Effect of gravitational force on type-J counter-current chromatography by mathematical analysis

The gravitational force exerts an important effect on the counter-current chromatography (CCC) and has been used to retain the stationary phase and improve the efficiency in the various CCC separations. This paper deals with the effect of gravitational force on type-J CCC, one of the most popular CCC methods by the mathematical analysis for the first time. The theoretical analyses reveal a close relationship between the effect of gravitational force, the placed orientation of type-J CCC apparatus, and the revolutional speed. Two placed orientations are more suitable for preparative CCC separation: one is common horizontal, and the other upright. Thus, there are three optimum conditions for type-J CCC separation, the first using horizontal apparatus at very low revolutional speed around 10rpm in the gravitational filed, the second by use of upright apparatus at moderate revolutional speed around 100rpm in the three-dimensional complex force field composed of centrifugal and orthogonal gravitational force, and the third employing the apparatus placed at any orientation including horizontal and upright CCC apparatus at high revolutional speed above 300rpm in the centrifugal force field. Therefore, we should consider the effect of gravitation force on CCC at the selection of proper operational conditions according to properties of two immiscible phases, the desired revolutional speed and the parameters of apparatus in order to utilize efficiently the effect of gravitational force. These analyses and results will benefit to improve the efficiency of CCC separation, especially large-scale industrial preparation.     

二羟基二过碘酸合镍(IV)氧化氨基丙酸的动力学

在碱性介质中研究了二羟基二过碘酸合镍（Ⅳ）配离子（DDN）氧化α－氨基丙酸的动力学，结果表明，反应对DDN为一级，对α－氨基丙酸为正分数级，准一级速率常数，k_(obs)，随［OH~－］增加而增加，随［IO~-_4］增加而减小，无盐效应也未检出自由基1/k_(obs)对［IO~-_4］有直线关系，表明二羟基一过碘酸合镍（Ⅳ）（DMN）是氧化剂的活性物种，据此很出了一个包括DDN与DMN存在前期平衡和内层一步双电子转移的反应机理．导出的速率方程园满地解释了全部实验现象，并且计算出速控步聚的速率常数，前期平衡常数和活化参数．     

Experimental and Theoretical Insight into the Kinetics and Mechanism of the Synthesis Reaction of 2,3‐Dihydro‐2‐phenylquinazolin‐4(1H)‐one Catalyzed in Formic Acid

An efficient and simple method has been developed for the synthesis of 2,3‐dihydro‐2‐phenylquinazolin‐4(1H )‐one catalyzed in formic acid. Also, the synthesis reaction between benzaldehyde and 2‐aminobenzamid was monitored spectrally. On the basis of the kinetic data obtained by the UV–vis spectrophotometry, both the first and second steps of the speculative five steps mechanism were enabled to be a rate‐determining step and also reaction showed second‐order kinetics. Considering information obtained by the stopped‐flow technique indicated that the first step is certainly a fast step. Moreover, the reaction was energetically and thermodynamically evaluated using theoretical methods and results were profoundly compared with the experimental approaches. Herein, theoretical rate constants were obtained using potential energy surfaces and the transition state theory at the B3LYP/6–311+G** level of theory. The Winger method was also applied to describe the tunneling effects. Calculations showed that the second step was the rate‐determining step in accordance with the experimental data. It is also found that the oxidation step was the fastest step in the proposed mechanism. For all five steps, two possibilities were considered for generating the probable product by using the thermodynamic parameters and kinetic data. Thermodynamic parameters also showed an exothermic reaction.     

碱性介质中二过碲酸合铜(III)氧化乙二醇的反应动力学及机理

本文采用分光光度法研究了碱性介质中二过碲酸合铜(III)(DTC)氧化乙二醇(Glgcol)在291.2-303.2K的反应动力学机理。结果表明, 反应对氧化剂(DTC)是一级, 对乙二醇也是一级, 准一级([Glycol]0>>[DTC]0)速率常数Kobs随着[OH^-]增加而增加, 随着[TeO4^2^-]增加而降低, 并且有负盐效应, 提出了一种含有前期平衡的反应机理。据此导出了一个能够解释全部实验事实的速率方程, 求出平衡常数、速控步骤的速率常数及298.2K时的活化参数。     

Kinetic analysis of genipin degradation in aqueous solution

Degradation of genipin (GP), a low toxicity natural protein crosslinking agent, in aqueous solution was monitored by HPLC at various pH levels. Degradation of GP was consistent with a mechanism consisting of a first order reaction with a reversible first step. Formation of the intermediate was slowest at more neutral pHs while formation of the irreversible product was correlated to increasing alkalinity. Degradation at all pHs was enhanced by the presence of phosphate ions. Degradation of GP most likely proceeds via the reversible opening of the dihydropyran ring by water followed by irreversible polymerization of the intermediate. Degraded solutions containing no detectable GP or intermediate, however, are still capable of crosslinking proteins.     

Kinetics of oxidation of ketoglutaric acids by alkaline chloramine-t solution

Kinetics of the oxidation of α-ketoglutaric and β-ketoglutaric acids by chloramine-T (CAT) have been investigated in highly alkaline media. The reactions show first order dependence in chloramine-T and fractional order in substrates. The order in hydroxide ions has been found to be second but shows a slight decrease at high concentration of alkali. No effect of p-toluene-sulphonamide was evident. Observed stoichiometry, positive effects of ionic strength and dielectric constant point to a mechanism involving formation of an intermediate in a termolecular rate determining slowest step among hypochlorite ion, hydroxide ion and enolic anion of keto acids followed by a fast step leading to products. Activation parameters have been computed and formaldehyde and formic acid were Identified as end-products.     

Investigation of phosphorus atomization using high-resolution continuum source electrothermal atomic absorption spectrometry

The atomization of phosphorus in electrothermal atomic absorption spectrometry has been investigated using a high-resolution continuum source atomic absorption spectrometer and atomization from a graphite platform as well as from a tantalum boat inserted in a graphite tube. A two-step atomization mechanism is proposed for phosphorus, where the first step is a thermal dissociation, resulting in a fast atomization signal early in the atomization stage, and the second step is a slow release of phosphorus atoms from the graphite tube surface following the adsorption of molecular phosphorus at active sites of the graphite surface. Depending on experimental conditions only one of the mechanisms or both might be active. In the absence of a modifier and with atomization from a graphite or tantalum platform the second mechanism appears to be dominant, whereas in the presence of sodium fluoride as a modifier both mechanisms are observed. Intercalation of phosphorus into the graphite platform in the condensed phase has also been observed; this phosphorus, however, appears to be permanently trapped in the structure of the graphite and does not contribute to the absorption signal.     

Kinetics and mechanism of chromium(III) catalyzed oxidation of 1,10-phenanthroline by alkaline permanganate

The kinetics of chromium(III) catalyzed oxidation of 1,10-phenanthroline by permanganate in alkaline medium at a constant ionic strength has been studied spectrophotometrically. The reaction between permanganate and 1,10-phenanthroline in alkaline medium exhibits 4:1 stoichiometry (KMnO₄:1,10-phenanthroline). The reaction shows first order dependence on [permanganate] and [chromium(III)] and less than unit order dependence in 1,10-phenanthroline, zero order in alkali concentrations. The results suggest the formation of a complex between the 1,10-phenanthroline and the chromium(III) which reacts further with one mole of permanganate species in the rate-determining step, resulting in the formation of a free radical, which again reacts with three moles of permangante species in a subsequent fast step to yield the products. The reaction constants involved in the mechanism were evaluated. The activation parameters were computed with respect to the slow step of the mechanism.This revised version was published online in December 2005 with corrections to the Cover Date.     

The “dimer nucleophile mechanism” for reactions with rate‐determining first step: Derivation of the whole kinetic law and further treatment of kinetic results

Overwhelming evidence has been previously reported for the existence of the so‐called “dimer nucleophile mechanism” in aromatic nucleophilic substitutions by amines in aprotic solvents, for which the most prominent feature is the fourth‐order kinetics (third order in amine) that has been observed with many different substrate–nucleophile systems, especially those in which departure of the nucleofuge is the rate‐determining step. The mechanism has been confirmed by several other features, although other alternative mechanisms were suggested to explain the fourth‐order kinetics, no one has been able to explain the other above‐mentioned features. The present paper affords additional experimental evidence and derivation of the kinetic expressions for reactions with good nucleofugues, where the first step is rate determining. The work involves studies of the reactions of 2,4‐dinitrofluorobenzene and 2,4‐dinitrochlorobenzene with aniline and with alkyldiamines in toluene. The novelty of this work lies in the selection of substrate–nucleophile systems exhibiting kinetic behavior that allows estimations of the different k's involved. The satisfactory agreement between the quotients of k's calculated from sets of data obtained under different reaction conditions hereby reported indicates that the assumptions made are correct and that the whole treatment applied to the kinetic data is justified. All together, the results fit well with the reaction scheme involving the dimer nucleophile mechanism, adding new evidence to this mechanism that it is well established in the current literature. © 2010 Wiley Periodicals, Inc. Int J Chem Kinet 42: 735–742, 2010     

一种用于大容量逆流色谱制备的立式多层螺旋管行星式离心机

Owing to no complications caused by solid supports, such as adsorptive sample loss and deactivation, tailing of solute peaks, and contamination, countercurrent chromatography (CCC) has been an area of intense research since the first introduction of CCC in 1970,[1] and various apparatus and broad applications have been advanced[2,3]. For these developments, the type-J synchronous planet centrifuge has received considerable attention, which relies not only on its relatively simple mechanic design, but also on its high partition efficiency and short elution time caused by mixing and settling for the efficient chromatographic separations. In the past, however, almost all of type-J centrifuges rotated slowly were disposed horizontally due to the original design and some experiments that gravis plays an important role at a low rotary speed as similar to type-V rotating multilayer helical tube in unit gravity[4-9]. In fact,we discovered that the upright apparatus holds more retention of stationary phase than the horiziontal aparatus when large standard tubings were used as mutilayer coil column and the aparatus was operated under same contions. We report here a new coil planet centrifuge with four upright cylindrical columns for large scale countercurrent chromatographic preparation. The design principle and apparatus of UCCC is as samilar to type-J multilayer coil planet centrifuge. Four uptight cylindrical column holders are symmetrically arranged around the centrifuge axis as similar to the type-J HSCCC with three horizontal multilayer coils connected in series[8] . A series of experiments indicat that upright CCC has many advantages over the horizontal CCC when using a large-bore tube as multilayer coil column for large scale countercurrent chromatographic separation.Upright CCC provide a versatile countercurrent chromatographic method for large-scale preparation from very crude sample. It has good preparative capacity and flexible suitability to various sample and two-phase system.The present apparatus not only can be operated at a high speed as similar as commonly used HSCCC for the system having short settling time and but also can be run at a low speed for the system having relative long settling time. Because of automatical control and seal-free flow through device, the uptight CCC apparatus may be readily scaled up to industrial preparation.     

Mechanism and kinetics of thermal decomposition of precipitates of the zinc oxide-aluminium oxide system from non-isothermal tg curves

Kinetics of decomposition of the precipitates of the ZnO&2sbndAl₂O₃ system, prepared by coprecipitation and mechanical mixing of the individual precipitates, have been studied. The decomposition of zinc basic carbonate is a first order rate process with an activation energy of 34.5 kcal/mole (Coats and Redfern equation). The decomposition of aluminium hydroxide is also best described as a first order rate process with one break in the Coats and Redfern plot corresponding to activation energies of 29.4 and 8.3 kcal/mole respectively. The entire course of decomposition of coprecipitated as well as mechanically mixed samples cannot be described by any one of the many rate equations available. Consequently, the Coats and Redfern equation has been employed. The plots indicate one or two breaks and thus two to three values of activation energy are reported. From the results it is to be concluded that decomposition of these precipitates is a heterogeneous process. The first step is definitely the decomposition of zinc basic carbonate followed by decomposition of aluminium hydroxide and/or interaction of the two precipitates resulting in the formation of “precursor” to spinel. The results of our earlier investigation on the same system (especially the formation of precursors) are well supported by the results reported in this investigation. p]A new equation (a modified form of the Elovich equation) has been proposed for such heterogeneous decomposition processes. The proposed equation also appears to be the general form of the equations where diffusion is the rate controlling process.     

铱（III）离子催化铈（IV）离子氧化异丁醇的反应动力学及机理

在酸性介质中用氧化还原滴定法研究了铈（IV）离子在痕量铱（III）离子催化作用下,于25～40 ℃区间氧化异丁醇（BA）的反应动力学.结果表明反应对铈（IV）离子为一级,对异丁醇的表观反应级数为正分数.准一级速率常数kobs随[H＋]及催化剂[Ir(Ⅲ)]增加而增大,随[HSO4-]增加而减小.在氮气保护下,反应不能引发丙烯酰胺聚合,说明在反应中没有自由基产生.提出了催化剂、底物和氧化剂间生成双核加合物的反应机理,通过kobs与HSO4-的依赖关系,找到本反应体系的动力学活性物种是Ce(SO4)2＋,并计算出平衡常数、速控步骤的速率常数及相应的活化参数.     

Buildup mechanism of carboxymethyl cellulose and chitosan self-assembled films

Films with different numbers of layers have been built by alternating the adsorption of carboxymethyl cellulose (CMC) and chitosan (CHI) at different pH levels. The adsorption process was recorded by quartz crystal microbalance (QCM). The results showed that under all pH conditions considered, the growth of the films is nonlinear. The film construction performed at pH 4.0 (preferred assembly pH) with different numbers of bilayers (CMC/CHI as one bilayer) was also observed step by step by atomic force microscopy (AFM). Comparing the growth process from QCM with the surface morphological changes from AFM shows the existence of an inhomogeneous structure for the first nine bilayers, and, after a coalescence of islands, an increase in the number of bilayers was demonstrated. The possible growth mechanism was also evaluated.     

Combustion experiments of polystyrene by use of a modified bayer-ICI-shell apparatus

The combustion of polystyrene by use of a quartz tube modified Bayer-ICI-Shell apparatus yields, beside the main component styrene, a lot of other products known as biological hazards like benzene, naphthalene and biphenyl. The experiments have been performed in air atmosphere. According to DIN 4102, technical polystyrene mainly used in the building industry has been burnt and the composition of the resulting combustion products has been compared with that produced from the Bayer-ICI-Shell (BIS) experiments. The fire gases adsorbed on charcoal XAD 4 and XAD 2 have been desorbed in carbon disulfide as a solvent.It is concluded that a combination of XAD 4 and charcoal is the most efficient adsorbent. In addition, a method for quantitative determination of fire gas containing decomposition products is discussed.     

Kinetic studies for sorption of some metal ions from aqueous acid solutions onto TDA impregnated resin

Summary Kinetic studies for sorption of uranium, thorium and cobalt ions from hydrochloric acid solutions using tri-dodecyl amine (TDA) loaded on Amberlite XAD4 (polystyrene resin supplied by Rohm and Haas) using the batch technique, have been evaluated and assessed. Analysis of the respective data in accordance with three kinetic models revealed that the particle diffusion mechanism is the rate determining step, and the sorption for each metal ion on the impregnated sorbent follows the first order reversible kinetics. Values of the first order rate constants, rate constants of intraparticle transport, and the particle diffusion coefficients for the studied ions were determined. Sorption isotherms, which have been evaluated from the distribution coefficients for these ions, were found in good fit with the Langmuir and Freundlich isotherms.     

RDX geometries, excited states, and revised energy ordering of conformers via MP2 and CCSD(T) methodologies: insights into decomposition mechanism

The geometries, harmonic frequencies, elec-tronic excitation levels, and energetic orderings of various conformers of RDX have been computed at the ab initio MP2 and CCSD(T) levels, providing more reliable results than have been previously obtained. We observe that the various local minimum-energy conformers are all competitive for being the absolute minimum and that, at reasonable temperatures, several conformers will appreciably contribute to the population of RDX. As a result, we have concluded that any mechanistic study to investigate thermal decomposition can reasonably begin from any one of the cyclohexane conformers of RDX. As such, it is necessary to consider the transition states for each RDX conformer to gauge what the activation energy is. Homolytic bond dissociation has long been speculated to be critical to detonation; we report here the most accurate estimates of homolytic BDEs yet calculated, likely to be accurate within 3 kcal mol(-1). The differences in energy for homolytic BDEs among all the possible RDR conformers are again small, such that most all of the conformers can reasonably be speculated as the next step in the mechanism starting from the RDR radical.     

Hybrid DFT study of the mechanism of quercetin 2,3-dioxygenase

The mechanism of the copper-containing enzyme quercetin 2,3-dioxygenase has been studied using hybrid density functional theory. This enzyme cleaves the O-heterocycle of a flavonol using dioxygen and releases carbon monoxide. Two different pathways for the dioxygen attack on the copper complex have been investigated, and the one where the first attack is on copper is found to be the energetically preferred one. By using this pathway the problem of having to go through a spin-orbit-induced spin crossing is also avoided. The adduct has three unpaired spins and is ideally suited for forming a dioxygen bridging structure, which occurs in the next step. Rather than cleaving the O-O bond in the next step, another C-O bond between dioxygen and the substrate is first formed. Finally, the O-O bond is cleaved, and CO is released in one concerted transition state with a very low barrier. The results are in good agreement with experimental findings. The mechanism is compared to the ones for other similar enzymes studied recently by similar methods.     

Theoretical insights into heme-catalyzed oxidation of cyclohexane to adipic acid

Adipic acid is a key compound in the chemical industry, where it is mainly used in the production of polymers. The conventional process of its generation requires vast amounts of energy and, moreover, produces environmentally deleterious substances. Thus, there is interest in alternative ways to gain adequate amounts of adipic acid. Experimental reports on a one-pot iron-catalyzed conversion of cyclohexane to adipic acid motivated a theoretical investigation based on density functional theory calculations. The process investigated is interesting because it requires less energy than contemporary methods and does not produce environmentally harmful side products. The aim of the present contribution is to gain insight into the mechanism of the iron-catalyzed cyclohexane conversion to provide a basis for the further development of this process. The rate-limiting step of the process is discussed, but considering the accuracy of the calculations, it is difficult to ensure whether the rate-limiting step is in the substrate oxidation or in the generation of the catalytically active species. It is shown that the slowest step in the substrate oxidation is the conversion of cyclohexanol to cyclohexane-1,2-diol. Hydrogen-atom transfer from one of the OH groups of cyclohexane-1,2-diol makes the intradiol cleavage occur spontaneously.     

Spectroelectrochemical investigation of a flavoprotein with a flavin-modified gold electrode

A flavin-modified gold electrode was developed in order to catalyze the electrochemical oxidoreduction of flavoproteins. Surface modification was carried out by a two-step procedure. In the first step a mixed self-assembled monolayer obtained by adsorption of activated and nonactivated 3,3'-dithiopropionic acid (free acid and N-succinimidyl ester) was formed, followed by the covalent attachment of a N(10)-hexylamino-alkylated flavin derivative via an amide bond in the second step. The electrochemical properties of the flavin-modified electrode are presented and discussed. The redox potential of the attached flavin was measured at various pH values and the electron-transfer rate constant between electrode and flavin was determined as k0 = 5 s(-1) independent of pH. The flavin-modified electrode was successfully applied to the electrochemical and spectroelectrochemical investigation of the flavoprotein WrbA from Escherichia coli that shows some structural similarities to flavodoxins. It is concluded that the electron transfer "electrode --> flavin --> flavoprotein" occurs by a two-step hopping mechanism where the first step is rate determining. Kinetic details are discussed. Furthermore, it turned out that, in contrast to flavodoxins, where the semiquinone state is stabilized, WrbA rapidly takes up two electrons, directly leading to the fully reduced form. The presented electrode surface modification may generally lend itself for spectroelectrochemical investigations of flavoproteins.