一种测定MDR肿瘤细胞内外阿霉素浓度的方法

研究提出K562／A细胞内外阿霉素浓度的反相高效液相色谱-荧光测定法．细胞内阿霉素浓度测定采用Lichrospher C18色谱柱,甲醇-0．01％醋酸(50：50,V／V)流动相,流速1．0mL／min,柱温35℃;细胞外阿霉素浓度测定采用Lichrospher C18色谱柱,甲醇-0．01％醋酸(55：45,V/V)流动相,流速0．8mL／min,柱温35℃．荧光检测器波长λex=495nm,λem=560nm,均以盐酸柔红霉素为内标．研究结果表明,该方法简单、准确、线性范围宽、检测限低,精确度和回收率良好,可用于多药耐药肿瘤细胞内外阿霉素浓度的动态变化规律研究．     

(R,S)-α-羟基苯丁酸乙酯的HPLC手性分离

建立了手性柱HPLC法测定盐酸贝那普利的中间体(R)-α-羟基苯丁酸乙酯中的(S)-α-羟基苯丁酸乙酯。采用Chiralcel OD-H色谱柱,流动相正己烷-异丙醇（体积比90：10),流速1．0mL／min,检测波长254nm,进样体积20μL,按外标法以峰面积计算(R)-α-羟基苯丁酸乙酯中的(S)-α-羟基苯丁酸乙酯的含量。(S)体的线性范围5．5～23．8μg／mL,检出限0．47μg／mL(S／N=3),回收率为96％～103％,精密度RSD为2．1％(n=6)。     

使用限进介质色谱柱的柱切换高效液相色谱法直接进样测定大鼠血浆中舒必利

提出一种直接进样测定大鼠血浆中舒必利浓度的高效液相色谱方法,使用限进介质色谱柱作为预柱在线去除血浆蛋白后,将舒必利通过柱切换转移到分析柱中进行分析。限进介质色谱柱为CAPCELLPAKMFSCX阳离子交换柱（20×4．0mmi．d．,5μm）,分析柱为Kromasil C18柱（150×4．6mm i．d．,5μm）,限进介质柱预分离时流动相为PH=6．88的50mmol／L磷酸盐缓冲液乙腈（100：5,V／V）,切换后分析流动相为PH=6．83的50mmol／L磷酸盐缓冲液-乙腈（100：10,V／V）。流速均为1mL／min,检测波长为240nm。该方法检出限为17ng／mL,定量限为50ng／mL。舒必利在50～1400ng／mL之间线性良好（r=0．9997）,高中低浓度的日内、日间相对标准偏差分别为1．5％～4．2％及2．0％～5．2％,方法回收率为98．8％～104．1％．     

反相高效液相色谱法测定罗红霉素的含量

以Kromasil C18柱为色谱柱、0．067mol/L磷酸二氢铵缓冲液一乙腈(体积比为65：35)为流动相,选择210nm为检测波长,用反相高效液相色谱法测定罗红霉素的含量。罗红霉素的浓度在0．5～8．0mg／mL范围内与色谱峰面积呈良好线性关系,线性相关系数为0．9999,平均回收率为100．97％,测定结果的相对标准偏差为0．36％(n=9)。该方法操作简单、快速,可用于罗红霉素含量的测定。     

高效液相色谱法测定肉制品中甘草抗氧化物的含量

建立了测定肉制品中甘草抗氧化物含量的方法。样品经流动相提取,采用C．8色谱柱分离,以甲醇-0．2mol／L乙酸铵-冰乙酸（体积比70：29：1）为流动相,流速为1．0mL／min,波长为250nm,以保留时间进行定性,峰面积进行定量。甘草酸在1．0-80．0μg／mL范围内线性关系良好,回归方程为y=8．55×10^-5x-0．599（r=0．9997）,检出限为1．0mg／kg,定量限为3．0mg／kg,加标回收率为95．7％-103．4％,测定结果的相对标准偏差为1．57％-3．53％（n=6）。该方法适用于检验机构日常检验中大批量肉制品中甘草抗氧化物含量的测定。     

HPLC法测定苦参碱阴道凝胶中的有关物质

用HPLC法测定苦参碱阴道凝胶中的有关物质，采用ODS色谱柱，以pH=4．0的0．25％(体积分数)磷酸缓冲溶液-三乙胺-乙腈(体积比为96：0．2：4)为流动相，流速为1．0mL／min，检测波长为210nm，苦参碱的浓度为0．786～1．834μg/mL时与色谱峰面积有良好的线性关系，相关系数为0．9994。有关物质含量测定结果稳定，相对标准偏差为2．33％。     

高效液相色谱法测定金羚感冒胶囊中阿司匹林的含量

用高效液相色谱法测定金羚感冒胶囊中阿司匹林的含量：采用RP-C18色谱柱,体积比为30：70的甲醇-0．03mol／L磷酸二氢钾溶液(用磷酸调节至pH=2．4)作流动相,流速为1．0mL／min,检测波长为280nm,阿司匹林色谱峰面积与其浓度在146.8～734μg／mL内线性关系良好,相关系数r=0．9998,阿司匹林的平均回收率为99．70％,相对标准偏差为0.18％(n=5)。     

高效液相色谱法测定生姜中的6-姜酚

用C18色谱柱，以V(甲醇)：V(水)：V(冰乙酸)=35：64：1溶液作流动相，进样量5μL，在流速1．0mL／min下，可不经分离直接测定生姜中的6-姜酚。方法RSD小于1．00％，回收率97％～102％，相关系数0．9999。     

固相萃取-高效液相色谱法测定水中的多环芳烃

建立了固相萃取-一高效液相色谱法测定水中多环芳烃的方法。水样经L-18固相萃取柱吸附后用二氯甲烷洗脱,氮吹干后换甲醇溶剂。反相C18柱为色谱柱;水、甲醇为流动相进行梯度洗脱,流速为1．0mL／min;柱温为30℃;检测器为荧光检测器、紫外检测器。方法的检出限为0．00006-0.03μg／L,回收率为80％～110％,测定结果的相对标准偏差为0．1％～3．6％（n=5）。方法适合于水中16种多环芳烃的测定。     

依替膦酸钠及其有关物质的反相离子对色谱分析

建立用于依替瞵酸钠含量测定及有关物质俭查的分析方法。采用反相离子对高效液相色谱法,蒸发光散射俭测器检测,以Hypersil C8 BDS柱为固定相,流动相为甲醇-含8mmol／L正戊胺的5mmol／L乙酸铵缓冲液(用乙酸调节pH至7．0)(体积比为5：95),流速为1．0mL／min,柱温为室温,方法的线性范围为110～994μg／mL,回归方程为lg A=2．105lg ρ 1．972(r=0．9999)方法的回收率为99％～102％．RSD为0．70％(n=9)．在该色谱条件下．依替膦酸钠与其有关物质(包括残留的合成原料亚磷酸及氧化分解产物磷酸盐)的分离良好：本法不需特殊的样品处理过程．快速,特异性好．适用于依替瞵酸钠的常规检测,为该药的质量控制提供了新的可靠的分析手段。     

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.     

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.     

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.     

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.     

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.