色谱-质谱联用技术在农药残留中的应用

农药残留严重危害人类健康,需要进行有效检测和严格控制。色谱-质谱联用技术的飞速发展使其在农药残留检测中得到了广泛应用。本文概述了色谱-质谱联用技术和农药残留以及色谱-质谱联用技术在农药残留中的应用,并展望了色谱-质谱联用技术的应用前景。     

强极性农药残留检测方法的研究进展

草甘膦等强极性农药大量应用于农业中,其本体及代谢物广泛残留于食品、土壤、水质及生态环境中,因其具有一定的毒害性,如何检测备受人们关注。本文对近年来强极性农药残留检测方法的研究进行了总结,包括衍生法-色谱-质谱联用、非衍生法-液相色谱-质谱联用、离子色谱及离子色谱-串联质谱、毛细管电泳法、ICP-MS或ICP-MS/MS与色谱的联用、快速检测技术（酶联免疫吸附法、免疫传感器法、离子迁移谱（IMS）法、分子印迹-化学传感器法、电化学法）等技术的研究现状和应用情况,为强极性农药及其代谢物残留检测提供参考。     

蜂产品中氯霉素残留检测方法的研究进展

本文综述了近年来蜂产品中氯霉素残留的主要检测方法及其研究进展, 包括微生物法、免疫分析法、色谱分析法和生物传感器法。其中, 免疫分析法着重介绍了酶联免疫法, 色谱分析法则主要介绍了高压液相色谱和色谱-质谱联用技术。最后, 对现有检测方法进行了比较分析。     

恩诺沙星及其代谢产物在南美白对虾体内药代动力学研究

目的研究恩诺沙星(enrofloxacin,ENR)及其代谢产物环丙沙星(ciprofloxacin,CIP)在虾体内的组织分布和药物代谢随时间的变化规律。方法在(26±2)℃的养殖水温下,以30 mg/(kg·bw)的投喂剂量对南美白对虾进行单次投喂药饵给药,采用高效液相色谱-串联质谱技术(high performance liquid chromatographytandem mass spectrometry,HPLC-MS/MS)进行测定ENR与CIP的含量,其药-时数据通过DAS 2.0动力学软件分析。结果 ENR在南美白对虾体内药时数据符合一级吸收二室模型,而其代谢产物CIP在南美白对虾体内象不符合房室模型。ENR在肝胰腺和肌肉中的最快达峰时间(T_(peak))为1和8 h,达峰浓度(C_(max))分别为24451.2和14212.1μg/kg;药时曲线下面积分别为971766.2和116847.4μg/(L·h);消除半衰期(t1/2β)分别为59.5和33.6 h。CIP在肝胰腺和肌肉中的最快达峰时间(T_(peak))为8和20 h;达峰浓度(C_(max))分别为598.8和4566.6μg/kg。肝胰腺和肌肉的ENR残留量低于最大残留限量(maximum residual limit,MRL)分别为384 h和480 h,而肝胰腺和肌肉中的CIP分别从288和480 h开始低于检出限。结论在(26±2)℃养殖水温下,以30 mg/(kg·bw)剂量对南美白对虾进行单次投饵给药时,建议休药期不得低于20 d。     

全自动固相萃取-超高效液相色谱串联质谱法测定蜂蜜中的氯霉素

目的:建立全自动固相萃取超高效液相色谱-质谱联用测定蜂蜜中氯霉素的分析方法。方法:样品经乙酸乙酯提取,全自动固相萃取仪净化后,采用超高效液相色谱串联质谱法进行检测,内标法定量。结果:氯霉素在0.50~5.0 ng/mL范围内保持良好的线性,以3倍信噪比计算氯霉素的检出限为0.05μg/kg。结论:该方法自动化程度高,结果准确度和重现性好,检出限低,可满足蜂蜜中氯霉素残留的检测要求。     

禽畜肉中氯霉素残留量的液质联用分析方法

研究一种针对禽畜肉中氯霉素残留量的液质联用分析方法。采用乙酸乙酯萃取样品中的氯霉素,氮吹后用水溶解样品残渣,然后用正己烷除去样品溶液中的脂肪,对样品中的目标物进行净化前处理。以乙腈- 体积分数0.1%醋酸溶液作流动相,C18色谱柱对食品中的氯霉素残留进行分离,然后用电喷雾质谱负离子选择离子模式[ESI(-)-SIM]对氯霉素进行检测。本方法缩短了色谱分离时间,提高了检测灵敏度和分析结果可靠性,具有准确、快速以及灵敏度高的特点,能够适应大规模样品的快速分析要求。     

代谢组学在发酵食品有毒代谢产物分析中的研究进展

食品发酵过程中可形成一些有毒代谢产物,对发酵食品产生了一定的安全隐患。代谢组学作为一门新兴技术,可对生物代谢过程中产生的小分子代谢产物实现实时分析与监测。应用气相色谱-质谱联用、离子色谱、反相高效液相色谱、高效液相色谱结合串联质谱、液相色谱-电喷雾电离飞行时间质谱等代谢组学技术分析酒饮料、葡萄酒、奶酪、香肠、酱油等食品中的有毒代谢产物,可实时监测食品发酵过程中的氨基甲酸乙酯、生物胺和亚硝酸盐的形成与变化状况,为提高发酵食品的安全控制水平和推动代谢组学在发酵食品领域的应用提供借鉴与参考。      

代谢组学在发酵食品有毒代谢产物分析中的研究进展

食品发酵过程中可形成一些有毒代谢产物,对发酵食品产生了一定的安全隐患。代谢组学作为一门新兴技术,可对生物代谢过程中产生的小分子代谢产物实现实时分析与监测。应用气相色谱-质谱联用、离子色谱、反相高效液相色谱、高效液相色谱结合串联质谱、液相色谱-电喷雾电离飞行时间质谱等代谢组学技术分析酒饮料、葡萄酒、奶酪、香肠、酱油等食品中的有毒代谢产物,可实时监测食品发酵过程中的氨基甲酸乙酯、生物胺和亚硝酸盐的形成与变化状况,为提高发酵食品的安全控制水平和推动代谢组学在发酵食品领域的应用提供借鉴与参考。     

恩诺沙星及其代谢物在俄罗斯鲟多组织中的 代谢及消除研究

目的研究恩诺沙星及其代谢产物环丙沙星在俄罗斯鲟中的代谢及消除规律,制定恩诺沙星在俄罗斯鲟体内的休药期。方法在水温12～15℃条件下,以60 mg/(kg?bw)剂量对体重为(750±50) g的健康俄罗斯鲟灌服恩诺沙星,灌服后的0～3360 h内不间断采样,使用高效液相色谱-串联质谱仪测定各组织内恩诺沙星及其代谢产物含量。结果灌药后,恩诺沙星在俄罗斯鲟鳃、血浆、肌肉、肝脏、肾脏、皮肤中达峰时间Tmax分别为0.25、9、12、12、18、24 h;肾脏、肝脏、皮肤、肌肉、鳃、血浆达峰浓度Cmax分别为31.863、23.435、21.434、18.640、10.342、2.599 mg/kg;消除半衰期以皮肤最大t1/2为394.431 h、血浆最小为129.6 h。鳃中药物浓度有2个峰值,第1次达峰时,血浆中药物浓度远低于鳃,推测与受试鱼进食习惯或组织结构有关。代谢产物环丙沙星代谢及消除趋势与恩诺沙星大致相同,血浆最早达峰, Tmax为12 h,达峰浓度以肝脏和肾脏较高,Cmax分别为6.876mg/kg和5.648mg/kg。结论从水产品质量安全角度应用本研究结果:以皮肤和肌肉作为可食性组织,恩诺沙星和环丙沙星残留总量不超过0.1 mg/kg至少需要100 d。     

色谱-质谱联用技术在食品检测中的应用

色谱-质谱联用技术是近年来迅速发展的一类技术。本文综述了色谱-质谱联用技术在食品检测中的应用,分别介绍了气相色谱-质谱联用技术、液相色谱-质谱联用技术、离子色谱-质谱联用技术的原理和技术特点,并结合具体实例对各项技术的应用加以阐述。在食品检验过程中,应根据未知样品的特点,选择适当的色谱-质谱联用技术,建立起高效、灵敏的检测方法,对其进行定性定量分析,以保证食品安全。     

鲤鱼油中脂肪酸的GC/MS(气相色谱-质谱)分析

采用超声波提取方法从淡水鱼鲤鱼的鱼肉中提取鱼油，经皂化后采用四甲基氢氧化胺法对其脂肪改进行酯化，并通过GC／MS联用机对鲤鱼油中的脂肪酸进行了分离和鉴定，共鉴定出20种化合物。     

磺胺甲噁唑和磺胺嘧啶在青石斑鱼组织中的分布及代谢规律

通过一次性投喂各含有200 mg/kg磺胺甲噁唑（sulfamethoxazole,SMZ）和磺胺嘧啶（sulfadiazine,SDZ）的饲料,研究两种药物在青石斑鱼中各组织分布与消除规律。采用超高效液相色谱-串联质谱检测青石斑鱼各组织中SMZ和SDZ的含量,并用内标法定量。结果表明,SMZ在青石斑鱼各组织中的最大含量：肝脏、背肌、血浆、肾脏和鳃依次为827.97μg/kg、776.70μg/kg、610.29μg/L、432.14μg/kg和345.18μg/kg。SDZ在青石斑鱼各组织中的最大含量：肝脏、背肌、鳃、血浆和肾脏依次为895.30μg/kg、660.55μg/kg、431.88μg/kg、419.56μg/L和310.67μg/kg。SMZ在青石斑鱼各组织中的半衰期：肾脏、鳃、背肌、血浆和肝脏半衰期依次为26.65、21.00、20.38、18.73h和16.90h。SDZ在青石斑鱼各组织中的半衰期：肾脏、血浆、鳃、背肌和肝脏依次为31.50、27.72、24.75、21.66h和18.24h。SMZ和SDZ在青石斑鱼肝脏中半衰期最短,代谢速度最快;在肾脏中半衰期最长,代谢速度最慢。在水温（25±2）℃条件下,SMZ和SDZ各200mg/kg的剂量同时单次投喂青石斑鱼,建议休药期不低于3d。SMZ和SDZ代谢规律研究为磺胺类药物在水产品中的合理使用提供了参考。     

An improved microbial assay for the detection of chloramphenicol residues in shrimp tissues

An improved microbial assay was developed for the detection of chloramphenicol (CAP) residues in shrimp muscle using Photobacterium leiognathi (L-2 strain) isolated from squid, as test organism, using a pad plate technique. CAP spiked in shrimp muscle tissues at concentrations ranging from 1 to 100 μg/kg was extracted using ethyl acetate and ammonium hydroxide. The assay showed a maximum inhibition zone of 23.0 mm for 100 μg/kg and a minimum inhibition zone of 9.3 mm for 1 μg/kg. The method had a good recovery of 95.63% with a minimum detection limit of 1 μg/kg. It can be performed within 18 h following simple extraction. The method therefore proved to be advantageous over chromatographic procedures as it was inexpensive, quite sensitive and can be adopted for rapid screening of CAP in shrimp tissues.     

液相色谱-质谱联用分析动物内脏和肌肉组织中的全氟化合物

建立液相色谱- 质谱联用检测动物内脏(猪心、猪肝、猪肾、鸡心和鸡肝)和肌肉(猪里脊肉和鸡胸肉)组织中11 种全氟化合物(PFCs)的分析方法。11 种PFCs 包括9 种常见PFCs 和2 种调聚酸。首先考察对比了WAX和MAX两种固相萃取小柱对11 种PFCs 的回收情况,最终选用WAX 柱对样品的萃取液进行净化。通过样品前处理方法的比较和优化,对动物内脏和肌肉组织分别采用离子对液液萃取和碱消解法。最后分析检测了农贸市场上的猪肝等多种实际样品,除了PFTA 和2 种调聚酸回收率较低外,其他8 种PFCs 的实际样品的加标回收都在80%～120% 之间,方法检出限为0.002～0.032ng/g。     

低温等离子体对南美白对虾肌肉蛋白质性质和结构的影响

目的 研究低温等离子体（cold atmospheric plasma, CAP）对南美白对虾肌肉蛋白质性质和结构的影响。方法 采取不同等离子体条件（电压：20、40、60 kV;时间：1、2、3 min）对南美白对虾肌肉蛋白进行处理,通过分析肌浆蛋白、肌原纤维蛋白、表面疏水性、总巯基含量、Ca2+-ATPase活性、十二烷基硫酸钠-聚丙烯酰胺电泳(sodium dodecyl sulfate polyacrylamide gel electrophoresis, SDS-PAGE)指标,探讨了CAP对南美白对虾肌肉蛋白的影响。结果 与对照组相比,随着处理时间和电压的增加,虾体的肌浆蛋白、肌原纤维蛋白含量、总巯基含量、Ca2+-ATPase活性均显著下降（P<0.05）,而表面疏水性显著升高（P<0.05）。处理条件为60 kV、3 min时,样品各指标变化最明显。SDS-PAGE电泳显示肌原纤维蛋白的肌球蛋白重链条带增强,副肌球蛋白条带逐渐消失,在分子量为25 kDa附近出现新的蛋白条带。结论 CAP处理能导致南美白对虾肌肉氧化,蛋白质变性。     

Seasonal Variations in Fatty Acid Composition of Different Tissues of Mirror Carp,Cyprinus Carpio,in Orenler Dam Lake,Afyonkarahisar, Turkey

The seasonal variations of fatty acids compositions in the muscle, liver, and ovarian tissues of mirror carp (Cyprinus carpio) living in Örenler Dam Lake were determined by using gas chromatography. The results obtained were subjected to statistical analyses by employing SPSS software and p < 0.05 was accepted as significant value. In the statistical analyses, multiple comparisons tests were performed. The results showed that monounsaturated fatty acids levels were found to be higher than that of polyunsaturated fatty acids and saturated fatty acids in all seasons. Palmitic and stearic acid levels were the highest in ovaries (19.95% in winter and 7.79% in summer, respectively). Oleic and palmitoleic levels were at the highest levels in liver tissues (34.53% in summer and 18.37% in winter, respectively). Docosahexaenoic (C22:6ω3, DHA), eicosapentaenoic (C20:5ω3, EPA), eicosatrienoic acid, and arachidonic (C20:4ω6, AA) levels were at the highest level as 17.27, 2.54, and 8.41% in ovaries in the winter and 6.37% in muscle tissues in the spring, respectively. ω3/ω6 ratios were 0.62–0.98 in muscle, 1.54–2.82 in the liver, and 2.82–3.89 in the ovaries. From the point of total fatty acid variations, the highest variations were observed as follows: muscle in spring (26.73%), liver in winter (33.85%), and ovaries in winter 36.38%.     

Determination and confirmation of chloramphenicol in honey, fish and prawns by liquid chromatography-tandem mass spectrometry with minimum sample preparation: validation according to 2002/657/EC Directive

A reliable, simple and sensitive liquid chromatography-electrospray ionisation-tandem mass spectrometry (LC-ESI-MS/MS) confirmation method has been developed for chloramphenicol (CAP) determination in honey, fish and prawns. For honey, samples were extracted with ethyl acetate, an aliquot was evaporated to dryness and re-dissolved in mobile phase. For fish and prawns, tissues were extracted with acetonitrile and chloroform. The organic layer was evaporated to dryness and the residue was re-constituted with water: acetonitrile (90:10). LC separation was achieved on a C18 column with gradient elution using a mobile phase of acetonitrile and water. Analysis was carried out on a triple-quadrupole tandem mass spectrometer in multiple reaction monitoring (MRM) mode via electrospray interface operated in negative ionisation mode, with deuterated chloramphenicol-d(5) (d(5)-CAP) as internal standard. Method validation was performed according to the criteria of Commission Decision 2002/657/EC. Four identification points were obtained for CAP with one precursor ion and two product ions. The limit of detection (LOD) was 0.02 μg kg(-1). Linear calibration curves were obtained over concentration ranges of 0.1-1.0 μg kg(-1) in tissues. Mean recoveries ranged from 85.5% to 115.6%, with the corresponding intra- and inter-day variation ranging from 1.0% to 22.5%, depending on matrix type and level of concentration. The decision limit (CCα) and detection capability (CCβ) of the method were obtained for all matrices: 0.04 and 0.06 μg kg(-1), respectively, for prawns and fish and 0.05 and 0.09 μg kg(-1) for honey.     

Oxytetracycline and oxolinic acid residues in kuruma prawn (Penaeus japonicus) and the effect of cooking procedures on the residues

Tissue distribution and residue depletion of oxytetracycline (OTC) and oxolinic acid (OA) were studied in the kuruma prawn (Penaeus japonicus). The prawn were kept in tanks with recirculated artificial seawater at a salinity of 22-23@1000. The water temperature was maintained at 25 degrees C. The average body weight was 22.9 +/- 4.9 g for OTC and 22.5 +/- 3.6 g for OA. The drug was mixed with the diet and orally administered through a catheter to the prawn. The doses of OTC and OA, respectively, were 50 mg/kg body weight. At each sample time, four prawns were sacrificed and tissues were sampled. OTC and OA levels were determined by high-performance liquid chromatography. At the highest levels, the concentrations of OTC were in the other: shell (13.57 micrograms/g) > hemolymph (12.20 micrograms/mL) > muscle (8.30 micrograms/g). For OA, the order was: shell (20.74 micrograms/g) > hemolymph (7.06 micrograms/mL) > muscle (2.05 micrograms/g). The elimination half-lives of hemolymph and muscle were 44.7 and 46.8 hours for OTC and 55.0 and 107.9 hours for OA, respectively. Residual OTC could not be detected in hemolymph and muscle at 20 days after dosing. Residual OA disappeared from hemolymph and muscle at 25 days after dosing. A 25-day period for OTC and 30-day period for OA could be regarded as the proper withdrawal time established for kuruma prawn by the Pharmaceutical Law in Japan. However, the elimination half-lives of shell for OTC and OA could not be calculated because both drug residues persisted in shell tissues, and the elimination phase was not completed during the experimental period. Residual OTC (14.10 +/- 2.26 micrograms/g, n = 6) and OA (0.32 +/- 0.06 microgram/g, n = 7) were detected in exuviae at 3 days and 4 days after dosing, respectively. Residual OTC was reduced to 50-70% in muscle by the usual methods of cooking (boiling, baking at 200 degrees C and frying at 180 degrees C), whereas reduction levels in shell were only 20-30%. Residual OA was reduced to 20-30% in muscle and shell by the cooking. These results confirm that the cooking procedures could only reduce but not completely eliminate these drug residues in prawn.     

Heavy Metal in Edible Portions (Muscle and Skin) and Other Organs (Gill,Liver and Intestine) of Selected Freshwater Fish Species

In this study, the concentrations of copper, zinc, manganese, iron, cobalt, calcium, magnesium, nickel, lead, chrome and boron elements in muscle, gill, skin, intestine and liver of selected fish species (Rutilus rutilus, Carassius carassius, and Cyprinus carpio) from Porsuk Dam Lake/Turkey were determined. The element analyses were performed with inductive coupled plasma-optic emission spectroscopy following microwave digestion techniques. Metal accumulation levels of tissues and species were remarkably different. Concentrations of Ni, Pb, Cr and B in all tissues of the species were found to be below the detection limit (BDL) with ICP-OES. Irrespective of the fish species and tissues, the concentrations (mg kg^?1 wet weight) of the other matals varied in the following ranges: Cu, below detection limit (BDL)-17.15; Zn, 9.08–699.60; Mn, BDL-8.23; Fe, 4.42–137.17; Co, BDL-1.49; Ca, 144.40–14376.60 and Mg, 95.81–903.23. The metal levels in muscle of the species were found below the limits proposed by FAO, WHO, and Turkish Food Codes, and these are safe for human consumption. However, heavy metal accumulation in skin and liver of some species was as high as non-permitted limits.     

文蛤特异性过敏原免疫识别的初步研究

目的：贝类是人类最优质的食用蛋白资源之一,也是联合国粮农组织公布的八大类过敏食物之一,贝类过敏反应严重影响着过敏人群的身体健康和生活质量,为此开展贝类过敏原的识别检测研究很有必要。方法：通过问卷调查初步了解食物过敏现状,获取自诉贝类过敏患者血清和正常人阴性对照血清,采用特异性IgE 检测试剂盒筛选贝类过敏血清,应用组织捣碎提取蛋白、聚丙烯酰胺凝胶电泳和免疫印迹等实验方法研究文蛤特异性过敏原。结果：文蛤肌肉主要蛋白的相对分子量约为200kD 以上、200、90、80、70、46、36 和24kD,其中能被贝类过敏血清特异性识别的90kD 组分约占文蛤肌肉总蛋白的10%～20%,且主要为盐溶性蛋白。结论：文蛤的特异性过敏原为90kD 蛋白组分。