稀散元素硒、碲量子点的合成和应用及其催化动力学分析方法的研究
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摘要
在生物大分子如蛋白质、DNA的检测分析中，由于研究对象含量低，检测条件要求苛刻，需要一些高灵敏度的分析方法，常用的方法如放射性同位素分析，荧光分析等方法。放射性同位素分析在使用中不仅会对研究对象造成损害，使其变性、失活，而且对操作者也存在一定的危害风险，实验废弃物处理也是一个难题；荧光分析因其具有较高的灵敏度，操作简便、快速，广泛应用于生物样品的分析，如分子荧光光谱分析，荧光显微镜成像分析等。但多数生物样品，自身只能被激发出极弱的荧光或根本不发射荧光，无法直接进行荧光分析，因此，多采用有机荧光染料对其进行标记，根据有机荧光染料与生物样品作用时荧光强度的变化，进行间接的定性定量分析。有机荧光染料最致命的缺点是在紫外光照射条件下，易发生光漂白和光降解，光解产物还会对生物体产生损伤，而且有机荧光染料的激发范围窄，发射峰存在严重的拖尾，不能满足长时间、高灵敏性、多颜色、多通道的生物检测的要求。
近年来，具有优异光学性能的半导体荧光纳米粒子——量子点(QDs)，作为传统有机荧光染料的替代者，在生物荧光分析和标记领域中引起人们的极大兴趣。量子点是由Ⅱ-Ⅵ族和Ⅲ-Ⅴ族元素组成的半导体纳米粒子，具有纳米尺度的量子点显示出特殊的光学特征：荧光强度大且稳定，抗光漂白能力强，激发光谱宽，发射光谱窄，较大的斯托克斯位移和较窄而且对称的荧光光谱，且发射波长可通过改变量子点的粒径大小和组成来控制等优点。无论是应用尺寸控制的量子点作为译码标签的多元平行分析目标物，还是功能化的量子点在不同的领域内进行原位成像，示踪细胞的新陈代谢过程，在单细胞水平上展示了它应用于医学与生命科学的巨大潜力。
基础的研究已揭示分析试验中的离子与量子点表面的原子能够相互发生某些物理化学作用，导致量子点表面的微环境改变，表现为对量子点荧光有显著改变。利用这一性质，对量子点的表面进行功能化修饰，使其能够高选择性的识别某一阴离子或阳离子，这一性质使其在金属离子检测方面显示出巨大的优势。
电化学生物传感器因其具有检测快速，成本低廉，易于集成化和自动化等优点，在基因检测、抗癌药物筛选、药物作用机理研究以及疾病的诊断与治疗等方面逐渐成为一个极具生命力的检测研究手段。量子点优良的光谱特征和电化学活性使其在设计各类新颖、高性能电化学生物传感器方面表现出巨大的科学研究价值与实际应用价值，引起研究人员的极大关注。
以稀散元素硒(Se)、碲(Te)为主要原料，合成的量子点具有较高的稳定性和优异的光学、电化学性能。而硒、碲两种元素，更是在半导体感光器件，计算机，通讯及宇航开发，能源，医药卫生，健康保健以及高技术装备等重要领域发挥着巨大的作用，成为关系到国计民生的战略性资源。众所周知，稀散元素硒、碲在自然界中的储量都比较低(稀)，伴生于其它金属或矿物中，基本无独立矿物存在(散)，因此硒、碲的分析方法引起了人们极大的关注和重视。
本文在水相中合成了CdSe QDs和CdTe QDs，对光学性能和稳定性优良的CdTe QDs，合成的条件进行了讨论，提出了新的Te前体的合成路线，应用多种手段对CdTe QDs的光学性能和结构进行表征，计算量子产率，研究了散射光对荧光测定的影响，并提出了消除方法，讨论了不同尺寸CdTe QDs相互作用时的荧光强度的变化。应用CdTe QDs作为ⅠB，ⅡB族的金属离子的荧光探针，研究了它们相互作用的实验条件及选择性。通过研究CdTe QDs、DNA和柔红霉素(DNR)之间的作用，设计了基于荧光共振能量转移(FRET)的DNA探针。以CdTe QDs作为增敏剂，构建了高灵敏度、高选择性的DNA电化学传感器。并且研究了基于硒、碲对S~(2-)化合物还原亚甲基蓝(MB)的反应，利用催化动力学方法，测定痕量硒、碲。论文主要研究内容如下：
第一部分主要研究了稀散元素硒、碲化合物量子点的合成方法及生物大分子和无机离子检测方面的应用。
第一章序言对查阅的文献进行综述，主要包括以下内容：首先对量子点的概念及其物理性能、光学性能和潜在的毒性进行介绍；其次对量子点的合成方法进行了介绍，传统的有机相合成，水相合成、表面修饰和水相转化的最新研究进展；再次从生物标记、细胞成像、荧光共振能量转移和离子检测等方面介绍了量子点的荧光标记应用，以及量子点在免疫传感器、酶传感器和DNA传感器等领域应用的研究进展；最后阐述了本论文的主要研究意义、研究内容和创新之处。
第二章主要介绍了硒、碲化合物量子点的合成。本章以NaHSe和NaHTe为Se和Te的前体合成了CdSe QDs和CdTe QDs，并比较了二者的荧光光谱性质及稳定性，结果表明CdTe QDs具有更优越的光谱性质和更高的稳定性。对CdTeQDs的合成条件进行了讨论，得到最优条件：Cd~(2+)，Te~(2-)，MPA合成配比的为n_(Cd2+)：n_(Te2-)为2：1，n_(MPA)：n_(Te2-)为5：1，pH值为9．0，温度为96℃。采用新的Te前体合成方法，以金属Al作为还原剂，合成(NH_4)_2Te，与传统的NaHTe还原的方法相比，(NH_4)_2Te稳定性好，反应条件温和，便于大量制备和长期储存，使合成路线更加合理，操作更加方便。
第三章主要对所合成的CdTe QDs的性质及结构进行表征。利用紫外-可见光吸收光谱仪，荧光光谱光谱仪，对不同尺寸的QDs的光学性能进行表征，尺寸可以通过控制反应时间调谐。随QDs尺寸的增加，吸收光谱和荧光发射光谱都发生显著红移；应用紫外-可见光谱带边吸收方法，透射电镜和X-射线粉末衍射对QDs尺寸进行估计。X-射线粉末衍射谱证实了本实验室所合成的CdTe QDs属立方闪锌矿结构；红外光谱图可得知MPA的巯基与CdTe QDs发生了作用，达到了钝化CdTe QDs表面的目的；以罗丹明B的乙醇溶液为参照物，计算CdTeQDs的量子产率为28%；研究了散射光产生的原因，及其对荧光测定的影响，并提出了消除散射光的方法；提出了不同尺寸CdTe QDs相互作用时的“叠加效应”或“猝灭效应”，并对其产生原因进行探讨。
第四章主要研究了碲化镉量子点与ⅠB，ⅡB族金属离子的作用。讨论了发射峰位于540nm，570 nm，600 nm的3种粒径的CdTe量子点与Cu(Ⅱ)，Ag(Ⅰ)，Hg(Ⅱ)，Au(Ⅲ)离子相互作用时荧光强度的变化，为这些离子的检测选择合适粒径的CdTe量子点。在实验中发现，Cu(Ⅱ)，Hg(Ⅱ)，Au(Ⅲ)离子对3种CdTe QDs的荧光强度有明显的猝灭作用，Ag(Ⅰ)离子对600 nm的CdTe量子点的荧光强度有明显的猝灭作用，而对540nm，570 nm的CdTe量子点的荧光强度作用为先增强，后猝灭。在一定的条件下，体系的相对荧光强度(△F=F_0-F)与Cu(Ⅱ)，Ag(Ⅰ)，Hg(Ⅱ)，Au(Ⅲ)离子的浓度呈线性关系。掩蔽剂EDTA与Cu~(2+)或Ag~+发生络合作用，会削弱Cu~(2+)/Ag~+对CdTe QDs荧光强度的影响。对Au(Ⅲ)的模拟样品进行测定，相对标准偏差为1．6%。对猝灭机理进行了探讨。
第五章主要研究了CdTe量子点-DNA与柔红霉素(DNR)相互作用。根据吸收光谱和荧光光谱，推断出DNR与DNA发生了嵌插作用，CdTe QDs与DNA可能存在着非嵌插的吸附作用，CdTe QDs与DNR之间没有直接的吸附作用，但DNR对CdTe QDs的荧光有很强的猝灭作用，其形式为能量转移猝灭。通过盐效应实验和热变性实验进一步加以印证DNR与DNA的嵌插作用。计算了Stern-Volmer曲线的猝灭常数K_(SV)，以及热力学参数△H，△G，△S，对二元体系的作用形式及荧光猝灭形式进行判断。在三元体系实验中，不同的混合顺序，产生了不同的荧光效果，对其原因进行了描述，并在此基础上，设计了基于荧光共振能量转移的DNA探针。
第六章研究了CdTe量子点标记的DNA电化学传感器。本章利用碳纳米管和CdTe量子点(QDs)组装的电化学传感器，建立了一种识别DNA的新方法。将带有有氨基的单链DNA探针，共价键合固定在带有羧基的碳纳米管修饰的金电极上，然后与CdTe QDs标记的目标DNA进行杂交。利用差分脉冲法(DPV)和循环伏安法(CV)对目标DNA的固定和杂交进行表征，通过电活性指示剂柔红霉素(DNR)的DPV峰电流变化，对互补DNA，非互补DNA和单碱基错DNA序列进行识别。相比较未标记CdTe QDs的目标DNA，标记CdTe QDs的目标DNA序列的电流响应值的灵敏度明显提高。对DNA电化学传感器的检测反应条件进行优化：DNR的浓度为1．67×10~(-5)mol/L，DNA杂交时间为80 min，杂交温度为55℃。目标DNA的浓度在1．0×10~(-13)～1．0×10~(-8)mol/L范围内，其对数值与其响应的DPV信号(还原峰电流)成线性关系，检测限为3．52×10~(-14)mol/L(S/N=3，n=9)。线性方程为△I=50．22+3．5671 lgC_(DNA)，相关系数为0．9966。对浓度为1．0×10~(-10)mol/L的目标DNA样品进行重复测定，相对标准偏差RSD=4．8%(n=5)，有良好的重现性。
第二部分主要研究了稀散元素硒、碲的催化动力学分析方法。其中第一章序言主要包括以下内容：首先分别介绍了硒、碲的分析检测的样品处理、分离富集和分析方法的研究进展；其次详细介绍了催化动力学分光光度法，硒、碲的催化动力学分光光度法研究进展；最后阐述了本论文的主要研究意义、研究内容和创新之处。
第二章主要研究了催化动力学光度法测定痕量硒的方法。基于硒(Ⅳ)催化硫代乙酰胺在碱性条件下还原亚甲基蓝的反应，测定痕量的硒。由于催化反应的的反应速率在一定范围内与催化剂的用量有一定的比例关系，因此可根据反应速度与催化剂的关系进行定量分析。通过测定催化反应及非催化反应的吸光度之差的变化斜率(即反应速率)，实现定量分析生物样品中痕量硒的目的。硒含量在0．1～1．0μg/15mL范围内服从朗伯比尔定律，回归方程为y=0．0195x-0．0024，相关系数r=0．995，测定了枸杞子中的硒的含量，相对标准偏差为5．4%(n=4)，加标回收率为90%～96%，计算了催化反应的表观活化能为38．24kJ·mol~(-1)。本法灵敏度高，重现性好。
第三章主要研究催化动力学光度法测定碲。基于Te(Ⅳ)催化S~(2-)还原亚甲基蓝褪色反应，建立了新的测定微量碲的动力学分析方法。研究了催化反应条件，并测定了催化反应的表观活化能为68．94 kJ·mol~(-1)。Te(Ⅳ)浓度在20～220ng·mL~(-1)范围内服从比尔定律，回归曲线的线性方程为y=0．0038x+0．2191，相关系数r=0．9995，方法的检出限为3．04 ng·mL~(-1)。研究了硒、碲的分离方法，应用于粗硒粉中微量碲的测定，相对标准偏差为3．1%(n=7)，加标回收率为98．4%～100．4%。
实验结果表明：本论文所提出的以稀散元素硒、碲合成的量子点，替代传统有机荧光染料，用于生物大分子和无机离子的荧光分析的研究，立题不但具有较重要的科学研究价值、学术价值，同时也具有很好的实际应用价值；研究方案设计科学合理，技术方法选择正确有效；为进一步深入研究打下了很好的基础。
The detection of biomacromolecule, such as protein and DNA, need someanalysis method of high sensitivity because of the low content of research object andthe harsh detection condition. The common method is fluorescence analysis,radioactive isotope analysis. Radioactive isotope analysis not only damages thesample but also do harm to the researchers. The disposal of experiment is also aproblem. Because of its high sensitivity, simple and rapid operation, fluorescenceanalysis is widely applied to detect biological samples, such as fluorescence spectrumanalysis and fluorescence microscope imaging analysis. For most biological samples,weak or little fluoscence can be excitated from themselves. So organic fluorochromeis usually adopted to label them and qualitative and quantitative analysis is indirectlycarried out according to the change of fluorescence intensity in the reaction betweenorganic fluorochrome and biological samples. The fatal defect of organicfluorochrome is that photobleaching and photodegradation are easily happen underthe illumination of ultraviolet light and photodecomposition product may damage theorganism. In addition, organic fluorochrome has narrow excitation range and hasserious tailing in its emission peak. So it can not satisfy the need for long time, highsensitivity, multicolor and multicenter biological detection.
In the recent years, semiconductor fluorescence nano-patricle—quantum dots(QDs), which possess excellent optical properties, have drawn intense attention as thereplacer of traditional organic fluorochrome in the field of bioluminescence analysisand biological labeling. Quantum dots are semiconductor nano-patricle which consistsofⅡ-ⅥorⅢ-Ⅴrace element. The quantum dots of nanometer scale show specialoptical characteristics: high and stable fluorescence intensity, strong anti- photobleaching ability, broad excitation spectrum,narrow emission spectrum, largerstokes shift, size-tunable, narrow and symmetric emission spectra, emissionwavelength can be controlled by the change of size and composition. Whether thesize-controlled quantum dots are applied as decoding labels in parallel analysis ofmultiple targets, or functionalized quantum dots are applied to in situ imaging andtracing the course of cell metabolism in different fields, in single cell leveldemonstrated its great potential for medical and life sciences applications.
Basal studies have revealed that the ion in the analysis can react with the atom onthe surface of quantum dots, certain physical and chemical effects occur, leading tothe surface of quantum dots changes in micro-environment and the fluorescence ofquantum dots changes significantly. Take advantage of this nature, the surface ofquantum dots can be modified to enable it to identify a certain anion or cation withhigh selectivity. Because of the nature, it shows huge advantage in the detection ofmetal ion.
Because of its rapid, low-cost, easy integration and automation, etc.,electrochemical biosensor has gradually become a important analysis means in thegenetic testing, anti-cancer drug screening, drug mechanism studies, as well asdiagnosis and treatment of disease areas. It exhibited enormous science andapplication value that excellent spectral characteristics and electrochemical activity ofQuantum dots was caused greatly concern in the novel, high-performanceelectrochemical biosensor.
The quantum dots which synthesized by using rare and scattered elements Se andTe have high stability and excellent optical electrochemical properties. Selenium andtellurium play an important part in photosensitive semiconductor devices, computer,communications and aerospace development, energy, medicine and health care, theimportant high-tech equipment areas,they also are the strategic resources which areclosely related to the national economy and people's life. As well as we know, thereserve of rare and scattered elements selenium, tellurium is relatively low (rare) inthe nature, they associates with other metals or minerals and without self-mineralsbasically. So the Analysis methods for selenium and tellurium arise great concern.
In this paper, we synthesize the CdSe QDs and CdTe QDs by aqueous approach. The synthesis conditions of the CdTe QDs, which has excellent optical properties andstability, are discussed. New synthesis route of Te precursor has been put forward.Many instruments are used to characterize the optical properties and structure of CdTeQDs. Quantum yield has been calculated. The influence of scattered light on thedetection of fluorescence has been studied and elimination method has been proposedtoo. The changes of fluorescence intensity in the interaction between CdTe QDs ofdifferent sizes are discussed. CdTe QDs is used as fluorescence probe for metal ionsofⅠB,ⅡB race .For their interaction, experimental conditions and selectivity arestudied too. fluorescence resonance energy transfer (FRET)-based DNA probes aredesigned by studying the interaction among CdTe QDs、DNA and daunorubicin(DNR). DNA electrochemical sensor with high-sensitivity and high selectivity isconstructed with CdTe QDs as sensitizer. In addition, the catalytic effect ofselenium, tellurium for the redox reaction between sulfide and methylene blue (MB)are studied. Trace selenium, tellurium are detected by catalytic kinetics method.Major research paper is as follows:
The first part mainly studies the synthesis and application on biomacromoleculeand inorganic ions of QDs which composed of rare and scattered element Se, Tecompound.
Chapter one mainly contains literature review: First of all, we present theconception, the physical performance, the optical performance and potential toxicityof QDs. Secondly, we present synthetic method of QDs, and the latest researchprogress of traditional organically preparation, aqueous synthesis, surfacemodification and aqueous transform; Thirdly, we present the application of QDs suchas biological marking, cell imaging, fluorescence resonance energy transfer, iondetection, and improving on the application of immunosensor,enzymaticsensor,DNA sensor. Eventually, we present the main research meaning, research contentsand innovation of this article.
Chapter two mainly present the synthesis of QDs which composed of Se,Tecompounds. We prepare CdSe QDs and CdTe QDs which taking NaHSe and NaHTeas precursors of Se and Te, and compare the fluorescent spectrum properties andstability of them; the result indicates QDs has more superior spectrum properties and higher stability. We discuss the synthetic condition of QDs, and get the optimumcondition: the molar ratio of Cd~(2+), Te~(2-), and MPA,n_(Cd2+):n_(Te2-)is 2:1,n MPA:n_(Te2-)is5:1,pH is 9.0, the temperature is 96℃.We adopt a new Te precursors prepartionmethod, regard metal Al as reducing agent to prepare(NH_4)_2Te. Comparing with thetraditional method, the stability of (NH_4)_2Te is superior to NaHTe . And(NH_4)_2Te dueto the mild condition of reaction, easy to synthesis in a large amount and store for along time, it is more convenient and reasonable to synthesize.
Chapter three mainly signifies the property and the structure of CdTe QDs. Weutilize UV-vis absorb spectrogram, the fluorescent spectrocomparator to signify theoptical performance of different size of QDs, and the size can be controlled byreaction time. With the increasing of the size of QDs, absorption spectrum andfluorescent emission spectrometry become prominently red shift; We use UV-visspectrum absorption edge method, transmission electron microscopy and X-raypowder diffraction to estimate the size of QDs. X-ray powder diffraction has verifiedthat CdTe QDs formated in the laboratory belong to the cubic zincblende structure; IRspectroscopy indicate that CdTe QDs capped with MPA react with CdTe QDs, andachieve the purpose to passivat the surface of CdTe QDs; taking ethanol solution ofrhodamine B as the object of reference, calculate the quantum yield of CdTe QDs is28%; we also study the reason why it produces the scattered light, and the influence todetermine fluorescence, and put forward the method to dispel scattered light; wepropose different size of CdTe QDs interacting with each other may arise“additiveeffects”or“quenching effects”, and discuss the reason why it produce.
Chapter four mainly study tellurium cadmium quantum dots react with metal ioninⅠB andⅡB. Discuss the changes of fluorescent intensity while the emission peak in540nm, 570 nm, 600 nm CdTe QDs react with Cu (Ⅱ) ,Ag(Ⅰ) ,Hg(Ⅱ) ,Au(Ⅲ) ion. Wefind in the experiment, Cu (Ⅱ) ,Hg(Ⅱ) ,Au(Ⅲ) has obvious quenching function to thefluorescent intensity of CdTe QDs .Ag (Ⅰ) quench CdTe QDs at 600 nm while it firstincrease and then quenching fluorescent intensity of CdTe QDs at 540nm,570nm.Under certain condition, system relatively fluorescent intensity(△F=F_0-F)arelinear relationship with Cu (Ⅱ), Ag(Ⅰ), Hg(Ⅱ), Au(Ⅲ) ion. The shelter pharmaceuticalEDTA complex function with Cu~(2+)orAg~+, and it will weaken the influence of Cu~(2+)/Ag~+ to the fluorescence intensity of CdTe QDs. Determine simulation sampleAu (Ⅲ), and its relatively deviation standard is 1.6%. Finally we carried on thediscussion in quenching mechanism.
In the fifth chapter, we discuss the interaction between the CdTe QDs -DNAwith daunorubicin (DNR) that based on absorption and fluorescence spectra. Weconclude that DNR can insert the base of the DNA。The DNR and CdTe QDs areindirect adsorption, but have a strong fluorescence quenching that is the form ofenergy transfer quenching。Salt effect and thermal denaturation experiments canfurther prove that the insert functioning between the DNA and the DNR. WeCalculate the Stern-Volmer quenching constant curve Ksv, as well as thethermodynamic parameters△H,△G,△S, and determine the interact form of binarysystem and the form of fluorescence quenching。In the ternary system, differentmixture order can produced a different fluorescence effects, its causes are described,and on this basis, we design the DNA probe that based on fluorescence resonanceenergy transfer.
In the sixth chapter, we described a novel DNA electrochemical biosensor thatwas prepared base on CdTe quantum dots (QDs) and carbon nanotubes (CNTs)modified gold electrode. The ss-DNA probe was covalently attached onto a carboxylcarbon nanotubes modified gold electrode through amines of the DNA bases usingN-hydroxysulfosuccinimide (NHS) and N-(3-dimethylamion) propyl-N'-ethylcarbodiimidehy- drochloride (EDC). After hybridization with the target ssDNA-CdTequantum dots (QDs) nanoconjugates,differential pulse voltammetry(DPV) and cyclicvoltammetry (CV) were used to sensitive detection of the target DNA withdaunomycin (DNR) as the indicator. This DNA electrochemical sensor coulddifferentiate the completely complementary DNA sequence, non-complementaryDNA sequence and Single base mismatch DNA sequence, indicating a goodselectivity. Compared with target DNA sequences without CdTe QDs, CdTe QDslabels on target DNA could obviously improve the sensitivity. Hybridizationconditions determining the sensitivity of the electrochemical assay was investigated.The electrochemical responses suggested that optimal detection of hybridizationoccurred at 55℃for 80 minimums. Under optimal conditions, DNR concentration of 1.67×10~(-5) mol/L was chosen as the optimal accumulation concentration. The peakcurrent signal suggested that almost linear with the logarithm of oligodeoxynucleotide(ODN) concentration in the range 1.0×10~(-13)～1.0×10~(-8)mol/L with the minimumdetection limit of 3.52×10~(-14) mol/L based on the ratio of signal-to-noise of 3, linearregression equation is△I=50.22 +3.5671 1gC_(DNA) with the correlation coefficient of0.9966. The relative standard deviation (RSD) was 4.8% (n=5) with target DNAsample concentration of 1.0×10~(-10) mol/L. It indicated that a satisfactoryreproducibility could be obtained by this DNA electrochemical biosensor.
The catalytic kinetic analysis methods of rare and scattered elements-seleniumand tellurium are studied in the second part. The first chapter, preamble includes thefollowing contents: Firstly, we introduce analytical methods development of thesample handling, separation and preconcentration of selenium and tellurium;Secondly, we introduce catalytic kinetic spectrophotometric method in details, thedevelopment of catalytic kinetic spectrophotometric method of selenium and tellurium;finally, we present the main research meaning, research contents and innovation ofthis article.
Chapter two studies the method of catalytic kinetic spectrophotometricdetermination of trace selenium. Based on the reaction of methylene blue reductingthioacetamide with selenium (Ⅳ) as catalyses under alkaline conditions, this paperdetermines the trace selenium. Because reaction rate of catalytic reaction has a certainratio relationship with the amount of catalyst in a certain range, the quantitativeanalysis is made according to the relation between the reaction rate and catalyst. Bymeasuring the variation slope (i.e., reaction rate) of difference of the absorbancechanges between the Catalytic reaction and non-catalytic reaction, the quantitativeanalysis of trace selenium in biological samples is realized. The Selenium content inthe range of 0.1～1.0μg/15mL conforms to the Lambert-Beer's law, regressionequation is y=0.0195x-0.0024, correlation coefficient r=0.995, the selenium contentin medlar is measured and the relative standard deviation is 5.4% (n=4), recoveryrate is 90%～96%, calculated the apparent activation energy of catalytic reaction for38.24kJ mol~(-1).This method is high sensitivity and reproducibility.
Chapter three studies determination of tellurium by catalytic kinetic spectrophotometric. Based on Te (Ⅳ) catalytic reduction S~(2-) fading reaction ofmethylene blue, a new Kinetic Determination of Trace Tellurium analysis isestablished. By studying the catalytic reaction conditions, the apparent activationenergy of catalytic reaction is determined for 68.94 kJ mol~(-1).Te (Ⅳ) concentration isin the range of 20-220 ng mL~(-1) Beer's law is obeyed, the linear regression curveequation is y=0.0038 x+0.2191,correlation coefficient r=0.9995, detection limit is3.04 ng mL~(-1).The studied separation method of selenium and tellurium is applied fordetermination of trace tellurium of coarse selenium powder. The relative standarddeviation is 3.1% (n =7) and the recovery rate is 98.4%～100.4%.
The result of experiment indicate: the research which quantum dots weresynthesized by using rare & scattered elements selenium & tellurium and used influorescence analysis of biomacromolecule and inorganic ions to replace traditionalorganic fluorochrome not only has important science and learned value, but also hasbetter practically application value. The research project is reasonable, the experimentmeans is effectual. It is beneficial to high level research.
近年来，具有优异光学性能的半导体荧光纳米粒子——量子点(QDs)，作为传统有机荧光染料的替代者，在生物荧光分析和标记领域中引起人们的极大兴趣。量子点是由Ⅱ-Ⅵ族和Ⅲ-Ⅴ族元素组成的半导体纳米粒子，具有纳米尺度的量子点显示出特殊的光学特征：荧光强度大且稳定，抗光漂白能力强，激发光谱宽，发射光谱窄，较大的斯托克斯位移和较窄而且对称的荧光光谱，且发射波长可通过改变量子点的粒径大小和组成来控制等优点。无论是应用尺寸控制的量子点作为译码标签的多元平行分析目标物，还是功能化的量子点在不同的领域内进行原位成像，示踪细胞的新陈代谢过程，在单细胞水平上展示了它应用于医学与生命科学的巨大潜力。
基础的研究已揭示分析试验中的离子与量子点表面的原子能够相互发生某些物理化学作用，导致量子点表面的微环境改变，表现为对量子点荧光有显著改变。利用这一性质，对量子点的表面进行功能化修饰，使其能够高选择性的识别某一阴离子或阳离子，这一性质使其在金属离子检测方面显示出巨大的优势。
电化学生物传感器因其具有检测快速，成本低廉，易于集成化和自动化等优点，在基因检测、抗癌药物筛选、药物作用机理研究以及疾病的诊断与治疗等方面逐渐成为一个极具生命力的检测研究手段。量子点优良的光谱特征和电化学活性使其在设计各类新颖、高性能电化学生物传感器方面表现出巨大的科学研究价值与实际应用价值，引起研究人员的极大关注。
以稀散元素硒(Se)、碲(Te)为主要原料，合成的量子点具有较高的稳定性和优异的光学、电化学性能。而硒、碲两种元素，更是在半导体感光器件，计算机，通讯及宇航开发，能源，医药卫生，健康保健以及高技术装备等重要领域发挥着巨大的作用，成为关系到国计民生的战略性资源。众所周知，稀散元素硒、碲在自然界中的储量都比较低(稀)，伴生于其它金属或矿物中，基本无独立矿物存在(散)，因此硒、碲的分析方法引起了人们极大的关注和重视。
本文在水相中合成了CdSe QDs和CdTe QDs，对光学性能和稳定性优良的CdTe QDs，合成的条件进行了讨论，提出了新的Te前体的合成路线，应用多种手段对CdTe QDs的光学性能和结构进行表征，计算量子产率，研究了散射光对荧光测定的影响，并提出了消除方法，讨论了不同尺寸CdTe QDs相互作用时的荧光强度的变化。应用CdTe QDs作为ⅠB，ⅡB族的金属离子的荧光探针，研究了它们相互作用的实验条件及选择性。通过研究CdTe QDs、DNA和柔红霉素(DNR)之间的作用，设计了基于荧光共振能量转移(FRET)的DNA探针。以CdTe QDs作为增敏剂，构建了高灵敏度、高选择性的DNA电化学传感器。并且研究了基于硒、碲对S~(2-)化合物还原亚甲基蓝(MB)的反应，利用催化动力学方法，测定痕量硒、碲。论文主要研究内容如下：
第一部分主要研究了稀散元素硒、碲化合物量子点的合成方法及生物大分子和无机离子检测方面的应用。
第一章序言对查阅的文献进行综述，主要包括以下内容：首先对量子点的概念及其物理性能、光学性能和潜在的毒性进行介绍；其次对量子点的合成方法进行了介绍，传统的有机相合成，水相合成、表面修饰和水相转化的最新研究进展；再次从生物标记、细胞成像、荧光共振能量转移和离子检测等方面介绍了量子点的荧光标记应用，以及量子点在免疫传感器、酶传感器和DNA传感器等领域应用的研究进展；最后阐述了本论文的主要研究意义、研究内容和创新之处。
第二章主要介绍了硒、碲化合物量子点的合成。本章以NaHSe和NaHTe为Se和Te的前体合成了CdSe QDs和CdTe QDs，并比较了二者的荧光光谱性质及稳定性，结果表明CdTe QDs具有更优越的光谱性质和更高的稳定性。对CdTeQDs的合成条件进行了讨论，得到最优条件：Cd~(2+)，Te~(2-)，MPA合成配比的为n_(Cd2+)：n_(Te2-)为2：1，n_(MPA)：n_(Te2-)为5：1，pH值为9．0，温度为96℃。采用新的Te前体合成方法，以金属Al作为还原剂，合成(NH_4)_2Te，与传统的NaHTe还原的方法相比，(NH_4)_2Te稳定性好，反应条件温和，便于大量制备和长期储存，使合成路线更加合理，操作更加方便。
第三章主要对所合成的CdTe QDs的性质及结构进行表征。利用紫外-可见光吸收光谱仪，荧光光谱光谱仪，对不同尺寸的QDs的光学性能进行表征，尺寸可以通过控制反应时间调谐。随QDs尺寸的增加，吸收光谱和荧光发射光谱都发生显著红移；应用紫外-可见光谱带边吸收方法，透射电镜和X-射线粉末衍射对QDs尺寸进行估计。X-射线粉末衍射谱证实了本实验室所合成的CdTe QDs属立方闪锌矿结构；红外光谱图可得知MPA的巯基与CdTe QDs发生了作用，达到了钝化CdTe QDs表面的目的；以罗丹明B的乙醇溶液为参照物，计算CdTeQDs的量子产率为28%；研究了散射光产生的原因，及其对荧光测定的影响，并提出了消除散射光的方法；提出了不同尺寸CdTe QDs相互作用时的“叠加效应”或“猝灭效应”，并对其产生原因进行探讨。
第四章主要研究了碲化镉量子点与ⅠB，ⅡB族金属离子的作用。讨论了发射峰位于540nm，570 nm，600 nm的3种粒径的CdTe量子点与Cu(Ⅱ)，Ag(Ⅰ)，Hg(Ⅱ)，Au(Ⅲ)离子相互作用时荧光强度的变化，为这些离子的检测选择合适粒径的CdTe量子点。在实验中发现，Cu(Ⅱ)，Hg(Ⅱ)，Au(Ⅲ)离子对3种CdTe QDs的荧光强度有明显的猝灭作用，Ag(Ⅰ)离子对600 nm的CdTe量子点的荧光强度有明显的猝灭作用，而对540nm，570 nm的CdTe量子点的荧光强度作用为先增强，后猝灭。在一定的条件下，体系的相对荧光强度(△F=F_0-F)与Cu(Ⅱ)，Ag(Ⅰ)，Hg(Ⅱ)，Au(Ⅲ)离子的浓度呈线性关系。掩蔽剂EDTA与Cu~(2+)或Ag~+发生络合作用，会削弱Cu~(2+)/Ag~+对CdTe QDs荧光强度的影响。对Au(Ⅲ)的模拟样品进行测定，相对标准偏差为1．6%。对猝灭机理进行了探讨。
第五章主要研究了CdTe量子点-DNA与柔红霉素(DNR)相互作用。根据吸收光谱和荧光光谱，推断出DNR与DNA发生了嵌插作用，CdTe QDs与DNA可能存在着非嵌插的吸附作用，CdTe QDs与DNR之间没有直接的吸附作用，但DNR对CdTe QDs的荧光有很强的猝灭作用，其形式为能量转移猝灭。通过盐效应实验和热变性实验进一步加以印证DNR与DNA的嵌插作用。计算了Stern-Volmer曲线的猝灭常数K_(SV)，以及热力学参数△H，△G，△S，对二元体系的作用形式及荧光猝灭形式进行判断。在三元体系实验中，不同的混合顺序，产生了不同的荧光效果，对其原因进行了描述，并在此基础上，设计了基于荧光共振能量转移的DNA探针。
第六章研究了CdTe量子点标记的DNA电化学传感器。本章利用碳纳米管和CdTe量子点(QDs)组装的电化学传感器，建立了一种识别DNA的新方法。将带有有氨基的单链DNA探针，共价键合固定在带有羧基的碳纳米管修饰的金电极上，然后与CdTe QDs标记的目标DNA进行杂交。利用差分脉冲法(DPV)和循环伏安法(CV)对目标DNA的固定和杂交进行表征，通过电活性指示剂柔红霉素(DNR)的DPV峰电流变化，对互补DNA，非互补DNA和单碱基错DNA序列进行识别。相比较未标记CdTe QDs的目标DNA，标记CdTe QDs的目标DNA序列的电流响应值的灵敏度明显提高。对DNA电化学传感器的检测反应条件进行优化：DNR的浓度为1．67×10~(-5)mol/L，DNA杂交时间为80 min，杂交温度为55℃。目标DNA的浓度在1．0×10~(-13)～1．0×10~(-8)mol/L范围内，其对数值与其响应的DPV信号(还原峰电流)成线性关系，检测限为3．52×10~(-14)mol/L(S/N=3，n=9)。线性方程为△I=50．22+3．5671 lgC_(DNA)，相关系数为0．9966。对浓度为1．0×10~(-10)mol/L的目标DNA样品进行重复测定，相对标准偏差RSD=4．8%(n=5)，有良好的重现性。
第二部分主要研究了稀散元素硒、碲的催化动力学分析方法。其中第一章序言主要包括以下内容：首先分别介绍了硒、碲的分析检测的样品处理、分离富集和分析方法的研究进展；其次详细介绍了催化动力学分光光度法，硒、碲的催化动力学分光光度法研究进展；最后阐述了本论文的主要研究意义、研究内容和创新之处。
第二章主要研究了催化动力学光度法测定痕量硒的方法。基于硒(Ⅳ)催化硫代乙酰胺在碱性条件下还原亚甲基蓝的反应，测定痕量的硒。由于催化反应的的反应速率在一定范围内与催化剂的用量有一定的比例关系，因此可根据反应速度与催化剂的关系进行定量分析。通过测定催化反应及非催化反应的吸光度之差的变化斜率(即反应速率)，实现定量分析生物样品中痕量硒的目的。硒含量在0．1～1．0μg/15mL范围内服从朗伯比尔定律，回归方程为y=0．0195x-0．0024，相关系数r=0．995，测定了枸杞子中的硒的含量，相对标准偏差为5．4%(n=4)，加标回收率为90%～96%，计算了催化反应的表观活化能为38．24kJ·mol~(-1)。本法灵敏度高，重现性好。
第三章主要研究催化动力学光度法测定碲。基于Te(Ⅳ)催化S~(2-)还原亚甲基蓝褪色反应，建立了新的测定微量碲的动力学分析方法。研究了催化反应条件，并测定了催化反应的表观活化能为68．94 kJ·mol~(-1)。Te(Ⅳ)浓度在20～220ng·mL~(-1)范围内服从比尔定律，回归曲线的线性方程为y=0．0038x+0．2191，相关系数r=0．9995，方法的检出限为3．04 ng·mL~(-1)。研究了硒、碲的分离方法，应用于粗硒粉中微量碲的测定，相对标准偏差为3．1%(n=7)，加标回收率为98．4%～100．4%。
实验结果表明：本论文所提出的以稀散元素硒、碲合成的量子点，替代传统有机荧光染料，用于生物大分子和无机离子的荧光分析的研究，立题不但具有较重要的科学研究价值、学术价值，同时也具有很好的实际应用价值；研究方案设计科学合理，技术方法选择正确有效；为进一步深入研究打下了很好的基础。
The detection of biomacromolecule, such as protein and DNA, need someanalysis method of high sensitivity because of the low content of research object andthe harsh detection condition. The common method is fluorescence analysis,radioactive isotope analysis. Radioactive isotope analysis not only damages thesample but also do harm to the researchers. The disposal of experiment is also aproblem. Because of its high sensitivity, simple and rapid operation, fluorescenceanalysis is widely applied to detect biological samples, such as fluorescence spectrumanalysis and fluorescence microscope imaging analysis. For most biological samples,weak or little fluoscence can be excitated from themselves. So organic fluorochromeis usually adopted to label them and qualitative and quantitative analysis is indirectlycarried out according to the change of fluorescence intensity in the reaction betweenorganic fluorochrome and biological samples. The fatal defect of organicfluorochrome is that photobleaching and photodegradation are easily happen underthe illumination of ultraviolet light and photodecomposition product may damage theorganism. In addition, organic fluorochrome has narrow excitation range and hasserious tailing in its emission peak. So it can not satisfy the need for long time, highsensitivity, multicolor and multicenter biological detection.
In the recent years, semiconductor fluorescence nano-patricle—quantum dots(QDs), which possess excellent optical properties, have drawn intense attention as thereplacer of traditional organic fluorochrome in the field of bioluminescence analysisand biological labeling. Quantum dots are semiconductor nano-patricle which consistsofⅡ-ⅥorⅢ-Ⅴrace element. The quantum dots of nanometer scale show specialoptical characteristics: high and stable fluorescence intensity, strong anti- photobleaching ability, broad excitation spectrum,narrow emission spectrum, largerstokes shift, size-tunable, narrow and symmetric emission spectra, emissionwavelength can be controlled by the change of size and composition. Whether thesize-controlled quantum dots are applied as decoding labels in parallel analysis ofmultiple targets, or functionalized quantum dots are applied to in situ imaging andtracing the course of cell metabolism in different fields, in single cell leveldemonstrated its great potential for medical and life sciences applications.
Basal studies have revealed that the ion in the analysis can react with the atom onthe surface of quantum dots, certain physical and chemical effects occur, leading tothe surface of quantum dots changes in micro-environment and the fluorescence ofquantum dots changes significantly. Take advantage of this nature, the surface ofquantum dots can be modified to enable it to identify a certain anion or cation withhigh selectivity. Because of the nature, it shows huge advantage in the detection ofmetal ion.
Because of its rapid, low-cost, easy integration and automation, etc.,electrochemical biosensor has gradually become a important analysis means in thegenetic testing, anti-cancer drug screening, drug mechanism studies, as well asdiagnosis and treatment of disease areas. It exhibited enormous science andapplication value that excellent spectral characteristics and electrochemical activity ofQuantum dots was caused greatly concern in the novel, high-performanceelectrochemical biosensor.
The quantum dots which synthesized by using rare and scattered elements Se andTe have high stability and excellent optical electrochemical properties. Selenium andtellurium play an important part in photosensitive semiconductor devices, computer,communications and aerospace development, energy, medicine and health care, theimportant high-tech equipment areas,they also are the strategic resources which areclosely related to the national economy and people's life. As well as we know, thereserve of rare and scattered elements selenium, tellurium is relatively low (rare) inthe nature, they associates with other metals or minerals and without self-mineralsbasically. So the Analysis methods for selenium and tellurium arise great concern.
In this paper, we synthesize the CdSe QDs and CdTe QDs by aqueous approach. The synthesis conditions of the CdTe QDs, which has excellent optical properties andstability, are discussed. New synthesis route of Te precursor has been put forward.Many instruments are used to characterize the optical properties and structure of CdTeQDs. Quantum yield has been calculated. The influence of scattered light on thedetection of fluorescence has been studied and elimination method has been proposedtoo. The changes of fluorescence intensity in the interaction between CdTe QDs ofdifferent sizes are discussed. CdTe QDs is used as fluorescence probe for metal ionsofⅠB,ⅡB race .For their interaction, experimental conditions and selectivity arestudied too. fluorescence resonance energy transfer (FRET)-based DNA probes aredesigned by studying the interaction among CdTe QDs、DNA and daunorubicin(DNR). DNA electrochemical sensor with high-sensitivity and high selectivity isconstructed with CdTe QDs as sensitizer. In addition, the catalytic effect ofselenium, tellurium for the redox reaction between sulfide and methylene blue (MB)are studied. Trace selenium, tellurium are detected by catalytic kinetics method.Major research paper is as follows:
The first part mainly studies the synthesis and application on biomacromoleculeand inorganic ions of QDs which composed of rare and scattered element Se, Tecompound.
Chapter one mainly contains literature review: First of all, we present theconception, the physical performance, the optical performance and potential toxicityof QDs. Secondly, we present synthetic method of QDs, and the latest researchprogress of traditional organically preparation, aqueous synthesis, surfacemodification and aqueous transform; Thirdly, we present the application of QDs suchas biological marking, cell imaging, fluorescence resonance energy transfer, iondetection, and improving on the application of immunosensor,enzymaticsensor,DNA sensor. Eventually, we present the main research meaning, research contentsand innovation of this article.
Chapter two mainly present the synthesis of QDs which composed of Se,Tecompounds. We prepare CdSe QDs and CdTe QDs which taking NaHSe and NaHTeas precursors of Se and Te, and compare the fluorescent spectrum properties andstability of them; the result indicates QDs has more superior spectrum properties and higher stability. We discuss the synthetic condition of QDs, and get the optimumcondition: the molar ratio of Cd~(2+), Te~(2-), and MPA,n_(Cd2+):n_(Te2-)is 2:1,n MPA:n_(Te2-)is5:1,pH is 9.0, the temperature is 96℃.We adopt a new Te precursors prepartionmethod, regard metal Al as reducing agent to prepare(NH_4)_2Te. Comparing with thetraditional method, the stability of (NH_4)_2Te is superior to NaHTe . And(NH_4)_2Te dueto the mild condition of reaction, easy to synthesis in a large amount and store for along time, it is more convenient and reasonable to synthesize.
Chapter three mainly signifies the property and the structure of CdTe QDs. Weutilize UV-vis absorb spectrogram, the fluorescent spectrocomparator to signify theoptical performance of different size of QDs, and the size can be controlled byreaction time. With the increasing of the size of QDs, absorption spectrum andfluorescent emission spectrometry become prominently red shift; We use UV-visspectrum absorption edge method, transmission electron microscopy and X-raypowder diffraction to estimate the size of QDs. X-ray powder diffraction has verifiedthat CdTe QDs formated in the laboratory belong to the cubic zincblende structure; IRspectroscopy indicate that CdTe QDs capped with MPA react with CdTe QDs, andachieve the purpose to passivat the surface of CdTe QDs; taking ethanol solution ofrhodamine B as the object of reference, calculate the quantum yield of CdTe QDs is28%; we also study the reason why it produces the scattered light, and the influence todetermine fluorescence, and put forward the method to dispel scattered light; wepropose different size of CdTe QDs interacting with each other may arise“additiveeffects”or“quenching effects”, and discuss the reason why it produce.
Chapter four mainly study tellurium cadmium quantum dots react with metal ioninⅠB andⅡB. Discuss the changes of fluorescent intensity while the emission peak in540nm, 570 nm, 600 nm CdTe QDs react with Cu (Ⅱ) ,Ag(Ⅰ) ,Hg(Ⅱ) ,Au(Ⅲ) ion. Wefind in the experiment, Cu (Ⅱ) ,Hg(Ⅱ) ,Au(Ⅲ) has obvious quenching function to thefluorescent intensity of CdTe QDs .Ag (Ⅰ) quench CdTe QDs at 600 nm while it firstincrease and then quenching fluorescent intensity of CdTe QDs at 540nm,570nm.Under certain condition, system relatively fluorescent intensity(△F=F_0-F)arelinear relationship with Cu (Ⅱ), Ag(Ⅰ), Hg(Ⅱ), Au(Ⅲ) ion. The shelter pharmaceuticalEDTA complex function with Cu~(2+)orAg~+, and it will weaken the influence of Cu~(2+)/Ag~+ to the fluorescence intensity of CdTe QDs. Determine simulation sampleAu (Ⅲ), and its relatively deviation standard is 1.6%. Finally we carried on thediscussion in quenching mechanism.
In the fifth chapter, we discuss the interaction between the CdTe QDs -DNAwith daunorubicin (DNR) that based on absorption and fluorescence spectra. Weconclude that DNR can insert the base of the DNA。The DNR and CdTe QDs areindirect adsorption, but have a strong fluorescence quenching that is the form ofenergy transfer quenching。Salt effect and thermal denaturation experiments canfurther prove that the insert functioning between the DNA and the DNR. WeCalculate the Stern-Volmer quenching constant curve Ksv, as well as thethermodynamic parameters△H,△G,△S, and determine the interact form of binarysystem and the form of fluorescence quenching。In the ternary system, differentmixture order can produced a different fluorescence effects, its causes are described,and on this basis, we design the DNA probe that based on fluorescence resonanceenergy transfer.
In the sixth chapter, we described a novel DNA electrochemical biosensor thatwas prepared base on CdTe quantum dots (QDs) and carbon nanotubes (CNTs)modified gold electrode. The ss-DNA probe was covalently attached onto a carboxylcarbon nanotubes modified gold electrode through amines of the DNA bases usingN-hydroxysulfosuccinimide (NHS) and N-(3-dimethylamion) propyl-N'-ethylcarbodiimidehy- drochloride (EDC). After hybridization with the target ssDNA-CdTequantum dots (QDs) nanoconjugates,differential pulse voltammetry(DPV) and cyclicvoltammetry (CV) were used to sensitive detection of the target DNA withdaunomycin (DNR) as the indicator. This DNA electrochemical sensor coulddifferentiate the completely complementary DNA sequence, non-complementaryDNA sequence and Single base mismatch DNA sequence, indicating a goodselectivity. Compared with target DNA sequences without CdTe QDs, CdTe QDslabels on target DNA could obviously improve the sensitivity. Hybridizationconditions determining the sensitivity of the electrochemical assay was investigated.The electrochemical responses suggested that optimal detection of hybridizationoccurred at 55℃for 80 minimums. Under optimal conditions, DNR concentration of 1.67×10~(-5) mol/L was chosen as the optimal accumulation concentration. The peakcurrent signal suggested that almost linear with the logarithm of oligodeoxynucleotide(ODN) concentration in the range 1.0×10~(-13)～1.0×10~(-8)mol/L with the minimumdetection limit of 3.52×10~(-14) mol/L based on the ratio of signal-to-noise of 3, linearregression equation is△I=50.22 +3.5671 1gC_(DNA) with the correlation coefficient of0.9966. The relative standard deviation (RSD) was 4.8% (n=5) with target DNAsample concentration of 1.0×10~(-10) mol/L. It indicated that a satisfactoryreproducibility could be obtained by this DNA electrochemical biosensor.
The catalytic kinetic analysis methods of rare and scattered elements-seleniumand tellurium are studied in the second part. The first chapter, preamble includes thefollowing contents: Firstly, we introduce analytical methods development of thesample handling, separation and preconcentration of selenium and tellurium;Secondly, we introduce catalytic kinetic spectrophotometric method in details, thedevelopment of catalytic kinetic spectrophotometric method of selenium and tellurium;finally, we present the main research meaning, research contents and innovation ofthis article.
Chapter two studies the method of catalytic kinetic spectrophotometricdetermination of trace selenium. Based on the reaction of methylene blue reductingthioacetamide with selenium (Ⅳ) as catalyses under alkaline conditions, this paperdetermines the trace selenium. Because reaction rate of catalytic reaction has a certainratio relationship with the amount of catalyst in a certain range, the quantitativeanalysis is made according to the relation between the reaction rate and catalyst. Bymeasuring the variation slope (i.e., reaction rate) of difference of the absorbancechanges between the Catalytic reaction and non-catalytic reaction, the quantitativeanalysis of trace selenium in biological samples is realized. The Selenium content inthe range of 0.1～1.0μg/15mL conforms to the Lambert-Beer's law, regressionequation is y=0.0195x-0.0024, correlation coefficient r=0.995, the selenium contentin medlar is measured and the relative standard deviation is 5.4% (n=4), recoveryrate is 90%～96%, calculated the apparent activation energy of catalytic reaction for38.24kJ mol~(-1).This method is high sensitivity and reproducibility.
Chapter three studies determination of tellurium by catalytic kinetic spectrophotometric. Based on Te (Ⅳ) catalytic reduction S~(2-) fading reaction ofmethylene blue, a new Kinetic Determination of Trace Tellurium analysis isestablished. By studying the catalytic reaction conditions, the apparent activationenergy of catalytic reaction is determined for 68.94 kJ mol~(-1).Te (Ⅳ) concentration isin the range of 20-220 ng mL~(-1) Beer's law is obeyed, the linear regression curveequation is y=0.0038 x+0.2191,correlation coefficient r=0.9995, detection limit is3.04 ng mL~(-1).The studied separation method of selenium and tellurium is applied fordetermination of trace tellurium of coarse selenium powder. The relative standarddeviation is 3.1% (n =7) and the recovery rate is 98.4%～100.4%.
The result of experiment indicate: the research which quantum dots weresynthesized by using rare & scattered elements selenium & tellurium and used influorescence analysis of biomacromolecule and inorganic ions to replace traditionalorganic fluorochrome not only has important science and learned value, but also hasbetter practically application value. The research project is reasonable, the experimentmeans is effectual. It is beneficial to high level research.
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