双（取代环戊二烯基）二氯化锆的晶体结构分析

用Ｘ－射线晶体结构衍射法测定了双［１－苄基－１－乙基丙基环戊二烯基］二氯化锆［η５－Ｃ５Ｈ４Ｃ（Ｃ２Ｈ５）２ＣＨ２Ｃ６Ｈ５］２ＺｒＣｌ２（Ｉ）及（１，２－二异丁基－１，２－甲基－乙基桥联）双环戊二烯基二氯化锆［η５－Ｃ５Ｈ４Ｃ（ＣＨ３）（Ｃ４Ｈ９－ｉ）Ｃ（ＣＨ３）（Ｃ４Ｈ９－ｉ）Ｃ５Ｈ４－η５］ＺｒＣｌ２（Ⅱ）的结构。二者皆为单斜晶系，（Ｉ）的空间群为Ｐ２／ｎ，ａ＝１２．５８２（３），ｂ＝７．９９２（２），ｃ＝１４．９７９（３）Ａ，β＝１０１．６８（１）°，Ｖ＝１４７４．９（９）Ａ３，Ｍｒ＝６１２．８４，Ｚ＝２，Ｄｘ＝１．３８ｇ／ｃｍ３，μ＝５．６９ｃｍ（－１），Ｆ（０００）＝６４０，Ｒ＝０．０３３，Ｒω＝０．０３６。（Ⅱ）的空间群为Ｃｃ，ａ＝１３．３０９（３），ｂ＝９．５９１（１），ｃ＝１６．４４９（８）Ａ。β＝４．８３（３）°，Ｖ＝２０９．２（２）Ａ３，Ｍｒ＝４５８．６３，Ｚ＝４，Ｄｘ＝１．４５６ｇ／ｃｍ３，μ＝７．７７ｃｍ（－１），Ｆ（０００）＝９５２，Ｒ＝０．０５１，Ｒω＝０．０６１。化合物（Ｉ）以重叠式存在，两个苄基处于反式。晶体（Ⅱ）以交叉式存在，甲基、异丁基以反式构象存在。     

高效液相色谱手性流动相法拆分甲状腺素对映体

运用高效液相色谱手性流动相法（ＨＰＬＣ－ＣＭＰ）对影响甲状腺素对映体（Ｄ－,Ｌ－Ｔ４）分离方法的因素：三乙胺（ＴＥＡ）浓度,流动相ｐＨ值,铜离子（Ｃｕ２＋）浓度,Ｌ－脯氨酸（Ｌ－ｐｒｏ）浓度,柱温以及流动相的流速进行了系统的研究。同时,考察了色谱方法分离Ｔ４对映体的线性关系,精密度和准确度。线性响应范围为０．６～３．２　ｎｍｏｌ　（Ｄ－,Ｌ－Ｔ４）,线性相关系数为ｒＤ－Ｔ４＝０．９９８０,ｒＬ－Ｔ４＝０．９９９０,日内和日间的精密度分别为ＲＳＤ＜２．３％（ｎ＝６）,ＲＳＤ＜３．１５％（ｎ＝５）。结果表明本实验所得的色谱条件较文献报道的优越,分离条件简单,重现性好。ＨＰＬＣ－ＣＭＰ法测定甲状腺素对映体其意义在于该方法可为定量测定药品及人体血液中Ｄ－,Ｌ－Ｔ４两种异构体,为治疗药物监测（ＴＤＭ）和药物不良反应监测（ＡＤＲｓ）提供了依据。     

Lewis酸催化1,4-脱水-2,3-二-氧-(对迭氮基苯甲基)-α-D-核糖的选择性开环聚合反应

在低温下用三氟化硼乙醚催化１，４－脱水－２，３－二－氧－（对迭氮基苯甲基）－α－Ｄ－核糖（ＡＤＡＢＲ）的阳离子选择性开环聚合反应，首次合成了具有１，５－开环α－结构的聚合物。单体ＡＤＡＢＲ由１，４－脱水－α－Ｄ－核糖在ＤＭＦ溶剂中与对溴甲基迭氮基苯反应获得。聚合物的结构由比旋光度、１Ｈ－ＮＭＲ和１３Ｃ－ＮＭＲ及ＩＲ谱确认。用五氟化锑为催化剂则得到了同时含有α－呋喃单元和β－吡喃单元混合结构的聚合物。研究了催化剂及其用量、聚合反应时间对聚合反应的影响，讨论了聚合反应机理。为研究１，４－脱水－２，３－二－氧－（对迭氮基苯甲基）－α－Ｄ－吡喃核糖的聚合活性以及便于测试迭氮基的含量对聚合物光刻性能的影响，还初步研究了单体ＡＤＡＢＲ与１，４－脱水－２，３－二－氧－苯甲基－α－Ｄ－吡喃核糖（ＡＤＢＲ）的共聚反应。从共聚物的结构分析可以认定共聚物具有１，５－α－结构，并且单体１，４－脱水－２，３－二－氧－苯甲基－α－Ｄ－吡喃核糖在实验条件下具有较高的活性。     

罗丹明B合锌（Ⅱ）配合物的合成,分子结构与性质研究

合成了ＲＢ－Ｚｎ配合物,晶体结构分析结果表明配合物组成为「Ｚｎ（ＲＢ）（ＯＡｃ）２（Ｈ２Ｏ）」晶体属单斜晶系、空间群为Ｐ２１／ｎ（＃１４）,晶胞参数为ａ＝１．０２９８（２）ｎｍ,ｂ＝１．８９０１（４）ｎｍ,ｃ＝１．６６６０（６）ｎｍ;β＝１０５．２４（３）°;Ｚ＝４,Ｄｃａｌ＝１．３６７ｇ／ｃｍ＾３。研究了配合物的物质的量电导,ＩＲ和荧光光谱,同时对配体配合物的半导体行为进行了考察。     

N─苯基邻苯二甲酰亚胺和N─对甲苯基邻苯二甲酰亚胺的晶体和分子结构

报道一种新类型的有机电子晶体Ｎ－苯基邻苯二甲酰亚胺（１）（Ｃ＿（１４）Ｈ＿９ＮＯ＿２）和Ｎ－对甲苯基邻苯二甲酰亚胺（２）（Ｃ＿（１５）Ｈ＿（１１）ＮＯ＿２）的晶体和分子结构，（１）属正交晶系，空间群为Ｐｃａｂ，ａ＝７．６４９（４），ｂ＝１１．６５９（２），ｃ＝２３．７３９（３）Ａ，Ｖ＝２１１７．０Ａ￣３，Ｚ＝８，Ｄ＿ｃ＝１．４０１ｇ／ｃｍ￣３，Ｍ＿ｒ＝２２３．２３，μ＝０．８８５ｃｍ￣（－１），最终偏离因子Ｒ＝０．０５３，Ｒ＿ω＝０．０４８；（２）属正交晶系，空间群为Ｐｎａ２＿１，ａ＝７．６２４（２），ｂ＝１１．２３７（１），ｃ＝１３．８５６（２）Ａ，Ｖ＝１１８７．０　Ａ３，Ｚ＝４，Ｄ＿ｃ＝１．３２８ｇ／ｃｍ￣３，Ｍｒ＝２３７．２６，μ＝２．７６４ｃｍ－１，最终偏离因子Ｒ＝０．０３６，Ｒ＿ω＝０．０３２。晶体结构测定结果表明，邻苯二甲酰亚胺的内酰亚胺碳、氮、氧原子与其苯并环共平面。化合物（２）中的甲基碳原子与取代基苯环共平面，苯并酰亚胺平面与取代苯环平面间的夹角分别为５８．４°（化合物１）和５６．２°（化合物２）。     

N─苯基邻苯二甲酰亚胺和N─对甲苯基邻苯二甲酰亚胺的晶体和分子结构

报道一种新类型的有机电子晶体Ｎ－苯基邻苯二甲酰亚胺（１）（Ｃ＿（１４）Ｈ＿９ＮＯ＿２）和Ｎ－对甲苯基邻苯二甲酰亚胺（２）（Ｃ＿（１５）Ｈ＿（１１）ＮＯ＿２）的晶体和分子结构，（１）属正交晶系，空间群为Ｐｃａｂ，ａ＝７．６４９（４），ｂ＝１１．６５９（２），ｃ＝２３．７３９（３）Ａ，Ｖ＝２１１７．０Ａ￣３，Ｚ＝８，Ｄ＿ｃ＝１．４０１ｇ／ｃｍ￣３，Ｍ＿ｒ＝２２３．２３，μ＝０．８８５ｃｍ￣（－１），最终偏离因子Ｒ＝０．０５３，Ｒ＿ω＝０．０４８；（２）属正交晶系，空间群为Ｐｎａ２＿１，ａ＝７．６２４（２），ｂ＝１１．２３７（１），ｃ＝１３．８５６（２）Ａ，Ｖ＝１１８７．０　Ａ３，Ｚ＝４，Ｄ＿ｃ＝１．３２８ｇ／ｃｍ￣３，Ｍｒ＝２３７．２６，μ＝２．７６４ｃｍ－１，最终偏离因子Ｒ＝０．０３６，Ｒ＿ω＝０．０３２。晶体结构测定结果表明，邻苯二甲酰亚胺的内酰亚胺碳、氮、氧原子与其苯并环共平面。化合物（２）中的甲基碳原子与取代基苯环共平面，苯并酰亚胺平面与取代苯环平面间的夹角分别为５８．４°（化合物１）和５６．２°（化合物２）。     

四氢糠基环戊二烯稀土氯化物的合成及表征

报道了四氢糖基环戊烯基稀土氯化物的合成，用元素分析，红外光谱，质谱和核磁共振谱表征这类化合物的组成为（Ｃ４Ｈ７ＣＯＨ２Ｃ５Ｈ４）２ＬｎＣ１（Ｌｎ＝Ｎｄ，Ｇｄ，Ｄｙ，Ｅｒ），测定了（Ｃ４Ｈ７ＯＣＨ２Ｃ５Ｈ４）２ＤｙＣｌ的晶体结构属正交晶系，Ｐ２，２１２１空间群，晶胞参数：α＝１．１８０９（３）ｎｍ，ｂ＝１．２１４９（４）ｎｍ，ｃ＝１．３３７７（５）ｎｍ，ｚ＝４，Ｄｃ＝１．７２ｇ／ｃｍ＾３，Ｒ＝０．０     

在线流动注射液－液萃取系统在原子吸收光谱法中的研究及应用

本文对用于原子吸收光谱分析的在线液－液萃取流路系统进行了研究，采用了一种新型、适用、简便的相分隔器和相分离器，并用该流路系统对矿石、人发中的Ｃｕ（ＦＡＡＳ）以及矿石中痕量Ａｕ进行了测定（ＧＦＡＡＳ）。在水相和有机相的流量比为２５：１，采样频率为２０ｈ￣（－１）时，用ＦＡＡＳ法测定Ｃｕ的ＲＳＤ为１．９％（ｎ＝１０）、ＤＬ（３σ）为１．０μｇ．Ｌ￣（－１）；用ＧＦＡＡＳ法测定Ａｕ的ＲＳＤ为４．９％，ｎ＝１０、ＤＬ（３σ）为０．０８μｇ．Ｌ￣（－１）　。     

手性助剂诱导下的α,β-不饱和酮的不对称加氢反应及其在合成(R)-麝香酮中的应用

在ＴＨＦ溶液中，４０－６０℃及０．３－０．５ＭＰａ氢压条件下，［ＲｕＣｌ２（ｃｈｔ）］２＋（Ｓ）－ＢＩＮＡＰ手性催化剂体系催化不饱和手性缩酮２选择加氢，再经脱去手性二醇，即可高立体选择性地制得（Ｒ）－３－甲基环十五烷酮（４，（Ｒ）－（－）－麝香酮），化学收率≥９５％，光学纯度≥９７％．手性缩酮２由Ｄ－苏糖醇或Ｄ－葡萄糖衍生的手性二醇３与３－甲基环十五烯－２－酮１生成．     

HPLC/ECD测定人血小板中5-羟色胺浓度

用ＨＰＬＣ／ＥＣＤ法测定血小板５－ＨＴ,运用 ＷａｔｅｒｓμＢｏｎｄａｐａｋ Ｃ柱,３,４二羟基苄胺（ＤＨ－ＢＡ）作内标,以 ０.０７ ｍｏｌ／Ｌ乙酸钠缓冲液＋乙腈为流动相（２０＋１）,每１Ｌ缓冲液含 ０．０５ ｍｏｌ／Ｌ柠檬酸、２．５ ｍｍｏｌ／Ｌ庚烷磺酸钠、０．１ｍｍｏｌ／Ｌ Ｎａ_２ＥＤＴＡ,流速０．８ ｍＬ／ｍｉｎ。ＤＨＢＡ和 ５－ＨＴ的保留时间分别为５．４和１１．５ ｍｉｎ,线性范围为０．０２５～１ｍｇ／Ｌ（ｒ＝ ０．９９９７）。５－ＨＴ日内 ＲＳＤ低于１．８７％,日间ＲＳＤ低于８．５４％,方法回收率为１００．４％±２．３％。提示本方法快速简便,灵敏准确,适用于临床基础研究。     

Stimultaneous quantitative analysis using dual capillary columns of different polarities

Complex organic mixtures, such as coal liquefaction and oil shale products and by-products, are comprised of hundreds or thousands of individual components. State-of-the-art high resolution gas chromatography does not always provide sufficient resolution to allow accurate quantitation or identification of many compounds of interest. The concept of dual capillary column chromatography combines the different resolving characteristics of two capillary columns coated with different stationary phases into a single chromatographic run. In this approach, both columns are connected to the same injection port. Analysis of complex mixtures in this fashion can confirm the identification and quantitation of components on two columns of different polarity with little increased analysis time, can provide a means of obtaining quantitative data for individual components which are known to coelute on any one column, and can alert one to unknown coelution problems that would be undetected by gas chromatographic analysis on a single capillary column. Simultaneous dual column analysis was applied to three samples, the neutral polycyclic aromatic hydrocarbon (PAH) fraction of a Solvent Refined Coal-II (SRC-II) heavy distillate, the nitrogen-containing polycyclic aromatic compound (N-PAC) fraction of an SRC-II heavy distillate, and the basic fraction from a shale oil process water. Fused silica capillary columns coated with SE-54 and Durawax 3 were used for the analyses of the heavy distillate, while SE-54 an Carbowax 20M capillary columns were used for the analysis of the process water.     

Development of an on-line coupling of liquid-liquid extraction, normal-phase liquid chromatography and high-resolution gas chromatography producing an analytical marker for the prediction of mutagenicity and carcinogenicity of bitumen and bitumen fumes.

A fast and fully automated system for the determination of polycyclic aromatic compounds (PACs) is described. The system has been developed to produce an analytical 'marker', correlating chemical characteristics (including PAC analysis) with mutagenicity and carcinogenicity. The products of interest are bitumen fumes, bitumen and other (heavy or even residual) oil products, regardless of their boiling range. Dimethyl sulphoxide (DMSO) extractables obtained from a flow-injection analysis (FIA) system are introduced on-line in a normal-phase liquid chromatographic (NPLC) system. Here, the PACs are separated from the DMSO and possible co-extracted heavy residual species. The final step incorporates on-line gas chromatographic analysis of the three-to-six-ring PAC fraction, followed by flame-ionisation detection for quantification. It was demonstrated that data obtained from samples in the distillate lubrication-oil range correlate well with data obtained from the manual DMSO-extraction method standardised by the Institute of Petroleum as IP346.     

Solubility of Organic Solvents. I. Gas Chromatographic Determination of Olive Oil-Gas Partition Coefficients

A gas chromatographic method of measuring the olive oil-gas partition coefficients is described. It is based on the relationship existing between the retention time of each substance and its solubility in olive oil used as a stationary liquid phase. The validity of this method has been tested by varying the length of the column, the percentage of liquid phase and the flow rate of the carrier gas. Using this technique, the partition coefficients of 24 hydrocarbons, 8 aliphatic, 6 aromatic and 10 chlorinated, have been determined (see Table 4).     

重油中含硫芳烃二维液相色谱分离平台开发及应用

基于氯化钯配位交换色谱柱和氨基键合正相色谱柱，利用自动阀切换系统，构建了在线二维液相色谱分离平台。通过优化液相色谱分离条件，实现减压蜡油样品中含硫芳烃的在线富集与多环芳烃的环数分离。利用傅里叶变换离子回旋共振质谱对分离后的含硫芳烃和芳烃组分进行分子水平表征，得到更为详细的化合物类型与碳数分布信息。根据计算得到的平均结构信息，可以提供分离后组分典型的分子结构式，并对芳环结构和侧链位置进行了推测。建立的分析表征方法可以加深对重馏分油中含硫芳烃化合物的分子水平认识，为重油加工过程的原料选择与工艺条件优化提供技术支持。     

离子液体作高效液相色谱流动相添加剂分离测定芳香胺

建立了以离子液体作反相高效液相色谱流动相添加剂分离测定邻苯二胺、苯胺和对甲苯胺3种芳香胺的方法。实验以C18反相色谱柱为分离柱,采用紫外检测方法,考察了检测波长、甲醇含量、咪唑离子液体烷基链长度、离子液体溶液浓度等条件对分离和测定的影响,并与其它分离测定芳香胺的方法进行了比较。优化的色谱条件为:以甲醇/1-丁基-3-甲基咪唑四氟硼酸盐水溶液(3.0mmol/L,乙酸调节pH 3.5)=30/70(V/V)为流动相;检测波长254 nm;流速1.0mL/min;柱温30℃。在此条件下,3种芳香胺达到基线分离,在6.5 min之内分离完全;在1～40 mg/L范围内,线性回归方程的相关系数达到0.99以上;检出限为0.07～0.41 mg/L。将本方法应用于废水的测定,加标回收率在92.3%～96.7%之间,相对标准偏差小于3.5%。     

Retention indices as identification tool in pyrolysis-capillary gas chromatography

Pyrolysis-capillary gas chromatography (Py-cGC) represents important method to identify the analytes in the mixture after thermal degradation. This combines high effective analyte separation on-line coupled with thermal degradation process that depends on analyte structure. System of retention indices has been used for identification of the analytes after on-line pyrolysis and chromatographic separation. The pyrolysate composition has been studied during thermal degradation of polymethylmethacrylate (PMMA) at different pyrolysis temperatures and chromatographic column conditions. Homologues series of n-alkanes have been used for calculation of pyrolysate Kováts retention indices (I) and compared with mass spectrometric (MS) data of pyrolysate model mixture. To identify PMMA thermal degradation products the high density polyethylene (HDPE) as additive standard producing triplets of the olefin homologous series during co-pyrolysis has been used. These homologous series enable to calculate programmed temperature retention indices (ITPGC) to identify the analytes present in the pyrolysate. Calculated I values were compared with published I values databases to identify analytes yielded at different pyrolysis temperatures.     

Effects of the types of zeolites on catalytic upgrading of pyrolysis wax oil

Because zeolites play an important role in an upgrading catalyst for heavy hydrocarbons in industrial refinery processes, the effects of the zeolite type on the upgrading of pyrolysis wax oil are investigated in this study. Raw pyrolysis wax oil was obtained from the pyrolysis of municipal plastic wastes in a commercial rotary kiln pyrolysis plant (Dongmyong RPF Co.). The catalystic experiments are performed for the three different types of commercial zeolites with different physicochemical properties in a continuous fixed bed reactor at 450 °C for 1 h as a MAT(micro-activity test) method: HZSM-5 (pure), zeolite Y (HY; pure or including 20% clay) and mordenite (HM; including 20% clay or alumina) catalysts. The highest conversion of pyrolysis wax oil into light hydrocarbons such as gas products and gasoline-range hydrocarbons is obtained for the HZSM-5 catalyst among them, and the composition of liquid products is found to become in the main aromatic components due to a shape selectivity. For the case of zeolite Y(HY), medium activity and the highest fraction of branched hydrocarbons with a high octane number, as well as a high fraction of aromatic products are shown. However, the mordenite (HM) with one-dimensional pore structure shows the lowest conversion of pyrolysis wax oil into light hydrocarbons and a very high fraction of paraffin product in the liquid product like the characteristics of raw pyrolysis wax oil.     

全二维气相色谱-飞行时间质谱联用技术分析重馏分油中芳烃组成

通过对升温速度、二维补偿温度、调制周期等关键实验参数的优化,建立了全二维气相色谱-飞行时间质谱(GC×GC-TOF MS)分析重馏分油中芳烃组分的方法,得到了重馏分油芳烃组分按环数分布的二维点阵图。根据谱库检索、标准化合物对照及文献报道,对重馏分油芳烃组分中菲、甲基菲及芘、苯并蒽等常见多环芳烃(PAH)进行了准确定性,并将该方法应用到重馏分油加氢处理工艺研究中,对菲、芘的加氢处理产物进行了定性分析。该研究为重馏分油芳烃组分的准确定性提供了新的技术手段,为加深对油品加氢规律的认识提供了技术支持。全二维气相色谱与普通一维色谱对比,在重馏分油的芳烃组分分析上体现了极大优势。     

Multidimensional Gas Chromatography–Mass Spectrometry Method for Fingerprinting Polycyclic Aromatic Hydrocarbons and Their Alkyl-Homologs in Crude Oil

The composition of polycyclic aromatic hydrocarbons in crude oil is usually too complex to use standard capillary gas chromatography to separate all of the components. In this study, a multidimensional gas chromatography–mass spectrometry (GC-MS) technique was used to analyze polycyclic aromatic hydrocarbon fractions of crude oil collected from the Dongying oil field in the Bohai Sea. A DB-17MS column (30?m?×?0.25?mm?×?0.25?µm) was used as a prefractionating column and only selected heart-cuts were transferred to the second chromatographic dimension (HP-5MS, 15?m?×?0.25?mm?×?0.25?µm) by a pressure-adjusted continual flow-type switching device for quantification of the polycyclic aromatic hydrocarbons. The chromatographic elements and parameters, such as detector selection and column combinations, were optimized. Naphthalene, phenanthrene, fluorene, dibenzothiophene, chrysene, and their C₁–C₄ alkyl homologs were identified. The profile of the polycyclic aromatic hydrocarbons obtained using the multidimensional GC-MS method was compared with the results obtained by traditional one-dimensional GC-MS.     

Selective high-performance liquid chromatographic purification of bispecific monoclonal antibodies.

The recent development of improved production techniques for bispecific monoclonal antibodies (biMAbs) has significantly increased interest in specific purification procedures. In this investigation, a general high-performance liquid chromatographic (HPLC) purification method is proposed that allows highly purified biMAbs to be obtained from mouse ascites fluid containing a mixture of different antibodies, i.e., parental MAbs, active biMAb and a mixture of randomly assembled heavy and light chains. Proteins from ascites fluid were precipitated with ammonium sulphate and applied to a high-performance protein A column to separate the total immunoglobulin fraction. BiMAbs were isolated from other immunoglobulins by two subsequent passages through a high-performance hydroxyapatite (HPHT) column. This purification protocol combines specificity of protein A for immunoglobulin G (IgG) and high selectivity of hydroxyapatite for different IgG idiotypes. All purification steps were performed rapidly and reliably by HPLC. This method was applied to the purification of six different biMAbs with consistently high yields, purity and homogeneity. This general purification method may prove extremely valuable when highly pure preparation of biMAbs is required, as for in vivo use.