基于HPLC指纹图谱和化学模式识别的关节痛消颗粒的质量评价研究

采用HPLC法建立关节痛消颗粒的指纹图谱用于其质量评价。采用Welch C18色谱柱(4.6 mm×250 mm, 5μm),流动相为乙腈-0.1%磷酸水溶液,梯度洗脱,流速0.8 mL·min^-1,柱温35℃,检测波长为330nm,对建立指纹图谱的主要特征峰进行标定,采用相似度软件,结合系统聚类分析(HCA)、主成分分析(PCA)和SIMCA 13.0软件进行偏最小二乘法-判别分析(PLS-DA),分析制剂中化学指纹信息。建立了专属性、精密度、重复性和稳定性均良好的关节痛消颗粒HPLC指纹图谱,15批制剂的指纹图谱相似度为均大于0.9,确定共有峰为15个,共有4个主要特征峰得到明确的化学指认,其中已标定的色谱峰11(淫羊藿苷)、7(松果菊苷)、4(肉桂酸)是影响样品质量的标志性差异物质。通过HPLC指纹图谱和化学模式识别可较好的辨识关节痛消颗粒的标志性成分,为其质量标志物的辨识提供了参考。     

苦参配方颗粒的高效液相色谱指纹图谱研究及定量分析

研究了苦参配方颗粒的指纹图谱和含量测定。采用高效液相色谱法,在C18柱上以乙腈-磷酸氢二钠水溶液(20 mmol/L,磷酸调pH 7.1)进行梯度洗脱,柱温35℃,检测波长220 nm,用指标成分氧化苦参碱、氧化槐果碱和苦参碱进行了定位,并在同一色谱条件下同时测定了它们的含量。确定了15个共有峰,其中7、8和11号峰分别为氧化苦参碱、氧化槐果碱和苦参碱。10批样品平均相似度为0.99以上,三个成分的含量分别为:氧化苦参碱50.0~79.8 mg/g;氧化槐果碱13.5~18.1 mg/g;苦参碱16.5~30.1 mg/g。结果表明:指纹图谱与指标成分含量测定相结合,可提高苦参配方颗粒的内在质量控制水平。     

高效液相色谱-管碟法联合分析牛黄解毒片中抑菌物质黄芩苷、甘草苷

联合运用高效液相色谱法和管碟法分析牛黄解毒片中抑菌物质黄芩苷、甘草苷。以Diamonsil C₁₈柱(250mm×4.6 mm,5μm)为分析柱,0.15%磷酸水溶液为流动相A、乙腈为流动相B,流量为1.0 mL/min,检测波长为280nm,柱温为30℃,进样体积为10μL。采用高效液相色谱法测定12批不同厂家的牛黄解毒片,记录色谱图;运用《中药色谱指纹图谱相似度评价系统》(2012年版)建立指纹图谱,并进行相似度评价和共有峰指认。采用管碟法,以阿莫西林为对照,测定牛黄解毒片对金黄色葡萄球菌的抑菌活性;使用SPSS 21.0软件对牛黄解毒片的抑菌活性指标值与指认峰峰面积进行灰色关联度分析。建立高效液相色谱指纹图谱,12批不同厂家牛黄解毒片的相似度均不低于0.937,并确认甘草苷与黄芩苷为共有峰;甘草苷的灰色关联度值为0.696,黄芩苷的灰色关联度值为0.680。黄芩苷与甘草苷是牛黄解毒片中的2种抑菌物质。     

邓老凉茶颗粒的超高效液相色谱质谱联用指纹图谱研究

建立了适用于邓老凉茶颗粒质量控制的超高效液相色谱质谱联用指纹图谱分析方法。样品采用甲醇索氏萃取60 min,萃取液采用超高效液相色谱质谱法进行指纹图谱分析。色谱柱采用Waters ACQUITY HSST3 C18(150 mm×3.0 mm,1.8μm),以0.5%甲酸-乙腈为流动相进行梯度洗脱,流速为0.8 mL/min,柱温35℃。质谱采用负离子ESI模式,选择基峰离子流质量色谱图进行指纹图谱研究。32个共有峰在15 min内得到良好分离,其中15个共有峰通过对照品进行了确证。通过《中药色谱指纹图谱相似度评价系统2004A版》对邓老凉茶颗粒样品进行相似度分析,15个批次样品的相似度均达到0.960以上,表明邓老凉茶颗粒的产品质量稳定性很好。以32个共有峰的相对峰面积进行主成分分析,邓老凉茶颗粒样品之间的细微质量差异得到明显区分。该方法快速、高效、可靠,可有效地用于邓老凉茶颗粒的质量控制。     

高效液相色谱法测定感冒止咳颗粒中黄芩苷的含量

采用高效液相色谱(HPLC)法,用C18色谱柱,甲醇-水-冰乙酸为(55:45:1,V/V/V)流动相,在波长276 nm处测定感冒止咳颗粒中黄芩苷的含量.黄芩苷在0.101～1.01μg范围内与峰面积有良好的线性关系(r=0.9998),平均回收率为100.26%,相对标准偏差为1.52%(n=6).该法操作简便,分析速度快,结果准确,可用于感冒止咳颗粒中黄芩苷含量的测定.     

益肾排石方的指纹图谱及功效关联物质的作用机制北大核心CSCD

应用液质联用技术分析了益肾排石方中的化学成分,建立高效液相色谱法(HPLC)指纹图谱,结合生物信息学技术对关键成分、关键靶点和通路进行了预测分析。应用超高效液相串联质谱技术(UHPLC-MS/MS)对益肾排石方中的化学成分进行了鉴定。10批益肾排石方样品,应用HPLC建立指纹图谱,标记共有峰,进行共有峰归属,并进行相似度评价。应用生物信息学技术,基于指认出的成分,建立了“中药-成分-靶点”网络图,通过GEO数据库获得了肾结石相关的差异基因。对方中功效关联物质的作用机制进行了进一步的分析,并进行了分子对接验证。通过数据库匹配、元素组成和碎片结构分析,共从益肾排石方中鉴定出32种成分;在对10批益肾排石方的指纹图谱的建立过程中,通过对照品指认确定了王不留行黄酮苷、松脂醇二葡萄糖苷、虎杖苷、黄芩苷、黄芩素、汉黄芩苷、芦丁、木蝴蝶苷A、大黄酸、异橙黄酮、芦荟大黄素、白杨素、大黄酚、厚朴酚、大黄素甲醚、汉黄芩素和大黄素17个共有峰,10批益肾排石方相似度结果均在合理范围内,且17个共有峰均能归属到虎杖、黄芩、牛膝、柴胡、金钱草、枳实、大黄、厚朴、杜仲和王不留行10味中药。结合生物信息学筛选了ESR1和PTGS1为关键基因,与17种药效成分进行分子对接验证,预测大黄酸和王不留行黄酮苷为关键成分。     

超高效合相色谱法定性与定量分析补肾健脑颗粒

用超高效合相色谱法(Ultra performance convergence chromatography,UPC2)建立补肾健脑颗粒及各药材提取物的指纹图谱,对补肾健脑颗粒主要色谱峰进行归属分析,并测定有效成分β-蜕皮甾酮和松果菊苷的含量。样品经乙醇提取后,进样1μL,用Waters ACQUITY UPC2TMBEH柱(100 mm×3.0 mm,1.7μm)分离,柱温为40℃,以超临界CO2-0.05%H3PO4-甲醇溶液为流动相,梯度洗脱,流速为0.8 m L/min。分析补肾健脑颗粒和各药材提取物的UPC2指纹图谱,利用各峰相对保留时间、紫外光谱图及部分对照品归属主峰。结果表明,补肾健脑颗粒UPC2指纹图谱中15个主峰来源明确,其中12号峰为β-蜕皮甾酮,含量为380μg/g,15号峰为松果菊苷,含量为9.562 mg/g。与HPLC和UPLC法相比,本方法简便、快速,精密度高,重现性好。     

银黄口服液的质量控制及其高效液相色谱指纹图谱的研究

利用高效液相色谱方法,建立了复方银黄口服液及其原料药材黄芩和金银花的指纹图谱,测定了银黄口服液中黄芩苷 和绿原酸的含量。以Lichrospher C18色谱柱(250 mm×4.6 mm i.d.,5 μm)为分离柱,以甲醇和0.1%磷酸水溶液为流动 相进行二元梯度洗脱,流速0. 6 mL/min,在254 nm波长下检测。采用夹角余弦和相关系数的方法,计算6批银黄口服液指 纹图谱的相似度均在0.99以上,表明银黄口服液的质量未见显著差异。将银黄口服液指纹图谱中的共有峰与原料药材黄芩 和金银花的指纹图谱中的共有峰相比较,对其归属进行确认,大部分共有峰可以匹配。     

基于指纹图谱、量值传递及化学计量学的薏苡竹叶散质量评价

建立高效液相指纹图谱进行外部质量控制,结合化学计量学探究内部质量影响因素,通过量值传递规律确定制备工艺稳定性,全面完善薏苡竹叶散（YZP）质量评价系统。利用《中药色谱指纹图谱相似度评价系统》（2012.130723版本）绘制15批YZP指纹图谱并评价相似度;选择Origin 2019b 64Bit进行聚类分析（CA）,利用SIMCA 14.1进行主成分分析（PCA）和正交偏最小二乘判别分析（OPLS-DA）,获得导致质量差异的主要成分;测定15批淡竹叶药材和YZP中荭草苷和异荭草苷的含量,探究样品制备过程中的量值传递规律。结果表明,15批YZP指纹图谱得到21个共有峰,指认了6种成分,分别为9号峰（异荭草苷）、10号峰（荭草苷）、13号峰（牡荆素）、14号峰（异牡荆素）、15号峰（连翘酯苷A）和20号峰（连翘苷）,相似度在0.956～0.995之间,符合相关规定;CA结果显示,15批YZP被分为两类,PCA共得到3个主成分,累计贡献率82.4%,OPLS-DA得出10个贡献率较大成分,包括已指认出的9号峰（异荭草苷）、13号峰（牡荆素）和20号峰（连翘苷）,有利于进一步质量评价;15批...     

王老吉广东凉茶颗粒的超高效液相色谱指纹图谱研究

建立了适用于王老吉广东凉茶颗粒质量控制的超高效液相色谱指纹图谱分析方法。样品采用甲醇超声萃取30 min,萃取液用超高效液相色谱法进行指纹图谱分析。色谱柱采用Waters ACQUITY HSS T3 C18(3.0mm×150 mm,1.8μm),以0.5%甲酸-乙腈为流动相进行梯度洗脱,流速为0.8 mL/min,柱温35℃。28个共有峰在18 min内得到良好分离,通过对照品对其中4个峰进行了确证。对王老吉广东凉茶颗粒样品进行了相似度分析,23个批次样品的相似度均达到0.95以上;以28个共有峰的相对峰面积进行主成分分析,23批次样品均落在同一区域。相似度评价和主成分分析结果均表明,王老吉广东凉茶颗粒的产品质量稳定性好。该方法快速、高效、稳定,可用于王老吉广东凉茶颗粒的质量控制。     

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.