毛细管气相色谱法测定化妆品中的酞酸酯

建立了用毛细管气相色谱配氢火焰离子化检测器测定化妆品中6种酞酸酯(邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二乙酯(DEP)、邻苯二甲酸二丁酯(DBP)、邻苯二甲酸丁基苄基酯(BBP)、邻苯二甲酸二(2-乙基己)酯(DEHP)和邻苯二甲酸二正辛酯(DOP))的方法。样品用甲醇超声提取,经高速冷冻离心,清液经干燥脱水过0.5 μm滤膜过滤,直接注入气相色谱仪进行分析。然后,经过气相色谱-电子电离-质谱检测分析,确证气相色谱-氢火焰检测的阳性检出结果。用保留时间定性,外标法定量。6种酞酸酯的回收率为82.90%～     

超高效液相色谱法测定香型中性笔墨水中10种PAEs

建立超高效液相色谱–二极管阵列检测器测定香型中性笔墨水中邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二乙酯(DEP)、邻苯二甲酸二正丙酯(DPP)、邻苯二甲酸丁基苄酯(BBP)、邻苯二甲酸二正丁酯(DBP)、邻苯二甲酸二正戊酯(DAP)、邻苯二甲酸二环己酯(DCHP)、邻苯二甲酸二正己酯(DHP)、邻苯二甲酸二(2-乙基己基)酯(DEHP)和邻苯二甲酸二正辛酯(DNOP)10种邻苯二甲酸酯(PAEs)的方法。样品采用甲醇涡旋超声提取,色谱柱为Waters ACQUITY UPLC BEH C_(18)柱(100 mm×2.1 mm,1.7μm),以乙腈–水为流动相进行梯度洗脱,用PDA检测器检测,10 min内完成10种邻苯二甲酸酯的检测。10种邻苯二甲酸酯的质量浓度在5.0~200.0 mg/L范围内与其色谱峰面积呈良好的线性关系,线性相关系数均大于0.999,检出限为3.2~4.0 mg/kg;在高低两个添加水平下,10种邻苯二甲酸酯的回收率为96.3%~104.1%,测定结果相对标准偏差为0.1%~2.9%(n=6)。该方法样品处理简单,提取效率高,分离效果好,且灵敏度高,能快速准确测定香型中性笔墨水中10种邻苯二甲酸酯。     

高效液相色谱二极管阵列检测器测定化妆品中的6种酞酸酯

建立了用高效液相色谱二极管阵列检测器测定化妆品中6种酞酸酯——邻苯二甲酸二甲酯(DMP)、二乙酯(DEP)、二丁酯(DBP)、丁基苄基酯(BBP)、二(2-乙基己)酯(DEHP)和二正辛酯(DOP)的方法一样品用甲醇超声提取．高速冷冻离心,经0．5μm滤膜过滤．直接注入高效液相色谱．在280nm波长进行分析用保留时间结合酞酸酯紫外光谱定性．外标法定量该法的回收率为85％～110％．精密度RSD为0．058％～2．84％．检出限：DMP．DEP、BBP和DBP均为5ng．DEHP和DOP为10ng,该方法准确度和灵敏度高．样品用量少．前处理简单。可同时测定化妆品中6种酞酸酯化合物。     

胶束电动毛细管色谱测定塑料食品包装袋中邻苯二甲酸酯类化合物的研究

采用胶束电动毛细管色谱法对5种邻苯二甲酸酯类化合物(邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二乙酯(DEP)、邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二(2-乙基己基)酯(DEHP))和邻苯二甲酸二正辛酯(DOP))进行了分离研究,考察了溶液的pH值、胶束浓度和有机改性剂等对分离的影响。结果表明:以5 mmol/L硼砂-25 mmol/L十二烷基硫酸钠(SDS)-15%(体积分数)甲醇溶液为电泳缓冲液(pH 9.2),采用压力进样方式,25 kV恒压下进行分离,在波长200 nm处检测,各组分在17 min内可达到基线分离。DMP、DEP、DBP、DEHP和DOP的检出限分别为0.13 mg/L、0.14 mg/L、0.38 mg/L0、.13 mg/L和0.10 mg/L。本法应用于塑料食品袋中邻苯二甲酸酯类化合物的测定,回收率范围为81.80%~118.87%,峰面积的相对标准偏差(RSD)小于4.30%(n=10),测定结果满意。     

两种色谱法对塑料食品包装袋中邻苯二甲酸酯类化合物的分析

建立了毛细管气相色谱和薄层色谱测定5种邻苯二甲酸酯类化合物（邻苯二甲酸二甲酯（DMP）、邻苯二甲酸二乙酯（DEP）、邻苯二甲酸二丁酯（DBP）、邻苯二甲酸二正辛酯（DOP）和邻苯二甲酸二（2．乙基己基）酯（DEHP））的方法。样品用乙醇浸泡，超声提取，0．5p．m滤膜过滤。进行气相色谱和薄层扫描分析。气相色谱回收率：88．85％-120．19％，精密度RSD为1．6％-3．2％，检出限DMP、DEP、DBP、DOP和DEHP分别为2．0、1．8、2．6、3．2和3．1ng，两种方法均样品用量少，分离效果好。区别在于前者灵敏度、回收率高，后者样品前处理简单、费用低。各有优势。     

计算机拟合技术研究C18柱在富集PAEs时的萃取条件

利用固相萃取技术富集了水中5种邻苯二甲酸酯类(邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二乙酯(DEP)、邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二(2-乙基己基)酯(DEHP)、邻苯二甲酸二辛酯(DOP)).借助均匀设计法及计算机回归建模优化技术对5种PAEs的固相萃取条件进行了设计与优化,得到最佳固相萃取条件为: 洗脱剂配比: V(正己烷)∶V(丙酮)=30∶1,洗脱体积2 mL,洗脱流速为4 mL/min,上样流速8 mL/min.富集后的样品用带电子捕获检测器的毛细管气相色谱检测,方法的线性范围为1～1000 μg/L (DMP,DEP,DOP),0.2～100 μg/L (DBP,DEHP);线性回归方程的相关系数为0.9970～1.000,检出限为0.02～0.4 μg/L,方法回收率为69%～117%,相对标准偏差为2.2%～9.5%.     

基质固相分散-液相色谱-质谱法测定蔬菜中的邻苯二甲酸酯

采用基质固相分散-液相色谱-质谱法测定保护地蔬菜中邻苯二甲酸酯(PAEs)含量,并分析了蔬菜中PAEs污染状况,研究了水和洗涤液浸泡对蔬菜中PAEs的消除效果。蔬菜样品经弗罗里硅土和石墨化碳黑研磨均匀后,用乙酸乙酯淋洗净化,再用液相色谱/电喷雾质谱法测定。PAEs的添加回收率为82.7%~105.7%;RSD为1.7%~6.1%;检出限为邻苯二甲酸二甲酯(DMP):0.99ng;邻苯二甲酸二乙酯(DEP):0.75ng;邻苯二甲酸二丁酯(DBP):0.70ng;邻苯二甲酸二异辛酯(DEHP):1.9ng。本方法前处理简单,具有较高的准确度和灵敏度。黄瓜、番茄、西葫芦中4种PAEs总量分别为2.02、1.26、0.91mg/kg;洗涤实验结果表明,水和洗涤液浸泡可显著降低蔬菜中的PAEs含量。     

水产中多种酞酸酯气-质联用分析研究

将气相色谱-电子轰击离子源-质量法(GC-EI-MS)应用于水产中多种酞酸酯的分析,其前处理方法采用超声提取-柱层析净化预分离。该方法具有较大的线性范围(20.0~800μg/kg,相关系数大于0.9995),较好的精密度(RSD≤14%),较低的检出限(LODDMP=0.711μg/kg;LODDEHP=5.67μg/kg),加标回收率在63.7%~116%之间。应用于文蛤、海带和章鱼样品分析,均检测出DBP和DEHP,在海带和章鱼中还分别检测出少量的DMP与DEP。     

液相微萃取-气相色谱法测定水样中邻苯二甲酸酯

建立了水试样中5种痕量邻苯二甲酸酯的单液滴液相微萃取-气相色谱检测方法。确定了对单液滴液相微萃取(SDME)的最佳实验条件。DMP、DEP、DBP、DEHP和DOP的方法检出限分别为0.042、0.0037、0.0097、0.045和0.23μg/L。将该方法应用于某江水、湖水、自来水和饮用纯净水试样的检测,相对标准偏差(RSD)在1.4%~14.0%;回收率在90.8%~107.0%。本方法简单、快速并且成本低、可信度高。     

快速提取-超高效液相色谱法测定唇膏中11种酞酸酯

建立快速提取–超高效液相色谱法测定唇膏中11种酞酸酯的检测方法。将唇膏样品涂覆在定量滤纸上,用甲醇涡旋超声提取,色谱柱采用Waters ACQUITY UPLC BEH C_(18)柱(100 mm×2.1 mm,1.7μm),流动相为乙腈–水,梯度洗脱,流量为0.5 mL/min,用PDA检测器检测,检测波长225 nm。以3倍空白噪音计,邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二乙酯(DEP)的检出限分别为1,2 mg/kg;邻苯二甲酸二丙酯(DPRP)、邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二戊酯(DPP)、邻苯二甲酸二己酯(DHXP)、邻苯二甲酸丁基苄基酯(BBP)、邻苯二甲酸二(2–乙基)己酯(DEHP)、邻苯二甲酸二正辛酯(DNOP)的检出限为3 mg/kg;邻苯二甲酸二异壬酯(DINP)、邻苯二甲酸二异癸酯(DIDP)的检出限为30 mg/kg。方法的加标回收率为86.6%~98.6%,测定结果的相对标准偏差为0.6%~6.0%(n=6)。该方法样品处理简单,提取效率高,分离效果好且灵敏度高,结合色谱图和紫外光谱图,能快速准确测定唇膏中11种酞酸酯。     

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.