Separation of five oligostilbenes from Vitis amurensis by flow‐rate gradient high‐performance counter‐current chromatography

A rapid and efficient high‐performance counter‐current chromatography (HPCCC) method was developed to separate five oligostilbenes from the roots of Vitis amurensis. An n‐hexane/ethyl acetate/methanol/water system (4:8:4:10, v/v/v/v) was selected as an optimal two‐phase solvent system of which the upper phase was used as the stationary phase and the lower phase was used as the mobile one. Partition coefficient values for the target compounds under these optimized conditions were 0.28 ( 1 , ampleosin A), 7.12 ( 2 , (+)‐g‐viniferin), 2.26 ( 3 , vitisin A), 5.38 ( 4 , wilsonol C), and 11.23 ( 5 , vitisin B). Flow‐rate gradient HPCCC (4 mL/min in 0–70 min, 8 mL/min in 70–250 min) was applied to isolate the target compounds in as high purity as possible within the shortest possible run time. Under these conditions, ampelopsin A (12.1 mg), (+)‐g‐viniferin (10.4 mg), vitisin A (2.8 mg), wilsonol C (3.2 mg), and vitisin B (37 mg) were isolated with >95% purity from 150 mg of enriched oligostilbene extract. Although the K_D of the last eluted compound, vitisin B (K_D = 11.23), was relatively large, it was eluted in 115–145 min using the two‐phase solvent system. This study shows that HPCCC is an efficient tool for the isolation and purification of natural products.     

Separation and purification of antioxidants from Ampelopsis heterophylla by counter‐current chromatography

In this study, bioactive components from Ampelopsis heterophylla were separated by counter‐current chromatography (CCC). The antioxidant activity of the crude extract was initially evaluated by an online HPLC method. Five compounds in the crude extract exhibited good antioxidant activities, namely, hyperoside ( 1 ), isoquercitrin ( 2 ), rutin ( 3 ), kaempferol‐3‐rutinoside ( 4 ), and quercetin ( 5 ). These compounds were further separated by CCC with biphasic solvent systems and their structures were identified by MS and NMR spectroscopy. All the compounds exhibited significant 1,1‐diphenyl‐2‐picryl‐hydrazyl radical scavenging activities with IC₅₀ values at 18.2 ± 1.3, 17.0 ± 1.4, 24.2 ± 1.2, 38.1 ± 1.7, and 9.0 ± 1.2 μM, respectively. The scavenging ratios of the compounds against hydroxyl radicals were 65 ± 5, 68 ± 4, 96 ± 2, 70 ± 4, and 98 ± 2%, respectively.     

Enantioseparation of chiral aromatic acids by multiple dual mode counter‐current chromatography using hydroxypropyl‐β‐cyclodextrin as chiral selector

This work concentrates on extending the utilization of multiple dual mode (MDM) counter‐current chromatography in chiral separations. Two aromatic acids, 2‐(6‐methoxy‐2‐naphthyl)propionic acid (NAP) and 2‐phenylpropionic acid (2‐PPA), were enantioseparated by MDM counter‐current chromatography using hydroxypropyl‐β‐cyclodextrin (HP‐β‐CD) as chiral selector. The two‐phase solvent systems consisting of n‐hexane/ethyl acetate 0.1 mol/L phosphate buffer pH 2.67 containing 0.1 mol/L HP‐β‐CD (7.5:2.5:10 for NAP and 7:3:10 for 2‐PPA, v/v/v) were used. Conventional MDM and modified MDM were compared according to peak resolution under current separation mechanism. The influence of elution time after the first‐phase inversion and number of cycles for MDM were investigated. Peak resolution of NAP and 2‐PPA increased from 0.62 to 1.05 and 0.72 to 0.84, respectively, using optimized MDM conditions. Being an alternative elution method for counter‐current chromatography, MDM elution greatly improved peak resolution in chiral separations.     

An interesting two‐phase solvent system and its use in preparative isolation of aconitines from aconite roots by counter‐current chromatography

Two‐phase solvent system plays crucial role in successful separation of organic compounds using counter‐current chromatography (CCC). An interesting two‐phase solvent system, composed of chloroform/ethyl acetate/methanol/water, is reported here, in which both phases contain sufficient organic solvents to balance their dissolving capacities. Adjusting the solvent system to get satisfactory partition coefficients (K values) for target compounds becomes relatively simple. This solvent system succeeded in sample preparation of aconitine (8.07 mg, 93.69%), hypaconitine (7.74 mg, 93.17%), mesaconitine (1.95 mg, 94.52%) from raw aconite roots (102.24 mg, crude extract), benzoylmesaconine (34.79 mg, 98.67%) from processed aconite roots (400.01 mg, crude extract), and yunaconitine (253.59 mg, 98.65%) from a crude extract of Aconitum forrestii (326.69 mg, crude extract).     

Application of supercritical fluid extraction coupled with counter–current chromatography for extraction and online isolation of unstable chemical components from Rosa damascena

Supercritical fluid extraction (SFE) coupled with high‐speed counter‐current chromatography (HSCCC) was successfully used for the extraction and online isolation of the unstable compounds from Rosa damascene in a single extraction and separation operation in two stages. The solvent systems of SFE/HSCCC were optimized with the help of multiexponential function model. At the first stage, the upper phase of the solvent system of n‐butanol–tert‐butyl methyl ether–acetonitrile–0.1% aqueous TFA (1.7:1.0:0.8:4.0, v/v/v/v) was used as both the SFE entrainer and the HSCCC stationary phase, and the target compounds were eluted with the corresponding lower phase to separate the hydrophobic compounds. At the second stage, the upper phase of the solvent system of n‐hexane–ethyl acetate–methanol–water (3.2:1.0:2.8:2.6, v/v/v/v) was used as both the SFE entrainer and the HSCCC stationary phase, followed by elution with the corresponding lower phase to separate the moderate hydrophobic compounds. Six compounds including formononetin, delphinidin, cyaniding, 5,6,4′‐trihydroxy‐7,8‐dimethoxy flavone, 5,3′‐dihydroxy‐7,8‐dimethoxy flavone, and 5‐hydroxy‐6,7,8,3′,4′‐pentamethoxy flavone were successfully separated in one extraction–separation operation within 300 min. The targeted compounds were identified by MS and NMR spectroscopy. This research has opened up great prospects for industrial application of SFE/HSCCC to the extraction and separation of unstable compounds.     

A rapid and convenient method for preparative separation of three indissolvable polyphenols from Euphorbia pekinensis by the flexible application of solvent extraction combined with counter‐current chromatography

A rapid and convenient method was established to preparatively isolate the three ellagic acid types of compounds, which were the main polyphenols in Euphorbia pekinensis, by flexibly applying solvent extraction combined with counter‐current chromatography (CCC). The total extract (extracted using 95% ethanol) of E. pekinensis was pretreated by two simple steps before CCC isolation, following the procedure: the total extract was extracted by classical solvent extraction using petroleum ether and ethyl acetate, respectively, and then the ethyl acetate extract was suspended using 95% ethanol, after being allowed to stand overnight, the sediment was obtained. Partial sediment (100 mg) was then directly separated by CCC with a two‐phase solvent system composed of chloroform‐95% ethanol‐water‐85% formic acid (50:50:50:5, v/v/v/v). About 22 mg of 3,3′‐dimethoxy ellagic acid (1), 12 mg of 3,3′‐di‐O‐methyl‐4‐O‐(β‐d ‐xylopyranosyl)ellagic acid (2), and 35 mg of ellagic acid (3) with purities of 96.0, 95.2, and 95.4% were obtained respectively in one step within 4 h. After being purified by washing with methanol, the purities of the three compounds obtained were all above 98%. The purities were determined by HPLC and their chemical structures were further identified by ¹H and ¹³C NMR spectroscopy. The recoveries were calculated as 84.6, 85.7, and 89.5%, respectively. The result demonstrated that the present isolation method was rapid, economical and efficient for the preparative separation of polyphenols from E. pekinensis.     

锌电极放电过程及失效机制数值分析

锌-空气电池是一种高能量的电池体系.实验表明, 在大功率工作条件下, 锌电极的材料利用率随电流密度的增加而急剧下降. 为探索其在大功率工作条件下的放电机理, 本文针对这一过程建立了一维数学模型, 通过数值求解模拟多个物理量如离子浓度、传递电流密度、电极孔隙度、固体氧化锌等在电极内部的分布变化情况, 在此基础上分析电极的性能. 数值结果分析表明, 固体氧化锌对电极内质量传输过程的限制是导致电极失效的根本原因. 其析出时间及在电极内部的集中分布位置对电极性能有显著影响; 而仅当其体积分数超过30%-35%的范围后才开始显著限制传质过程. 讨论了电极的优化措施, 模拟表明更高的溶液电导率,更大的电极孔隙度有利于增加大功率工作条件下电极的材料利用率. 但最重要的是保持电极内部氢氧根离子的浓度在一个较高的值,对于封闭式电极可以通过补液实现, 理想情况为设计一个电解液循环式的锌电极.     

Design of a reaction field using a linear‐combination‐based isotropic periodic sum method

In our previous study (Takahashi et al., J. Chem. Theory Comput. 2012, 8, 4503), we developed the linear‐combination‐based isotropic periodic sum (LIPS) method. The LIPS method is based on the extended isotropic periodic sum theory that produces a ubiquitous interaction potential function to estimate homogeneous and heterogeneous systems. The LIPS theory also provides the procedure to design a periodic reaction field. To demonstrate this, in the present work, a novel reaction field of the LIPS method was developed. The novel reaction field was labeled LIPS‐SW, because it provides an interaction potential function with a shape that resembles that of the switch function method. To evaluate the ability of the LIPS‐SW method to describe in homogeneous and heterogeneous systems, we carried out molecular dynamics (MD) simulations of bulk water and water–vapor interfacial systems using the LIPS‐SW method. The results of these simulations show that the LIPS‐SW method gives higher accuracy than the conventional interaction potential function of the LIPS method. The accuracy of simulating water–vapor interfacial systems was greatly improved, while that of bulk water systems was maintained using the LIPS‐SW method. We conclude that the LIPS‐SW method shows great potential for high‐accuracy, high‐performance computing to allow large scale MD simulations. © 2014 Wiley Periodicals, Inc.     

Joint Destruction of Cadmium and Copper at Alternating Current Electrolysis in Sodium Hydroxide Solution

The dependence of the metal oxidation rate on the current density and temperature of joint destruction in sodium chloride was studied. It is established that the dependence of the oxidation rate of copper is linear and generally do not differ from the dependencies established at individual oxidation of copper in the solution of sodium chloride with concentration 46.5% wt. In contrast to the oxidation rate of copper, the oxidation rate dependence of cadmium has extreme character and the oxidation rate of cadmium at its joint oxidation of copper increased in 2-3 times indicating that the mutual influence of electrodes at the electrochemical process with alternating current. Thus, the obtained dependences can predict operating electrolysis parameters a obtain copper-cadmium oxide system of the given composition.     

Interplay of Hückel and Möbius Aromaticity in Metal-Metal Quintuple Bonded Complexes of Cr,Mo, and W with Amidinate Ligand: Ab initio DFT and Multireference Analysis**

The aromaticity of metal-metal quintuple bonded complexes of the type M₂L₂ (M=Cr, Mo, and W; L=amidinate) are studied employing gauge including magnetically induced ring current (GIMIC) analysis and electron density of delocalized bonds (EDDB). It is found that the complexes possess two types of aromaticity: i) Hückel aromaticity through delocalization of ligand π electrons with metal-metal δ-bond-forming 6 conjugated electrons (4π and 2δ) ring; ii) Craig-Möbius aromaticity through delocalization of π electrons of both the ligands with metal d-orbitals in Craig type orientation forming 10π electrons ring with a double twist. Extended transition state natural orbital chemical valence (ETS-NOCV) and canonical molecular orbital natural chemical shielding (CMO-NCS) analysis confirm the Craig-Möbius type arrangement of the orbitals. Furthermore, the unprecedented Hückel and Möbius type aromaticity is confirmed from the plot of the current pathways using 3D line integral convolution (3D-LIC) plots. The metal-metal bond order also increases down the group as justified from the complete active space self-consistent field (CASSCF) analysis. Due to an increase in the π and δ electron conjugation, both the Hückel and Möbius aromaticity increase down the group.