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.     

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。     

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.     

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。     

当归不同药用部位化学成分变化规律研究

采用LC-MS分离鉴定当归不同药用部位中的化学成分,应用中药色谱指纹图谱相似度评价系统对当归不同药用部位进行液相色谱图相似度评价,使用SPSS 13.0分析软件,对当归不同药用部位鉴定出的每个色谱峰的相对含量进行T检验.结果表明:初步鉴定出当归不同药用部位的共有成分12种,即阿魏酸、6,7-环氧藁本内酯、洋川芎内酯F、洋川芎内酯I、洋川芎内酯H、阿魏酸松柏酯、洋川芎内酯A、丁基苯酞、E-藁本内酯、E-丁烯基苯酞、Z-藁本内酯、Z-丁烯基苯酞,当归不同药用部位色谱图整体之间相似度比较高,均在0.972以上.T检验结果表明,当归头、当归身、当归尾与全当归化学成分部分化合物相对百分含量存在显著性差异,说明当归不同药用部位的化学成分含量与其全当归相比均具有一定的差异,当归分部位用药有一定的物质基础.     

不同菌种发酵水豆豉风味多肽的差异

为缩短发酵周期,使人工接种发酵的水豆豉产品风味与自然发酵的风味相同,筛选出适合工业化生产的发酵菌粉,确定不同菌种发酵对水豆豉产品中多肽及风味肽的影响,采用LC-MS/MS(液质联用)技术检测3种发酵工艺生产的水豆豉产品中多肽的氨基酸序列,分析对比多肽序列及所属蛋白的类别。结果表明:A_3菌粉人工接种发酵、自然发酵和纳豆菌粉发酵的3个样品中分别检测出186、176和445条多肽,分别分解自23种、21种和31种蛋白。3种不同菌株发酵的产品中鉴定出47条相同的主体风味肽,其中A_3菌粉发酵产品中共检测到88条主体风味肽与自然发酵的风味肽相同,其多肽含量和种类更接近,风味也更接近。     

普洱茶发酵过程中外源接种黄曲霉产毒研究

以云南大叶种晒青茶为原料,接种产毒黄曲霉进行模拟普洱茶发酵试验,并在发酵结束时通过LC-MS/MS法对茶样进行黄曲霉毒素检测,研究普洱茶发酵过程中黄曲霉的生长及产毒情况。结果表明,在普洱茶发酵过程中,接种的黄曲霉能在茶叶中生长繁殖,初期生长较快,但随发酵时间的延长,黄曲霉在茶叶中的生长明显受到抑制,其数量逐渐下降。发酵终止时,未在茶样中检测出黄曲霉毒素。     

高效液相色谱-质谱法测定猪组织中硝基咪唑类药物残留量

建立了一种高灵敏度和高选择性的检测猪组织中硝基咪唑类药物残留的高效液相色谱-大气压化学电离质谱(APCI)法,可同时进行猪组织中3种硝基咪唑类药物残留的确证分析.本方法检测猪肌肉、肝脏、肾脏和皮下组织中硝基咪唑类药物的检测限为0.5～1μg/kg;空白组织添加硝基咪唑类药物水平为0.5、1、2或4μg/kg时,测得回收率:肌肉为61.1%～85.4%,肝脏为62.3%～80.4%,肾脏为61.6%～82.0%,皮下组织为63.6%～84.1%.     

牛奶中吡利霉素残留检测高效液相色谱-串联质谱法研究

建立了牛奶中吡利霉素残留检测的高效液相色谱-串联质谱(HPLC-MS/MS)法。液相色谱条件为:色谱柱为Waters XBridge C18柱(150 mm×2.1 mm,5μm),流动相为乙腈-0.01mol/L乙酸铵溶液(30∶70,V/V),柱温为30℃,流速为0.2 mL/min,进样量为10μL。质谱条件为:电喷雾离子源(ESI ),多反应监测(MRM)方式进行采集;监测离子质荷比(m/z)为411.5>112.0,411.5>363.4。以吡利霉素的同分异构体异吡利霉素作内标,内标法定量。结果表明:吡利霉素的线性范围为20~400 ng/mL,相关系数R2=0.999 9;方法检测限为2 ng/mL,定量限为5ng/mL;从50、100和150 ng/mL三个添加浓度检测结果可以看出,方法的平均回收率为90.4%~104.3%(n=6),批内、批间RSD均小于5%。     

液相色谱-质谱联用技术在检测食品中兽药残留的应用

动物性食品安全问题现已成为一个全球性的议题。动物性食品药残超标、安全性差的问题十分突出。建立一种准确、灵敏、可靠的分析动物性食品中兽药残留的方法刻不容缓。介绍了液相色谱-质谱联用技术(LC-MS)应用于动物性食品中几种常见兽药残留的检测方法。