in the 12-2-12/EOAN system, whereas the normal hexagonal phases in 12-s-12/EOAN (s = 3, 4, 5, 6, 8) systems and the micellar phase in the 12-10-12/EOAN system were observed. Such a dramatic phase transition induced by the spacer chain length was due to the unique solvent characteristics of EOAN compared to those of water and its counterpart ethylammonium nitrate.

Phase behaviour and temperature-responsive properties of a gemini surfactant/Brij-30/water system.

The phase behaviour of a ternary system composed of cationic gemini surfactant 2-hydroxypropyl-1,3-bis(myristyldimethylammonium chloride) (14-3(OH)-14(2Cl)), nonionic surfactant polyoxyethylene laurel ether (C12H25(OCH2CH2)10OH, Brij-30) and H2O was studied and its phase diagram was determined. In several different phase regions identified in the phase diagram, the viscoelastic worm-like micellar solution region was investigated. The focus of the investigation was the increase in the viscosity of the micellar solution with the temperature and the Brij-30 content, as suggested by a partial region of the triangular phase diagram. With an increase in the Brij-30 content or temperature, one-dimensional micellar growth occurred, and a maximum appeared in the zero-shear viscosity, η0, versus Brij-30 content or temperature curves; this was true for mixed solutions containing 14-3(OH)-14(2Cl) and Brij-30 in different mass ratios (WBrij-30/W14-3(OH)-14(2Cl)). After the maximum point, the decrease in viscosity is the result of the micellar shortening in the size with Brij-30 content and of the micellar branching in the network structure with temperature. This rheological analysis was performed to investigate the structural changes in different solutions as well as the effects of various factors on micellar growth. Various techniques were used to study the phase-transition processes occurring in this system, including cryogenic transmission electron microscopy, small-angle X-ray scattering measurements, and differential scanning calorimetry. The transition mechanisms of the aggregates were analysed on the basis of the obtained results.

ß-Cyclodextrin induced hierarchical self-assembly of a cationic surfactant bearing an adamantane end group in aqueous solution.

A cationic surfactant with adamantane as the end group, 1-[11-((adamantane-1-carbonyl)oxy)-undecyl]pyridinium bromide (AP), has been synthesized. Its ß-cyclodextrin (ß-CD) induced hierarchical self-assembling behaviors in aqueous solution were investigated using transmission or scanning electron microscopy methods and small-angle X-ray scattering measurements. Like conventional single chain surfactants, micelles could be formed by AP itself in dilute solutions. However, the dramatic phase transitions of these micelles occurred when host-guest inclusions between AP and ß-CD were sequentially produced at different host/guest molar ratios (R), corresponding to the supramolecules with different chemical structures. The AP micelles could be changed into spherical unilamellar vesicles by adding ß-CD to reach an R value of 1 : 1. Such vesicles then evolved into multi-wall nanotubes or hydrogels when the ß-CD amount was further increased to obtain an R value of 2 : 1. The unique structural characteristics of these supramolecular aggregates come from their "monolayer-like" walls, which have rarely been reported in the past for CD/surfactant inclusion complexes. The interesting results obtained here not only enrich the ß-CD/surfactant aggregation systems, but also provide a novel and facile strategy to tune the morphology and structure of aggregates.

Highly luminescent and stable lyotropic liquid crystals based on a europium ß-diketonate complex bridged by an ethylammonium cation.

Soft lanthanide luminescent materials are impressive because of their tunable and self-assembling characteristics, which make them an attractive emerging materials field of research. In this report, novel luminescent lyotropic liquid crystals (LLCs) with four different mesophases have been fabricated by a protic ionic liquid (IL) based europium ß-diketonate complex EA[Eu(TTA)4] (EA = ethylammonium, TTA = 2-thenoyltrifluoro-acetone) and an amphiphilic block copolymer (Pluronic P123). The protic IL, ethylammonium nitrate (EAN), was used as both the solvent and linkage to stabilize the doped complexes. Analyses by single-crystal X-ray diffraction for EA[Eu(TTA)4] and Fourier transform infrared spectroscopy for the LLC materials reveal convincingly that the ethylammonium cations establish an effective connection with both the carbonyl group of the ß-diketonate ligand and the EO blocks of the amphiphilic block copolymer P123 via strong hydrogen bonding interactions. Due to this, an extremely long decay time of the excited state is obtained in EA[Eu(TTA)4] and excellent photostability of the luminescent LLCs could be achieved. The long-period ordered structures of the luminescent LLCs have been investigated by small-angle X-ray scattering measurements and the best luminescence performance was found in the most organized mesophase. Noteworthy, the LLCs could yield an effective confining effect on the europium complex accompanied by a sizeable elongation of the excited-state lifetime and an enhancement of the energy transfer efficiency, which reaches a remarkably high value of 52.6%. More importantly, the modulated luminescence properties observed in the four mesophase structures offer the potential and powerful possibility for these unique composite LLCs to be used in the fabrication of soft luminescent materials with tunable functions.

Controllable enzymatic superactivity of α-chymotrypsin activated by the electrostatic interaction with cationic gemini surfactants.

Surfactant plays a critical role in enzymatic multi-functionalization processes. However, a deep understanding of surfactant-enzyme interactions has been lacking up until now due to the extreme complexity of the mixed system. This work reported the effect of cationic gemini surfactants, alkanediyl-α,ω-bis(dimethyldodecylammonium bromide) (C12C S C12Br2, S = 2, 6, and 10) on the enzymatic activity and conformation of α-chymotrypsin (α-CT) in phosphate buffer solution (PBS, pH 7.3). The enzymatic activity was assessed by the rate of 2-naphthyl acetate (2-NA) hydrolysis measured by UV-vis absorption. The superactivity of α-CT in the presence of C12C S C12Br2 appears in the concentration region below the critical micelle concentration (cmc) of the surfactant, and its maximum superactivity is correlated to the spacer length of C12C S C12Br2. Subtle regulation of the charge density of headgroups of the cationic surfactant can be achieved through partial charge neutralization of cationic headgroups by introducing inorganic counterions or oppositely charged surfactant, demonstrating that the electrostatic interaction plays the crucial role for emergence of the superactivity. The interaction between C12C S C12Br2 (S = 2,6, and 10) and α-CT was characterized by isothermal titration calorimetry (ITC), and the obtained endothermic enthalpy change indicates that the interaction induces the change in conformation and enzymatic superactivity. The methodologies of fluorescence spectroscopy, circular dichroism (CD), and differential scanning calorimetry (DSC) show that the gemini surfactants with different spacer lengths induct and regulate the secondary, tertiary and even fourth structures of the protein. The present work is significant to get deeper insight into the mechanism of the activation and denaturation of enzymes.

The investigation of the binding behavior between ethyl maltol and human serum albumin by multi-spectroscopic methods and molecular docking.

This paper was designed to investigate the interaction of ethyl maltol with human serum albumin (HSA) under physiological condition by fluorescence, synchronous fluorescence, three-dimensional fluorescence, Fourier transformation infrared spectra, and molecular docking method. Spectroscopic analysis of the emission quenching at different temperatures revealed that the quenching mechanism of HSA by ethyl maltol was static quenching mechanism. The binding constants of ethyl maltol-HSA complexes were observed to be 2.59, 1.88, 1.54, 1.13×10(4) M(-1) at 289, 296, 303 and 310 K, respectively. The thermodynamic parameters, ΔH(0) and ΔS(0) were calculated to be -28.61 kJ mol(-1) and -14.59 J mol(-1) K(-1). Energy transfer from tryptophan to ethyl maltol occurred by a FRET mechanism, and the donor-acceptor distance (3.04 nm) had been determined according to Förster's theory. Molecular docking studies revealed that ethyl maltol situated within subdomain IIA (site I) of HSA. Fluorescence displacement experiments also proved the binding sites between ethyl maltol and HSA.

Imidazolium ionic liquids as antiwear and antioxidant additive in poly(ethylene glycol) for steel/steel contacts.

Three imidazolium-based ionic liquids containing sterically hindered phenol groups were synthesized. The cation was 1-(3,5-ditert-butyl-4-hydroxybenzyl)-3-methyl-imidazolium, and the anions were tetrafluoroborates, hexafluorophosphates, and bis(trifluoromethylsulfonyl)imide. The physical properties of the synthetic products and of poly(ethylene glycol) (PEG) with the additive were evaluated. The oxidative stability of 0.5 wt % 1-(3,5-di-tert-butyl-4-hydroxybenzyl)-3-methyl-imidazolium hexafluorophosphates in PEG were assessed via rotating bomb oxidation test (RBOT), thermal analysis, and copper strip test. The tribological behaviors of the additives for PEG application in steel/steel contacts were evaluated on an Optimol SRV-IV oscillating reciprocating friction and wear tester as well as on MRS-1J four-ball testers. The worn steel surface was analyzed by a JSM-5600LV scanning electron microscope and a PHI-5702 multifunctional X-ray photoelectron spectrometer. RBOT test, thermal analysis, and copper strip test results revealed that synthesized ionic liquids possessed excellent antioxidant properties. Tribological application results revealed that these could effectively reduce friction and wear of sliding pairs compared with the PEG films used without the additives. Specifically, (BHT-1)MIMPF(6) exhibited better antiwear properties at an optimum concentration of 1 wt %. At this level, its antiwear property significantly improved by 100 times with respect to using just the PEG base oil. Boundary lubrication films composed of metal fluorides, organic fluorines, organic phosphines, and nitride compounds were formed on the worn surface, which resulted in excellent friction reduction and antiwear performance.

Bisimidazolium ionic liquids as the high-performance antiwear additives in poly(ethylene glycol) for steel-steel contacts.

Bisimidazolium ionic liquids [C(10)(m(2)im)(2)(NTf(2))(2), C(10)(m(2)im)(2)(PF(6))(2), and C(10)(m(2)im)(2)(BF(4))(2)] with different anions were evaluated as the antiwear additives in poly(ethylene glycol) at room temperature. Results showed that they could effectively reduce the friction and wear of sliding pairs compared with the cases without these additives. Especially, C(10)(m(2)im)(2)(NTf(2))(2) showed better antiwear properties with an optimum concentration of 3 wt %, by which a significant improvement of its antiwear property by dozens of times with respect to the base oil was achieved. The excellent tribological properties are attributed to the formation of high-quality physical adsorption films and tribochemical product during friction and the good miscibility of ionic liquids with base oil.