[Cu2（Gly—GlyO）2（4,4‘—bpy）（OH）2].9H2O配合物的合成,晶…

将Ｇｌｙ－ＧｌｙＯ，４，４＇－联吡啶与Ｃｕ（ＮＯ３）２．Ｈ２Ｏ在二次水溶液中反应，合成出以４，４＇－ｂｐｙ为中继基，Ｃｌｙ－ＧｌｙＯ为螯环的新型双核铜配合物，经Ｘ射线单晶结构分析确定该配合物晶体的化学结构式为［（Ｈ２ＮＣＨ２ＣＯＮＨＣＨ２ＣＯＯ）Ｃｕ（ＯＨ）（Ｃ１０Ｈ８Ｎ２）Ｃｕ（ＯＨ）（Ｈ２ＮＣＨ２ＣＯＮＨＣＨ２ＣＯＯ）］．９Ｈ２Ｏ。晶体属Ｐ１空间群，晶胞参数α＝１．１４１２ｎｍ，ｂ＝１．２２９     

Ge—132在机体内代谢产物的实验证实

评述了Ｇｅ－１３２的安全性，对大鼠口服Ｇｅ－１３２代谢产物的研究表明，Ｇｅ－１３２的基本骨架ＧｅＣＨ２ＣＨ２ＣＯＯＨ没有变化，即它不会降解为ＧｅＯ２或其他的无机锗化合物。     

新相LaBa2Cu2MO7（M=Ga,Co）合成及其电学特征

用固相反应法制备出ＬａＢａ＿２Ｃｕ＿２ＭＯ＿７（Ｍ＝Ｇａ，Ｃｏ）新相。Ｘ射线衍射分析认为其属四方晶系，Ｌａ－Ｂａ＿２Ｃｕ＿２ＧａＯ＿７的；ＬａＢａ＿２Ｃｕ＿２ＣｏＯ＿７的。电阻和温度关系曲线测定表明均为半导体。     

三水合希土氯化物(镨、钆)与18－冠－6配合物的热化学研究

制备了ＲＥＣｌ３．３Ｈ２Ｏ（ＲＥ＝Ｐｒ，Ｇｄ）与１８Ｃ６的固态配合物，其化学组成为：ＲＥＣｌ３，１８Ｃ６．３Ｈ２Ｏ。对其进行了ＩＲ，溶解度、ＤＴＧ和ＴＧ分析，推测了热分解机理，测量了２９８．１５Ｋ时１８Ｃ６及两种配合物在无水乙醇中的积分，及ＲＥＣｌ３，３Ｈ２Ｏ在１８Ｃ６－Ｃ２Ｈ２ＯＨ溶液中的溶解配位热效应，依据本文所设计的热化学循环，求得了ＲＥＣｌ３，３Ｈ２Ｏ（ｓ）与１８Ｃ６（ｓ）生成ＲＥＣｌ３，     

LB膜技术对葡萄糖氧化酶分子构象的影响

利用π－Ａ曲线、布儒斯特角显微镜（ＢＡＭ）及ＣＤ光谱对葡萄糖氧化酶（ＧＯＤ）的甲醇溶液铺展在ＣｄＣｌ２水溶液和纯水表面上形成的单分子膜进行了研究，以了解ＧＯＤ分子的自组和折叠情况，发现甲醇或者ＣｄＣｌ２都能ＧＯＤ分子更加疏水，易形成单分子膜，铺展在ＣｄＣｌ２溶液上比铺展在纯水上更加能使ＧＯＤ的单分子膜排列紧密，在表面压较高时，能观察到形成了第二层膜，并且使ＧＯＤ分子的构象从β－折叠片向α－螺旋转变     

层间反应法制备CaGa2S4∶Ce电致发光器件

报道了用层间反应法制备ＣａＧａ２Ｓ４∶Ｃｅ薄膜，用电子束蒸发法交替沉积ＣａＳ∶Ｃｅ和Ｇａ２Ｓ３膜，然后经一定的处理，获得ＣａＧａ２Ｓ４∶Ｃｅ膜。Ｘ射线衍射、ＳＴＥＭ显微照片和ＥＤＸ等分析结果表明，产物为结晶度较好、符合ＣａＧａ２Ｓ４∶Ｃｅ化学计量比的发光薄膜，并得到了Ｃｅ３＋的蓝色发光谱。     

停流法研究Cu（Ser）2及Cu（Gly—Gly）2催化O2^—岐化反应动力学

采用停流法对ＰＨ＝７．８的磷酸盐缓冲液体系中丝氨酸铜Ｃｕ（Ｓｅｒ）２和甘氨酰甘氨酸铜Ｃｕ（Ｇｌｙ－Ｇｌｙ）２催化超氧了脑子自由基Ｏ２－歧化反应的动力学进行了研究，求得不同温度下的催化速率常数ｋｃａｔ、反应级数ｎ、活化能Ｅｎ及指前因子Ａ，初步探讨了Ｃｕ（Ｓｅｒ）２和Ｃｕ（Ｇｌｙ－Ｇｌｙ）２催化Ｏ２－歧化反应机理，证实了第一步反应为整体反应过程的速控步骤。     

取代型钨镓杂多配合物的导电性及其磁性

合成了过渡金属取代的钨镓杂多配合物α－Ｎａ７「ＧａＷ１１Ｃｏ（Ｈ２Ｏ）Ｏ３９」．１６Ｈ２Ｏ，α－Ｎａ７Ｈ２「ＧａＷ１０Ｃｏ２（Ｈ２Ｏ）２Ｏ３９」．１６Ｈ２Ｏ和α－ＮａｎＨｍ「ＧａＷ９ＭＥ（Ｈ２Ｏ）３Ｏ３７」．１６Ｈ２Ｏ「Ｍ＝Ｃｏ（Ⅱ），Ｎｉ（Ⅱ，）Ｖ（Ⅴ）」，通过红外，紫外，ＩＣＰ，ＴＧ－ＤＴＡ，ＥＰＲ，ＸＰＳ，＾１８３ＷＮＭＲ，极谱等手段进行了表征。     

层间反应法制备CaGa2S4：Ce电致发光器件

报道了用层间反应法制备了ＣａＧａ２Ｓ４：Ｃｅ薄膜，用电子束蒸发交替沉积ＣａＳ：Ｃｅ和Ｇａ２Ｓ３膜，然后经一定处理，获得了ＣａＧａ２Ｓ４；Ｃｅ膜。Ｘ射线衍射，ＳＴＥＭ显微归照片ＥＤＸ等分析结果表明，产物为结晶度较好，符合ＣａＧａ２Ｓ４；Ｃｅ化学计量比的发光薄膜，并得到了Ｃｅ＾３＋的蓝色发光谱。     

Gd（ClO_4）_3·3H_2O－18C6－CH_3CN三元体系25℃相平衡研究及配合物的合成与表征

采用半微量相平衡方法研究了Ｇｄ（ＣｌＯ_４）_３·３Ｈ_２Ｏ－１８Ｃ６－ＣＨ_３ＣＮ三元体系在２５℃时的溶解度，测定了饱和溶液的折光率。结果表明，该体系在２５℃时形成两种化学计量的配合物，其组成分别为：Ｇｄ（ＣｌＯ_４）_３·１８Ｃ６·３Ｈ_２Ｏ·２ＣＨ_３ＣＮ和Ｇｄ（ＣｌＯ_４）_３·２（１８Ｃ６）·３Ｈ_２Ｏ·２ＣＨ_３ＣＮ，制备了固态配合物，用化学分析及元素分析、ＩＲ、ＤＴＧ、ＴＧ及ＤＳＣ等研究了配合物的组成与性质。     

不同介质对Pt/GC电极制备及其性能的影响

应用循环伏安法(CV),扫描电子显微镜(SEM)和电化学原位红外反射光谱(in situFTIRS)研究了不同介质对碳载铂纳米薄膜电极(Pt/GC)的表面结构以及该薄膜电极对甲酸电催化氧化性能的影响.结果表明,使用不同介质的镀铂溶液,均可电沉积出分布较为均匀的Pt粒子,但其尺寸与形貌却相差很大.当以H2SO4作介质,由循环伏安法于玻碳电极上电沉积Pt得到的(Pt/GC1)电极,其Pt粒子粒径约100~200 nm;而在HClO4介质得到的(Pt/GC2)电极,则含有两种Pt微晶:其一是立方体形,粒径约200 nm,其二为菜花状,粒径约400 nm.电化学循环伏安和原位红外反射光谱测试指明,不同介质制备的Pt/GC电极对甲酸的电催化氧化均表现出与本体铂电极(Pt)相类似的特性,即可通过活性中间体或毒性中间体将甲酸氧化至CO2,但不同结构的Pt/GC电极具有不同的电催化活性.进一步以Sb或Pb修饰Pt/GC电极,不仅可以有效地抑制毒性中间体CO的生成,而且还能显著提高其电催化活性.比较本文研究的7种电极,其电催化活性顺序依次为:Sb-Pt/GC2>Pb-Pt/GC2>Pb-Pt/GC1>Sb-Pt/GC1>Pt/GC2>Pt/GC1>Pt.     

The group specific component/vitamin D binding protein (GC/DBP) system in the analysis of disputed paternities

The group-specific component (GC) was discovered in 1959, and in the same year a vitamin D binding protein (DBP) in human plasma was found; however, their identity was established as late as 1975. In the GC/DBP system three common alleles, GC*1F, GC*1S, and GC*2, determine six GC phenotypes: 1F, 1S, 2, 1F-1S, 2-1F and 2-1S, these common alleles having been found in all human populations studied. In addition, more than 120 GC variants have been discovered, with varying frequencies in different populations. The distribution of the common GC phenotypes and the presence of rare GC variant phenotypes render the GC/DBP system useful for the analysis of disputed paternities.     

溶胶-凝胶血红蛋白电化学传感器的研制

运用溶胶-凝胶技术将血红蛋白(Hb)固载于玻碳电极(GC)表面,制得Hb/Sol-Gel/GC修饰电极,找出了制备Hb/Sol-Gel/GC修饰电极的最佳实验条件,建立了一种测定过氧化氢的新的、灵敏的方法.同时对该电极与过氧化氢的作用机理进行了探讨.     

聚邻苯二胺/镍氢氧化物修饰电极的研究

采用循环伏安法(CV)在聚邻苯二胺修饰玻碳电极表面络合Ni2+,然后将其置于NaOH溶液中CV扫描成功制备了镍氢氧化物/聚邻苯二胺/玻碳修饰电极(Ni(OH)2/PoPD/GC).通过CV探讨了聚合和负载机理,电化学交流阻抗谱(EIS)表征了电极修饰过程中界面阻抗变化,扫描电镜表征了PoPD膜负载Ni(OH)2后的形态...     

金复合介孔SBA-15吸附血红蛋白在H2O2电催化反应中的应用

以P123嵌段共聚物表面活性剂为模板剂制备介孔氧化硅SBA-15,并用沉积-沉淀(DP)法在SBA-15介孔表面负载纳米Au颗粒制备得到金复合介孔SBA-15材料(Au-SBA-15).再以Au-SBA-15材料制备玻碳修饰电极,将血红蛋白固定于修饰电极上用循环伏安法考察其对不同浓度H₂O₂溶液的电催化反应.在固定了血红蛋白的Hb/Au-SBA-15/GC修饰电极上,H₂O₂在+0.95 V处出现了氧化峰,且随着H₂O₂浓度的增大峰电流不断增加,说明金复合介孔氧化硅材料具有良好的生物兼容性,有利于血红蛋白的固定,其修饰电极对H₂O₂溶液具有一定的电催化作用.     

Characterization of a 2‐Benzo[c]cinnoline Modified Glassy Carbon Electrode by Raman Spectroscopy,Electrochemical Impedance Spectroscopy,and Ellipsometry

This work describes the characterization of the grafted 2‐benzo[c]cinnoline (2BCC) molecules at a glassy carbon (GC) electrode surface by voltammetry and spectroscopy. Attachment of the molecule to the carbon substrate was achieved by the electrochemical reduction of 2‐benzo[c]cinnoline diazonium salt (2BCC‐DAS). GC electrode modification was carried out in aprotic solution with 2BCC diazonium salt. Dopamine (DA) and ascorbic acid (AA) were used to prove the surface modification to see the blockage of the electron transfer. The presence of 2BCC at the GC electrode surface was characterized by cyclic voltammetry and Raman spectroscopy. Raman spectroscopy was used to monitor molecular bound properties of the adsorbates at the 2BCC‐GC surface and confirm the attachment of 2BCC molecules onto the GC surface. The thickness of the 2BCC film on GC was also investigated by ellipsometric measurement.     

Comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry detection: analysis of amino acid and organic acid trimethylsilyl derivatives, with application to the analysis of metabolites in rye grass samples

First, standard mixtures of trimethylsilyl (TMS) derivatives of amino acid and organic acid are analyzed by comprehensive two-dimensional (2D) gas chromatography (GC) coupled to time-of-flight mass spectrometry (GC × GC/TOFMS) in order to illustrate important issues regarding application of the technique. Specifically of interest is the extent to which the peak capacity of the 2D separation space has been utilized and the procedure by which the derivative standards are identified in the 2D separations using the mass spectral information. The resulting 2D separation is found to make extensive use of the GC × GC separation space provided by the complementary stationary phases employed.Second, in order to demonstrate GC × GC/TOFMS on two real sample types, trimethylsilyl metabolite derivatives were analyzed from extracts of common lawn grass samples (i.e., perennial rye grass), as a means to provide insight into both the pre and post harvest physiology. Various chemical components in the two rye grass extract samples were found to either emerge or disappear in relation to the trauma response. For example, a significant difference in the peak for the TMS derivative of malic acid was found. The successful analysis of various components was readily facilitated by the 2D separation, while a 1D separation would have produced too much peak overlap, thus impeding the analysis. The importance of using a GC × GC separation approach for the analysis of complex samples, such as metabolite extracts, is therefore demonstrated. The real-time analysis capability of GC × GC/TOFMS for multidimensional metabolite analysis makes this technique well suited to the high-throughput analysis of metabolomic samples, especially compared to slower, stopped-flow type separation approaches.     

Effects of pressure drop on absolute retention matching in comprehensive two-dimensional gas chromatography

Comprehensive two-dimensional gas chromatography (GC x GC) analysis has the capability to resolve many more components of complex mixtures than traditional single column GC analysis. There is an increasing need to provide reliable identification of these separated components; time-of-flight mass spectrometry (TOFMS) is the most appropriate technology to achieve this task. Rather than require MS for all GC x GC separations, it is desirable to assign peak identities to specific peak positions in the GC x GC separation space, and this necessitates matching peak retentions in the two experiments - GC x GC-FID and GC x GC-TOFMS. The atmospheric vs. vacuum outlet conditions confound this task. It is shown here that by employing a supplementary gas supply, provided to a T-union between the column outlet and the MS interface, it is possible to generate 2D chromatograms for GC x GC-FID and GC x GC-TOFMS that are essentially exactly matched. There is no degradation in separation performance or efficiency in the second column in the system interfaced to the T-union. Since the GC x GC-FID experiment uses hydrogen for maximum efficiency, and GC x GC-TOFMS uses helium carrier, translation of (conditions/retentions) must account for the different viscosities of the carrier gases. Translation of conditions is based on well-known principles established in single column analysis. Tabulated data illustrate that retention reproducibility was of the order of better than 4 s for the average first dimension retention difference, and about 40 ms for the average second dimension retention difference when comparing GC x GC-FID and GC x GC-TOFMS results. This should provide considerable support for identification in routine GC x GC-FID analysis of specific sample types, once the peaks in 2D separation space have been assigned identities through GC x GC-TOFMS analysis.     

导数测量技术在气相色谱信号处理中的应用

介绍了导数测量技术在气相色谱信号处理中的应用。导数-气相色谱的热导检测器对苯的灵敏度和敏感度分别达到270kV·L/kg和0.3μg／L。与可分辨导数色谱峰相对应的常规色谱峰最小分离度为2．8。在被测组分质量浓度为8．1～810g／L的范围内,导数峰上峰高、下峰高、总峰高、峰面积均与质量浓度呈线性关系,其线性相关系数分别为0．9911,0．9982,0．9960和0.9991。     

Molecular structure retention relationships in comprehensive two-dimensional gas chromatography

Comprehensive two-dimensional gas chromatography (GC x GC) offers new opportunities to develop relationships between molecular structure and retentions in the two dimensional (2D) separation space defined by the GC x GC retention in each dimension. Whereas single dimension GC provides only one retention property for a solute, and hence the specific relationship between retention and chemical property is not readily apparent or derivable, the 2D presentation of compounds in GC x GC provides a subtle and exquisite correlation of chemical property and retention unlike any other GC experiment. The 'orthogonality' of the two separation dimensions is intimately related to the manner in which different separation mechanisms, available through use of two dissimilar phases, are accessible to the different chemical compounds or classes in a sample mixture, and indeed the specific chemical classes present in the sample. The GC x GC experiment now permits various processes such as chemical decompositions, molecular interconversions, various non-linear chromatography effects, and processes such as slow reversible interactions that may arise with stationary phases or in the injector or column couplings, to be identified and further investigated. Here, we briefly review implementation of the GC x GC method, consider the molecular selectivity of GC x GC, and highlight a selection of molecular processes that can be probed by using GC x GC.