停流—荧光动力学分析法测定痕量钛的研究

利用自行组装的停流-荧光动力学分析仪,采用停流法汇合流体动力注入技术,研究了钛与3.5-二溴水杨基荧光酮的荧光增强动力学反应性质,讨论了流速、进样时间对方法灵敏度和精密度的影响,提出了一个快速、简便、精确测定钛的分析方法,并用于稀土样品及合成样品中痕量钛的测定.方法检测限为8×10~(-3)ppm,大多数元素的干扰均可用动力学方法消除.     

枸橼酸莫沙必利的合成

分别以邻羟基对氨基苯甲醇钠，对氟苯甲醛，邻苯二甲酰亚胺为起始原料，制得3个中间体，用其中2个中间体经偶合，环化后与第3个中间体反应，再经成盐制得产品，其摩尔总收率为31．5％。     

Synthesis of functional polymers—Vinylidene fluoride based fluorinated copolymers and terpolymers bearing bromoaromatic side‐group

The radical co‐ and terpolymerization of 4‐[(α,β,β‐trifluorovinyl)oxy]bromo benzene (TFVOBB) with 1,1‐difluoroethylene (or vinylidene fluoride, VDF, or VF₂), hexafluoropropene (HFP), perfluoromethyl vinyl ether (PMVE), and chlorotrifluroroethylene (CTFE) is presented. Although TFVOBB could be thermocyclodimerized, it could not homopolymerize under radical initiation. TFVOBB could be copolymerized in solution under a radical initiator with VDF or CTFE comonomers, while its copolymerization with HFP or PMVE were unsuccessful. The terpolymerization of TFVOBB with VDF and HFP, or VDF and PMVE, or VDF and CTFE also led to original fluorinated terpolymers bearing bromoaromatic side‐groups. The conditions of co‐ and terpolymerization were optimized in terms of the nature of the radical initiators, and of the nature of solvents (fluorinated or nonhalogenated). Various monomer concentrations in the co‐ and terpolymers were assessed by ¹⁹F and ¹H‐NMR spectroscopy. The thermal and physico chemical properties were also studied. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5077–5097, 2004     

Spectroscopic study on the complex formation of chromogenic bridged calixarenes with aliphatic amines

The complex formation between chromogenic capped calix 4 arene derivatives comprising indophenol indicator group(s), and aliphatic amines has been studied by UV/Vis spectroscopy. The equilibrium constants have been determined in ethanol, and—for one ligand—also in dimethylsulfoxide. The results have been interpreted in terms of various types of host–guest interactions and of steric effects.     

The influence of hard‐segments on two‐phase structure and shape memory properties of PCL‐based segmented polyurethanes

Poly(ε‐caprolactone)‐based segmented polyurethanes (PCLUs) were prepared from poly(ε‐caprolactone) diol, diisocyanates (DI), and 1,4‐butanediol. The DIs used were 4,4′‐diphenylmethane diisocyanate (MDI), 2,4‐toluenediisocyanate (TDI), isophorone diisocyanate (IPDI), and hexamethylene diisocyanate (HDI). Differential scanning calorimetry, small‐angle X‐ray scattering, and dynamic mechanical analysis were employed to characterize the two‐phase structures of all PCLUs. It was found that HDI‐ and MDI‐based PCLUs had higher degree of microphase separation than did IPDI‐ and TDI‐based PCLUs, which was primarily due to the crystallization of HDI‐ and MDI‐based hard‐segments. As a result, the HDI‐based PCLU exhibited the highest recovery force up to 6 MPa and slowest stress relaxation with increasing temperature. Besides, it was found that the partial damage in hard‐segment domains during the sample deformation was responsible for the incomplete shape‐recovery of PCLUs after the first deformation, but the damage did not develop during the subsequent deformation. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 557–570, 2007     

Diethoxyphosphorylimine of methyl trifluoropyruvate in cyclocondensation with 1,3-C,N-and-N,N-binucleophiles

Reaction of diethoxyphosphorylimine of methyl trifluoropyruvate with 1,3-C,N-and-N,N-binucleophiles led to a variety of N-phosphorylated fluorine-containing heterocycles, including the fused ones. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2176–2178, November, 2007.     

Liquid Chromatography-Mass Spectrometry Determination of Six 5-Nitroimidazoles in Animal Feedstuff

A liquid chromatography-mass spectrometry method for the determination of the coccidiostats metronidazole, ronidazole, dimetridazole, secnidazole, tinidazole and ipronidazole in feedstuff was developed. The 5-nitroimidazoles were extracted from animal feed with a pH 2 phosphate buffer solution followed by a solid phase extraction procedure based on HLB cartridges. The liquid chromatographic separation of the extracts was performed on a C₁₈ bonded silica column applying a gradient of elution with pH 4.3 ammonium acetate buffer solution and acetonitrile. Quantification for each 5-nitroimidazole was carried out monitoring its molecular ion [M + H]⁺ obtained by positive electrospray ionisation mode. A pool of feedstuffs was used to optimise and validate the method. Linearity, quantification limit, intra-day and inter-day reproducibility and accuracy were estimated using this pool of feedstuffs spiked with the drugs. For the confirmatory assay, several fragment ions from each 5-nitroimidazole were obtained and monitored. The method was applied successfully to determine 5-nitroimidazoles in feedstuff at level of 0.05 mg kg⁻¹.     

Synthesis and properties of tricyclo[6.4.1.0]trideca-1,3(6),7,9,11-pentaene

A new cyclobutene-fused 1,6-methano[10]annulene was synthesized by pyrolysis of the sulfone and sulfinate adducts of 3,4-bis(methylene)-1,6-methano[10]annulene and its physical and chemical properties were disclosed.     

Synthesis of Methyl 2-(5-Arylidene-2,4-dioxotetrahydrothiazol-3-yl)propionates

A series of methyl 2-(arylidene-2,4-dioxotetrahydrothiazol-3-yl)propionates were prepared. A study of the 3D structure was performed. The log P values are given for all the synthesized compounds.     

Crystallographic report: Crystal structure of tetra(4‐methyl‐5‐imidazole‐carboxyaldehyde)zinc(II) diperchlorate

The central zinc(II) atom in the title complex is tetrahedrally coordinated by four nitrogen atoms derived from 4‐methyl‐5‐imidazolecarboxyaldehyde ligands with Zn? N in the range 2.007(3) to 2.026(4) Å. Copyright © 2003 John Wiley & Sons, Ltd.