顶空固相微萃取-气相色谱-质谱联用分析纺织品中挥发性有机物

建立了顶空固相微萃取（HSSPME）-气相色谱（GC）-质谱（MS）联用测定纺织品中甲苯、4-乙烯基环己烯、苯乙烯、萘和1-苯基环己烯5种挥发性有机物（VOCs）的分析方法。选择聚二甲基硅氧烷（PDMS）作为萃取涂层,优化了SPME的萃取条件,包括平衡时间、萃取时间、萃取温度、顶空体积、离子强度、搅拌速度、解吸温度和时间以及GC—MS仪器条件。对于甲苯、4-乙烯基环己烯、苯乙烯、萘和1-苯基环己烯方法线性范围分别为0．087～870、3．32～3320、2．28～2280、0．015～150和0．050～50．0ng／g;检出限分别为0．005、0．042、0．670、0．008和0．011ng／g。实际样品加标回收率在80．1％～122％之间,RSD在0．8％～8．6％之间。方法符合纺织品中痕量VOCs的快速分析要求。     

Molecular Thermodynamics for Chemical Process Design

Thermodynamic properties are essential for quantitative process design to produce chemical products. Caloric properties are required for heat balances, but these properties are usually available or estimated easily. More important—and often much more difficult to estimate—are the chemical potentials of components in mixtures; it is these potentials which determine phase equilibria, as required for separation operations, and chemical equilibria, as required for chemical reactors and for separation operations based on chemical reactions. Molecular thermodynamics is an engineering-oriented science for calculating the desired chemical potentials from a minimum of experimental data. This applied science, based on classical and statistical thermodynamics, yields chemical potentials through models that are based on molecular physics and physical chemistry. Selected examples are cited to illustrate the applicability of molecular thermodynamics: group-contribution methods for obtaining chemical potentials in highly nonideal mixtures as required for distillation-column and process-safety design; equation of state for precipitation of uniform-sized crystals from supercritical fluids; molecular-orbital calculations to guide process development for alternatives to environmentally dangerous chlorofluorohydrocarbons; molecular-simulation calculations for separation of gas mixtures with porous adsorbents; equilibria in two-phase aqueous systems for separation of protein mixtures; and, finally, extended polymer-solution thermodynamics to guide synthesis of hydrogels suitable for protein recovery from soybeans and for novel drug-delivery devices.     

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.     

Data processing in metabolic fingerprinting by CE-UV: application to urine samples from autistic children

Metabolic fingerprinting of biofluids such as urine can be used to detect and analyse differences between individuals. However, before pattern recognition methods can be utilised for classification, preprocessing techniques for the denoising, baseline removal, normalisation and alignment of electropherograms must be applied. Here a MEKC method using diode array detection has been used for high-resolution separation of both charged and neutral metabolites. Novel and generic algorithms have been developed for use prior to multivariate data analysis. Alignment is achieved by combining the use of reference peaks with a method that uses information from multiple wavelengths to align electropherograms to a reference signal. This metabolic fingerprinting approach by MEKC has been applied for the first time to urine samples from autistic and control children in a nontargeted and unbiased search for markers for autism. Although no biomarkers for autism could be determined using MEKC data here, the general approach presented could also be applied to the processing of other data collected by CE with UV-Vis detection.     

电荷注入检测器电感耦合等离子体光谱仪测定非金属元素的分析性能

研究了电荷注入检测器ICP光谱仪测定非金属元素的分析性能。以S、P、As、Se为代表的非金属元素在170－800nm波段内最灵敏的谱线均处于175－200nm远紫外区内。在此区内等离子体有很低的光谱背景发射和良好的谱线测量和背景测量的光度精度。标准曲线线性动态范围在4个数量级。给出了As,Se,S,P主要分析线的灵敏度、线背比、背景等效浓度及检出限。在纯水溶液中的检出限分别为：As 189.142nm 0.003mg/L,P213.618nm 0.005mg/L,S 180.731nm 0.01mg/L,Se 196.090nm 0.009mg/L.     

Simultaneous quantification of volitinib and gefitinib in rat plasma by HPLC–MS/MS for application to a pharmacokinetic study in rats

A rapid, simple, and accurate procedure was developed and validated for the simultaneous quantification of two anticancer agents, volitinib and gefitinib in rat plasma by high‐performance liquid chromatography with tandem mass spectrometry. The samples were separated by gradient elution from a cyano column within five minutes, using 0.1% formic acid in acetonitrile and 10 mM ammonium formate solution (pH 3.0) as mobile phase. When plasma samples were deproteinated by adding methanol, the analytes in the extract were detected in the positive ionization mode with the tracer ion mass of 346.1 → 145.1 for volitinib and 446.8 → 128.1 for gefitinib. The assay was determined to be valid in the concentration ranges of 2 to 1000 ng/mL for volitinib, and of 1 to 500 ng/mL for gefitinib. Intra‐ and interday accuracies ranged from 88.0 to 104.7% for volitinib and from 90.3 to 101%, for gefitinib. The precision of the assay ranged from 2.1 to 9.71% for volitinib and 2.31 to 12.1% for gefitinib. This method was successfully applied to a pharmacokinetic study of volitinib and gefitinib after the administration of an intravenous or oral dose, indicating that the developed assay can be used to simultaneously determine the concentrations of volitinib and gefitinib in rat plasma.     

Separation of Imazalil and T824 in Cucurbits—Part one: Comparison of HPLC Reversed-Phase Columns

Abstract

Seven reversed-phase columns, HRPB, Kromasil 100-5-C18, S5ODS2B, Vydac 218TP, YMC Polymer C18, Zorbax SBPhenyl and Zorbax SBCN, were compared with the polymeric Hamilton PRP-1 used so far, for ability to separate and determine imazalil and its degradation product, T824. Zorbax SBCN presented the best performance with sharp peak shape for both compounds, the height for imazalil being much superior to that from the PRP-1 column. It presented the best N and a under the conditions selected and gave a k' of 4.39 and 3.00 for imazalil and T824, respectively. The retention time for T824 was the second greatest of the columns, which is likely to be advantageous for the extracts of interest. As far as time of analysis is concerned, it presented a shorter total time of ca 8 minutes using a ratio of 6:4 for the mobile phase of acetonitrile:water. That ratio was confirmed to give higher and sharper peaks for both compounds and to lead to a lower limit of detection for imazalil and for T824. The better separation obtained for imazalil and T824 with this column is attributed to the reduction of the strong adsorption of basic compounds due to the steric protection of silanol groups.     

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.     

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.     

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.     

Feasibility of using solid sampling graphite furnace atomic absorption spectrometry for preparation of spiked filter papers with Cu and Zn as standards for direct solid analysis

An approach was developed for the preparation of cryogenic ground spiked filter papers with Cu and Zn for use as synthetic calibrating standards for direct solid microanalysis. Solid sampling graphite furnace atomic absorption spectrometry was used to evaluate the microhomogeneity and to check the applicability of the synthetic calibrating standards for the direct determination of Cu and Zn in vegetable certified reference materials. The found concentrations presented no statistical differences at the 95% confidence level. The homogeneity factors ranged from 2.7 to 4.2 for Cu and from 6.4 to 11.5 for Zn.     

Disposable Electrochemical Sensor for Food Colorants Detection by Reduced Graphene Oxide and Methionine Film Modified Screen Printed Carbon Electrode

A facile synthesis of reduced graphene oxide (rGO) and methionine film modified screen printed carbon electrode (rGO-methionine/SPCE) was proposed as a disposable sensor for determination of food colorants including amaranth, tartrazine, sunset yellow, and carminic acid. The fabrication process can be achieved in only 2 steps including drop-casting of rGO and electropolymerization of poly(L-methionine) film on SPCE. Surface morphology of modified electrode was studied by scanning electron microscopy (SEM). This work showed a successfully developed novel disposable sensor for detection of all 4 dyes as food colorants. The electrochemical behavior of all 4 food colorants were investigated on modified electrodes. The rGO-methionine/SPCE significantly enhanced catalytic activity of all 4 dyes. The pH value and accumulation time were optimized to obtain optimal condition of each colorant. Differential pulse voltammetry (DPV) was used for determination, and two linear detection ranges were observed for each dye. Linear detection ranges were found from 1 to 10 and 10 to 100 µM for amaranth, 1 to 10 and 10 to 85 µM for tartrazine, 1 to 10 and 10 to 50 µM for sunset yellow, and 1 to 20 and 20 to 60 µM for carminic acid. The limit of detection (LOD) was calculated at 57, 41, 48, and 36 nM for amaranth, tartrazine, sunset yellow, and carminic acid, respectively. In addition, the modified sensor also demonstrated high tolerance to interference substances, good repeatability, and high performance for real sample analysis.     

有机脱模剂中多环芳烃的高效液相色谱测定

建立了有机硅类和金属皂类脱模剂中多环芳烃的高效液相色谱测定方法。方法所用色谱柱为多聚C18(LC-PAH)柱,流动相为乙腈/水,采用梯度淋洗方式,开始时为体积分数40%乙腈,28min后变为82%乙腈,48min后变成100%乙腈,保持8min。方法的线性范围为0.10~200mg/L,线性相关系数为0.9993~1.0000,平均回收率分别为68.55%~101.2%(有机硅类)和75.29%~99.89%(金属皂类),精密度RSD分别为1.6%~8.1%(有机硅类)和1.8%~6.8%(金属皂类),检出限(S/N=3)分别为0.05~0.10mg/L(有机硅类)和0.05~0.20mg/L(金属皂类)。该方法可以满足有机硅类和金属皂类脱模剂中多环芳烃的检测要求。     

LC-ESI-MS/MS analysis for the quantification of morphine, codeine, morphine-3-beta-D-glucuronide, morphine-6-beta-D-glucuronide, and codeine-6-beta-D-glucuronide in human urine

A liquid chromatographic-electrospray ionization-tandem mass spectrometric method for the quantification of the opiates morphine, codeine, and their metabolites morphine-3-beta-D-glucuronide (M-3-G), morphine-6-beta-D-glucuronide (M-6-G) and codeine-6-beta-D-glucuronide (C-6-G) in human urine has been developed and validated. Identification and quantification were based on the following transitions: 286 to 201 and 229 for morphine, 300 to 215 and 243 for codeine, 462 to 286 [corrected] for M-3-G, 462 to 286 for M-6-G, and 476 to 300 for C-6-G. Calibration by linear regression analysis utilized deuterated internal standards and a weighting factor of 1/X. The method was accurate and precise across a linear dynamic range of 25.0 to 4000.0 ng/ml. Pretreatment of urine specimens using solid phase extraction was sufficient to limit matrix suppression to less than 40% for all five analytes. The method proved to be suitable for the quantification of morphine, codeine, and their metabolites in urine specimens collected from opioid-dependent participants enrolled in a methadone maintenance program.     

Exploring the applicability of density functional tight binding to transition metal ions. Parameterization for nickel with the spin-polarized DFTB3 model

In this work, we explore the applicability and limitations of the current third order density functional tight binding (DFTB3) formalism for treating transition metal ions using nickel as an example. To be consistent with recent parameterization of DFTB3 for copper, the parametrization for nickel is conducted in a spin-polarized formulation and with orbital-resolved Hubbard parameters and their charge derivatives. The performance of the current parameter set is evaluated based on structural and energetic properties of a set of nickel-containing compounds that involve biologically relevant ligands. Qualitatively similar to findings in previous studies of copper complexes, the DFTB3 results are more reliable for nickel complexes with neutral ligands than for charged ligands; nevertheless, encouraging agreement is noted in comparison to the reference method, B3LYP/aug-cc-pVTZ, especially for structural properties, including cases that exhibit Jahn–Teller distortions; the structures also compare favorably to available X-ray data in the Cambridge Crystallographic Database for a number of nickel-containing compounds. As to limitations, we find it is necessary to use different d shell Hubbard charge derivatives for Ni(I) and Ni(II), due to the distinct electronic configurations for the nickel ion in the respective complexes, and substantial errors are observed for ligand binding energies, especially for charged ligands, d orbital splitting energies and splitting between singlet and triplet spin states for Ni(II) compounds. These observations highlight that future improvement in intra-d correlation and ligand polarization is required to enable the application of the DFTB3 model to complex transition metal ions. © 2018 Wiley Periodicals, Inc.     

基于纳米材料的电化学免疫传感器在传染性病原体POCT中的应用

传染性病原体POCT对于及时有效控制传染病尤为关键。相比于传统检测方法,基于电化学免疫传感器的传染性病原体检测具有快速、灵敏、准确、易于小型化和集成化等优势,尤其适用于传染病POCT。新兴的纳米材料因其独特的理化性质可用于修饰传感器界面或作为生物分子的固载基质以及信号标记物等,有助于构建出高选择性和高灵敏度的电化学免疫传感器。在本文中,我们着重阐述了不同结构的纳米材料修饰的电化学免疫传感器在传染性病原体POCT检测中的应用,进一步介绍了基于纳米材料的电化学免疫传感器与不同检测技术联用在传染性病原体POCT中的应用,并对其发展前景做出了展望。     

Aggregation kinetics of latex microspheres in alcohol-water media

We report zeta potential and aggregation kinetics data on colloidal latex particles immersed in water-alcohol media. Zeta potential values show absolute maxima for volume fractions of alcohol of 0.10 and 0.05 for ethanol and 1-propanol, respectively. For methanol, no maximum of the absolute value of the zeta potential was found. Aggregation kinetics was studied by means of a single-cluster optical sizing equipment and for alcohol volume fractions ranging from 0 to 0.1. The aggregation processes are induced by adding different potassium bromide concentrations to the samples. We expected to find a slowdown of the overall aggregation kinetics for ethanol and 1-propanol, and no significant effect for methanol, as compared with pure water data. That is, we expected the zeta potential to govern the overall aggregation rate. However, we obtained a general enhancement of the aggregation kinetics for methanol and 1-propanol and a general slowdown of the aggregation rate for ethanol. In addition, aggregation data under ethanol show a slower kinetics for large electrolyte concentration than that obtained for intermediate electrolyte concentration. We think that these anomalous behaviors are linked to layering, changes in hydrophobicity of particle surfaces due to alcohol adsorption, complex ion-water-alcohol-surface structuring, and competition between alcohol-surface adsorption and alcohol-alcohol clustering.     

Recommendations for evaluation of computational methods

The field of computational chemistry, particularly as applied to drug design, has become increasingly important in terms of the practical application of predictive modeling to pharmaceutical research and development. Tools for exploiting protein structures or sets of ligands known to bind particular targets can be used for binding-mode prediction, virtual screening, and prediction of activity. A serious weakness within the field is a lack of standards with respect to quantitative evaluation of methods, data set preparation, and data set sharing. Our goal should be to report new methods or comparative evaluations of methods in a manner that supports decision making for practical applications. Here we propose a modest beginning, with recommendations for requirements on statistical reporting, requirements for data sharing, and best practices for benchmark preparation and usage.     

The Micellar Dissociation Concentration of Polyoxyethylene Mono N-Decylether Nonionic Surfactants in Water

This paper will demonstrate a method for determining the micellar dissociation concentration (MDC) of polyoxyethylene mono n-decylether nonionic surfactants in water. Turbidity and surface tension measurements were applied to commercial samples without further purification. Complicated curves containing turbidity maxima and surface tension minima were obtained for some impure samples. It is difficult to determine the critical micellar concentration (CMC) for impure surfactants. Explanations are given for all curves obtained for pure and impure samples and the method of identifying the MDC values is illustrated. It is more practical for surfactant users to determine the MDC values in their own laboratory than to search for the CMC values in the literature when the surfactants arc impure.