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1.
We present a detailed study of a salt-free cationic/anionic (catanionic) surfactant system where a strongly alkaline cationic surfactant (tetradecyltrimethylammonium hydroxide, TTAOH) was mixed with a single-chain fluorocarbon acid (nonadecafluorodecanoic acid, NFDA) and a hyperbranched hydrocarbon acid [di-(2-ethylhexyl)phosphoric acid, DEHPA] in water. Typically the concentration of TTAOH is fixed while the total concentration and mixing molar ratio of NFDA and DEHPA is varied. In the absence of DEHPA and at a TTAOH concentration of 80 mmol·L(-1), an isotropic L(1) phase, an L(1)/L(α) two-phase region, and a single L(α) phase were observed successively with increasing mixing molar ratio of NFDA to TTAOH (n(NFDA)/n(TTAOH)). In the NFDA-rich region (n(NFDA)/n(TTAOH) > 1), a small amount of excess NFDA can be solubilized into the L(α) phase while a large excess of NFDA eventually leads to phase separation. When NFDA is replaced gradually by DEHPA, the mixed system of TTAOH/NFDA/DEHPA/H(2)O follows the same phase sequence as that of the TTAOH/NFDA/H(2)O system and the phase boundaries remain almost unchanged. However, the viscoelasticity of the samples in the single L(α) phase region becomes higher at the same total surfactant concentration as characterized by rheological measurements. Cryo-transmission electron microscopic (cryo-TEM) observations revealed a microstructural evolution from unilamellar vesicles to multilamellar ones and finally to gaint onions. The size of the vesicle and number of lamella can be controlled by adjusting the molar ratio of NFDA to DEHPA. The dynamic properties of the vesicular solutions have also been investigated. It is found that the yield stress and the storage modulus are time-dependent after a static mixing process between the two different types of vesicle solutions, indicating the occurrence of a dynamic fusion between the two types of vesicles. The microenvironmental changes induced by aggregate transitions were probed by (19)F NMR as well as (31)P NMR measurements. Upon replacement of NFDA by DEHPA, the signal from the (19)F atoms adjacent to the hydrophilic headgroup disappears and that from the (19)F atoms on the main chain becomes sharper. This could be interpreted as an increase of microfluidity in the mixed vesicle bilayers at higher content of DEHPA, whose alkyl chains are expected to have a lower chain melting point. Our results provide basic knowledge on vesicle formation and their structural evolution in salt-free catanionic surfactant systems containing mixed ion pairs, which may contribute to a deeper understanding of the rules governing the formation and properties of surfactant self-assembly.  相似文献   

2.
The molar enthalpies of solution of 2-aminopyridine at various molalities were measured at T=298.15 K in double-distilled water by means of an isoperibol solution-reaction calorimeter. According to Pitzer’s theory, the molar enthalpy of solution of the title compound at infinite dilution was calculated to be DsolHm = 14.34 kJ·mol-1\Delta_{\mathrm{sol}}H_{\mathrm{m}}^{\infty} = 14.34~\mbox{kJ}\cdot\mbox{mol}^{-1}, and Pitzer’s ion interaction parameters bMX(0)L, bMX(1)L\beta_{\mathrm{MX}}^{(0)L}, \beta_{\mathrm{MX}}^{(1)L}, and CMXfLC_{\mathrm{MX}}^{\phi L} were obtained. Values of the relative apparent molar enthalpies ( φ L) and relative partial molar enthalpies of the compound ([`(L)]2)\bar{L}_{2}) were derived from the experimental enthalpies of solution of the compound. The standard molar enthalpy of formation of the cation C5H7N2 +\mathrm{C}_{5}\mathrm{H}_{7}\mathrm{N}_{2}^{ +} in aqueous solution was calculated to be DfHmo(C5H7N2+,aq)=-(2.096±0.801) kJ·mol-1\Delta_{\mathrm{f}}H_{\mathrm{m}}^{\mathrm{o}}(\mathrm{C}_{5}\mathrm{H}_{7}\mathrm{N}_{2}^{+},\mbox{aq})=-(2.096\pm 0.801)~\mbox{kJ}\cdot\mbox{mol}^{-1}.  相似文献   

3.
1H, 19F, 31P NMR, DSC, and XRD methods are used to study ionic mobility and structural transformations in the CsSbF3(H2PO4) compound (I). Radical changes in 1H, 19F, 31P NMR spectra above 390 K are associated with a crystalline disordered phase which forms in I at 400–420 K. This phase demonstrates high ionic mobility and further transforms (above 425 K) into the amorphous (glassy) phase. We have determined the types of ionic mobility in this compound and in its amorphous product. According to the NMR data, the diffusion in the proton sublattice of the disordered and amorphous phases proceeds even at room temperature.  相似文献   

4.
Abstract  The title complexes and have been synthesized in excellent yields by reacting Co(OAc)2·4H2O with H2L1 and H2L2, respectively, in acetonitrile solution. Here, [L1]2− and [L2]2− are the deprotonated forms of N,N-bis(2-hydroxybenzyl)-N′,N′-dimethylethylenediamine and N,N-bis(2-hydroxybenzyl)-2-picolylamine, respectively. The crystal structures of and were determined by x-ray crystallography. In , each cobalt atom has distorted trigonal bipyramid geometry, while in , each cobalt atom has distorted octahedral geometry. Variable temperature magnetic moment measurements show weak antiferromagnetic interaction in . The magnetic characterization for is in agreement with the presence of Co(II) and Co(III) centers. Graphical Abstract  The title complexes and have been synthesized in excellent yields by reacting Co(OAc)2·4H2O with dianionic N2O2 coordinating ligands. In complex 1, each cobalt atom has distorted trigonal bipyramid geometry, while in complex 2, each cobalt atom has distorted octahedral geometry. Variable temperature magnetic moment measurements show weak antiferromagnetic interaction in complex 1. The magnetic characterization for complex 2 is in agreement with the presence of Co(II) and Co(III) centers. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

5.
Metastability and phase coexistence are important concepts in colloidal science. Typically, the phase diagram of colloidal systems is considered at the equilibrium without the presence of an external field. However, several studies have reported phase transition under mechanical deformation. The reason behind phase coexistence under shear flow is not fully understood. Here, multilamellar vesicle (MLV)‐to‐sponge (L3) and MLV‐to‐Lα transitions upon increasing temperature are detected using flow small‐angle neutron scattering techniques. Coexistence of Lα and MLV phases at 40 °C under shear flow is detected by using flow NMR spectroscopy. The unusual rheological behavior observed by studying the lamellar phase of a non‐ionic surfactant is explained using 2H NMR and diffusion flow NMR spectroscopy with the coexistence of planar lamellar–multilamellar vesicles. Moreover, a dynamic phase diagram over a wide range of temperatures is proposed.  相似文献   

6.
以频率扫描和稳态剪切实验研究了140 mmol·L-1羧酸盐gemini 表面活性剂(C14Φ2C14)在100 mmol·L-1 NaBr 条件下溶液的流变行为. 在低剪切频率时, 溶液呈现出具有单一松弛时间特性的Maxwell 流体行为.通过活的高分子模型(living polymer model)分析,C14Φ2C14体系在25℃ 时形成了很长的蠕虫胶束(3.6-6.8μm). 冷冻透射电镜也观察到蠕虫胶束的形成. 这些胶束相互缠绕, 形成了很黏稠的溶液(零剪切粘度高达1.10×104 Pa·s), 外观呈现胶状. 随着温度升高至70℃, 体系的相对粘度仍旧保持很高(1.8×104), 这在阴离子表面活性剂蠕虫胶束溶液中是很少见的. 体系的流动活化能(Ea)约为(141±5) kJ·mol-1. 利用动态光散射测定了C14Φ2C14聚集体的尺寸分布, 证实了这个表面活性剂在5-10 mmol·L-1的低浓度时生成了约100 nm的大聚集体, 这些大聚集体随着表面活性剂浓度的增加很容易转化成棒状直至蠕虫胶束.  相似文献   

7.
Alternating copolymers of glycolic (G) and lactic (L) acid were prepared by the condensation of the preformed dimers: LLG and LracG. By size exclusion chromatography (THF, PS standards), poly(LLG) exhibited a molecular weight (Mn) of 15.6 kg mol?1, with a weight average molecular weight (Mw) of 26.9 kg mol?1 and a PDI of 1.72. The Mn for poly(LracG) was 9.2 kg mol?1, with a Mw of 12.9 kg mol?1 and a PDI of 1.40. The NMR spectra of poly(LLG) were consistent with an isotactic microstructure. NMR spectra of the racemic poly(LracG) were consistent with an atactic structure. The methylene region of the 1H NMR spectrum showed a tetrad level of resolution of the nearby stereochemical relationships, for example, iii. Resonances for other groups in both the 1H and 13C NMR spectra gave only a triad level of resolution. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4704–4711, 2008  相似文献   

8.
The isothermal pseudo-ternary-phase diagram was determined at 25 degrees C for systems composed oflecithin, water, and, as oil, either isooctane or decane. This was accomplished by a combination of polarizing microscopy, small-angle X-ray scattering, and NMR techniques. The lecithin-rich region of the phase diagram is dominated by a lamellar liquid-crystalline phase (Lalpha). For lecithin contents less than 60% and low hydration (mole ratio water/lecithin = W0 < 5.5), the system forms a viscous gel of branched cylindrical reverse micelles. With increase in the water content, the system phase separates into two phases, which is either gel in equilibrium with essentially pure isooctane (for lecithin < 25%) or a gel in equilibrium with Lalpha (for lecithin > 25%). These two-phase regions are very thin with respect to water dilution. For 8 < W0 < 54 very stable water-in-oil emulsions form. It is only after ripening for more than 1 year that the large region occupied by the emulsion reveals a complex pattern of stable phases. Moving along water dilution lines, one finds (i) the coexistence of gel, isooctane and Lalpha, (ii) equilibrium between reverse micelles and spherulites, and, finally, (iii) disconnected reverse micelles that fail to solubilize water for W0 > 54. This results in a Winsor II phase equilibrium at low lecithin content, while for lecithin > 20% the neat water is in equilibrium with a reverse hexagonal phase and an isotropic liquid-crystalline phase. The use of the decane as oil does not change the main features of the phase behavior.  相似文献   

9.
The aqueous mixed systems of twin tail cationic surfactants didodecyldimethylammonium bromide, ditetradecyldimethylammonium bromide, and dihexadecyldimethylammonium bromide with pluronic L64 have been studied to determine the bulk aggregation and interactional behavior. Various experimental techniques, namely small-angle neutron scattering (SANS), fluorescence, conductivity, and surface tension, have been employed to investigate the mixed micellization. The SANS data analysis has been employed to determine the shapes of different aggregates formed. Pure twin tail cationic surfactants form vesicles whereas the micelles of pure pluronic L64 are spherical. The mixed systems (surfactant + L64) also form spherical micelles, and the spherical shape of mixed micelles is predominantly controlled by pluronic L64. Various interfacial parameters such as surface excess (Γ max), minimum area per molecule (A min), and thermodynamic parameters such as the standard Gibbs free energy of micellization (DGmic0 \Delta G_{{mic}}^{{0}} ), Gibbs free energy of adsorption (DGads0 \Delta G_{{ads}}^{{0}} ), and effective Gibbs free energy (DGeff0 \Delta G_{{eff}}^{{0}} ) have been determined from the surface tension measurements. The results were interpreted on the basis of pseudophase separation model and regular solution theory. The interactions of each surfactant with pluronic L64 are found to be nonideal and antagonistic. The repulsive nature of the interaction is explained on the basis of the changes in the microenvironment of micelles of pluronic L64. Micelles of pluronic L64 are less hydrophobic and contains significant amount of water, and inclusion of hydrophobic alkyl chains of twin tail cationic surfactants disturbs this microenvironment of pluronic L64 micelle.  相似文献   

10.
The local and medium-range structure of the 20CaO·20Al2O3·60SiO2 glass generated by classical molecular dynamics simulations has been compared to NMR experiments by computing the 27Al and 17O NMR parameters and NMR spectra from first-principles simulations. The calculation of the NMR parameters (chemical shielding and quadrupolar parameters), which are then used to simulate solid-state MAS and 3QMAS NMR spectra, is achieved by the gauge including projector augmented-wave and the projector augmented-wave methods on the DFT-PBE relaxed structure. The NMR spectra calculated with the present approach are found to be in excellent agreement with the experimental data, providing an unambiguous view of the local and medium-range structure of aluminosilicate glasses.  相似文献   

11.
Phase behavior of ternary systems containing 3‐dodecyloxy‐2‐hydroxypropyl trimethyl ammonium bromide (R12TAB), benzyl alcohol and water have been studied at 25±0.1°C. Ternary phase diagram of the systems shows a clear, isotropic, and low‐viscous region, a L phase, two liquid crystalline phases (lamella and hexagonal liquid crystal), and a coexisted phase of the liquid crystalline and micelles. 2H nuclear magnetic resonance (2H NMR) technology and polarizing‐light microscope were employed to confirm the symmetry structure of the liquid crystals and the boundaries for the different phases. In L phase, three types of different micelle regions (reverse micelles, normal micelles, and bicontinuous structures zones) were confirmed by means of the electric conductivity and the proton nuclear magnetic resonance spectroscopy (1H NMR) measurements. The microcosmic structures of the micelle were investigated, and the solubilizing position of benzyl alcohol were located according to the chemical shift of protons.  相似文献   

12.
In the phase diagram of an excellent extractant of rare earth metal ions, di(2-ethylhexyl) phosphate (HDEHP, commercial name P204), mixing with a cationic trimethyltetradecylammonium hydroxide (TTAOH) in water, a birefringent Lalpha phase was found, which consists of densely stacked multilamellar vesicles. The densely stacked multilamellar vesicles are remarkably deformed, as observed by means of cryotransmission electron microscopy (cryo-TEM). Further, self-assembled structures-oligovesicular vesicles, bilayer cylinders, and tubes joining with vesicles-were also observed. The self-assembled phase is transparent, anisotropic, and highly viscous, possessing elastic properties determined by rheological measurements. This is the first time that birefringent Lalpha phase with remarkably deformed amphiphilic bilayer membranes has been constructed through combining a hydrophobic organic extractant having double chains with a water-soluble surfactant having a single chain, which may direct primarily toward acquiring an understanding of the mechanism of salt-free catanionic vesicles and secondarily to determine if vesicle-extraction technology utilizing extractants is possible.  相似文献   

13.
The aqueous self-assembly of a novel lysine-derived surfactant with a gemini-like architecture, designated here as 12-Lys-12, has been experimentally investigated for the amphiphile alone in water and in a mixture with dodecyltrimethylammonium bromide (DTAB). The neat surfactant forms interesting micrometer-sized rigid tubules in the dilute region, resulting in very viscous solutions. For the catanionic mixture with DTAB, various single and multiphase regions were identified (up to a total surfactant concentration of 1.5 wt %) by means of combined polarizing light microscopy, cryo-TEM, and NMR. In the DTAB-rich side, for a mixing molar ratio in the range 2 < DTAB/12-Lys-12 < 4, a region of stable, unilamellar vesicles can be found. Furthermore, it was found that upon addition of 12-Lys-12 to pure DTAB solutions, the mixed micelles grow and beyond a given mixing ratio, vesicles assemble and coexist with small micelles. The transition is not continuous, since there is a narrow mixing range where phase separation occurs. Self-diffusion measurements and cryo-TEM imaging show that the average vesicle radius is on the order of 30-40 nm.  相似文献   

14.
The composition and equilibria in solutions of the products of reaction of HfF4(dmso)2 with monodentate phosphoryl-containing bases L = Ph3PO, Bu3PO, and (Me2N)3PO in CH2Cl2 are studied by 19F NMR. Octahedral molecular complexes cis-[HfF4L2] and minor amounts of trans-[HfF4L2] and fac-[HfF3L3]+ cations were the main products for all ligands. The oxytrifluoride complex (μ-O)[HfF3(Bu3PO)2]2 and the [HfF5(Bu3PO)] anion were identified in the case of Bu3PO. The conclusion about the formation of the hafnium oxytrifluoro complex was verified via hydrolysis of the product of reaction between HfF4 and Ph3PO upon exposure to air. As a result, (μ-O)[HfF3(Ph3PO)2]2 were detected; fine-structure 19F NMR resonance lines were obtained and the spin–spin coupling constant JFF was measured for the first time. Hydrolysis via adding a Bu4NOH solution in i-PrOH to the HfF4L2 solutions in CH2Cl2 did not yield the expected zirconium oxyfluoro complexes with the smaller number of fluorine atoms. Due to deeper hydrolysis, equilibrium in fluoride complexes shifted towards species with higher fluorine contents, [ZrF5L] and [ZrF6]2–, resulting in the formation of Hf(O)x(OH)у(i-PrOH)z complexes that were not observed in the 19F NMR spectra and the substitution of the released fluoride ions for molecular ligands in HfF4L2 complexes.  相似文献   

15.
We have established and analyzed the sequences of phase transitions in synthesis of layered compounds in the AnBn–1O3n family ( \textA3\textII\textLnB3\textV\textO12 {\text{A}}_3^{\text{II}}{\text{LnB}}_3^{\text{V}}{{\text{O}}_{{12}}} (AII = Ba, Sr, Ln = La, Nd, BV = Nb, Ta) and La4Ti3O12 with n = 4) from coprecipitated hydroxocarbonate and hydroxide systems, including steps involving the formation, solid-phase reaction, or structural rearrangement of intermediates.  相似文献   

16.
The preparation of a carbon ceramic electrode modified with SnO2 (CCE/SnO2) using tin dibutyl diacetate as precursor was optimized by a 23 factorial design. The factors analyzed were catalyst (HCl), graphite/organic precursor ratio, and inorganic precursor (dibutyltin diacetate). The statistical treatment of the data showed that only the second-order interaction effect, catalyst × inorganic precursor, was significant at 95% confidence level, for the electrochemical response of the system. The obtained material was characterized by scanning electron microscopy (MEV), X-ray diffraction (XRD), RAMAN spectroscopy, XPS spectra, and voltammetric techniques. From the XPS spectra, it was confirmed the formation of the Si–O–Sn bond by the shift in the binding energy values referred to Sn 3d3/2 due to the interaction of Sn with SiOH species. The incorporation of SnO2 provided an increment of the electrode response for levofloxacin, with Ipa = 147.0 μA for the ECC and Ipa = 228.8 μA for ECC/SnO2, indicating that SnO2 when incorporated into the silica network enhances the electron transfer process. Under the optimized working conditions, the peak current increased linearly with the levofloxacin concentration in the range from 6.21×10?5 to 6.97×10?4 mol L?1 with quantification and detection limits of 3.80×10?5 mol L?1 (14.07 mg L?1) and 1.13×10?5 mol L?1 (4.18 mg L?1), respectively.  相似文献   

17.
A comparative analysis of 6,7Li NMR spectra is performed for the samples of monoclinic lithium titanate obtained at different synthesis temperatures. In the 7Li NMR spectra three lines are found, which differ in quadrupole splitting frequencies v Q and according to ab initio EFG calculations are assigned to three crystallographic sites of lithium: Li1 (v Q ~ 27 kHz); Li2 (v Q ~ 59 kHz); Li3 (v Q ~ 6 kHz). The dynamics of lithium ions is studied in a wide temperature range from 300 K to 900 K. It is found that the narrowing of 7Li NMR spectra as a result of thermally activated diffusion of lithium ions in the low-temperature Li2TiO3 sample is observed at a higher temperature in comparison with a sample of high-temperature lithium titanate. Based on the analysis of 6Li NMR spectra it is assumed that there is mixed occupancy of lithium and titanium sites in the corresponding layers of the crystal structure of low-temperature lithium titanate, which hinders lithium ion transfer over regular crystallographic sites.  相似文献   

18.
Effect of enantiomers of a monodentate ligand on the stereoisomerism of mixed octahedral cis-tetrafluoro complexes of d0 transition metals has been studied by 19F{1H} and 31P{1H} NMR by the example of TiF4 complexation in CH2Cl2 with Ph2P(O)CH2CH(OH)Me (L) containing asymmetric carbon atom in the aliphatic hydrocarbon group that constitutes a racemic mixture of enantiomers. Composition of complexes formed in solution has been determined, conclusion has been drawn on the relative stereochemical configuration of the chiral and meso stereoisomers of octahedral complex cis-TiF4L2 on the basis of analysis of 19F NMR spectra, using the heterotropism concept.  相似文献   

19.
ABSTRACT

The effect of benzyl alcohol on the micellar size and shape of CTAB in KBr solution has been investigated by means of viscosity, LLS (laser light scattering), and NMR measurements. The surfactant CTAB (cetyltrimethylammonium bromide) and KBr content are kept constant at 0.01 mol.L?1 and O.l?1 mol.. The data from the various techniques are quantitatively in agreement. The viscosity of 0.01 mol.L?1 CTAB/ 0.01mol.L?1 KBr micellar system has a marked maximum at benzyl alcohol content 0.6%(v/v), where the size of rod micelles are largest. The results from 'H-NMR spectra of CTAB molecules show that before the maximum viscosity, benzyl alcohol is located in the interfacial region of CTAB micelles in the presence of KBr salt. If more benzyl alcohol is added, it starts solubilizing in the palisades of the micelles.  相似文献   

20.
KCNE1 is known to modulate the voltage‐gated potassium channel α subunit KCNQ1 to generate slowly activating potassium currents. This potassium channel is essential for the cardiac action potential that mediates a heartbeat as well as the potassium ion homeostasis in the inner ear. Therefore, it is important to know the structure and dynamics of KCNE1 to better understand its modulatory role. Previously, the Sanders group solved the three‐dimensional structure of KCNE1 in LMPG micelles, which yielded a better understanding of this KCNQ1/KCNE1 channel activity. However, research in the Lorigan group showed different structural properties of KCNE1 when incorporated into POPC/POPG lipid bilayers as opposed to LMPG micelles. It is hence necessary to study the structure of KCNE1 in a more native‐like environment such as multi‐lamellar vesicles. In this study, the dynamics of lipid bilayers upon incorporation of the membrane protein KCNE1 were investigated using 31P solid‐state nuclear magnetic resonance (NMR) spectroscopy. Specifically, the protein/lipid interaction was studied at varying molar ratios of protein to lipid content. The static 31P NMR and T1 relaxation time were investigated. The 31P NMR powder spectra indicated significant perturbations of KCNE1 on the phospholipid headgroups of multi‐lamellar vesicles as shown from the changes in the 31P spectral line shape and the chemical shift anisotropy line width. 31P T1 relaxation times were shown to be reversely proportional to the molar ratios of KCNE1 incorporated. The 31P NMR data clearly indicate that KCNE1 interacts with the membrane. Copyright © 2017 John Wiley & Sons, Ltd.  相似文献   

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