Applications of Photo-labile O-nitrobenzyl Compounds for Selective Cell Labeling and Controlled Drugs Release

得益于光触发技术的非侵入性以及优越的时空分辨性，光标记化合物被广泛 地应用于有机化学、生物化学、材料化学以及纳米科学等领域。邻硝基苄基类化 合物具有合成简单、结构易于修饰、光化学量子产率高、可标记基团丰富等优点， 是目前使用最为广泛的光敏基团。本论文以邻硝基苄基光敏基团为研究对象，致 力于发展其在分析生物化学相关领域的应用研究，在选择性细胞标记、荧光成像 以及药物可控释放系统的构建方面，开展了一系列工作。 本论文共分为五章。 第一章为前言，首先简要介绍了光触发技术、光敏基团的结构及其光裂解机 理，并综述了光敏基团在生物活性分子功能调控、荧光染料标记、药物控制释放、 表面性质调...Due to the non-invasive property and high spatiotemporal resolution character of photo-trigger technology, caged compounds have been widely used in organic chemistry, biochemistry and nanoscience. O-nitrobenzyl compounds are the most common photo-labile groups that possess advantages of simple synthesis, facile modification and high photochemical quantum yield. In this thesis, we focused our ...学位：理学博士院系专业：化学化工学院化学系_分析化学学号：2052007015359

车载动力电池材料的发展趋势

近几年，全球新能源汽车受到了各国政府的大力扶持与推广，车载动力电池作为新能源汽车的核心部件之一备受关注。对车载动力电池的具体需求、动力电池常见正负极材料技术特征等作了梳理与总结，并提出了未来车载动力电池材料发展趋势。希望能给车载动力电池产业相关企业提供一定的参考。</p

The preparation of ZnSe Qdots in aqueous solution and the effects of photo-induced fluorescence enhancement

在水相中,以巯基乙酸(TgA)为稳定剂制备了具有短波长荧光的znSE量子点.研究了znSE量子点光诱导荧光增敏的机理,并提出通过补加zn2+和TgA以提高光诱导荧光增敏效率以及所得znSE量子点的稳定性这一新思路.研究结果表明,提高补加的zn2+和TgA的量即可增加znSE量子点表面znS壳层的厚度,更好地钝化其表面,从而不仅可显著提高znSE量子点的荧光量子产率(最高可接近15%),而且可大大地提高其表面的抗氧化性和荧光稳定性.ZnSe Qdots with short wavelength-fluorescence were prepared in aqueous solution with thioglycolic acid(TGA) as capping reagent.The mechanism of photo-induced fluorescence enhancement was studied and it was proposed a novel approach involved in the addition of compensatory Zn2+ ions and TGA to the original ZnSe solution to increase the efficiency of photo-induced fluorescence enhancement and stability of ZnSe Qdots.The research indicated that the thickness of ZnS shell increases with the increase of the quantity of Zn2+ ions and TGA.The ZnS shell made a better passivation of the ZnSe Qdot surface,thus resulted in not only higher fluorescence quantum yield(maximal 15%),but also higher stability of ZnSe Qdots.It was expected that the proposed approach would also provide a novel route to increase the fluorescence quantum yield and stability of other types of Qdot prepared in aqueous solution.浙江省自然科学基金资助项目(Y4080518

蒿芩清胆汤及其拆方对湿热型流感病毒性肺炎及NF-κB水平的作用研究

目的:通过观察蒿芩清胆汤及其拆方对湿热型流感病毒性肺炎及NF-κB的干预作用,以期探讨其治疗机制。方法:通过气候仓、肥甘饮食加流感病毒滴鼻感染造模成功后,蒿芩清胆汤及其拆方组以相应中药干预,比较各组肺指数、光镜下病变程度半定量、肺组织NF-κB mRNA表达水平。结果:蒿芩清胆汤及其拆方均能不同程度降低肺指数、肺部病理改变及NF-κB mRNA表达水平,其中全方效果最佳。结论:蒿芩清胆汤具有抗湿热型流感病毒性肺炎的作用,其机制可能与抑制NF-κB活化从而减少其下游炎性细胞因子分泌,截断"炎症瀑布"效应有关

Synthesis of Thermo-sensitive Block Copolymer and the Post-control of Its Lower Critical Solution Temperature with Light Triggering

利用原子转移自由基聚合(ATrP),以端基修饰2-溴-2-甲基丙酰基的聚乙二醇(PEg-br)引发温敏单体n-异丙基丙烯酰胺(nIPAM)和光活性单体邻硝基苄基丙烯酸酯(nbAE)共聚,制备得到具有光响应特性的温敏嵌段共聚物.动态光散射实验和紫外-可见吸收光谱表明,该聚合物的低临界溶解温度(lCST)可以通过紫外光照(λ≥310nM)进行后调控,在10MMOl/l PH 7.4磷酸缓冲液(PbS)中,可获得聚合物lCST达约26℃的调控幅度.该光响应温敏嵌段共聚物具有良好的水溶性,lCST可调控范围广,产物稳定,有望应用于建立新型药物控制释放系统.Thermo-sensitive block copolymer was synthesized by using atom transfer radical polymerization(ATRP) with PEG-Br,N-isopropyl acrylamide(NIPAM) and o-nitrobenzyl acrylate(NBAE) as macroinitiator,temperature sensitive monomer and light responsive monomer,respectively.The synthesized copolymer was characterized by dynamic light scattering and UV-VIS absorption.The results showed that lower critical solution temperature(LCST) of the polymer can be finely tuned within a relative broad range(~26 ℃) in 10 mmol/L,pH 7.4 phosphate buffered saline by UV irradiation(λ ≥ 310 nm).This novel light responsive and thermo-sensitive block copolymer demonstrated wide LCST tunability,good aqueous solubility and stability,should have great potential in applications such as controlled drug delivery.国家自然科学基金项目(20835005;21075101); 厦门市科技计划项目(3502Z20113006

Study on the Interaction Mechanism of DNA and Tb~(3+) by Fluorimetry

研究了脱氧核糖核酸(DNA)与Tb3+的相互作用,发现DNA能增敏Tb3+的特征荧光,且热变性DNA对Tb3+的荧光增敏作用比DNA强几十倍.基于上述实验现象,探讨了四种核苷酸d-AMP,d-CMP,d-GMP,d-TTP及四种核苷dA、dC、dG、dT与Tb3+相互作用的荧光光谱,发现DNA对Tb3+的荧光增敏除与鸟嘌呤碱基有关外,还有可能与磷酸基有关.进一步选择了含有不同数目磷酸基的核苷酸GMP、GDP、GTP及dG研究磷酸基的作用,实验结果表明不含磷酸基的dG不增敏Tb3+的荧光,而分别含有1、2、3个磷酸基的GMP、GDP、GTP三种核苷酸对Tb3+的荧光增敏程度依次为GTP>GDP>GMP,认为DNA对Tb3+的荧光增敏是鸟嘌呤碱基和磷酸基共同作用的结果.The Interaction between Tb~(3+) and DNA was studied.Based on the fluorescence spectrum of Tb~(3+),it can be concluded that DNA can enhance the fluorescence intensity of Tb~(3+),and the interaction between Tb~(3+) and thermal denatured DNA is more effective than DNA.We studied the interaction mechanisms of Tb~(3+) and seven kinds of nucleotide,which are deoxyadenosine monophosphate(d-AMP)、deoxyguanosine monophosphate(d-GMP)、deoxycytidine monophosphate(d-CMP) deoxythymidine triphosphate(d-TTP)、guanosine monophosphate(GMP)、guanosine diphosphate(GDP) and guanosine triphosphate(GTP).The experiment results showed that the interaction between Tb~(3+) and nucleotides which have Guanine is notable,and the others do not react with Tb~(3+).We also studied the interaction between Tb~(3+) and four kinds of nucleoside,including deoxyadenosine(dA),deoxyguanosine(dG),deoxycytidine(dC) and deoxythymidine(dT).The experiment results showed that the four kinds nucleoside don't react with Tb~(3+).So the fluorescence enhancement to Tb~(3+) may be also related to phosphate groups.In order to make this conclusion more clearly,the interaction of Tb~(3+) with dG、GMP、GDP and GTP were studied.It showed that dG which doesn't have phosphate group can not react with Tb~(3+).But the three kinds of nucleotide GMP、GDP、GTP,which have one、two and three phosphate groups respectively react with Tb~(3+),and the order of fluorescence intensity enhancement is:GTP>GDP>GMP.It showed that phosphate groups participate the reaction between DNA and Tb~(3+).So we can concluded that DNA enhancing the fluorescence intensity of Tb~(3+) is the results of the synchronous effect by Guanine and phosphates

Effects of pH on the Photo-induced Fluorescence Enhancement of Water-soluble ZnSe Quantum Dots

在水相中以巯基乙酸(TGA)为稳定剂,通过Zn2+离子和NaHSe反应合成了ZnSe量子点(ZnSe QDs).新合成的ZnSe QDs几乎无荧光,经紫外光照处理后呈现强的带边发射,量子产率显著提高.由于紫外光照可以诱导键合在ZnSeQDs表面的TGA发生光解产生S2-离子,因而与溶液中过量的Zn2+离子及TGA共同作用,在ZnSe QDs表面上形成ZnS壳层,电镜实验结果直接揭示了紫外光照处理后ZnSe QDs粒径的显著增加.研究发现,pH值的变化直接影响ZnSeQDs表面TGA的光催化光解,导致了ZnSe QDs的光诱导增敏作用对溶液pH值的依赖关系.在碱性条件下(pH 8~12),光诱导增敏效率随着溶液pH值的提高而增强,同时ZnSe QDs对光的稳定性也随之增强.ZnSe nanocrystals(QDs) were prepared in aqueous solution by the reaction between Zn2+ and NaHSe in the presence of thioglycolic acid(TGA).The fresh by prepared ZnSe QDs have no fluorescence emission.However,a dramatical increase of the fluorescence intensity which belongs to the band edge emission of ZnSe QDs was obtained after an UV-irradiation treatment,due to the formation of a structure shell of ZnS on the ZnSe particle surface via the reaction of Zn2+ and sulfide ions.And the sulfide ions in the reaction were produced from the photodecomposition of TGA molecular attached on the surface of the ZnSe QDs.The core-shell structure eliminated the surface defect of ZnSe QDs and gave rise to a great enhancement of fluorescence intensity.HRTEM images proved the dramatically growth of the size of ZnSe QDs after UV-irradiation directly.The change of pH value of the solution was found to affect the photodecomposition of TGA attached on the surface of ZnSe QDs,which result in the relevancy of pH value and photo-induce photoluminescence(PL) enhancement efficiency of ZnSe QDs.At the pH range between 8 and 12,the PL efficiency was increased with the increment of the pH value,and the photo-stability of the QDs became better simultaneously

Sensitive Sensor for Mercury Ion in Aqueous Solution by “Naked-eye” and Fluorescence Recognition

联系人简介: 赵一兵，男，博士，教授，博士生导师，主要从事荧光探针分析和药物释放研究． E-mail: ybzhao@ xmu.edu.cn[中文文摘]设计合成了一种以耐尔蓝为母体的Hg2+光学探针分子1-苯甲酰-3-{2-[9-(乙氨基)-10-甲基-9H-苯并[α]苯酚-5-胺基]乙基}硫脲盐酸盐(NBET).在pH=7.4的Tris-HCl缓冲液中,探针分子最大吸收波长为640 nm,此时溶液为淡蓝色;加入汞离子可以诱导探针分子在640 nm处的吸收降低,并在556 nm处产生新的吸收峰,溶液变为浅紫色,而其它金属离子的加入未引起显著变化,基于此可对水溶液中的痕量Hg2+进行裸眼识别.荧光光谱显示,汞离子可以特异性地猝灭探针分子在660 nm处的荧光发射.该探针分子的灵敏度、选择性及荧光量子产率高,激发/发射波长长,可以实现水溶液中0.005μmol/L Hg2+的荧光检测.[英文文摘]A sensitive and selective Nile blue-based optical sensor 1-benzoyl-3-{ 2-［9-( ethylamino) -10-methyl- 9H-benzo[α]phenoxazin-5-ylamino］ethyl} thiourea hydrochloride( NBET) in aqueous solution for Hg2 + was synthesized． The maximum absorption peak of the probe molecule appeared at 640 nm，and decreased upon the addition of Hg2 + in 0.05 mol /L Tris-HCl buffer solution at pH = 7.4，a new peak of absorption at 556 nm was observed.The color of the solution changed from light blue to light purple.There was neglectable change upon the addition of other metal ions.Fluorescence monitoring revealed a fluorescence quenching of the probe’s characteristic emission at 660 nm upon the addition of Hg2 +.The probe possessed the advantages of near-infrared excitation and emission and high fluorescence quantum yield in aqueous solution and offer an opportunity to detect Hg2 + by a“naked-eye”manner.Limit of detection of fluorescence spectral for Hg2 + was found to be 0. 005 μmol /L in aqueous solution．国家自然科学基金(批准号:20875079,20835005)资

博斯腾湖水环境现状研究

课题旨在通过对博斯腾湖湖水、沉积物以及水生生物的分析，出、入湖河流水系水质现状的监测，结合湖区工业废水、农业灌溉废水和城镇生活废水的分析，确定博斯腾湖湖水化学特征、水环境质量及流域的水污染现状和发展趋势，为博斯腾湖流域水资源的规划、开发利用和水功能区域的规划、管理提供基础数据和科学依据。课题取得的成果不仅对博斯腾湖整体生态环境的保护和促进博斯腾湖生态系统的良性循环有非常重要的科学价值，而且可对博斯腾湖的环境管理提供科学的依据，最终实现数字化管理的目标。根据巴音郭楞蒙古自治州政府和有关部门的要求，经协商，由巴州环保局、监测站、南京大学联合成立博斯腾湖水环境现状研究课题组。经过课题组的共同努力，于2003年12完成了实地调查和室内分析测试工作，2004年8月完成了课题报告