高效液相色谱法测定超滤后血清中的假尿苷

用高效液相色谱法（ＨＰＬＣ）直接测定了超滤后血清中的假尿苷（ＰＳＥ）,平均回收率为９７．７８％,在０．０９３～６μｍｏｌ范围内呈线性关系（γ＝０．９９５６）,急性白血病患者血中ＰＳＥ水平显著高于正常对照组（Ｐ＜０．０１）。该方法简单、方便、迅速,可用于恶性病的病情及疗效监测。     

反相高效液相色谱法测定唾液和血清咖啡因浓度及药代动力学参数的研究

用反相高效液相色谱法测定４０只Ｗｉｓｔａｒ雄性大鼠和２４例健康人静注咖啡因（ＣＡＦ）ｌｍｇ／ｋｇ或口服４ｍｇ／ｋｇ后血清及唾液ＣＡＦ浓度,并根据血药或唾药时间数据计算其药动学参数。大鼠的血夯时间数据符合二室开放模型。各肝损害组与正常组（每组１０只）的ｔ＿（１／２）β,Ｖ＿ｃ,Ｋ＿（２１）差异显著（均Ｐ＜０．０１＝。提示血清ＣＡＦ药动学参数可定量检测肝代谢功能。２４例健康人唾液与血清ＣＡＦ浓度及ｔ＿（ｌ／２）均有良好相关性（ｒ＝０．９７２２,ｎ＝１２０,Ｐ＜０．００１;γ＝０．９９５５,Ｐ＜０．００１。     

高效液相色谱法测定人血浆中甲磺酸培氟沙星浓度

建立了一种测定人血浆中甲磺酸培氟沙星的匠相液相色谱方法,用的是ＺｏｒｂａｘＯＤＳＣ＿（１８）柱和用三乙醇胺调节成ｐＨ为３．０的甲醇－０．０４ｍｏｌ／ＬＨ＿３ＰＯ＿４溶液（８０：２０,Ｖ／Ｖ）的流动相,检测在２７６ｎｍ处进行,流量为１ｍＬ／ｍｉｎ,线性范围是６．０１×１０￣（－８）～３．０１×１０￣（－５）ｍｏｌ／Ｌ（γ＝０．９９９８）,检测极限为６．０１×１０￣（－８）ｍｏｌ／Ｌ,平均回收率为９７．５７±３．０４％,日内与日间的ＣＶ分别为３．２９％和５．０８％。     

混合粘合剂碳糊电极的制备及分析应用 Ⅱ.氯硝安定的溶出伏安法测定

本文提出用丙三醇－液体石腊混合粘合剂碳糊电极阴极溶出伏安法测定氯硝安定。在ｐＨ９．５的ＮＨ＿３－ＮＨ＿４Ｃｌ缓冲溶液中，氯硝安定在碳糊电极上于－０．７３Ｖ（Ｐ＿１）和－１．３３Ｖ（Ｐ＿２）处产生两个阴极溶出峰，利用Ｐ＿１峰可测定微量的氯硝安定。在８．０×１０￣（－８）～１．１×１０￣（－５）ｍｏｌ／Ｌ范围内，波高与浓度线性关系良好，检测Ｔ１民达４．０×１０，８ｍｏｌ／Ｌ。该法用于血清中氯硝安定测定，相对误差在１０％以内。     

毛细管气相色谱法测定大白鼠生物膜标本中磷脂脂肪酸的含量

用十七烷酸（Ｃ＿（１７：０））作内标,对大白鼠红细胞膜、肝徽粒体膜、心肌细胞线粒体膜等生物细胞膜中磷脂脂肪酸含量进行毛细管气相色谱分析。通过低温差速离心,从大白鼠血、肝及心组织中获得纯净的红细胞膜、肝微粒体膜及心肌细胞线粒体膜。用正己烷萃取去掉可能残存于膜样品中的游离脂肪酸,用氯仿甲醇混合提取液提取膜类脂,以５％三氯化用甲醇溶液加热回流,使磷脂脂肪酸水解并甲酯化,其平均酯化率为９４．５％。对各次加入不同量Ｃ＿（１２：０）→Ｃ＿（２２：６）的回收率为９４．５％～９９．８％。     

铜（Ⅱ）锌（Ⅱ）－氟哌酸体系电化学行为及示波极谱法研究

铜（Ⅱ）和锌（Ⅱ）分别在０．１ｍｏｌ／ＬＫＨ＿２ＰＯ＿４－Ｎａ＿２ＨＰＯ＿４缓冲溶液（ｐＨ６．５）和０．２５ｍｏｌ／ＬＮＨ＿４Ｃｌ溶液中，与氟哌酸形成良好的络合吸附波，峰电位分别为－０．２６Ｖ和－１．２８Ｖ（ｖｓ；ＳＣＥ）；络合比分别为１：３和１：２；峰电流与铜（Ⅱ）和锌（Ⅱ）的浓度均在４．０×１０￣（－７）～５．０×１０￣（－６）ｍｏｌ／Ｌ范围内呈线性关系，检测限分别为７．０×１０￣（－８）和５．０×１０￣（－８）ｍｏｌ／Ｌ。用线性扫描和循环伏安法等手段研究体系的行为，表明均具吸附性，而铜（Ⅱ）－氟哌酸体系属络合物中铜（Ⅱ）的两电子还原的可逆过程。     

关于液相色谱保留值公式的补充

本文介绍了液相色谱保留值公式研究的历史,根据色谱保留值公式的统一形式运用液相吸附公式得到ｌｎｋ＇＝Ａ＋Ｂｌｎ（Ｃ＿（Ｂ＿１）／θ＿（Ｂ＿１））＋ＣＣ＿（Ｂ＿１）。当强溶剂浓度Ｃ＿（Ｂ＿１）不至太低时有ｌｎｋ＇≈Ａ＋ＢｌｎＣ＿（Ｂ＿１）＋ＣＣ＿（Ｂ＿１）：作者证明了当强溶剂浓度Ｃ＿（Ｂ＿１）→０时,ｋ＇→常数,从而纠正了长期存在于色谱热力学理论中Ｃ＿（Ｂ＿１）→０,ｋ＇→∞的谬误。     

血液病与微量元素关系的研究

研究了血液病与微量元素的关系,发现再生障碍性贫血患者治疗前血清Ｃｕ升高（Ｐ〈０．０５）,缓解后Ｃｕ恢复正常。骨髓增生异常综合征（ＭＤＳ）中ＲＡ＋ＲＡＳ组Ｃｕ及Ｃｕ／Ｚｎ比值高,Ｚｎ值降低不明显;ＲＡＥＢ＋ＲＡＥＢ－Ｔ组Ｃｕ及Ｃｕ／Ｚｎ高,Ｚｎ值明显降低（Ｐ〈０．０５）。急性白血病、淋巴瘤、多发性骨髓瘤及慢粒患者血清Ｃｕ、Ｚｎ及Ｃｕ／Ｚｎ比值与对照组比较均呈显著差异（Ｐ〈０．０５￣０．０１）,而缓解     

新型四胺大环锌（Ⅱ）配合物的晶体结构

１，４，７，１０－四氮杂环十二烷（ｃｙｃｌｅｎ）与２－氯甲基吡啶反应获得新型八齿配体１，４，７，１０－四（２－甲基吡啶基）－１，４，７，１０－四氮杂环十二烷（Ｌ）。该配体与Ｚｎ（ＣｌＯ＿４）＿２在水溶液中反应生成无色晶体ＺｎＬ（ＣｌＯ＿４）＿２（１）。晶体结构测定表明：化合物１，Ｃ＿３２Ｈ＿４０－Ｃｌ＿２Ｎ＿８Ｏ＿８Ｚｎ，属单斜晶系，空间群Ｐ２＿１／ｃ，α＝９．８２２（５），ｂ＝１０．７２１（３），ｃ＝３３．９００（２）Ａ，β＝９０．５４（４）°，Ｖ＝３５７０（４）Ａ３，Ｄ＿ｃ＝１．４９ｇ／ｃｍ￣３，Ｚ＝４，Ｆ（０００）＝１６６４，Ｍｒ＝８０１．０。１８８８个可观测衍射点参与修正，Ｒ＝０．０６９，Ｒｗ＝０．０７２。在化合物１中，Ｚｎ原子采取六配位的变形八面体构型，在４个吡啶侧臂之中，只有相对的两个参与配位，而另外的两个有一个远离配位中心，另一个吡啶上的氮原子与锌原子之间存在因二级化学键而引起的弱相互作用。     

Fe（Ⅲ）－TEA－5－Br－PADAP－H_2O_2体系中催化波的研究及其应

在０．２ｍｏｌ·Ｌ￣（－１）ＮＨ＿４Ｃｌ－ＮＨ＿３·Ｈ＿２Ｏ底液中，（ｐＨ为９．２６），得到一个极为灵敏的Ｆｅ（Ⅲ）－ＴＥＡ－５－Ｂｒ－ＰＡＤＡＰ－Ｈ＿２Ｏ＿２配合吸附催化波，其峰电位为－０．７１Ｖ（ｖｓ．ＳＣＥ）。铁浓度在１．８×１０￣（－１０）～５．４×１０￣（－６）ｍｏｌ·Ｌ￣（－１）范围内与二阶导数波高呈线性关系。对该极谱波的性质进行了研究，证明是一种配合吸附催化波，并成功地应用于各类水样，钒催化剂中微量或痕量铁的测定。     

标准气浓度对定量误差影响的探讨

In the trace gas analysis,experimental results show that the relative error can be kept in the range of±10% even in case where the difference in concentration between the standard mixture and sample gas is up to100 times.When the exponential dilution is used for calibration,the standard mixtures of higher concentra-tion with less period of time in the dilution procedure give quite accurate data.     

非晶硅太阳能电池生产工艺用氣分析方法研究

本文对非晶硅太阳能电池制造工艺过程所用的无机氢化物烷类气体硅烷、硼烷、磷烷、甲烷和氢及其混合气的配制与分析方法进行了研究,以微机控制配气、检测程序、气相色谱法分成分析杂质,电容法测水分,方法已应用于工艺过程分析。     

Dependence of the relative retention of organic compounds on the nature and pressure of the carrier gas and on the thickness of the PEG-20M film in the capillary column

The effects of the carrier gas nature and pressure on the relative retention values of organic compounds were studied using a series of capillary columns differing in the film thickness of the polar stationary phase (PEG-20M). Relative retention depends linearly on the carrier gas pressure. This dependence becomes more pronounced in the following order of carrier gases: helium < nitrogen < carbon dioxide. The limiting relative retention at a carrier gas pressure approaching zero rather than relative retention values measured experimentally (relative retention time, Kovats retention index,etc.) is an invariant characteristic of a compound subjected to chromatography. For the carrier gases studied, the limiting retention values almost does not depend on the nature of the carrier gas used. The limiting indicating the complex absorption-adsorption nature of these parameters. Dissolution of a carrier gas in the stationary liquid phase has an effect on the relative retention. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2177–2186, December, 1997.     

Analysis of the Sulfonylurea Herbicide Metsulfuron-Methyl and Its Metabolites in the Soil of Cereal Crops. Comparative Analytical Chemistry of the Sulfonylureas

Abstract

For the analysis of metsulfuron-methyl in the crop soils with a sensitivity limit of 0.3 μg kg^?1 dry soil, in the soil extract metsulfuron-methyl was separated from its soil metabolites and the soil impurities by repeated thin-layer chromatographies (TLC). In the cleaned soil extract, diazomethane transformed metsulfuron-methyl 1 into N,N′ -dimethyl metsulfuron-methyl 2 (methyl 2-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)methylamino]carbonyl]methylamino]sulfonyl]benzoate). In the gas-liquid chromatograph with detection by electron capture (GC-EC) and in the combined gas chromatograph-mass spectrometer (GC-MS), 2 was transformed into 1-dioxy-2-N-methyl-3-keto-1,2-benzisothiazole 3 which was measured by GC-EC with confirmation by GC-MS. The metsulfuron-methyl soil metabolites 2-sulfonamido-methylbenzoate 6, 1-dioxy-3-keto-1,2-benzisothiazole (saccharin) 7 and 2-sulfonamidobenzoic acid 8 were analyzed in the soil of winter wheat crops by a procedure similar to the one for metsulfuron-methyl. After their separation and purification in the soil extracts by TLC, 7 and 8 were methylated, and analyzed as 3 in the GC-EC and GC-MS apparatus where the generated 6 was quantitatively transformed into 3; 6 was analyzed as such with the GC and GC-MS apparatus wherein it was transformed into 3. The sensitivity limit for each metabolite was 0.3 μg of equivalents of metsulfuron-methyl kg^?1dry soil. The syntheses of the analysis standards of the metsulfuron-methyl derivatives 2 and 3, and of the metsulfuron-methyl metabolites 6, 7 and 8 are described. The transformation pathways of metsulfuron-methyl and of its derivatives are different from those of the pyridine-pyrimidine sulfonylurea herbicides flupyrsulfuron-methyl and rimsulfuron. The soil analysis of a sulfonylurea -by means of one of its transformation product- needs a previous study of the chemical reactivity of the sulfonylurea. This leads to the analysis procedures for the main soil metabolites of the sulfonylurea.     

由聚合物结构预测气体的透过性能

本文利用基团加和法,对20多种常见聚合物的自由体积和内聚能进行了计算。发现氧气和氮气在聚合物膜中的透过率与自由体积和内聚能的比值有直接关系。此比值越大,气体的透过率越大,透过率的对数与自由体积和内聚能的比值基本呈线性关系。据此,对未知聚合物可根据其化学结构,从已有的基团数据计算该比值,从而预测它对氧气和氮气的透过性能。     

Flow of the carrier gas in open-tubular capillary columns in temperature-programmed gas chromatography

A second-order non-linear partial different equation was derived to describe the dependence of carrier gas pressure in the column on the column distance and the time under temperature programmed conditions. This equation was solved numerically by the modified finite difference method for various column parameters. Constant inlet and outlet pressures were used as boundary conditions. The retention times calculated on assumption of a constant pressure profile along the column. Significant differences between retention times of corresponding solutes calculated by the two methods were found, especially when relatively long columns(L>50m) with small internal diameter(d<0.3mm)and high temperature program rates (r>5°/min)are used.     

变压器油中溶解气体奥斯特瓦尔德系数的测定方法

设计了一套以气相色谱测定变压器油中溶解气体奥斯特瓦尔德系数的装置。它包括恒温水浴、磁力搅拌器、油气平衡瓶、六通阀以及在线气相色谱仪。测定了20℃和50℃温度下变压器油中溶解气体CH4、C2H2、C2H4、C2H6和C3Hg的奥斯特瓦尔德系数和平衡时间,测量的重复性误差RSD小于1．2％。为气相色谱在线分析变压器油中溶解气体积累了重要的基础数据。     

The determination of aldehydes in the exhaust gases of LPG fuelled engines

Summary The exhaust gas of a LPG fuelled engine is drawn through two bubblers in series in an ice bath, and filled with saturated 2,4-dinitrophenylhydrazine in 2M HCl. After heating the derivatives are extracted with toluene-cyclohexane and 1l samples injected on-column on a OV1 capillary column. Using an FID the lower limit of detection is 15–18 pg for formaldehyde (about 8–10 ppbv for a 16l exhaust sample). Taking the blank into account, the limit is about 40 ppbv.The exhaust gases of a LPG-fuelled engine contain formaldehyde, acetaldehyde, propionaldehyde, acrolein and acetone. Carbonyl compounds of more than 3 C-atoms were not found in detectable amounts. The engine was rund under stoichiometric, lean and rich air/fuel conditions. Under rich conditions the concentrations of the aldehydes were: formaldehyde 2.8 ppm, acetaldehyde 1.3 ppm, propionaldehyde 0.06 ppm, acrolein 0.03 ppm, acetone 0.17 ppm; under stoichiometric conditions: 4.5, 1.6, 0.10, 0.03 and 0.18 ppm respectively; under lean conditions 17.0, 2.9, 0.13, 0.07 and 0.27 ppm respectively. These figures demonstrate the necessity of measuring aldehydes in exhaust gases of LPG-fuelled engines.     

Comparison of three methods for natural gas dehydration

This paper compares three methods for natural gas dehydration that are widely applied in industry:(1) absorption by triethylene glycol, (2) adsorption on solid desiccants and (3) condensation. A comparison is made according to their energy demand and suitability for use. The energy calculations are performed on a model where 105 Nm3/h water saturated natural gas is processed at 30 °C. The pressure of the gas varies from 7 to 20 MPa. The required outlet concentration of water in natural gas is equivalent to the dew point temperature of -10 °C at gas pressure of 4 MPa.