N-烷基壳聚糖玻璃化转变温度的研究

采用差示扫描量热(DSC)法和热释电流(TSC)法研究了N-烷基壳聚糖的玻璃化转变行为. DSC法中采用二次扫描以消除溶剂和热历史的影响, 并利用物理老化方法来增强N-烷基壳聚糖在DSC曲线上的玻璃化转变区域的热焓吸热峰, 以克服DSC法的不灵敏性. 两种研究方法的结果一致表明, 三种N-烷基壳聚糖的玻璃化转变均发生在110～150 ℃温区内；取代的柔性烷基越大, 玻璃化转变温度(Tg)越低；但N-甲基壳聚糖例外, 其Tg略高于壳聚糖, 空间阻碍在这里起决定的作用.     

New 6-(4-Bromophenyl)-imidazo[2,1-b]thiazole Derivatives: Synthesis and Antimicrobial Activity

Summary.  New 4-alkyl/aryl-1-((6-(4-bromophenyl)-imidazo[2,1-b]thiazol-3-yl)-acetyl)-3-thiosemicarbazides and 3-alkyl/aryl-2-(((6-(4-bromophenyl)-imidazo[2,1-b]thiazol-3-yl)-acetyl)-hydrazono)-4-thiazolidinones were synthesized from 6-(4-bromophenyl)-imidazo[2,1-b]thiazole-3-acetic acid hydrazide. Their structures were elucidated by elemental analyses and spectroscopic data. All compounds were tested for antibacterial and antifungal activities. The antimicrobial activities of the compounds were assessed by the microbroth dilution technique. The compounds were also evaluated for antituberculosis activity against Mycobacterium tuberculosis H₃₇Rv (ATCC 27294); they exhibited varying degrees of inhibition in the in vitro primary screening at 6.25 μg · cm⁻³. The most active compound was 3-(4-nitrophenyl)-2-(((6-(4-bromophenyl)-imidazo[2,1-b]thiazol-3-yl)-acetyl)-hydrazono)-4-thiazolidinone. Corresponding author. E-mail: nurayulusoy@yahoo.com Received December 10, 2001. Accepted (revised) March 1, 2002     

The Synthesis of Novel Methotrexate-like Compounds

Summary. Methotrexate (MTX) is a folate antagonist used in treatment of several chronic inflammatory and neoplastic conditions. In this study, new MTX-like compounds that may-be potential anticancer agents were synthesized and their structures were determined by IR, UV, GC-MS, ¹H NMR, and ¹³C NMR spectra. Also, in this study, a series structurally related to MTX or folate analogous compounds were evaluated whether they have inhibitory properties on the dihydrofolate reductase activity (DHFR).     

Co(II), Ni(II) and Cu(II) complexes of 1,4-di-(1-hydroxyimino-2-phenyl-2-oxo-ethylamino)benzene

The ligand has been prepared from ω-chloroisonitrosoacetophenone and 1,4-phenylenediamine in the presence of NaHCO₃. The ligand have a C=O group and an –NH–R group adjacent to the oxime group. The Ni(II), Cu(II) and Co(II) complexes of the synthesized ligand were prepared and their structures were identified using FTIR, UV-Vis spectral data, elemental analysis, thermal analysis and magnetic moment measurements. The metal-ligand ratios were found to be 3:2. The ligands were found to coordinate to the metal ions via the oxime nitrogen, oxime oxygen, one of the carbonyl group and amide nitrogen atoms. Thermal analyses data reveals that the water in the complexes was found to be non-coordinated to the metal ions. In the trinuclear structures, the metals have the tetrahedral environments.     

(S)-3-苯基-2-氨基丙硫醇盐酸盐的合成

以L 苯丙氨酸为原料经还原反应得到氨基醇,用Boc基团进行氨基保护后得到(S) 3 苯基 2 叔丁氧羰基氨基 1 丙醇,甲磺酰化后与硫代乙酸钾在DMF中反应得到(S) 3 苯基 2 叔丁氧羰基氨基 1 丙硫醇乙酸酯,再分别脱除乙酰基,氨基保护基后得到(S) 3 苯基 2 氨基丙硫醇盐酸盐.并用元素分析、红外光谱、核磁共振等手段对中间体和目标化合物进行了表征.     

Synthesis of a Novel Core-shell Type Acrylic-polyurethane Hybrid Emulsion Containing Siloxane and Fluorine as well as Water and the Oil Resistances of Cured Film

Aqueous acrylic-polyurethane dispersions have become one of the major types of materials used in coating, paint and adhesive industries, because of excellent properties and environmental advantages1-5. However, some properties for cured film such as water…     

Synthesis of novel unsymmetrical phthalocyanines substituted with crown ether and nitro groups

This work reports on the synthesis of new unsymmetrically substituted phthalocyanines (M = Zn, Cu, Co, Ni) bearing three benzo-15-crown-5 units through oxy bridges and a nitro group. Phthalocyanines were prepared by a statistical condensation of 4-nitro phthalonitrile and 1-{[(benzo-15-crown-5)-4′-yl]oxy}phthalonitrile in the presence of anhydrous metal salts. All the target unsymmetrical phthalocyanines were separated by column chromatography and characterized elemental analyses, ¹H NMR, IR, mass and UV–Vis spectral data. Electrochemical behaviors of Cu (II) phthalocyanine by cyclic voltammetry and differential pulse voltammetry techniques gave two common phthalocyanine ring reductions and one ring oxidation processes. Peak-to-peak separation of the processes II and III (388 mV) and the measure of gap (1.672 V) between the HOMO and LUMO for the complex, fits a phthalocyanine with electrochemically inactive metal center.     

Alcohol-soluble functional vic-dioxime bearing alcoholhexylsulfanyl moieties: preparation, spectroscopy and electrochemistry

A new alcohol soluble functionalized vic-dioxime, bis-[(1-hydroxyhexyl)-(8,9-hydroxyimino)-7,10-dithiahexacosane (LH₂), and its alcohol-soluble mono and dinuclear complexes (Ni^II, Cu^II, Co^II, Mn^II, Pd^II and UO ₂ ^II ) have been prepared from 6-mercapto-1-hexanol and (E,E)-dichloroglyoxime under high dilution basic conditions. Reactive polyalcohol moieties appended at the periphery of the oxime containing two different heteroatoms (S-, O-), serve as a weak exocyclic binding sites for Pd^II and Ag^I metal ions and also provide solubility for the vic-dioxime complexes in low molecular-weight alcohols. Both mono-nuclear (LH)₂M and homodinuclear (LH)₂(UO₂)₂(OH)₂ and heterotrinuclear (LH)₂MM ₂ ^′ Xn, where M = Co^II M′ = Pd^II, X = Cl⁻, n = 4 and Ag^I X = NO ₃ ⁻ , n = 2) complexes have been obtained with a 1:2, 2:2, 3:2 metal/ligand ratio, respectively. Electronic spectra of the modified vic-dioximes exhibit monitorable changes in UV. All mono and dinuclear-complexes are soluble in common organic solvents. The elemental analysis, ¹H-n.m.r, i.r., u.v–vis, and f.a.b.–m.s data and by cyclic and differential pulse voltammetry measurements are presented.     

Dissociation constants of some Schiff bases and stability constants of their copper,cobalt, nickel and zinc complexes

The stoichiometry and stability constant of metal complexes with 4-(3-methoxy-salicylideneamino)-5-hydroxynaphthalene-2,7-disulfonic acid monosodium salt (H₂L) and 4-(3-methoxysalicylideneamino)-5-hydroxy-6-(2,5-dichlorophenylazo)-2,7-naphthalene disulfonic acid monosodium salt (H₂L¹) were studied by potentiometric titration. The stability constants of H₂L and H₂L¹ Schiff bases have been investigated by potentiometric titration and u.v.–vis spectroscopy in aqueous media. The dissociation constants of the ligand and the stability constants of the metal complexes were calculated pH-metrically at 25 °C and 0.1 m KCl ionic strength. The dissociation constants for H₂L were obtained as 3.007, 7.620 and 9.564 and for H₂L¹, 4.000, 6.525, 9.473 and 10.423, respectively. The complexes were found to have the formulae [M(L)₂] for M = Co(II), Ni(II), Zn(II) and Cu(II). The stability of the complexes follows the sequence: Zn(II) < Co(II) < Cu(II) < Ni(II). The high stability of H₂L¹ towards Cu(II) and Ni(II) over the other ions is remarkable, in particular over Cu(II), and may be of technological interest. Concentration distribution diagram of various species formed in solution was evaluated for ligands and complexes. The formation of the hydrogen bonds may cause this increased stability of ligands. The pH-metric data were used to find the stoichiometry, deprotonation and stability constants via the SUPERQUAD computer program.     

笃斯茎中六种无机元素含量分析

应用原子吸收光谱法测定了内蒙古地产的笃斯茎、叶中的Cu,Fe,Zn,Mn,Ca,Mg等六种人体必需微量元素及宏量元素的含量。从而为评价笃斯的品质及其药理、药效提供了具有一定价值的数据。