Needle‐trap device for the sampling and determination of chlorinated volatile compounds

A needle‐trap device, with immobilized sorbent inside the syringe, coupled with GC–MS was applied for air sampling and determination of chlorinated volatile organic compounds such as dichloromethane, trichloromethane, and tetrachloromethane. The application of a needle trap packed with combination of three sorbents including Tenax TA, Carbopack X, and Carboxen 1000 resulted in detection limits of few pg for chlorinated volatile compounds and recoveries of 99.2–102.8%. The extraction and desorption parameters were optimized within the study. As a result, the precision determined as RSD was equal to 5.05 and 3.03 and 6.52% for dichloromethane, trichloromethane, and tetrachloromethane, respectively. The storage time for chlorinated compounds up to 48 h and reusability of the needle‐trap device were verified. The obtained results have proved the ability of needle traps to compete with other solventless sampling and sample preparation extraction techniques.     

室温离子液体作溶剂顶空气-质联用测定药物中溶剂残留

基于室温离子液体无蒸汽压、良好溶解性和分散性的特点,用室温离子液体[bm im][PF6]作溶剂顶空气-质联用测定非那雄胺中二氯甲烷、三氯甲烷及二氧六环的残留量,优化了顶空气-质联用分析条件。二氯甲烷、三氯甲烷及二氧六环的检出限分别为0.2、0.02和0.50 ng,线性相关系数大于0.99;相对标准偏差(RSD)0.39%~4.60%;回收率为90.5%~111.9%。室温离子液体作为顶空溶剂的灵敏度有所提高。     

Single molecule studies of quantum dot conjugates in a submicrometer fluidic channel

A microfluidic and optical system was created for the detection and analysis of single molecules in solution. Fluidic channels with submicrometer dimensions were used to isolate, detect and identify individual quantum dots conjugated with organic fluorophores. The channels were fabricated in fused silica with a 500 nm square cross section. The resulting focal volume of approximately 500 aL reduced fluorescent background and increased the signal to noise ratio of single molecule detection. The channels also enabled the rapid detection of 99% of quantum dots and organic fluorophores traversing the focal volume. Conjugates were driven through the channels electrokinetically at 2.3 kV cm(-1), excited with a single 476 nm wavelength laser and detected with a confocal microscope. Fluorescence emission was collected simultaneously from green (500-590 nm) and red (610-680 nm) regions of the spectrum. Signal rejection was minimized by the narrow and symmetric emission spectra of the quantum dots. To demonstrate efficient multicolor detection and characterization of single molecule binding, Qdot 655 Streptavidin Conjugates were bound to Alexa Fluor 488 molecules and individually detected. Photon counting histogram analysis was used to quantify coincident detection and degree of binding. Fluorescence correlation spectroscopy was used to measure the mobility of bound and unbound species. The union of fluidic channels with submicrometer dimensions and quantum dots as fluorescent labels resulted in efficient and rapid multiplexed single molecule detection and analysis.     

顶空液相微萃取-气相色谱法测定盐酸雷尼替丁中二氯甲烷和三氯甲烷的残留量

采用顶空液相微萃取与气相色谱联用技术测定雷尼替丁中二氯甲烷和三氯甲烷的残留量。自制了萃取液保护装置。考察了萃取溶剂的种类、萃取时间、萃取温度、萃取液的体积对二氯甲烷和三氯甲烷萃取效果的影响。以正十三烷为萃取剂,在60 ℃下萃取30 min,萃取液滴体积2 μL。二氯甲烷含量在1～10 μg/g范围内与色谱峰高呈线性关系,相关系数(r2)为0.9733;三氯甲烷含量在1～10 μg/g范围内与色谱峰高呈线性关系,r2为0.9724。二氯甲烷和三氯甲烷的最低检出限分别为0.0273 μg/g和0.0410 μg/g,加标回收率分别为93.6%～102%和98.1%～103%。方法简便易行,测定结果准确。     

Determination of non-metallic elements by capacitively coupled helium microwave plasma atomic emission spectrometry with capillary gas chromatography

A capacitively coupled microwave helium plasma with a tubular tantalum electrode was evaluated as an element selective detector for gas chromatography (GC). The end of a 10-m bonded fused capillary column was directly inserted into the tubular electrode without any switching system. A heated copper tube was used to house the part of the GC column that protruded from the oven. The optimisation of operating parameters, line selection, background emission and horizontal and vertical observation position is described. Analytical figures of merit including sensitivity, reproducibility, signal to background ratio, selectivity, dynamic range and limit of detection (LOD), were evaluated for carbon, hydrogen, chlorine and bromine emission. Limits of detection in the low ng range (20 pmol) were obtained for halogenated compounds using carbon emission, whereas LODs in the 0.1 micrograms range (2 nmol) were obtained using chlorine or bromine emission lines.     

Enthalpies of sorption of linear hydrocarbons (C2–C8) and chloroderivatives of methane and ethylene on the surface of hydrotalcite

Differential molar adsorption enthalpies (DMAE) were determined by gas chromatographic measurements of specific retention volume of vapors on the surface of two forms of Mg–Al hydrotalcite. A linear dependence of the DMAE on the number of the carbon atoms in hydrocarbons was observed for both form of hydrotalcite. The dependence of the differential molar adsorption enthalpies on the number of chlorine atoms in organic molecules is discussed. A linear dependence of DMAE on the molecular weight of chloroderivatives of methane and ethylene on the basic form in an order monochloromethane < dichloromethane < trichloromethane or vinylidene chloride < 1,1-dichloroethylene < trichloroethylene was found.     

Synthesis and Spectroscopic Properties of Cyclotriphosphazenes Containing 6-（4-Hydroxyphenyl）-2,2′-bipyridine Side Groups

Two novel cyclotriphosphazene derivatives containing 6- （4-hydroxyphenyl）-2,2′-bipyridine （hopbp） side groups, N3 P3 （dobp） 2 （hopbp） 2 （ 1 ） and N3 P3 （dobp） （hopbp） 4 （2） （ dobp = 2,2′-dioxybiphenyl）, were synthesized and characterized. These compounds display strong fluorescent emission both in solution and in solid state. Their absorption and emission spectra are sensitive to proton： the addition of HBF4 to the methanol and dichloromethane solution（9： 1, volume ratio） of compound 1 led to a red-shift from 350 to 460 nm for the emission spectrum, and the process was also characterized by isosbestic points of absorption spectra at 267, 287 and 313 nm.     

多孔有机笼毛细管电色谱手性柱的制备及应用

多孔有机笼(POCs)是一种新型的具有稳定有序三维空腔结构的多孔材料。通过2-羟基-1,3,5-均苯三甲醛与1R,2R-1,2-二苯基乙二胺发生席夫碱的缩合反应,合成了一种具有羟基功能基团的单一手性POCs材料;将其均匀涂敷在毛细管壁上制成色谱柱,利用电色谱柱成功拆分了二氢黄酮、吡喹酮、萘普生和3,5-二硝基-N-(1-苯乙基)苯甲酰胺4种手性化合物。探究了分离电压、缓冲溶液浓度及其pH值等因素对手性拆分的影响,获得了4种手性物质在POCs色谱柱上的最佳拆分条件。实验研究表明,二氢黄酮、吡喹酮、萘普生和3,5-二硝基-N-(1-苯乙基)苯甲酰胺获得优化分离效果所需的工作电压分别为13、14、14和12 kV;二氢黄酮适宜Tris-H₃PO₄缓冲溶液浓度为0.075 mol/L,吡喹酮、萘普生和3,5-二硝基-N-(1-苯乙基)苯甲酰胺适宜Tris-H₃PO₄缓冲溶液浓度为0.100 mol/L; 4种手性物质得到最佳分离效果时的pH值均为3.51。二氢黄酮、吡喹酮、萘普生和3,5-二硝基-N-(1-苯乙基)苯甲酰胺均达到基线分离,分离度分别为2.99、2.10、2.58和3.59。该POCs色谱柱还成功拆分了o,m,p-碘苯胺、o,m,p-硝基苯胺两种位置异构体。该研究表明POCs手性电色谱柱具有良好的手性识别能力,是一种优秀的手性分离材料,具有很大的电色谱手性分离应用前景。     

Synthesis and Spectroscopic Properties of Cyclotriphosphazenes Containing 6-(4-Hydroxyphenyl)-2,2''-bipyridine Side Groups

Two novel cyclotriphosphazene derivatives containing 6-(4-hydroxyphenyl)-2,2'-bipyridine(hopbp)side groups,N_3P_3(dobp)_2(hopbp)_2(1)and N_3P_3(dobp)(hopbp)_4(2)(dobp=2,2'-dioxybiphenyl),were synthesized and characterized.These compounds display strong fluorescent emission both in solution and in solid state.Their absorption and emission spectra are sensitive to proton:the addition of HBF4 to the methanol and dichloromethane solution(9∶1,volume ratio)of compound 1 led to a red-shift from 350 to 460 nm for the emission spectrum,and the process was also characterized by isosbestic points of absorption spectra at 267,287 and 313 nm.     

Liquid crystalline nanosheet colloids with controlled particle size obtained by exfoliating single crystal of layered niobate k(4)nb(6)o(17)

Colloidally dispersed niobate nanosheets with the thickness of 1.8 nm and controlled mean lateral sizes of 0.15-7.8 mum were prepared and their liquid crystallinity was examined. The nanosheet colloids with different lateral sizes were obtained by exfoliation of single crystals of layered niobate K4Nb6O17 and subsequent ultrasonication. Naked-eye and microscope observations of the nanosheet colloids between crossed polarizers revealed liquid crystallinity of the sols characterized by birefringence as functions of the lateral sizes and concentration of the nanosheets. The nanosheet colloids with smaller lateral sizes (0.15-1.9 mum) varied from isotropic to biphasic (isotropic + liquid crystalline), and finally to fully liquid crystalline states as the colloid concentration increased. The phase transition concentrations (from isotropic to biphasic and biphasic to liquid crystalline) decreased with increasing aspect ratio (lateral-to-thickness ratio) of the nanosheets, almost in accordance with the prediction by Onsager theory, indicating that the liquid crystallinity is explained basically by excluded-volume effect between the nanosheets. On the other hand, the colloids with larger lateral sizes (6.2 and 7.8 mum) stably kept liquid crystalline state even at very low concentration (5.1 x 10-6 in volume fraction), which was much lower than that expected from the theory.     

静态顶空/气相色谱-质谱法同时测定化妆品中22种有毒挥发性有机溶剂残留

以2015版《化妆品安全技术规范》中规定的常见禁用及限用有毒挥发性有机溶剂为研究对象,建立了静态顶空/气相色谱-质谱法(SHS/GC-MS)同时测定化妆品中22种有毒挥发性有机溶剂(VOC)(二氯甲烷、顺式-1,2-二氯乙烯、反式-1,2-二氯乙烯、2-氯-1,3-丁二烯、三氯甲烷、1,2-二氯乙烷、苯、四氯化碳、三氯乙烯、甲苯、四氯乙烯、氯苯、乙苯、三溴甲烷、间二甲苯、对二甲苯、苯乙烯、邻二甲苯、异丙苯、1,4-二氯苯、1,2-二氯苯、六氯丁二烯)残留的检测方法。试样在80℃下30 min静态顶空,经DB-1柱分离后,采用选择离子监测模式(SIM)进行定性定量分析。优化了顶空、色谱和质谱参数,结果表明:22种VOC在0.5~50 ng/m L浓度范围内均呈良好的线性关系,相关系数均大于0.99,在1.0,2.0,5.0 ng/m L 3个浓度加标水平下的平均回收率为80.3%~102.7%,相对标准偏差(RSD,n=6)为6.4%~9.9%,检出限为0.2~5.0 ng/g。结果表明,该方法简便、灵敏、准确,具有良好的重现性和稳定性,适合于化妆品中22种VOC残留的筛查和确证检测。     

Determination of orbifloxacin in rabbit plasma by high-performance liquid chromatography with fluorescence detection.

A simple and sensitive high-performance liquid chromatography method is developed for the determination of orbifloxacin (ORB) in rabbit plasma. Sample preparations are carried out by adding phosphate buffer (pH 7.4, 0.1 M) and extracting with trichloromethane. ORB and the internal standard, norfloxacin (NOR), are separated on a reversed-phase column using an aqueous phosphate buffer-acetonitrile (80:20, v/v) mobile phase. The concentrations of ORB and NOR eluting from the column with retention times of 2.16 and 3.09 min, respectively, are monitored by fluorescence detection at 338 (excitation) and 425 nm (emission). The method is shown to be linear from 4 to 1500 ng/mL (regression coefficient r2 = 0.999). The quantitation and detection limits are 4 and 9 ng/mL, respectively. Mean recovery is determined as 92% by the analysis of plasma standards containing 150, 750, and 1500 ng/mL. Inter- and intra-assay precisions were 4 and 3%, respectively.     

Reaction of porous silicon with both end-functionalized organic compounds bearing alpha-bromo and omega-carboxy groups for immobilization of biomolecules

Both end-functionalized (alpha-bromo and omega-carboxy) compounds were first tested for the radical reaction on the silicon-hydride (Si-H) terminated porous silicon (PSi) with/without the presence of diacyl peroxide initiator under microwave irradiation. Then the carboxylic acid monolayers (CAMs) assembled on PSi through the robust Si-C bonds were converted to amino-reactive linker, N-hydroxysuccinimide (NHS)-ester, terminated monolayers. And finally two proteins of bovine serum albumin (BSA) and lysozyme (Lys) were immobilized through amide bonds. The optimum PSi membrane for protein immobilization without collapse, with parameters of porous radii 4-10 nm and depth 0.2-4.6 mum, was prepared from the (100)-oriented p-type silicon wafer. The chemically converted surface products were monitored with Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and field emission scanning electron microscopy (FESEM).     

Influence of Water Vapor on CCl4 and CHCl3 Conversion in Gliding Discharge

The effect of initial concentration of tetrachloromethane and trichloromethane on their conversion in gliding discharge was determined. The conversion of CCl₄ and CHCl₃ was carried out in air containing 20 or 8000 ppm of water vapor. The flow rate of the air containing 1.2, 2.5, or 6.0 vol% of CCl₄ or CHCl₃ was 200 Nl/h. The amount of tetrachloromethane and trichloromethane reacted was determined for a constant value of specific energy which was varied with 2.0 and 4.0 VAh/Nl. The amounts of CCl₄ and CHCl₃ reacted were a linear function of the initial concentration of these compounds in the inlet gas. The results obtained have shown that water vapor present in the air has a favorable effect on the conversion of tetrachloromethane and trichloromethane in gliding discharge.     

The ability of a novel sorptive polymer to determine the freely dissolved fraction of polar organic compounds in the presence of fulvic acid or sediment

A novel plastic material, poly(ethylene-co-vinyl acetate-co-carbon monoxide) (PEVAC), was evaluated as an absorptive passive equilibrium sampler for determination of the freely dissolved fraction of seven polar organic contaminants (POCs) in the presence of fulvic acid and sediment. The seven compounds selected were imidacloprid, carbendazim, metoprolol, atrazin, carbamazepine, diazinon and chlorpyrifos, i.e. a mixture of pharmaceuticals and pesticides having logarithmic octanol/water partition coefficients (log K _OW) ranging from 0.2 to 4.77. The experiments demonstrated that the PEVAC sampler is well suited for determination of the freely dissolved fraction of chemicals in aquatic environments. Generally, the freely dissolved fraction of the POCs decreased with increasing hydrophobicity. However, strong interactions with functional groups of the organic matter seemed to dominate the partitioning for imidacloprid and carbendazim, having logarithmic dissociation partition coefficient log D < 1.47, and for metoprolol, which is positively charged at neutral pH.     

Decomposition of Chloromethanes in Gliding Discharges

Gliding discharge plasma was used for decomposition of tetrachloromethane and trichloromethane. Air containing 8000 ppm or 20 ppm of water vapor was the carrier gas. The course and yield of the process were studied as a function of initial concentration of tetrachloromethane and trichloromethane, gas flow rate, and water vapor content. The conversion was high in all cases—it reached 90% for tetrachloromethane and 100% for trichloromethane. The conversion rate of the chloromethane compounds increased with increasing initial concentration of these compounds in the reaction mixture. Changing the water vapor content in the reaction mixture from 20 ppm to 8000 ppm increased the conversion rate of chloromethanes.     

Molecular complexes of dimethyl sulfoxide with tri‐ and dichloromethane

Crystals of molecular complexes of dimethyl sulfoxide with trichloromethane (chloroform), (CH₃)₂SO·2CHCl₃, (I), and dichloromethane, (CH₃)₂SO·CH₂Cl₂, (II), have been grown in situ. In both compounds, the components are linked together by (Cl)C—H...O interactions. The dimethyl sulfoxide molecules in (I) are bound into chains by C—H...O interactions. In (II), pairs of the components form centrosymmetric rings, linked into a three‐dimensional network by C—H...O contacts and dipole–dipole interactions between dimethyl sulfoxide molecules.     

Strategies for monitoring the emerging polar organic contaminants in water with emphasis on integrative passive sampling

Although polar organic contaminants (POCs) such as pharmaceuticals are considered as some of today's most emerging contaminants few of them are regulated or included in on-going monitoring programs. However, the growing concern among the public and researchers together with the new legislature within the European Union, the registration, evaluation and authorisation of chemicals (REACH) system will increase the future need of simple, low cost strategies for monitoring and risk assessment of POCs in aquatic environments. In this article, we overview the advantages and shortcomings of traditional and novel sampling techniques available for monitoring the emerging POCs in water. The benefits and drawbacks of using active and biological sampling were discussed and the principles of organic passive samplers (PS) presented. A detailed overview of type of polar organic PS available, and their classes of target compounds and field of applications were given, and the considerations involved in using them such as environmental effects and quality control were discussed. The usefulness of biological sampling of POCs in water was found to be limited. Polar organic PS was considered to be the only available, but nevertheless, an efficient alternative to active water sampling due to its simplicity, low cost, no need of power supply or maintenance, and the ability of collecting time-integrative samples with one sample collection. However, the polar organic PS need to be further developed before they can be used as standard in water quality monitoring programs.     

Improved method for extraction of aroma compounds in aged brandies and aqueous alcoholic wood extracts using ultrasound

This work presents a rapid method for dichloromethane extraction of aroma compounds from brandies and aqueous-alcoholic wood extracts, in brandy-like ageing conditions, using ultrasound. The dichloromethane extracts were injected in split mode on a gas chromatographic (GC) system, separated on a DB-WAX capillary column and detected by flame ionisation. The method allowed satisfactory quantification of 37 volatile compounds in brandies (alcohols, esters, acids, furanics, aldehydes and phenols) and 16 volatile compounds in aqueous-alcoholic oak extracts. Linear responses were obtained (0.99-1.00). The repeatability and the detection and quantification limits were also evaluated. The analysis of spiked samples showed that matrix effects do not affect the method performance for the majority of the volatile compounds analysed.     

Theoretical limiting concentration for mineralization of trichloromethane and dichloromethane in aqueous solutions by AOPs

It is widely stated that most organic contaminants could be completely mineralized by Advanced Oxidation Processes(AOPs). This statement means that the concentration of the organic contaminant at equilibrium(limiting concentration,LC)is low enough to be neglected.However,for environmental safety,especially drinking water safety,this statement needs to be verified from chemical engineering thermodynamic analysis.In this paper,trichloromethane(CHCl3)and dichloromethane(CH2Cl2) are selected as the model system...