测定玻璃体和房水中维拉帕米含量的高效液相色谱法

研究了用ＨＰＬＣ 测定兔眼玻璃体和房水中维拉帕米含量的方法。用丙咪嗪为内标， 采用Ｓｐｈｅｒｉｃａｌ Ｃ１８色谱柱分离， 以甲醇－ ０ ．０４ ｍｏｌ／Ｌ 醋酸铵－ 乙腈－ 二乙胺（ 体积比１ ∶１ ∶０ ．５ ∶０ ．０２） 为流动相， 检测波长为２７８ｎｍ 。样品用正己烷－ 异丁醇提取后进样， 分析速度快。 样品及内标的保留时间分别为４ ．６３ ｍｉｎ 及９ ．２３ ｍｉｎ ； 线性范围为２ ．５ ～１００ ｍｇ／Ｌ， 相关系数ｒ 为０ ．９９９ ７ 。方法的回收率为１００ ．３ ％ （ ｎ ＝ ５） ，ＲＳＤ 为３ ．６３％ ， 日内ＲＳＤ 为０ ．５ ％ ～３ ．６１ ％ ， 日间ＲＳＤ 为３ ．７５ ％ ～４ ．８０ ％ ， 最低检测质量浓度为０．２５ ｍｇ／ Ｌ。 应用该法测定了创伤家兔玻璃体和房水中维拉帕米浓度的变化。     

吡罗昔康凝胶有效成分的高产液相色谱研究

本文提出了采用内标法，将ＨＰＬＣ用于吡罗昔康凝胶有效成分测定的新方法，讨论了流流动相及内标的选择，进样和空白基质的影响等，在优化的实际条件下，吡罗昔康浓度在０．０２－０．２ｍｇ／ｍＬ范围内，其浓度与吡罗昔康和内标的峰面积之比呈线性关系。应用于实际样品分析，其结果与紫外分光光度法一致，平均回收率为９９．６％，相对标准偏差为１．０％，方法简单，准确度高，专属性强，可有竽吡罗昔康凝胶样品的稳定性考察和质量控制。     

HPLC/ECD测定人血小板中5-羟色胺浓度

用ＨＰＬＣ／ＥＣＤ法测定血小板５－ＨＴ,运用 ＷａｔｅｒｓμＢｏｎｄａｐａｋ Ｃ柱,３,４二羟基苄胺（ＤＨ－ＢＡ）作内标,以 ０.０７ ｍｏｌ／Ｌ乙酸钠缓冲液＋乙腈为流动相（２０＋１）,每１Ｌ缓冲液含 ０．０５ ｍｏｌ／Ｌ柠檬酸、２．５ ｍｍｏｌ／Ｌ庚烷磺酸钠、０．１ｍｍｏｌ／Ｌ Ｎａ_２ＥＤＴＡ,流速０．８ ｍＬ／ｍｉｎ。ＤＨＢＡ和 ５－ＨＴ的保留时间分别为５．４和１１．５ ｍｉｎ,线性范围为０．０２５～１ｍｇ／Ｌ（ｒ＝ ０．９９９７）。５－ＨＴ日内 ＲＳＤ低于１．８７％,日间ＲＳＤ低于８．５４％,方法回收率为１００．４％±２．３％。提示本方法快速简便,灵敏准确,适用于临床基础研究。     

5-(对-羟基苯基):-5-苯基乙内酰脲的反相高效液相手性分离测定法

以β－ＣＤ为手性流动相添加剂、苯巴比妥为内标,于ＦＬＣ－Ｃ８反相柱上建立了鼠肝微粒体中５－（对－羟基苯基）－５－苯基乙内酰脲（ｐ－ＨＰＰＨ）外消旋体的拆分方法。测得ｐ－ＨＰＰＨ对映体的线性范围为０．５～１１０ｍｇ／Ｌ（ｒ＝０．９９９６）;最低检出量为５ｎｇ（Ｓ／Ｎ＝３）;Ｓ－ｐ－ＨＰＰＨ的回收率为９３．６％±２．８％,Ｒ－ｐ－ＨＰＰＨ的回收率为９４．７％±１．８％;日内和日间精密度ＲＳＤ值均小于２％。所建立的方法具有结果准确、操作方便等特点。     

SDM—1型耐硫催化剂甲烷化反应动力学：I.本征动力学模型

本文研究了ＳＤＭ－１型城市煤气耐硫甲烷化催化剂的本征动力学，在５７３－６７３Ｋ，０．３０－１．２０ＭＰａ的反应条件下，原料气的组成为Ｈ２ ４２－４５％，ＣＯ１１－２４％，ＣＨ４ １．８－１５％，ＣＯ２５．８－１７％，余者为Ｎ２气，采用幂函数模型回归的动力学方法为：     

气相色谱法快速测定家用气雾杀虫剂中丙烯菊酯、氯菊酯、增效醚含量

用气相色谱法定量测定了家用气雾杀虫剂中的丙烯菊酯、氯菊酯和增效醚。色谱柱为５％ＱＦ－１／Ｃｈｒｏ－ｍｏｓｏｒｂＷＨＰ,以邻苯二甲酸二苯酯为内标物,测得的回收率分别为１００％,１０２％,９９．９％;变异系数为０．１３,０．５６,０．４８,方法简便、快速、准确。     

电感耦合等离子体质变法测定高纯氧化铕中Cr,Mn,Co,Ni,Cu,Cd和Pb

报道敢用电感耦合等离子体质谱直接测定高纯氧化铕中Ｃｒ，Ｍｎ，Ｃｏ，Ｎｉ，Ｃｕ，Ｃｄ，Ｐｂ等杂质的方法，选择了仪器工作条件，讨论了谱干扰和基体效应。采用Ｒｈ作内标，减小了基体的影响。本法检出限为０．１２－２．２８μｇ／Ｌ，加标回收率为８８．６％－１０８．３％，相对标准偏差为３．２－７．９％，方法简便，快速。     

微分电位溶出法连测血清中铜铅镉锌

报道了微分电位溶出法先在０．００２５ｍｏｌ．Ｌ＾－１ＨＣｌ－０．３ｍｏｌ．Ｌ＾－１ＮＨ４Ｃｌ底液中连测血清中Ｃｕ、Ｐｂ、Ｃｄ，再加Ｃａ＾３＋０．６μｇ、０．３ｍｌＮＨ４Ｆ（２ｍｏｌ．Ｌ＾－１）于底液，稀释一倍后测Ｚｎ。Ｃｕ采用标准曲线法，Ｐｂ、Ｃｄ、Ｚｎ采用标准加入法。在选定条件下，四元素的线性关系良好。测试血汪有相对标准偏差≤４．６％，平均回收率为９３．３％－１０１．３％，结果令人满意。     

微分电位溶出法测定人发中铜铜镉锌的研究

本文报道了０．００２５ｍｏｌ．Ｌ＾－１ＨＣｌ－０．２ｍｏｌ．Ｌ＾－１ＮＨ４Ｃｌ底液中连续测定人发中铜、铅、镉、锌的微分电位溶出法。四元素峰电位分别为－０．２０Ｖ，－０．４６Ｖ，－０．６７Ｖ，－１．０２Ｖ（ＳＣＥ），峰形好，灵敏度高，干扰少，测定发样相对标准偏差≤４．３％，回收率为９７．６％－１０４．６％。并对ＨＮＯ３－ＨＣｌＯ４和ＮＨＯ３－Ｈ２Ｏ２消化发样进行了比较。     

空气—C2H2火焰原子吸收光谱法测定中草药（鸦胆子,补骨脂）中…

用空气－Ｃ２Ｈ２火焰原子吸收光谱法测定了中草药中的Ｆｅ、Ｍｇ含量，讨论了测定条件，结果令人满意，方法的回收率：Ｆｅ９８．２０％－１０４．９％，ＣＶ１．０６％－１．０７％，Ｍｎ９９．４％－１０１％，ＣＶ＝０．５２％－１．９４％。     

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%.     

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.     

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.     

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.     

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.     

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.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

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.