Estimation of the Relative Stabilities of the E,Z-Isomers of α,β-Dialkylsubstituted Methyl Vinyl Ethers by Various Computational Methods

The relative thermodynamic stabilities (relative enthalpies) of the E,Z-isomers of ,-dialkylsubstituted methyl vinyl ethers MeOC(R₁)=CHR₂ have been estimated by various computational methods including molecular mechanics, semiempirical, ab initio, and DFT calculations. The best performance, approaching the accuracy of the experimental method of chemical equilibration, is shown by the DFT calculations. Ab initio methods, provided that electron correlation is taken into account, are also satisfactory, but clearly less successful than the DFT calculations. The reliability of the semiempirical methods AM1 and PM3 is considerably less good, and varies in an unpredictable manner from case to case. The poorest general performance is shown by the MM2 and MM3 calculations, which may overestimate the relative stability of the Z isomer by as much as 18 kJ mol^–1.     

Preparation of amino acid nanoparticles at varying saturation conditions in an aerosol flow reactor

In this article, we describe the synthesis of new and ion-selective nanofiltration (NF) membranes using polyvinylidene fluoride (PVDF) nanofibers and hyperbranched polyethylenimine (PEI) as building blocks. These new nanofibrous composite (NFC) membranes consist of crosslinked hyperbranched PEI networks supported by PVDF nanofibrous scaffolds that are electrospun onto commercial PVDF microfiltration (MF) membranes. A major objective of our study was to fabricate positively charged NF membranes that can be operated at low pressure with high water flux and improved rejection for monovalent cations. To achieve this, we investigated the effects of crosslinker chemistry on membrane properties (morphology, composition, hydrophobicity, and zeta potential) and membrane performance (salt rejection and permeate flux) in aqueous solutions (2,000?mg/L) of four salts (NaCl, MgCl₂, Na₂SO₄, and MgSO₄) at pH 4, 6, and 8. We found that an NFC?CPVDF membrane with a network of PEI macromolecules crosslinked with trimesoyl chloride has a high water flux (~30?L?m^?2?h^?1) and high rejections for MgCl₂ (~88 %) and NaCl (~65 %) at pH 6 using a pressure of 7?bar. The overall results of our study suggest that PVDF nanofibers and hyperbranched PEI are promising building blocks for the fabrication of high performance NF membranes for water purification.     

A Thermodynamic, 13C NMR,and 17O NMR Study of Isomeric 4,7-Dihydro-1,3-dioxepins and 4,5-Dihydro-1,3-dioxepins

The relative thermodynamic stabilities of 4,7-dihydro-1,3-dioxepin (4,6-dioxacycloheptene, 1a) and 4,5-dihydro-1,3-dioxepin (3,5-dioxacycloheptene, 1b), and of a number of their 2-substituted derivatives, have been determined by base-catalyzed chemical equilibration in DMSO solution. Without exception, the 4,5-dihydro isomer is the dominating species at thermodynamic equilibrium. The relative stability of the b form is promoted by the presence of a single alkyl group on C-2, whereas two alkyl groups on C-2 have an opposite effect. In general, the thermodynamic parameters H _m and _Sm , of isomerization vary unexpectedly with the pattern of substitution at C-2. These trends appear to be derived from significant substituent-induced conformational changes in the b isomer, as suggested by ¹³C and ¹⁷O NMR chemical shift data.