Poly(carboxyethyl acrylate-co-ethylene glycol dimethacrylate) precursor monolith with bonded octadecyl ligands for use in reversed-phase capillary electrochromatography

A carboxy precursor monolithic column, namely poly(carboxy ethyl acrylate-co-ethylene glycol dimethacrylate) was first produced in a 100 μm i.d. fused-silica capillary and subsequently surface bonded with n-octadecyl (C₁₈) ligands by a post-polymerization functionalization process with octadecylamine in the presence of N,N´-dicyclohexylcarbodiimide. The bonding of octadecyl ligands was achieved via an amide linkage between the carboxy functions of the precursor monolith and the amino group of the octadecylamine compound. The resulting C₁₈ monolith exhibited a very low electroosmotic flow (EOF), a fact that required the incorporation of small amounts of 2-acrylamido-2-methylpropane sulfonic acid (AMPS) in the polymerization solution to produce a precursor monolith with fixed negative charges of sulfonate groups. This may indicate that the conjugation of the carboxy functions with octadecylamine occurred to a large extent so that the amount of residual carboxy functions was sparsely dispersed and not enough to produce a desirable EOF. The EOF velocity of the C₁₈ column having fixed negative charges provided by the incorporated AMPS increased with increasing ACN content of the mobile phase signaling an increased binding of mobile phase ions to the polar amide linkages near the monolithic surface, and a decreased viscosity of the mobile phase, both of which would result in increased EOF velocity. The C₁₈ monolithic column constituted a novel nonpolar sorbent for reversed-phase capillary electrochromatography for nonpolar solutes, e.g., alkylbenzenes, alkylphenyl ketones, and polyaromatic hydrocarbons, and slightly polar compounds including phenol and chlorophenols. The C₁₈ monolithic column exhibited relatively high selectivity toward chlorophenols differing by one chloro substituent.     

Exploration of the electrical double-layer structure: Influence of electrolyte components on the double-layer capacitance and potential of maximum entropy

Understanding the electrical double-layer structure is of paramount importance for designing efficient electrochemical energy conversion systems. Under this aspect, this short review explores the influence of the electrolyte on parameters such as the double-layer capacitance and the potential of maximum entropy. Investigation of those parameters offers a deeper understanding on how the interfacial structure changes near reaction conditions. As a consequence, one can tune the catalyst activity by creating a more favorable environment in the electrolyte. The aim of this short review is to provide the reader with recent studies examining the electrode/electrolyte interface from experimental and theoretical standpoints.     

替考拉宁手性柱高效液相色谱法拆分萘哌地尔对映体及分离机制

在极性有机相条件下用替考拉宁手性柱(Chirobitotic T)直接分离萘哌地尔对映体。考察了三乙胺、醋酸的浓度、比例及柱温、流速对拆分的影响。应用Molecular operation Environment(MOE)软件模拟R/S-萘哌地尔与替考拉宁的相互作用,结合热力学参数探讨其分离机制。结果表明,随着甲醇中三乙胺和醋酸的浓度变小,分离度增大;三乙胺与醋酸的体积比为1∶1时,分离度最好。温度和流速的升高都会使分离度降低。优化后条件为:流动相为甲醇-三乙胺-醋酸(100∶0.002∶0.002,V/V),流速1 mL/min,柱温30℃。在此条件下,萘哌地尔对映体达到了最佳分离,分离度为2.0,理论塔板数达到5100。结合热力学参数和分子模拟结果表明,引起手性识别的主要作用力包括氢键、立体阻碍和π-π作用力。     

Spotlight on the Effect of Electrolyte Composition on the Potential of Maximum Entropy: Supporting Electrolytes Are Not Always Inert

The influence of electrolyte pH, the presence of alkali metal cations (Na⁺, K⁺), and the presence of O₂ on the interfacial water structure of polycrystalline gold electrodes has been experimentally studied in detail. The potential of maximum entropy (PME) was determined by the laser-induced current transient (LICT) technique. Our results demonstrate that increasing the electrolyte pH and introducing O₂ shift the PME to more positive potentials. Interestingly, the PME exhibits a higher sensitivity to the pH change in the presence of K⁺ than Na⁺. Altering the pH of the K₂SO₄ solution from 4 to 6 can cause a drastic shift in the PME. These findings reveal that, for example, K₂SO₄ and Na₂SO₄ cannot be considered as equal supporting electrolytes: it is not a viable assumption. This can likely be extrapolated to other common “inert” supporting electrolytes. Beyond this, knowledge about the near-ideal electrolyte composition can be used to optimize electrochemical devices such as electrolyzers, fuel cells, batteries, and supercapacitors.     

Further conformational aspects of the amino-acid histidine: crystal and molecular structure of histidine dihydrochloride

Histidine dihydrochloride crystallizes in the orthorhombic system, space groupP2₁2₁2₁, with unit-cell dataa = 6.970(4),b = 16.165(7),c = 8.964(6)Å,V _c = 1010.0ų andZ = 4. Intensities for 1360 independent reflections were collected on an automated diffractometer. The structure was solved by standard heavy-atom methods and refined by full-matrix least squares, based onF, to anR-value of 0.027. The final weightedR-value and goodness-of-fit are 0.029 and 1.9, respectively. The histidine residue exists in the crystal as the carboxylic acid with protonation of the primary amine nitrogen and the imidazole ring. The overall conformation of the molecule is extended, similar to that observed inL-histidine,DL-histidine hydrochloride dihydrate, and one of the two independent molecules in the structure ofL-N-acetylhistidine. There is an extensive array of hydrogen bonds formed in the crystal, which, presumedly, together with the observed electrostatic interactions, account for the adopted molecular conformation.This investigation was supported by the donors of the Petroleum Research Fund, administered by the Americal Chemical Society, and by a National Institutes of Health Biomedical Science Support Grant. The diffraction equipment was purchased through a grant from the National Science Foundation.     

The chemistry of the “insoluble red woods.” Part 15. The crystal structures of 7-benzyloxy-6,2′,3′,4′-tetramethoxy- and 2,6,7,2′,3′,4′-hexamethoxy-isoflav-3-ene

The reaction of 7-benzyloxy-6,2,3,4-tetramethoxyisoflavylium perchlorate with 1-(2,4-dimethoxyphenyl)-3-(3,4-dimethoxyphenyl)-prop-l-ene and of 6,7,2,3,4-pentamethoxyisoflavylium perchlorate with the same propene yielded respectively 7-benzyloxy-6,2,3,4-tetramethoxyisoflav-3-ene (5) and 2,6,7,2,3,4-hexamethoxyisoflav-3-ene (7) whose structures have been established by X-ray crystallography. Crystals of (5) are monoclinic, space groupP2₁/a (No. 14) with four molecules in a unit cell of dimensionsa=8.528(2),b=13.294(3),c=19.629(4) Å,=99.92(2)°. Crystals of (7) are also monoclinic, space groupC2/c (No. 15) with eight molecules in a unit cell of dimensionsa=28.088(3),b=10.662(3),c=12.869(1) Å,=97.32(1)°. Both structures were solved by direct methods and refined by full-matrix least-squares calculations to finalR values of 0.053 and 0.041 for 1673 and 1424 observed data for (5) and (7) respectively. The molecular dimensions are in accord with accepted values.For Part 14 see Whalley, W. B., Ferguson, G., and Khan, M. A., (1980)J. Chem. Res. (M), 2219.