Accelerated solvent extraction and pH‐zone‐refining counter‐current chromatographic purification of yunaconitine and 8‐deacetylyunaconitine from Aconitum vilmorinianum Kom

This study aimed to seek an efficient method to extract and purify yunaconitine and 8‐deacetylyunaconitine from Aconitum vilmorinianum Kom. by accelerated solvent extraction combined with pH‐zone‐refining counter‐current chromatography. The major extraction parameters for accelerated solvent extraction were optimized by an orthogonal test design L₉ (3)⁴. Then a separation and purification method was established using pH‐zone‐refining counter‐current chromatography with a two‐phase solvent system composed of petroleum ether/ethyl acetate/methanol/water (5:5:2:8, v/v) with 10 mM triethylamine in the upper phase and 10 mM HCl in the lower phase. From 2 g crude extract, 224 mg of 8‐deacetylyunaconitine (I) and 841 mg of yunaconitine (II) were obtained with a purity of over 98.0%. The chemical structures were identified by ESI‐MS and ¹H and ¹³C NMR spectroscopy.     

A square‐pyramidal copper(II) complex with strong intramolecular hydrogen bonds: diaqua(N,N′‐dimethylformamide‐κO)bis[2‐(diphenylphosphoryl)benzoato‐κO]copper(II)

In the title Cu^II complex, [Cu(C₁₉H₁₄O₃P)₂(C₃H₇NO)(H₂O)₂], the molecule is bisected by a twofold axis relating the two 2‐(diphenylphosphoryl)benzoate (ODPPB) ligands. The asymmetric unit consists of a Cu^II metal centre on the symmetry axis, an ODPPB ligand, one water ligand and one dimethylformamide (DMF) ligand (disordered around the twofold axis). The Cu^II ion has fivefold coordination provided by two carboxylate O atoms from two ODPPB ligands, two O atoms from two coordinated water molecules and another O atom from a (disordered) DMF molecule, giving a CuO₅ square‐pyramidal coordination geometry. The ODPPB ligand adopts a terminal monocoordinated mode with two free O atoms forming two strong intramolecular hydrogen bonds with the coordinated water molecules, which may play a key role in the stability of the molecular structure, as shown by the higher release temperature for the coordinated water molecules than for the coordinated DMF molecule. The optical absorption properties of powder samples of the title compound have also been studied.     

Three New C19‐Diterpenoid Alkaloids from Aconitum forrestii

A further study of the alkaloid constituents of Aconitum forrestii led to the isolation of three new C₁₉‐diterpenoid alkaloids, named 14‐acetoxy‐8‐O‐methylsachaconitine ( 1 ), 14‐acetoxyscaconine ( 2 ), and 8‐O‐ethylcammaconine ( 3 ). Their structures were determined by UV, IR, and MS, 1D‐ and 2D‐NMR analyses.     

Atmospheric degradation mechanisms of a simulant organophosphorus pesticide isopropyl methyl methylphosphonate: A theoretical consideration

Calculations using density functional theory were performed to explore the mechanisms for atmospheric degradation of isopropyl methyl methylphosphonate (IMMP). The potential energy surface profiles for OH‐initiated reaction of IMMP were constructed, and all possible degradation channels were considered. Rate constants were further calculated using transition state theory. It was established from these calculations that H‐abstractions from alkyl groups have much lower energy barriers than substitutions of alkoxyl groups, and four possible H‐abstraction channels are competitive. Investigations into the secondary reactions under the presence of O₂/NO were also performed. It is shown that O₂ addition, reaction of peroxide radicals with NO to form RO radicals, and removal of ·RO are the major degradation pathways for alkyl radicals. Four selected products, CH₃OP(O)(CH₃)OC(O)CH₃, CH₃OP(O)(O)CH₃, (CH₃)₂CHOP(O)(CH₃)OH, and (CH₃)₂CHOP(O)(CH₃)OCH?O, are predicted to be the major products in this study. © 2013 Wiley Periodicals, Inc.     

Microwave‐assisted Aqueous Multicomponent Reaction: Facile Synthesis of Polyfunctionalized Indoline‐spiro Fused Pyran Derivatives

A green and highly efficient method for the synthesis of polyfunctionalized indoline‐spiro fused pyran derivatives has been established. This reaction was conducted by reacting readily available and inexpensive starting materials, such as isatins, cyclic‐1,3‐dicarbonyl compounds, and malononitrile in aqueous media without any catalysts under microwave irradiation. The present green synthesis shows fascinating properties such as the use of water as the reaction solution, concise one‐pot conditions, short reaction periods (8–14 min), and easy purifications. The synthesis could also set a good example to GAP (Group‐Assistant‐Purification) chemistry in which purification via chromatography can be avoided and the pure products can be easily acquired only by washing the crude products with 95% EtOH.     

Highly Efficient Synthesis of Tricyclic Perimidines under Microwave Heating

A new and efficient access to (Z)‐N‐(2‐argio‐1‐(1H‐perimidin‐2‐yl)vinyl)benzamide derivatives from readily available substrates in HOAc is described with aid of microwave irradiation. The results of our study provide a simple, straightforward synthetic route to these interesting classes of 2‐substituted perimidines analogs in excellent yields.     

Distinct Stepwise Reduction of a Nickel?Nickel‐Bonded Compound Containing an α‐Diimine Ligand: From Perpendicular to Coaxial Structures

A nickel? nickel‐bonded complex, [{Ni(μ‐L^.?)}₂] ( 1 ; L=[(2,6‐iPr₂C₆H₃)NC(Me)]₂), was synthesized from reduction of the LNiBr₂ precursor by sodium metal. Further controllable reduction of 1 with 1.0, 2.0 and 3.0 equiv of Na, respectively, afforded the singly, doubly, and triply reduced compounds [Na(DME)₃] ? [{Ni(μ‐L^.?)}₂] ( 2 ; DME=1,2‐dimethoxyethane), [Na(Et₂O)]Na[(L^.?)Ni? NiL^2?] ( 3 ), and [Na(Et₂O)]₂Na[L^2?Ni? NiL^2?] ( 4 ). Here L represents the neutral ligand, L^.? denotes its radical monoanion, and L^2? is the dianion. All of the four compounds feature a short Ni? Ni bond from 2.2957(6) to 2.4649(8) Å. Interestingly, they display two different structures: the perpendicular ( 1 and 2 ) and the coaxial ( 3 and 4 ) structure, in which the metal? metal bond axis is perpendicular to or collinear with the axes of the α‐diimine ligands, respectively. The electronic structures, Ni? Ni bonding nature, and energetic comparisons of the two structure types were investigated by DFT computations.     

主成分分析-近红外光谱法快速测定婴儿配方乳粉中必需脂肪酸

利用主成分分析法将婴儿乳粉的近红外光谱数据与必需脂肪酸含量建立校正模型,并采用交互验证和外部检验两种方式来考察模型的可靠性。得到模型校正相关系数(R2)0.8704,均方估计残差(RMSEC)和交互校验均方残差(RMSECV)分别为0.6275和0.8907,应用所建立的必需脂肪酸近红外模型对婴儿乳粉必需脂肪酸含量进行预测,并将预测值和化学测量值进行配对t检验,结果表明两者无显著差异。     

阳离子聚丙烯酰胺水分散液的制备及表征

通过丙烯酰胺(AM)与甲基丙烯酰氧乙基三甲基氯化铵(DMC)的水相分散共聚合制得阳离子聚丙烯酰胺(CPAM)水分散液.以红外光谱(FTIR),核磁共振(1H-NMR),光学显微照片(OP)证实了产物结构与形成机理;研究了引发剂类型及用量,无机盐选择及用量,分散剂用量及单体配比对CPAM转化率、分子量及分散液黏度的影响.结果表明,采用2,2’-偶氮二[2-(2-咪唑啉-2-代)丙烷]二氢氯化物(VA-044)和过硫酸钾(KPS)/甲醛次硫酸氢钠(SFS)复合引发剂,在硫酸铵浓度28%～32%,同时添加少量硫酸锂或氯化钠,分散剂0.5%～1.5%(所有物质用量皆对总反应体系而言)条件下,可在高转化率同时得到分子量较高、流动性良好的CPAM水分散液.