基于UHPLC-Q-TOF/MS的不同产地普洱生茶化学成分差异研究

为了更加全面地了解产地对普洱生茶品质与化学成分的影响,本研究选取来自临沧市、普洱市、西双版纳州三大产区12个茶山(自然村)的普洱生茶样品,采用超高效液相色谱-四级杆-飞行时间质谱(UHPLC-Q-TOF/MS)对不同产地普洱生茶的非挥发性代谢物表型进行了研究。结果表明:不同产地普洱生茶的化学成分在含量上具有较大差异,且具有明显的产地特征。采用主成分分析,可以对来自西双版纳自治州(包括勐腊县、勐海县、景洪市)、普洱市、临沧市3个地级行政区的普洱生茶进行有效区分,也可以对来自普洱茶产区的东南、西南、西北3个区域的普洱生茶进行有效区分。进一步鉴定了普洱生茶中79种主要成分,并对其在12个茶山(自然村)的普洱生茶中的含量分布,以及与不同产地普洱生茶滋味品质的关系进行了分析。本研究表明,基于UHPLC-Q-TOF/MS的茶叶非挥发性化学成分轮廓可以作为普洱生茶产地判别的依据。     

用液相色谱串联质谱法测定渔业水样中6种农药的含量

本文建立了一种快速检测渔业水质样本中酰胺类除草剂乙草胺、丙草胺、丁草胺、三嗪类除草剂莠去津、烟碱类杀虫剂噻虫嗪、三唑类杀菌剂苯醚甲环唑6种农药含量的液相色谱串联质谱法。采用乙腈-水-甲酸梯度洗脱、电喷雾电离方式、多反应监测模式测定考察检出限、线性范围、日内精密度及日间精密度。在三种加标浓度下,该方法的回收率为78.2%~104.7%。用液相色谱-四级杆-飞行时间质谱对疑似目标物质进行定性,用精确质量数、同位素丰度比和二级碎片解析方式等解析定性结构。该方法能够满足检测这六种农药的要求,能准确定性,自建的谱库可为渔业污染事故鉴定和水产品质量安全风险评估做支撑。     

Characterizing the pigmented traditional rice cultivars grown in temperate regions of Kashmir (India) for free and bound phenolics compounds and in vitro antioxidant properties

The purpose of the research was to identify the phenolic and flavonoid compounds of seven different traditional pigmented whole rice cultivars grown in the temperate regions of Kashmir so as to study their relationship with in vitro antioxidant capacities. The completely pigmented rice cultivars were found to have higher phenolic, flavonoid, anthocyanin contents and exhibited higher antioxidant capacities than the light colored and sparely colored rice cultivars. A total of 40 compounds had been identified in the analyzed rice cultivars that were found to be distributed in 6 major categories with 6-phenolics, 6-flavonoids, 11-hydroxycinnamic acid derivatives, 7-hydroxybenzoic acid derivatives, 3-anthocyanins and 7-flavonoid glucosides of different flavonoid compounds. Among the free and bound fractions for each cultivars the light and sparsely colored depicted higher content of phenolics and in vitro antioxidant properties in bound faction, while the completely pigmented cultivars showed higher antioxidant properties in free fractions. The anthocyanins quercetin-3-O-galactoside, cyanidin-3-O-rutinoside and pelargonidin-3-O-diglucoside had been identified by LC-MS existing in the free fractions of the analyzed rice cultivars whereas, the free fraction of acetone + H₂O possessed higher percentage of phenolic compounds as compared to methanolic extracts and bound fractions. The black colored cultivars possessed higher DPPH scavenging activity and lipid peroxidation inhibition.     

氯虫苯甲酰胺和毒死蜱在水稻中的分布降解研究

本研究采用LC-MS检测技术，系统研究了氯虫苯甲酰胺和毒死蜱及其代谢物（3，5，6-TCP）在两种水稻各器官的动态消解规律与分布特征，旨在为两种农药的科学合理使用及后期稻米安全风险评估提供科学依据。在穗期施药后定期分析水稻各器官中农药及代谢物的残留量，结果表明两种农药及代谢物在水稻甬优各器官中的残留量高于中浙优，在水稻中的残留量均呈叶 > 籽粒 > 茎 > 根的分布规律，根中呈先上升后下降的变化趋势，茎、叶和籽粒中的残留量随施药时间的延长逐渐减小；毒死蜱在水稻各器官降解速率较快，在施药后14 d降解率达99%以上；稻壳和糠承载90%左右农药及代谢物残留；高剂量施药使两种农药及代谢物在籽粒各部位的含量增高，但对其分布特征无影响。研究表明选择种植水稻品种中浙优的同时降低施药剂量既可达到防治效果也能降低稻米食用风险。     

自动QuEChERS方法结合液相色谱串联质谱对玉米中133种农药的多残留分析

基于QuEChERS(快速、简单、廉价、高效、耐用、安全)方法,借助自动QuEChERS前处理设备,结合LC-MS/MS测定手段,建立了简单、高效的同时检测玉米中133种农药多残留分析方法——自动QuEChERS。本方法将QuEChERS提取和净化两个步骤在同一设备上一次完成,操作要求低,解放了劳动力,提高了工作效率,进一步提高了实验重现性。结果表明:所有待测农药在3个添加浓度(20、100、500μg·kg~(-1))的回收率在70%~120%之间(n=5),相对标准偏差小于15%。最低定量限达到2μg·kg~(-1),在2~500μg·kg~(-1)线性范围内,相关系数大于0.99。     

Analysis of Mycosporine-Like Amino Acids in Selected Algae and Cyanobacteria by Hydrophilic Interaction Liquid Chromatography and a Novel MAA from the Red Alga Catenella repens

Mycosporine-like amino acids (MAAs), a group of small secondary metabolites found in algae, cyanobacteria, lichens and fungi, have become ecologically and pharmacologically relevant because of their pronounced UV-absorbing and photo-protective potential. Their analytical characterization is generally achieved by reversed phase HPLC and the compounds are often quantified based on molar extinction coefficients. As an alternative approach, in our study a fully validated hydrophilic interaction liquid chromatography (HILIC) method is presented. It enables the precise quantification of several analytes with adequate retention times in a single run, and can be coupled directly to MS. Excellent linear correlation coefficients (R² > 0.9991) were obtained, with limit of detection (LOD) values ranging from 0.16 to 0.43 µg/mL. Furthermore, the assay was found to be accurate (recovery rates from 89.8% to 104.1%) and precise (intra-day precision: 5.6%, inter-day precision ≤6.6%). Several algae were assayed for their content of known MAAs like porphyra-334, shinorine, and palythine. Liquid chromatography-mass spectrometry (LC-MS) data indicated a novel compound in some of them, which could be isolated from the marine species Catenella repens and structurally elucidated by nuclear magnetic resonance spectroscopy (NMR) as (E)-3-hydroxy-2-((5-hydroxy-5-(hydroxymethyl)-2-methoxy-3-((2-sulfoethyl)amino)cyclohex-2-en-1-ylidene)amino) propanoic acid, a novel MAA called catenelline.     

液相色谱串级质谱同时测定木制品中3种有机磷酸酯阻燃剂

为建立有效的阻燃剂的使用规范和为监管制度提供理论依据，本文建立了微波辅助萃取，液相色谱串级质谱法同时测定木制品中3种有机磷阻燃剂分析方法，并考察了萃取溶剂、萃取条件、流动相对试验结果的影响。结果表明，以丙酮为萃取溶剂，70℃微波辅助萃取30 min，利用多反应检测MRM模式，TCEP、TDCP在线性范围0.02～1.0 mg/kg，TCPP在线性范围0.002～0.2 mg/kg内质量浓度与响应值呈现良好的线性关系，定量下限分别为27、50、8μg/kg，加标回收率82.7%～98.3%，相对标准偏差1.8%～10.8%。该方法操作简单，提取效果较好，能够有效的检测木制品中三种有机磷酸酯阻燃剂。     

山核桃水溶性成分中神经营养活性因子的分离与鉴定

本研究旨在揭示山核桃水溶性成分的神经营养活性及活性因子。利用脱脂山核桃水溶性提取物处理SH-SY5Y细胞,用倒置相差显微镜观察细胞突触生长,用q PCR检测相关基因表达,使用HPLC及LC-MS对山核桃水溶性成分神经营养活性因子进行分离鉴定。结果显示,山核桃的水溶性成分能够显著促进SH-SY5Y细胞的突触生长,并可以显著上调SH-SY5Y细胞NF160基因的表达。HPLC及LCMS检测结果发现其水溶性成分主要组成为胞苷、尿苷、鸟苷、腺嘌呤、腺苷等。由此可知,山核桃水溶性成分通过上调NF160基因表达具有神经营养活性。     

几种经济红藻中茉莉酸合成途径的关键物质

为研究几种经济红藻中茉莉酸合成途径的关键物质,实验采用液相色谱—质谱联用技术(LC-MS)对茉莉酸生物合成途径相关物质建立检测方法,并对龙须菜、坛紫菜受到机械损伤时各物质的变化情况进行检测。以100%甲醇提取茉莉酸(JA)、茉莉酸甲酯(MeJA)、12-氧-植物二烯酸(12-OPDA)和13-氢过氧化亚麻酸(13-HpOTE),利用XBridge TM C18色谱柱,以甲醇/水为流动相分离4种物质。优化条件下4种物质得到良好分离,加标回收率为81.23%～90.25%,检测限为0.04～0.56 ng/mL,灵敏度高。坛紫菜、龙须菜和真江蓠3种红藻中,坛紫菜中未检测到JA和13-HpOTE,4种物质均在另外2种藻中检测到。龙须菜受机械损伤胁迫后,4种物质在短时间内得到积累,其中13-HpOTE响应迅速。研究表明,红藻中可能存在类似于植物的茉莉酸合成途径,并参与对损伤的胁迫响应。