农产品中6种有机溶剂残留的气相色谱-质谱检测方法

建立了蔬菜、粮食等农产品中6种有机溶剂残留(甲苯、邻二甲苯、间二甲苯、对二甲苯、N,N-二甲基甲酰胺(DMF)和二甲基亚砜(DMSO)的液液萃取/气相色谱-质谱分析方法。不同类型的样品经乙腈-水溶液或乙腈溶剂提取后,用Agilent DB-624(30.0 m×250μm×1.4μm)毛细管色谱柱分离,在GC-MS选择离子监测(SIM)模式下检测,以保留时间和特征离子丰度比定性,外标法定量。结果表明,该方法对不同样品中4种苯系物在0.005~0.500 mg/L,DMF在0.025~0.125 mg/L,DMSO在0.050~0.500 mg/L浓度范围内线性关系良好,相关系数(r)为0.992 0~0.997 1。6种有机溶剂的平均加标回收率为60.1%~115.2%,相对标准偏差不大于11.0%。苯系物、DMF和DMSO的方法检出限(S/N=3)分别为0.002~0.050,0.010~0.025,0.060~0.150 mg/kg。该方法准确、快速、灵敏,可用于各种农产品中有机溶剂残留的监控。     

不同复合体系对含钛高炉渣光催化还原Cr(VI)影响

采用煅烧的硫酸盐掺杂的含钛高炉渣(sulfate-modified titanium-bearing blast furnace slag,STBBFS)作为光催化剂,研究了Cr(VI)-柠檬酸[Cr(VI)-CA]复合体系和Cr(VI)-柠檬酸-硝酸铁[Cr(VI)-CA-FN]复合体系对STBBFS催化剂光催化活性的影响.结果表明:酸性条件下,不同复合体系对STBBFS催化剂光催化活性的促进作用按Cr(VI)-CA-FN复合体系>Cr(VI)-CA复合体系>Cr(VI)单一体系增强.Cr(VI)-CA复合体系在pH=2.5,反应50 min后STBBFS催化剂光催化活性为0.426 mg·min-1·g-1时将溶液中的Cr(VI)全部还原;而Cr(VI)-CA-FN复合体系在pH=2.5,反应16 min后STBBFS催化剂光催化活性为1.2425 mg·min-1·g-1时将溶液中的Cr(VI)全部还原.两种复合体系中,Cr(VI)离子的光催化还原过程都遵循L-H动力学规律,虽然加入CA和FN后,降低了吸附对光催化还原Cr(VI)的影响,但是Cr(VI)吸附至催化剂表面仍然是整个反应过程的关键.     

不同复合体系对含钛高炉渣光催化还原Cr(VI)的影响

采用煅烧的硫酸盐掺杂的含钛高炉渣(sulfate-modified titanium-bearing blast furnace slag, STBBFS)作为光催化剂, 研究了Cr(VI)-柠檬酸[Cr(VI)-CA]复合体系和Cr(VI)-柠檬酸-硝酸铁[Cr(VI)-CA-FN]复合体系对 STBBFS催化剂光催化活性的影响. 结果表明: 酸性条件下, 不同复合体系对STBBFS催化剂光催化活性的促进作用按Cr(VI)-CA-FN复合体系＞Cr(VI)-CA复合体系＞Cr(VI)单一体系增强. Cr(VI)-CA复合体系在pH＝2.5, 反应50 min后STBBFS催化剂光催化活性为0.426 mg•min―1•g―1时将溶液中的Cr(VI)全部还原; 而Cr(VI)-CA-FN复合体系在pH＝2.5, 反应16 min后STBBFS催化剂光催化活性为1.2425 mg•min―1•g―1时将溶液中的Cr(VI)全部还原. 两种复合体系中, Cr(VI)离子的光催化还原过程都遵循L-H动力学规律, 虽然加入CA和FN后, 降低了吸附对光催化还原Cr(VI)的影响, 但是Cr(VI)吸附至催化剂表面仍然是整个反应过程的关键.     

助溶剂在离子液体催化制备5-羟甲基糠醛中的应用

本文研究了不同助溶剂对酸性离子液体催化制备5-羟甲基糠醛的(HMF)的影响.以果糖为反应原料,二甲基亚砜(DMSO)、二甲基乙酰胺(DMA)、二甲基甲酰胺(DMF)以及乙二醇(EG)四种不同的有机溶剂作为助溶剂,运用酸性离子液体催化制备5-羟甲基糠醛.结果表明:以DMSO作为反应助溶剂,38.5wt%的果糖反应液在催化...     

聚(N-乙烯基己内酰胺)在二元水溶液中的温度响应性相变行为

用浊度法研究了聚(N-乙烯基己内酰胺)(PNVCL)在不同浓度的几种非质子溶剂如二甲基亚砜(DMSO)、N,N-二甲基甲酰胺(DMF)、四氢呋喃(THF)、1,4-二氧六环和质子溶剂(几种低级醇)的水溶液中低临界溶液温度(LCST)的变化情况.结果表明:PNVCL的LCST随DMF、THF、1,4-二氧六环和CH3OH...     

超积累植物李氏禾叶细胞干粉对Cr(VI)的吸附特性研究

借助拟合吸附动力学和等温热力学方程, 研究了湿生超积累植物李氏禾叶细胞干粉对Cr(VI)的吸附性能. 考察了pH值、吸附时间等多种因素对吸附性能的影响; 利用扫描电镜(SEM), X射线能谱(EDS)对李氏禾干粉表面形貌及元素分布进行了表征. 结果表明, 该吸附是单分子吸附的伪二级动力学过程, 吸附过程包含两个步骤: Cr(VI)离子通过静电作用富集在干粉材料表面, 随后干粉表面存在的功能配位官能团会与Cr(VI)发生化学作用. 结合红外光谱图发现对铬起吸附作用的主要是含O, N功能原子的配位官能团, 并且不同功能原子与Cr(VI)的作用方式不同.     

超积累植物李氏禾叶细胞干粉对Cr(Ⅵ)的吸附特性研究

借助拟合吸附动力学和等温热力学方程,研究了湿生超积累植物李氏禾叶细胞干粉对Cr(VI)的吸附性能.考察了pH值、吸附时间等多种因素对吸附性能的影响;利用扫捕电镜(SEM),X射线能谱(EDS)对李氏禾干粉表面形貌及元素分布进行了表征,结果表明,该吸附是单分子吸附的伪二级动力学过程,吸附过程包含两个步骤:Cr(VI)离子通过静电作用富集在十粉材料表面,随后干粉表面存在的功能配位官能团会与Cr(VI)发生化学作用.结合红外光谱图发现对铬起吸附作用的主要是含O,N功能原子的配位官能团,并且不同功能原子与Cr(VI)的作用方式不同.     

IC-ICP-MS联用法测定玩具材料中可迁移的六价铬与三价铬

建立了一种IC与ICP-MS联用分析玩具材料中可迁移的Cr(III)与Cr(VI)的分析方法。采用胃酸模拟溶液萃取玩具材料中的Cr(III)与Cr(VI),萃取液用氨水调至中性,以NH4Cl为流动相,季铵盐离子交换柱为分离柱的离子色谱分离,最后用ICP-MS外标法定量。Cr(III)和Cr(VI)的线性范围分别为0.05～5 mg/kg和0.005～0.5 mg/kg;加标回收率90.0%～105.4%;RSD为2.0%～7.2%;Cr(III)和Cr(VI)的检出限(S/N=3)分别为0.25μg/L和0.029μg/L。     

C3对称性芳香三羧酸配体构筑的稀土-有机骨架化合物的合成、结构及荧光性质

以稀土离子(La,Ce,Pr,Nd)与具有C3对称结构的芳香羧酸配体N,N’,N″-三(4-苯甲酸基)-1,3,5-苯三甲酰胺(BTMC)为构筑单元,合成了4个同构的三维非穿插金属-有机骨架化合物[Ln(BTMC)(DMF)]·3H2O·2.5DMF[Ln=La(1),Ce(2),Pr(3),Nd(4)].采用单晶X射线衍射、粉末X射线衍射(PXRD)、红外光谱和热重分析对其结构及稳定性进行了表征,并测试了它们捕获不同金属离子(La3+,Ce3+,Pr3+,Nd3+,Cd2+,Cr3+,Cu2+)及吸附染料甲基橙和曙红的固态荧光光谱变化.结果表明,化合物对金属离子及染料均有一定吸附作用,捕获Cr3+后荧光强度变化最大,说明对Cr3+具有较好的识别作用.     

基于双核{Zn_2(COO)_4}次级构筑单元的二维发光配位聚合物的晶体结构和对Fe~(3+)的检测（英文）

使用H_2L配体(H_2L=2-(1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl)terephthalic acid)和Zn~(2+)通过水热反应,合成了一例基于双核{Zn_2(COO)_4}次级构筑单元的二维发光配位聚合物[Zn_2(L)_2(DMSO)_2(DMF)](1)(DMSO=二甲亚砜,DMF=N,N-二甲基甲酰胺)。拓扑分析表明1结构中的双核{Zn_2(COO)_4}单元可视为4连接节点,并与作为连接子的L~(2-)形成(4,4)-网拓扑构型。1表现出对Fe~(3+)离子的选择性发光猝灭响应,检测限为2.8μmol·L~(-1)。1对Fe~(3+)的检测具有良好的抗干扰性,且可通过DMF溶剂洗涤实现再生,可多次循环使用。     

Electrochemical and spectroelectrochemical studies on UO(2)(saloph)L (saloph = N,N'-disalicylidene-o-phenylenediaminate,L=dimethyl sulfoxide or N,N-dimethylformamide)

To examine properties of pentavalent uranium, U(V), we have carried out electrochemical and spectroelectrochemical studies on UO(2)(saloph)L [saloph = N,N'-disalicylidene-o-phenylenediaminate, L = dimethyl sulfoxide (DMSO) or N,N-dimethylformamide (DMF)]. The electrochemical reactions of UO(2)(saloph)L complexes in L were found to occur quasireversibly. The reduction processes of UO(2)(saloph)L complexes were followed spectroelectrochemically by using an optical transparent thin layer electrode cell. It was found that the absorption spectra measured at the applied potentials from 0 to -1.650 V versus ferrocene/ferrocenium ion redox couple (Fc/Fc(+)) for UO(2)(saloph)DMSO in DMSO have clear isosbestic points and that the evaluated electron stoichiometry equals 1.08. These results indicate that the reduction product of UO(2)(saloph)DMSO is [U(V)O(2)(saloph)DMSO](-), which is considerably stable in DMSO. Furthermore, it was clarified that the absorption spectrum of the [U(V)O(2)(saloph)DMSO](-) complex has a very small molar absorptivity in the visible region and characteristic absorption bands due to the 5f(1) orbital at around 750 and 900 nm. For UO(2)(saloph)DMF in DMF, the clear isosbestic points were not observed in the similar spectral changes. It is proposed that the UO(2)(saloph)DMF complex is reduced to [U(V)O(2)(saloph)DMF](-) accompanied by the dissociation of DMF as a successive reaction. The formal redox potentials of UO(2)(saloph)L in L (E(0), vs Fc/Fc(+)) for U(VI)/U(V) couple were determined to be -1.550 V for L = DMSO and -1.626 V for L = DMF.     

{[Gd(DMF)3(DMSO)(H2O)3](μ-CN)[Fe(CN)5]}·2H2O的合成，结构表征和磁性

A new cyano-bridged Gadolinium^Ⅲ-Iron^Ⅲ complex {[Gd(DMF)₃(DMSO)(H₂O)₃](μ-CN)[Fe(CN)₅]}·2H₂O (DMF=N,N-dimethylformamide; DMSO=dimethylsulfoxide) was synthesized by the grinding reaction method. It crysta-llizes in the triclinic, space group P1 with cell parameters: a=0.90363(2) nm, b=1.250 78(3) nm, c=1.41303(1) nm, α=93.174(1)°, β=94.406(1)°, γ=91.817(2)°, and V=1.588 87(5) nm³, D_c=1.582 g·cm^-3, Z=2, M_r=756.72, F(000)=760, μ=2.645 mm^-1. The slightly distorted square-antiprism eightfold-coordinated Gd(Ⅲ) and the approxi-mately oriented octahedrally sixfold-coordinated Fe(Ⅲ) are linked by a cyano-bridge group to construct a dinuclear compound. The {[Gd(DMF)₃(DMSO)(H₂O)₃](μ-CN)[Fe(CN)₅]} species are held together via hydrogen bonds to form a three-dimensional framework. The Gd(Ⅲ)-Fe(Ⅲ) interaction is antiferromagnetic. CCDC: 223430.     

Chromium(VI) Forms Thiolate Complexes with gamma-Glutamylcysteine, N-Acetylcysteine, Cysteine, and the Methyl Ester of N-Acetylcysteine

Reaction of potassium dichromate with gamma-glutamylcysteine, N-acetylcysteine, and cysteine in aqueous solution resulted in the formation of 1:1 complexes of Cr(VI) with the cysteinyl thiolate ligand. The brownish red Cr(VI)-amino acid/peptide complexes exhibited differential stability in aqueous solutions at 4 degrees C and ionic strength = 1.5 M, decreasing in stability in the order: gamma-glutamylcysteine > N-acetylcysteine > cysteine. (1)H, (13)C, and (17)O NMR studies showed that the amino acids act as monodentate ligands and bind to Cr(VI) through the cysteinyl thiolate group, forming RS-Cr(VI)O(3)(-) complexes. No evidence was obtained for involvement of any other possible ligating groups, e.g., amine or carboxylate, of the amino acid/peptide in binding to Cr(VI). EPR studies showed that chromium(V) species at g = 1.973-4 were formed upon reaction of potassium dichromate with gamma-glutamylcysteine and N-acetylcysteine. Reaction of potassium dichromate or sodium dichromate with N-acetylcysteine and the methyl ester of N-acetylcysteine in N,N-dimethylformamide (DMF) also led to the formation of RS-Cr(VI)O(3)(-) complexes as determined by UV/vis, IR, and (1)H NMR spectroscopy. Thus, an early step in the reaction of Cr(VI) with cysteine and cysteine derviatives in aqueous and DMF solutions involves the formation of RS-CrO(3)(-) complexes. The Cr(VI)-thiolate complexes are more stable in DMF than in aqueous solution, and their stability towards reduction in aqueous solution follows the order cysteine < N-acetylcysteine < gamma-glutamylcysteine < glutathione.     

Self-assembly of an Unprecedented Cynao-bridged One-dimensional 4f-3d Complex[Eu(DMF)4(H2O)2Cr(CN)6] H2O

Recently, there has been considerable interest in cyano-bridged lanthanide(Ⅲ) hexacyanometalate(Ⅲ) complexes LnM(CN)₆·nH₂O (M=Fe, Cr and Co) because of their potential as catalytic, semiconductive, and magnetic materials.^[1-8] In this study, we employed N,N-dimethylformamide (DMF) as a hybrid ligand to construct a bimetallic complex[Eu(DMF)₄(H₂O)₂Cr(CN)₆]·H₂O. It was synthesized as yellow crystals by the self-assembly of anhydrous EuCl₃ and (Bu₄N)₃[Cr(CN)₆] in MeOH and DMF. Single-crystal X-ray diffraction analysis shows that it consists of a cyano-bridged chain structure. The Eu atom is eight-coordinate with a distorted bicapped square antiprism geometry. Six oxygen atoms of two water molecules and four DMF molecules and two nitrogen atoms of the bridging CN ligands are bound to Eu with the Eu-O distance ranging from 2.368(7) to 2.447(8) Å. The bridging cyanides coordinate to the Europium(Ⅲ) ion[N(l)-Eu=2.543(9) Å and N(3)-EuA=2.543(8) Å] in a bent fashion with the bond angles of 164.0(9) for C(1)-N(1)-Nd and 155.1(7)。for C(3)-N(3)-EuA (A denotes the symmetry transformation:-x+l,y-l/2,-z+3/2). Each Cr(CN)₆ coordinates to two Eu(Ⅲ) ions using two cis cyanide ligands, while each Eu(DMF)₄(H₂O)₂ group connects two Cr(CN)₆ moieties in a cis fashion, giving rise to an unprecedented chain structure. Crystal data:monoclinic, space group P2₁/c, a=13.151(2), b=12.905(2), c=19.186(2) Å, β=109.70(1)°, V=3065.5(7) ų,Z=4, ρ_obs=1.531 Mg m^-3, S=1.024,R1=0.0540, R_w=0.1616.     

Absorption of nitrogen dioxide in organic solvents

The absorption of NO(2) at low levels in nitrogen, by N,N-dimethylformamide (DMF) and dimethyl sulphoxide (DMSO), has been investigated. Parts-per-million levels of NO(2), were collected with an efficiency of 90% in DMF and 65-70% in DMSO. The absorption efficiency in DMF depends on the gas flow-rate and the bubbling time, but in DMSO it is independent of time.     

Solution structures of chromium(VI) complexes with glutathione and model thiols

Chromium(VI) complexes of the most abundant biological reductant, glutathione (gamma-Glu-Cys-Gly, I), are among the likely initial reactive intermediates formed during the cellular metabolism of carcinogenic and genotoxic Cr(VI). Detailed structural characterization of such complexes in solutions has been performed by a combination of X-ray absorption fine structure (XAFS) and X-ray absorption near-edge structure (XANES) spectroscopies, electrospray mass spectrometry (ESMS), UV-vis spectroscopy, and kinetic studies. The Cr(VI) complexes of two model thiols, N-acetyl-2-mercaptoethylamine (II) and 4-bromobenzenethiol (III), were used for comparison. The Cr(VI)-thiolato complexes were generated quantitatively in weakly acidic aqueous solutions (for I and II) or in DMF solutions (for II) or isolated as a pure solid (for III). Contrary to some claims in the literature, no evidence was found for the formation of relatively stable Cr(IV) intermediates during the reactions of Cr(VI) with I in acidic aqueous solutions. The Cr(VI) complexes of I-III exist as tetrahedral [CrO(3)(SR)](-) (IVa) species in the solid state, in solutions of aprotic solvents such as DMF, or in the gas phase (under ESMS conditions). In aqueous or alcohol solutions, reversible addition of a solvent molecule occurs, with the formation of five-coordinate species, [CrO(3)(SR)L](-) (IVb, probably of a trigonal bipyramidal structure, L = H(2)O or MeOH), with a Cr-L bond length of 1.97(1) A (determined by XAFS data modeling). Complex IVb (L = H(2)O) is also formed (in an equilibrium mixture with [CrO(4)](2)(-)) at the first stage of reduction of Cr(VI) by I in neutral aqueous solutions (as shown by global kinetic analysis of time-dependent UV-vis spectra). This is the first observation of a reversible ligand addition reaction in Cr(VI) complexes. The formation of IVb (rather than IVa, as thought before) during the reactions of Cr(VI) with I in aqueous solutions is likely to be important for the reactivity of Cr(VI) in cellular media, including DNA and protein damage and inhibition of protein tyrosine phosphatases.     

Kinetics and mechanism of the reaction between dimethylformamide and chromium(VI)

The kinetics of oxidation of N,N‐dimethylformamide by chromium(VI) has been studied spectrophotometrically in aqueous perchloric acid media at 20°C. The rate showed a first‐order dependence on both [Cr(VI)] and [DMF], and increased markedly with increasing [H⁺]. The order with respect to [HClO₄] was found to lie between 1 and 2. The rate was found to be independent of ionic strength as well as of any inhibition effect of Mn(II). The formation of superoxochromium(III) ion was detected in an aerated solution of chromium(VI), DMF and HClO₄. The proposed mechanism, involving two reaction pathways, leads to the rate law, rate = K_a1 [HCrO₄⁻] [DMF] (k_I K_a2 [H⁺]²+k_II[H⁺]). The first pathway, with rate constant k_I, involves the formation of chromium(V) and a free radical. The second pathway, with rate constant k_II, involves the formation of Cr(IV), CO₂ and dimethylamine. © 1999 John Wiley & Sons, Inc. Int J Chem Kinet 31: 409–415, 1999     

在Cr(Ⅵ)和4-氯酚复合污染系统中多孔石墨相氮化碳的协同光催化效应

随着工农业的迅速发展,多组分复合污染系统广泛分布于自然环境中,例如电镀废水、污水处理厂污泥、城市生活垃圾等.自1972年光催化劈裂水产氢被发现以来,光催化技术已被广泛应用于解决环境污染问题.一方面,光生电子在酸性条件下能将重铬酸根(Cr2O72–)中高毒性的Cr(VI)还原成低毒性的Cr(Ⅲ).另一方面,水中有机污染物通过光催化氧化过程可被降解为二氧化碳和水.然而在目前的光催化领域,大部分研究者专注于新型光催化剂的开发,并在单组份光催化系统中测试所开发材料的光催化活性,而忽视了蕴藏在光催化反应本身中的科学问题.事实上,将光催化技术应用于复合污染系统具有非常大的现实意义.少数研究者试图通过光催化过程处理多组分废水.然而,在复合污染系统中的协同光催化效应和机理尚未明确.近几年,基于可见光响应、环境友好、成本低等优点,作为一种不含金属的半导体光催化剂,石墨相氮化碳(g-C3N4)已被广泛应用于环境光催化领域.然而在实际应用中,g-C3N4的光催化活性却较差,因为聚集态层状结构不但限制了光生载流子的表面迁移,而且还增加了光催化反应的传质阻力.因此,人们尝试形貌控制策略来提高g-C3N4的光催化活性,例如氮化碳纳米片、空心球、量子点的构建.在前期工作中,我们通过一种简单的前驱体预处理策略使用盐酸和乙二醇共处理的三聚氰胺作原料成功制备出了多孔石墨相氮化碳(pg-C3N4),因其具有丰富的多孔微观结构而表现出了卓越的光催化活性.本文初步研究了在酸性条件下使用所制备g-C3N4或pg-C3N4光催化还原水中Cr(Ⅵ)成Cr(Ⅲ)的反应.然后在不同pH条件下进一步研究了在Cr(Ⅵ)和4-氯酚(4-CP)复合污染系统中的协同光催化效应.结果发现,与单组分光催化系统相比,在Cr(Ⅵ)和4-CP复合污染系统中Cr(Ⅵ)的还原效率和4-CP的降解效率同时提高,即在Cr(Ⅵ)和4-CP复合污染系统中存在协同光催化效应.最后讨论了在Cr(Ⅵ)和4-CP复合污染系统中的协同光催化效应可归因于pg-C3N4的电子转移作用加速了Cr2O72–和4-CP之间的氧化还原反应.在用稀H2SO4调节pH至3的Cr(VI)和4-CP复合污染系统中,由于Cr2O72–中氧原子的电子云密度较低,因此Cr2O72–和4-CP之间的氧化还原反应通过pg-C3N4的电子转移作用易于进行,因而表现出明显的协同光催化效应.     

Solvation of Piperidine in Nonaqueous Solvents

Russian Journal of Physical Chemistry A - The enthalpies of solvation of piperidine (Ppd) in methanol (MeOH), ethanol (EtOH), N,N‑dimethylformamide (DMF), and dimethylsulfoxide (DMSO) are...     

Polarographic behaviour of uranium (VI) in organic solutions

Polarographic determination of uranium (VI) has been studied in the organic extraction phase TBP—diluent along with a selected aprotic solvent (i. e. dimethyl sulfoxide or N,N-dimethylformamide). DMF was found more suitable because it dissolves the organic extraction phase better than DMSO. U (VI) extracted in TBP-kerosene, n-hexane, cyclohexane, n-dodecane, benzene, from nitric acid medium can be determined in an organic solution (e. g. 50% DMF-30% TBP-20% kerosene) where it gives a well defined wave. In the organic solution, nitric acid added and/or extracted from the aqueous phase was found as an excellent supporting electrolyte for uranium determination.