基于香豆素骨架的Fe3 荧光探针的研究进展

本文综述了近十年来以香豆素为荧光基团的Fe~(3+)探针研究进展,并对该类探针的结构设计、作用机理及应用给出简要介绍,最后展望了该类Fe~(3+)荧光探针的研究和发展方向。     

谷胱甘肽和凋亡酶-3响应的环肽分子荧光探针

设计、合成了一类新型谷胱甘肽(glutathione,GSH)和凋亡酶-3(Caspase-3)响应的环肽分子荧光探针.该类探针主要由能量共振转移(FRET)分子荧光对、Caspase-3特异性识别多肽序列和GSH响应双硫键组成,分为不含穿膜肽序列(CP)和包含穿膜肽序列(cp CP)的两种不同环肽分子荧光探针.2种环肽分子荧光探针均能实现在GSH和Caspase-3同时存在情况下的精确成像,同时具有良好的响应性、特异性和高信噪比.该类环肽分子荧光探针在细胞培养环境中具有良好的稳定性和生物相容性.利用该探针,可以实现对星形孢菌素(STS)诱发的细胞凋亡进行实时、原位的成像监测,并对抗肿瘤药物阿霉素(DOX)和顺铂(cisplatin)诱导的细胞凋亡进行成像.这种具有多重响应并能用于精确成像的分子荧光探针将极大地促进疾病的精确诊断.     

肿瘤缺氧荧光探针的研究进展

缺氧是临床多种疾病共有的病理过程,研究缺氧的发生和发展规律,对恶性肿瘤及相关疾病的诊断具有重要的科学意义和应用价值.缺氧特异性荧光探针是指能对缺氧敏感物质进行选择性荧光检测进而评价相关体系缺氧状况的一类分析试剂,由于其检测的高灵敏性和高时空分辨能力,已成为研究热点之一.本文基于荧光探针检测肿瘤缺氧的不同反应机理,着重讨论了缺氧荧光探针的设计方法、检测机理及其生物应用,并对该类探针的发展趋势和应用前景进行了展望.     

罗丹明基“OFF-ON”型荧光探针研究的一些新进展

综述了近年来罗丹明衍生物在分子探针方面研究的一些新进展, 系统阐述了该类探针分子的构筑及探针分子片段由内酰胺螺环构架(无荧光/OFF型)到开环蒽醌体系(有荧光/ON型)转化过程中, 伴随着荧光的变化在离子和小分子检测方面的应用.     

一种用于检测有机溶剂中水含量的喹喔啉探针的研究

设计合成了喹喔啉类衍生物荧光探针QP,该探针显示出典型的遇水荧光淬灭特性,可用于有机溶剂中水含量的检测。研究结果表明：当DMF和丙酮中水的体积含量分别为10%和5%的时,探针的荧光完全淬灭,检测限分别为0.001 21%和0.004 68%;同时,通过理论计算,讨论了探针荧光遇水淬灭的机理,为该类探针的结构设计提供一定的理论理论参考。     

基于邻苯二胺氧化反应的生物分子比色/荧光探针

邻苯二胺(OPD)易被多种氧化剂氧化生成黄色荧光物质2, 3-二氨基吩嗪(OPDox),这一独特响应机制为反应型比色/荧光探针的设计提供了思路。基于OPD氧化反应的比色/荧光探针已被广泛应用于金属离子和有机小分子的检测中。近年来,由于该类探针灵敏度高、响应速度快、抗干扰能力强,在对细胞和组织内生物分子的识别方面备受青睐。本文综述了近年来(2014～2021年)基于OPD氧化反应的比色/荧光探针对生物硫醇、活性氧、尿酸、酶、抗原等重要生物分子检测的研究进展,并对此类探针的应用问题和发展前景进行了评述。     

活性氧簇的小分子荧光探针研究进展

在参与体内各种化学反应的生物活性分子中,活性氧(reactive oxygen species,ROS)是一类非常重要的物质,它们具有氧化性,能够维持细胞内的氧化还原平衡,与细胞的生长或凋亡息息相关.因此,对于细胞内活性氧簇的荧光分析一直以来都受到广大研究人员的密切关注.然而由于ROS本身自有的一些特性,如存在寿命短、反应活性高等,该类荧光分析始终面临着一些难题,如选择性较低、副反应较多.总结了近十几年来细胞中活性氧的荧光识别与检测的研究进展,着重介绍了各类荧光探针的设计机理与生物应用,并对未来该类探针的发展进行了展望.     

基于氧杂蒽结构可控官能化的荧光探针研究新进展

荧光分子探针技术在表达分子间识别行为及复杂生命和环境体系的内状态信息方面具有非常优异的性能,氧杂蒽及其衍生物螺连隐色体结构变化伴随的分子荧光变换模型,广泛且深入的应用于构建新型功能光敏探针分子.近年来此类探针的合成设计及功能化调控研究异常活跃,新的突破不断涌现.综述了新近基于氧杂蒽及其衍生物的荧光探针在金属阳离子、pH、阴离子识别检测方面的研究进展,并简要阐释了该类探针分子的构筑,识别检测机理以及探针在生物成像和环境监测等方面的应用.     

基于香豆素骨架的重金属和过渡金属离子荧光探针的研究进展

按照对不同金属离子的识别归类总结了近五年来以香豆素为荧光基团的重金属和过渡金属离子(Cr3+,Cd2+,Pb2+和Hg2+;Fe3+,Co2+,Ni2+,Cu2+,Zn2+和Ag+)荧光探针的研究进展,并简要介绍了该类探针的设计、作用机理及应用,展望了该领域的发展趋势。     

检测活性氮物种的荧光探针

活性氮是一类具有高生物化学活性的含氮原子的化学物种。这类活性物种具有特殊的生理功能,并在生命体的生理和病理过程中起着至关重要的作用。因此,设计开发用于选择性识别和高灵敏检测生物体内的活性氮物种的技术具有十分重要的意义。荧光探针作为一种具有高灵敏度、高选择性、对生物样品损伤小的实时原位的可视化检测技术,为深入阐明活性氮物种在生理和病理过程中所起的作用提供了一个便利有效的检测手段,并已在检测活性氮物种领域中得到了广泛应用。活性氮物种荧光探针可以进一步阐述活性氮物种特殊的生理功能,提高人们对该类物种在细胞信号转导方面的认知。本文根据活性氮物种的种类对荧光探针进行了分类,详细介绍了近四年来用于检测活性氮物种的荧光探针的研究进展,主要探讨了探针的设计方法、荧光响应机制及其生物应用,并对探针的设计合成和应用前景进行了展望。     

检测痕量Hg~(2+)的DNA电化学生物传感器

通过自组装方法将修饰有二茂铁基团的富T序列DNA分子(DNA-Fc)固定在金电极表面,得到了一种基于DNA修饰电极的电化学汞离子(Hg2+)传感器.当溶液中有Hg2+存在时,Hg2+可与修饰电极上DNA的T碱基发生较强的特异结合,形成T-Hg2+-T发卡结构,使DNA分子构象发生改变,其末端具有电化学活性的二茂铁基团远离电极表面,电化学响应随之发生变化.示差脉冲伏安法(DPV)结果显示:DNA末端二茂铁基团的还原峰在0.26V(vs饱和甘汞电极(SCE))附近,峰电流随溶液中Hg2+浓度的增加而降低;Hg2+浓度范围在0.1nmol·L-1-1μmol·L-1时,电流相对变化率与Hg2+浓度的对数呈现良好的线性关系.该修饰电极对Hg2+的检测限为0.1nmol·L-1,可作为痕量Hg2+检测的电化学生物传感器.干扰实验也表明,该传感器对Hg2+具有良好的特异性与灵敏度.     

双氰基二苯代乙烯型双光子荧光汞离子探针

分别以双氰基二苯代乙烯(DCS)和双[2-(2-羟乙基硫基)乙基]氨(HSA)为双光子荧光团和汞离子受体,合成了双光子荧光汞离子探针(DHg),并对其结构进行了分析.实验结果表明,DHg在甲苯、乙腈和水中的荧光量子产率(Φ)分别为0.78,0.42和0.20,对汞离子的络合常数通过单、双光子荧光滴定分别拟合为lg K=5.47±0.02和lg K=5.34±0.02.DHg在水溶液中对汞离子具有优良的选择性和高的灵敏性,可用于中性环境中汞离子的检测.DHg的双光子吸收截面(δTPA)在水溶液中高达840 GM,可用于细胞中汞离子的检测与成像.     

基于T-T碱基错配的荧光传感器特异性检测汞离子

在本文中,我们研制了一种基于T-T碱基错配特异性键合汞离子的荧光传感器用于汞离子的检测。该传感器由两条分别标记了荧光基团（F）和淬灭基团（Q）的DNA探针组成,并且含有两对用于结合汞离子的T-T错配碱基。当汞离子存在时,两条探针之间形成T-Hg2+-T结构,作用力增强,从而拉近了荧光基团与淬灭基团之间的距离,发生能量转移,使荧光信号在一定程度上被淬灭。在优化的条件下,我们使用该传感器对汞离子进行检测,动力学响应范围为50nM到1000nM,线性相关方程为y= 5281.13 - 1650.56 lg[Hg2+] ( R2 = 0.985),检测下限为79nM。此外,我们还考察了该传感器的选择性,当用其它干扰离子（浓度都为1.0µM）代替待测离子进行实验时,没有发生明显的荧光淬灭,说明该传感器具有较高的选择性。该传感器的构建为汞离子的检测提供了一条快速、简便的新途径。     

Thermoresponsive core cross-linked micelles for selective ratiometric fluorescent detection of Hg2+ ions

We report on the fabrication of core cross-linked (CCL) micelles possessing thermoresponsive cores and their application as sensitive and selective ratiometric Hg(2+) probes with thermo-tunable detection efficiency. Well-defined double hydrophilic block copolymer (DHBC) bearing naphthalimide-based Hg(2+)-reactive moieties (NUMA, 4), PEO-b-P(NIPAM-co-NAS-co-NUMA), was synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization, where PEO, NIPAM, and NAS represent poly(ethylene oxide), N-isopropylacrylamide, and N-acryloxysuccinimide. At 25 °C, PEO-b-P(NIPAM-co-NAS-co-NUMA) unimers in aqueous solution can act as ratiometric Hg(2+) probes with a detection limit of ～10.1 nM. After core cross-linking of the micellar nanoparticles formed at elevated temperatures, structurally stable CCL micelles with well-solvated PEO coronas and thermoresponsive cores embedded with Hg(2+)-reactive NUMA moieties were obtained. Upon Hg(2+) addition, the aqueous dispersion of CCL micelles exhibit a colorimetric transition from yellowish to colorless and a fluorometric emission transition from green to bright blue. Moreover, Hg(2+) detection limits of CCL micelles were considerably enhanced to 3.0 and 1.8 nM at 25 and 40 °C, when the thermoresponsive cores are at their swollen and collapsed state, respectively. The high selectivity of CCL micelles to Hg(2+) over other common cations was also demonstrated. Furthermore, in vitro studies revealed that CCL micelles can effectively enter into living cells and sensitively respond to the presence of Hg(2+) ions via the change of fluorescence emission color. This work represents the first example of DHBC-based CCL micelle acting as highly selective and sensitive ratiometric metal ion probes. The structural stability, water dispersibility, biocompatibility, and most importantly the thermo-tunable detection sensitivity of this novel type of CCL micelle-based sensing systems augur well for their future applications as multifunctional nanocarriers for drug delivery, sensing, imaging, and diagnosis.     

三波长分光光度法研究纳米TiO2对Hg2+的光催化还原效果

利用自制微型纳米TiO₂光催化反应器对不同初始浓度的Hg²⁺溶液进行光催化还原实验,利用Hg²⁺-硫氰酸盐-罗丹明B离子缔合物分光光度法测定溶液中剩余Hg²⁺的浓度,表征Hg²⁺的光催化还原效果.采用三波长分光光度法有效地消除了TiO₂悬浮体系中的浑浊对测定的干扰.讨论了光催化还原的最佳条件及其在消除工业废水中有毒物质Hg(Ⅱ)方面的应用.结果表明:纳米TiO₂对低浓度Hg²⁺溶液光催化还原效果显著,还原率可达90%以上,并且可以大幅降低工业废水中Hg(Ⅱ)的浓度.     

野酸枣氮掺杂荧光碳量子点高灵敏检测Hg2+

以天然产物野酸枣和色氨酸为原料,通过水热法一步合成量子产率为16.9%的氮掺杂荧光碳量子点。该碳量子点具有良好的水溶性和耐光性,在高盐环境中也呈现出了较高的稳定性。应用荧光光谱、透射电子显微镜(TEM)、傅里叶变换红外光谱(FTIR)和X射线光电子能谱(XPS)对碳量子点进行了表征。此外,Hg^2+能够有效地猝灭碳量子点的荧光,猝灭机理为电子转移的动态猝灭。基于此,可将碳量子点作为荧光探针检测Hg^2+。方法对Hg^2+的检测范围为1~50 nmol/L,检出限为0.26 nmol/L,能够应用于实际水样中Hg2+含量的测定。     

Assembly of a new family of mercury(II) zwitterionic thiolate complexes from a preformed compound [Hg(Tab)2](PF6)2 [Tab = 4-(trimethylammonio)benzenethiolate

Reactions of Hg(OAc)2 with 2 equiv of TabHPF6 [TabH = 4-(trimethylammonio)benzenethiol] in MeCN/MeOH afforded a mononuclear linear complex [Hg(Tab)2](PF6)2 (1). By using 1 as a precursor, a new family of mercury(II) zwitterionic thiolate complexes, [Hg2(Tab)6](PF6)4.2MeCN (2.2MeCN), [Hg(Tab)2(SCN)](PF6) (3), [Hg(Tab)2(SCN)2] (4), [Hg(Tab)I2] (5), {[Hg(Tab)2]4[HgI2][Hg2I6]}(PF6)2(NO3)4 (6), [Hg(Tab)2][HgI4] (7), [Hg(Tab)2][HgCl2(SCN)2] (8), [Tab-Tab]2[Hg3Cl10] (9), and [Hg2(Tab)6]3(PF6)Cl11 (10), were prepared and characterized by elemental analysis, IR spectra, UV-vis spectra, 1H NMR, and single-crystal X-ray crystallography. The [Hg2(Tab)6]4+ tetracation of 2 or 10 contains an asymmetrical Hg2S2 rhomb with an inversion center lying on the midpoint of the Hg...Hg line. The Hg atom of the [Hg(Tab)2]2+ dication of 3 is coordinated to one SCN-, forming a rare T-shaped coordination geometry, while in 4, the Hg atom of [Hg(Tab)2]2+ is coordinated to two SCN-, forming a seesaw-shaped coordination geometry. Through weak secondary Hg...S coordinations, each cation in 3 is further linked to afford a one-dimensional zigzag chain. The trigonal [Hg(Tab)I2] molecules in 5 are held together by weak secondary Hg...I and Hg...S interactions, forming a one-dimensional chain structure. In 6, the four [Hg(Tab)2]2+ dications, one HgI2 molecule, one [Hg2I6]2- dianion, one PF6-, and four NO3- anions are interconnected by complicated secondary Hg...I and Hg...O interactions, forming a scolopendra-like chain structure. The secondary Hg...I interactions, [Hg(Tab)2]2+ and [HgI4]2- in 7, are combined to generate a one-dimensional chain structure, while [Hg(Tab)2]2+ and [HgCl2(SCN)2]2- in 8 are interconnected by secondary Hg...N interactions to form a one-dimensional zigzag chain structure. Compound 9 consists of two [Tab-Tab]2+ dications and one [Hg3Cl10]4- tetraanion. The facile approach to the construction of 2-8 and 10 from 1 may be applicable to the mimicking of a coordination sphere of the Hg sites of metallothioneins.     

Computational studies of the coordination stereochemistry, bonding, and metal selectivity of mercury

Knowledge of the bonding and selectivity of organic mercury, [H3C-Hg]+ (MeHg+), and inorganic Hg2+ for protein and DNA functional groups is important for understanding the mechanism of heavy metal poisoning. Herein, we elucidate (1) the differences between inorganic Hg2+ and organic MeHg+ in their interactions with different ligands of biological interest, (2) the protein and DNA functional groups that Hg2+ and MeHg+ target in aqueous solution, and (3) the likelihood of "soft" Hg2+ displacing the "borderline" Zn2+ bound to "harder" nitrogen/oxygen-containing side chains such as His and Asp/Glu. The results reveal that, relative to Hg2+, the lower positive charge on MeHg+ results in a longer and weaker bond with a given ligand, in accord with the observed kinetic lability of MeHg+ complexes. They also indicate that negatively charged or polar amino acid side chains containing S-/O-/S/N donors could coordinate to both organic MeHg+ and inorganic Hg2+. In addition, Gua and Cyt could also coordinate to MeHg+ and disrupt Gua...Cyt base pairing. A key novel finding is that Hg2+ is a far better electron acceptor than Zn2+, and can thus accept more negative charge from the Zn ligands than the native Zn2+, thus enhancing Hg-ligand interactions and enabling Hg2+ to displace the native cofactor from zinc essential enzymes and "structural" Zn proteins. The results herein support several possible mechanisms for Hg poisoning. Ways that mercury poisoning could be prevented in cells are discussed.     

DNA银纳米簇在功能核酸荧光生物传感器中的应用

DNA银纳米簇(DNA-AgNCs)是以DNA为模板, 通过碱基杂环上的N原子与Ag⁺结合, 用NaBH₄将Ag⁺还原得到的具有荧光性质的新兴纳米探针. 由于DNA-AgNCs具有合成方法简单、 生物相容性好和荧光发射波长可调等优点, 使其在分析检测等领域具有广泛的应用. 本文对DNA-AgNCs的合成和荧光性质两个方面进行了综述, 分类总结了以DNA-AgNCs为无标记荧光探针在功能核酸荧光生物传感器方面的应用, 对其不足与应用潜力进行展望, 以期为未来的研究与应用提供借鉴.     

Ratiometric and Near‐Infrared Molecular Probes for the Detection and Imaging of Zinc Ions

The detection and imaging of Zn²⁺ in biological samples are of paramount interest owing to the role of this cation in physiological functions. This is possible only with molecular probes that specifically bind to Zn²⁺ and result in changes in emission properties. A “turn‐on” emission or shift in the emission color upon binding to Zn²⁺ should be ideal for in vivo imaging. In this context, ratiometric and near‐IR probes are of particular interest. Therefore, in the area of chemosensors or molecular probes, the design of fluorophores that allow ratiometric sensing or imaging in the near‐IR region is attracting the attention of chemists. The purpose of this Focus Review is to highlight recent developments in this area and stress the importance of further research for future applications.