不同个体足部人体气味的鉴别研究

运用SPME-GC/MS法对5位个体的足部人体气味进行了采样分析,通过比较气味样品中共有成分的相对峰面积比的差异和样品中的非共有成分的不同,并使用斯皮尔曼秩相关法对来自5位个体的足部人体气味样品进行了鉴别,样品均得到了有效地区分。     

二碘荧光素、荧光素稀土配合物的合成及性质的研究

本文报导了一种合成二碘荧光素、荧光素稀土配合物的新方法,得到了定组成的固体配合物,并对它们的一系列性质进行了研究。通过化学分析、元素分析确定了它们的组成。     

Protein profiles and identification of high performance liquid chromatography isolated proteins of cancer cell lines using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) has been used to rapidly profile the protein content of human cell lysates from MCF-10 cell and variant lines. The method was used to study the protein profiles of these cells as they progressed from normal breast epithelium to fully malignant cells. Distinct differences in the protein profiles were observed with progression, and specific proteins associated with carcinogenesis (p53, c-myc, and c-erbB-2) were heavily expressed in these cells as detected by MALDI-TOFMS. These proteins were also isolated using non-porous reversed-phase high performance liquid chromatography (NP-RP-HPLC) and mass analyzed by MALDI-TOFMS to provide molecular weight information without interference from other proteins in the whole cell lysates, and to avoid suppression effects in mixtures of proteins detected by MALDI-TOFMS. In order to confirm the identity of these oncoproteins, the cell lysates were subjected to one-dimensional (1-D) gel separation and subsequently electroblotted onto a poly(vinylidene difluoride) (PVDF) membrane for further analysis. Trypsin and cyanogen bromide digestions were performed on these proteins eluted from excised PVDF bands which were then analyzed by MALDI-TOFMS. The identity of these proteins was confirmed by database matching procedures.     

大分子聚酯配体及其钆（Ⅲ）配合物的合成和核磁弛豫性能研究

通过二乙三胺五乙酸二酐（ＤＴＰＡＡ）分别与Ｎ－正丁基、正辛基、苄基、对甲苯磺酰基、苯基和对溴苯基取代二乙醇胺共聚，制得一系列大分子配体及其钆（ＩＩＩ）配合物．对所合成的配体和钆配合物进行了表征，并测试了部分钆配合物的核磁弛豫性能．     

Synthesis and characterization of novel alkoxy nonionic biosurfactants

A series of novel alkoxy nonionic biosurfactants were synthesized by ring-opening reaction of methoxy poly(ethylene glycols) and alkylene oxide. The chemical structures of these biosurfactants were confirmed by Fourier-transform infrared spectroscopy (FTIR) and ¹HNMR spectra. The surface tensions of these nonionic biosurfactants in the aqueous solutions were determined using a surface tensionmeter. The results showed that the critical micelle concentrations decreased with the increase of hydrophobic chain. However, due to the effect of intermolecular hydrogen bonding, the critical surface tensions of these nonionic biosurfactants increased with increasing the hydrophobic chain and were lower than those of conventional nonionic biosurfactants. Meanwhile, the effects of electrolytes on surface tension of these nonionic biosurfactants were slight. Due to the excellent surface activity, these alkoxy nonionic biosurfactants could have great potential in cleansing, oil recovery, and drug delivery.     

Effects of peak anomalies with the hydrophilic or hydrophobic properties of reservoirs during serial injection on a capillary electrophoresis microchip

Several anomalies, e.g., in peak shape, migration time, and baseline drift, all due to pressure-driven backflow, were previously reported to occur during serial injection on capillary electrophoresis (CE) chips. Since these anomalies were worse for polydimethylsiloxane (PDMS) microchips than for glass microchips, reproducible data on PDMS microchips were difficult to obtain. In this paper, we found that these problems were affected by the hydrophilic or hydrophobic properties of the reservoirs on the microchip and demonstrated that these anomalies were reduced by converting the hydrophobic properties of the reservoirs on the PDMS microchip into hydrophilic ones. Thus, compared with hydrophobic reservoirs, hydrophilic reservoirs were suitable for the formation of a stable plug. Several chip designs were suggested to reduce these pressure-driven backflows.     

SYNTHESIS AND CHARACTERIZATION OF POLYBENZOTHIAZOLAMIDES

Aromatic polybenzothiazolamides were prepared by low temperature solution method by condensing the 2, 2'-diarnino-6, 6'-bibenzothiazole with four different acid chlorides in quantitative yield. These polymers were characterized by IR and NMR. Viscosities of these polyamides range from 0.42 to 1 dl/gm. All these polymers were stable upto 300℃in air.     

A novel derivatization approach for simultaneous determination of glyoxal, methylglyoxal, and 3-deoxyglucosone in plasma by gas chromatography-mass spectrometry

A two-step derivatization approach has been developed to enable the simultaneous analysis of glyoxal, methylglyoxal, and 3-deoxyglucosone by the most efficient and widely applied GC-MS methodology. These three analytes are reactive carbonyl compounds associated with the formation of advanced glycation and lipoxidation end products, a process thought to contribute to uremic toxicity and referred to as "carbonyl stress". Effective analysis of these compounds would facilitate understanding these compounds' role in diabetes-related complications. Plasma samples were deproteinized by acetonitrile, followed by a two-step derivatization approach. Pooled plasma samples from healthy individuals were used as the "blank" for preparing calibration standards. The concentrations of the analytes in the "blank" were first determined by standard addition method. Calibration parameters were accordingly established and used to analyze these compounds in plasma samples collected from healthy individuals and diabetic patients. Analytical findings are comparable with those reported in the literature. Quantitation data can be further improved by making available and using isotopically labeled analogs of these analytes as the internal standards.     

几种含苯乙炔基的硅-硅链高聚物的研究

采用含苯乙炔基的二氯硅烷和另外几种二氯硅烷,通过在甲苯中钠缩合的方法,合成了六种含苯乙炔基的聚硅烷。测试了聚合物的红外光谱,紫外光谱和核磁共振谱,测定了聚合物本体及掺杂后的电阻率。聚硅烷还可与某些电子受体形成复合物,形成的复合物在紫外尤谱上都有新的吸收峰出现。     

含铽配合物的合成及其荧光性研究

采用稀土铽金属醇盐与丙烯酸、乙酰丙酮、中性配体(邻菲啰啉或联吡啶）反应，在非水介质下合成具有高聚合活性的含铽配合物单体，通过元素分析、红外光谱、紫外光谱确定了它们的组成和结构，合成的铽配合物单体溶于一般的有机溶剂并能强烈吸收紫外光谌芤杭胺勰┳刺卵芯空庑┑ヌ宓挠庑浴T谧罴鸭し⒉ǔは拢蔷芊⑸滹胱拥奶卣饔猓ド越虾谩Q返淖刺叭芗恋募远耘浜衔锏牡ヌ宓挠庑杂薪洗笥跋欤行耘涮辶诜茊⒘拎さ囊芴岣咚堑挠夥⑸淝慷取     

金属卟啉催化下环己烷羟基化反应中的Hammett关系

合成了40个卟啉环上具有不同取代基的单铁、锰卟啉和u-氧桥连双铁、锰卟啉,研究了这些金属卟啉模拟细胞色素P－450单充氧酶在温和条件下催化环己烷羟基化的反应.首次用线性自由能关系对金属卟啉仿生催化反应和金属卟啉自氧化反应进行相关分析,获得一些新的结果和规律.在此基础上,对金属卟啉仿生催化反应的可能机理进行了探讨.     

Oxidation of monoglyceride, diglyceride, and triglyceride monolayers by aqueous potassium permanganate solution

Studies were carried out on the oxidative degradation of monoolein, monolinolein, diolein, dilinolein, triolein and trilinolein monolayers by injecting KMnO₄ solution under the monolayers. The effect of the initial surface pressure on oxidative degradation was also studied by measuring changes in the surface pressure and surface potential with time. The surface shear viscosities of these six lipids were measured in order to predict their molecular interactions at the air/water interface. The rates of oxidation for these lipids were found to be in the following order: dilinolein> monolinolein> monoolein> trilinolein> diolein> triolein. Interestingly, the surface shear viscosities of these six lipids were found to decrease in the same order. In the present study, an attempt has been made to correlate the effect of the initial surface pressure, the number of double bonds and the number of hydroxyl groups with the oxidation of these lipids by potassium permanganate solution.     

Controllable preparation of magnetic polymer microspheres with different morphologies by miniemulsion polymerization

Magnetic poly(styrene-co-acrylic acid-co-acrylamide) microspheres were prepared by water-in-oil-in-water (W/O/W) miniemulsion polymerization of monomers in the presence of Fe3O4 nanoparticles. The copolymerizable monomers of acrylic acid and acrylamide were used not only to modify the surfaces of the microspheres with functional groups, but also to act as viscosity regulators to control the morphology and size of these microspheres. It was experimentally observed that the surfaces of these microspheres were functionalized with NH2 groups produced by copolymerization, the morphologies (sphere, ringlike, and one-hole) of the microspheres were controlled by the concentration of copolymerizable monomers, and all samples prepared were superparamagnetic. The possible mechanism of formation of these magnetic microspheres is also discussed.     

Direct measurement of surface complex loading and surface dipole and their effect on simple device behavior

Tin complexes of phenoxide ligands having a range of dipole moments were prepared on the surface of indium-tin oxide (ITO). Surface complex loadings and stoichiometries were measured by quartz crystal microgravimetry. Work functions of ITO substrates treated with these various surface complexes were measured using a Kelvin probe. Surface complex dipole moments were then calculated based on measured surface loadings. Changes in the ITO work function effected by surface phenoxide complex introduction correlate with these surface complex dipole moments and with total surface dipole per unit area, and current densities in simple hole-only diode devices also correlate with these total surface dipoles.     

Anion exchange liquid chromatography--inductively coupled plasma-mass spectrometry detection of the Co2+, Cu2+, Fe3+ and Ni2+ complexes of mugineic and deoxymugineic acid

Phytosiderophores, such as mugineic and deoxymugineic acid, are produced by graminaceous plant species in response to Fe deficiency conditions normally experienced in calcareous and alkaline non-calcareous soils. As these phytosiderophores have the ability to form thermodynamically stable complexes with other metal cations present in the growing medium, they have also been implicated in the transport and bioavailability of these metals in the environment. However, routine analytical methodology to detect the various metal complexes formed by these phytosiderophores is lacking. Therefore, as these complexes are negatively charged over a wide range of pH values, anion exchange liquid chromatography (AE LC) coupled to inductively coupled plasma-mass spectrometry (ICP-MS) was investigated as a means to separate and quantify these complexes. The metal-phytosiderophore complexes were prepared at pH 7 and separated by NaOH or NH4NO3 gradient elution on a Dionex AS11 anion exchange column. Of the metals tested only the Co2+ and Ni2+ complexes of mugineic and deoxymugineic acid were detected when using a 0-20mM NaOH gradient elution profile. However, the phytosiderophore complexes of Cu2+ and Fe3+ were also detected when using NH4NO3 as the mobile phase at pH 7. Base-assisted hydrolysis of the latter two complexes is proposed to explain their apparent 'instability' in the high pH NaOH mobile phase. The absolute detection limits of the developed methodologies for these metal complexes ranged from 0.1 to 2.8pmol. As phytosiderophore complexes with Cd2+ and Zn2+ were not detected, it was concluded that the dissociation kinetics of these metal-phytosiderophore complexes were too rapid for these complexes to be observed in the present chromatographic conditions.     

人肝癌细胞系HLE细胞表面抗原多肽的纳升电喷雾串联质谱从头测序分析

肿瘤细胞表面的抗原多肽能够被细胞毒T淋巴细胞特异性识别而引起免疫应答,因此有可能用于研制基于多肽的抗肿瘤疫苗。用弱酸将人肝癌细胞系HLE细胞表面抗原多肽和人正常肝细胞表面多肽洗脱后,经RP-HPLC分离,选择HLE细胞表面特异性多肽进行纳升电喷雾串联质谱(nanoESI-MS/MS)测序,共测定5个色谱峰中的20个多肽序列,分子量分布范围为1000~2000 Da。借助M asSeq软件分析出其中12个多肽的序列。经数据库查寻,其中的3个肽段分别来自钙调节蛋白、核蛋白S19和伴侣蛋白10。这些多肽的生物学功能及与肿瘤的关系值得深入研究。该研究表明nanoESI-MS/MS是测定微量混合多肽序列的最有效方法。     

匀胶铬版表面界面微观构成的X射线光电子能谱表征

用Ｘ射线光电子能谱（ＸＰＳ）研究了几种不同工艺制备的匀胶铬版表面、铬膜内部以及各层之间界面处的微观化学组成和化学状态，讨论了不同工艺对铬版材料微观构成及宏观特性的影响。     

Thermoanalytische und IR-spektroskopische Untersuchungen an polymorphen Arzneistoffen: Amcinonid, Indalpin, Metahexamid und Moclobemid

Summary In these four drugs three to five polymorphic modifications each were found. All these compounds exist in the commercial products in a low temperature phase and can be transformed into high temperature modifications by heating. The investigations were carried out by means of thermomicroscopy, differential scanning calorimetry and infrared spectroscopy.     

ULTRAVIOLET PHOTOIRRADIATION OF DAUNOMYCIN AND DNA–DAUNOMYCIN COMPLEXES

Abstract— Daunomycin and daunomycin–DNA complexes have been irradiated with UV light for up to 1 h. The drug was degraded to a variety of precipitates, all of which were devoid of the sugar moiety and these precipitates were further degraded by photobleaching. The precipitates have been fractionated by HPLC. The major component (resulting from 10min irradiation of a deoxygenated drug solution) was characterized by proton NMR and field desorption mass spectrometry as a modified aglycone (ring A was aromatic and was de-acetylated). The production of hydrogen peroxide, photobleaching and the formation of precipitate were all inhibited by the addition of DNA. All of these effects appear to depend on the free drug concentration in solution. In the absence of DNA, all of these effects were enhanced by the presence of oxygen and diminished if the solutions were deoxygenated with argon.     

电感耦合等离子体原子发射光谱测定当归补血汤中铅、铬、镉、砷

采用电感耦合等离子体原子发射光谱测定了当归、黄芪及两种药材不同配伍形式的水煎液中铅、铬、镉、砷等金属元素含量。比较了不同提取方法及磷脂类化合物对当归补血汤中这些金属元素溶出的影响。实验表明,当归、黄芪生药材及水煎液经硝酸消化,样品消解完全,能满足电感耦合等离子体-原子发射光谱(ICP-AES)检测的要求。方法加标回收率为83.0%~96.0%,相对标准偏差为0.36%~4.67%,且当归∶黄芪配比为1∶5时水煎液中重金属元素溶出率低于1∶1配比,证实了当归补血汤经典配方的合理性,为其临床疗效提供了有效依据。