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荧光二阶校正法在生物体液和食品中应用性研究

Applications of Fluorescence Coupled with Second-order Calibration Methods in Biological Fluid and Food Analysis

【作者】 张娟

【导师】 吴海龙;

【作者基本信息】 湖南大学 , 分析化学, 2012, 硕士

【摘要】 化学计量学是一门新兴化学分支学科,由化学与数学、统计学、计算机科学等学科交叉产生,其宗旨是通过解析化学量测数据最大限度地获取化学及相关信息。现代分析化学的特征使仪器分析与化学计量学相结合用于复杂体系中多组分的定量分析成为必然。多维校正是化学计量学领域中最为活跃的部分,其中二阶校正具有“二阶优势”,能够在未知干扰存在下实现感兴趣组分的定量分析。二阶校正能以“数学分离”代替或增强“物理、化学分离”,已被广泛应用于生物医药、食品化学、环境化学等领域中实际分析难题的解决。荧光方法是一种高灵敏度检测技术。本论文中将三维荧光光谱与化学计量学中二阶校正方法相结合对生物体液和食品中待分析物进行了定量分析研究。主要内容如下:在第2章中,细胞培养基成分复杂,含有多种荧光干扰物质。利用三维荧光光谱法分别与平行因子分析方法及自加权交替三线性分解方法相结合,实现了细胞培养基样中山姜素的直接定量测定。乙氧喹啉(ethoxycarbonyl quinoline,EQ)是目前国内外广泛使用的抗氧化剂,常被用于饲料、食品,以防止其中的脂肪和蛋白在贮存过程中变质。第3章提出了一种新的乙氧喹啉常规定量检测方法,即采用激发发射矩阵荧光结合化学计量学中基于交替三线性分解算法的二阶校正方法定量测定了牛奶样中乙氧喹啉的含量,效果较为理想。在第4章中,双酚A (bisphenol A,BPA)和双烯雌酚(dienestrol,DE)是两种内分泌干扰物,对人体和环境均会造成不良影响,在奶粉中残留的可能性比较大。本章利用双酚A和双烯雌酚自身的荧光性质,借助于二阶校正方法的“二阶优势”,对奶粉样中这两种物质进行了的同时快速定量分析。在第5章中,己烯雌酚(diethylstilbestrol,DES)是第一个人工合成非甾体类雌激素,有研究证明DES具有致畸和致癌的毒性。DES是脂溶性物质,很难降解,容易在动物体内残留,即便排出体外也会在水源和土壤中富集,造成环境污染恶性循环,同时通过食用有DES残留的动物源食品也会增加患癌症的风险。己烯雌酚自身不具有荧光。它经浓硫酸氧化后水解产物具有较强荧光,在不同酸度环境下,呈现不同的物质形态。该章通过三维荧光光谱仪扫描了一系列不用pH值下的样本,得到三维数据。利用化学计量学方法实现了对三维数据中有用信息的提取,获得了体系水解产物各可能形态在不同pH值环境下的相对分布情况。

【Abstract】 Chemometrics is a developing subdiscipline of chemistry. The aim ofchemometrics is focus on extracting chemical information by applying the methodsof mathematics, statistics and computer sciences. The characteristics of modernanalytical chemistry make the determination of components of interest in complexsystem using instrumental analysis combined with chemometrics inevitable. Themulti-way calibration is one of the most active domains of chemometrics. Thesecond-order calibration methodologies have the second-order advantage whichallow for quantitation of analytes even in the presence of unexpected sampleconstituents. It can replace or enhance the ‘physical or chemical separation’ with‘mathematical separation’ strategy through separating the signals of target analytesaway from those of uncalibrated background or interferences. Such methods are usedwidely to resolve the difficult problems from various fields, especially biochemistryand pharmaceutical chemistry, food chemistry, environmental chemistry. As isknown, the fluorescence spectroscopy has high sensitivity. The research work in thisdissertation focuses on the determination of the analytes of interest in biologicalfluid and food by applying the three-dimensional fluorescence coupled with thesecond-order calibration methods. The main contents are as following.In chapter2, the composition of the cell culture medium is complicated. Itcontains many chemicals which have fluorescence properties. A newspectrofluorimetric method has been developed for the quantitative determination ofthe alpinetin content in cell culture medium samples. This method combinedthree-dimensional fluorescence with chemometric second-order calibration methodsbased on parallel factor analysis (PARAFAC) and self-weighted alternating trilineardecomposition (SWATLD) algorithms. Ethoxycarbonyl quinoline is antioxidantcommonly used by domestic and foreign. It is usually used to prolong the shelflife offeedstuff and food by protecting them against deterioration caused by oxidation. Inchapter3, a new method using excitation-emission matrix fluorescence coupled withsecond-order calibration method based on alternating trilinear decomposition (ATLD)algorithm for determining ethoxycarbonyl quinoline in milk samples is presented.The results are satisfied.In chapter4, bisphenol A (BPA) and dienestrol (DE) are endocrine and disrupting chemicals. They will have bad effect on human health and theenvironment. They are potential substances in the milk. The application offluorescence techniques with the aid of the second-order calibration method to thequantitative analysis of them in milk samples is advantageous because of the highsensitivity that can be achieved. In chapter5, diethylstilbestrol (DES) is one of thenonsteroidal estrogen. Some studies show that it can cause teratogens andcarcinogenic effects. DES is poor degradable. Residues of DES exist extensively inanimals, source of water and soil. That can create a vicious circle of environmentalpollution. Moreover, eating the animal products with the residues of DES canincrease the risk of cancer. DES without inherent fluorescence properties can reactwith concentrated sulphuric acid. After the reaction, the product has strongfluorescence intensity. At different pH levels, the aqueous solution of the productshows different existing states. We obtain the three-way data by scanning thesamples whose pH values are different using the luminoscope. The relativedistributions of hydrolysate at the situation of different pH levels are gained, sincethe chemometric method can extract useful information from the three-way data.

  • 【网络出版投稿人】 湖南大学
  • 【网络出版年期】2013年 03期
  • 【分类号】Q503;TS207.3;O657.3
  • 【被引频次】2
  • 【下载频次】198
  • 攻读期成果
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