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1.
采用新型荧光衍生试剂2-(11H-苯[a]咔唑)-乙酸(BCA)进行柱前衍生并经荧光检测对脂肪胺进行高效液相色谱(HPLC)分离和质谱定性.衍生物荧光激发和发射波长为λex=285 nm,λem=384 nm.60 ℃下在乙腈溶剂中用N-乙基-N′-[(3-二甲氨基)丙基]碳二亚胺盐酸盐(EDC)作催化剂, 衍生反应15 min后获得稳定的荧光产物.在Hypersil BDS C18 (4.0 mm×200 mm, 10 μm) 色谱柱上, 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(APCI Source)正离子模式进行质谱定性, 实现了各种脂肪胺衍生物的快速、准确测定.脂肪胺的线性回归系数不小于0.999 8 , 检出限(S/N=3)为5.73 ~31.3 fmol.  相似文献   

2.
合成了一种新的荧光试剂[1,2-苯并-3,4-二氢咔唑-9-乙基肼基甲酸酯(以下简写作BCEC)]并在酒中脂肪醛高效液相色谱(HPLC)分离及测定中作为柱前衍生试剂.衍生反应在乙腈溶剂中,用三氯乙酸作催化剂并在60 ℃条件下进行,并能在10 min后获得稳定的荧光产物.用Zorbax Eclipse XDB C8(4.6 mm×150 mm,5 μm)作色谱柱,并以不同浓度的乙腈-水溶液作流动相进行梯度淋洗.采用荧光检测,检测的激发波长为333 nm,发射波长为390 nm.采用在线质谱检测对10种脂肪醛进行定性鉴定,醛的物质的量在0.166 5~83.3 fmol之间与其色谱峰面积呈线性关系,相关系数均优于0.999 9 ,被测各醛的检出限(S/N=3)在3.75~16.65 fmol之间.  相似文献   

3.
采用新型荧光衍生试剂2-(9-吖啶酮)-乙酸(AAA)进行柱前衍生并经荧光检测对脂肪胺进行了高效液相色谱(HPLC)分离和在线质谱定性.衍生物荧光激发和发射波长为λex=404nm,λem=440nm.30℃下在乙腈溶剂中用N-乙基-N′-[(3-二甲氨基)丙基]碳二亚胺盐酸盐(EDC)做催化剂,衍生反应20min后获得稳定的荧光产物.在HypersilBDSC18(4.6mm×100mm,5μm)色谱柱上,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柱后质谱定性,实现了各种脂肪胺衍生物的快速、准确测定.该方法具有良好的重现性,多数脂肪胺的线性回归系数大于0.9996,检测限为12.09~25.52fmol.  相似文献   

4.
黄金蝉若虫体蛋白水解液的荧光标记及电喷雾质谱鉴定   总被引:1,自引:0,他引:1  
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.  相似文献   

5.
在HypersilODS2色谱柱上,利用新型荧光试剂1,2-苯并-3,4-二氢咔唑-9-乙基肼基甲酸酯(BCEC)作柱前衍生化试剂,采用梯度洗脱对5种中性糖荧光衍生物进行了优化分离.65℃下在乙腈溶剂中以冰乙酸作催化剂,衍生反应6.5h后获得稳定的荧光产物,衍生反应完全.激发和发射波长分别为λex=333nm,λem=390nm.线性回归系数均在0.999以上,检测限为24.3~62.1fmol.  相似文献   

6.
以冰醋酸为溶剂和催化剂,苯偶酰/9,10-菲醌、3-吲哚甲醛/3-咔唑甲醛及醋酸铵经"一锅"反应高效合成了系列含吲哚或咔唑结构单元的多取代咪唑衍生物.考察了反应物配比、溶剂的选择和用量及温度等因素对反应的影响,研究了所合成化合物的光物理性能;筛选出对p H值敏感且结构独特的两个化合物作为p H荧光探针,检测在其作用下MCF-7细胞在不同p H值环境中的荧光成像,结果表明探针2-(9-苄基-9H-咔唑-3-基)-4,5-二苯基-1H-咪唑(2d)和2-(9-苄基-9H-咔唑-3-基)-1H-菲并[9,10-d]咪唑(4)都可用作检测活细胞内p H变化的p H荧光探针.  相似文献   

7.
利用Suzuki偶联反应合成了3种侧链含有不同电子受体的可溶性D-A型聚咔唑衍生物:聚[(9-(2-己基葵基)-9 H-咔唑)-(9-(4-硝基苯基)-9 H-咔唑)](PCz-NO_2)、聚[(9-(2-己基葵基)-9 H-咔唑)-(4-(9 H-咔唑-9-基)苯甲醛)](PCz-CHO)和聚[(9-(2-己基葵基)-9 H-咔唑)-(4-(9 H-咔唑-9-基)苯甲腈)](PCz-CN)。基于这3种聚合物的存储器件(器件结构:Al(200nm)/高分子(90nm)/氧化铟锡(ITO)均表现出典型的电双稳电子开关效应和非易失性一次写入多次读出(WORM)型存储性能。随着共轭聚合物光学带隙的增加[2.26eV(PCz-NO_2)→2.79eV(PCzCHO)→3.20eV(PCz-CN)],相应器件的启动阈值电压逐渐增大(-1.70V→-1.81V→-1.89V);而电流开关比(ON/OFF)则依次减小(6.63×10~4→4.08×10~4→5.68×10~3)。含氰基的聚咔唑衍生物需要的开启电压最大,展现出来的电流开关比在3种聚合物中则最小。  相似文献   

8.
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。  相似文献   

9.
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)。  相似文献   

10.
以咔唑、三苯基氯硅烷及2-溴芴为原料,经甲基化、硼酸化、Ullmann偶联、Suzuki偶联等反应合成了两种新型咔唑衍生物--3,6-二(9,9-二甲基-9H-2-芴基)-9-苯基-9H-咔唑(1a)和3,6-二[(4-三苯硅基)苯基]-9-苯基-9H-咔唑(1b),其结构经1H NMR和元素分析表征.用UV-Vis,荧光光谱和循环伏安曲线研究了1a和1b的光电性能.  相似文献   

11.
Exhaled aliphatic aldehydes were proposed as non-invasive biomarkers to detect increased lipid peroxidation in various diseases. As a prelude to clinical application of the multicapillary column–ion mobility spectrometry for the evaluation of aldehyde exhalation, we, therefore: (1) identified the most abundant volatile aliphatic aldehydes originating from in vitro oxidation of various polyunsaturated fatty acids; (2) evaluated emittance of aldehydes from plastic parts of the breathing circuit; (3) conducted a pilot study for in vivo quantification of exhaled aldehydes in mechanically ventilated patients. Pentanal, hexanal, heptanal, and nonanal were quantifiable in the headspace of oxidizing polyunsaturated fatty acids, with pentanal and hexanal predominating. Plastic parts of the breathing circuit emitted hexanal, octanal, nonanal, and decanal, whereby nonanal and decanal were ubiquitous and pentanal or heptanal not being detected. Only pentanal was quantifiable in breath of mechanically ventilated surgical patients with a mean exhaled concentration of 13 ± 5 ppb. An explorative analysis suggested that pentanal exhalation is associated with mechanical power—a measure for the invasiveness of mechanical ventilation. In conclusion, exhaled pentanal is a promising non-invasive biomarker for lipid peroxidation inducing pathologies, and should be evaluated in future clinical studies, particularly for detection of lung injury.  相似文献   

12.
Rate coefficients for gas‐phase reaction between nitrate radicals and the n‐C6–C10 aldehydes have been determined by a relative rate technique. All experiments were carried out at 297 ± 2 K, 1020 ± 10 mbar and using synthetic air or nitrogen as the bath gas. The experiments were made with a collapsible sampling bag as reaction chamber, employing solid‐phase micro extraction for sampling and gas chromatography/flame ionization detection for analysis of the reaction mixtures. One limited set of experiments was carried out using a glass reactor and long‐path FTIR spectroscopy. The results show good agreement between the different techniques and conditions employed as well as with previous studies (where available). With butanal as reference compound, the determined values (in units of 10?14 cm3 molecule?1 s?1) for each of the aldehydes were as follows: hexanal, 1.7 ± 0.1; heptanal, 2.1 ± 0.3; octanal, 1.5 ± 0.2; nonanal, 1.8 ± 0.2; and decanal, 2.2 ± 0.4. With propene as reference compound, the determined rate coefficients were as follows: heptanal, 1.9 ± 0.2; octanal, 2.0 ± 0.3; and nonanal, 2.2 ± 0.3. With 1‐butene as reference compound, the rate coefficients for hexanal and heptanal were 1.6 ± 0.2 and 1.8 ± 0.1, respectively. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 35: 120–129, 2003  相似文献   

13.
A stainless steel fiber was coated with a gate-opening controlled metal-organic framework ZIF-7 via a sol-gel method and applied to the solid-phase microextraction of aldehydes (hexanal, heptanal, octanal, nonanal, decanal) from exhaled breath by lung cancer patients. The effects of temperature and time on the sorption and desorption were optimized. Under optimum condition, the modified fiber displays enrichment factors (typically ranging from 300 to 10,000), low limits of detection (0.61–0.84 μg L?1), and wide linear ranges of hexanal, heptanal (5–500 μg L?1) and octanal, nonanal, decanal (10–1000 μg L?1). The high extraction capability for aldehydes is thought to result from (a) the combined effects of the large surface area and the unique porous structure of the ZIF-7, (b) the hydrophobicity and gate-opening effect of the sorbent, (c) the high selectivity of the window, and (d) the presence of unsaturated metal-coordination sites. The coated fiber is thermally stable and can be re-used >150 times. The relative standard deviation (RSD) for six replicate extractions using a single fiber ranged from 1.4–15.3% for intra-day and 2.4–16.1% for inter-day. The fiber-to-fiber reproducibility for three fibers prepared in parallel was in the range of 2.4–12.6% (RSD). The method was applied to the extraction of aldehydes from real samples and to the quantitation by gas chromatography. Recoveries from spiked samples ranged from 84 to 113%.
Graphical abstract A metal-organic framework ZIF-7 coated stainless steel fiber was prepared via sol-gel method. The self-made fiber was applied in the solid phase microextraction of aldehydes from exhaled breath of lung cancer patients.
  相似文献   

14.
We describe a simple derivatization method to determine aldehydes. This method is based on derivatization with D-cysteine and consecutive liquid chromatography-tandem mass spectrometry (LC-MS/MS). The optimum derivatization conditions of aldehydes with D-cysteine were 10 min at 50°C and pH 7.0. The formed alkyl thiazolidine-4-carboxylic acid derivatives were directly injected in LC-MS/MS. In the established condition, the method was used to detect eight aldehydes in beverages. The limit of detection (LOD) and limit of quantification (LOQ) of the aldehydes were 0.2-1.9 μg L(-1) and 0.7-6.0 μg L(-1) and the relative standard deviation was less than 2.0% at concentrations of 0.1 mg L(-1) and 1.0 mg L(-1) with the exception of octanal. All the beverage samples had detectable levels of methanal (0.033-0.145 mg L(-1)), ethanal (0.085-2.12 mg L(-1)), propanal (ND to 0.250 mg L(-1)), butanal (ND to 0.003 mg L(-1)), pentanal (ND to 0.471 mg L(-1)), hexanal (ND to 0.805 mg L(-1)), heptanal (0.019-3.91 mg L(-1)) and octanal (0.029-0.118 mg L(-1)).  相似文献   

15.
Peanut oil is favored by consumers due to its rich nutritional value and unique flavor. This study used headspace solid-phase microextraction (HS-SPME) combined with gas chromatography (GC) and gas chromatography–mass spectrometry (GC-MS) to examine the differences in the peanut oil aroma on the basis of variety, roasting temperatures, and pressing components. The results revealed that the optimal conditions for extracting peanut oil were achieved through the use of 50/30 μm DVB/CAR/PDMS fibers at 60 °C for 50 min. The primary compounds present in peanut oil were pyrazines. When peanuts were roasted, the temperature raised from 120 °C to 140 °C and the content of aldehydes in peanut oil increased; however, the content of aldehydes in No. 9 oil at 160 °C decreased. The components of peanut shell oil varied depending on the peanut variety. The most marked difference was observed in terms of the main compound at the two roasting temperatures. This compound was a pyrazine, and the content increased with the roasting temperature in hekei oils. When the roasting temperature was lower, No. 9 oil contained more fatty acid oxidation products such as hexanal, heptanal, and nonanal. When the roasting temperature increased, No. 9 oil contained more furfural and 5-methylfurfural. Heren oil was easier to oxidize and produced nonanal that possessed a fatty aroma.  相似文献   

16.
A new technique, headspace single-drop microextraction (HS-SDME) with in-drop derivatization, was developed. Its feasibility was demonstrated by analysis of the model compounds, aldehydes in water. A hanging microliter drop of solvent containing the derivatization agent of O-2,3,4,5,6-(pentaflurobenzyl)hydroxylamine hydrochloride (PFBHA) was shown to be an excellent extraction, concentration, and derivatization medium for headspace analysis of aldehydes by GC-MS. Using the microdrop solvent with PFBHA, acetaldehyde, propanal, butanal, hexanal, and heptanal in water were headspace extracted and simultaneously derivatized. The formed oximes in the microdrop were analyzed by GC-MS. HS-SDME and in-drop derivatization parameters (extraction solvent, extraction temperature, extraction time, stirring rate microdrop volume, and the headspace volume) and the method validations (linearity, precision, detection limit, and recovery) were studied. Compared to liquid-liquid extraction and solid-phase microextraction, HS-SDME with in-drop derivatization is a simple, rapid, convenient, and inexpensive sample technique.  相似文献   

17.
Ma J  Xiao R  Li J  Li J  Shi B  Liang Y  Lu W  Chen L 《Journal of separation science》2011,34(12):1477-1483
A simple, fast, sensitive and cost-effective method based on headspace solid-phase microextraction (HS-SPME) with on-fiber derivatization coupled with gas chromatography-mass spectrometry was developed for the determination of six typical aldehydes, 2E-hexenal, heptanal, 2E-heptenal, 2E,4E-heptadienal, 2E-decenal and 2E,4E-decadienal in laboratory algae cultures. As derivatization reagent, O-2,3,4,5,6-(pentafluorobenzyl) hydroxylamine hydrochloride, was loaded onto the poly(dimethylsiloxane)/divinylbenzene fiber for aldehydes on-fiber derivatization prior to HS-SPME. Various influence factors of extraction efficiency were systematically investigated. Under optimized extraction conditions, excellent method performances for all the six aldehydes were attained, such as satisfactory extraction recoveries ranging from 67.1 to 117%, with the precision (relative standard deviation) within 5.3-11.1%, and low detection limits in the range of 0.026-0.044 μg/L. The validated method was successfully applied for the analysis of the aldehydes in two diatoms (Skeletonema costatum and Chaetoceros muelleri), two pyrrophytas (Prorocentrum micans and Scrippsiella trochoidea) and Calanus sinicus eggs (feeding on the two diatoms above).  相似文献   

18.
采用基于超高效液相色谱与串联四极杆飞行时间质谱仪(Ultra-high performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry,UHPLC-Q-TOF MS)联用的代谢组学方法,通过分析大鼠尿液内源性代谢物的变化,研究黄芩-栀子药对治疗糖尿病肾病的作用机制。利用高脂高糖饲料喂养并腹腔注射链脲佐菌素(STZ)建立糖尿病大鼠模型。给药12周后,采用UHPLC-Q-TOF MS对正常对照组、模型组、黄芩-栀子药对治疗组的尿液样品进行代谢轮廓分析。利用正交偏最小二乘判别分析(Orthogonal partial least squares discriminant analysis,OPLS-DA)对实验数据进行分析,挑选出对各组分分离贡献较大(VIP>1,p<0.05)的化合物在Human Metabolome Database(HMDB)等数据库进行质谱信息匹配,共鉴定出糖尿病肾病潜在生物标记物31个,给药后回调生物标记物16个。研究结果表明,黄芩-栀子药对通过影响胆汁酸的合成与代谢、尿毒素代谢、能量代谢、色氨酸代谢、苯丙氨酸代谢、酪氨酸代谢等通路对糖尿病肾病起到治疗作用,其中胆汁酸的合成与代谢、尿毒素代谢和能量代谢可能是黄芩-栀子药对发挥治疗作用的主要途径。与单味药相比,配伍后的药对具有了新的药理作用。  相似文献   

19.
对比减压和常压条件下提取的柴胡挥发油在成分、含量及药效方面的差异,考察挥发油的品质,优选提取方法。采用气相色谱-质谱联用(GC-MS)法分析柴胡挥发油成分及其相对含量,再采用气相色谱法建立挥发油中己醛、庚醛、正辛醛和反式-2,4-癸二烯醛的含量检测方法,测定不同压力下提取的柴胡挥发油有效成分含量,通过背部皮下注射酵母混悬液复制大鼠发热模型,将常压、减压提取的柴胡挥发油溶于1%吐温80后腹腔注射给药,测定大鼠不同时间点的体温变化情况,利用单因素方差分析(Single factor analysis of variance)进行组间比较。结果显示:减压提取与常压提取的挥发油成分和含量存在差异,己醛、庚醛、正辛醛和反式-2,4-癸二烯醛在减压提取方法中的提取率更高,同时该方法提取的挥发油对干酵母引起的发热药效更显著。由此可见,减压提取能有效减少热敏性成分被破坏,提高有效成分的提取效率,提取的柴胡挥发油具有更显著的药效,品质优于常压提取。  相似文献   

20.
The volatile compounds of wild gilthead sea bream (Sparus aurata) were analyzed by sensory and instrumental analyses. Simultaneous distillation and extraction (SDE) with dichloromethane were used for extraction of volatile components. According to sensory analysis, the aromatic extract obtained by SDE was representative of sea bream odour. A total of 46 compounds were identified and quantified in sea bream. Aldehydes and alcohols were the most dominant volatiles in sea bream, as they accounted for the largest proportion. Hexanal, heptanal, nonanal, (Z)-4-heptenal, octanal, (E)-2-nonenal, decanal, benzenacetaldehyde, (E,E)-2,4-decadienal, 1-octen-3-ol and (E)-1,5-octadien-3-ol were potent aroma compounds on the basis of odour activity values (OAVs). Within these, decanal (OAV: 1110) and (E)-2-nonenal (OAV: 447.5) were the most powerful contributors to the aroma of the sea bream.  相似文献   

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