一种蒽醌类荧光探针的合成及对氟离子的检测性能

以1,4-二羟基蒽醌为荧光团,叔丁基二甲基氯硅烷为识别基团,设计合成了新型氟离子探针分子1,4-二-(叔丁基-二甲基-硅氧基) 蒽醌(AQTB1),其结构经¹H NMR, ¹³C NMR和MS(ESI)表征。采用FL和UV-Vis详细研究了响应时间、溶液pH值、干扰离子、氟离子浓度对探针AQTB1检测性能的影响。结果表明：探针AQTB1在pH=3~12的缓冲溶液中,实现了对氟离子的高效检测,并不受干扰离子影响。通过FL, IR和MS(ESI)对探针AQTB1检测机理进行研究,结果表明：加入氟离子后,探针分子中的Si-O键断裂,荧光较弱的AQTB1转化为荧光较强的1,4-二羟基蒽醌,实现氟离子的精确定量。实际样品分析实验中,3种不同水样中氟离子的加标回收率为88.0%～109.5%,相对标准偏差(RSD)低于8.5%。     

一种可视化检测硫化氢的苯并噻唑类荧光增强型探针

以叠氮基为识别基团,合成和表征了一种苯并噻唑类荧光增强型硫化氢探针(FL),并研究了它的光谱性质.实验结果表明,FL对硫化氢有较高的选择性和灵敏度,且响应快速,抗干扰能力强,细胞毒性低,它的检出限度为8.78×10-7 mol·L-1,在He La活细胞和各种水体样品中对硫化氢的检测表明FL具有潜在的应用价值.     

Fluoride anion sensing mechanism of a BODIPY‐linked hydrogen‐bonding probe

The sensing mechanism of a fluoride‐anion probe BODIPY‐amidothiourea ( 1c ) has been elucidated through the density functional theory (DFT) and time‐dependent density functional theory (TDDFT) calculations. The theoretical study indicates that in the DMSO/water mixtures the fluorescent sensing has been regulated by the fluoride complex that formed between the probe 1c /two water molecules and the fluoride anion, and the excited‐state intermolecular hydrogen bond (H‐B) plays an important role in the fluoride sensing mechanism. In the first excited state, the H‐Bs of the fluoride complex 1cFH₂ are overall strengthened, which induces the weak fluorescence emission. In addition, molecular orbital analysis demonstrates that 1cFH₂ has more obvious intramolecular charge transfer (ICT) character in the S₁ state than 1cH₂ formed between the probe 1c and two water molecules, which also gives reason to the weaker fluorescence intensity of 1cFH₂ . Further, our calculated UV‐vis absorbance and fluorescence spectra are in accordance with the experimental measurements. © 2018 Wiley Periodicals, Inc.     

一种基于DPA识别基团的可视化检测锌离子的荧光增强型探针

以N,N-二(2-吡啶甲基)胺(DPA)为识别基团,设计合成了一种用于检测Zn2+的荧光增强型探针WN,在CH3CH2OH/TrisHCl(1∶9,V/V,pH=7.4)缓冲溶液中研究了它对Zn2+的识别特性。实验结果表明,WN对Zn2+有较高的选择性和灵敏度,它们之间的结合比为1∶1,对Zn2+的检出限为1.14×10-8 mol·L-1。WN能够快速地可视化检测Zn2+,在HeLa活细胞中对Zn2+的荧光显微成像表明WN可应用于生物体的检测。     

一种基于DPA识别基团的可视化检测锌离子的荧光增强型探针

以N,N-二（2-吡啶甲基）胺（DPA）为识别基团,设计合成了一种用于检测Zn²⁺的荧光增强型探针WN,在CH₃CH₂OH/Tris-HCl（1：9,V/V,pH=7.4）缓冲溶液中研究了它对Zn²⁺的识别特性。实验结果表明,WN对Zn²⁺有较高的选择性和灵敏度,它们之间的结合比为1：1,对Zn²⁺的检出限为1.14×10^-8mol·L^-1。WN能够快速地可视化检测Zn²⁺,在HeLa活细胞中对Zn²⁺的荧光显微成像表明WN可应用于生物体的检测。     

以香豆素为母体快速检测内源性甲醛的荧光探针

基于甲醛(FA)与肼易发生亲核加成反应,从而阻断肼与荧光母体间电子传递的光诱导电荷转移(PET)机理,设计合成了以香豆素为母体的甲醛荧光探针3-苯并噻唑-7-肼香豆素(Coun)。 实验结果显示,Coun与FA的最佳反应时间为4 min,极大地提高了检测效率,检测限为5×10^-6 μmol/L。 该探针具有良好的细胞膜通透性,可应用于生物领域,检测细胞内的甲醛含量。     

A Turn‐On Fluorescent Probe for Highly Selective and Sensitive Detection of Palladium

A novel turn‐on fluorescent probe for the detection of palladium has been designed. The probe can selectively and sensitively detect palladium in solution, and the limit of detection was calculated to be 11.4 nmol·L^?1. Furthermore, the probe was successfully used for fluorescence imaging of palladium in living cells.     

基于二苯基咪唑的氟离子荧光探针的合成及性能

本文设计制备了一种二苯基咪唑衍生化的荧光探针1,利用紫外-可见吸收光谱和荧光光谱研究探针对阴离子的选择性。在探针的乙腈溶液中引入F_^-后,606 nm处的荧光强度发生明显的猝灭,并且可通过裸眼识别F_^-。探针对F_^-的识别表现出高灵敏性以及较好的抗干扰能力,检测限可低至9.43×10_^-8 mol L_^-1。此外,制备的1+F_^-体系对湿度较敏感,在水分影响下该体系的颜色和荧光强度能够实现可逆恢复。     

量子点荧光探针检测抗坏血酸

以巯基丙酸（MPA）为稳定剂水相合成了高荧光CdTe量子点. 向量子点溶液中加入Mn2+,由于量子点表面状态发生改变而使其荧光淬灭,加入抗坏血酸后量子点荧光又得以恢复,且荧光恢复程度与抗坏血酸的浓度线性相关,从而建立了基于量子点的荧光“开关”探针检测抗坏血酸的新方法. 当CdTe量子点的浓度为1.67 uM（量子点的尺寸为1.91nm）,加入的Mn2+浓度为0.25 mM时,在优化的实验条件下,检测抗坏血酸的线性范围为0.25~16 uM,检出限为36 nM. 相对标准偏差为2.5%(10 uM, n=11). 该探针可用于维生素C药片和人血浆中抗坏血酸的快速、灵敏和选择性检测.     

A Long‐Wavelength Fluorescent Probe for Saccharides Based on Boronic‐Acid Receptor

A single boronic acid‐based fluorescent probe (compound CSP) for saccharides was designed and synthesized. The probe, with an α,β‐unsaturated ketone conjugated into the coumarin fluorophore, was synthesized by 4 steps from the commercial material 4‐diethylamino salicylaldehyde. The electron push‐pull effect is enhanced with the N,N‐diethyl amino as the electron donor and the carbonyl as the electron acceptor. Both the absorption (463 nm) and emission (616 nm) maxima of CSP are in the visible wavelength region with a Stokes shift of about 150 nm, which ensures CSP a potential probe for biological application. Under near physiological conditions, significant fluorescence enhancement of CSP was observed upon the addition of some saccharides, namely, D‐sorbitol, D‐fructose, D‐glucose, D‐mannose and D‐galactose. The probe showed relatively high sensitivity towards D‐fructose and D‐sorbitol, and their detection limits were 0.05 mmol/L and 0.1 mmol/L, respectively.     

Test‐Strip‐Based Fluorometric Detection of Fluoride in Aqueous Media with a BODIPY‐Linked Hydrogen‐Bonding Receptor

The measurement of biologically relevant anions, such as fluoride, is an important task in analytical chemistry, in particular, for dental health and osteoporosis. Although a large number of fluoride probes are known, the applicability under relevant conditions is limited to a few examples. To improve this situation, BODIPY‐amidothiourea dyes with varying hydrogen‐bond donating strengths were developed, the most H‐acidic of which ( 1 c ) could detect F^? from an inorganic source (NaF) in 50 % aqueous solution (DMSO/water 1:1, v/v) with 0.01 ppm sensitivity through selective fluorescence quenching by a photoinduced electron‐transfer (PET) process. Use of the probe and a reference dye with a test‐strip assay and a portable and rapidly recording lateral‐flow fluorescence reader made determination of F^? in neat aqueous solutions, such as spiked water samples and toothpaste extracts, possible in a self‐referenced manner, achieving a detection limit of 0.2 ppm.     

选择性检测谷胱甘肽的荧光探针

本文设计合成了一种基于BODIPY衍生物选择性检测谷胱甘肽的比率式荧光探针1。荧光探针1中BODIPY的3位连有苯乙炔基团,5位连有咪唑盐离去基团,利用其与谷胱甘肽和半胱氨酸反应机理的不同实现了对谷胱甘肽的选择性检测。紫外可见吸收光谱和荧光光谱实验结果表明探针分子1与谷胱甘肽反应后的光谱发生明显红移,可以实现对谷胱甘肽的比率式检测。探针分子1对谷胱甘肽有极高的选择性,不受其它氨基酸尤其是半胱氨酸的干扰。荧光滴定实验表明探针分子1可实现对谷胱甘肽的定量检测,检测限为3.3×10-8 mol/L。探针分子成功地应用于活体细胞中检测谷胱甘肽。     

荧光猝灭型硼氟二吡咯类Cu2+探针的合成及其生物细胞成像的应用

设计合成了一个反应型的硼氟二吡咯(BODIPY)类荧光探针1,该探针以吡啶-2-羧酸苯酚酯基为识别基团。通过~1H NMR、~(13)C NMR和HRMS表征了1的结构,并解析了其晶体结构。光谱分析实验结果显示,探针1具有高的荧光量子产率(0.79),对Cu~(2+)具有较强的选择性识别性能,并能成功应用到生物细胞中Cu~(2+)的成像检测。     

联苯类比率型荧光探针检测水中硫化氢

以叠氮基为识别基团,4.4'-联苯二甲酸为初始原料,合成了一种可用于H_2S检测的联苯类比率型荧光探针2-叠氮基-4,4'-联苯二甲酸乙酯(WN),并通过~1H NMR、~(13)C NMR以及MS等技术手段对其结构进行了表征。以检测水溶液中硫化氢为目的,系统地研究了其荧光特性。研究结果表明,WN对硫化氢具有高选择性和灵敏度,且对生物硫醇(Cys,Gsh)、活性氧化物(H_2O_2,ClO~-)、各种阴阳离子(H_2PO_4~-,SO_4~(2-),Cl~-,HCO_3~-,CO_3~(2-),Mg~(2+),Zn~(2+),K~+,Ca~(2+),Na~+)有很强的抗干扰能力,在较宽的pH值范围内,仍然表现出良好的荧光性能,在1.1~350μmol/L范围内,NaHS的浓度与荧光强度呈现良好的线性关系,相关系数R~2=0.9943,检出限度为1.07×10~(-6)mol/L。通过对3种不同水样的测试,表明探针WN在水体中H_2S的检测方面具有一定的应用意义。     

一种基于喹唑啉酮衍生物的荧光探针对次氯酸根离子的识别

次氯酸根(ClO~-)在人体免疫系统中发挥着重要的作用,其识别与检测备受关注。本文设计合成了一种含有喹唑啉酮骨架的腙型荧光探针(HEMQ),并通过~1H NMR、~(13)C NMR、高分辨质谱(HRMS)表征了其结构。探针HEMQ在V(乙醇)∶V(水)=1∶1(c(PBS)=0.02 mol/L,pH=8.7)溶液中对ClO~-具有良好的选择性且响应快速,荧光发生显著猝灭。探针HEMQ对ClO~-具有较高的灵敏度,检测限为1.0×10-4mol/L。此外,ClO~-可引起探针溶液由黄色到无色的颜色变化,因此HEMQ可作为比色、荧光双通道响应的ClO~-探针。     

A BODIPY‐based Fluorescent Probe for Thiophenol

Thiophenol has been listed as one of the main sources of pollution. Sensitive probes for thiophenol are very significant. Herein, a BODIPY‐based fluorescent probe, named BDP, for poisonous thiophenol detection has been reported. BDP shows rapid response (15 s) and clear fluorescence enhancement (30 folds) to thiophenol in solution. The intensity of fluorescence and concentration of thiophenol have a good linear relationship. The detection limit is as low as 13.6 nmol · L⁻¹. BDP is stable towards pH and light radiation. Cell experiments demonstrate that BDP has good cell membrane penetrability, low cell toxicity and excellent imaging properties in living cells. Therefore, BDP has significant value on the detection of thiophenol in solution and in living cell.     

A Nitro‐Functionalized Metal–Organic Framework as a Reaction‐Based Fluorescence Turn‐On Probe for Rapid and Selective H2S Detection

The toxic gas H₂S has recently emerged as one of the important signaling molecules in biological systems. Thus understanding the production, distribution, and mode of action of H₂S in biological system is important, but the fleeting and reactive nature of H₂S makes it a daunting task. Herein we report a biocompatible, nitro‐functionalized metal–organic framework as reaction‐based fluorescence turn‐on probe for fast and selective H₂S detection. The selective turn‐on performance of MOF remains unaffected even in presence of competing biomolecules.     

Novel Coumarin-based Fluorescent Probe for Selective Detection of Bisulfite Anion in Water

Coumarins and its analogues have been widely used as chromophore in design of fluorescent probe, while less coumarin‐based fluorescent probe was reported for detection of anion in water. In this article, coumarin‐based fluorescent probes with salicylaldehyde functionality as recognition unit have been developed for selective detection of bisulfite anions in water. Four novel fluorescent probes were synthesized from 4‐haloresorcinol in three steps. The chemoprobe exhibited selective response to bisulfite over other anions. Moreover, the detection mechanism was studied. Upon bisulfite added, the fluorescent intensity of the probes was enhanced highly due to the nucleophilic addition reaction of formyl group with bisulfite anion.     

A Pyrene-based Probe for Antimony with Special Excimer Fluorescence

Py-IPH, a pyrene-based fluorogen with good thermal and mechanical stability was simply prepared by the Schiff base reaction and applied in the detection of antimony. Py-IPH presented special excimer fluorescence in the mixture of THF and water with 80 % of water, and exhibited perfect fluorescent response to antimony. The mechanism was demonstrated to be the increasing speed of the formation of pyrene excimers in the system owing to the coordination between antimony and IPH group in Py-IPH. Moreover, based on the special interaction between Py-IPH and antimony, it could distinguish antimony with other cations well with high specificity and selectivity.