Molecular mechanics calculations (MM2 and MM3) on enamines and aniline derivatives

The MM2 and MM3 force fields have been extended to cover this class of compounds. Structures, vibrational spectra, and other data for 13 compounds were examined and can be reproduced satisfactorily by MM3. Except for the spectra, the other data can be reproduced somewhat less well by MM2. © 1994 by John Wiley & Sons, Inc.     

Preparation and structural characterization of the hexatungsten cluster complex (EDTEH)2[W6(μ3-Cl)8Cl6], (EDTEH=(MeO2CCH2)2N(H)CH2CH2N(CH2CO2Me)2+

The hexanuclear tungsten cluster complex [W₆(₃-Cl)₈Cl₆]^2–,1 was isolated as a salt of the cation (MeO₂CCH₂)₂N(H)CH₂CH₂N(CH₂CO₂Me)₂₊, EDTEH⁺, by crystallization from methanol solvent of the product obtained from the reaction of (H₃O)₂[W₆(₃-Cl)₈Cl₃] with the disodium salt of ethylenediaminetetraacetic acid. The compound was charcterized by single-crystal X-ray diffraction analysis. The cluster anion contains an octahedral arrangement of six tungsten atoms with chloride ligands bridging the eight triangular faces of the cluster and one chloride ligand terminally coordinated to each of the six tungsten atoms. The cation (EDTEH)⁺ achieves its positive charge by protonation of one of the nitrogen atoms. Crystal data: space group = P2₁/a,a=10.689(2) Å,b=22.931(6) Å,c=12.093(3) Å, =98.41(2)°,Z=2, 2476 reflections,R=0.028.     

Potentiometric pH response of membranes prepared with various aminated-poly (vinyl chloride) products

The preparation and potentiometric pH response properties of membranes formulated with various aminated-poly(vinyl chloride) (PVC-NH₂) products are described. Products containing secondary and/or primary amino functional groups are obtained by modifying PVC with mono- and/or diamines, respectively. Blank membranes prepared with either type of aminated-polymer exhibit nearly Nernstian potentiometric pH responses over different pH ranges. In general, membranes based on diamino products exhibit pH response over a wider range (5–10.5) than membranes formulated with monoamino products (<8.0). These potentiometric results are used to estimate the basicity of the various primary and secondary amino sites in the membrane phases.Dedicated to Professer W. Simon on the occasion of his 60th birthday     

反相高效液相色谱分离-安培法检测酚类化合物

本文报道了RP-HPLC-安培法检测测定酚类化合物的条件。在Shim-pack CLC-C_8柱上用含0.05mol/L NaH_2PO_4缓冲溶液的5％甲醇水溶液洗脱分离,于E+1.0V处检测。线性范围在0～7μg/ml,检测限达ng/ml。     

茶碱抗体的制备及鉴定

茶碱在临床上是一种非常有用的药剂。本文报道一种新的茶碱抗血清的制各及鉴定方法．用混合酸酐法合成抗原，借助于紫外光谱对其进行定性和定量分析。用混合免疫法免疫兔子，用免疫扩散法对抗血清进行鉴定。     

Aggregate manganese Schiff base moieties by terephthalate or acetate: dinuclear manganese and trinuclear mixed metal Mn2/Na complexes

A reaction system consisting of terephthalic acid, NaOH, inorganic Mn(II) or Mn(III) salt, and salicylidene alkylimine resulted in dinuclear manganese complexes (salpn)(2)Mn(2)(mu-phth)(CH(3)OH)(2) (1, salpn = N,N'-1,3-propylene-bis(salicylideneiminato); phth = terephthalate dianion), (salen)(2)Mn(2)(mu-phth)(CH(3)OH)(2) (2, salen = N,N'-ethylene-bis(salicylideneiminato)), (salen)(2)Mn(2)(mu-phth)(CH(3)OH)(H(2)O) (3), and (salen)(2)Mn(2)(mu-phth) (4), while the absence of NaOH in the reaction led to a mononuclear Mn complex (salph)Mn(CH(3)OH)(NO(3)) (5, salph = N,N'-1,2-phenylene-bis(salicylideneiminato)). In addition, a trinuclear mixed metal complex H[Mn(2)Na(salpn)(2)(mu-OAc)(2)(H(2)O)(2)](OAc)(2) (6) was obtained from the reaction system by using maleic acid instead of terephthalic acid. Five-coordinate Mn ions were found in 4 giving rise to an intermolecular interaction and constructing a one-dimensional linear structure. Antiferromagnetic exchange interactions were observed for 1-3, and a total ferromagnetic exchange of 4 was considered to stem from intermolecular magnetic coupling. (1)H NMR signals of phenolate ring and alkylene (or phenylene) backbone of the diamine are similar to those reported in the literature, and the phth protons are at -2.3 to -10.1 ppm. Studies on structure, bond valence sum analysis, and magnetic properties indicate the oxidation states of the Mn ions in 6 to be +3, which are also indicated by ESR spectra in dual mode. Ferromagnetic exchange interaction between the Mn(III) sites was observed with J = 1.74 cm(-1). A quasireversible redox pair at -0.29V/-0.12V has been assigned to the redox of Mn(2)(III)/Mn(III)Mn(II), implying the intactness of the complex backbone in solution.     

Separation and determination of protocatechuic aldehyde and protocatechuic acid in Salivia miltorrhrza by capillary electrophoresis with amperometric detection

Capillary electrophoresis with amperometric detection was applied to separate and determine protocatechuic aldehyde and protocatechuic acid in Salivia miltorrhrza preparations. The electrode used was a 0.3 mm diameter carbon disk electrode fixed in a wall-jet with amperometric detection. Under the optimum conditions, the two analytes were separated completely within 8 min. Excellent linearity was obtained in the concentration ranges of 0.25-100.0 microg ml(-1) and 0.50-100.0 microg ml(-1) for protocatechuic aldehyde and protocatechuic acid, respectively. The detection limits were 0.10 microg ml(-1) of protocatechuic aldehyde and 0.25 microg ml(-1) of protocatechuic acid, which were found to be lower than those of other methods that determine protocatechuic aldehyde (3,4-dihydroxybenzaldehyde) and protocatechuic acid (3,4-dihydrobenzoic acid) simultaneously. The mean recoveries of protocatechuic aldehyde and protocatechuic acid were 97.4% and 103.3%. This method has been successfully applied to monitor these two components in real samples such as Salivia miltorrhrza and its two traditional Chinese medicinal preparations.     

Noble gas-transition metal complexes: coordination of ScO+ by multiple Ar, Kr, and Xe atoms in noble gas matrixes

The combination of matrix isolation infrared spectroscopic and density functional calculation results provides strong evidence that the transition metal monoxide cation, ScO+, coordinates five noble gas atoms in forming the [ScO(Ng)5]+ (Ng = Ar, Kr, or Xe) complexes in noble gas matrixes.     

Cyclopalladated ferrocenylimine: a highly effective catalyst for the borylation/suzuki coupling reaction

The cyclopalladated ferrocenylimine was an efficient catalyst for the borylation/Suzuki coupling reaction. The catalytic loading for the reaction containing bromoarenes was 1 mol %. When iodobenzene was used, the catalytic loading was as low as 0.1 mol %. Furthermore, the cyclopalladated ferrocenylimine also exhibited excellent catalytic power in the case of substrates containing electron-donating substituents, with yields reaching 93% or higher.     

π-二苯铬(0)苯溶液的氧化反应

本文报道在苯溶液中,于中性条件下,过氧化氢与π-二苯铬(0)反应,可得到熔点为71℃的红色针状结晶。以差示扫描量热法测定其熔点、混合熔点和熔融热,还经元素分析、红外光谱、质谱及~1H核磁共振谱等鉴定,证明该结晶是由二克分子苯酚和一克分子苯醌形成的分子缔合物。π-二苯铬(0)苯溶液与过氧化氢反应的历程是:π-二苯铬(0)被氧化生成高价铬离子.此离子又使苯氧化成苯酚和苯醌,进一步形成酚醌分子缔合物。