2-[2-(7H-二苯并[a,g]咔唑)-乙氧基]-乙基氯甲酸酯对脂肪胺类化合物的荧光标记及质谱鉴定

利用新型荧光标记试剂2-[2-(7H-二苯并[a,g]咔唑-乙氧基)-乙基氯甲酸酯作为柱前衍生化试剂, 在Eclipse XDB-C8反相色谱柱上,采用梯度洗脱,实现了12种脂肪胺类化合物完全基线分离.检测最佳激发和发射波长分别为300和400 nm.通过荧光检测及离子阱大气压化学电离源(APCI Source)正离子模式实现了在线的柱后质谱鉴定.对土壤中脂肪胺类化合物的测定快速、准确,具有良好的重现性.荧光定量检测的回归系数大于0.9991; 检出限为10.1～0.3 fmol.     

氨基酸衍生物在毛细管区带电泳下的分离研究

采用新合成的荧光试剂咔唑-9-乙基氯甲酸酯作为柱前衍生试剂,利用毛细管区带电泳法对衍生氨基酸进行分离,考察了该试剂用于毛细管区带电泳法进行氨基酸分离的关键条件,实现了12种氨基酸的快速基线分离.     

咔唑-9-乙基氯甲酸酯柱前衍生氨基酸胶束电动色谱分离

采用一种新型紫外、荧光衍生试剂咔唑-9-乙基氯甲酸酯对9种氨基酸(丝氨酸、苏氨酸、甘氨酸、谷氨酸、天冬氨酸、缬氨酸、异亮氨酸、亮氨酸、苯丙氨酸)进行柱前衍生,采用胶束电动色谱模式在14 min内完成分离。分离条件：以pH 9.0的 20 mmol/L硼酸盐-30 mmol/L十二烷基硫酸钠(SDS)溶液（含3%(体积分数)乙腈)为缓冲溶液,柱温25 ℃,分离电压18 kV,紫外检测波长214 nm。该方法的线性范围为0.025~0.25 mmol/L,检出限为2.15~2.46 μmol/L。     

氮杂环荧光试剂2-(11H-苯[a]咔唑)乙基氯甲酸酯对胺类化合物标记及质谱鉴定

含氮类荧光试剂2-(11H-苯[a]咔唑)乙基氯甲酸酯(BCEC-Cl)经柱前衍生处理后,采用荧光检测及柱后在线质谱鉴定对食品中胺类化合物进行了测定。标记反应在pH9的硼酸缓冲液中进行,3min后获得稳定的荧光产物。衍生物于λex=279nm激发条件下产生强烈荧光,其发射波长在λem=380nm处。产物的分离在EclipseXDB-C8色谱柱(150mm×4.6mm,5μm)上进行,采用梯度洗脱对12种脂肪胺衍生物进行了优化分离。采用大气压化学电离源(APCISource)正离子模式进行在线的柱后质谱鉴定,实现了多种脂肪胺衍生物的快速、准确测定。建立的方法具有良好的重现性,回归系数大于0.9996,检出限为1.8~14fmol。     

黄金蝉若虫体蛋白水解液的荧光标记及电喷雾质谱鉴定

采用2-[2-(7H-二苯并[a,g]咔唑-乙氧基)-乙基]氯甲酸酯(DBCEC-Cl)作为柱前衍生试剂, 于室温下,在硼酸钠缓冲液(pH 9.0)中,金蝉若虫体蛋白水解液中氨基酸的完全衍生化在5 min即可完成.在Hypersil BDS C18色谱柱 (200 mm×4.6 mm, 5 μm) 上, 采用梯度洗脱实现了各衍生物的完全基线分离.最佳荧光检测为λex/λem=300/395 nm.在线串联的ESI/MS正离子质谱数据显示:所有衍生物均给出m/z 338 5,294.5的特征碎片离子峰.荧光条件下的线性回归系数大于0.9992; 检出限为2.6～24 fmol.本方法灵敏、可靠、重现性好.对实际黄金蝉若虫体蛋白水解液中氨基酸的测定,结果满意.     

GC Analysis of Amino Acids Using Trifluoroacetylacetone and Ethyl Chloroformate as Derivatizing Reagents in Skin Samples of Psoriatic and Arsenicosis Patients

The separation and determination of 19 amino acids were examined using two stages derivatization with trifluoroacetylacetone and ethyl chloroformate from the column HP-5 (30 m × 0.32 mm id) with film thickness 0.25 ??m at an initial column temperature 100 °C for 2 min with ramping of 20 °C min^?1 up to 250 °C with nitrogen flow rate of 3 mL min^?1. The detection was performed by flame ionization detector. Total separation time was 10 min. The separation was repeatable with relative standard deviation (RSD) (n = 5) within 1.5?C1.9 and 1.3?C1.7% in terms of retention time and peak height/peak area, respectively. The method was applied for the determination of amino acids from skin samples of psoriatic patients (n = 6), arsenicosis patients (n = 5) and normal subjects (n = 9) and variation in the contents of the amino acids was noted. The RSDs for the determination were obtained within 3%.     

2-(11H-苯[a]咔唑)乙基氯甲酸酯柱前衍生化用于氨基酸的高效液相色谱分析

利用新型荧光试剂2-(11H-苯[a]咔唑)乙基氯甲酸酯(BCEC-Cl)作为柱前衍生化试剂,在HypersilBDS C18(200mm×4.6mm,5μm)反相色谱柱上,采用梯度洗脱对20种氨基酸衍生物进行了分离检测。在乙腈与Na2B4O7缓冲液中,室温下BCEC-Cl与氨基酸反应5min可实现完全衍生。检测的激发和发射波长分别为λex=279nm,λem=380nm。采用柱后质谱电喷雾离子源(ESI source)正离子模式,实现了水解牛血清白蛋白中氨基酸和油菜蜂花粉中氨基酸的定性定量检测。荧光定性检测的线性回归系数均大于0.9990,检出限为1.49~19.74fmol(S/N=3)。     

荧光衍生试剂1-［2-(对甲苯磺酸酯)乙基］-2-苯基咪唑［4,5-f］9,10-菲的合成及其在长链脂肪酸分析中的应用

合成了新的荧光衍生试剂1-［2-(对甲苯磺酸酯)乙基］-2-苯基咪唑［4,5-f］9,10-菲(TSEPIP),并将其作为柱前衍生化试剂,在Eclipse XDB-C8色谱柱上采用梯度洗脱实现了11种长链(C20~C30)游离脂肪酸(FFA)衍生物的基线分离。利用柱后在线的串联质谱并以大气压化学电离源（APCI）的正离子模式实现了各组分的质谱定性。对土壤及3种苔藓(东亚毛灰藓、锦丝藓、羽平藓)中FFA组分的定量结果表明,苔藓植物从土壤中富集了大量的长链游离脂肪酸。荧光检测的激发波长和发射波长分别为260 nm和380 nm。线性回归系数大于0.9996,检测限为26.19~76.67 fmol。所建立的方法具有良好的重现性,对实际样品的测定结果令人满意。     

小波神经网络-遗传算法用于2-(9-咔唑)乙基氯甲酸酯衍生化氨基酸的胶束电动力学色谱分离优化

将小波神经网络和遗传算法应用到2-(9-咔唑)-乙基氯甲酸酯衍生化氨基酸的胶束电动力学色谱分离优化。小波神经网络结合正交试验设计用于分离过程的多因素模型建立。以训练好的小波神经网络模型为目标函数,采用实数编码的遗传算法搜寻确定最佳分离条件,在此条件下分离得到的归一化分离度积与正交试验设计中最佳条件相比,提高了12．5％。     

2-(6,7-Dimethoxy-2,3-Naphthalimido)ethyl Trifluoromethanesulfonate as a Labeling Reagent for Carboxylic Acids in Liquid Chromatography

A new, highly reactive and sensitive labeling reagent, 2-(6,7-dimethoxy-2,3-naphthalimido)ethyl trifluoromethanesulfonate, (6,7-DMNE-OTf), has been synthesized and used to determine several carboxylic acids by high-performance liquid chromatography. Reactions of the reagent with long-chain, saturated monocarboxylic acids proceed to completion within 5 min in acetone at room temperature in the presence of 18-crown-6 as a catalyst. The acid derivatives could be readily eluted with acetonitrile-water (90:10). The detection limits (signal-to-noise RATIO = 3) with ultraviolet and fluorescence detection are 10 fmol (λ_max = 282 nm) and 3 fmol (λ_ex = 282 nm, λ_em = 456 nm), respectively.     

5-羰基咪唑苯并吖啶酮对芳香胺类化合物的荧光标记及质谱鉴定

利用新型双敏感探针5-羰基咪唑苯并吖啶酮(IEBA)作柱前衍生试剂,在Aka-sil-C18反相色谱柱上,采用梯度洗脱,25min内实现6种芳香胺衍生物的快速基线分离,并通过离子阱大气压化学电离源(APCI Source)正离子模式进行在线的柱后质谱鉴定。IEBA与芳香胺的亲核取代产物不仅具有强烈的荧光,也表现出强烈的质谱离子化能力。对染色剂中芳香胺类化合物的测定快速、准确,具有良好的重现性。最大激发和发射波长为λex/λem=272/505nm,荧光定量检测的相关系数大于0.9999,检出限为0.19～0.04ng/mL。     

Phase-Transfer Catalysed Permanganate Oxidations Using Tris[2-(2-Methoxyethoxy)Ethyl]Amine (Tda-1)

Oxidation of arylmethanols with KMnO₄/TDA-1 under phase-transfer conditions at room temperature gives good to excellent yields of benzaldehydes. A number of other functional groups are also oxidised efficiently with the same reagent system.     

氨基清除树脂辅助合成2-(7-氟-3-氧-3,4-2H-苯并[b][1,4]噁嗪-6-基)异吲哚1,3-二酮

采用氨基清除树脂辅助合成方法,由6-氨基-7-氟-4-取代基-3(4H)-酮与取代邻苯二甲酸酐在冰醋酸中加热反应制备了2-(7-氟-3-氧-3,4-2H-苯并[b][1,4]噁嗪-6-基)异吲哚-1,3-二酮类化合物,纯度86％～95％．其结构经^1H NMR,IR和MS表征。     

Synthesis,Characterization and Antibacterial Activity of 3-(2-(Heterocyclo-2-ylthio)-ethoxy)benzo[d]isothiazoles

Seven novel 3-(2-(heterocyclo-2-ylthio)ethoxy)benzo[d]isothiazoles(3a~3g) have been synthesized and characterized by ESI-MS and 1H and 13 C NMR spectra. The crystal structures of 3a and 3g have been determined. Compound 3a(C_(11)H_(11)N_5O_1S_2) belongs to the monoclinic system and 3g(C_(12)H_(11)N_3OS_3) to the triclinic system. The title compounds show excellent in vitro antibacterial activities, with the minimum inhibitory concentrations varying from 4 to 32 ug/m L.     

Synthesis of Ethyl 2-Hydroxy-3-[aryl(2-naphthylamino)methyl]-2-cyclopentenecarboxylates and Ethyl 3-Arylmethylene-2-(2-naphthylamino)-1-cyclopentenecarboxylates

Condensation of N-arylmethylene-2-naphthylamines with ethyl 2-oxocycopentanecarboxylate in the presence of HCl or CH₃COOH yields ethyl 2-hydroxy-3-[aryl(2-naphthylamino)methyl]-2-cyclopentenecarboxylates and ethyl 3-arylmethylene-2-(2-naphthylamino)-1-cyclopentenecarboxylates, respectively.     

Synthesis of 2-[2-(2-aminophenyl)ethyl]-6-R-quinnoline-4-carboxylic acids from 2-[2-(2-nitrophenyl)ethenyl]-6-R-quinoline-4-carboxylic Acids

Russian Journal of Organic Chemistry -     

A Convenient Synthesis of N-[2-(Heteroarylhydrazono) Ethyl]Benzamides

The synthesis of N-[2-(heteroarylhydrazono)ethyl]benz-amides starting from (Z)-2-benzoylamino-3-chloro-2-propenoic acid and heteroarylhydrazines is reported.