New Zn(II) complexes based on biologically active substituted acetic acid and nitrogen donor ligands: synthesis,crystal structure and biological applications

The complexes [Zn(phenylacetato)₂(2-aminopyridin)₂] (3), [Zn(phenylacetato)₂(1,10-phenanthroline)]·H₂O (4), and [Zn(phenylacetato)₂(2,9-dimethyl-1,10-phenanthroline)]·0.5 H₂O (5) were prepared and characterized by IR-, UV–Visible, ¹H and ¹³C NMR spectroscopy, and single crystal X-ray diffraction. BNPP hydrolysis of the complexes and their parent nitrogen ligands showed that the hydrolysis rate of bis-(4-nitrophenyl) phosphate (BNPP) was 1.7 × 10⁵ L mol^?1 s^?1 for 3, 3.1 × 10⁵ L mol^?1 s^?1 for 4 and 4.3 × 10⁴ L mol^?1 s^?1 for 5. Antibacterial activities show the effect of complexation on activity against Gram-positive (S. epidermidis, S. aureus, E. faecalis, M. luteus and B. subtilis) and Gram-negative (K. pneumonia, E. coli, P. mirabilis and P. aeruginosa) bacteria using the agar well diffusion method. Complex 4 showed good activity against G? bacteria except P. aeruginosa, and against G+ bacteria except E. ferabis. Complex 5 showed no activity against G? bacteria, low activity against M. luteus and B. subtilis bacteria and high activity against S. epidemidis and S. aureus. Complex 3 did not show any activity against G? or G+ bacteria.     

分散固相萃取结合气相色谱-高分辨质谱快速筛查酱油中多种氯丙醇

建立了酱油中1，3-二氯-2-丙醇、2，3-二氯-1-丙醇、3-氯-1，2-丙二醇和2-氯-1，3-丙二醇的分散固相萃取-气相色谱-高分辨质谱快速筛查检测方法。样品采用乙酸乙酯提取，提取液浓缩后经N-丙基乙二胺净化，气相色谱-高分辨质谱测定，内标法定量。结果表明，该方法对于酱油中4种氯丙醇的定量限为0.5~10 μg/kg。在3个浓度水平下的加标回收率为78%~103%；相对标准偏差均不大于8.8%。该方法快速、简便、准确、灵敏，可作为酱油中4种氯丙醇的有效检测方法。     

胶束溶液中高氯酸二水(四胺)合钴(Ⅲ)配合物催化磷酸二酯水解的研究

本文合成了疏水性高氯酸二水（四胺）合钴（Ⅲ）配合物，研究了它与非离子表面活性剂Brij35形成的金属2胶束催化二（对硝基苯酚）磷酸二酯水解的动力学及其机理。结果表明此金属胶束对磷酸二酯水解的速率大约提高10^4倍，这主要是由于表面活性剂胶束的pH效应和浓聚效应所致，暗示着顺式二水类配合物形成的金属胶束是一个潜在的磷酸二酯水解剪切的催化剂。     

Sulfur Compounds. 183. A Derivative of Perthiocarbonic Acid H2CS4: X-ray structural analysis of bis(triphenylmethyl) perthiocarbonate (Ph3C)2CS4

The molecular structure of Ph₃CSSC(S)SCPh₃ · CS₂ has been determined by X-ray structural analysis. The substance crystallizes in the triclinic crystal system [a = 884.9(2) pm, b = 1 039.5(2) pm, c = 2 064.6(3) pm, α = 75.86(1)°, β = 79.83(2)°, γ = 77.31(5)°, Z = 2, space group P1 ]. The CS₃ group is planar; the S? S-bond (201.4 pm) forms an angle of 5.7° with the CS₃ plane. The torsional angle CSSC equals 96.3°. (Ph₃C)₂CS₄ was obtained by reaction of TosNSCl₂ (Tos = p-MeC₆H₄SO₂) with Ph₃CSH in CS₂ in the presence of triethylamine. The reaction mechanism is discussed.     

Synthesis of aromatic liquid crystals with asymmetric diester based on rod-like multi-ring system by two-step esterification method

A novel method of two-step esterifications was developed to synthesize compounds with asymmetric double ester groups. By using this method, six rod-like double ester compounds were prepared with p-hydroxy benzaldehyde, p-hydroxy benzoic acid bicyclohexyl carboxylic acid, cyclohexyl benzoic acid and biphenyl carboxylic acid substituted by n-propyl and n-pentyl as main reactants. The structures and properties of target compounds were confirmed by IR, MS, ¹H NMR, elemental analysis, differential scanning calorimetry (DSC) and hot stage polarizing optical microscope (HS-POM). Typical yields of the target molecules were more than 70%. All the molecules have mesophases with the textures of nematic type, indicating a rod-like molecule with a longer rigid skeleton can keep its mesophases. There was no clearing point observed for any of the derivatives before they decomposed so that the temperature ranges of the mesophases could not be determined. The energy differences between frontier molecular orbitals (HOMO-LUMO) (E_g) of the compounds were calculated by cyclic voltammetry (CV). The terminal ring system has an obvious influence on the energy levels and the energy gaps (E_g).     

HPLC–ELSD法测定三乙醇胺单、双、三酯季铵盐的含量

建立正相高效液相色谱–蒸发光散射检测法测定工业样品中的三乙醇胺单、双、三酯季铵盐的含量。以正己烷–甲醇–四氢呋喃(体积比85∶10∶5,加0.5 mL三氟乙酸调节至pH 3.50)为流动相,等度洗脱三乙醇胺单、双、三酯季铵盐,色谱柱为HP–氨基正相柱,柱温27℃,流量1.0 mL/min,蒸发光散射检测器漂移管温度80℃,载气流量2.6 L/min。三乙醇胺单、双、三季铵盐质量浓度的自然对数与各自对应的色谱峰面积和的自然对数呈良好的线性,相关系数(r~2)分别为0.991 4,0.996 7,0.991 5。测定结果的相对标准偏差为0.6%~2.6%(n=6),加标回收率分别为98.6%,101.2%,97.9%。该方法准确快速,可以为三乙醇胺单、双、三酯季铵盐的生产工艺优化提供理论数据。     

Aqueous Diels-Alder Reactions of Cyclopentadicnc with Symmetric Diester of Fumarate or Maleate

Cis- or irans- dimethyl and diethyl ester of bicyclo[2,2,1]hept-5-ene-2,3-die(2 or 4) were used as pesticides 1-4 in the fourties and fifties of the century to prevent orkill mosquito, fly and flea. The of's-dimethyl ester Za was also added to cosmetics forthe same purpose 5. The diethyl and dipropyl esters (2b and Zc) could be used to makerubber and elastomers6'7. Besides, this kind of compounds are important intermediatesfor synthesis of some drugs.The Diels-Alder reaction of cyclopentadie…     

Catalytic Hydrolysis of Phosphate Diester with Metal Complexes of Macrocyclic Tetraamine in Comicellar Solution

Four novel pyridine or benzene ring‐containing pendant macrocyclic dioxotetraamines 2,6‐dixo‐l,4,7,10‐tetraazacyclododecane ligands have been synthesized. Their metal complexes have been investigated as catalysts for the hydrolysis of bis(p‐nitrophenyl) phosphate (BNPP) in aqueous comicellar solution. The results indicate mat the hydrophobic interaction between substrate and metal complex, the nature of transition metal ion, and the micellar microenvironment are important factors for the hydrolysis of BNPP. Large rate enhancement (up to over two‐three orders of magnitude) employing 5 has been observed.     

Determination of Polyethylene Glycol Monoester Acrylate and Polyethylene Glycol Diester Acrylate Using Reversed-Phase High-Performance Liquid Chromatography

A procedure was developed for the determination of polyethylene glycol monoester acrylate (PEGMA) and polyethylene glycol diester acrylate (PEGDA) by reversed-phase high performance liquid chromatographic (RP-HPLC) with UV detector. Sample was well separated on an SinoChrom ODS-BP (C-18) column (200 × 4.6 mm i.d., 5 μm) with mobile phases composed of acetonitrile-phosphate buffer solution (0.05 mol · L^?1 pH = 6.86) in the ratio of 42:58 (v/v). The PEGMA and PEGDA were detected by UV detector at 205 nm, and quantitatively analyzed with an external standard of methyl acrylate. For PEGMA, the linear response ranged from 0.40 × 10^?5 mol · L^?1 to 2.00 × 10^?3mol · L^?1 (r² > 0.999), the detection limit was 0.12 × 10^?5 mol · L^?1, the recovery rate was found to be 93.4%–99.7%. For PEGDA, the linear response ranged from 0.20 × 10^?5 mol · L^?1 to 1.00 × 10^?3mol · L^?1 (r² > 0.999), the detection limit was 0.04 × 10^?5 mol · L^?1, the recovery rate was found to be 99.1% ～ 105.8%. This quantitative method can also be used in the HPLC analysis of other α,β-unsaturated esters.     

乌头类双酯型生物碱对嗜热四膜虫生长代谢的微量热学研究

建立灵敏表征乌头类双酯型生物碱(DDA)对嗜热四膜虫生长代谢影响的评价方法. 采用微量热法, 在不同给药条件下, 以表达功率-时间曲线(热谱曲线)的特征参数生长速率常数(k)、半数抑制浓度(IC₅₀)、最大输出功率(P_max)及达峰时间(t_p)和总产热量(Q_t)为指标, 对嗜热四膜虫生长代谢程度进行客观地量化评价. 结果表明, 随着3种DDA浓度的增加, 达峰时间t_p延长, 生长速率常数k、最大输出功率P_max等随之降低, 且生长速率常数k与相应的浓度间呈现良好的线性关系: r_乌头碱＝0.9910 (IC₅₀＝207.7 μg•mL^－1); r_新乌头碱＝0.9923 (IC₅₀＝412.5 μg•mL^－1); r_次乌头碱＝0.9977 (IC₅₀＝1497 μg•mL^－1). 同时由半抑制浓度IC₅₀得到3种DDA毒性的大小顺序: 乌头碱＞新乌头碱＞次乌头碱. 初步构效关系研究表明, 在化合物C(3)上引入羟基(OH)以及N原子上引入乙基(CH₂CH₃)均可明显增加双酯型生物碱对嗜热四膜虫的毒性作用.