固相萃取液相色谱编程荧光法测定水质中的4-氟苯胺和联苯胺

建立了固相萃取-液相色谱编程荧光法同时测定水中4-氟苯胺和联苯胺的分析方法。采用Cleanert-PCX阳离子交换固相萃取柱富集水中的4-氟苯胺和联苯胺,用5%氨水-甲醇洗脱,以乙腈-水(内含10 mmol/L的乙酸铵溶液)(20/80,V/V)为流动相,采用液相色谱荧光检测器(4-氟苯胺λex/λem=286 nm/354 nm,联苯胺λex/λem=292 nm/395 nm)分析。4-氟苯胺和联苯胺在2.0~200μg/L和1.0~100μg/L范围内,相关系数均大于0.999,方法检出限分别为0.02μg/L和0.01μg/L。在3个浓度水平加标的平均回收率为75.2%~104%,相对标准偏差在2.1%~7.6%之间。     

荧光光度法测定环境水样中的苯酚和对苯二酚

建立了荧光光度法直接测定环境水样中的苯酚和对苯二酚的新方法.通过β-环糊精增敏,三维荧光扫描选择测量波长,在波长对为λex/λem=273/307 nm时测定苯酚,苯酚的线性范围为0～1×10-4 mol/L,检出限为6.6×10-8 mol/L;在波长对为λex/λem=295/331 nm时测定对苯二酚, 对苯二酚的线性范围为0～1.5×10-5 mol/L,检出限为5.2×10-9 mol/L,回收率达到93.5%～103.5%.     

高效液相色谱-荧光分析法同时测定人体尿液中黄蝶呤与异黄蝶呤

建立了高效液相色谱-荧光法同时测定癌症病人尿液中黄蝶呤及异黄蝶呤的新方法。选择荧光检测波长λex=345nm,λem=420nm。以磷酸盐缓冲溶液(pH=7.5)-甲醇(体积比为98∶2)为流动相,流速1.0mL/min,黄蝶呤与异黄蝶呤含量分别在0.0013～0.945μg/mL及0.00017～0.118μg/mL范围内与色谱峰面积呈良好的线性关系,线性相关系数分别为0.9999和0.9996,检出限分别为0.5ng/mL和0.05ng/mL,加标平均回收率在86.2%～107.5%之间。方法应用于癌症病人尿样分析,取得了较好的结果。     

一种测定MDR肿瘤细胞内外阿霉素浓度的方法

研究提出K562／A细胞内外阿霉素浓度的反相高效液相色谱-荧光测定法．细胞内阿霉素浓度测定采用Lichrospher C18色谱柱，甲醇-0．01％醋酸(50：50，V／V)流动相,流速1．0mL／min，柱温35℃；细胞外阿霉素浓度测定采用Lichrospher C18色谱柱，甲醇-0．01％醋酸(55：45，V/V)流动相，流速0．8mL／min，柱温35℃．荧光检测器波长λex=495nm，λem=560nm，均以盐酸柔红霉素为内标．研究结果表明，该方法简单、准确、线性范围宽、检测限低，精确度和回收率良好，可用于多药耐药肿瘤细胞内外阿霉素浓度的动态变化规律研究．     

高效液相色谱法测定水中硝基苯和苯胺含量

建立了高效液相色谱直接进样快速分析水样中苯胺和硝基苯的方法.操作条件为:进样量5 μL;流速1 mL/min;流动相为V(乙腈)∶ V(3.85 g/L乙酸铵+3 g/L乙酸)=65∶ 35混合液;苯胺用荧光分析,λex/λem =280/340 nm;硝基苯用紫外分析,波长为262 nm;分离柱为Eclipse XDB2-C8 柱(150 mm×4.6 mm, 5 μm);测试时间为3.2 min;样品前处理方法:1.0 mL水样与1.0 mL甲醇混匀,用微孔滤膜(0.45 μm, 有机系)过滤.苯胺和硝基苯标准曲线的线性相关系数均 >0.999.测试苯胺、硝基苯时,仪器精密度分别为1.56%和0.13%.方法的回收率在89%～110%之间.仪器对苯胺和硝基苯的检出上限分别是50和200 mg/L; 苯胺和硝基苯的方法检出限分别是18和21 μg/L.     

反相高效液相色谱法测定人尿中利凡诺

建立了运用反相高效液相色谱法测定人尿中利凡诺的方法.采用Spherisorb C18色谱柱(250 mm×4.6 mm i.d.,5 μm);流动相: V(甲醇)∶V(乙腈)∶V(0.2 mol/L NH4Ac)=60∶37∶3;流速: 1.0 mL/min;柱温: 40 ℃;荧光检测器: 激发波长360 nm,发射波长500 nm.在5 ng/mL～1 μg/mL质量浓度范围内,呈现良好线性(r=0.9999),检出限为1 ng/mL.     

超高压液相色谱荧光检测法快速测定水中痕量苯胺与联苯胺

建立了直接进样/超高压液相色谱荧光检测法快速分析水中苯胺和联苯胺的新方法。通过研究流动相、水样pH值、水样电导率和滤器材质的影响,确定了最优化的实验方案。水样直接通过0.22μm微孔滤膜(聚四氟乙烯材质)过滤,以乙腈-3.85 g/L醋酸铵(25∶75)为流动相,荧光检测器(苯胺λex/λem=232nm/329 nm,联苯胺λex/λem=292 nm/383 nm)在0.8 min内完成分析。苯胺和联苯胺在1.0～100.0μg/L范围内线性关系良好,相关系数均大于0.999,仪器精密度(n=10)分别为0.4%和0.5%,方法检出限(S/N=3)分别为0.023μg/L和0.024μg/L,方法定量下限(S/N=10)为0.078μg/L和0.079μg/L,方法回收率为86%～106%。该方法具有前处理简单、方法检出限低、分析速度快等优点,适用于水体中苯胺和联苯胺的快速检测。     

柱切换-荧光检测反相高效液相色谱法测定血浆中特布他林浓度

采用柱切换技术 荧光检测反相高效液相色谱法测定血浆中特布他林 (TB)浓度。使用LunaC8( 2 )和KromasilC18为分析柱 ( 1 5 0mm× 4.6mm ,5 μm)和预处理柱 ( 2 5mm× 4.6mm ,5 μm) ,流动相分别为pH 3 0 ,0 .0 3 3mol/L磷酸盐缓冲液∶甲醇∶乙腈 ( 92∶7∶1 )和水∶甲醇∶乙腈 ( 97∶2∶1 ) ,流速均为 1 .0ml/L。血浆样品经乙腈沉淀蛋白后进样 ,切换时间为 3 .2～ 4.2min。荧光检测 ,λex为 2 80nm ,λem为 3 0 9nm。以沙丁胺醇作内标 ,按内标法定量。标准曲线线性范围为 0 .8～ 3 2 μg/L ;最低定量限为 0 .8μg/L;TB和内标的保留时间分别为 8.7和 9.3min;日内RSD小于 4% ,日间RSD小于 9% ,方法回收率在 93 %～ 1 1 2 %。     

2,3,4-三羟基苯乙酮缩-2-羧基苯胺与铜的高灵敏度荧光反应及其应用

合成了新荧光试剂 2 ,3,4 三羟基苯乙酮缩 2 羧基苯胺 (TAFA)。详细研究了试剂与铜的荧光反应新体系的最佳适宜条件。在 pH 9.0的乙醇 /水 (3.5∶6 .5 ,V/V)溶液中 ,该试剂与铜离子形成稳定的络合物 ,组成比为 1∶1(金属∶试剂 ) ,λex/em=4 2 2 .4 / 5 6 1.6nm。所建立的铜的荧光分析方法的线性范围为 0 .5～ 12 0 .0μg/L ;检出限为 0 .2 6 μg/L。方法成功地应用于矿泉水和水中痕量铜的测定。     

高效液相色谱共振瑞利散射联用方法检测大鼠血清中的西索米星

用高效液相色谱与共振瑞利散射方法联用对西索米星进行检测.采用滂胺天蓝(PSB)作为分子识别探针,C18反相色谱柱进行分离.流动相为含0.22％三氟乙酸的20 mmol/L醋酸钠和甲醇(92:8,V/V),流速为0.5 mL/min.柱后探针溶液流速为0.1 mL/min.共振瑞利散射(RRS)检测波长设为λex=λem...     

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.