Direct Fluorometric Analysis of PAHs in Water and in Urine Following Liquid Solid Extraction

A method for the determination of PAHs in aqueous media based on synchronous fluorescence analysis directly on a solid phase after extraction was evaluated. Tests were conducted for (i) the simultaneous analysis of naphthalene, phenanthrene, anthracene, and pyrene in water at a parts per billion concentration level using a 0V1 sorbing phase block and (ii) the analysis of 1-hydroxyphenanthrene (1-OHPh) and 1-hydroxypyrene (1-OHPy) in human urine using a small sheet cut from a C18 silica fiberglass extraction disk (ENVI-Disk). Because the linear dynamic concentration range is dependent on both the immersion time and the concentration range, in all cases, an optimum immersion time must be determined to preserve linearity of intensity versus concentration. Calibration curves were determined for a concentration lower than 15 ppb in the case of 1-OHPh and at a concentration lower than 1.5 ppb in the case of 1-OHPy. In all cases the limits of detection were estimated to be lower than 0.2 ppb, i.e., for 1-OHPh and 1-OHPy, in the lowest concentration limit these metabolites were found in the urine of persons unexposed or weakly exposed to PAHs.     

Extraction of Uranium(VI) by Triphenylarsine and Triphenylphosphine Oxides from Nitric Acid Medium

The extraction of UO²⁺ ₂ from nitric acid solutions by two neutral donors ligands (L), triphenylarsine oxide (Ph₃AsO) and triphenylphosphine oxide (Ph₃PO), in chloroform is investigated. At low HNO₃ acid concentrations (<2 M), UO₂ ²⁺ is highly extracted as simple cation by Ph₃AsO and slightly extracted by Ph₃PO. The extraction constant of UO₂ ²⁺ from low nitric acid medium is found to equal 1212 ± 120. At higher HNO₃ concentration (>2 M), UO₂ ²⁺ is extracted by ion association mechanism as UO₂ (NO₃)₂- 2L, and the distribution ratio of UO₂ ²⁺ using Ph₃PO is found to be higher than that of Ph₃AsO. This is interpreted by the extraction competition of HNO₃ for Ph₃AsO. Spectroscopic investigations in the visible and IR regions supported the results obtained.     

2-(2-喹啉偶氮)-5-二甲氨基苯酚固相萃取光度法测定铀的研究

合成了新试剂2-(2-喹啉偶氮)-5-二甲氨基苯酚(QADMAP),用红外光谱、核磁共振氢谱、质谱、可见吸收光谱和元素分析鉴定了其结构。研究了QADMAP与铀的显色反应,在pH 7.8的三乙醇胺-盐酸缓冲介质中,Triton X-100和氟离子存在下,QADMAP与铀(Ⅵ)和氟离子反应生成1∶1∶1紫色三元稳定络合物,络合物的λ_max＝590 nm,ε＝1.05×105 L·mol-1·cm-1,铀含量在0～20 μg·10 mL-1内符合比尔定律。环境水样中的铀用TBP萃淋树脂固相萃取柱分离和富集后用该方法测定,方法相对标准偏差在2.2%～3.6%之间,标准回收率在94%～105%。     

Tb1-xGdxA3(A=邻氨基苯甲酸,x=0-1)固体配合物的光谱分析和荧光增强

合成了一系列组成为Tb1-xGdxA3(A=邻氨基苯甲酸，x=0-1.0)的固体配合物。利用红外光谱和荧光光谱研究了配合物的结构和荧光性质。红外光谱的结果表明，掺表配合物的结构与未掺杂的邻氨基苯甲酸铽相似。荧光光谱的结果显示，Gd^3 对Tb^3 的发光有明显的增敏作用，并对荧光增敏的机理进行了探讨。     

2-[2-(5-溴喹啉)-偶氮]-5-二乙氨基苯酚固相萃取光度法测定环境样品中镉的研究

合成了新试剂2-[2-(5-溴喹啉)-偶氮]-5-二乙氨基苯酚(5-Br-QADEAP),试剂结构通过元素分析,红外光谱和核磁共振氢谱鉴定。研究了5-Br-QADEAP与镉的显色反应,在pH 8.0的硼酸-氢氧化钠缓冲介质中,Triton X-100存在下,5-Br-QADEAP与镉反应生成2∶1稳定络合物,体系最大吸收波长λ_max=595 nm,摩尔吸光系数ε=1.60×105 L·mol-1·cm-1,样品中的镉用强阴离子交换固相萃取柱固相萃取预分离和富集后用该方法测定,方法相对标准偏差在2.5%～3.2%之间,标准回收率在96%～105%,结果令人满意。     

Fluorescence enhancement of lanthanide(III) perchlorate by 1,10-phenanthroline in bis(benzoylmethyl) sulfoxide complexes and luminescence mechanism

Two novel ternary rare earth complexes LnL₅L′(ClO₄)₃2H₂O (Ln=Eu(III), Tb(III); L=bis(benzoylmethyl) sulfoxide, L′=phen) were synthesized and characterized by elemental analysis, coordination titration analysis, molar conductivity, IR, TG-DSC,¹H NMR and UV spectra. The fluorescence spectra illustrated that both the Eu(III) and Tb(III) ternary complexes displayed strong characteristic metal-centered fluorescence in solid state. After the introduction of the second ligand phen group, the relative emission intensities and fluorescence lifetimes of the ternary complex EuL₅L′(ClO₄)₃2H₂O (L=C₆H₅COCH₂SOCH₂COC₆H₅, L′=phen) enhanced more obviously than that of the binary complex EuL₅(ClO₄)₃3H₂O. This indicated that the presence of both organic ligands bis(benzoylmethyl) sulfoxide and the second ligand phen could sensitize fluorescence intensities of Eu(III) ions, and the introduction of phen group was resulted in the enhancement of the fluorescence properties of the Eu(III) ternary rare earth complexes. The phosphorescence spectra are also discussed.     

离子交换树脂-固相萃取富集-电感耦合等离子体光谱法测定水中重金属元素

建立了离子交换树脂-固相萃取富集-电感耦合等离子体光谱(ICP-AES)联用测定水中的重金属元素Zn,Mn,Cu,Co,Ni,Cd,Pb的方法。实验采用Dowex50WX8强酸型阳离子交换树脂,通过优化富集分离条件和排除共存离子的干扰,最终确定最佳的样品pH,样品流速,洗脱液种类和浓度,样品体积分别为3.0~4.0,3.0 mL·min-1,3.0 mol·L-1 HNO₃,200 mL。方法中各元素的检出限和定量限范围分别为0.09~0.45和0.31~1.50 μg·L-1,加标回收率和相对标准偏差RSD(n=6)分别为95.3%～104.2%和1.25%～4.12%。采用该方法测定不同地区的样品,并与直接采用ICP-MS法进行对比,其测定结果基本吻合。实验表明该方法的检出限,定量限可以满足水中重金属元素Zn,Mn,Cu,Co,Ni,Cd,Pb的检测要求,准确性和精密度好,结果可靠,适用于测定水中Zn,Mn,Cu,Co,Ni,Cd,Pb。     

氯磺酚偶氮硫代若丹宁固相萃取光度法测定水中的汞

研究了氯磺酚偶氮硫代若丹宁(HSCT)与汞的显色反应,在pH 3.6的HAc-NaAc缓冲介质中,HSCT与汞反应生成2∶1稳定络合物,该络合物可被C₁₈ 固相萃取小柱定量萃取富集,富集倍数达80倍,小柱上保留的络合物用DMF洗脱后用分光光度法测定,在洗脱液中络合物λ_max＝545 nm,ε＝6.24×104L·mol-1·cm-1。汞含量在0～1.5 μg·mL-1内符合比尔定律,方法用于水样中μg·L-1级汞含量的测定,相对标准偏差在1.8%～2.2%之间,标准回收率在93％～106％之间,结果令人满意。     

Direct Analysis of Thallium in Solid Samples of Bovine Liver and Tomato Leaves by Laser Excited Atomic Fluorescence Spectrometry Using a Graphite Furnace

Laser excited atomic fluorescence spectrometry (LEAFS) with a N₂-laser pumped dye laser with a Shimadzu GFA-4A graphite furnace is used to determine thallium in solid samples of bovine liver and tomato leaves. The linear range for thallium under the studied conditions is 0–50 pg. The instrumental LEAFS detection limit for thallium was 100 fg. Solid samples from National Institute of Standards and Technology were analyzed by this method. The content of thallium in bovine liver and tomato leaves was 0.059 and 0.055 μg/g with relative standard deviation of 12.5% and 15.8% respectively; the results obtained are within the reported limit.     

Statistical Physics on the Space (x, v) for Dissipative Systems and Study of an Ensemble of Harmonic Oscillators in a Weak Linear Dissipative Medium

We use the phase space position-velocity (x, v) to deal with the statistical properties of velocity dependent dynamical systems, like dissipative ones. Within this approach, we study the statistical properties of an ensemble of harmonic oscillators in a linear weak dissipative media. Using the Debye model of a crystal, we calculate at first order in the dissipative parameter the entropy, free energy, internal energy, equation of state and specific heat using the classical and quantum approaches. For the classical approach we found that the entropy, the equation of state, and the free energy depend on the dissipative parameter, but the internal energy and specific heat do not depend of it. For the quantum case, we found that all the thermodynamical quantities depend on this parameter. PACS: 05.20.Gg, 05.30.Ch, 05.20.-y, 05.30.-d     

盐水溶液中单硼酸盐物种(B(OH)3和B(OH)-4)的拉曼光谱定量分析

盐湖是天然存在的水和盐类共存的复杂体系,卤水中硼酸盐的赋存形态及分布规律较一般水溶液更为复杂,通常随盐类的浓缩富集而发生复杂的聚合、缔合等作用,存在严重的过饱和性,不利于盐湖硼及其他盐类的分离提取。因此,开展盐湖卤水体系中硼酸盐物种分布规律及离子间相互作用机制研究具有重要的实际意义。激光拉曼光谱因具有原位、无损、且水峰干扰小等特点,被广泛应用于硼酸盐溶液结构光谱学研究中,并表现出较大的优越性。近年来,以化学计量学为核心的现代拉曼光谱定量分析技术已成为快速准确获取复杂体系目标物量关系的有效手段,对光谱解析中面临的光谱重叠、背景干扰、基线漂移等问题具有强大的优势,在分析领域中得到了广泛而深刻的应用。基于化学计量学算法,采用拉曼光谱技术探究了三种回归模型(内标法、多元线性回归和偏最小二乘法)对盐水溶液中单硼物种B(OH)₃和B(OH)^-₄的定量分析,并通过外标样进行方法评估。研究表明,多元线性回归和偏最小二乘法对外标样的预测结果更为准确,相对误差均在1%以内,但前者对低硼含量的预测效果更佳。进一步地,根据建立的多元线性回归模型...     

Phase Space Analysis and Anisotropic Universe Model in f(T) Gravity

In this paper, we study the stability of locally rotationally symmetric(LRS) Bianchi I universe model in f(T) gravity through phase space analysis. We assume that the f(T) gravity can be treated as effective dark energy behaving like perfect fluid, and suggest that there are interactions between pressureless matter as well as dark energy.We construct the corresponding autonomous system of equations to check the stability of the model for non phantom,vacuum and phantom phases. It is concluded that critical points remain more stable in phantom phase as compared to non phantom and vacuum cases. Finally, we discuss the cosmological behavior of the model through some cosmological parameters.     

Analysis of some elements in three Chrysolina (Coleoptera, Chrysomelidae) species by EDXRF spectrometry

In this investigation, the concentration levels of potassium, calcium, iron, nickel and cadmium for three Chrysolina species were measured in the region of Erzurum (Turkey) located at latitude 40°17′ north and longitude 41°17′ east. The concentrations measured by energy dispersive X-ray fluorescence (EDXRF) spectrometry were analysed. Photons of 59.5 keV and 5.9 keV emitted, respectively, by an annular ²⁴¹Am and ⁵⁵Fe radioactive source were used to excite the characteristic X-rays of various elements present in the insect samples. These results are presented and discussed in this paper.     

Multivariate Image Analysis of Magnetic Resonance Images with the Direct Exponential Curve Resolution Algorithm (DECRA): Part 1: Algorithm and Model Study

Antalek and Windig recently presented a fast method to resolve a series of NMR mixture spectra, where the contribution of the components varies with a decaying exponential [B. Antalek and W. Windig,J. Am. Chem. Soc.118, 10,331–10,332 (1996); W. Windig and B. Antalek,Chemom. Intell. Lab. Syst.37, 241–254 (1997)]. The method was called DECRA (direct exponential curve resolution algorithm). In this paper DECRA will be applied to two series of magnetic resonance images. The signal of one series is based uponT₂relaxation, and the other is based uponT₁relaxation. In order to evaluate the technique, the magnetic resonance images of a phantom where used. A transformation is introduced to enable the application of DECRA to aT₁series of magnetic resonance images. A separate paper in this issue will describe the application of the techniques to magnetic resonance images of the human brain.     

基于EEMs及PARAFAC的洪湖、东湖与梁子湖CDOM组成特征分析

国内外关于长江中下游地区如洪湖、东湖及梁子湖等大中型浅水湖泊DOM组成特征的分析较少,本文基于2007年9月—10月洪湖、东湖与梁子湖34个站点野外实地采样数据,运用三维荧光图谱(EEMs)与平行因子分析(PARAFAC)模型,着重分析了三个湖泊CDOM吸收荧光特性及组成特征。结果表明,CDOM在350 nm处吸收系数a(350)在三个湖泊表现为洪湖极显著高于东湖与梁子湖(p<0.001);三个湖泊CDOM光谱斜率S_280～500与a(350)呈极显著负相关(R2=0.781, p<0.001)且洪湖S_280～500值极显著低于东湖与梁子湖(p<0.01);光谱斜率比值S_R值也表现为洪湖显著低于东湖与梁子湖(p<0.05)。PARAFAC模型解析得到两个类腐殖质组分(C1, C2),两个类蛋白质组分(C3,C4),其中组分C1与C2呈极显著正相关(R2=0.884,p<0.001),组分C3与C4亦为极显著正相关(R2=0.677,p<0.001),这表明三个湖泊CDOM组分C1与C2,C3与C4来源相似,然而统计结果并未发现四个荧光组分与DOC及Chl-a浓度之间存在任何显著性相关关系。三个湖泊荧光指数FI₂₅₅(HIX),FI₂₆₅,FI₃₁₀(BIX)与FI₃₇₀值均表现为东湖显著高于梁子湖(p<0.05),极显著高于洪湖(p<0.01),这意味着东湖富营养化程度高于洪湖与梁子湖。     

Magnetic resonance imaging on CO(2) miscible and immiscible displacement in oil-saturated glass beads pack

In this study, the displacement processes were observed as gaseous or supercritical CO₂ was injected into n-decane-saturated glass beads packs using a 400-MHz magnetic resonance imaging (MRI) system. Two-dimensional images of oil distribution in the vertical median section were obtained using a spin-echo pulse sequence. Gas channeling and viscous fingering appeared obviously in immiscible gaseous CO₂ displacement. A piston-like displacement front was detected in miscible supercritical CO₂ displacement that provided high sweep efficiency. MRI images were processed with image intensity analysis methods to obtain the saturation profiles. Final oil residual saturations and displacement coefficients were also estimated using this imaging intensity analysis. It was proved that miscible displacement can enhance the efficiency of CO₂ displacement notably. Finally, a special coreflood analysis method was applied to estimate the effects of capillary, viscosity and buoyancy based on the obtained saturation data.     

Fe3O4@[Cu3(btc)2]磁性分散微固相萃取-液相色谱串联质谱法测定水样中四环素类抗生素残留

本文合成了磁性金属有机骨架材料Fe₃O₄@[Cu₃(btc)₂],并作为分散微固相萃取的吸附剂用于四环素类抗生素的富集. 对萃取的条件,包括萃取时间、溶液pH和洗脱溶剂对四环素类抗生素萃取效率的影响进行了研究. 结果显示Fe₃O₄@[Cu₃(btc)₂]可以有效富集四环素类抗生素,而四环素类抗生素与Fe₃O₄@[Cu₃(btc)₂]之间的静电相互作用主导了这一过程. 利用分散微固相萃取结合液相色谱-串联质谱法对天然水中的四种四环素类抗生素(土霉素,四环素,金霉素和多西环素)残留进行了测定. 四种抗生素的检出限(S/N=3)为0.01∽0.02 μg/L,定量限(S/N=10)为0.04∽0.07 μg/L. 河水和养殖水中四环素三个水平的加标回收率为70.3%∽96.5%,相对标准偏差为3.8%∽12.8%. 结果表明,基于磁性金属有机骨架材料的分散微固相萃取可以从水中简单、快速、高效地富集四环素类抗生素.     

Analysis of 13C-mixed Triacylglycerol in Stool by Bulk (Ea-IRMS) and Compound Specific (GC/MS) Methods

Abstract

This paper was presented in poster form at the 17th International Congress of Nutrition, August 27-31, Vienna. Austria (Annals of Nutrition & Metabolism 2001; 45(Suppl.1):349). Some of the data were also presented in poster form at the British Society of Gastroenterology Meeting, March 18-21, Glasgow, UK (Gut 2001; 48(Suppl.1):A91).

The ¹³C-mixed triacylglycerol (MTG) breath test is used to measure intraluminal fat digestion. In normal digestion. 20–40% of the ingested ¹³C label is recovered in breath CO₂. We aimed to identify the proportions of ingested label excreted in stool, as well as breath following ingestion of ¹³C-MTG by children with impaired exocrine pancreatic function and healthy controls. ¹³C enrichment of breath samples was measured by continuous flow isotope ratio mass spectrometry (IRMS) and cumulative percent dose recovered (cPDR) in 10 h was calculated. Total ¹³C of a faecal fat extract from each stool was measured by elemental analyser-IRMS, and ¹³C enrichment and concentration of the TBDMS derivative of octanoic acid was measured by GC/MS after hydrolysis of the fat extract. Stool 5-day cPDR was calculated. Mean breath cPDR was 35%. Mean cPDR in stool by combustion-IRMS and GC/ MS, respectively, was 0.8% and 1.0%. Therefore, the remaining 64% of the ¹³C label must remain in the body and variability in breath cPDR is due to postabsorptive rather than predigestive factors.     

Investigation of inter-molecular hydrogen bonding in the binary mixture (acetone + water) by concentration dependent Raman study and ab initio calculations

This paper reports that vibrational spectroscopic analysis on hydrogen-bonding between acetone and water comprises both experimental Raman spectra and ab initio calculations on structures of various acetone/water complexes with changing water concentrations. The optimised geometries and wavenumbers of the neat acetone molecule and its complexes are calculated by using ab initio method at the MP2 level with 6-311+G(d,p) basis set. Changes in wavenumber position and linewidth (fullwidth at half maximum) have been explained for neat as well as binary mixtures with different mole fractions of the reference system, acetone, in terms of intermolecular hydrogen bonding. The combination of experimental Raman data with ab initio calculation leads to a better knowledge of the concentration dependent changes in the spectral features in terms of hydrogen bonding.     

Investigation of hydrogen bonding in neat dimethyl sulfoxide and binary mixture (dimethyl sulfoxide + water) by concentration-dependent Raman study and ab initio calculation

In this study,our vibrational spectroscopic analysis is made on hydrogen-bonding between dimethyl sulfoxide and water comprises both experimental Raman spectra and ab initio calculations on structures of various dimethyl sulfoxide/water clusters with increasing water content.The Raman peak position of the v(S=O) stretching mode of dimethyl sulfoxide serves as a probe for monitoring the degree of hydrogen-bonding between dimethyl sulfoxide and water.In addition,the two vibrational modes,namely,the CH 3 symmetric stretching mode and the CH 3 asymmetric stretching mode have been analysed under different concentrations.We relate the computational results to the experimental vibrational wavenumber trends that are observed in our concentration-dependent Raman study.The combination of experimental Raman data with ab initio calculation leads to a better knowledge of the nature of the hydrogen bonding and the structures of the hydrogen-bonded complexes studied.