Extension of the Wilson-NRF Gibbs Energy Model in Correlating Vapor-Liquid and Liquid-Liquid Phase Behavior of Polymer-Polymer Aqueous Two-Phase Systems

In this work, the proposed model by Pazuki et al. based on the Local Composition Concept (LCC), has been used in correlating the vapor-liquid phase behavior of polymer solutions and the liquid-liquid phase behavior of aqueous two-phase systems. The Flory-Huggins model has been used as the combinatorial part of the proposed model, as well as the model proposed by Pazuki et al. was considered as the residual term. The proposed model has been used in correlating the vapor-liquid phase behavior for a number of PEG-Water systems at constant temperature. The results obtained from the proposed model have been compared with those obtained from the Poly-NRTL and the Poly-Wilson models. The results showed that the proposed model can accurately correlate the VLE data for PEG-Water systems. Also, the proposed model has been used to obtain phase behavior of aqueous two-phase systems for PEG-DEX-Water systems. The results obtained from the proposed model have been compared with those obtained from the UNIQUAC and the UNIQUAC-NRF models. The results showed that the proposed model can accurately correlate liquid-liquid phase behavior of aqueous two-phase systems than the UNIQUAC and the UNIQUAC-NRF models.     

Optical switching and alignment of antiferroelectric liquid crystals containing an azo group

The optical properties of two kinds of photochromic antiferroelectric liquid crystal (AFLC) containing an azo group have been examined. Depending on the substituting group at the chiral centre, these AFLCs showed different photoinduced phase transitions by Ar⁺ laser light irradiation. This phase transition has led to a new form of optical switching controlled by a bias voltage. In addition, it was found that these AFLCs caused an azimuthal photoalignment effect regulated by linearly polarized Ar⁺ laser light irradiation. These phenomena were applied to image storage.     

Preparation and Characterisation of Meloxicam Hydroxy Propyl <Emphasis Type="Italic">β</Emphasis>-Cyclodextrin Inclusion Complex

Meloxicam is a non steroidal anti inflammatory drug, used in the treatment of rheumatoid and osteoarthiritis. It is practically insoluble in water and its prolonged use is associated with the incidence of side effects like gastro intestinal perforations, ulcerations and bleeding. Therefore, an attempt has been made to improve the aqueous solubility of the drug by making an inclusion complex using hydroxy propyl β cyclodextrin(HPβ-CD). The complexes were prepared by physical mixture and freeze drying method. The different methods employed for evaluation such as DSC, XRD, SEM and FT-IR studies indicated complete formation of the complex by freeze drying method in a molar ratio of 1:2. The prepared complexes showed improved in-vitro dissolution profile as compared to the pure drug.     

Synthesis of functionalized rab GTPases by a combination of solution- or solid-phase lipopeptide synthesis with expressed protein ligation

Prenylated proteins with non-native functionalities are generally very difficult to obtain by recombinant or enzymatic means. The semisynthesis of preparative amounts of prenylated Rab guanosine triphosphatases (GTPases) from recombinant proteins and synthetic prenylated peptides depends largely on the availability of functionalised prenylated peptides corresponding to the proteins' native structure or modifications thereof. Here, we describe and compare solution-phase and solid-phase strategies for the generation of peptides corresponding to the prenylated C terminus of Rab7 GTPase. The solid-phase with utilisation of a hydrazide linker emerges as the more favourable approach. It allows a fast and practical synthesis of pure peptides and gives a high degree of flexibility in their modification. To facilitate the analysis of semisynthetic proteins, the synthesised peptides were equipped with a fluorescent group. Using the described approach, we introduced fluorophores at several different positions of the Rab7 C terminus. The position of the incorporated fluorescent groups in the peptides did not influence the protein-ligation reaction, as the generated peptides could be ligated onto thioester-tagged Rab7. However, it was found that the positioning of the fluorescent group had an influence on the functionality of the Rab7 proteins; analysis of the interaction of the semisynthetic Rab7 proteins with REP (Rab escort protein) and GDI (guanosine diphosphate dissociation inhibitor) molecules revealed that modification of the peptide side chains or of the C-terminal isoprenoid did not significantly interfere with complex formation. However, functionalisation of the C terminus was found to have an adverse effect on complex formation and stability, possibly reflecting low structural flexibility of the Rab GDI/REP molecules in the vicinity of the lipid-binding site.     

一种甲醇直接气相羰基化新催化剂

本世纪７０年代Ｍｏｎｓａｎｔｏ公司成功开发了甲醇液相羰化ＲｈＩ催化体系，使甲醇羰化生产醋酸成为重要的工业过程．然而，由于此工艺产物与催化剂分离复杂、铑资源紧缺以及体系中还必须加大量的碘甲烷（或氢碘酸）作促进剂，设备腐蚀严重．８０年代以来，甲醇气相羰...     

IR spectra,conformational lability,and intermolecular interactions in long-chain aliphatic compounds

Investigations of the conformational lability and intermolecular interactions in long-chain aliphatic compounds (LACs), namely, in carboxylic acid derivatives (alkyl- and alkoxybenzoic acids; alkylcyclohexanecarboxylic acids and their completely or partially fluoroalkyl-substituted derivatives), 4-cyano-4-p-alkoxybiphenyls, 4-cyano-4-p-alkylbiphenyls, and cholesterol p-n-butyloxybenzoate are reviewed. Major attention is paid to experimental and theoretical IR spectroscopy data. Differential thermal analysis, polarization microscopy, and X-ray diffraction data are also taken into account. A more detailed treatment is presented on IR spectrum simulation based on data about the conformational lability of molecules and their specific (H-bonding) intermolecular interactions. The first mechanism is responsible for the conformational type of polymorphism in LACs and for the structure of the latter in solid crystal (SC) and liquid crystal (LC) states and in isotropic liquids (ILs). The second mechanism complements the structure-forming aspect of polymorphism in carboxylates, which is due to a rearrangement of hydrogen bond systems in H-complexes during polymorphic transitions to the LC and IL states. Both mechanisms are reflected in IR absorption spectra. A more adequate interpretation is possible in order to explain the many spectral features associated with the structure of LAC polymorphs and their H-complexes if these mechanisms are taken into account.Original Russian Text Copyright © 2004 by L.M. BabkovTranslated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 3, pp. 389–397, May–June, 2004.     

Tailoring Morphology of PVDF-HFP Membrane via One-step Reactive Vapor Induced Phase Separation for Efficient Oil-Water Separation

Poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP) receives increasing attention in membrane separation field based on its advantages such as high mechanical strength, thermal and chemical stability. However, controlling the microporous structure is still challenging.In this work, we attempted to tailor the morphology of PVDF-HFP membrane via a one-step reactive vapor induced phase separation method.Namely, PVDF-HFP was dissolved in a volatile solvent and then was cast in an ammonia water vapor atmosphere. After complete evaporation of solvent, membranes with adjustable porous structure were prepared, and the microstructures of the membranes were analyzed by scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and X-ray diffraction characterizations. Based on the results, a mechanism of dehydrofluorination induced cross-linking of PVDF-HFP has been suggested to understand the morphology tailoring.To our knowledge, this is the first report of one-step reactive vapor induced phase separation strategy to tailor morphology of PVDF-HFP membrane. In addition, the membranes prepared in the ammonia water vapor exhibited enhanced mechanical strength and achieved satisfactory separation efficiency for water-in-oil emulsions, suggesting promising potential.     

Chromatographic evaluation of perphenylcarbamoylated β-cyclodextrin bonded stationary phase for micro-high performance liquid chromatography and pressurized capillary electrochromatography

Application of mono (6^A-N-ethylenediamine-6^A-deoxy) perphenylcarbamoylated β-cyclodextrin (β-CD) bonded stationary phase (CSP) in micro-high performance liquid chromatography (micro-HPLC) and pressurized capillary electrochromatography (p-CEC) was firstly presented. A series of racemic α-amidophosphonates were resolved in reversed- and normal-phase modes on this CSP. The investigated chromatographic parameters include retention factor (k′), separation factor (α) and resolution (Rs) of solutes. In addition, the structural variation of the solutes and the experimental factors affecting chiral separations have been examined, including the percentage of alcohol modifier, the linear velocity (u) of the mobile phase, electrical field strength, etc. Baseline separation was achieved for most of the entities. Hydrophobic interaction, steric effect and π-π interaction contribute to the possible mechanism. Comparative results indicate that higher Rs value up to 3.1 was found in micro-HPLC, higher efficiency up to 29,970 in p-CEC.     

Positive ion chemistry of esters of carboxylic acids in air plasma at atmospheric pressure

Ionization of esters of carboxylic acids RCOOR' (R = H, alkyl; R' = alkyl) within the air plasma of the Atmospheric Pressure Chemical Ionization (APCI) source occurs largely via H(+)-transfer and, to a minor extent, via NO(+) association. The protonated ester MH(+) is normally observed as M(2)H(+) and as higher aggregates (M(3)H(+), M(3)H(+)(H(2)O)) also at high source temperature. The behavior of M(2)H(+) upon collisional activation is consistent with the reported dissociation of proton-bound dimers to MH(+) species that, in turn, fragment according to the known paths of lowest energy. In addition, other important product ions form within the plasma, some in very high relative abundance, which are attributed to ion-molecule condensation reactions between neutral M and either MH(+) or M(2)H(+) resulting in the elimination of CO, R'OH, alkene from the alkoxy moiety of the ester and HCOOH. A general scheme is proposed to account for the experimental observations, which suggest that the encounter complex formed between MH(+) and M or between M(2)H(+) and M may either collisionally relax to the protonated dimer or trimer, respectively, or react via covalent bond forming and cleaving steps to eliminate stable neutral molecules. The proposed scheme is supported by both the observed concentration dependence and the temperature dependence of the products relative abundances within the plasma. Such reactions can be the dominant process, as in the case of formate esters. A second significant ionization route involves addition of NO(+) to form M(n)NO(+) (n = 1, 2, 3). An additional product corresponding to [M(2)NO(+) - CO(2)] is also observed with iso- and n-butyl formate esters.