反应型香豆素探针的合成及其对废水中汞离子的检测

以间苯二酚为原料合成了一种新型反应型的香豆素二硫缩醛荧光探针(L1),并通过结构确征.在pH 6.15～9.96时,探针L1可以高选择性对Hg2+进行荧光检测,检测限低至1.6 nmol/L;同时提出了L1对Hg2+的传感机制,并通过核磁研究证实.在紫外线灯下,肉眼可检测到荧光的颜色变化.实际应用研究表明,荧光探针L1...     

以香豆素为母体的荧光探针的合成、离子识别及拟合计算研究

设计合成了含噻唑和腙结构的香豆素类钴离子荧光探针分子CCo,其结构用1HNMR和13CNMR进行了表征,考察了其光谱性能和电化学性能,并对其结构进行了拟合计算研究。CCo在常见金属离子(Cd2+、Co2+、Na+、Mn2+、Fe3+、Pb2+、Hg2+、Cu2+、Zn2+、Cu+、K+、Mg2+、Ag+、Ni2+、Cr3+)中能够选择性地识别Co2+。滴加Co2+后探针吸收光谱红移60 nm,荧光光谱蓝移75 nm。探针分子溶液在三电极系统及四丁基高氯酸胺作电解质下能用于Hg2+的检测。通过拟合计算进一步验证了探针吸收光谱峰值与实验值一致。     

基于萘酰亚胺为发光团的Hg~(2+)荧光探针的表征

成功将一种萘酰亚胺衍生物表征为高选择性Hg2+荧光探针,在优化测试条件下,实现Hg2+的检测,并用核磁滴定法对探针与Hg2+的结合模式进行了表征。     

一种罗丹明结构的汞离子荧光探针的制备及性能

以罗丹明6G和4-溴-1,8-萘二甲酸酐为原料,合成了新型荧光分子探针R6G-NA,通过核磁共振1H NMR、13C NMR和质谱MS等方法对其进行了结构表征。通过荧光光谱及可见光光谱测定,对荧光探针R6G-NA的识别性质进行了研究,结果表明:探针R6G-NA在乙醇-水溶液(p H=7)体系中,与Hg2+作用具有明显的荧光增强响应,在波长550 nm,Hg2+浓度小于90μmol/L的条件下,荧光强度与Hg2+浓度近似呈线性关系,可用于检测水溶性体系中微量Hg2+;在R6G-NA的乙醇-水溶液体系中加入Hg2+,溶液色度的变化可用可见分光光度计进行测量。进行了其他阳离子共存下的竞争试验以及对Hg2+的可逆性试验,结果表明探针R6G-NA对Hg2+具有良好的选择性和可逆性。     

一种罗丹明类Hg~(2+)和pH双功能荧光探针及其选择识别性能

以罗丹明B、水合肼和对羟基苯甲醛为原料,合成了一种新型的荧光增强型识别Hg2+和pH双功能荧光探针,即对羟基苯甲醛罗丹明B腙(HRBH)。用FT IR、1 H NMR和13 C NMR对其分子结构进行了表征,并通过荧光光谱对探针的识别性能进行了研究。研究结果表明:当N,N-二甲基甲酰胺(DMF)为溶剂时,探针HRBH对Hg2+具有良好的选择识别性,并且基本不受其他金属离子的影响;通过Job’s曲线可知,探针与Hg2+的配合比为1∶1;Hg2+浓度在3×10-5~7×10-5 mol/L的范围内,探针HRBH的荧光强度与Hg2+浓度呈现出较好的线性关系,线性相关系数为0.9903;探针对pH值的响应区间为3~6,并具有良好的可逆性。     

一种新型喹啉衍生物的合成及其对Hg2+的检测

以吡喃并喹啉为荧光团,吡咯啶二硫代甲酸铵为识别基团,合成了一种新的荧光探针分子,7-苯基-6H-吡喃[4,3-b]喹啉-2-吡咯啶二硫代乙酰胺.采用红外光谱、核磁共振谱和质谱对其结构进行了表征,并对其荧光性质进行了研究.结果表明,该化合物可以作为检测Hg2+的比率荧光探针,对于Hg2+有着很好的选择性及很高的灵敏度,在...     

α-呋喃甲醛缩间苯二甲酰腙对铜离子的识别研究

设计合成了荧光传感分子α-呋喃甲醛缩间苯二甲酰腙(m-PB-Fu),应用吸收和荧光光谱研究其在乙腈中对过渡金属离子的响应。结果表明,m-PB-Fu的吸收光谱对Cu2+、Hg2+和Pb2+均有响应,配位能力相近,对Zn2+、Ni2+和Cd2+响应则很弱;但它的荧光发射光谱对Cu2+表现出高选择性响应,荧光增强达100倍。初步探讨了受体分子与Cu2+结合模式与荧光增强原因。     

含吡嗪、喹啉荧光探针的合成及其对金属离子的识别研究

设计合成了3个含有吡嗪基团的荧光探针分子和喹啉基团的荧光探针分子,其结构通过红外(FT-IR)、质谱(MS)、核磁共振氢谱(1HNMR)进行表征,通过吸收光谱和荧光光谱研究了不同金属离子对目标探针分子的影响。结果表明:Cd2+使401 nm处荧光蓝移了20 nm;Co2+、Hg2+、Pb2+、Zn2+使357 nm处荧光分别红移了20、50、1401、40 nm;Cd2+、Hg2+使349 nm处荧光分别红移了707、5 nm。     

一种BAPTA荧光探针的合成、光谱性能与识别机制

以苯乙烯类发色团苯并咪唑作为荧光基团、多羧酸受体作为识别基团,基于分子内电荷转移机制定向构筑探针结构,合成得到一种对Zn2+、Cu2+、Hg2+具有响应的荧光探针.定性及定量识别实验显示,探针对目标物Zn2+、Cu2+、Hg2+表现特征响应,探针与目标物1:1定量结合,荧光性能随pH、时间变化而相对稳定、线性关系良好,...     

反应型二芳基乙烯-罗丹明探针的合成及其对水样中汞离子的检测

研制并鉴定了一种新型的高灵敏度,高选择性的Hg2+探针,即罗丹明酰肼与带有羧酸官能团结构的二芳基乙烯相结合形成探针1O。探针1O对Hg2+检测具有高效地选择性、灵敏性。除此之外,二芳基乙烯是光致变色材料之一,探针1O除了具有罗丹明结构性能之外也具有光致变色性能,因此在紫外光和白光的交替照射下也能发生可逆现象。最后,该传感器1O被开发利用于定量定性检测实际环境水样中的Hg2+。     

A highly selective ratiometric fluorescent sensor for Hg2+ based on 1,8‐naphthalimide

A sulfur probe based on 1,8‐naphthalimide was designed and synthesised, and its sensing behaviour towards a mercury ion was investigated by fluorescence spectroscopy. The probe showed higher selective recognition towards Hg²⁺ than towards other metal ions in methanol solution. Compared with 4‐amino‐substituted naphthalimide derivatives, the probe exhibited different fluorescent characteristics for sensing Hg²⁺. The novel, reaction‐based probe is recommended for selective recognition of Hg²⁺ with significant fluorescence change.     

Fluorescent,Recombinant-Protein-Conjugated,Near-Infrared-Emitting Quantum Dots for in Vitro and in Vivo Dual-Color Molecular Imaging

Near-infrared (NIR)-emitting fluorescent probes are widely used for molecular imaging at the whole-body level. However, NIR-emitting fluorescent probes emitting over λ=700 nm are not suitable for molecular imaging at the cellular level, because most of the conventional fluorescence microscopes have very low optical sensitivity in the NIR region. Thus, to achieve fluorescence imaging at the cellular and whole-body levels by using single probes, visible and NIR-emitting dual-color fluorescent probes are desirable. For dual-color fluorescence molecular imaging, we synthesized fluorescent, recombinant-protein-conjugated, NIR-emitting quantum dots (QDs), in which the recombinant protein consists of enhanced green fluorescent protein (EGFP) and the immunoglobulin binding domain (B1) of protein G. This dual-color fluorescent QD probe binds the Fc region of immunoglobulin G (IgG) through its B1 domain at the QD surface and acts as a molecular-imaging probe at both the cellular and whole-body levels. In this paper, we present the synthesis of fluorescent, recombinant protein (HisEGFP-GB1)-conjugated, NIR-emitting QDs and their application to the dual-color molecular imaging of breast cancer cells in vitro and in vivo.     

A sensitive and selective near-infrared fluorescent probe for mercuric ions and its biological imaging applications

A new mercury(II) near-infrared region fluorescent probe 3,9-dithia-6-monoazaundecane-tricarbocyanine has been designed and synthesized. It consists of two functional moieties: the tricarbocyanine performs as the near-infrared region fluorophore, and the 3,9-dithia-6-monoazaundecane acts as the selected binding site for metal ions. The near-IR excitation and emission profiles of the probe can minimize cell and tissue damage and avoid native fluorescence from natural cellular species. It exhibits fluorescence increase upon the binding of the Hg(2+) based on the inhibition of the photoinduced electron transfer quenching mechanism. Excellent sensitivity and selectivity for mercuric ions are observed with this probe. The value of the system is demonstrated by its use in monitoring the real-time uptake of Hg(2+) within HepG2 cells and five day old zebrafish. The synthesis and remarkable properties of it help to extend the development of metal ions fluorescent probes for biological applications.     

Lessons in Organic Fluorescent Probe Discovery

Fluorescent probes have gained profound use in biotechnology, drug discovery, medical diagnostics, molecular and cell biology. The development of methods for the translation of fluorophores into fluorescent probes continues to be a robust field for medicinal chemists and chemical biologists, alike. Access to new experimental designs has enabled molecular diversification and led to the identification of new approaches to probe discovery. This review provides a synopsis of the recent lessons in modern fluorescent probe discovery.     

基于次氯酸根离子的新型比率型荧光探针及其应用

以2-苯并噻唑-5-甲基苯酚为原料,合成了一种基于次氯酸根离子的比率型荧光探针ZN1,并对其进行了次氯酸根离子的检测性能测试。结果表明:该探针可以快速灵敏、选择性地识别次氯酸根离子,其检测下限为0.96μmol/L,并将该探针应用于实际水样中次氯酸根离子含量的检测,在自来水、雨水中的回收率均大于84%。此外,利用质谱和核磁谱图开展的检测机理研究表明,探针的识别机理与次氯酸的氧化脱氢作用和激发态分子内质子转移(ESIPT)过程破坏有关。     

氟离子荧光探针的研究进展

氟离子是电负性最强、离子半径最小的阴离子,是一个强路易斯碱,在化学、生物学、医学和军事等方面都具有重要作用。适量的氟化物摄入人体可以预防龋齿、治疗骨质疏松症,但是过量的摄入会导致氟斑牙、氟骨症、尿石症以及癌症等疾病,因此氟离子的识别与检测具有重要意义。化学荧光探针具有选择性好、灵敏度高、方便快捷、成本低廉等优点,近年来化学研究者设计合成了大量的氟离子荧光探针。根据识别机理不同,氟离子荧光探针主要划分为3种:氢键型、路易斯酸受体型、氢键和路易斯酸混合型。综述了近年来不同类型的氟离子荧光探针的研究进展,总结了氢键型和路易斯酸型氟离子荧光探针的优缺点,对未来氟离子荧光探针的研究方向进行了展望。     

Detecting Cysteine in Bioimaging with a Near-Infrared Probe Based on a Novel Fluorescence Quenching Mechanism

Near-infrared (NIR) fluorescent probes are very significant for detecting cysteine in biological systems. Herein, we report a highly selective and sensitive NIR turn-on fluorescent probe (BDP-NIR) based on BODIPY with large Stokes shift (105 nm) for detecting Cys. We clarified the sensing mechanism based on the different thiol-induced S_NAr substitution/rearrangement reaction of the probe with cysteine and homocysteine/glutathione, which leads to the corresponding amino- and thiol-BODIPY dyes with distinct photophysical properties. Moreover, a novel mechanism of fluorescence quenching was demonstrated by density functional theory calculation. The reason for the fluorescence quenching of the probe might be intersystem crossing (from singlet to triplet excited state). Moreover, BDP-NIR had a high linear dynamic range of 0–500 μM, which was promising for detecting cysteine quantificationally. Significantly, BDP-NIR was capable of sensing endogenous cysteine in living cells and in vivo.     

A One‐Step Staining Probe for Phosphatidylethanolamine

Phosphatidylethanolamine (PE) is an abundant phospholipid in cellular membranes, but relatively little is known about the kinetics of PE in biological membrane systems. Characterizing PE on a cellular level has been challenging owing to a lack of proper molecular tools. The lantibiotic duramycin and its structural analogue, cinnamycin, are currently the only known polypeptides that have an established stereospecific structure for binding membrane PE with high affinity and high specificity. These lantibiotics are recognized for their potential as molecular probes for studying PE kinetics in various membranes. However, owing to their antibiotic nature, duramycin and cinnamycin exhibit appreciable levels of cytotoxicity at low micromolar concentrations in cultured mammalian cells by inducing membrane distortion and possible PE redistribution. These issues can potentially complicate study design and data interpretation. Here, we report the construction of a molecular probe consisting of duramycin attached to the C terminus of green fluorescent protein (GFP) by a PEG linker at a stoichiometry of 1. The construct retained specific binding toward PE and essentially no cytotoxicity compared to native duramycin. The biological utilities of this probe were demonstrated in a number of cellular staining studies involving PE dynamics. The availability of a one‐step, nontoxic molecular probe for PE will enable characterization of the biology of this important phospholipid.     

用于常见环境污染物检测的柔性荧光传感器

随着工业化进程的不断推进,环境污染问题日益突出,研发针对不同种类污染物检测的传感器及其阵列对治理环境污染、保障人们健康生活意义重大。近几年,具有检测灵敏度高、响应速度快等特征的荧光分子探针逐渐成为污染物检测的重要工具,将其通过物理或化学方法固定于柔性基质表面制备的荧光传感薄膜是一种发展潜力巨大的微痕量物质检测装置,具有操作简单、便于携带、尺寸可调和不污染待测体系等优势,尤其是对当前引起广泛关注的智能可穿戴材料的研究具有极大的促进作用。本文主要综述了近几年基于荧光探针技术的柔性传感薄膜与器件对常见气相、液相环境污染物进行检测的研究现状,并针对该领域目前存在的一些问题进行了总结与展望。
关键词:荧光探针;柔性传感;薄膜;检测技术;研究进展
中图分类号:O657.3???? 文献标识码:? A??? 文章编号:1003-5214 (2020) 01-0000-00     

Novel (phenylethynyl)pyrene-LNA constructs for fluorescence SNP sensing in polymorphic nucleic acid targets

We describe fluorescent oligonucleotide probes labeled with novel (phenylethynyl)pyrene dyes attached to locked nucleic acids. Furthermore, we prove the utility of these probes for the effective detection of single-nucleotide polymorphisms in natural nucleic acids. High-affinity hybridization of the probes and excellent fluorescence responses to single-base mismatches in DNA/RNA targets are demonstrated in model dual-probe and doubly labeled probe formats. This stimulated us to develop two diagnostic systems for the homogeneous detection of a drug-resistance-causing mutation in HIV-1 protease cDNA and RNA gene fragments. Target sequences were obtained by analysis of 200 clinical samples from patients currently receiving anti-HIV/AIDS combination therapy at the Russian Federal AIDS Center. Using these fluorescent oligonucleotides, we were able to detect the target mutation despite all the challenges of the natural targets, that is, the presence of additional mutations, neighboring sequence variation, and low target concentration, which typically reduce binding and effectiveness of sensing by fluorescent oligonucleotides.