基于近红外光谱的维生素C片无损鉴别分析

基于近红外光谱技术与化学计量学方法,建立了一种国内外不同品牌维生素C片的无损鉴别方法。采集了国内外8个品牌的维生素C片共计40个样本的近红外光谱数据,比较了完整样品以及粉末样品的近红外光谱,采用连续小波变换技术消除背景干扰和基线漂移,基于标准偏差与相对标准偏差的变量筛选方法筛选出具有代表性的波数点,结合主成分分析方法对国内外不同品牌维生素C片进行鉴别分析。结果表明:原始光谱存在着明显的背景干扰和基线漂移现象,且粉末样品的重现性要优于完整样品;单纯使用原始光谱无法辨别来自不同品牌的维生素C片;连续小波变换可以有效消除背景干扰,提高模型鉴别能力;完整样品的鉴别准确率优于粉末样品,说明国内外不同品牌维生素C片主要成分基本一致,可能是辅剂和工艺上存在细微差异。通过结合近红外光谱分析技术与化学计量学方法,可实现对国产以及进口不同品牌维生素C片的鉴别分析。     

高效液相色谱-荧光检测法测定敬钊毒素-I的磷脂膜结合活性

敬钊毒素-I(JZTX-I)是一种能够抑制心肌钠通道失活的新型蜘蛛神经毒素,该文结合高效液相色谱与色氨酸荧光测定技术研究了JZTX-I的磷脂膜结合活性。脂质体共沉淀实验表明,JZTX-I具有不依赖于带负电荷磷脂组成的生物膜结合活性。当加入由酸性或中性磷脂构成的脂质体后,JZTX-I能够分别产生6.4和4.7 nm的蓝移以及7.4和8.0 nm的红移激发漂移,显示JZTX-I能够插入磷脂膜,同时该分子疏水表面的色氨酸残基处于一个运动受限的界面区域。荧光淬灭实验进一步证实,与脂质体结合能够减少该毒素分子表面色氨酸残基的溶剂暴露。该研究结果为阐明JZTX-I的离子通道门控调节机制提供了新的信息。     

One—Pot Synthese of 3,4—Dihydropyrimidine—2（1H）—thiones Catalyzed by La（OTf）3

A general and practical procedure for the syntheses of 3,4-di-hydropyrimidine-2(1H)-thiones by a one-pot condensation of aldehyde,β-ketoester or β-diketone and thiourea using La(OTf)3 as the catalyst is described.Mild reaction conditions,excellent yields as well as the environmentally friendly character of La(OTf)3 make it an important alternative to the classic acid-catalyzed Biginelli‘s reaction.     

Ag-MoO3催化丙烯直接气相环氧化反应的原位红外研究

制备了对丙烯直接气相环氧化具有较好催化性能的Ag-MoO3催化剂, 采用原位FT-IR技术研究了丙烯、环氧丙烷及丙烯+氧气的混合气在Ag和Ag-MoO3催化剂表面上的吸附及反应行为. 研究表明, 丙烯在Ag和Ag-MoO3催化剂表面上吸附后, 均不发生化学反应, 而环氧丙烷吸附后在较高温度下则发生开环和聚合反应直至产生积炭. 与Ag催化剂相比, 在Ag-MoO3催化剂上, MoO3的加入在降低催化剂活性的同时, 在一定程度上抑制了产物环氧丙烷的开环及深度反应, 使环氧丙烷的选择性提高. 另外, 在较低的反应温度和较短的滞留时间下, 环氧丙烷发生深度反应的程度明显降低.     

纳米稀土-介质薄膜光电发射光谱和能带结构

用真空蒸发沉积的方法制备了纳米稀土(La、Nd、Sm)粒子 BaO介质薄膜.研究表明薄膜的光电发射光谱响应阈值受纳米稀土粒子形状和大小的影响,球形纳米稀土(Sm)粒子 BaO介质薄膜的光谱响应阈值波长为720 nm,条状纳米稀土(La和Nd)粒子 BaO介质薄膜阈值波长分别为650 nm和660 nm.研究得到纳米稀土粒子 介质薄膜等效界面位垒高度在1.7～2.0 eV之间.由于纳米稀土粒子与BaO介质各自逸出功不同,当构成薄膜后使得纳米粒子周围的空间电荷分布发生变化,纳米粒子周围的能带发生弯曲.     

SYNTHESIS AND CHARACTERIZATION OF PHTHALAZINONE POLY(ARYL ETHER SULFONE KETONE)WITH CARBONYL GROUP*

A kind of novel heat-resistant, high performance engineering thermoplastic phthalazinone poly(aryl ether sulfoneketone) (PPESK) containing a carboxyl group in its side chain was prepared by the nucleophilic displacement reaction of 4-(4-hydroxylphenyl)-1(2H)-phthalazinone with di(4-chlorophenyl) sulfone, 4,4'-difluoro-benzophenone and phenolphthalin insulfolane in the presence of K_2CO_3 to produce high molecular weight polymers which can be dissolved in some polarsolvents such as chloroform and nitrobenzene at room temperature and can be easily can into flexible, yellowish andtransparent films. PPESK is an amorphous polymer having a decomposition temperature above 400℃, which indicates that ithas high thermal stability. At the same time, the thermal properties of PPESKs with dicyandiamide (DICY) as curing agentindicated that the heat-resistance properties of the PPESKs are improved after curing. The apparent activation energy (ΔE) ofthe cross-linking reaction and the reaction order (n) of PPESK/DICY were found to be 52.2 kJ/mol and ca. 1.0, respectively.Therefore, the cross-linking reaction is approximately a first order reaction.     

7-(对甲酰基苯偶氮)-8-羟基喹啉-5-磺酸的合成及其双波长分光光度法测定镓

7－（对甲酰基苯偶氮）－8－羟基喹啉－5－磺酸是一新显色剂。该试剂在微碱性介质中（pH＝7．5）与镓形成黄色络合物。络合物λmax＝392nm，摩尔吸光系数ε392＝2．24×104L·mol-1·cm-1。同时在500nm呈现负峰，用双峰观波长法测定镓ε392～500＝6．89×104L·mol-1·cm－1，灵敏度是单波长法的三倍多．线性范围0～2．0×10－5mol／L。用拟定的方法测定了掺硅的GaAS材料及岩石中的镓，加入回收率为106％～110％；方法的相对标准偏差小于1．6％。     

铜离子对烟草多酚氧化酶变性和复性影响的热力学研究(英)

在有无5 mmol·L^-1 CuSO₄存在的两种情况下，运用荧光光谱研究了烟草多酚氧化酶在盐酸胍诱导下的变性和复性平衡。烟草多酚氧化酶在6.0 mol·L^-1盐酸胍变性30 min(25 ℃)即完全失活。荧光光谱结果表明：铜离子能够提高烟草多酚氧化酶的结构稳定性和抗盐酸胍变性的能力，进而影响烟草多酚氧化酶在盐酸胍诱导下的变性和复性过程。没有外源铜存在的情况下，盐酸胍诱导的烟草多酚氧化酶变性和复性是一个可逆的二态过程；在5 mmol·L^-1 CuSO₄存在的条件下，由于结合了Cu²⁺的酶的中间态稳定性增加，显示特征荧光，结果显示，外源铜存在时，盐酸胍诱导的烟草多酚氧化酶变性和复性是一个可逆的三态过程。根据相应模型，进行了热力学计算。上述实验结果得到酶活性测定的进一步证实，在6 mol·L^-1盐酸胍中放置5，10，15，20，25，30 min，烟草多酚氧化酶的剩余活性分别为18.7%，11.7%，8.9%，6.6%，3.6%，0.06%，但在5 mmol·L^-1 CuSO₄存在的条件下，剩余活性则分别为60.3%，44.6%，42.5%，40.2%，25.6%，25.3%。     

四氮大环-金属配合物与DNA作用的电化学及谱学研究

Mononuclear copper（Ⅱ）, nickel（Ⅱ） and cobalt（Ⅲ） tetracoordinate macrocyclic complexes were synthesized and spectroscopically characterized. The crystal structure of the three compounds were determined by X-ray crystallography. The electrochemical experimental results indicate that the three complexes could interact with DNA mainly by electrostatic interaction. The interaction of tetracoordinate macrocyclic cobalt（Ⅲ） complex with DNA was studied by cyclic voltammetry and UV-vis spectroscopy. The experimental results reveal that tetracoordinate macrocyc- lic cobalt（Ⅲ） complex could interact with DNA by electrostatic interaction to form a 1 ： 1 DNA association complex with a binding constant of 7.50 ×10^3 L·mol^-1.     

超分子钴(Ⅱ)配合物[CoL(H2O)2]n的合成与结构表征

A mononuclear Cobalt(Ⅱ) complex [CoL(H₂O)₂]_n (H₂L: 4,4′,6,6′-Tetrabromo-2,2′-[ethylenedioxybis(nitrilomethylidyne)]diphenol), has been synthesized and structurally characterized by elemental analysis, IR and X-ray diffraction single crystal structure analysis. The crystal of the complex belongs to monoclinic space group P2₁/c with a=2.516 8(3) nm, b=1.023 43(18) nm, c=0.789 17(14) nm, β=91.375(2)°, V=2.032 1(5) nm³, Z=4, D_c=2.317 Mg·m^-3, μ(Mo Kα)=8.747 mm^-1, F(000)=1 356, R₁=0.049 7, wR₂=0.110 4. The crystal structure of [CoL(H₂O)₂]_n indicates that the complex consists of one cobalt(Ⅱ) atom, one L^2- unit and two coordinated water molecules, and the coordination number of the cobalt(Ⅱ) atom is six. One-dimensional chain supramolecular structure is formed by intermolecular hydrogen bonds and π-π stacking of neighboring benzene rings. CCDC: 652649.