反相高效液相色谱法测定人血浆中利培酮及其代谢物的质量浓度

建立了测定人血浆中利培酮及其活性代谢物9-羟利培酮质量浓度的反相高效液相色谱方法。用Zor－baxODSC18色谱柱,以V（甲醇）：V（水）：V（1mol／L醋酸铵）：V（3mol／L氨水）＝300：50：3：1为流动相,检测波长为280nm,流速为0．8mL／min。利培酮的线性范围为2～600μg／L（r＝0．996）,回收率为（98．2±3．5）％,日内与日间的标准偏差分别为4．12％和4．83％;9-羟利培酮的线性范围为2～800μg／L（r＝0．998）,回收率为（97．8±3．8）％,日内与日间的标准偏差分别为4．28％和4．81％。     

法呢基苯乙酮及其黄烷酮化合物的全合成

以2，4，6-三羟基苯乙酮和法呢基溴为原料，经一步反应以52．0％和6．5％的收率同时得到3-法呢基-2，4，6-三羟基苯乙酮（1）和4-法呢氧基-2，6-二羟基苯乙酮（2）；然后以化合物1和3，4-二羟基苯甲醛为原料，经羟基保护、缩合、环化和去保护基共6步反应，以19．8％的总收率全合成了（±）-6-法呢基-3'，4'，5，7-四羟基黄烷酮（3）．化合物1、2和3均是从澳大利亚植物Borroniaramosa中分离得到的新天然产物，此次为首次合成．     

丙二酸单苯酰胺的固相法合成及其在Eaton试剂或多聚磷酸作用下的环化反应

苯胺及取代的苯胺和Meldrum’s acid在固相无催化剂条件下反应,合成了丙二酸单苯酰胺（1a-1f）,收率81．0％～92．2％．化合物1a-1f在Eaton试剂（五氧化二磷＋甲基磺酸）或多聚磷酸为环化试剂的条件下发生Friedel—Crafts分子内环化反应,以63．2％～93．8％和56．5％～81．3％的收率方便地得到4-羟基喹啉-2-酮衍生物（2a-2f）．产物的结构通过IR,^1H NMR和元素分析得以证实．     

固相萃取-气相色谱-质谱法测定猪组织中沙丁胺醇残留量

建立了动物组织中沙丁胺醇残留量固相萃取-气相色谱-质谱分析方法。动物组织样品经过葡萄糖醛甙酶酶解后调节pH至9．5，然后用异丙醇／乙酸乙酯混合溶剂液液分配去除杂质，旋转浓缩后用乙酸铵缓冲溶液溶解经SCX固相萃取（SPE）柱净化，洗脱液经氮气吹干后用双三甲基硅基三氟乙酰氨（BSTFA）衍生，采用选择离子模式（86、350、369、440）进行测定，外标法定量。检出限为0．10μg/kg。在添加浓度0．5～5．0μg/kg范围内，平均添加回收率在66．4％～82．4％，相对标准偏差（批内）（CV）在3．5％～5．9％之间；批间（CV）在2．2％～4．8％之间。衍生物的峰面积与样品浓度在0．002～0．50mg／L范围内呈良好的线性关系，线性回归系数大于0．999。     

固相微萃取-气相色谱/质谱法分析白胡椒粉的风味成分

采用固相微萃取采集白胡椒粉的挥发性成分,用色谱／质谱法分析鉴定,并用总离子流色谱峰的峰面积进行归一化定量分析其风味成分,鉴定出石竹烯（20．88％）,1-甲氧基-4-（2-丙烯基）苯（20．57％）,β-水芹烯（15．27％）,3-蒈烯（14．56％）,1-甲基-3-异丙基苯（3．62％）,β-蒎烯（2．69％）,芳樟醇（2．69％）,香叶烯（2．36％）,墨榄香烯（2．10％）,胡椒烯（1．32％）等48种化合物。     

假蒟挥发油化学成分气质联用分析研究

采用常规水蒸气蒸馏法提取出假岛精油,经气相色谱-质谱联机分析,分出60多个峰,鉴定出67种化合物,它们主要是2,4,5-三甲氧基-1-丙烯基苯3．20％）,顺-石竹烯（13．33％）,1,2-二甲氧基-4-（1-丙烯基）苯（12．63％）,细辛（9．94％）,4-甲氧基-6-（2-丙烯基）-1,3-苯并二恶茂（5．71％）,δ-杜松烯（3．03％）etc,占总峰面积的67．84％。     

30％毒死蜱微乳剂在甘蓝及土壤中的残留动态研究

利用气相色谱（配FPD检测器）分析测定了30％毒死蜱微乳剂在甘蓝和土壤中的残留消解动态和最终残留量。毒死蜱色谱峰面积与质量浓度在0．01～0．5mg／L范围内呈良好的线性关系,相关系数,为0．9992。甘蓝和土壤中毒死蜱的最低检出浓度均为0．005mg／kg,在0．01,0．02,0．1mg／kg3个添加水平下,甘蓝及土壤中毒死蜱的平均回收率分别为80．1％～96．4％和82．1％-98．7％,变异系数分别为1．2％～5．0％和2．5％-3-3％（n=10）。残留消解动态的结果表明：毒死蜱在甘蓝中的半衰期为5．8～10．5d,在土壤中的半衰期为8．0～10．5d。毒死蜱在收获期甘蓝及土壤中最终残留量均低于我国规定的限量值（1．0mg／kg）。     

左旋氧氟沙星的荧光光谱法研究

提出了一种测定左旋氧氟沙星（LEV）的荧光光谱新方法。该法基于电子受体氯冉酸（CL）和2,3-二氰-5,6-二氯-1,4-对苯醌（DDQ）与电子给体左旋氧氟沙星之间的荷移反应,显示这两种受体能强烈增敏LEV的荧光强度。对影响反应的不同变量和参数进行了研究,建立了两种荧光光谱法测定LEV的新体系：（1）CL体系,线性范围为0．06～3．6μg／mL,检出限为0．02μg／mL;（2）DDQ体系,线性范围为0．12～2．2μg／mL,检出限为0．04μg／mL。所提方法已用于制剂中左旋氧氟沙星含量的测定,回收率分别为99．72％～99．36％和99．36％～98．86％。     

以钼酸盐阴离子柱撑镁铝水滑石为前驱物的加氢脱硫催化剂 Ⅱ.MoS2/Mg(Al)O的吸附性能和HDS催化活性

 通过对氧吸附量、吸附热及反应动力学参数的测定,表征了MoS2在Mg（Al）O上的分散状态及能量性质．结果表明,硫化态MoS2和氧化态MoO3一样,以单分子层分散在载体Mg（Al）O的表面,而且两者的分散阈值均为4．77μmol／m2,说明MoO3硫化后仍保持其原来的分散状态．以噻吩为吸附质,MoS2／Mg（Al）O催化剂的吸附热随着MoO3含量的变化而变化：有三种不同的区域,即Q1＝23．2～23．8kJ／mol（w（MoO3）＝6．02％～9．34％）,Q2＝15．5～16．1kJ／mol（w（MoO3）＝11．89％～15．83％）,Q3≈30．0kJ／mol（w（MoO3）＞21．65％）．MoS2／Mg（Al）O催化剂上噻吩HDS反应的活化能随着MoO3含量的变化情况与吸附热的变化情况相似．随着MoO3含量的增加,催化剂的活性线性升高达极大值后又下降．     

固相萃取-气相色谱法测定北京市水样中的邻苯二甲酸酯

研究了使用毛细管柱（OV-1701）分离、FID作为检测器的气相色谱法测定水中5种邻苯二甲酸酯（PAEs）[邻苯二甲酸二乙酯（DEP）,邻苯二甲酸二丁酯（DBP）,邻苯二甲酸丁基苄基酯（BBP）,邻苯二甲酸二（2-乙基己基）酯（DEHP）,邻苯二甲酸二环己酯（DCHP）]的色谱条件。5种PAEs检出限在0．1～0．3μg／L之间,所测PAEs的质量浓度在0．5～100μg／L范围内,RSD在2．2％～3．3％之间,各物质校正曲线（质量浓度与峰面积）的相关系数在0．9970～0．9993之间。利用固相萃取技术萃取水中PAEs,回收率在82．5％～110．5％之间,RSD在1．1％～4．0％之间。北京市吴家村污水处理厂4个采样点中邻苯二甲酸酯浓度在（0．7～193．3）μg／L之间。北京市南护城河的3个采样点中邻苯二甲酸酯浓度在（0．1～241．8）μg／L之间。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.