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您的位置:中国色谱网 >> 资讯 >> 技术应用 >> 图书期刊 >> 《色谱》2013年第2期内容摘要
《色谱》2013年第2期内容摘要
2013年2月6日 来源:中国色谱网 责编:李华静

 

93~94

DOI: 10.3724/SP.J.1123.2013.01042

收稿日期: 2013-01-21

 

 

收稿日期:2013-01-21

磁性固相萃取吸附剂研究的新进展

丁兰,王慧

(吉林大学化学学院, 吉林 长春 130012)

 

Recent research progress in magnetic adsorbent

DING Lan, WANG Hui

 

1海胆状磁性二氧化钛微球的合成及在磷酸化多肽选择性富集中的应用

蛋白质的磷酸化修饰与多种生物学过程密切相关,如DNA损伤修复、转录调节、信号传导、细胞凋亡等。磷酸化蛋白质及多肽的研究有助于阐明上述过程的机理,进一步认识生命活动的本质。然而它们的相对低丰度和负电性为研究者带来了不小的困难,因此低丰度的磷酸化蛋白质或多肽的选择性富集一直是极具挑战性的研究课题之一。目前有许多金属氧化物被修饰于磁性材料表面用于选择性吸附磷酸化蛋白质和多肽的研究。其中,二氧化钛(TiO2)由于其对磷酸化蛋白质和多肽具有较高的选择性和稳定性,且易于制备,因此受到了极大的关注。相比传统的球形TiO2纳米粒子,棒状TiO2纳米粒子具有更高的表面积/体积比,能够提供更多的吸附活性位点。许国旺课题组[1]目前制备了一种海胆状磁性金红石型TiO2纳米棒,将其应用于磷酸肽的选择性富集或磷酸胆碱类化合物的选择性转移过程中,获得了令人满意的结果。具体的制备方法如下:首先将Fe3O4表面包裹一层二氧化硅(SiO2),然后在反应体系中逐滴滴加钛酸四丁酯(Ti[OBu]4)溶液,形成二氧化钛低聚物后,对其进行煅烧,使单分散Fe3O4@SiO2表面形成锐钛矿的纳米晶种;将制备的锐钛矿纳米晶种在水热条件下生长为海胆状TiO2磁性纳米粒子(金红石型)。这种海胆状磁性TiO2纳米粒子对含磷酸的分子具有很高的选择性,能够选择性地从复杂的样品中富集磷酸肽,或在代谢组学研究中选择性除去血浆中一些磷酸胆碱类化合物,降低了基质效应,提高了低丰度代谢物的检测灵敏度。

2磁性表面分子印迹聚合物的合成与应用

固相萃取技术目前已经广泛应用于环境样品、食品以及生物样品中的目标分析物的浓缩和净化。传统的固相萃取方法中使用的吸附剂由于选择性差,因而不能对复杂基质样品中的目标分析物进行有效的和选择性的富集和净化。分子印迹聚合物(MIP)以其对模板分子高度的选择性,且化学、机械和热稳定性好等优点,目前已经被广泛应用于各种固相萃取、药物控制释放、色谱分离和传感器装置等领域中。为了改善传统的分子印迹聚合物所存在的结合位点分布不均匀、结合位点包埋过深、结合位点难以接近以及模板分子渗漏等问题,许多研究人员开始尝试制备具有内核结构的分子印迹聚合物,即表面分子印迹聚合物。表面分子印迹聚合物可以提高目标分子的质量传递速率,降低模板分子再结合所需时间。TiO2、SiO2和Fe3O4等相继被用于表面分子印迹聚合物的制备过程中。Xiao等[2]提出以磁性碳纳米管(MCNTs)为核制备对加替沙星具有选择性吸附的磁性表面分子印迹聚合物。其制备方法如下:首先利用水热反应制备磁性MCNTs;然后,以加替沙星为模板,甲基丙烯酸为功能单体,乙二醇二甲基丙烯酸酯为交联剂,以偶氮二异丁腈为引发剂合成了MCNTs@MIP表面分子印迹聚合物。MCNTs@MIP克服了传统的表面分子印迹聚合物中无机内核材料易漏易碎的缺点。将MCNTs@MIP用于血清中加替沙星的选择性富集,获得了令人满意的结果。MCNTs@MIP对加替沙星具有非常好的选择性识别,而对血清中的其他抗生素(帕珠沙星)和蛋白质等杂质吸附量较低,因而能有效地降低基质效应。值得一提的是MCNTs@MIP经过再生后还可以重复使用,实验结果表明其重复使用5次后,依然对加替沙星具有很好的选择性吸附。

3磁性氧化碳纳米管用于细胞内核酸相关蛋白质的提取

核酸相关蛋白质在基因调控和蛋白质表达过程中具有非常重要的作用。对细胞内核酸相关蛋白质的整体分析有助于更好地理解核酸和相关蛋白质之间的相互作用。然而,由于缺乏高效的目标蛋白质组提取方法,核酸相关蛋白质的大规模分析还具有很大难度。目前的研究表明功能化碳纳米管具有优异的生物相容性,大的比表面积,且对核酸及连接核酸的蛋白质具有很强的吸附作用,因此近年来在核酸的相关研究领域(如基因载体、核酸传感器等)得到了广泛的应用。最近邹汉法课题组[3]首次使用磁性氧化碳纳米管从细胞中高效提取了一组核酸及相关蛋白质。该方法先用强酸将多层碳纳米管氧化获得氧化碳纳米管(oMWCNTs),随后用水热法使Fe3O4纳米颗粒沉积在氧化碳纳米管上,形成磁性氧化碳纳米管(oMWCNT@Fe3O4)。之后,利用oMWCNT@Fe3O4富集细胞内核酸及相关蛋白质,实现了活细胞核酸相关蛋白质的规模化提取和鉴定。实验结果表明,oMWCNT@Fe3O4对体外培养的细胞内核酸的萃取率接近100%。更重要的是,连接在核酸上的相关蛋白质也能够很好地被oMWCNT@Fe3O4捕获,证明了这一方法对少量细胞样品中核酸相关蛋白质组学分析具有非常重要的意义。进一步的研究显示,大多数被识别的核酸相关蛋白质是亲水弱酸性蛋白质,这些蛋白质包含了很多重要的细胞功能,如基因表达、基因代谢和信号传导等。在未来的研究中,这一方法还可以应用于系统生物学以进一步了解基因的表达和调控。

4一步法制备具有C8修饰的磁性介孔限制性通过吸附剂及应用

Liu等[4]以十六烷基三甲基溴化铵(CTAB)为致孔剂,采用溶胶-凝胶法一步合成了一种内孔修饰C8的磁性介孔微球(C8-Fe3O4@mSiO2)并用于分析鼠血浆中的安定(diazepam)。首先将Fe3O4纳米粒子和CTAB分散在水中并超声处理30 min后加入氢氧化钠水溶液稀释并进一步超声以获得稳定的悬浮液;接着在60 ℃下对悬浮液加热30 min后,加入原硅酸四乙酯、n-辛基-三乙氧基硅烷和乙醇的混合溶液,继续加热12 h;获得的产物除去CTAB后真空干燥,备用。这种“一步”合成法步骤简便,合成周期短,且可通过添加不同的硅烷化试剂将其他的官能团键合在磁性介孔微球孔道的内表面上。由于制备的C8-Fe3O4@mSiO2结构特殊,使得基质中小分子药物可进入介孔孔道内,并通过疏水作用吸附在C8基团上,而大分子化合物(如蛋白质)则由于尺寸排斥效应不能进入介孔孔道中。因此这一材料无需其他的样品净化步骤即可直接从富含蛋白质的生物样品中萃取小分子的药物。此外,C8-Fe3O4@mSiO2还可通过结合其他分子识别材料(如分子印迹聚合物),进一步提高其选择性。

5磁性管内固相微萃取技术

1997年,管内固相微萃取技术(IT-SPME)被首次提出,这一技术使萃取、解吸附和进样自动完成,有效地缩短了分析时间,改善了分析结果的精密度和准确性。但由于吸附剂用量相对较小,IT-SPME对目标分析物的萃取效率很低。为解决这一问题,许多研究人员不断努力以提高这一技术的萃取效率,如采用新的吸附剂或使用毛细管整体柱等。最近,Moliner-Martínez等[5]提出一种磁性IT-SPME技术,有效地改善了目标化合物的萃取效率。他们将合成的磁性Fe3O4@SiO2微球固定在石英毛细管柱中,将这一毛细管柱放置在一个可以改变磁场强度的电磁线圈中,该毛细管柱两端连接在一个六通阀上。利用这一装置萃取抗磁性的目标分析物,使其富集在磁场强度小的区域。相比传统的IT-SPME技术,磁性IT-SPME对目标化合物具有更高的萃取效率。在传统的IT-SPME萃取过程中,目标分析物伴随着流动相的流动被局部吸附在毛细管内壁上,这种吸附是不完全的,且大部分目标分析物尚未被吸附便被流动相带走。但在磁性IT-SPME过程中,外加磁场将毛细管内壁的Fe3O4@SiO2微球磁化,并产生了不同的磁场梯度。抗磁性目标化合物被捕获在磁场强度较低的区域,而且由于管内SiO2形成交联结构进一步提高了这一技术对目标分析物的吸附能力。在解吸附过程中,通过改变外加磁场的两极,Fe3O4@SiO2微球的磁性被快速反转,从而使其将吸附的目标分析物释放到流动相中;引入分析柱分离后,进入检测器中进行分析。通过对乙酰水杨酸、对乙酰氨基酚、阿替洛尔、双氯芬酸和布洛芬这5种药物的分析测定,证实磁性IT-SPME技术对目标化合物具有很高的萃取效率(70%~100%),因而解决了传统IT-SPME对目标分析物(尤其是极性化合物)萃取效率低(10%~30%)的缺点,具有很好的发展前景。

 

95~101

DOI: 10.3724/SP.J.1123.2012.09002

*通讯联系人.E-mail: fwsfqm@126.com(傅武胜);E-mail: 2die2005@163.com(严小波).

基金项目: 国家自然科学基金项目(81172671);卫生部公益性科研专项课题(200902009);福建省杰出青年基金项目(2011J06011);福建省医学创新课题(2011-CX-21).收稿日期: 2012-09-03

 

油脂性食品中脂肪酸氯丙醇酯检测方法的研究进展

严小波1,2*, 吴少明1,2, 里南3, 吕华东1,2, 傅武胜1,2*

(1. 福建省人兽共患病研究重点实验室, 福建省疾病预防控制中心, 福建 福州 350001;2. 福州大学食品安全分析与检测教育部重点实验室, 福建 福州 350001;3. 福建农林大学, 福建 福州 350002)

摘要: 脂肪酸氯丙醇酯污染是近年来国际上新出现的热点食品安全问题之一,尤其是3-氯-1,2-丙二醇脂肪酸酯(3-MCPD酯)污染问题更为突出。3-MCPD酯在食用油、婴幼儿奶粉等多种食品中的含量较高,以3-MCPD的最大耐受剂量(TDI)评估时所引起的健康风险较高。国外已对3-MCPD酯等氯丙醇酯的检测方法、污染调查和形成机制等开展了不少的研究,国内开展的研究较少。本文主要对油脂食品中3-MCPD酯的检测方法(包括前处理过程,如3-MCPD酯的提取、水解和衍生)、3-MCPD酯总量以及3-MCPD单酯和双酯的检测方法进行了综述。

关键词: 脂肪酸氯丙醇酯;检测方法;油脂性食品;综述

文章编号: 1000-8713(2013)02-0095-07

 

Development of the determination methods of fatty acid esters of chloropropanediols in fat-rich foods

YAN Xiaobo1,2*, WU Shaoming1,2, LI Nan3, L Huadong1,2, FU Wusheng1,2*

(1. Fujian Provincial Key Laboratory of Zoonosis Research, Fujian Center for Disease Control and Prevention, Fuzhou 350001, China; 2. Key Laboratory of Analysis and Detection for Food Safety (Fuzhou University), Ministry of Education, Fuzhou 350001, China; 3. Fujian Agriculture and Forestry University, Fuzhou 350002, China)

Abstract: Fatty acid esters of chloropropanediols are a kinds of newly emerged food contaminants, especially 3-monochloropropane-1,2-diol (3-MCPD) esters that have been detected in many foodstuffs such as infant formula and edible oils at relatively high levels. Based on the Tolerable Dose Intake (TDI) of 3-MCPD, the intake of 3-MCPD from 3-MCPD esters may cause the health risk to human beings. The researches for the analysis of 3-MCPD esters have been carried out in some institutes abroad, but there were only a few in China. This paper reviews the methods for the determination of 3-MCPD esters in fat-rich foods, including the extraction, hydrolysis, the derivatization of 3-MCPD esters, the total amount of 3-MCPD esters and the amounts of monoesters and diesters of 3-MCPD.

Key words: fatty acid esters of chloropropanediols; determination methods; fat-rich foods; review

 

102~110

DOI: 10.3724/SP.J.1123.2012.10019

*通讯联系人.Tel: (010)80727777-1142,E-mail: zhangyangjun6314@yahoo.com.cn.

基金项目: 国家重大科学计划项目(2012CB910603,2010CB912704);国家高技术研究发展规划项目(2012AA020202);国家重大科学仪器设备开发专项项目(2011YQ030139,2011YQ06008408,2012YQ12004407);国家自然科学基金项目(20735005,21275159).

收稿日期: 2012-10-25

 

采用磁性载体制备的固定化酶反应器的载体粒径对蛋白质酶解性能的影响

张姣1,2, 周廉淇2, 田芳2, 张养军2*, 钱小红2

(1. 中南大学药学院, 湖南 长沙 410013; 2. 蛋白质组学国家重点实验室, 北京蛋白质组研究中心, 军事医学科学院放射与辐射医学研究所, 北京 102206)

摘要: 研究了以不同粒径的磁性颗粒为载体的固定化酶反应器在蛋白质酶解过程中,其粒径大小对团聚、酶解效率和漏切位点等的影响。实验结果表明,纳米级颗粒的酶负载量为亚微米级的3.5倍左右。但当酶固定量相同时,酶解效率基本相当。而在一定程度上加大磁性颗粒的粒径后,团聚现象得到明显改善。选择磁性载体粒径为20 nm的固定化酶反应器,对其性能进一步考察。结果显示胰蛋白酶与牛血清白蛋白(BSA)的质量比为1:1时,即能于1 min内实现快速酶解;当酶解10 min时,其零漏切位点肽段数和蛋白质序列覆盖率基本达到稳定,并明显优于溶液酶解水平。通过对漏切位点的统计分析比较,发现固定化酶解与溶液酶解时的漏切位点规律基本类似。因此,采用不同粒径磁性载体制备的固定化酶反应器均可在蛋白质组学研究中提供快速、高效的酶解。

关键词: 磁性颗粒;固定化酶反应器;蛋白质组学;蛋白质酶解

文章编号: 1000-8713(2013)02-0102-09

 

Effects of the size of magnetic particles of immobilized enzyme reactors on the digestion performance

ZHANG Jiao1,2, ZHOU Lianqi2, TIAN Fang2, ZHANG Yangjun2*, QIAN Xiaohong2

(1. School of Pharmaceutical Sciences, Central South University, Changsha 410013, China; 2. State Key Laboratory of Proteomics, Beijing Proteome Research Center, Beijing Institute of Radiation Medicine, Beijing 102206, China)

Abstract: We applied immobilized enzyme reactors prepared with different sizes of magnetic particles into protein and proteome digestion. In addition, the influences of different sizes of the magnetic particles were studied on the reunion, enzyme efficiency and leakage sites. The experimental results showed that in comparison with the submicron magnetic particles, the amount of trypsin immobilized on the magnetic nanoparticles was 3.5 times more than that of the submicron magnetic particles. However, the enzymatic efficiency was at the same level when the same amount of trypsin was used, and the reunion phenomenon was obviously improved when the size of the magnetic nanoparticles increased. Taking the immobilized enzyme reactor of 20 nm magnetic nanoparticles as an example, the digestion performance was further examined. The experimental results showed that rapid digestion could be achieved within 1 min when the mass ratio of the trypsin and bovine serum albumin was 1:1. The peptide number of 0 missed cleavage site and the sequence coverage changed little after the protein was digested for 10 min. It was concluded that the digestion efficiency of the immobilized enzyme reactor was much better than that of the in-solution digestion. When the immobilized enzyme reactors and the free trypsin were used for digestion, little differences of the leakage sites were found. Therefore, the immobilized enzyme reactors prepared with different sizes of magnetic particles can be applied in proteomic research for quick and efficient digestion.

Key words: magnetic nanoparticles; immobilized enzyme reactor; proteomics; protein digestion

 

111~116

DOI: 10.3724/SP.J.1123.2012.09037

*通讯联系人.Tel: (0592)3269935,E-mail: Xudm@xmciq.gov.cn.

基金项目: 厦门市科技计划项目(3502Z20092009和3502Z20102013).

收稿日期: 2012-09-25

 

非衍生化液相色谱-串联质谱法测定动物源性食品中8种生物胺

吴云辉1, 周爽2, 徐敦明2*

(1. 厦门海洋职业技术学院, 福建 厦门 361100; 2. 厦门出入境检验检疫局检验检疫技术中心, 福建 厦门 361026)

摘要: 采用液相色谱-串联质谱技术建立了同时测定动物源性食品中组胺(HIS)、色胺(TRP)、2-苯乙胺(2-PHE)、腐胺(PUT)、尸胺(CAD)、酪胺(TYR)、亚精胺(SPD)和精胺(SPM)8种生物胺(BAs)的分析方法。样品用乙腈-甲酸水溶液提取,用强阳离子交换柱(MCX)净化。在不进行衍生化的条件下,采用亲水作用色谱(HILIC)柱、以5 mmol/L的乙酸铵溶液和甲醇为流动相分离8种生物胺。结果表明,8种生物胺的线性范围为0.001~100 μg/L,相关系数(r2)均大于0.99。方法的检出限(LODs,信噪比为3)在0.001~1 μg/kg之间,定量限(LOQs,信噪比为10)在0.003~5 μg/kg之间。在8种基质中3个加标水平的回收率都在73.9%~106.3%之间,加标含量范围为0.003~50 μg/kg,相对标准偏差(RSD, n=6)在5.65%~18.6%之间。方法的灵敏度和回收率高,选择性好,能满足日常动物源性食品检测工作的要求。

关键词: 液相色谱-串联质谱;强阳离子交换柱;净化;生物胺;食品

文章编号: 1000-8713(2013)02-0111-06

 

Determination of eight biogenic amines in animal-derived foodstuffs by high performance liquid chromatography-tandem mass spectrometry without derivatization

WU Yunhui1, ZHOU Shuang2, XU Dunming2*

(1. Xiamen Ocean Vocational College, Xiamen 361100, China; 2. Inspection and Quarantine Technology Center, Xiamen Entry-Exit Inspection and Quarantine Bureau, Xiamen 361026, China)

Abstract: A method for the determination of histamine (HIS), tryptamine (TRP), 2-phenylethylamine (2-PHE), putrescine (PUT), cadaverine (CAD), tyramine (TYR), spermidine (SPD), spermine (SPM) in animal-derived foodstuffs was established using high performance liquid chromatography-tandem mass spectrometry. The samples were extracted with acetonitrile-formic acid aqueous solution, and purified with strong cationic exchange (MCX) cartridge. Without derivatization, the eight biogenic amines (BAs) were separated by hydrophilic interaction chromatographic (HILIC) column with the mobile phases of 5 mmol/L ammonium acetate and methanol. The linearities were excellent in the range of 0.001-100 μg/L with the correlation coefficients above 0.99. The limits of detection (LODs, S/N=3) of the method were between 0.001 μg/kg and 1 μg/kg, and the limits of quantification (LOQs, S/N=10) were between 0.003 μg/kg and 5 μg/kg. The recoveries of BAs spiked in eight matrices were between 73.9% and 106.3% at the spiked levels ranged from 0.003 μg/kg to 50 μg/kg. The relative standard deviations (RSDs, n=6) were in the ranges of 5.65%-18.6%. The method can meet the requirements of the daily work for the determination of BAs in animal-derived foodstuffs.

Key words: liquid chromatography-tandem mass spectrometry (LC-MS/MS); strong cationic exchange (MCX) cartridge; purification; biogenic amine; food

 

117~121

DOI: 10.3724/SP.J.1123.2012.10005

*通讯联系人.Tel: (0571)63122616,E-mail: dm2616@163.com.

基金项目: 国家林业局林业公益性行业科研专项经费(201204414).

收稿日期: 2012-10-11

 

固相萃取-高效液相色谱-串联质谱联用测定竹笋中残留的7种杀虫剂农药

丁明1,2*, 钟冬莲1, 汤富彬1, 方伟2

(1. 中国林业科学研究院亚热带林业研究所, 浙江 富阳 311400; 2. 浙江农林大学, 浙江 临安 311300)

摘要: 建立了高效液相色谱-串联质谱(HPLC-MS/MS)同时测定竹笋中丁烯氟虫腈、毒死蜱、氯虫苯甲酰胺、氟虫腈、吡虫啉、茚虫威和辛硫磷7种农药残留的分析方法。样品用乙腈提取后,经PSA固相萃取小柱净化,采用Atlantis T3色谱柱分离,以0.1%甲酸水溶液(含5 mmol/L乙酸铵)和乙腈为流动相,梯度洗脱分离,在电喷雾离子源正、负离子模式下采用质谱多反应监测(MRM)模式检测。结果表明,7种农药在10~100 μg/L范围内具有良好的线性关系(相关系数r为0.9900~0.9994); 4、8、32 μg/kg添加水平下的平均回收率为76.0%~102.6%;相对标准偏差为3.2%~11.0%;7种农药的检出限为0.02~0.5 μg/kg,定量限为0.08~1.5 μg/kg。该方法准确度、灵敏度高,简单、快速,可满足竹笋中7种杀虫剂残留同时检测的要求。

关键词: 高效液相色谱-串联质谱;农药残留;竹笋

文章编号: 1000-8713(2013)02-0117-05

 

Determination of seven pesticide residues in bamboo shoots by high performance liquid chromatography-tandem mass spectrometry coupled with solid-phase extraction

DING Ming1,2*, ZHONG Donglian1, TANG Fubin1, FANG Wei2

(1. Research Institute of Subtropical Forestry, Chinese Academy of Forestry, Fuyang 311400, China; 2. Zhejiang Agriculture and Forestry University, Lin’an 311300, China)

Abstract: A simple and efficient method based on solid-phase extraction (SPE) and high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) was developed for the determination of butylene fipronil, chlorpyrifos, chlorantraniliprole, fipronil, imidacloprid, indoxacarb and phoxim residues in bamboo shoots. The sample was extracted with acetonitrile and purified by a primary secondary amine (PSA) solid-phase extraction cartridge. The detection of targets was performed by HPLC-MS/MS with multiple reaction monitoring (MRM) mode. All the seven pesticides were completely separated in 15 min with an excellent linear relationship. The limits of detection and the limits of quantification for the seven pesticides were 0.02-0.5 μg/kg and 0.08-1.5 μg/kg, respectively. The recoveries of the seven pesticides spiked in a bamboo shoot sample at the levels of 4, 8, 32 μg/kg were in the range from 76.0% to 102.6% (the RSD≤11.0%, n=3). The method was successfully applied to the real bamboo shoot samples. The method has high accuracy and sensitivity, and is simple and quick. It can meet the requirement of the simultaneous determination of the seven pesticides in bamboo shoots.

Key words: high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS); pesticide residues; bamboo shoots

 

122~126

DOI: 10.3724/SP.J.1123.2012.09047

*通讯联系人.Tel: (021)64252145,E-mail: weibingzhang@ecust.edu.cn.

基金项目: 国家青年科学基金项目(21105027).

收稿日期: 2012-10-08

 

超高效液相色谱-串联四极杆质谱法测定葡萄中单咖啡酰酒石酸酯、单香豆酰酒石酸酯和单阿魏酰酒石酸酯

张凌怡, 王智聪, 张维冰*

(华东理工大学化学与分子工程学院, 上海 200237)

摘要: 建立了超高效液相色谱-串联四极杆质谱测定葡萄汁、皮和籽中羟基桂皮酒石酰酯类化合物含量的方法。采用的色谱柱为Waters UPLC HSS T3 (150 mm×2.1 mm, 1.7 μm),流动相为含0.1%甲酸的水-乙腈体系,梯度洗脱,流速0.3 mL/min,柱温35 ℃;质谱采用电喷雾离子源、负离子多反应检测模式。对单香豆酰酒石酸酯和单阿魏酰酒石酸酯,其含量以单咖啡酰酒石酸酯当量表示。结果表明,单咖啡酰酒石酸酯在25~2000 μg/L范围内线性关系良好(r2=0.9989);检出限为0.25 μg/L,定量限为25 μg/L;在250、750、1200 μg/L添加水平下单咖啡酰酒石酸酯的平均回收率为97.7%~99.5%,相对标准偏差小于2.5%。实验结果表明,葡萄汁、皮和籽中羟基桂皮酒石酰酯类化合物的含量差异显著。该方法简单快速、灵敏度高、回收率高、准确性好,可用于葡萄产品中单咖啡酰酒石酸酯、单香豆酰酒石酸酯和单阿魏酰酒石酸酯的分析。

关键词: 超高效液相色谱-串联质谱;羟基桂皮酒石酰酯;单咖啡酰酒石酸酯;单香豆酰酒石酸酯;单阿魏酰酒石酸酯;葡萄汁;葡萄皮;葡萄籽

文章编号: 1000-8713(2013)02-0122-05

 

Determination of caftaric acid, p-coutaric acid and fertaric acid in grape juice, peel and seeds by ultra-high performance liquid chromatography-tandem quadrupole mass spectrometry

ZHANG Lingyi, WANG Zhicong, ZHANG Weibing*

(School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237, China)

Abstract: An ultra-high performance liquid chromatography-tandem quadrupole mass spectrometry (UPLC-MS/MS) method was developed for the determination of hydroxycinnamoyltartaric esters, such as caftaric acid, p-coutaric acid and fertaric acid in grape juice, peel and seed. The target analytes were separated on a Waters UPLC HSS T3 column (150 mm×2.1 mm, 1.7 μm) at 35 ℃ with gradient elution at a flow rate of 0.3 mL/min. The grape juice was freeze-centrifuged, the supernatant was diluted with 20% methanol. The grape peel and grape seed samples were extracted with 80% ethanol. The extract was cleaned-up on-line with the analytical column by valve switching technology. The mobile phases were water-acetonitrile (both containing 0.1% formic acid). The identification and quantification were achieved by MS/MS in multiple reaction monitoring (MRM) mode via negative electrospray ionization. As lack of commercial standards, p-coutaric acid and fertaric acid were quantified by caftaric acid equivalent. The developed method showed a good linearity over the range of 25-2000 μg/L with good correlation coefficient (r2=0.9989). The limit of detection was 0.25 μg/L, and the limit of quantification was 25 μg/L. The average recoveries of caftaric acid were between 97.7%-99.5% and the precisions were within 2.5% at the spiked levels of 250, 750 and 1200 μg/L. The working solutions were stable for 74 h at room temperature. The results showed that there are significant differences of hydroxycinnamoyltartaric esters distribution in grape juice, peel and seeds. Therefore, this method, owing to its simplicity, rapidity, good recovery, high sensitivity and accuracy, can be used for the analysis of caftaric acid, p-coutaric acid and fertaric acid in grape juice, peel and seeds.

Key words: ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS); hydroxycinnamoyltartaric esters; caftaric acid; p-coutaric acid; fertaric acid; grape juice; grape peel; grape seed

 

127~132

DOI: 10.3724/SP.J.1123.2012.09017

*通讯联系人.Tel: (020)39358270,E-mail: lwyll@gzhtcm.edu.cn.

基金项目: 国家科技部“十二五”科技支撑计划项目(2011BAI01B02).

收稿日期: 2012-09-17

 

灰色系统理论在中药色谱指纹图谱模式识别中的应用研究

魏航1, 林励2*, 张元1, 王莲婧2, 陈沁群1

(1. 广州中医药大学医学信息工程学院, 广东 广州 510006; 2. 广州中医药大学中药学院, 广东 广州 510006)

摘要: 建立了基于灰色系统理论的中药色谱指纹图谱模式识别模型。运用基于范数与信息熵赋权法的灰色关联分析,求出各待比较图谱特征变量数据序列与理想图谱特征变量数据序列之间的灰色关联度,并依据模糊匹配中的“最大匹配度”原则进行判断,从而达到品种识别和质量评价的目的。该模型在56批次不同品种化橘红药材样品的高效液相色谱分析中取得较满意的结果: 熵权与范数的灰色关联分析均能准确识别出毛橘红与光橘红两个品种,克服了传统相似度或灰色关联在化橘红色谱指纹图谱分析中的误判问题;对药材中化学成分的种类与含量十分接近的毛橘红不同栽培品种的识别率超过92.85%。此外,该模型计算量较少,整个模式识别过程通过计算机编程实现,操作简单。实验结果显示,灰色系统理论在中药色谱指纹图谱模式识别中有良好的适应性。

关键词: 灰色系统理论;中药;色谱指纹图谱;模糊匹配;模式识别

文章编号: 1000-8713(2013)02-0127-06

 

Research on the application of grey system theory in the pattern recognition for chromatographic fingerprints of traditional Chinese medicine

WEI Hang1, LIN Li2*, ZHANG Yuan1, WANG Lianjing2, CHEN Qinqun1

(1. School of Medical Information Engineering, Guangzhou University of Chinese Medicine, Guangzhou 510006, China; 2. School of Chinese Materia Medica, Guangzhou University of Chinese Medicine, Guangzhou 510006, China)

Abstract: A model based on grey system theory was proposed for pattern recognition in chromatographic fingerprints (CF) of traditional Chinese medicine (TCM). The grey relational grade among the data series of each testing CF and the ideal CF was obtained by entropy and norm respectively, then the principle of “maximal matching degree” was introduced to make judgments, so as to achieve the purpose of variety identification and quality evaluation. A satisfactory result in the high performance liquid chromatographic (HPLC) analysis of 56 batches of different varieties of Exocarpium Citrus Grandis was achieved with this model. The errors in the chromatographic fingerprint analysis caused by traditional similarity method or grey correlation method were overcome, as the samples of Citrus grandis ‘Tomentosa’ and Citrus grandis (L.) Osbeck were correctly distinguished in the experiment. Furthermore in the study on the variety identification of Citrus grandis ‘Tomentosa’, the recognition rates were up to 92.85%, although the types and the contents of the chemical compositions of the samples were very close. At the same time, the model had the merits of low computation complexity and easy operation by computer programming. The research indicated that the grey system theory has good applicability to pattern recognition in the chromatographic fingerprints of TCM.

Key words: grey system theory; traditional Chinese medicine (TCM); chromatographic fingerprint (CF); fuzzy matching; pattern recognition

 

133~138

DOI: 10.3724/SP.J.1123.2012.09023

*通讯联系人.Tel: (020)39352136,E-mail: godhs@tom.com.

基金项目: 国家自然科学基金项目(81173525).

收稿日期: 2012-09-17

 

pH/溶剂双梯度反相高效液相色谱法同时测定氨酚曲麻片中的5种有效成分

禤学怡, 黄丽娜, 潘晓玲, 李宁*

(广东药学院, 广东 广州 510006)

摘要: 建立了一种pH/溶剂双梯度反相高效液相色谱(HPLC)同时测定氨酚曲麻片中对乙酰氨基酚、咖啡因、水杨酰胺、盐酸伪麻黄碱、盐酸曲普利啶5种有效成分的方法。通过对溶剂梯度和pH/溶剂双梯度体系的优化,得到分离5种成分的最佳色谱体系。采用Diamonsiol C18色谱柱(250 mm×4.6 mm, 5 μm),以甲醇、0.05 mol/L醋酸铵水溶液和0.08 mol/L醋酸水溶液组成三元流动相体系,pH/溶剂双梯度洗脱,流速为1.0 mL/min;柱温为30 ℃。采用分段变波长检测: 0~6 min, 280 nm; 6~7 min, 257 nm; 7~14 min, 280 nm; 14 min, 233 nm。片剂中的5种成分在25.5 min内能达到基线分离,对乙酰氨基酚、盐酸伪麻黄碱、咖啡因、水杨酰胺、盐酸曲普利啶5种成分的线性范围分别为0.055~0.998 g/L、0.053~0.946 g/L、0.007~0.129 g/L、0.035~0.622 g/L和0.002~0.039 g/L,相关系数r均大于0.9990;检出限(以信噪比为3(S/N=3)计)分别为0.09、6、0.02、0.128和0.02 mg/L,回收率为97.9%~102.8%。该方法能在短时间内同时分离酸性、中性和碱性化合物,能提高被测物的柱效,减少半峰宽和拖尾,可应用于氨酚曲麻片中5种成分的含量分析。

关键词: pH/溶剂双梯度;高效液相色谱法;对乙酰氨基酚;咖啡因;水杨酰胺;盐酸伪麻黄碱;盐酸曲普利啶;氨酚曲麻片

文章编号: 1000-8713(2013)02-0133-06

 

Simultaneous determination of five cold medicine ingredients in paracetamol triprolidine hydrochloride and pseudoephedrine hydrochloride tablets by pH/organic solvent double-gradient high performance liquid chromatography

XUAN Xueyi, HUANG Lina, PAN Xiaoling, LI Ning*

(Guangdong College of Pharmacy, Guangzhou 510006, China)

Abstract: A pH/organic solvent double-gradient mode in reversed-phase high performance liquid chromatography (HPLC) has been established as a new approach to the simultaneous determination of acetaminophen, caffeine, salicylamide, pseudoephedrine hydrochloride and triprolidine hydrochloride in paracetamol triprolidine hydrochloride and pseudoephedrine hydrochloride tablets. Through the optimization of the organic solvent gradient mode and pH/organic solvent double-gradient mode, the optimum double-gradient HPLC system of the five cold medicine ingredients has been built. The determination was carried out on a Diamonsiol C18 column (250 mm×4.6 mm, 5 μm). The mobile phase consisted of methanol, 0.05 mol/L ammonium acetate solution and 0.08 mol/L acetic acid solution. The column temperature was set at 30 ℃. The flow rate was 1.0 mL/min. The sample was measured at multiple wavelengths: 0-6 min, 280 nm; 6-7 min, 257 nm; 7-14 min, 280 nm; 14 min, 233 nm. The separation of the five cold medicine ingredients in the tablets was achieved in 25.5 min. The linear ranges of acetaminophen, pseudoephedrine hydrochloride, caffeine, salicylamide and triprolidine hydrochloride were 0.055-0.998 g/L, 0.053-0.946 g/L, 0.007-0.129 g/L, 0.035-0.622 g/L and 0.002-0.039 g/L, respectively, with their correlation coefficients greater than 0.9990. The detection limits (S/N=3) were 0.09, 6, 0.02, 0.128 and 0.02 mg/L, respectively. Their mean recoveries were 97.9%-102.8%. The advantage of the method is the simultaneous determination of acidic, neutral and basic compounds. It also can improve the column efficiency of the analyte, compress the half-peak width and reduce the trailing. The optimized and validated method can be used for the simultaneous determination of the five cold medicine ingredients in the tablets.

Key words: pH/organic solvent double-gradient; high performance liquid chromatography (HPLC); acetaminophen; caffeine; salicylamide; pseudoephedrine hydrochloride; triprolidine hydrochloride; paracetamol triprolidine hydrochloride and pseudoephedrine hydrochloride tablets

 

139~142

DOI: 10.3724/SP.J.1123.2012.09029

*通讯联系人.Tel: (0411)84379562,E-mail: chenjp@dicp.ac.cn.

基金项目: 国家重点基础研究发展计划(“973”计划)项目(2009CB421602).

收稿日期: 2012-09-19

 

固相萃取-高效液相色谱法测定地表水中的苯并三唑和苯并噻唑

王金成1, 熊力2, 张海军1, 王龙星1, 金静1, 陈吉平1*

(1. 中国科学院大连化学物理研究所, 辽宁 大连 116023; 2. 大连工业大学, 辽宁 大连 116034)

摘要: 建立了固相萃取-高效液相色谱分析地表水中苯并噻唑、苯并三唑、5-甲基-苯并三唑、5-氯-苯并三唑及5,6-二甲基-苯并三唑的方法。地表水样品采用HLB固相萃取柱富集净化后,在甲醇-水(55:45, v/v)流动相中用ZORBAX SB-C18色谱柱(250 mm×4.6 mm, 5 μm)分离,紫外检测,外标法定量。结果表明,5种目标化合物在0.064~80 mg/L范围内均呈良好的线性关系,线性相关系数均大于0.9999,仪器检出限为1.9~3.2 μg/L。空白自来水样中的加标回收率为87.8%~125.6%,相对标准偏差(n=3)为0.4%~9.4%。应用该方法测定了大连自来水及辽河入海口水样,在辽河入海口地表水中检出苯并噻唑、苯并三唑、5-甲基-苯并三唑、5-氯-苯并三唑。

关键词: 固相萃取;高效液相色谱法;苯并三唑;衍生物;苯并噻唑;地表水

文章编号: 1000-8713(2013)02-0139-04

 

Simultaneous determination of benzotriazoles and benzothiazole in surface water by solid phase extraction and high performance liquid chromatography

WANG Jincheng1, XIONG Li2, ZHANG Haijun1, WANG Longxing1, JIN Jing1, CHEN Jiping1*

(1. Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China; 2. Dalian Polytechnic University, Dalian 116034, China)

Abstract: A simple method based on solid phase extraction (SPE) coupled with high performance liquid chromatography (HPLC) was developed for the determination of 1H-benzotriazole (BT), 5-methyl-1H-benzotriazole (5-M-BT), 5,6-dimethyl-1H-benzotriazole (5,6-DM-BT), 5-chloro-1H-benzotriazole (5-Cl-BT) and benzothiazole (BTH) in surface water. The extraction and clean-up of the surface water sample were performed on an HLB solid-phase extraction cartridge. The separation of the five compounds was achieved on a ZORBAX SB-C18 column (250 mm×4.6 mm, 5 μm) with methanol-water (55:45, v/v) as mobile phase and ultraviolet detection. The quantification was achieved by external standard method. The results showed that good linearities were observed in the ranges of 0.064-80 mg/L with the correlation coefficients ≥ 0.9999 and the instrumental limits of detection for the five target compounds were in the range of 1.9-3.2 μg/L. The average recoveries of the five target compounds were 87.8%-125.6% and the relative standard deviations (n=3) were 0.4%-9.4%. This method was applied to the analysis of the surface water samples from the Dalian tap water and the Liaohe River estuary. The results showed that BT, 5-M-BT, 5-Cl-BT and BTH were found in the water from the Liaohe River estuary.

Key words: solid phase extraction (SPE); high performance liquid chromatography (HPLC); benzotriazoles; derivatives; benzothiazole; surface water

 

143~146

DOI: 10.3724/SP.J.1123.2012.09024

*通讯联系人.E-mail: smith1981@yahoo.cn.

基金项目: 国家自然科学基金项目(21106011, 21276034);辽宁省教育厅科学研究一般项目(L2012195).

收稿日期: 2012-09-17

 

反气相色谱法测定有机溶剂型木质素的溶解度参数

于雅晨, 李坤兰, 马英冲*, 魏立纲

(大连工业大学轻工与化学工程学院, 辽宁 大连 116034)

摘要: 采用反气相色谱法(IGC),于333.15~373.15 K温度范围内测定了有机溶剂型木质素的溶解度参数(δ2)及相关指标。以正辛烷(n-C8)、正癸烷(n-C10)、正十二烷(n-C12)和正十四烷(n-C14)为探针溶剂,计算了探针溶剂的特性保留体积(V0g)、摩尔吸收焓(ΔHs1)、无限稀释摩尔混合焓(ΔH1)、摩尔蒸发焓(ΔHv)、无限稀释活度系数(Ω1)以及探针溶剂与有机溶剂型木质素的Flory-Huggins相互作用参数(χ12)。结果表明,上述4种探针溶剂在测定的温度范围内均为有机溶剂型木质素的不良溶液;在同一温度下,参数χ12随着探针溶剂碳数的增加而降低。测得的有机溶剂型木质素的δ2为19.03 (J\5cm-3)1/2

关键词: 反气相色谱;溶解度参数;有机溶剂型木质素

文章编号: 1000-8713(2013)02-0143-04

 

Determination of the solubility parameter of organosolv lignin by inverse gas chromatography

YU Yachen, LI Kunlan, MA Yingchong*, WEI Ligang

(School of Light Industry and Chemical, Dalian Polytechnic University, Dalian 116034, China)

Abstract: An inverse gas chromatographic (IGC) method has been used to measure the solubility parameters (δ2) of organosolv lignin at the absolute temperatures from 333.15 K to 373.15 K. The test probe solvents were n-octane (n-C8), n-decane (n-C10), n-dodecane (n-C12), and n-tetradecane (n-C14). The specific retention volumes of the solvents (V0g), the molar enthalpy of sorption (ΔHs1), the partial molar enthalpy of mixing at infinite dilution (ΔH1), the molar enthalpy of vaporization (ΔHv), the activity coefficients at infinite dilution (Ω1), and Flory-Huggins inter action parameters (χ12) between organosolv lignin and probe solvents were obtained. The results showed that the above four probes are poor solvents for organosolv lignin; at the same temperature, the χ12 reduced with the increase of the carbon number of probe solvents. The average solubility parameter of organosolv lignin was determined as 19.03 (J\5cm-3)1/2.

Key words: inverse gas chromatography (IGC); solubility parameter; organosolv lignin

 

147~150

DOI: 10.3724/SP.J.1123.2012.10006

*通讯联系人.E-mail: xjuwq@sina.com.

基金项目: 新疆大学石油天然气精细化工重点实验室开放课题基金项目(XJDX0908-2010-05).

收稿日期: 2012-10-11

 

反相气相色谱法表征1-烯丙基-3-甲基氯代咪唑离子液体的表面性质

陈亚丽, 王强*, 邓丽霜, 张正方, 唐军

(新疆大学理化测试中心, 新疆 乌鲁木齐 830046)

摘要: 采用反相气相色谱(IGC)技术研究了不同温度下1-烯丙基-3-甲基氯代咪唑([AMIM]Cl)的表面性质。以正己烷、正庚烷、正辛烷和正壬烷作为非极性探针分子测定[AMIM]Cl在343.15、353.15、363.15和373.15 K温度下的表面色散自由能;以二氯甲烷、三氯甲烷、丙酮、乙酸乙酯、四氢呋喃作为极性探针分子测定离子液体Lewis酸碱性质,并测定了吸附自由能和吸附自由焓变等热动力学参数。实验结果表明,[AMIM]Cl的酸解离平衡常数Ka为0.34,碱解离平衡常数Kb为1.68,其表面呈Lewis两性偏碱性特点。在343.15、353.15、363.15和373.15 K温度下,[AMIM]Cl的表面色散自由能分别为52.26、50.82、46.08和42.05 mJ/m2。这一结果对研究离子液体的表面性质及应用有指导作用。

关键词: 反相气相色谱;1-烯丙基-3-甲基氯代咪唑;离子液体;表面性质;表面色散自由能;Lewis酸碱参数

文章编号: 1000-8713(2013)02-0147-04

 

Characterization of surface properties of 1-allyl-3-methylimidazolium chloride ionic liquid by inverse gas chromatography

CHEN Yali, WANG Qiang*, DENG Lishuang, ZHANG Zhengfang, TANG Jun

(Center for Physical and Chemical Analysis, Xinjiang University, Urumqi 830046, China)

Abstract: The determination of the dispersive component of surface free energies (γds) at different temperatures and Lewis acid-base parameters of 1-allyl-3-methylimidazolium chloride ionic liquid ([AMIM]Cl) were investigated by means of inverse gas chromatography (IGC). Four n-alkanes, including n-hexane (C6), n-heptane (C7), n-octane (C8) and n-nonane (C9), were chosen as the apolar probes to characterize the dispersive component of the surface free energies at 343.15, 353.15, 363.15 and 373.15 K, respectively; and dichloromethane (DCM), trichloromethane (TCM), tetrahydrofuran (THF), ethyl acetate (EtAc), acetone (Acet) as the polar probes to estimate the Lewis acid-base parameters to judge the interactions between [AMIM]Cl and the solvents. The IGC characterizations encompassed the adsorption thermodynamic parameters to acid-base surface interactions, including the standard enthalpy (ΔHsa) and the free energy change of adsorption (ΔGsa) at different temperatures. The results showed that the Lewis acid parameter Ka of [AMIM]Cl was 0.34, and the base parameter Kb was 1.68, which indicated it was Lewis amphoteric with predominantly basic character. Furthermore, the free energy of adsorption ΔGsa was also figured out. It was found that the γds of the [AMIM]Cl were 52.26, 50.82, 46.08 and 42.05 mJ/m2 at 343.15, 353.15, 363.15 and 373.15 K, respectively. The results are of great importance to the study of the surface properties and the application of ionic liquid.

Key words: inverse gas chromatography (IGC); 1-allyl-3-methylimidazolium chloride; ionic liquid; surface properties; dispersive component of surface free energy; Lewis acid-base parameters

 

151~154

DOI: 10.3724/SP.J.1123.2012.10004

*通讯联系人.E-mail: jiaiguo@sdu.edu.cn.

收稿日期: 2012-10-10

 

增强型绿色荧光蛋白的色谱分离和纯化

侯清华1,2, 宋淑亮1,2, 梁浩1,2, 王伟莉1,2, 吉爱国1,3*

(1. 山东大学(威海)国际生物技术研发中心, 山东 威海 264209; 2. 山东大学(威海)海洋学院, 山东 威海 264209; 3. 山东大学药学院, 山东 济南 250012)

摘要: 增强型绿色荧光蛋白(EGFP)是生物领域常用的标记物。在前期成功克隆表达EGFP的基础上,本实验建立了两步分离纯化EGFP的色谱方法,并验证其分离纯化效果,检验EGFP的活性。首先用金属螯合亲和色谱柱HisTrap HP对EGFP的重组菌体破碎上清液进行初步分离,再用葡聚糖凝胶排阻色谱柱Sephadex G-10 HR对其进行脱盐纯化。采用丙烯葡聚糖凝胶排阻色谱柱Sephacryl S-300 HR和十二烷基磺酸钠-聚丙烯酰胺凝胶电泳(SDS-PAGE)检测分离纯化后的EGFP纯度。最后通过荧光分光检测器和非变性聚丙烯酰胺凝胶电泳(Native-PAGE)验证分离纯化后的EGFP是否具有荧光活性。结果表明该方法可以简便快速地分离纯化EGFP,纯度超过98%,同时保持了EGFP的荧光活性。

关键词: 金属螯合亲和色谱;凝胶排阻色谱;增强型绿色荧光蛋白;分离;纯化

文章编号: 1000-8713(2013)02-0151-04

 

Isolation and purification of enhanced green fluorescent protein using chromatography

HOU Qinghua1,2, SONG Shuliang1,2, LIANG Hao1,2, WANG Weili1,2, JI Aiguo1,3*

(1. Weihai International Biotechnology R& D Center, Shandong University, Weihai 264209, China; 2. Marine School of Shandong University at Weihai, Weihai 264209, China; 3. Pharmaceutical School of Shandong University, Jinan 250012, China)

Abstract: Enhanced green fluorescent protein (EGFP) is a common biological marker. In this research, on the foundation of successful clone and expression of EGFP, a two-step chromatographic method was established to separate and purify EGFP, which includes the use of HisTrap HP immobilized metal affinity chromatography (IMAC) and Sephadex G-10 HR size exclusion chromatography in sequence. Sephacryl S-300 HR size exclusion chromatography and sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) were used to check out the purity of EGFP. At last, it was found that EGFP still had fluorescent activity using fluorescence spectrophotometric detection and Native-PAGE detection. This method can effectively separate the active EGFP. The purity of the obtained EGFP was more than 98%.

Key words: immobilized metal affinity chromatography (IMAC); gel exclusion chromatography (GEC); enhanced green fluorescent protein (EGFP); separation; purification

 

155~161

DOI: 10.3724/SP.J.1123.2012.09003

*通讯联系人.Tel: (0535)20109130,E-mail: lxchen@yic.ac.cn.

基金项目: 国家自然科学基金项目(21275158, 21105117);山东省自然科学基金项目(ZR2010BQ027);山东省优秀中青年科学家奖励基金项目(BS2009CL055);烟台市科技发展项目(2010158).

收稿日期: 2012-09-03

 

超声辅助分散液液微萃取-高效液相色谱测定水样中的4种邻苯二甲酸酯类增塑剂

马燕玲1,2, 陈令新1,2*, 丁养军1, 明永飞3, 李金花2

(1. 曲阜师范大学化学与化工学院, 山东 曲阜 273165; 2. 中国科学院烟台海岸带研究所, 中国科学院海岸带环境过程重点实验室, 山东 烟台 264003; 3. 鲁东大学生命科学学院, 山东 烟台 264025)

摘要: 建立了采用超声辅助分散液液微萃取技术结合高效液相色谱法(UA-DLLME-HPLC)对4种邻苯二甲酸酯(PAEs)进行富集、检测的方法,并成功应用于实际水样分析。实验中采用富集因子来评价萃取效率,考察并优化了影响萃取效率的主要因素,包括萃取剂类型和用量、分散剂类型和用量、超声时间、离子强度、萃取时间和pH值等。结果表明: 在最佳萃取条件下,该法对4种PAEs(邻苯二甲酸二甲酯、邻苯二甲酸二乙酯、邻苯二甲酸二丁酯和邻苯二甲酸二正辛酯)具有较高的富集能力,富集因子分别为71、144、169和159;检出限分别为3.78、1.77、3.07和3.30 μg/L。对实验室自来水、某品牌矿泉水以及湖水分别加标50、200及500 μg/L的回收率为82.99%~114.47%,相对标准偏差为1.93%~8.31%。该法简便、快速、环保,可以用于测定实际水样中的PAEs类增塑剂。

关键词: 分散液液微萃取;超声辅助;高效液相色谱;邻苯二甲酸酯;水样

文章编号: 1000-8713(2013)02-0155-07

 

Simultaneous determination of four phthalate esters in water samples using ultrasound-assisted dispersive liquid-liquid microextraction coupled with high performance liquid chromatography

MA Yanling1,2, CHEN Lingxin1,2*, DING Yangjun1, MING Yongfei3, LI Jinhua2

(1. College of Chemistry and Chemical Engineering, Qufu Normal University, Qufu 273165, China; 2. Key Laboratory of Coastal Zone Environmental Processes, Yantai Institute of Coastal Zone Research, Chinese Academy of Sciences, Yantai 264003, China; 3. College of Life Science, Ludong University, Yantai 264025, China)

Abstract: Ultrasound-assisted dispersive liquid-liquid microextraction coupled with high performance liquid chromatography(UA-DLLME-HPLC)was developed for the determination of four typical phthalate esters (PAEs). The analyzed PAEs included dimethyl phthalate(DMP), diethyl phthalate(DEP), dibutyl phthalate(DBP)and di-n-octyl phthalate(DnOP). The UA-DLLME parameters such as types/volumes of extraction/dispersion solvents, ultrasonic time, ionic strength and extraction time, were investigated. Enrichment factor (EF)was employed to evaluate the extraction efficiency. The conditions were finally chosen: CCl4 (40 μL)/acetonitrile (1.0 mL) as extraction/dispersion solvents; 30 g/L NaCl; ultrasound/centrifugation of 5 min. Under the optimized extraction conditions, UA-DLLME exhibited strong enrichment ability for the four PAEs. The EFs for DMP, DEP, DBP and DnOP obtained were 71, 144, 169 and 159, respectively. The limits of detection were 3.78, 1.77, 3.07 and 3.30 μg/L for DMP, DEP, DBP and DnOP, respectively. The satisfactory recoveries for three water samples at three spiked levels ranged from 82.99%-114.47%, with the relative standard deviations of 1.93%-8.31%. It is a convenient, speedy, environmentally benign method for the routine analysis of PAEs in water samples.

Key words: dispersive liquid-liquid microextraction (DLLME); ultrasound-assisted (UA); high performance liquid chromatography (HPLC); phthalate esters (PAEs); water sample

 

162~169

DOI: 10.3724/SP.J.1123.2012.09041

*通讯联系人.E-mail: docwu@126.com.

基金项目: 国家质检总局科技项目(2009QK325).

收稿日期: 2012-09-28

 

固相萃取-超高效液相色谱分离测定洗涤用品中4种荧光增白剂

冼燕萍, 郭新东, 罗海英, 吴玉銮* , 陈意光, 罗东辉, 吴文海

(广州市质量监督检测研究院 国家化妆品质量监督检验中心(广州), 广东 广州 510110)

摘要: 建立了固相萃取净化结合超高效液相色谱-二极管阵列检测器(UPLC-DAD)同时检测洗衣液、洗衣粉等洗涤用品中荧光增白剂351、85、28和71的分析方法。样品经2%(体积分数)甲酸水溶液-甲醇提取,经WAX固相萃取小柱净化后,采用Phenomenex Synergi Max-RP色谱柱(150 mm×2.0 mm),以乙腈-10 mmol/L乙酸铵为流动相实现待测物(包括顺式和反式异构体)的良好分离,以二极管阵列检测器检测,结合保留时间和光谱图定性,以标准曲线定量。结果表明,4种荧光增白剂在0.05~180 mg/L范围内线性关系良好,相关系数均大于0.9993;方法定量限(S/N=10)为1.5~15 mg/kg;添加水平为5~1500 mg/kg时,回收率为84.9%~105%,相对标准偏差(RSD, n=6)为3.2%~6.1%。应用本方法分析了15个样品,阳性样品检出率为53.3%。该法前处理简单,回收率高,精密度好,适用于洗涤用品中4种荧光增白剂的测定。

关键词: 固相萃取;超高效液相色谱-二极管阵列检测器;荧光增白剂;洗涤用品

文章编号: 1000-8713(2013)02-0162-08

 

Determination of four fluorescent whitening agents in laundry detergents by solid phase extraction combined with ultra-high performance liquid chromatography

XIAN Yanping, GUO Xindong, LUO Haiying, WU Yuluan*, CHEN Yiguang, LUO Donghui, WU Wenhai

(Guangzhou Quality Supervision and Testing Institute, National Centre for Quality Supervision and Testing of Cosmetics (Guangzhou), Guangzhou 510110, China)

Abstract: A new method was established to determine three stilbene-type disulfonate and one distyrylbiphenyl-type fluorescent whitening agents (FWA351, FWA85, FWA28 and FWA71) in laundry detergents by solid phase extraction (SPE) and ultra-high performance liquid chromatography with a diode array detector (UPLC-DAD). The fluorescent whitening agents were extracted from laundry detergents with 2% formic acid aqueous solution and methanol, and purified by WAX SPE column, and analyzed by UPLC-DAD on a Phenomenex Synergi Max-RP column (150 mm×2.0 mm), employing acetonitrile-10 mmol/L ammonium acetate as the mobile phase in a gradient elution mode. The fluorescent whitening agents were qualitatively determined by retention time, and confirmed by the ultraviolet spectrum. The results indicated that the target analytes were in the range of 0.05-180 mg/L with the correlation coefficients (r) greater than 0.9993, and the method limits of quantification (MLOQ) of target analytes were ranged from 1.5 mg/kg to 15 mg/kg (S/N=10). The feasibility of this method was demonstrated by the determination of FWAs in samples with spiked recoveries. The recoveries were in the range between 84.9% and 105%, and the precision (relative standard deviation, RSD) ranged from 3.2% to 6.1% (n=6). Among the 15 samples analyzed, the rate of positive samples was 53.3%, over 1000 mg/kg of FWA351 and FWA71 were detected. The method is simple, precise and has high recoveries for the determination of fluorescent whitening agents in laundry detergent samples.

Key words: solid-phase extraction (SPE); ultra-high performance liquid chromatography-diode array detector (UPLC-DAD); fluorescent whitening agents (FWAs); laundry detergents

 

170~173

DOI: 10.3724/SP.J.1123.2012.09035

*通讯联系人.Tel: (020)38290355,E-mail: linhd@iqtc.cn.

基金项目: 国家质检总局公益性行业科研专项(201110019);中国检验检疫科学研究院项目(2009JK011);“十二五”农村领域国家科技计划课题(2011BAD23B05-4);广东省科技基础条件建设项目(粤科财字【2008】658,【2010】185).

收稿日期: 2012-09-24

 

分散固相萃取-高效液相色谱法快速测定果蔬中的6种保鲜剂残留量

林海丹*, 邹志飞, 秦燕, 谢守新, 陈毓芳, 徐娟, 王岚, 陈楚莹

(广东出入境检验检疫局检验检疫技术中心, 广东 广州 510623)

摘要: 建立了采用分散固相萃取-高效液相色谱同时测定果蔬中2,4-滴、噻苯咪唑、乙萘酚、邻苯基苯酚、二苯醚和联苯6种保鲜剂残留量的方法。样品经乙腈提取(同时加入氯化钠和无水硫酸镁),提取液经酸性氧化铝分散固相萃取净化,采用Agilent TC C18色谱柱(250 mm×4.6 mm, 5 μm),以甲醇-0.02 mol/L的磷酸二氢钾溶液(pH 6)作为流动相,流速1.0 mL/min,梯度洗脱,用紫外检测器检测,检测波长为235 nm,外标法峰面积定量。6种保鲜剂在0.5~20 mg/L范围内线性关系良好,相关系数均大于0.99; 6种保鲜剂在样品中添加1、2和10 mg/kg 3个浓度水平的回收率为84.2%~99.1% (n=6),相对标准偏差为1.67%~10.3%;方法的定量限为1 mg/kg。该法简便、准确,适用于果蔬中6种保鲜剂残留量的检测。

关键词: 高效液相色谱;分散固相萃取;保鲜剂;果蔬

文章编号: 1000-8713(2013)02-0170-04

 

Rapid determination of six preservative residues in fruits and vegetables by high performance liquid chromatography using dispersive solid phase extraction

LIN Haidan*, ZOU Zhifei, QIN Yan, XIE Shouxin, CHEN Yufang, XU Juan, WANG Lan, CHEN Chuying

(Inspection and Quarantine Technology Center, Guangdong Entry-Exit Inspection and Quarantine Bureau, Guangzhou 510623, China)

Abstract: A dispersive solid phase extraction-high performance liquid chromatographic (HPLC) method was established for the simultaneous determination of 2,4-D, thiabendazole, 2-naphthol, o-phenyl phenol, diphenyl ether and biphenyl in the fruits and vegetables. The samples were vortexed for extraction with acetonitrile containing sodium chloride and anhydrous magnesium sulfate. The acetonitrile extraction was purified by acidic alumina dispersed solid phase extraction. The analysis was performed on an Agilent TC C18 column (250 mm×4.6 mm, 5 μm) and an ultraviolet detector at 235 nm with a mobile phase of methanol-0.02 mol/L (pH 6) potassium dihydrogen phosphate solution, at a flow rate of 1.0 mL/min with gradient elution. Good linearities were observed in the range of 0.5-20 mg/L with correlation coefficients greater than 0.99. The average recoveries of the six preservatives in fruits and vegetables were in the range of 84.2%-99.1% at three spiked levels of 1, 2 and 10 mg/kg (n=6) and the relative standard deviations (RSDs) were in the range of 1.67%-10.3%. The limits of quantification were 1 mg/kg. This method is simple, accurate and suitable for the determination of the six preservatives in fruits and vegetables.

Key words: high performance liquid chromatography (HPLC); dispersive solid phase extraction; preservatives; fruits and vegetables

 

174~178

DOI: 10.3724/SP.J.1123.2012.09020

*通讯联系人.E-mail: dzk0607@163.com.

基金项目: 湖南省高校创新平台开放基金项目(11k062).

收稿日期: 2012-09-17

 

高效液相色谱-间接光度法同时检测己内酰胺副产物中1-磺酸环己烷羧酸及硫酸根离子

颜志祥, 段正康*, 李立南, 李海涛, 陈秋云, 彭叶

(湘潭大学化工学院 绿色催化与反应工程国家重点实验室, 湖南 湘潭 411105)

摘要: 提出了一种能够同时检测具有紫外吸收(UV)的有机物和无紫外吸收的无机物含量的强阴离子交换色谱法(IEC)。以检测己内酰胺副产物中的1-磺酸基环己烷羧酸(SCCA)粗盐为具体实例开展研究。强阴离子色谱柱以及UV检测器被用于同时分析SCCA和硫酸根离子。本实验基于高效液相色谱-间接光度检测法(HPLC-IPD)原理来测定SCCA和硫酸根离子,选用具有强紫外吸收能力的邻苯二甲酸作为本底试剂加入到流动相中产生信号。硫酸根离子和SCCA分别在0.10~10.0 g/L和0.50~40.0 g/L范围内呈良好的线性关系,相关系数分别为0.99914和0.99997;加标回收率分别为98.50%~101.00%和93.33%~97.40%,定量限均为0.10 g/L,符合色谱检测要求。该方法具有良好的分离选择性,可用于SCCA和硫酸根离子的同时检测。

关键词: 阴离子交换色谱法;高效液相色谱;间接光度检测;硫酸根离子;1-磺酸基-环己烷羧酸;己内酰胺副产物;邻苯二甲酸;本底试剂

文章编号: 1000-8713(2013)02-0174-05

 

Simultaneous determination of 1-sulfo-cyclohexane carboxylic acid and sulfate anion in the by-products of caprolactam by high performance liquid chromatography-indirect photometric analysis

YAN Zhixiang, DUAN Zhengkang*, LI Linan, LI Haitao, CHEN Qiuyun, PENG Ye

(State Key Laboratory of Green Catalysis and Reaction Engineering, College of Chemical Engineering, Xiangtan University, Xiangtan 411105, China)

Abstract: An improved anion-exchange chromatographic method was developed for simultaneous quantification of 1-sulfo-cyclohexane carboxylic acid (SCCA) and sulfate anion in the by-products of caprolactam. An strong anion chromatographic column and an ultraviolet (UV) detector were chosen for the assay of SCCA and sulfate anion. Non-chromophore-containing sulfate anion is not directly adaptable to the commonly used ultraviolet detection of high performance liquid chromatography (HPLC). This paper reports the development and validation of an HPLC assay for SCCA and sulfate anion based on indirect ultraviolet detection. An ultraviolet-absorbing reagent (the probe), phthalic acid (PA), was added to the mobile phase to induce a signal for the compound. The proposed method was qualified based on the performance criteria of repeatability, intermediate precision and linearity. The limits of detection were 1.0 g/L for both the analytes. The linear ranges varied from 0.50 to 40.0 g/L for SCCA and from 0.10 to 10.0 g/L for sulfate anion, with the correlation coefficients of 0.99997 and 0.99914, and the recoveries of 93.33%-97.40% and 98.50%-101.00%, respectively. The established method can be used in practice to determine SCCA and sulfate anion simultaneously with perfect separation selectivity.

Key words: anion-exchange chromatography; high performance liquid chromatography (HPLC); indirect photometric detection; sulfate anion; 1-sulfo-cyclohexane carboxylic acid; by-products of caprolactam; phthalic acid; the probe reagent

 

 


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