基于罗丹明和BODIPY单元的FRET探针的合成及其对小分子α-酮戊二酸的检测

小分子α-酮戊二酸(α-KA)是人体新陈代谢的一种十分重要的产物,与多种疾病存在直接或者间接的关系,可以对临床诊断提供帮助。以BODIPY单元作为能量给体、罗丹明单元作为能量受体,利用二者存在重叠的光谱,本文设计了一种基于罗丹明和BODIPY单元的荧光共振能量转移(FRET)探针,通过将罗丹明与BODIPY的衍生物进行桥联,得到能够检测α-酮戊二酸的荧光比率型探针RDM-BO。研究表明,探针RDM-BO本身的荧光光谱与BODIPY单元类似,当探针与α-酮戊二酸发生反应时,RDM-BO中的罗丹明单元会发生开环反应,使分子的共轭发生变化,同时产生新的荧光峰,检测效果显著,检测限可达到3.14μmol·L-1。     

含均二苯乙烯荧光探针的合成及其对金属离子的识别研究

通过Wittig-Horner反应合成了两个含有均二苯乙烯发色团, 一端为N,N-双(2-乙酰氧乙基)氨基受体, 另一端分别为N,N-二甲氨基(DMDE)或N,N-二苯氨基(DPDE)的荧光探针分子. 进行了NMR和MS表征. 测试了加入不同金属离子时探针分子的吸收和荧光光谱变化. 加入Ag+和Zn2+, DMDE在420 nm处出现强的荧光峰, 在600 nm的荧光峰先增强后减弱, 认为发生了分子间的荧光共振能量转移. 而DPDE在加入Ag+和Zn2+, 420 nm处无荧光发射, 600 nm处的荧光红移并减弱.     

基于上转换荧光共振能量转移的ClO~-纳米探针

以"核-内壳-外壳"三层夹心结构上转换纳米材料(Sandwich Structure Upconversion Nanoparticles,SWUCNPs)为能量供体,异硫氰酸荧光素(FITC)为能量受体,构建了一种基于上转换荧光共振能量转移(UC-FRET)的纳米探针,其荧光猝灭效率高达95%。将该纳米探针用于水溶液中ClO~-的检测,ClO~-对配体的氧化使得能量供受体之间距离增大,上转换荧光恢复程度与ClO~-的浓度呈线性关系,线性范围为0.02~3.4mmol/L,检出限为0.008mmol/L。实验结果表明该纳米探针特异性强、灵敏度高、结构灵活。     

新型荧光/EPR双功能次氯酸探针的构建及性能

构建了一种新型香豆素-萘酰亚胺荧光/电子顺磁共振双功能探针CNNOH,并结合荧光光谱、电子顺磁共振(EPR)波谱和紫外-可见吸收光谱对其性能进行了研究.结果表明,该探针可结合荧光光谱的灵敏性和EPR波谱的特异性进行次氯酸的检测;由于香豆素与萘酰亚胺之间存在荧光共振能量转移(FRET)效应,探针分子具有较大的Stokes位移(135 nm),可有效避免由激发光导致的杂散光对检测的干扰.该双功能探针具有检出限低(0.214μmol/L)、反应速度快(~10 s)、检测范围宽(0~5 mmol/L)、选择性好及在生理条件下稳定的特点,预期在活体细胞检测方面有良好的应用前景.     

基于共振能量转移的生物传感器在食品安全检测中的应用研究进展

共振能量转移(Resonance energy transfer,RET)是一种发生在供体和受体之间的非辐射能量转移过程。RET的能量转移效率对供体和受体间的距离变化非常敏感,可被用于开发新型的光学生物传感器。与传统光学生物传感器相比,基于RET的生物传感器无需洗涤及分离过量标记物等步骤,可大幅简化检测流程。因RET具有灵敏度高、操作简便及速度快等优点,近年来,在医学诊断、生命科学研究、环境监控以及食品安全检测等领域备受关注。该文根据能量供体的不同,将RET分为3种类型：荧光共振能量转移(Fluorescence resonance energy transfer,FRET)、生物发光共振能量转移(Bioluminescence resonance energy transfer,BRET)和化学发光共振能量转移(Chemiluminescence resonance energy transfer,CRET)。并分别对基于上述3种RET类型的生物传感器在食品安全检测中的应用研究进展进行了综述,同时对其应用前景和发展趋势进行了展望。     

荧光光谱法研究黄藤素与牛血清白蛋白的相互作用

运用荧光光谱、紫外光谱法研究了中药黄藤素与牛血清白蛋白(BSA)的相互作用。实验结果表明,黄藤素与BSA形成基态复合物导致BSA内源荧光猝灭,猝灭机理主要为静态猝灭和非辐射能量转移。测定该反应的表观结合常数KA为1.650×105L.mol-1、结合位点数n为1.502;根据F rster能量转移理论,测得供体与受体间结合距离r为2.801 nm和能量转移效率E为0.190。     

一种新型一氧化氮比率型近红外荧光探针的制备及应用

该文以邻苯二胺修饰的［c］［1, 2, 5］噻二唑-5, 6-二胺作为一氧化氮（NO）识别基团和电子受体,芴衍生物作为荧光基团和电子供体,合成了一种新型检测NO的近红外荧光探针。通过紫外可见吸收光谱和荧光光谱研究探针分子的光谱学性质及检测NO的可行性。该探针与NO反应后生成苯并三氮唑结构,分子内电荷转移（ICT）效应加强,在近红外区的荧光明显增强。相较于传统的增强型或猝灭型NO荧光探针,该文制备的荧光探针通过比率计量荧光检测信号,实现了背景荧光低、抗干扰能力强的NO近红外荧光检测。该荧光探针受外界干扰小,且不与其他活性氧、活性氮反应,能够对不同浓度的NO产生快速、灵敏的荧光响应,对NO的检测线性范围为0～10 μmol/L,检出限为28.88 nmol/L。选择性实验表明,该探针对NO的响应具有专一性和抗干扰性。该文制备的比率型荧光探针能实现NO近红外荧光分析和检测,具有背景荧光低、抗干扰能力强的优点,可用于生物样品中NO的检测。     

量子点-罗丹明B比率型荧光探针的制备与性能

本文采用CdSe/Cd_xZn_(1-x)S核/合金壳量子点(QDs)作为荧光共振能量转移体系(FRET)的供体,通过巯基络合作用在其表面修饰一层L-半胱氨酸(Cys)分子,赋予QDs优异的水溶性能,再通过静电相互作用将罗丹明B(RhB)构筑于QDs-Cys表面,获得了一类新型的水溶性FRET体系.采用荧光光谱分析了pH以及供受体浓度比对FRET能量转移效率的影响.研究结果表明,通过静电结合构筑的QDs-Cys-RhB荧光共振能量转移体系对pH和供受体浓度具有敏感的荧光信号响应性能.当pH从10降到7时,FRET体系的荧光共振能量转移效率由49.39%增加到58.99%;当供受体浓度比为3:1时,FRET体系的能量转移效率高达61.09%.由此可见,通过表面络合与静电相互作用构筑的QDs-Cys-RhB荧光共振能量转移体系具有优异的光信号响应性,可以作为一类灵敏、精确的可调式比率型荧光探针,在生物检测、免疫分子等领域中具有广阔的应用前景.     

量子点的荧光共振能量转移在生物分析中的应用

量子点良好的光谱特性和自身优点,使其可以作为生物荧光探针,而替代传统荧光染料。近年来这方面的研究已经取得了一定的进展。目前,量子点在共振能量转移方面的研究,进一步扩展了它在生物分析中的应用。介绍了量子点基于共振能量转移原理在生物分析中的应用,即利用量子点设计的两种类的蛋白-蛋白特异性结合分析和3种生物传感器的模型设计。     

CdS量子点与曙红Y间的荧光共振能量转移研究

在水溶液中,量子点与有机荧光染料之间可能发生荧光共振能量转移(FRET)。本文以发射波长470nm的Cd S量子点为供体,曙红Y为受体,建立了Cd S量子点-曙红Y的FRET体系,研究了该体系的FRET参数。该体系受体供体数目比为8,猝灭效率为45.6%,增强效率为20.1%;供体-受体间的距离为4.4nm;临界能量转移距离为2.4nm。     

吖啶橙(AO)-藏红T(ST)荧光探针测定DNA的研究

简述了以荧光能量转移本系测定ＤＮＡ方法的发展过程，同时对吖啶（ＡＯ）－藏红Ｔ（ＳＴ）荧光探针测定ＤＮＡ的条件进行分析，证明了该法灵敏度高、线性范围宽、检出限低、选择性好、抗干扰能力强，该法为微曦ＤＮＡ测定分析工作提供了一个新的途径。     

Design and Synthesis of Chemiluminescent Cassettes Based on Energy Transfer

Chemiluminescent probes are being considered as a convenient option for optical imaging. Several strategies were reported to increase the probe chemiluminescence efficiency. In this study, a series of chemiluminescent cassettes based on adamantyl stabilized 1,2-dioxetanes (“Schaap's dioxetane”) linked to a fluorophore (BODIPY or dicyanoisophorone fluorophore) by a conjugated linker have been synthetized. Their chemiluminescent decomposition and the photoluminescence properties of their respective emissive species were investigated.     

荧光素-酚藏花红荧光能量转移用于测定Cu2+

重金属离子能引起水体的严重污染,由于它的积累性和不可降解性,目前重金属污染已成为人们广泛关注的热门话题,在食品、环境污染监督检验中被列为重点检测项目。目前测定重金属离子的主要仪器分析方法有：原子吸收光谱法、原子发射光谱法、ICP-质谱法、X-射线荧光光谱法、离子选择性电极、伏安法及库仑法等。这些方法的研究多有报导,但这些方法存在耗时、分析步骤复杂、分析仪器昂贵、采样频率低等缺点。     

Polyorganosiloxane-europium (III) host-guest inclusion system and its energy transfer luminescence

The Eu(III) ion, as a luminescent probe, is incorporated into a novel nanotube-contained polyorganosiloxane (POS), which is obtained by coupling of ladderlike polyvinylsilsesquioxane (Vi-T) with tetramethyldisiloxane (H-MM) via hydrosilylation, to form POS-Eu(III) composite. The results from fluorescent study demonstrate that the composite is actually a host-guest clathrate which includes the Eu(III) ions in the tubelike cavity of POS and moreover, the supramolecular clathrate exhibits an obvious energy transfer process which converts the UV light absorbed by POS into the visible light generated from the Eu(III) luminescence. Molecular simulation also gives support to the formation of such a clathrate and thus results in energy transfer process. Project supponed by the Research Foundation of Molecular Science Center and Director of Institute of Chemistry, the Chinese Academy of Sciences, and Foundation of Organic Solid Laboratory, the Chinese Academy of Sciences.     

基于罗丹明的重金属和过渡金属阳离子荧光分子探针研究进展

介绍了近五年来以罗丹明为母体的重金属和过渡金属阳离子荧光分子探针领域的研究进展.文中按照荧光团和识别基团之间连接臂的不同对国内外各研究组的工作进展进行归类总结,并对探针设计的思路、探针的性质和应用给出了简要介绍.     

Small molecule diffusion in a rubbery polymer near Tg: Effects of probe size,shape, and flexibility

A novel experimental approach involving fluorescence nonradiative energy transfer (NRET) is employed to study the Fickian diffusion of small molecules in rubbery poly(isobutyl methacrylate) (PiBMA) films near the glass transition, using a formalism that directly relates the small molecule translational diffusion coefficient, D, to changes in the normalized nonradiative energy transfer efficiency, E_N. Values of D for pyrene, 1,3-bis-(1-pyrene) propane (BPP), 1,3-bis-(1-pyrene) decane (BPD), 9,10-bis-phenyl ethynyl anthracene (BPEA), diphenyl Disperse Red 4 (DPDR4), and decacyclene in PiBMA are measured over temperatures ranging from approximately T_g to T_g + 25°C. Among these chromophores, significant differences in both the magnitude and temperature dependence of D are observed which are attributed to differences in molecule shape and flexibility, as well as molar volume. Other factors being equal, chromophore flexibility was shown both to increase the magnitude of D and to decrease its dependence on temperature, as does an increase in aspect ratio. For BPD, these effects are attributed to the ability of the flexible molecule to diffuse in a piecewise manner, requiring the cooperative mobility of fewer polymer chain segments than a rigid molecule of the same molar volume. For BPEA and DPDR4, this deviation from D being dominated by molar volume effects is attributed the to high aspect ratio of these elongated molecules. © 1996 John Wiley & Sons, Inc.     

Rational Design of Ratiometric Fe3+ Fluorescent Probes Based on FRET Mechanism

As the most abundant transition metal element in mammals, iron(Fe) plays a vital role in life activities. It is of great significance to study the variation of Fe³⁺ level in living organisms. In virtue of the advantages of high sensitivity, good selectivity and low damage to living systems, the fluorescence detection of Fe³⁺ has attracted much attention. Compared with the intensity-based fluorescent probe, the ratiometric fluorescent probe has less interference of environmental and can realize quantitative detection. In this study, four ratiometric Fe³⁺ fluorescent probes, R1, R2, R3 and R4_, were designed and synthesized using fluorescence resonance energy transfer(FRET) mechanism to achieve quantitative detection of Fe³⁺. In the FRET systems, 1,8-naphthalimide fluorophore derivatives were adopted as donors while rhodamine B derivatives were selected as receptors. The connection sites of the donor and acceptor in R3 and R4 are different from those in R1 and R2. All the four probes showed good response and selectivity to Fe³⁺. The energy transfer efficiencies of R3 and R4 were obviously higher than those of R1 and R2. This work provided a promising strategy for the development of fluorescent ratiometic Fe³⁺sensors.     

BioLeT: A new design strategy for functional bioluminogenic probes

By integrating photoinduced electron transfer (PET) into the design of functional bioluminogenic probes, Urano and his coworkers recently developed a new rational design strategy, BioLeT. It is expected that this BioLeT strategy will enable us to design and develop new bioluminescence probes for detecting various biomolecules with no catalytic or reactive activity.