电感耦合等离子体质谱法快速测定苦荞茶中铜、铅、镉、钴、镍

建立了用硝酸-高氯酸消解样品,电感耦合等离子体质谱法(ICP-MS)测定苦荞茶中铜、铅、镉、钴、镍的方法.方法具有灵敏度高、检出限低、精密度好、基体干扰少、准确可靠、快捷、简便的特点.各元素方法检出限(3SD,μg/L)分别为:铜0.009、铅0.023、镉0.015、钴0.022、镍0.035;方法精密度(RSD,n=12)分别为:铜2.5%～3.0%、铅2.1%～2.3%、镉3.0%～3.8%、钴2.5%～2.6%、镍1.5%～1.9%;各元素加标回收率分别为:铜95.0%～105.0%、铅95.0%～105.0%、镉98.0%～105.0%、钴95.0%～105.0%、镍95.0%～105.0%.在线用铑作为内标95.0%～105.0%.方法经国家一级标准物质验证,测定值与标准值吻合.应用于实际样品测定,结果满意.     

Dibenzomethanopentacene-Based Polymers of Intrinsic Microporosity for Use in Gas-Separation Membranes

Dibenzomethanopentacene (DBMP) is shown to be a useful structural component for making Polymers of Intrinsic Microporosity (PIMs) with promise for making efficient membranes for gas separations. DBMP-based monomers for PIMs are readily prepared using a Diels–Alder reaction between 2,3-dimethoxyanthracene and norbornadiene as the key synthetic step. Compared to date for the archetypal PIM-1, the incorporation of DBMP simultaneously enhances both gas permeability and the ideal selectivity for one gas over another. Hence, both ideal and mixed gas permeability data for DBMP-rich co-polymers and an amidoxime modified PIM are close to the current Robeson upper bounds, which define the state-of-the-art for the trade-off between permeability and selectivity, for several important gas pairs. Furthermore, long-term studies (over ≈3 years) reveal that the reduction in gas permeabilities on ageing is less for DBMP-containing PIMs relative to that for other high performing PIMs, which is an attractive property for the fabrication of membranes for efficient gas separations.     

Simultaneous determination of fluoroquinolones,sulfonamides and tetracyclines in sewage sludge by pressurized liquid extraction and liquid chromatography electrospray ionization-mass spectrometry

A new scheme for the quantitative determination of traces of fluoroquinolones (FQs), tetracyclines (TCs) and sulfonamides (SAs) in sewage sludge was developed. The compounds were simultaneously extracted from sewage sludge by pressurized liquid extraction (PLE). A novel and effective method for PLE was developed. Solid-phase extraction was used for cleaning up the extracts. Identification and quantification of the compounds was done using high-performance liquid chromatography with electrospray ionization mass spectrometry in selected reaction monitoring mode. The best recovery of FQs and TCs was obtained by using hydrophilic–lipophilic balance cartridges, recoveries ranged 59% for norfloxacin to 82% for ofloxacin and 95% for doxycycline; for SAs strong cation-exchange cartridges were more efficient, recoveries were 96% for sulfamethoxazole and 43% for sulfadimethoxine. Limit of quantification ranged from 0.1 ng/g for SAs to 160 ng/g for tetracycline. Method precision for TCs was 5.06% and 1.12%, and for SAs 0.43% and 2.01%. FQs precision ranged from 0.77% to 1.89%.     

Normal Coordinate Analysis for Polymer Systems: Capabilities and New Opportunities

Normal coordinate analysis is an important tool in studying the structure, dynamics, and physical properties of polymer systems. In this article the capabilities of normal coordinate analysis (NCA) are explored in some detail. The use of the eigenvalues and eigenvectors from NCA is catalogued for a wide variety of purposes: for assigning or interpreting polymer spectra, for structural determination, for constructing force fields, for computing heat capacity and other thermodynamic properties, and for computing other physical properties. Examples are given for crystals, melts, and amorphous systems. Also described are methods for characterizing the normal mode vectors that are especially useful for larger systems, in which a large amount of data must be analyzed or where visualization or animation fails. Finally, a recently developed method for eliminating negative eigenvalues in systems with tens of thousands of atoms, trajectory averaging, is presented. Also described are several advances in numerical linear algebra for speeding up the diagonalization phase and for computing physical properties without requiring full diagonalization of the Hessian matrix.     

Overview of Special Session B—Compositional and Structural Analysis of Biomass

Special Session B at the 29th Symposium on Biotechnology for Fuels and Chemicals was the first invited session at this symposium devoted to analytical methods. The special topic was added in response to numerous requests for information on new and innovative methods that could be applied in the growing renewable fuels industry. Presentation topics include analytical methods for the characterization and analysis of maize traits, tools for investigating cell wall limitations to enzymatic degradation, methods for customizing enzyme cocktails for biomass, new techniques for the analysis of carbohydrates, analytical methods that enhance our understanding of pretreatment, improved methods for monitoring process intermediates, and published standard analytical methods for biomass conversion processes.     

傅里叶变换近红外光谱法同时定量分析水溶液中乙醇、果糖和葡萄糖

利用乙醇、果糖和葡萄糖在波数为14000-7500cm^-1范围内的吸收值,在近红外谱区用偏最小二乘法（PLS）对体系进行建模,并通过内部和外部样品校验确认最佳数据预处理方法。结果表明,乙醇在0.05-0.25L/L,果糖在0.01-0.05g/mL及葡萄糖在0.005-0.009g/mL的范围内外部校验模型较好的分别是在PLS中所用的一阶偏导（平滑点数是5）、二阶偏导（平滑点数是5）和直线消除法的数据预处理方法所建立的模型,其外部校验预测结果的相对误差在2%左右。此方法具有可同时测定不同样品,简便快速及成本低等优点。     

Treatment of Anomalous Vapor Diffusion in Polymers

The mechanics of thermally-activated gaseous diffusion in polymers have long been studied for development of theoretical understanding of the interactive forces responsible for the non-linear nature of diffusion and the resultant enthalpic changes in the polymer. Methodologies and calculations have been developed in this work for treatment of experimental data for elimination of thickness-related anomalies in water vapor diffusion and for delineation of pressure effects. Linearized data for different polymer thicknesses and the attendant internal thermal effects have been generated by using calculated single molecule diffusion values. Equally linear data are obtained for different pressures by the use of a graphical method from which identical diffusion values are obtained, independent of material thickness and external pressure. True comparisons and classification of polymers as to their diffusivities are thus possible for development of barrier materials for food and drug packaging and for protective encapsulation of electronic devices. Results will be reported for three structurally different polymers. This revised version was published online in July 2006 with corrections to the Cover Date.     

Spectrophotometric and spectrofluorimetric methods for analysis of tramadol, acebutolol and dothiepin in pharmaceutical preparations

Sensitive spectrophotometric and spectrofluorimetric methods are described for the determination of tramadol, acebutolol and dothiepin (dosulepin) hydrochlorides. The two methods are based on the condensation of the cited drugs with the mixed anhydrides of malonic and acetic acids at 60 degrees C for 25-40 min. The coloured condensation products are suitable for the spectrophotometric and spectrofluorimetric determination at 329-333 and 431-434 nm (excitation at 389 nm), respectively. For the spectrophotometric method, Beer's law was obeyed from 0.5 to 2.5 microg ml(-1) for tramadol, dothiepin and 5-25 microg ml(-1) for acebutolol. Using the spectrofluorimetric method linearity ranged from 0.25 to 1.25 microg ml(-1) for tramadol, dothiepin and 1-5 microg ml(-1) for acebutolol. Mean percentage recoveries for the spectrophotometric method were 99.68+/-1.00, 99.95+/-1.11 and 99.72+/-1.01 for tramadol, acebutolol and dothiepin, respectively and for the spectrofluorimetric method, recoveries were 99.5+/-0.844, 100.32+/-0.969 and 99.82+/-1.15 for the three drugs, respectively. The optimum experimental parameters for the reaction has been studied. The validity of the described procedures was assessed. Statistical analysis of the results has been carried out revealing high accuracy and good precision. The proposed methods were successfully applied for the determination of the selected drugs in their pharmaceutical preparations with good recoveries. The procedures were accurate, simple and suitable for quality control application.     

Analysis of urinary biomarkers for exposure to alkyl benzenes by isotope dilution gas chromatography-mass spectrometry

A validated GC-MS method for the analysis of urinary metabolites of alkyl benzenes is reported. Metabolites for exposure to toluene, xylene and ethylbenzene were analyzed simultaneously using stable isotope substituted internal standards. The method entailed acidic deconjugation of urine samples followed by extractive alkylation with pentafluorobenzyl bromide as alkylating agent. The resulting pentafluorobenzyl derivatives of ortho-, meta-, para-cresol, mandelic acid (MA), hippuric acid (HA) and ortho-, meta-, para-methylhippuric acid (MHA) were then quantified by SIM. Optimized reaction conditions for the extractive alkylation step are reported. The derivatives were found to be sufficiently stable for overnight batch analysis. The LODs were below 0.1 micromol/L for the cresols and below 1 micromol/L for MA and the HAs. Within-batch precision for o-MHA was 7%, for m-MHA 5%, for p-MHA 5.2% and below 5% for the rest of the analytes.     

Evaluation of the detection of biomolecules in capillary electrophoresis by contactless conductivity measurement

The sensitivity of contactless conductivity detection to amino acids, peptides and proteins in CE was studied for BGE solutions of different pH values. The LOD and analytical characteristics were compared for acidic and basic conditions and better results were in most cases found for buffers of low pH values. Linear dynamic ranges varied between two orders of magnitude for amino acids and peptides and three orders of magnitude for larger proteins. The concentration detection limits were found to be between 1.2 and 7.5 microM for the amino acids tested and for the larger molecules they varied between 2.6 microM for leucine enkephalin and 0.2 microM for HSA when using a buffer at pH 2.1.     

Method validation and determination of lisdexamfetamine and amphetamine in oral fluid,plasma and urine by LC–MS/MS

Lisdexamfetamine (LDX) is a long‐acting prodrug stimulant indicated for the treatment of attention‐deficit/hyperactivity disorder and binge‐eating disorder symptoms. In vivo hydrolysis of LDX amide bond releases the therapeutically active d ‐amphetamine (d ‐AMPH). Since toxicological tests in biological samples can detect AMPH from the use of some legal medications, efficient methods are needed in order to correctly interpret the results. The aim of this study was to develop and validate an LC–MS/MS method for the simultaneous quantification of LDX and its main biotransformation product AMPH in human oral fluid, plasma and urine. Calibration curve range for both analytes was 1–128 ng/mL in oral fluid and plasma and 4–256 ng/mL in urine, being the lowest concentration the limit of quantification. Accuracy of the determined values of the target analytes for the five control levels ranged from 94.8 to 111.7% for oral fluid, from 91.3 to 100.2% for plasma and from 94.8 to 109.8% for urine. Imprecision for the five control levels did not exceeded 12.8% for oral fluid, 16.2% for plasma and 17.1% for urine. The method developed for the three matrices was validated and was also successfully applied to assess real samples, showing for the first time the detection of LDX in oral fluid.     

高纯度树状大分子聚酰胺-胺的合成与表征

以乙二胺为核,通过Michael加成,与丙烯酸甲酯交替反应,合成了0.5代到5.0代聚酰胺 胺树状大分子。 利用傅里叶变换红外光谱、核磁共振氢谱、液相色谱和元素分析等对各代产品进行了表征,探索了反应温度、时间及反应物配比对产物的影响,确定生成聚酰胺-胺(PAMAM)的半代产物时反应温度为25 ℃,整代产物时反应温度为35 ℃;0.5G的反应时间为18 h,1.0G、1.5G的反应时间为24 h,2.0G、2.5G反应36 h,3.0G、3.5G反应48 h,4.0G、4.5G反应3 d,5.0G反应4 d。 分离提纯是树状大分子制备中遇到的最大困难,通过选择性溶剂萃取的方法对产品分离纯化,筛选出乙醚作萃取剂、甲醇作溶剂交换剂,大大提高了产品的纯度。     

势阱中粒子能级与波函数微扰计算的代数递推公式

利用超位力定理(HVT)和Hellmann-Feynman 定理(HFT),导出了由有精确解的势阱的能级值用微扰法直接计算一维势阱的各级近似能级的普遍代数公式,并导出了由能级近似值计算定态波函数近似表达式的代数公式.给出了代数公式具体应用的几个典型一维势阱实例.此法可推广到二维势阱与三维势阱的情形.     

Rapid screening of inorganic and organic anions in liquid by‐products from hydrothermal treatment of biomass by capillary electrophoresis

A simple and rapid capillary electrophoresis method with capacitively coupled contactless conductivity detection (CE‐C⁴D) for the simultaneous determination of inorganic and organic anions in liquid product obtained from the hydrothermal treatment of biomass residues is presented. Under the optimal analytical conditions, limits of detection ranged from 1.8 to 9.4 μM for most target solutes and 53 μM for citrate. Relative standard deviations were below 0.5% for migration times and within 0.6–6.5% for peak areas for all solutes. The proposed method was successfully applied for the rapid determination and screening of inorganic and organic anions in liquid product produced following differing hydrothermal treatment temperatures for banana and pineapple biomass, and the contribution of organic acid formation to acidity in the liquid was evaluated. CE‐C⁴D could be a suitable method for the optimization or tailoring of HTT conditions for desired liquid product composition, and additionally for determination of the best variety(s) of biomass to use in such processes.     

液态水热容的量子校正

在不同温度下对液态水进行分子动力学模拟，研究各温度下液态水中各个原子的速度自相关函数密度谱，以考察液态水热容的量子校正随温度的变化规律．研究结果表明，水分子的三个内部振动模式对热容的量子校正不随温度变化，而转动和分子距平衡位置的摆动运动模式的量子校正随温度升高而逐步减小．对于分子动力学模拟结果经温度涨落计算所得的热容进行了量子校正，校正结果与实验值能符合．     

Simultaneous quantification of five anthraquinones in rat plasma by high-performance liquid chromatography with fluorescence detection

A sensitive high-performance liquid chromatographic method with fluorescence detection (excitation 435 and emission 515 nm) was established and validated for quantification of five anthraquinones (aloe-emodin, rhein, emodin, chrysophanol and physcion) in rat plasma. Following a single-step liquid-liquid extraction, the analytes and internal standard (1,8-dihydroxyanthraquinone) were separated on a reversed-phase C(18) column with water-phosphoric acid-methanol as mobile phase at a flow rate of 1 mL/min. The linear ranges of the calibration curves were 6.5-1300 ng/mL for aloe-emodin, 20-4000 ng/mL for rhein, 40-8000 ng/mL for emodin, 15-3000 ng/mL for chrysophanol and 13-2600 ng/mL for physcion. The lower limit of quantification was 6.5 ng/mL for aloe-emodin, 20 ng/mL for rhein, 40 ng/mL for emodin, 15 ng/mL for chrysophanol and 13 ng/mL for physcion. The mean accuracy was 94.3-105.1% for aloe-emodin, 90.3-108.8% for rhein, 92.6-106.7% for emodin, 95.8-103.8% for chrysophanol and 98.7-101.2% for physcion. The within-batch and between-batch precisions were < or = 5.5% and < or = 13.4%, respectively. This method is suitable for determining the five anthraquinones in plasma simultaneously and thus investigating the pharmacokinetics of anthraquinones from Xiexin decoction in rats.     

Post-column oxidative derivatization for the liquid chromatographic determination of phenothiazines

A first post-column chemical derivatization method for the liquid chromatographic determination of phenothiazines is presented. Peroxyacetic acid is introduced as a derivatizing agent for phenothiazines, yielding the colored radical cations or fluorescent sulfoxides, depending on reaction conditions. Both reaction products were successfully employed for the detection of the phenothiazines after their liquid chromatographic separation. The fluorescence spectroscopic detection of the sulfoxides proved to be the more robust and sensitive method. Limits of detection ranged from 4 nM for triflupromazine and trimeprazine to 300 nM for phenothiazine for the fluorescence spectroscopic detection of the sulfoxide and from 0.3 μM for phenothiazine and triflupromazine to 2 μM for trifluperazine for the UV–Vis spectroscopic detection of the radical cation. The calibration functions for the fluorimetric sulfoxide determination ranged from two to more than three decades, starting at the limit of quantification.     

水、甲醇和乙醇液体微结构性质的Car-Parrinello 分子动力学模拟

采用Car-Parrinello 分子动力学(CPMD)方法分别研究了水、甲醇和乙醇的液体微结构性质.研究结果显示:在水、甲醇和乙醇三个体系中O…O径向分布函数曲线的第一个峰位置分别为0.278、0.276 和0.275nm; O…H径向分布函数曲线的第一个峰位置分别为0.178、0.176和0.177 nm.表明基团(氢原子、甲基、乙基)的差异对O…O第一个峰的位置影响很小.但基团的差异对径向分布函数峰高的影响却很显著,由水到乙醇第一个峰的高度逐渐变高.空间分布函数表明氧原子和氢原子在溶剂分子周围有取向地分布,这与径向分布函数所表现出尖锐的第一个峰相一致.氢键分布分析显示,水、甲醇和乙醇的平均氢键数分别为3.62、1.99 和1.87,表明水形成了网状氢键结构,而甲醇、乙醇形成链状氢键结构.     

Determination of inorganic elements in animal feeds by NIRS technology and a fibre-optic probe

In the present work we study the use of near infra-red spectroscopy (NIRS) technology together with a remote reflectance fibre-optic probe for the analysis of the mineral composition of animal feeds. The method allows immediate control of the feeds without prior sample treatment or destruction through direct application of the fibre-optic probe on the sample.The regression method employed was modified partial least squares (MPLS). The calibration results obtained using forty samples of animal feeds allowed the determination of Fe, Mn, Ca, Na, K, P, Zn and Cu, with a standard error of prediction (SEP(C)) and a correlation coefficient (RSQ) of 0.129 and 0.859 for Fe; 0.175 and 0.816 for Mn; 5.470 and 0.927 for Ca; 2.717 and 0.862 for Na; 4.397 and 0.891 for K; 2.226 and 0.881 for P; 0.153 and 0.764 for Zn, and 0.095 and 0.918 for Cu, respectively.The robustness of the method was checked by applying it to 10 animal feeds samples of unknown mineral composition in the external validation.     

Extracellular vesicles based electrochemical biosensors for detection of cancer cells: A review

Extracellular vesicles (EVs) derived from cancer cells are considered as ideal biomarker for liquid biopsy in cancer diagnosis, and are stable and abundant. Electrochemical methods for the detection of EVs are preferred over conventional methods such as Western blotting and enzyme-linked immunosorbent assay for their high sensitivity and real-time detection. This article summaries studies proposing the electrochemical methods utilizing immunological and molecular methodologies for detecting EVs derived biomacromolecules such as miRNAs and transmembrane protein for cancer diagnosis. Moreover, the electrochemical detection methods are compared and future prospects for the development of electrochemical methods for EVs detection are concluded.