超高效液相色谱-四极杆-飞行时间质谱法快速筛查化妆品中18种香豆素类化合物

建立了化妆品中18种香豆素类化合物(二氢香豆素、7-羟基香豆素、6-甲氧基-7-羟基香豆素、6,7-二甲氧基香豆素、香豆素、7-甲氧基香豆素、4-甲基-7-羟基香豆素、补骨脂素、8-甲氧基补骨脂素、7-甲基香豆素、异补骨脂素、5-甲氧基补骨脂素、4-甲基-7-乙氧基香豆素、欧前胡素、2',4,8-三甲基补骨脂素、8-羟基补骨脂素、异欧前胡素、环香豆素)的超高效液相色谱-四极杆-飞行时间质谱快速筛查方法。膏霜、水剂、香波、散粉、唇膏等不同类型的化妆品样品经超声提取后,样品提取液高速离心处理,浓缩上清液,以Oasis HLB固相萃取柱净化,经Waters ACQUITY UPLC BEH C18色谱柱(150 mm×2.1 mm,1.7μm)在10min内完成有效分离后,采用大气压化学电离-四极杆-飞行时间质谱进行筛查分析。18种香豆素类化合物的定量下限为10~60μg/kg。在低、中、高3个加标水平的平均回收率为85.2%~95.1%,相对标准偏差为3.2%~8.6%。该方法准确、快速、灵敏,为化妆品样品的高通量快速筛查提供了可靠实用的技术手段。     

化妆品中8种呋喃香豆素的高效液相色谱法检测及质谱确证

建立了同时测定化妆品中8种呋喃香豆素类化合物(8-羟基补骨脂素、补骨脂素、异补骨脂素、8-甲氧基补骨脂素、5-甲氧基补骨脂素、三甲沙林、欧前胡素和异欧前胡素)的高效液相色谱分析方法及液相色谱-串联质谱确证方法。膏霜类、水剂类、香波类、散粉类、唇膏类等不同类型的化妆品样品分别经适宜的提取溶液进行超声提取,提取液以离心处理后,取上清液经微孔滤膜过滤后测定。采用Agilent Zorbax SB-Phenyl色谱柱(250 mm×4.6 mm, 5 μm)分离,以甲醇-乙腈-水三元流动相梯度洗脱,流速1.0 mL/min,柱温30 ℃,检测波长250 nm。8-羟基补骨脂素的定量限为0.25 mg/kg,补骨脂素、异补骨脂素、8-甲氧基补骨脂素、5-甲氧基补骨脂素、三甲沙林、欧前胡素、异欧前胡素的定量限为0.5 mg/kg。在低、中、高3种加标水平下,8种待测组分的平均回收率为85.0%～105.8%,相对标准偏差为0.41%～7.90%。采用本方法在一日内不同时间点(6个时间点,每隔1 h测定一次)和不同日期(6 d内)测定混合标准溶液,得到8个目标物峰面积的日内精密度均小于1%,日间精密度均小于2%。该方法准确、简便、快速,适用于不同类型化妆品中8种呋喃香豆素类化合物的测定。     

中空纤维液相微萃取-超高效液相色谱-串联质谱法测定儿童玩具中6种致敏香豆素类化合物

建立了超高效液相色谱-串联质谱测定儿童玩具中6种致敏香豆素类化合物(香豆素、7-甲基香豆素、7-甲氧基香豆素、7-乙氧基-4-甲基香豆素、4,6-二甲基-8-叔丁基香豆素和六氢香豆素)的分析方法。样品前处理采用中空纤维液相微萃取技术,优化后的萃取实验条件为:萃取剂正辛醇,搅拌速度700 r/min,萃取时间50 min,氯化钠加入量0.7 g。萃取液经ACQUITY UPLC BEH Phenyl色谱柱(150 mm×2.1 mm,1.7μm)分离,目标化合物在电喷雾离子源正离子模式下电离,采用多反应监测模式进行定性定量分析。结果表明,6种致敏香豆素类化合物的定量限为2μg/kg(7-乙氧基-4-甲基香豆素、4,6-二甲基-8-叔丁基香豆素)或10μg/kg(香豆素、六氢香豆素、7-甲基香豆素、7-甲氧基香豆素),在10~120μg/kg范围内不同加标水平下的平均回收率为70.8%~118.9%,相对标准偏差为0.19%~16.34%(n=6)。该法准确、灵敏、可靠,适用于玩具产品的实际检验工作和产品质量控制。     

化妆品中甲氧基补骨脂素同分异构体的液相色谱法分离和测定

建立了用高效液相色谱(HPLC)-二极管阵列检测器(DAD)测定化妆品中两种呋喃香豆素同分异构体-8-甲氧基补骨脂素(8-MOP)和5-甲氧基补骨脂素(5-MOP)的简便方法。样品用甲醇超声提取,高速冷冻离心,经0.45μm滤膜过滤,注入高效液相色谱,用DAD进行扫描检测,并在301 nm波长进行分析。用保留时间结合紫外光谱图定性,外标法定量,并且采用液质联用(LC/MS/MS)确证。测试结果对8-MOP的回收率为87.0%~105.0%,RSD为0.41%~5.3%,检出限为5.0 mg/kg;5-MOP的回收率为88.0%~105.0%,RSD为0.33%~4.1%,检出限为5.0 mg/kg。本文用DAD同时分离和检测了化妆品中的8-MOP和5-MOP,方法可用于化妆品安全性监控。     

气相色谱-质谱法同时测定化妆品中5种香豆素类化合物

应用气相色谱-质谱选择离子法同时测定化妆品中5种香豆素(7-甲氧基香豆素、二氢香豆素、7-甲基香豆素、醋硝香豆素和7-乙氧基-4-甲基香豆素)。用无水乙醇为提取剂来进行超声快速提取,GC/MS进行测定,外标法定量。5种香豆素的平均回收率(n=10)在85.4%～107.6%之间,相对标准偏差在5.6%～11%之间。     

化妆品中致敏原香豆素及其衍生物的高效液相色谱法测定及质谱确证

建立了化妆品中致敏原香豆素及其7种衍生物(二氢香豆素、7-甲氧基香豆素、7-甲基香豆素、7-乙氧基-4-甲基香豆素、环香豆素、双香豆素和醋硝香豆素)的高效液相色谱测定方法。样品以0.1 mol/L氢氧化钠溶液-乙腈(1∶9,体积比)混合溶液进行超声提取,提取液经高速离心及微孔滤膜过滤后,ZORBAX SB-C18(250 mm×4.6 mm,5μm)色谱柱分离,0.05 mol/L乙酸铵溶液(含0.25%乙酸)和乙腈为流动相梯度洗脱,二极管阵列检测器检测,外标法定量。疑似阳性样品采用高效液相色谱-串联质谱法进行确证。结果表明,香豆素及其衍生物在一定浓度范围内线性良好(r2≥0.999 6),定量下限为8~20 mg/kg。在低、中、高3个加标水平下,香豆素及其衍生物的平均回收率为84.6%~100.7%,相对标准偏差(n=6)为0.8%~9.7%。该方法准确、稳定性好、特异性强,能够为化妆品检验和日常生产质量控制提供科学依据及技术支持。     

高效液相色谱法测定化妆品中香豆素类化合物

应用高效液相色谱法测定化妆品中二氢香豆素、双香豆素、7-甲氧基香豆素和醋硝香豆素、7-甲基香豆素和7-乙氧基-4-甲基香豆素6种香豆素类化合物.用无水乙醇为提取剂进行超声快速提取,优化了液相色谱分离条件,外标法定量,6种香豆素的平均回收率(n=10)在83.2%～109.5%范围,相对标准偏差在6.2%～11.0%之间...     

超高效液相串联质谱法同时测定中成药中5-甲氧基补骨脂素、8-甲氧基补骨脂素和欧前胡素

建立了同时测定中成药都梁滴丸中5-甲氧基补骨脂素、8-甲氧基补骨脂素和欧前胡素的超高效液相-串联质谱检测方法。都梁滴丸以甲醇超声提取45 min,提取液稀释后经Waters Oasis HLB固相萃取小柱净化,采用WatersACQUITY UPLC BEHC18(50 mm×2.1 mm,1.7μm)色谱柱,以乙腈(A)和水(B)为流动相进行梯度洗脱。采用电喷雾电离正离子模式,多反应监测模式检测,以保留时间和离子比定性,外标法定量。方法的定量限8-甲氧基补骨脂素和5-甲氧基补骨脂素均为0.3 mg/kg;欧前胡素为0.75 mg/kg。3种化合物在25~500μg/L范围内均呈线性,相关系数r0.99。在高,中,低三种添加水平的平均回收率为82.0%~107.4%日内精密度(RSD%)为1.1%~12%。     

高效液相色谱-串联质谱法同时测定化妆品中的两种补骨脂素

建立了高效液相色谱-串联质谱（HPLC-MS/MS）测定化妆品中 8-甲氧基补骨脂素和 5-甲氧基补骨脂素含量的方法。以甲醇提取样品,以甲醇和水为流动相,经HPLC分离后以多级反应监测(MRM)测定。两种补骨脂素在2.0~100.0 μg/L范围内线性良好,检出限均为0.10 mg/kg,回收率分别在96.88%~101.81%和94.25%~101.26%之间,相对标准偏差分别在0.40%~6.02%和0.76%~4.26%之间。     

高效液相色谱法对化妆品中17种致敏原的同时测定

建立了同时测定化妆品中17种致敏原(茴香醇、苯甲醇、香豆素、肉桂醇、丁香酚、异丁香酚、香叶醇、芳樟醇、柠檬醛、2-辛炔酸甲酯、戊基肉桂醇、水杨酸苄酯、肉桂酸苯甲酯、戊基肉桂醛、α-异甲基紫罗兰酮、α-己基肉桂醛、苧烯)的高效液相色谱方法。不同类型的化妆品样品经无水乙醇超声提取,以15000 r/m in离心15 min,取上清液过滤后测定。采用Agilent ZORBAX Ec lipse XDB-C8(4.6 mm×250 mm,5μm)色谱柱,以乙腈-水为流动相梯度洗脱,流速1.0 mL/min,采用二极管阵列检测器多波长检测(210、230、250、275、300 nm)。17种致敏原的定量下限为10~500μg/kg,线性范围内相关系数均大于0.999。在高、中、低3个添加水平下的平均加标回收率(n=5)为85%~118%,相对标准偏差为1.5%~9.7%。该方法简便、快速、准确,适用于化妆品中17种致敏原的测定。     

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.     

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.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.