石油卟啉在反相─CN／C_（18）组合柱高效液相色谱中的分离与分析

 石油卟啉是原油和含油沉积物中的一种地质化学标记物，由于卟啉族是一种极其复杂的混合物，且含量甚微，因此，给分离和鉴定工作带来相当大的困难。采用─ＣＮ／Ｃ＿（１８）组合柱、甲醇－水梯度淋洗的反相高效液相色谱和高灵敏度鉴定的质谱对卟啉族进行研究，结果表明，在所建立的色谱系统中，卟啉的类型和同系物都得到较好的分离，色谱图有较好的重现性，在分离的基础上对有地质信息的卟啉标记物进行了质谱分析。     

电喷雾质谱法对重烷基苯的族组成分析与结构鉴定

建立了一种系统的分析重烷基苯的方法。通过柱色谱对重烷基苯进行了分离，将其分成了六个族组分，对这六个族组分进行红外、紫外以及荧光鉴定，确定了各族组分的归属，利用电喷雾质谱测定了第二到第五族组分磺酸盐的相对分子量分布，结合红外、紫外所测定的结果，及每族物质的不饱和度和通式，推算出了烷基芳烃部分的相对分子质量和烷基苯的碳数分布。     

某些卟啉和金属卟啉的反相液相色谱

〕用反相高效液相色谱分离某些对称取代的卟啉及其金属卟啉。根据卟啉和金属卟啉在可见区的光谱特征,通过对流出色谱峰的快速扫描就可简便地鉴定它们。考察了几个不对称取代的芳基卟啉和金属卟啉的分离和定性,如中位含不同数目的对羟基苯基和对甲氧基苯基的卟啉混合物（样A）和中位含不同数目的对氯苯基和苯基的卟啉锌混合物（样B）。选用装填YWG-C18（3～5微米）的φ5×150毫米色谱柱,用含水5％的甲醇为流动相,样A和样B都得到良好分离,用两个已知样鉴定出样A中的α-对羟基苯基β,γ,δ-三对甲氧基苯基卟啉,α,β-二对羟基苯基γ,δ-,二对甲氧基苯基卟啉和α,γ-二对羟基苯基β,δ-二对甲氧基苯基卟啉对样B中的三个色谱主峰,在同一柱上用按比例放大方法,收集、浓缩得毫克级结晶,经质谱、核磁共振波谱、紫外—可见光谱综合定性,确定出α-对氯苯基β,γ,δ-三苯基卟啉锌和中位四对氯苯基卟啉锌。上述方法也适用于其他类似的卟啉和金属卟啉的分离和鉴定。     

全二维气相色谱/飞行时间质谱(GC×GC/TOFMS)用于烟叶中挥发、半挥发性碱性化合物的组成研究

建立了烟叶中挥发性、半挥发性碱性化合物组成研究的全二维气相色谱/飞行时间质谱(GC×GC/TOFMS)分析方法, 并用所建立的方法对香料烟中碱性化合物进行了表征. 对比了一维气相色谱和全二维色谱方法用于烟叶碱性组分组成分析的效果. 一维色谱质谱方法共鉴定出45种碱性化合物. 用所建立的全二维气相色谱方法, 采用TOFMS谱图库检索结合全二维特有的包含结构信息的二维谱图, 通过族分离和结构谱图鉴定, 鉴定出了香料烟中挥发性、半挥发性碱性组分共92种. 包括吡咯类化合物6种, 吡啶类化合物39种, 吡嗪类化合物10种, 苯胺类化合物11种, 喹啉类化合物11种, 吲哚类4种和其他类化合物11种. 同时对不同类别的化合物在二维气相色谱上的分布模式进行了研究. 研究结果表明, 全二维色谱飞行时间质谱的高分辨率和特有的定性手段适合于烟叶这类复杂植物体系的化学组成研究.     

虎纹捕鸟蛛毒中次黄嘌呤核苷的分离与鉴定

本文从虎纹捕鸟蛛粗毒中经高效液相色谱分离纯化出一种组分，通过场解吸质谱和电子电离质谱鉴定为次黄嘌呤核苷，其含量为３．９％。同时，进一步用标准样品进行紫外、液相色谱对照验证，并对次黄嘌呤核苷以毒液中的一种成分的形式存在的作用进行了简单的讨论。     

全二维气相色谱/飞行时间质谱用于烟叶中酸性成分的分离与分析

建立了烟叶中酸性化合物(挥发性、 半挥发性羧酸类和酚类)组成研究的全二维气相色谱/飞行时间质谱(GC×GC-TOFMS)分析方法, 并用此方法对香料烟中的酸性化合物进行了表征. 用同时蒸馏萃取样品的前处理方法, 采用TOFMS谱图库检索结合全二维特有的包含结构信息的二维谱图, 通过族分离和结构谱图, 鉴定出了香料烟中143种挥发性及半挥发性酸性组分, 包括10种酸酐和呋喃二酮, 43种有机酸和90种酚类化合物. 同时对不同类别的化合物在二维气相色谱上的分布模式进行了研究. 结果表明, 全二维气相色谱飞行时间质谱的高分辨率非常适合于烟叶这类复杂体系的分离分析.     

反相高效液相色谱双梯度洗脱分离肽混合物及质谱分析

复杂肽段混合物的有效分离是高覆盖率地鉴定蛋白质混合物的前提。“鸟枪法”(Shotgun)蛋白质组学研究策略通常采用蛋白酶切、二维液相色谱-串联质谱分析肽段混合物从而鉴定蛋白质,其中高效率地分离肽段混合物是关键步骤之一。本文通过pH梯度结合有机溶剂梯度的反相高效液相色谱(RP-HPLC)进行一维液相色谱分离,按等时间间隔收集馏分并将一个梯度的前段的一个馏分与后段一个馏分混合,然后进行纳升级液相色谱-质谱联用(nanoRPLC-MS/MS)分析。将该方法应用于酵母蛋白质的分离和鉴定,实验结果为: 与常规的强阳离子色谱-反相液相色谱-质谱分离鉴定方法相比,采用pH梯度结合有机相梯度的RP-HPLC-RPLC-MS分离鉴定方法多鉴定到567个酵母蛋白质(簇,含有3035个唯一肽段);其中鉴定到肽段的pI分布范围为3.42～12.01,相对分子质量范围为587.67～3499.79;蛋白质的pI分布范围为3.82～12.19,相对分子质量范围为3446.55～432905。该结果表明这种方法在复杂体系蛋白质组分离鉴定中具有明显的优势,在蛋白质组学研究中有较好的应用前景。     

使用气相色谱、气相色谱-质谱和高效薄层色谱联合对半枝莲叶片内源激素成分的研究

植物体中的内源激素是调节植物生命活动的极微量存在的一种物质。过去采用生物方法鉴定这种物质只能测得其总活性,近年来应用色谱和色-质谱方法可把它们分离鉴定和定量测定。 半枝莲是一种春夏极易繁殖的花草,扦插易生根,萌芽力极强,是提取和研究植物内源激素很有经济价值的方便资源。本文用常规方法对半枝莲的植株叶片和扦插叶片中的内源激素进行提取,借助气相色谱(GC)、色-质谱(GC/MS)和高效薄层色谱(HPTLC)联合对提取液中内源激素进行了分离鉴定和定量测定。实验结果对指导林业生产具有一定的理论和实际意义。     

双质谱测定地卟啉取代基组成的解析方法及其应用

根据卟啉标样的双质谱特征，建立一种计算卟啉环上取代基组成的方法。卟啉的平均分子结构简式衡量其取代基的组成，尤其对地质体中相同碳数的卟啉“混合物”大环外取代基的构成十分有效。     

天然维生素E制品中杂质的分离与鉴定

利用高效液相色谱、气相色谱-质谱联用与高分辨质谱对天然维生素E制品中的杂质进行了分离分析与结构鉴定。采用正相高效液相色谱法分离天然维生素E的4种异构体及2种杂质,并对杂质馏分进行富集纯化。将气相色谱-质谱联用与高分辨质谱检测相结合,用于获得杂质的结构信息。通过比较杂质精确相对分子质量和解析质谱碎片离子,推断杂质为芝麻素及其同分异构体表芝麻素。经与芝麻素对照品保留时间及碎片离子数据比对,确证了对杂质结构的推断。所建立的杂质鉴定方法快捷、有效,可应用于天然维生素E制品的食品安全控制。     

纳米Co(OH)2/HY复合物的制备及其电化学电容性能

当材料以纳米尺度存在时，某些物理及化学性质将发生根本性变化。因而，纳米技术的概念绝不仅仅是尺寸的缩小，更应体现在物理概念、系统设计、材料合成及制造等方面所发生的根本性革命。随着21世纪的来临，人们正努力地将越来越多的纳米材料功能化，Co(OH)2通常用作Ni(OH）2电池活性材料的添加剂。关于Ni(OH）2的许多电化学性质已有大量报道，而对于Co(OH）2的研究却很少涉及。本文报道了一种新的纳米级Co(OH）2／HY复合物的制备方法，并将制得的复合物制成超级电容器电极，研究了其超电容特性。此外，还初步提出了Co(OH）2各向异性的形貌形成机理。     

C60(OH)n的快速制备及其机理研究

C60(OH)n在生物、医药、高分子材料等许多方面具有应用前景[1～3],其合成对C60衍生物的水溶液化学研究与合成新的有机化合物具有重要意义.     

细胞动力学研究IV.细菌非理想生长过程的热动力学

By using LKB2277 Bioactivity Monitor, we have determined the thermogenesis power curves of four kinds of bacteria: Brucella M5(55010), 83-980, 83-981 and E. coli. We have also derived the thermokinetic equation for the process of bacterial growth, which was untypical "S" , unideal growth, as:
Ln[P•(1-P/Pm)?-1]=ln[P0•(1-P0/Pm)?-1]+kt
From this equation, the rate constants of bacterial growth k wore obtained. This thermokinetic equation is very suitable for cell growth of separated culture, in which the thermogenesis curve is untypical. The model propoted by equationl(1) has been compared with the exponential and logistic models. This thermokinetic equation is very significant for the study of bacterial limited growth and their characteristics.     

Dark-to-bright optical responses of liquid crystals supported on solid surfaces decorated with proteins

Protein assays are critical analytical tools performed in various biochemical laboratories to quantify the concentration of proteins. In this study, we report the optical responses of a thin layer of liquid crystals supported on glass slides decorated with proteins and the utility of this phenomenon as a new "all-or-nothing" type of protein assay. It was found that the orientations of liquid crystals are very sensitive to the concentration of protein solution applied to the surface. When the protein concentration exceeds a critical value (IgG 5.0 microg/mL, BSA 6.0 microg/mL, FTIC-anti-biotin 0.40 microg/mL, and FITC-anti-IgG 0.37 microg/mL), the thin layer of liquid crystals gives a very sharp dark-to-bright optical response within a small concentration range. This characteristic is not observed in any traditional protein assays, which are based on the adsorption of UV or visible light. The optical response is also very precise and reproducible. It is not affected by the thickness of the liquid crystal cell or the amount of organosilanes coated on the glass slides. The liquid crystal-based protein assay may be very useful for screening purposes, especially when a simple positive or negative answer is desired.     

Local density functional study of the structural and electronic properties of C60 and XC60 (X=K, Rb, Cs)

Results of first principles local density total energy and atomic force calculations carried out for free C₆₀ and XC₆₀ (X=K, Rb, Cs) molecular clusters are reported. The optimization of the geometry results in the bond lengths between adjacent carbon atoms being 1.387 and 1.445 Å, which are in very good agreement with the latest X-ray diffraction values. Energy levels, charge distributions, and wavefunction characteristics are obtained and discussed. The results for C₆₀ are in very good agreement with recently measured photoemission energy distribution curves (EDC) for the valence band states. The highest occupied molecular orbitals (HOMO) are found to be fully occupied H_u states and are 1.7 eV below the lowest unoccupied molecular orbitals (LUMO) which are of T_1u symmetry. Similar results obtained for the XC₆₀ clusters show that rigid-band-like behavior is found in the electronic structures after putting an alkali atom at the center of a C₆₀ ball. In each case, the alkali atom is almost fully ionized with the transferred electron distributed over the surface shell of C₆₀; the center region of the ball has very low charge density.     

Design-atom approach for the quantum mechanical/molecular mechanical covalent boundary: a design-carbon atom with five valence electrons

A critical issue underlying the accuracy and applicability of the combined quantum mechanical/molecular mechanical (QM/MM) methods is how to describe the QM/MM boundary across covalent bonds. Inspired by the ab initio pseudopotential theory, here we introduce a novel design atom approach for a more fundamental and transparent treatment of this QM/MM covalent boundary problem. The main idea is to replace the boundary atom of the active part with a design atom, which has a different number of valence electrons but very similar atomic properties. By modifying the Troullier-Martins scheme, which has been widely employed to construct norm-conserving pseudopotentials for density functional calculations, we have successfully developed a design-carbon atom with five valence electrons. Tests on a series of molecules yield very good structural and energetic results and indicate its transferability in describing a variety of chemical bonds, including double and triple bonds.     

Electrochemiluminescence Behavior of Humic Acid

Humic substance, which interact strongly with toxic heavy metals^[1] and may be precursors of trihalomethane (THM) formed during water treatment with chlorine, are the major organic constituents of fresh water, sea-water and soils. Humic acid (HA) has a very complex structure and an accurate concentration is very difficult to determine.     

New Forms of Carbon

A number of novel carbon materials whose unique properties fit them for many uses have recently been developed. Pyrolytic graphites are excellent conductors of heat and electricity parallel to the surface, whereas they are semiconductors perpendicular to the surface. A similar anisotropy is found in graphite foils, which are impermeable, but also very flexible. Glasslike carbon, which is also impermeable, is, however, completely isotropic. Carbon foams and felts are extremely light and exhibit very good thermal insulation up to high temperatures. In addition to very high strength, carbon fibers have values of Young's modulus greater than that of any other fibers or wires. Carbon fiber/resin composites are therefore more rigid than any other known materials; their specific Young's modulus is five times that of steel.     

交联网络和浓溶液中高分子链运动的NMR研究Ⅲ.质子自旋-晶格弛豫时间与凝胶和浓溶液体系中高分子链段的运动

用自旋－晶格弛豫时间（Ｔ１）研究了溶胀的交联聚丙烯酰胺－丙烯酸网络和线型聚苯乙烯溶液中质子的弛豫行为。交联网络中，随着交联度增大，Ｔ１ＣＨ／Ｔ１ＣＨ２的值由１．１７逐渐趋近于１；而线型聚苯乙烯溶液中，Ｔ１ＣＨ／Ｔ１ＣＨ２的值由最稀浓度下的１．７过渡到１。说明在交联网络中，交联度很低时，链段的运动已经相当受约束；但交联度很大时，充分溶胀的交联网络中链段运动仍有一定自由度。而在线型高分子浓溶液中，链段的运动严重受阻，导致自旋扩散效应非常完全，彻底平均掉了各质子间Ｔ１时间的差异。     

Determination of the labile species of zinc by anodic stripping staircase voltammetry, with special reference to correlation with the toxicity to tetrahymena

Anodic stripping staircase voltammetry (ASSV) has been tested as a method to determine the concentration of “free” ions and very labile complexes of zinc. These species are thought to be primarily responsible for the toxic effect of zinc on the ciliated protozoan Tetrahymena pyriformis. ASSV and toxicological experiments were performed in an inorganic salt medium and the effects of Cu interference were studied. Even though the ASSV results were encumbered with problems, the results agreed well with the toxicological effects. In contrast, calculations based on the solubility product of Zn₃ (PO₄)₂·4H₂O could lead to erroneous results because kinetic and other effects result in very slow precipitation of zinc phosphate at the concentration levels in the salt medium used. In this medium there is a dose-dependent effect of zinc on Tetrahymena which is in agreement with the ASSV data, which indicate that all the zinc is in a labile form. The study emphasizes the importance of using experimental determinations in preference to theoretical models, which may predict quite erroneous results.