Reaction‐Diffusion Systems in Intracellular Molecular Transport and Control

Chemical reactions make cells work only if the participating chemicals are delivered to desired locations in a timely and precise fashion. Most research to date has focused on active‐transport mechanisms, although passive diffusion is often equally rapid and energetically less costly. Capitalizing on these advantages, cells have developed sophisticated reaction‐diffusion (RD) systems that control a wide range of cellular functions—from chemotaxis and cell division, through signaling cascades and oscillations, to cell motility. These apparently diverse systems share many common features and are “wired” according to “generic” motifs such as nonlinear kinetics, autocatalysis, and feedback loops. Understanding the operation of these complex (bio)chemical systems requires the analysis of pertinent transport‐kinetic equations or, at least on a qualitative level, of the characteristic times of the constituent subprocesses. Therefore, in reviewing the manifestations of cellular RD, we also describe basic theory of reaction‐diffusion phenomena.     

TLC Determination of Aliphatic Polyamines on Calcium Sulfate Layers

Biogenic polyamines are sensitive markers for various diseases including cancer. Polyamines are difficult to analyze by chromatography due to their high polarity and water-solubility so that derivatization is an essential step for their chromatographic analysis. Earlier studies have shown the efficacy of calcium sulfate (CaSO₄) as a TLC coating material for the separation of polar compounds. The aim of this study was to explore the potential of CaSO₄ for the analysis of aliphatic polyamines without derivatization. The TLC of six polyamines (ornithine, citrulline, putrescine, cadaverine, spermidine and spermine) was carried out on CaSO₄ and silica gel plates using 11 different mobile phases. The results showed that CaSO₄ is superior to silica for the separation of underivatized polyamines. The development time of the CaSO₄ plates was also about one-third shorter as compared to silica. Methanol was the only solvent to produce differential R _F values for the polyamines studied. Ornithine (R _F , 0–2) and citrulline (R _F , 1–3) were separated from cadaverine (R _F , 0.93), spermine (R _F , 0.85) and spermidine (R _F , 0.85). For quantitative analysis, the polyamines were eluted from the coating material scratched from the plate and the absorbance of the supernatant was measured at 550 nm. The limits of detection (LOD) and quantification (LOQ) were found to be 0.75 and 1.88 μg, respectively. The procedure was applied to the quantitative separation of polyamines in spiked human urine samples (12.5–50 μg). This is probably the first study reporting a TLC method for the separation of underivatized polyamines.     

Electrophotochemical Metal-Catalyzed Decarboxylative Coupling of Aliphatic Carboxylic Acids

An electrophotochemical dual metal-catalyzed protocol for decarboxylative arylation of simple aliphatic carboxylic acids with aryl halides is reported. The relative stabilities of catalytically active metal complexes simultaneously generated at anode and cathode are the key design elements for the success of this convergent paired electrolysis. This new electrophotocatalytic method is mild, robust, and most importantly, capable of accommodating simple primary aliphatic acids including acetic acid – ubiquitous and variegated structural motifs yet remain oddly challenging substrates – directly as native functional groups for decarboxylative C(sp²)−C(sp³) bond formation.     

Uncommon Interactions of Aliphatic Dicarboxylic Acids with Cyclodextrins

A relatively high and unexpected increase of inclusion complex stabilities could be detected in some half dissociated dicarboxylic acids (HA⁻ ions) with intramolecular H-bonding. The intermolecular hydrogen bonds between the protruding functional groups of the guest and the hydroxy groups of the host are known to enhance the stability of the cyclodextrin (CD) inclusion complexes. The enhanced inclusion of HA⁻ species is promoted, not by the intermolecular but by the intramolecular H-bond indirectly, resulting in a compact shape of the guest with more favourable space filling.This revised version was published online in July 2005 with a corrected issue number.     

Sensitive Determination of Five Priority Haloacetic Acids by Electromembrane Extraction with Capillary Electrophoresis

A method for sensitive determination of five priority haloacetic acids in drinking water has been developed for the first time based on electromembrane extraction (EME) prior to CZE with capacitively coupled contactless conductivity detection (CZE‐C⁴D). The target analytes were extracted from 10 mL of the sample solution (donor phase), through the supported liquid membrane (using a polypropylene membrane supporting 1‐octanol), and into 10 µL of 50 mmol/L NaAc solution (acceptor phase). The extracted solution was directly analyzed by CZE‐C⁴D without derivatization. Several factors that affect separation, detection and extraction efficiency were investigated. Under the optimum conditions, five haloacetic acids (monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, monobromoacetic acid, and dibromoacetic acid) could be well separated from other components coexisting in water samples within 23 min, exhibiting a linear calibration over two orders of magnitude (r?0.9943); the enrichment factors at 430–671 were obtained in a 30 min of extraction, and the limits of detection were in the range of 0.17–0.61 ng/mL. The intraday relative standard deviations for peak areas investigated at 10 ng/mL were between 1.2% and 9.7% for the combined EME‐CZE‐C⁴D procedure. This approach offers an attractive alternative to the officially proposed method for purified drinking water analysis, which requires derivatization procedure prior to gas chromatography analysis.     

Uncommon Interactions of Aliphatic Dicarboxylic Acids with Cyclodextrins

A relatively high and unexpected increase of inclusion complex stabilities could be detected in some half dissociated dicarboxylic acids (HA⁻ ions) with intramolecular H-bonding. The intermolecular hydrogen bonds between the protruding functional groups of the guest and the hydroxy groups of the host are known to enhance the stability of the cyclodextrin (CD) inclusion complexes. The enhanced inclusion of HA⁻ species is promoted, not by the intermolecular but by the intramolecular H-bond indirectly, resulting in a compact shape of the guest with more favourable space filling.     

Chromatographic Behaviour of Phenols on Aliphatic Amines Impregnated Thin Layers

Abstract

The chromatographic behaviour of 40 phenols on silica gel G plates impregnated with ethylenediamine, diethylenetriamine, triethylenetetramine and hexamine has been studied and its correlation with the equilibrium constants of the adducts formed by the interaction of phenols with ethylenediamine as an impregnant has been attempted. A suitable separation scheme for these phenols on silica gel G plates impregnated with ethylenediamine and hexamine has been worked out.     

Activity of Aliphatic Diperoxy Acids in the Luminol Chemiluminescence Reaction

The activity of dilute aqueous solutions of aliphatic diperoxysuccinic, -glutaric, -adipic, and -sebacic acids in the luminol chemiluminescence reaction is studied. This activity can be detected at a low (10^–6–10^–5M) concentration of luminol in weakly alkaline solutions; it increases as the alkyl chain length of the acid decreases. The best conditions for chemiluminescence have been selected. It has been shown that individual or total diperoxy acids can be determined by luminol chemiluminescence. The determination limit for diperoxyadipic acid used as an example has been estimated at 2.0 ng/mL.     

Synthesis of D-Mannite Esters of Aliphatic and Aromatic Acids

Mono- and diesters of D-mannite with aliphatic acids and mixed diesters with aliphatic and aromatic acids were synthesized by transesterification of their methyl esters. The structures of the products are confirmed by PMR, ¹³ C NMR, and IR spectra     

长链脂肪族二元酸的合成及其在缩聚反应中的应用

长链脂肪族二元酸一般是指含有10个或以上碳原子的饱和直链二元酸,其两端带有羧基官能团,可用于合成香料、特种尼龙工程塑料、热熔胶、涂料、增塑剂、高级润滑油等众多化工产品;由于其链段中含有长烷烃链段,具有优于短链二元酸的性质,使得相应的合成材料具有优越的性能,因此广泛应用于化工、轻工、国防、汽车工业、工程材料等领域;同时,还可用于开发新的聚合物产品。长链脂肪族二元酸在自然界中不单独存在,目前工业上主要通过化学合成法和生物发酵法生产。本文主要对长链脂肪族二元酸的合成方法进行综述,包括传统有机合成、生物技术转化、烯烃复分解、异构化-氢氧羰基化及聚乙烯端基功能化等,并简要概述长链脂肪族二元酸在缩聚反应(聚酯和聚酰胺)中的应用。最后,对合成方法待解决的问题进行了总结,并对未来发展方向进行了展望。     

Improved QSAR Analysis of the Toxicity of Aliphatic Carboxylic Acids

The results of a QSPR study of the toxicity of carboxylic acids in aqueous solution are reported. The molecular set comprises 35 carboxylic acids with the corresponding pK _a values in water. The set of molecular and topological parameters includes electrotopological state of the carboxy and methyl groups, molar refractivity, refractive index, n-octanol-water partition coefficient logKo/w, surface tension, and polarizability. Quite reasonable estimates are obtained, which improve the results of previous theoretical calculations.     

Physicochemical Properties of 1,2-Diacylhydrazines Derived from Aliphatic Carboxylic Acids

The solubility and resistance to oxidation and hydrolysis of 1,2-diacylhydrazines derived from acetic, propionic, butyric, and valeric acids were studied in view of possible application of these compounds for concentrating nonferrous metals. The pK ₁ and pK ₂ values of the 1,2-diacylhydrazines were determined. The stability of conformers and the electron density distribution in the coordination-active moiety were estimated by SCF MO LCAO semiempirical calculations in the MNDO-PM3 approximation.     

Vanillin Esters of Aliphatic Acids in the Synthesis of 4,7-Phenanthroline Derivatives

Condensation of vanillin esters of aliphatic acids with 6-aminoquinoline and cyclic c-diketones (1,3-cyclohexanedione and dimedone) afforded new 2-methoxy-4-(11-oxo-7,8,9,10,11,12-hexahydrobenzo[b][4,7]phenanthrolin-12-yl)phenyl esters of carboxylic acids.     

Simulation of Steam Distillation of Multicomponent Mixtures of Higher Aliphatic Acids

A mathematical model of steam distillation of multicomponent mixtures of higher aliphatic acids is proposed, based on solving the equation of equilibrium states for closed systems with account of the non-ideal behavior of a solution.     

Electron Transfer through Monolayers of Mixed Long-chain Aliphatic Acids and Alcohols

Properties of monolayers of cetyl, stearyl, and eicosyl alcohols and stearic and behenic acids and their mixtures are studied, along with the kinetics of a redox reaction of hemin adsorbed on these monolayers. Three-dimensional computer models of corresponding monolayers are constructed and compared with their electrochemical behavior. Properties of monolayers of cetyl alcohol in acid and alkaline solutions and stearyl alcohol in acid solutions correspond to package of molecules in a stretched conformation oriented normally to the electrode surface; for the other one-component systems, the monolayer structure is less regular. The hemin redox reaction rate has no correlation whatsoever with the monolayer thickness and is defined by the length of the electron transfer path (over a chain of covalent bonds and through van der Waals contacts between molecules). The stronger the deviation of the conformation of molecules from the stretched one, the shorter the effective path of the electron transfer. In mixed films of stearic acid and cetyl alcohol (1 : 6), it is sometimes possible to keep molecules of stearic acid in a stretched conformation, thus inhibiting the electron transfer along the hydrocarbon chain of this molecule to a maximum extent. The other mixed systems, while making the conformation more stretched, fail to provide for a completely regular structure.     

Silver‐Catalyzed Decarboxylative Trifluoromethylthiolation of Aliphatic Carboxylic Acids in Aqueous Emulsion

A silver‐catalyzed decarboxylative trifluoromethylthiolation of secondary and tertiary carboxylic acids under mild conditions tolerates a wide range of functional groups. The reaction was dramatically accelerated by its performance in an aqueous emulsion, which was formed by the addition of sodium dodecyl sulfate to water. It was proposed that the radical, which was generated from the silver‐catalyzed decarboxylation in the “oil‐in‐water” droplets, could easily react with the trifluoromethylthiolating reagent to form the product.     

Diffusion Transport in Reconstructed Semi-Crystalline Structure of Polyolefins

Summary: Diffusion of penetrants (e.g., monomers) in polyolefins is important not only in their manufacturing and down-stream processing, but also in packaging and separation applications. We propose a general methodology linking the semi-crystalline structure of polyolefins to their application properties. This methodology comprises of AFM imaging of semi-crystalline structure, reconstruction of 3D replica of semi-crystalline polymer and calculation of application properties (e.g., diffusivity) depending on 3D morphology. Our algorithm is capable to achieve realistic crystallinities of reconstructed samples up to 70% and to reconstruct spherulites with preferential orientation of lamellae. We demonstrate and discuss difficulties experienced during AFM imaging of HDPE morphology, particularly the dependence of resulting AFM image representing the distribution of crystalline domains on the sample preparation including etching.     

脂肪族α-氨基酸疏水自缔合作用的流动微量热法研究

建立了水溶液中脂肪族α- 氨基酸疏水自缔合相互作用的化学模型, 根据模型方程对由精密流动微量热法测得的α- 氨基酸水溶液的稀释焓数据进行回归分析, 得到等步自缔合作用的平衡常数(K)、焓变(ΔHm)和熵变(ΔSm)等热力学参数, 发现焓、熵之间存在很好的补偿关系. 同时计算了溶液中水的偏摩尔过量熵(SE1), 并根据脂肪族α- 氨基酸的水化模型对结果进行了讨论. 建立的化学模型参数能在一定程度上解释McMillan- Mayer模型中的同系焓作用系数的物理意义.