超高效液相色谱法同时测定肿节风中6个成分的含量

建立了同时测定肿节风中新绿原酸、绿原酸、隐绿原酸、咖啡酸、迷迭香酸、异嗪皮啶6个成分含量的超高效液相色谱方法。采用Waters Acquity UPLC BEH C_(18)柱(2.1 mm×50 mm,1.7μm)分离,以乙腈-水(各含0.1%甲酸)为流动相进行梯度洗脱,流速为0.5 mL·min~(-1),检测波长330 nm,柱温35℃;以异嗪皮啶为参照物,计算其与其余5种目标物的相对校正因子,并考察了不同色谱仪、色谱柱、流动相、流速、柱温对相对校正因子重现性的影响;通过相对校正因子计算各成分的含量,实现一测多评,同时采用外标法测定肿节风中各成分的量,并对一测多评计算值与外标法实测值进行配对t检验。肿节风中新绿原酸、绿原酸、隐绿原酸、咖啡酸、迷迭香酸、异嗪皮啶分别在0.522 0~26.09,1.482~74.13,0.591 0~29.49,0.632 5~31.29,2.612~130.5,0.970 4~48.73μg·mL~(-1)范围内线性关系良好(r≥0.999 7),仪器精密度、方法重复性、样品稳定性的相对标准偏差(RSD)均不大于1.9%,平均加标回收率为98.6%~101.5%,RSD(n=6)不大于1.9%。所建立的相对校正因子重现性良好,外标法实测值与一测多评法计算值无显著性差异(P0.05),均可用于肿节风中5个咖啡酰类和1个香豆素类成分的同时定量测定。     

RP-HPLC法同时测定复方公英片中3种活性成分的含量

本实验建立了RP-HPLC法同时测定复方公英片(板蓝根、蒲公英)中(R,S)-告依春、咖啡酸、阿魏酸3种成分的含量。采用Agilent ZORBAX SB-C_(18)(4.6mm×250mm,5μm)色谱柱,以甲醇(A)-0.1%磷酸水溶液(B)为流动相,梯度洗脱,流速1.0mL·min~(-1),柱温30℃,进样量5μL,检测波长为245nm((R,S)-告依春)、320nm(咖啡酸、阿魏酸)。结果(R,S)-告依春、咖啡酸、阿魏酸的质量浓度在0.595～5.950mg·mL~(-1)、0.291～2.91mg·mL~(-1)、0.009～0.082mg·mL~(-1)范围内与色谱峰面积呈良好的线性关系,精密度、稳定性和重复性良好,平均加样回收率分别为99.51%(RSD=1.75%)、99.50%(RSD=1.84%)、99.36%(RSD=1.69%)。该方法简便、快速、准确,可作为复方公英片的质量控制提供依据。     

超高效液相色谱-蒸发光散射检测法同时测定重楼消瘤方中5种皂苷类成分含量

建立了同时测定抗肿瘤中药复方——重楼消瘤方中重楼皂苷Ⅰ、重楼皂苷Ⅱ、重楼皂苷Ⅶ、柴胡皂苷a、柴胡皂苷d 5种皂苷类成分含量的超高效液相色谱-蒸发光散射检测(UPLC-ELSD)法。复方制剂经甲醇提取,采用Waters Cortecs UPLC C₁₈(150 mm×2.1 mm,1.6μm)色谱柱分离,乙腈-水为流动相进行梯度洗脱,蒸发光散射检测器进行检测,以外标法定量。结果显示,5种皂苷类成分的分离度良好,分别在7.1174～177.94μg/mL、 9.4072～235.18μg/mL、 8.8726～221.82μg/mL、 7.4862～187.15μg/mL、9.761 3～244.03μg/mL范围内线性关系良好,相关系数(r)为0.999 2～0.999 8,检出限为0.7～1.0μg/mL,定量下限为1.8～2.4μg/mL;平均回收率分别为93.9%、103%、102%、104%、105%,相对标准偏差(RSD)分别为3.8%、4.0%、4.2%、3.6%、3.2%。该方法简便、快速、准确,可同时对重楼消瘤方中的5个皂苷类成分进行分析,能有效地消...     

高效液相色谱双波长切换法测定石韦配方颗粒中8种有效成分

建立高效液相色谱双波长切换法同时测定石韦配方颗粒中原儿茶酸、咖啡酸、绿原酸、新绿原酸、隐绿原酸、异绿原酸A、异绿原酸B、异绿原酸C 8种成分含量。采用Waters Atlantis T3-C₁₈色谱柱(250 mm×4.6 mm,5μm),以乙腈-0.1%(体积分数)磷酸溶液作为流动相梯度洗脱,流量为1.0 mL/min,柱温为30℃,检测波长为260 nm和330nm,进样体积为10μL。8种成分在各自质量浓度范围内与色谱峰面积线性关系良好,相关系数均为0.999 9,方法检出限为16.45～89.15μg/L,加标平均回收率为95.76%～99.86%,测定结果的相对标准偏差为0.07%～0.44%(n=6)。该方法操作简单、高效,能同时检测石韦配方颗粒中8种成分的含量,可用于石韦配方颗粒样品中的含量测定及产品质量监控。     

高效毛细管电泳-紫外检测法快速分离测定三种抗肿瘤药物

肿瘤发生率近年呈明显升高趋势,建立快速、灵敏的抗肿瘤药物分离检测新方法,对指导临床用药,了解药物在体内的代谢等具有重要意义。建立了高效毛细管电泳-紫外检测法快速分离测定10-羟基喜树碱(10-Hydroxy camptothecin,10-HCPT)、6-巯基嘌呤(6-mercaptopurine,6-MP)、5-氟尿嘧啶(5-Fluorouracil,5-Fu)3种抗肿瘤药物的方法。考察了检测波长、分离电压、进样时间、缓冲液的pH值及离子强度对分离效果的影响。以未涂层熔融的石英毛细管(60.2cm×75μm,有效长度50cm)为分离柱,50.0 mmol·L~(-1)硼砂-200.0 mmol·L~(-1)硼酸(pH 8.4)为分离缓冲液,分离电压为21kV,柱温为25℃,0.5psi压力进样5s,于214 nm波长下检测,3种抗肿瘤药10min内能够完全分离。在最佳分析条件下,3类抗肿瘤药物分别在0.1～50.0μg·mL~(-1)、0.5～50.0μg·mL~(-1)、0.2～50.0μg·mL~(-1)范围内线性良好,相关系数r0.9990。对3种抗肿瘤药物平行测定7次,相对标准偏差(RSD)均低于0.85%,检出限(S/N)分别为0.05μg·mL~(-1)、0.2μg·mL~(-1)、0.1μg·mL~(-1),加标回收率为90.4%～103.8%。整个试验过程未使用有机溶剂,方法用于尿样、血样样品的测定,结果令人满意,为临床对10-HCPT、6-MP、5-Fu 3种抗肿瘤药物的用药监测提供了更加简单快速的分析方法。     

高效液相色谱法测定贯叶连翘中的4种成分

本文利用高效液相色谱法同时测定中药贯叶连翘中绿原酸、芦丁、金丝桃苷和槲皮素四种成分的含量。采用Tiahhe Kromasil C18 100 A(5μm,250mm×4.6 mm)反相色谱柱;流动相为V(乙腈)∶V(水)=20∶80(含0.02%三氟乙酸);紫外检测波长270nm;流速1.0 ml/min;柱温40℃。绿原酸、芦丁、金丝桃苷和槲皮素线性范围分别为3.4~34μg.mL-1(r=0.9993),1.8~18μg.mL-1(r=0.9998),2.3~23μg.mL-1(r=0.9999),3.5~35μg.mL-1(r=0.9991),平均回收率(n=5)分别为98.4%(RSD=1.48%),101.8%(RSD=0.74%),103.7%(RSD=0.77%),103.5%(RSD=1.28%)。方法线性范围宽、相对标准偏差低、精密度高、重现性好,应用于贯叶连翘及制剂样品的测定,结果令人满意。     

高效液相色谱-串联质谱法检测发酵液中的印楝素A

建立了一种高效液相色谱-电喷雾电离串联质谱联用仪(HPLC-MS/MS)检测发酵液中印楝素A的方法。样品经有机溶剂萃取,旋转蒸发浓缩,乙腈溶解定容,以Kinete C_(18)色谱柱(2.1 mm×100 mm,2.6μm)分离。流动相0.1%甲酸乙腈溶液和0.1%甲酸水溶液,体积比为45:55,总流速为0.2 mL·min~(-1)。电喷雾正离子电离(ESI~+)方式,多反应监测(MRM)模式下进行质谱检测,基质匹配外标法定量。目标物在6～48 ng·mL~(-1)之间线性关系良好,相关系数R=0.9993,检出限(3S/N)为0.5 ng·mL~(-1),日间重复性RSD=1.279%(n=3)。三个添加水平下(6、24、48 ng·mL~(-1))平均回收率为81.5%～87.4%,RSD为3.1%～4.4%。该方法样品前处理简单,分析时间短,准确度、精确度高,可用于发酵液中印楝素A的痕量检测。     

乙醇敏化钛黄与蛋白质作用的共振光散射光谱研究及其分析应用

研究了在乙醇存在下钛黄（TY）与蛋白质作用的共振光散射（RLS）光谱特征 。基于RLS的增强,建立了一种测定蛋白质的新方法。考察了各种影响因素,在优 化条件下确定了RLS强度与蛋白质浓度之间的关系。当TY浓度为4 * 10~(-5)mol· L~(-1)时,牛血清白蛋白（BSA）、人血清白蛋白（HSA）和溶菌酶(lysozyme)的线 性响应范围分别为0.1～6.0 μg·mL~(-1), 0.1～5.0 μg·mL~(-1), 0.2～3.0 μg·mL~(-1),检出限分别为12.7 ng·mL~(-1), 11.6 ng·mL~(-1)和18.8 ng· mL~(-1)。三种合成样品五次平行测定的回收率和相对标准偏差（RSD）分别为96. 0%～102.3%和0.8%～3.2%。将该方法与经典的Bradford方法分别用于人血清试样中 蛋白的测定,两种方法的分析结果经F-检验和双总体T-检验证明无显著性差异。     

HPLC法同时测定24种花中的5种活性成分含量

建立了高效液相色谱法(HPLC)同时测定24种花中绿原酸、金丝桃苷、槲皮素、木犀草素和异鼠李素含量的方法。采用C18柱(250 mm×4.6 mm,5μm),流动相为甲醇-0.2%冰乙酸溶液梯度洗脱,检测波长350 nm,柱温35℃,流速0.8 mL/min。绿原酸、金丝桃苷、槲皮素、木犀草素和异鼠李素分别在0.0208~104.00μg/mL(r=0.99993),0.017~85.00μg/mL(r=0.99998),0.0172~86.00μg/mL(r=0.99997),0.0304~152.00μg/mL(r=0.99997),0.0168~84.00μg/mL(r=0.99986)范围内与峰面积呈良好的线性关系,平均加标回收率(n=9)92.26%~99.09%,仪器精密度(n=6)RSD均小于3.1%,方法重复性(n=6)的RSD均小于3.6%。方法可同时测定这24种花中绿原酸和黄酮类物质的含量,可作为花中活性成分定量分析的方法。     

HPLC法测定地胆草中绿原酸的含量

建立了用高效液相色谱法测定地胆草中绿原酸含量。选择Agilent TC-C18色谱柱(250 mm×4.6 mm,5μm),甲醇-0.1%磷酸溶液(20∶80)为流动相,流速1.0 mL/min,检测波长328 nm,进样量10μL。结果表明,绿原酸0.044 9~4.488 0μg范围内线性关系良好(r=0.999 9),平均加样回收率为99.63%,RSD为0.61%(n=9)。所用方法专属性强、快速准确,可作为地胆草中绿原酸含量的测定方法。     

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.