固液萃取-高效液相色谱-串联质谱法同时测定土壤中阿特拉津及其降解产物

建立了高效液相色谱-串联质谱法(HPLC-MS/MS)同时检测土壤中阿特拉津及其降解产物残留的分析方法。样品以甲醇-水(4∶1,V/V)作为提取溶剂,使用涡旋振荡提取,采用HPLC-MS/MS法进行测定,外标法定量。在0.01、0.2和5.0mg/kg三个添加浓度水平下,阿特拉津及其降解产物的平均回收率在73.7%~104.7%之间,相对标准偏差为0.4%~5.1%;阿特拉津,羟基阿特拉津在土壤样品中的方法检出限均0.045μg/kg,而脱乙基阿特拉津、脱乙基脱异丙基阿特拉津及脱异丙基阿特拉津在土壤样品中的方法检出限则分别为0.090、0.45和0.90μg/kg。本方法的灵敏度较高,且简便、快速,能较好的解决目标物极性差别大及样品基质对检测结果的干扰等问题,可以满足土壤中阿特拉津及其降解产物残留检测的需要。     

土壤中残留的阿特拉津及其代谢产物的高效液相色谱和气-质谱联用分析

用一种简便、快速的前处理和高效液相色谱法（HPLC）对土壤样品中残留的阿特拉津及其主要代谢产物脱乙基阿特拉津、脱异丙基阿特拉津和2-羟基阿特拉津进行定量分析,样品添加回收率因土壤种类和化合物而异：78～121%（阿特拉津、脱乙基阿特拉津、脱异丙基阿特拉津）和40～75%（2-羚基阿特拉津）,最小检测浓度为0.005mg/kg;应用气-质联用法（GC/MS）对前三种化合物和脱乙基-脱异丙基阿特拉津进行了定性分析,谱库检索匹配程度达到90%以上。     

气相色谱法分析尿液样品中的阿特拉津及其代谢物

建立了尿液样品中阿特拉津(ATZ)及其代谢物脱乙基阿特拉津(DEA)、脱异丙基阿特拉津(DIA)、脱乙基脱异丙基阿特拉津(DEDIA)的气相色谱分析方法。样品经乙酸乙酯萃取、硫酸钠脱水、弗罗里硅土净化、浓缩后用气相色谱-电子俘获检测器分析。对样品萃取时的pH值等条件进行了优化,获得了较好的回收率。方法的检出限分别为DEDIA 0.0025 mg/L,DEA、DIA、ATZ 0.005 mg/L。4种化合物在进样量为0.2~8 ng时与其峰面积呈良好的线性关系。利用该方法对阿特拉津生产厂工人的尿液样品进行了分析,尿液中4种化合物的质量浓度为：DEDIA 0.003～0.301 mg/L,DEA 0.005～0.011 mg/L,DIA 0.006～0.276 mg/L,ATZ 0.005～0.012 mg/L。     

超高效液相色谱-串联质谱法快速测定牛奶中螺虫乙酯及其代谢物残留

建立了超高效液相色谱-串联质谱快速测定牛奶中螺虫乙酯及其代谢物残留的分析方法。牛奶经乙腈沉淀蛋白质,正己烷脱脂后,采用ESI源,在MRM模式下测定螺虫乙酯及其代谢物。结果表明,在0.5~50μg/L范围内,待测物色谱峰面积与其质量浓度间的线性关系良好(相关系数均大于0.998),检出限(LODs,S/N=3)和定量限(LOQs,S/N=10)分别为0.05~0.30μg/L和0.17~1.00μg/L。当添加水平为1.0、2.0和10μg/L时,方法的加标回收率为80.0%~108.8%,相对标准偏差(RSD)为4.8%~15.2%(n=6)。该法快速,灵敏,准确,能够满足牛奶中螺虫乙酯及其代谢物残留限量的检测要求。     

高效液相色谱-串联质谱法检测牛奶中多种苯并咪唑兽药残留

采用正交试验优化的QuEChERS方法处理样品,建立了牛奶中包括前体药物和代谢物在内12种苯并咪唑类(BZs)兽药残留的高效液相色谱-串联质谱检测方法.方法在1～500μg/kg范围内线性良好,相关系数为0.9980～0.9996,平均回收率72.4%～108.3%,RSD为1.4%～9.7%,检出限低于0.5μg/k...     

土壤中残留的阿特拉津及其代谢产物的高效液相色谱和气－质谱联用分析

用一种简便、快速的前处理和高效液相色谱法（ＨＰＬＣ）对土壤样品中残留的阿特拉津及其主要代谢产物脱乙基阿特拉津、脱异丙基阿特拉津和２－羟基阿特拉津进行定量分析，样品添加回收率因土壤种类和化合物而异：７８～１２１％（阿特拉津、脱乙基阿特拉津、脱异丙基阿特拉津）和４０～７５％（２－羟基阿特拉津），最小格测浓度为０．００５ｍｇ／ｋｇ；应用气－质联用法（ＧＣ／ＭＳ）对前三种化合物和脱乙基－脱异丙基阿特拉津进行了定性分析，谱库检索匹配程度达到９０％以上。     

气相色谱法分析尿液样品中阿特拉津及其代谢物

建立尿液样品中阿特拉津(ATZ)及其代谢物脱乙基阿特拉津(DEA)、脱异丙基阿特拉津(DIA)、脱乙基脱异丙基阿特拉津(DEDIA)的气相色谱分析方法。样品通过乙酸乙酯萃取,硫酸钠干燥,弗罗里硅土净化,浓缩后用气相色谱ECD检测器分析。对方法中pH值等条件进行了优化,获得了较好的回收率。方法的检出限为DEDIA:2.5ng/mL,DEA、DIA、ATZ:均为5ng/mL。利用本方法对阿特拉津生产工人的实际尿液样品进行了分析。     

高效液相色谱-串联质谱法测定沉积物中孔雀石绿及其代谢物

建立了沉积物中孔雀石绿及其代谢物(隐性孔雀石绿)的高效液相色谱-串联质谱检测方法.称取2 g沉积物样品,以乙腈和CH2Cl2超声萃取,旋转蒸发浓缩后,以30%甲醇定溶,经0.45μm滤膜过滤后,应用高效液相色谱-串联质谱测定沉积物中孔雀石绿及其代谢物残留量.本方法MG和LMG线性范围为0.5-100μg/L,相关系数为0.9982和0.9976,仪器检出限为0.2×10-9,定量限为0.5×10-9,MG回收率为44.5%～66.7%,LMG回收率31.4%～53.3%,方法检出限为2.0 ng/g.该方法适用于沉积物中痕量孔雀石绿及其代谢物的检测.     

高效液相色谱-串联质谱法同时测定农田土壤中31种三嗪类除草剂残留

建立了高效液相色谱-三重四极杆串联质谱(HPLC-MS/MS)同时检测农田土壤中31种三嗪类除草剂残留的分析方法。土壤样本经加速溶剂萃取,Oasis MCX固相萃取柱净化后,在多反应监测(MRM)正离子电喷雾模式下进行HPLC-MS/MS分析。色谱柱为Phenomenex Luna C18反相柱(150 mm×2.0 mm×3μm),流动相为梯度变化的乙腈和0.1%甲酸溶液。检出限(S/N≥3)为0.008~0.440μg/L,在各自的考察浓度范围内线性关系良好(r≥0.996);在0.40~40.0μg/kg添加水平内,平均加标回收率为76.9%~102.0%,RSD为3.4%~10.3%。利用本方法对沈阳地区农田表土的筛查发现,阿特拉津、西玛津、扑草净和脱乙基阿特拉津为该区域主要的三嗪类除草剂物种。     

环境水体中三嗪和酰胺类除草剂的固相萃取/气相色谱-质谱测定

研究了固相萃取/气相色谱-质谱联用技术测定水样中的12种三嗪类和酰胺类除草剂的方法.比较了两种不同的固相萃取柱MCX和C8对12种除草剂的吸附能力.用C18固相萃取柱萃取分析1 L水样,分别研究了上样速度、pH值、有机改性剂、不同的洗脱溶剂和用量及穿透体积对回收率的影响.用内标法定量,加标质量浓度分别为0.05、0.1、1.0μg/L时,除两种代谢物(去乙基阿特拉津和去异丙基阿特拉津)的回收率相对较低外,其它除草剂的回收率在82%～95%之间,方法检出限为0.010-0.035μg/L,用该方法可实现对环境水体中痕量三嗪和酰胺类除草剂的检测.     

Synthesis and structure of hydroxyisoxazolidines and derivatives of hydroxylamine and alkenals

The reactions of N-substituted hydroxylamines with alkenals serve as a method for the synthesis of the corresponding 2-substituted 3(5)-hydroxyisoxazolidines. The reaction pathway is determined by the nature of the substituent attached to the nitrogen atom. Ring-chain isomerism has been detected in these newly obtained compoundsTranslated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1270–1276, September, 1987.     

Synthesis and characterization of triazenide and triazene complexes of ruthenium and osmium

Triazenide [M(eta2-1,3-ArNNNAr)P4]BPh4 [M = Ru, Os; Ar = Ph, p-tolyl; P = P(OMe)3, P(OEt)3, PPh(OEt)2] complexes were prepared by allowing triflate [M(kappa2-OTf)P4]OTf species to react first with 1,3-ArN=NN(H)Ar triazene and then with an excess of triethylamine. Alternatively, ruthenium triazenide [Ru(eta2-1,3-ArNNNAr)P4]BPh4 derivatives were obtained by reacting hydride [RuH(eta2-H2)P4]+ and RuH(kappa1-OTf)P4 compounds with 1,3-diaryltriazene. The complexes were characterized by spectroscopy and X-ray crystallography of the [Ru(eta2-1,3-PhNNNPh){P(OEt)3}4]BPh4 derivative. Hydride triazene [OsH(eta1-1,3-ArN=NN(H)Ar)P4]BPh4 [P = P(OEt)3, PPh(OEt)2; Ar = Ph, p-tolyl] and [RuH{eta1-1,3-p-tolyl-N=NN(H)-p-tolyl}{PPh(OEt)2}4]BPh4 derivatives were prepared by allowing kappa1-triflate MH(kappa1-OTf)P4 to react with 1,3-diaryltriazene. The [Os(kappa1-OTf){eta1-1,3-PhN=NN(H)Ph}{P(OEt)3}4]BPh4 intermediate was also obtained. Variable-temperature NMR studies were carried out using 15N-labeled triazene complexes prepared from the 1,3-Ph15N=N15N(H)Ph ligand. Osmium dihydrogen [OsH(eta2-H2)P4]BPh4 complexes [P = P(OEt)3, PPh(OEt)2] react with 1,3-ArN=NN(H)Ar triazene to give the hydride-diazene [OsH(ArN=NH)P4]BPh4 derivatives. The X-ray crystal structure determination of the [OsH(PhN=NH){PPh(OEt)2}4]BPh4 complex is reported. A reaction path to explain the formation of the diazene complexes is also reported.     

Mass and NMR spectra of haplophyllidine and perforine and of their derivatives

Conclusions The mass and NMR spectra of haplophyllidine, perforine, and their derivatives have been studied. The influence of the open and cyclic forms of the molecular ion on the nature of the fragmentation has been discussed. The main routes of fragmentation of the compounds considered are due to the presence of substituents at C₈ and C₄.Khimiya Prirodnykh Soedinenii, Vol. 5, No. 4, pp. 273–279, 1969     

Crystal and molecular structure of aroyl- and acetylhydrazones of acet- and benzaldehydes

Aroyl- and acetylhydrazones of acet- (I) and benzaldehydes (IV) and benzoylhydrazones of acet- (II) and benzaldehydes (III) were studied by x-ray structural and quantum-chemical methods in order to establish their structures. Compund (I) was the EEZ structure in the crystal. Calculations and spectral data showed that the EEE form occurs in nonpolar solvents and in the gas phase. According to crystallographic data molecules (I)–(IV) are the E-isomers (relative to the N-N bond) and the hydrazone fragments are planar. Intermolecular N-H...O H-bonds from in the crystals. The data obtained suggest that the majority of acylhydrazones are conformationally rigid on dissolution although exceptions do occur. Apparently the reasons for the difference of acetyl- and benzoylhydrazones in electrocarboxylation reactions are electronic and not steric factors.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 75–81, January, 1991.     

Investigation of adhesion and mobility of polyurethane and epoxy-rubber glues and adhesives

The values of activation parameters in uncured and cured epoxy resins, rubbers, and blends thereof are investigated. The dependences of activation energy and adhesion strength of epoxy-rubber compositions on rubber content are determined. The correlation of adhesion and activation energy values for polyurethane rubber and epoxy-rubber compositions is shown.     

Preparation and characterization of diarylphosphazene and diarylphosphinohydrazide complexes of titanium, tungsten and ruthenium and phosphorylketimido complexes of rhenium

Reaction of the proligand Ph2PN(SiMe3)2 (L1) with WCl6 gives the oligomeric phosphazene complex [WCl4(NPPh2)]n, 1 and subsequent reaction with PMe2Ph or NBu4Cl gives [WCl4(NPPh2)(PMe2Ph)] (2) or [WCl5(NPPh2)][NBu4] (3), respectively. DF calculations on [WCl5(NPPh2)][NBu4] show a W=N double bond (1.756 A) and a P-N bond distance of 1.701 A, which combined with the geometry about the P atom suggests, there is no P-N multiple bonding. Reaction of L1 with [ReOX3(PPh3)2] in MeCN (X = Cl or Br) gives [ReX2(NC(CH3)P(O)Ph2)(MeCN)(PPh3)](X = Cl, 4, X = Br, 5) which contains the new phosphorylketimido ligand. It is bound to the rhenium centre with a virtually linear Re-N-C arrangement (Re-N-C angle = 176.6 degrees, when X = Cl) and there is multiple bonding between Re and N (Re-N = 1.809(7) A when X = Cl). The proligand Ph2PNHNMe2(L2H) reacts with [(C5H5)TiCl3] to give [(C5H5)TiCl2(Me2NNPPh2)] (6). An X-ray crystal structure of the complex shows the ligand (L2) is bound by both nitrogen atoms. Reaction of the proligands Ph2PNHNR2[R2 = Me2 (L2H), -(CH2CH2)2NCH3 (L3H), (CH2CH2)2CH2 (L4H)] with [{RuCl(mu-Cl)(eta6-p-MeC6H4iPr)}2] gave [RuCl2(eta6-p-MeC6H4iPr)L] {L = L2H (7), L3H (8), L4H (9)}. The X-ray crystal structures of 7-9 confirmed that the phosphinohydrazine ligand is neutral and bound via the phosphorus only. Reaction of complexes 7-9 with AgBF4 resulted in chloride ion abstraction and the formation of the cationic species [RuCl(6-p-MeC6H4iPr)(L)]+ BF4- {(L = L2H (10), L3H (11), L4H (12)}. Finally, reaction of complex 6 with [{RuCl(mu-Cl)(eta6-p-MeC6H4iPr)}2] gave the binuclear species [(eta6-p-MeC6H4iPr)Cl2Ru(mu2,eta3-Ph2PNNMe2)TiCl2(C5H5)], 13.     

Ti-V基储氢合金及其氢化物的物相结构与组分优化设计

Ti-V基储氢合金在室温、常压下即可表现出良好的储氢特性,且质量储氢容量明显高于传统AB₅型储氢合金,从而在氢气的精制和回收、运输和储存及热泵等方面有较早的应用。 此外,在混合气体分离、核反应堆中处理氢的同位素、镍氢电池及燃料电池负极材料等方面也得到了广泛的研究与关注。 基于目前Ti-V基储氢合金的研究现状,概述了该类合金的优势、限制性因素(包括成因)及改性手段。 此外,为了进一步理解Ti-V基合金储氢机理、构建合金组分与储氢特性之间的对应关系,本工作重点围绕Ti-V基储氢合金及其氢化物的结构、组分优化设计展开综述,并对其未来研究方向做出展望。     

The chemical transport of molybdenum and tungsten and of their dioxides and sulfides

Experiments have been made and an extensive thermodynamic discussion has taken place concerning the chemical transport of Mo, W, MoO₂, WO₂, MoS₂ and WS₂ in the presence of iodine. Efforts have been made to find the species via which Mo and W can migrate within the gas phase.Results: In each case the transport proceeds via the oxide iodides MoO₂J₂ and WO₂J₂ respectively, as already known for the dioxides. Thus the chemical transport of Mo, W, MoS₂ and WS₂ needs not only J₂ but also H₂O, usually liberated from the wall of the quartz ampoule.By means of J₂ + H₂O, the metals can be transported into the high temperature region of the ampoule (e.g., 1050 → 1150°C), whereas the transport of the sulfides proceeds in the opposite direction (e.g., 900 → 700°C).For the sulfide-transport the influence of the ratio of the transport agents $\text{J}{}_2\text{H}{}_2\text{O}$ has been discussed.The water content of the quartz glass out of which the ampoules are made is an important source for water, influencing the reactions.The addition of graphite which considerably lowers the H₂O partial pressure prevents any transport of the metals or the sulfides, which proves that the use of J₂ alone as a transport agent is insufficient in these cases.The gaseous iodides MoJ_x and WJ_z are without any importance under the experimental conditions used for the transport of the metals, their dioxides and sulfides.The partial pressures of MoO₂(OH)₂ and WO₂(OH)₂ under the experimental conditions chosen may usually be neglected. But in the system $\text{MoO}{}_2\text{H}{}_2\text{O}$ the transport via MoO₂(OH)₂ (1000 → 800°C) has been observed.The synthesis of MoO₂ and WO₂, starting with the elements or with powder of metal and trioxide is promoted by the addition of J₂. The reaction steps involved are discussed.