高效液相色谱法检测溴化丁基胶塞中11种抗氧剂及游离硫的浸出量及迁移量

采用Inertsil ODS-SP C18(250×4.6 mm,5μm)色谱柱,以0.1%乙酸水-甲醇-乙腈为流动相,进行梯度洗脱,流速为1.0 mL/min,检测波长为277 nm。胶塞提取溶剂分别为无水乙醇和模拟药液。11种抗氧剂及游离硫的分离度均大于1.5;在2.47~54.51μg/mL浓度范围内,线性关系良好(R^2均大于0.999);检出限为0.021~0.403μg/mL;以无水乙醇为提取溶剂时,加标回收率为82.8%~115.3%,相对标准偏差为1.1%~6.1%;以模拟药液为提取溶剂时,加标回收率为62.9%~103.2%,相对标准偏差为1.4%~5.6%。该方法可用于包材相容性试验中实际样品的检测。     

GC法同时测定酚氨咖敏片中4种组分

建立了同时测定酚氨咖敏片中对乙酰氨基酚、氨基比林、咖啡因和马来酸氯苯那敏4组分含量的毛细管气相色谱法。采用SE-30大口径毛细管色谱柱(30 m×0.53 mm,1.0μm),柱温190℃,汽化室温度220℃,检测器为FID,检测温度250℃,载气为高纯N2,分流比为1∶6,内标为盐酸麻黄碱,以无水乙醇为溶剂,样品无需衍生化处理,直接进样测定。样品中各组分完全分离,辅料无干扰,对乙酰氨基酚、氨基比林、咖啡因和马来酸氯苯那敏分别在20~2000μg/mL、15~1500μg/mL、10~500μg/mL和20~100μg/mL范围内线性关系良好(r0.999),各组分的平均回收率在99.6%~101.2%范围内,RSD2%。     

顶空气相色谱法同时测定新药CBT108中12种残留溶剂

采用顶空气相色谱技术,建立了同时测定新药CBT108中12种残留溶剂的方法。优化了平衡加热时间和程序升温时间以及制样的溶剂,并通过验证确定了本方法的合理性、准确性和可行性。在优化的实验条件下,采用DB-624型毛细管柱(6%氰丙基苯基-94%二甲基聚硅氧烷为固定液,30 m×0.53 mm×3.0μm)分离、氢火焰离子化检测器检测、内标法定量的分析方案,实现了甲醇、乙醇、乙醚、丙酮、乙腈、二氯甲烷、正己烷、乙酸乙酯、四氢呋喃、庚烷、甲苯和四氯化碳共12种残留溶剂的同时分离与测定。12种溶剂在各自的范围内线性关系良好,线性相关系数(R~2)均0.997;以10倍信噪比确定方法定量限,以3倍信噪比确定方法检出限,分别为:甲醇0.024μg/mL、0.0072μg/mL;乙醇0.1μg/mL、0.012μg/mL;乙醚0.01μg/mL、0.005μg/mL;丙酮0.1μg/mL、0.008μg/mL;乙腈1.025μg/mL、0.0615μg/mL;二氯甲烷0.09μg/mL、0.06μg/mL;正己烷0.0174μg/mL、0.0145μg/mL;乙酸乙酯0.25μg/mL、0.008μg/mL;四氢呋喃0.108μg/mL、0.014μg/mL;四氯化碳0.16μg/mL、0.0004μg/mL;庚烷0.0075μg/mL、0.005μg/mL;甲苯0.0445μg/mL、0.0014μg/mL。在3个添加水平下,12种残留溶剂的加标回收率在90.96%~108.67%之间,相对标准偏差为0.1%~5.7%。结果表明,本法简单、快速、重现性好、准确性高,可用于实际药品中以上12种残留溶剂的检测,并可对其它药物中残留溶剂的检测提供参考。     

高效液相色谱法测定红霉素、甲红霉素和罗红霉素的研究

建立了高效液相色谱-荧光法同时测定红霉素、甲红霉素、罗红霉素的方法。该方法以9-芴代甲氧苯酰氯(FMOC-CL)为衍生试剂,以V(乙腈)∶V(磷酸二氢钾)=3∶1为反应体系,于50℃反应1 h。液相色谱分析条件为:Extend-C18柱(4.6 mm i.d.×150 mm),乙腈-25 mmoL磷酸二氢胺(pH 7)为流动相,梯度淋洗;柱温30℃,流速1.5 mL/min,激发波长255 nm、发射波长315 nm。线性范围分别为红霉素0.5~100μg、甲红霉素0.5~100μg、罗红素0.1~150μg。检出限为红霉素1μg/mL、甲红霉素1μg/mL、罗红霉素0.25μg/mL。加标回收率为90%~97%,相对标准偏差为3.5%~7.9%。     

高效液相色谱法同时测定甘草酸及其发酵产物

建立甘草酸发酵液中甘草酸及其发酵产物乌拉尔甘草皂苷乙、3-O-β-D-葡萄糖醛酸-24-OH-18β-甘草次酸、单葡萄糖醛酸甘草次酸、18α-单葡萄糖醛酸甘草次酸和甘草次酸的RP-HPLC含量测定方法,为单葡萄糖醛酸甘草次酸的生产工艺研究及产品质量控制提供方法学基础。采用Kromasil C18(250 mm×4.6 mm,5μm)色谱柱,以甲醇(B)-1%乙酸溶液(A)为流动相进行梯度洗脱:0 min,63%B;40 min,66%B;50 min,75%B;70 min,90%B;80 min,90%B。体积流速:1.0 mL/min;进样量:10μL;柱温:25℃;检测波长:254 nm。甘草酸、乌拉尔甘草皂苷乙、3-O-β-D-葡萄糖醛酸-24-OH-18β-甘草次酸、单葡萄糖醛酸甘草次酸、18α-单葡萄糖醛酸甘草次酸和甘草次酸的线性范围分别为11.25~180.0μg/mL(r=0.9986);3.031~96.99μg/mL(r=0.9978);2.595~83.00μg/mL(r=0.9999);62.50~2000μg/mL(r=0.9999);11.25~180.0μg/mL(r=0.9980);1.560~50.00μg/mL(r=0.9992);平均回收率(n=9)分别为98.3%,101.2%,98.4%,101.9%,101.7%,97.42%,RSD分别为2.5%,1.4%,0.96%,2.8%,0.73%,0.32%。     

RP-HPLC法测定复方丹参片中的隐丹参酮、丹参酮Ⅰ和丹参酮ⅡA

建立了反相高效液相色谱法测定复方丹参片(丹参、三七、冰片)中的隐丹参酮、丹参酮Ⅰ和丹参酮ⅡA。采用DiamonsilTMC18(250×4.6 mm,5μm)色谱柱,以V(甲醇)∶V(水)=75∶25为流动相,流速为0.8 mL/min,检测波长270nm。隐丹参酮、丹参酮Ⅰ和丹参酮ⅡA分别在1.456~10.19μg/mL、2.160~15.12μg/mL和3.152~22.06μg/mL的范围内呈良好线性关系,平均回收率分别为99.21%(RSD=0.63%)、100.3%(RSD=1.0%)、99.87%(RSD=0.63%)。可用于复方丹参片的质量控制。     

高效液相色谱法测定九味石灰华散中羟基红花黄色素A和红景天苷的含量

建立了测定中药复方制剂九味石灰华散中羟基红花黄色素A和红景天苷含量的高效液相色谱方法.采用Kromasil C18色谱柱(5μm,250 mm×4.6 mm),以乙腈∶0.1%磷酸溶液(12∶88,V/V)为流动相,流速1.0 mL/min,羟基红花黄色素A的检测波长为403 nm,红景天苷的检测波长为275 nm.羟基红花黄色素A和红景天苷分别在0.288~180μg/mL和4.8~1 200μg/mL范围内呈良好的线性关系(r值为0.999 8~0.999 9),最低检出限分别为0.03μg/mL和0.5μg/mL(S/N=3),加标回收率分别为95.7%~97.4%和95.9%~98.6%.该方法简便、准确、重现性好,可用于九味石灰华散的质量控制.     

固相萃取-加压毛细管电色谱法测定水体中8种农药残留

采用固相萃取-反相加压毛细管电色谱-紫外检测技术,建立了水体中乐果、敌敌畏、克百威、甲萘威、莠去津、甲基对硫磷、马拉硫磷、百菌清8种农药残留的同时检测方法。在最佳条件下,8种目标农药的线性范围分别为:3.4~100μg/mL、8.1~120μg/mL、1.2~50μg/mL、0.2~50μg/mL、0.1~50μg/mL、3.7~100μg/mL、11.2~150μg/mL、2.1~100μg/mL,相关系数为0.9961~0.9997;检出限(S/N=3)在0.03~3.7μg/mL之间,加标回收率在71.0%~114.1%范围,相对标准偏差(RSD)为1.1%~9.8%。该方法简单、可靠、适用于水中多种农药残留的同时分析测定。     

顶空进样气相色谱法测定瑞替加滨中溶剂残留

建立瑞替加滨原料药中甲醇、异丙醇、乙酸乙酯残留溶剂的测定方法。以二甲基亚砜(DMSO)为溶剂,DB–WAX123–7032石英毛细管柱为色谱分离柱,FID检测器,程序升温,氮气为载气。甲醇、异丙醇、乙酸乙酯能得到良好分离,甲醇在29.23~292.30μg/m L范围内有良好的线性,线性相关系数为0.996,平均回收率为103.83%;异丙醇在49.96~499.60μg/m L范围内有良好的线性,线性相关系数r=0.996,平均回收率为105.16%;乙酸乙酯在51.59~515.90μg/m L范围内有良好的线性,线性相关系数为0.996,平均回收率为101.36%。甲醇、异丙醇、乙酸乙酯的检出限分别为0.036,0.213,0.062μg/m L,测定结果的相对标准偏差分别为4.96%,4.52%,4.34%(n=6)。该方法灵敏度高,可用于瑞替加滨原料药中有机溶剂的检测。     

在线固相萃取净化-高效液相色谱法测定人血浆中的霉酚酸

建立了在线固相萃取净化-高效液相色谱法联用(Online SPE-HPLC)测定人血浆中霉酚酸浓度的分析方法。联用系统以Capcell PAK MF Ph-1为净化柱,Poroshell 120?EC-C18为分析柱,血浆样品经甲醇沉淀蛋白后,直接进样分析。结果表明,霉酚酸在0.20~50.00μg/mL范围内线性关系良好,相关系数(r)为0.9998,检出限和定量下限分别为0.07、0.20μg/mL。在0.39、25.00、50.00μg/mL 3个质量浓度下的平均回收率为96.2%~105%,日内和日间相对标准偏差(RSD)分别为2.6%~3.1%和2.9%~3.3%。该法操作简便、快速,可用于人血浆中霉酚酸浓度的分析。     

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.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

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.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.