磷酸二氢根离子对香豆肼化合物的高选择性荧光增强

设计合成了荧光探针N,N-二.乙基氨基香豆素-3-肼基-2,4-二硝基苯肼(DC).光谱滴定实验显示,H2PO4-与DC能够以1∶1的化学计量比形成配合物.进一步的实验发现,和相同含量的DC溶液相比,该配合物溶液的相对光致荧光强度显著增强,同时伴有紫外吸收光谱红移,溶液颜色由橙黄色迅速变为紫色.其它阴离子,如F-、NO...     

硫杂杯芳烃基胶束自组装荧光化学传感器制备及其性能研究

以对叔丁基硫杂杯[4]芳烃（TCA）为受体、苝和十二烷基苯磺酸钠（SDBS）分别为荧光体和自组装模板剂,通过在水中的胶束自组装作用制备得到一种新型的“ON–OFF”型Cu2+荧光化学传感器。论文选用荧光猝灭率为考察指标,详细考察了受体TCA用量、自组装模板剂SDBS浓度、Cu2+浓度和共存金属离子等影响因素对胶束自组装荧光化学传感器Cu2+检测性能的影响情况。实验结果表明,当受体TCA与荧光体苝的摩尔浓度比值达到1 000,自组装模板剂SDBS浓度为50 mmol·L-1,该荧光化学传感器对水中铜离子具有较好的检测能力,待测Cu2+浓度在一定浓度范围内与荧光猝灭率呈线性相关。此外,荧光化学传感器的Cu2+检测性能基本不受Pb2+, Cd2+, Mn2+, Na+, K+, Ca2+, Mg2+, Al3+,Ni2+,Zn2+等共存金属离子干扰。该胶束自组装荧光化学传感器对Cu2+的选择性检测性能主要归因于胶束表面活性剂分子层中TCA受体对Cu2+的识别作用,而传感器荧光猝灭主要基于胶束内部的电荷转移或能量转移机制。     

螺吡喃光响应的汞、铬、银离子探针及相互作用光谱

合成并表征了1-羟乙基-3,3-二甲基-6′,8′-二叔丁基吲哚啉苯并螺吡喃配体1及其衍生物配体2。由于苯并螺吡喃6′,8′-二叔丁基斥电子基团的电子效应,开环体部花菁酚氧负离子上的负电荷难以分散,使其结构不稳定,配体1在紫外光照射下不直接开环,只有在极性较强的甲醇溶剂中受适当金属离子诱导才能形成有色开环体部花菁结构形式。配体1能较好地选择识别Hg2+,Cr3+和Ag+。当其相互作用时,不但紫外可见光谱及荧光光谱有明显“turn-on”变化,而且体系颜色明显地由无色变成黄色,目视识别效果直观明显。其他金属离子的存在对Ag+,Cr3+和Hg2+的识别几乎没有干扰。配体1与Ag+,Cr3+和Hg2+络合的化学计量比均为1∶1,检出限分别是：7.435 8×10-6, 6.126 8×10-6, 3.452 4×10-6 mol·L-1。通过配体2进一步证明了配体1和金属离子识别的结合模式。即螺吡喃结构中N1位取代侧链上的羟基,和其开环体酚氧负离子相互协调并与金属离子结合。     

罗丹明-三嗪荧光探针对Al3+和Cr3+的识别

用罗丹明B乙二胺分步取代三聚氯氰环上两个氯原子,得到对称结构的罗丹明-三嗪衍生物。在pH 4～6的乙醇溶液中,衍生物能选择性识别Al3+和Cr3+,荧光发射和紫外-可见吸收显著增强。衍生物对Al3+ 和Cr3+识别不受共存金属离子干扰。在一定条件下,可作为高选择性和高灵敏的Al3+或Cr3+荧光和比色增强型光谱探针。     

硫杂杯[4]荧光探针的离子识别及分子逻辑门研究

以硫杂杯[4]芳烃为母体,在其1,3-位连接羟乙基邻苯二甲酰亚胺,2,4-位以三氮唑为连接基,将苄基引入硫杂杯[4]芳烃的下沿,得到硫杂杯[4]-邻苯二甲酰亚胺衍生物荧光探针(s1)。探针s1发射强烈荧光,在CH₃CN介质中的相对荧光量子产率为0.43。在DMF/H₂O介质中,以310 nm为激发波长,Fe3+能选择性猝灭探针s1在390 nm处的荧光;在CH₃CN介质中,以245 nm为激发波长,I-能选择性猝灭探针s1在310 nm处的荧光,光谱滴定和等温滴定量热均测出探针s1与Fe3+或与I-形成1∶1配合物,结合常数均达105。结合自由能表明配合为自发过程。荧光猝灭检测Fe3+和 I-的浓度线性范围分别为1.0×10-7～1.6×10-4 mol·L-1和1.0×10-7～8.5×10-5 mol·L-1,检测限分别为2.30×10-8 mol·L-1和1.17×10-8 mol·L-1。同时,利用识别和竞争配合作用,控制Fe3+和F-的输入使探针s1发射荧光或荧光猝灭,构建了分子水平上的逻辑电路。红外光谱推测探针s1分子中三氮唑基的氮原子参与了识别Fe3+的配位,而探针s1分子中三氮唑环上的芳氢与I-形成氢键而实现识别。     

基于喹啉功能团的Zn^2＋荧光探针

合成了含有喹啉功能团的锌离子荧光探针,N′-(喹啉-2-亚甲基)-3-(-喹啉-2-亚甲基胺)苯甲酰肼(QQB),该探针与Zn2 结合后荧光发射光谱由405nm红移至510nm,且荧光强度增强,具有较高的检测灵敏度。生物体内含量较高的金属阳离子K 、Na 、Mg2 、Ca2 以及微量金属离子Mn2 、Co2 、Ni2 等对QQB-Zn2 的荧光强度无显著影响,表明QQB对锌离子具有较高的选择性。光谱滴定和ESI-MS谱表明QQB与Zn2 以1∶1的化学计量比形成配合物。     

一种基于C＝N异构化的高选择性镁离子荧光探针

设计合成了荧光传感分子2-羟基-1-萘甲醛缩1-氨基海因(L),通过吸收和荧光光谱研究其对金属离子的识别作用,结果表明该化合物对镁离子表现出高选择性响应,在最大发射波长448nm处,乙腈中加入Mg2+,荧光强度增强30倍,Job曲线表明该受体分子与Mg2+以2∶1计量比配位,并初步探讨了该受体分子与镁离子的结合模式和荧...     

水溶性汞离子荧光探针的研究新进展

汞离子(Hg2+)是剧毒的重金属元素之一,对汞离子的选择性识别尤其是汞离子的原位、实时、在线监测对于医学、生物学和环境科学都具有重要意义。本文综述了近5年来水溶性汞离子荧光探针的最新研究进展。按照作用机理来分,汞离子荧光分子探针主要可分为光诱导电荷转移(PET)、激发态分子内质子转移(ESIPT)、激基缔合物(Monomer/Eximer)的形成和消失、分子内电荷转移(ICT)、荧光共振能量转移(FRET)等。本文列举了每类探针代表性的化合物并分析比较了不同机理类型的水溶性汞离子荧光探针体系。     

基于氨基苯甲酰肼衍生物的铬离子荧光探针的合成及性能研究

以对氨基苯甲酸为母体通过系列化学衍生引入丹磺酰胺荧光基团及2-羟基-1-萘醛配位基团构筑了新型、简单的铬离子荧光探针L(1-(二甲基氨基)-5-(4-((2-羟基-1-萘亚甲基)甲酰肼基)苯基)萘磺酰胺)。运用核磁、质谱、元素分析和红外等手段表征了其结构,并通过荧光光谱法研究了探针分子L对Cr3+的识别作用。结果表明,当激发波长为350 nm时,单纯的探针分子L在473 nm(2-羟基-1-萘醛)和514 nm(丹磺酰胺)处显示连体双峰;当向探针分子L中加入Cr3+后,2-羟基-1-萘醛作为受体与Cr3+结合,丹磺酰胺发射峰红移至540 nm,并且强度增强5倍,量子产率Φ=0.28。探针分子L的背景荧光对Cr3+的识别无任何影响,识别过程推测是由CHEF效应和PET(光诱导电子转移)共同引起的。当加入其他金属离子(Na+,K+,Li+,Ca2+,Zn2+,Mn2+,Co2+,Cu2+,Cd2+,Hg2+,Pb2+,Ag+)时,在540 nm处荧光强度未增强,表明L对Cr3+具有高度专一的选择性。通过电喷雾质谱和Job’s plot 曲线确定L和Cr3+为1∶1的配位模式,探针L对Cr3+的最低检测限可达到4.0×10-6 mol·L-1。     

基于FRET机理的荧光探针的合成及其对汞离子的识别

基于FRET机理设计合成了一个包含罗丹明6G及香豆素的汞离子荧光探针Rh-6G-coumarin(RC),研究了它的光谱性能及对汞离子的识别作用。在V(C₂H₅OH)∶V(H₂O)=9∶1溶液中加入汞离子后,575 nm处荧光强度迅速增大,荧光由蓝色变为明亮的红色,同时溶液的颜色由黄色变为红色。溶液中其他金属离子,如Na⁺、K⁺、Mg²⁺、Fe²⁺、Co²⁺、Pb²⁺、Zn²⁺、Cd²⁺和Cr³⁺对汞离子的荧光识别没有太大影响。该探针可在较宽的pH ( 4~10)范围内识别汞离子。光谱滴定实验表明,汞离子与RC以2∶1的计量比形成了配合物。     

Coumarin-based Fluorescent Probes for H2S Detection

Although hydrogen sulfide (H₂S) has been known as a toxic gas with unpleasant rotten egg smell, the correlation between H₂S and physiological processes has attracted scientists to develop brand new methods to monitor such a gaseous molecule in vitro and in vivo. Herein, we described a couple of coumarin-based fluorescent probes (1a and 1b) that can be activated by reduction of azide to amine in the presence of H₂S. It should be emphasized that probe 1b demonstrated high selectivity and sensitivity for H₂S over other relevant reactive sulfur species in vitro, as well as identified exogenous H₂S in living cells.     

An NBD-based Sensitive and Selective Fluorescent Sensor for Copper(II) Ion

A new 7-nitrobenz-2-oxa-1,3-diazole (NBD) derived fluorescent probe (1) exhibiting high selectivity for Cu²⁺ detection, produced significant fluorescence quenching in the presence of Cu²⁺ ion, while the metal ions Ca²⁺, Cd²⁺, Co²⁺, Fe²⁺, Hg²⁺, Mg²⁺, Mn²⁺, Ni²⁺ and Zn²⁺ produced only minor changes in fluorescence. The apparent association constant (K _a) for Cu²⁺ binding in chemosensor 1 was found to be 1.22 × 10³ M⁻¹. The maximum fluorescence quenching activity caused by Cu²⁺ binding to 1 was observed over the pH range 6–10.     

A Novel Highly Sensitive and Selective Fluorescent Sensor for Imaging Copper (II) in Living Cells

In this work, we designed and synthesized a novel quinolin-based derivative which exhibited signaling behaviors for Cu²⁺. Upon the addition of Cu²⁺ to the solution of the molecule, it displayed an obvious fluorescence quenching in a linear fashion due to the formation of a 1:1 metal–ligand complex. This fluorescent sensor exhibited a rare sensitivity toward Cu(II) (the level of magnitude could be 6?×?10^?8), a rapid response (<10 s) and also high selectivity toward Cu²⁺ over other metal ions such as Na⁺, K⁺, Ca²⁺, Mg²⁺, Ba²⁺, Fe³⁺, Mn²⁺, Hg²⁺, Pb²⁺, Cd²⁺, Cr³⁺, Co²⁺, Zn²⁺ and Al³⁺. Simultaneously, the cell imaging experiments and filter paper test demonstrated its extensive applicability.     

A Novel Fluorescent Probe for the Highly Selective and Sensitive Detection of Palladium in Aqueous Medium

Based on the Pd⁰-catalyzed Tsuji-Trost allylic oxidative insertion reaction, we developed a fluorescent probe PdL1 for sensing Pd⁰. As expected, probe PdL1 exhibited high selectivity and excellent sensitivity in both absorbance and fluorescence detection of Pd⁰ in CH₃CH₂OH/PBS (10 mM, pH = 7.4, 6:4, v/v) solution. The detection limit was calculated to be as low as 15 nM, which can meet the selective requirements for practical application.     

A New Highly Sensitive and Selective Fluorescent Cadmium Sensor

Condensation product (L) of salicylaldehyde and semicarbazide behaves as a fluorescent sensor for Cd²⁺ ion, in 1:1 DMSO:H₂O, over Mn²⁺, Fe²⁺, Ni²⁺, Co²⁺, Cu²⁺, Pb²⁺ and Hg²⁺ ions. The emission peak of L at λ_max = 520 nm, on excitation with 420 nm wavelength photons, showed an enhancement in intensity of ca 60-fold when interacted with Cd²⁺ ion. The intensity was however found to remain unaltered when interacted with metal ions—Mn²⁺, Fe²⁺, Ni²⁺, Co²⁺, Cu²⁺, Pb²⁺ and Hg²⁺. The intensity increases by approximately 20 fold on interaction with Zn²⁺ ion. The increase in the fluorescent peak can be explained on the basis of photo induced electron transfer (PET) mechanism. A 1:1 complexation between Cd²⁺ and L with log β = 4.25 has been proved.     

Selective and Sensitive Fluorescent Detection of Picric Acid by New Pyrene and Anthracene Based Copper Complexes

New pyrene and anthracene based copper complexes 4 and 7 respectively were designed, synthesized and characterized. The fluorescence behaviour of both 4 and 7 were evaluated towards nitro aromatics and anions. Both 4 and 7 possess high selectivity for the detection of well-known explosive picric acid (PA) by showing maximum fluorescence affinity. Furthermore, complex 4 showed similar sensing efficiency towards PA at different pH ranges. It was also used for real world applications, as illustrated by the very fast detection of PA from soil samples observed directly by naked eye.     

基于CdTe量子点荧光猝灭-恢复方法测定依诺沙星的研究

水相合成了巯基丙酸保护的CdTe量子点。根据在Cu2+存在的情况下,CdTe量子点荧光恢复程度与依诺沙星浓度成正比的现象,建立了基于CdTe量子点荧光猝灭-恢复测定依诺沙星的新方法。考察了溶液pH值以及Cu2+浓度等对检测体系的影响。在p H=10的硼砂缓冲溶液中,在Cu2+浓度为2.3×10-5mol/L的条件下,依诺沙星浓度在8.0×10-7~3.0×10-5mol/L范围内与量子点荧光恢复程度呈良好的线性关系,检出限为7.2×10-8mol/L。该方法用于实际样品中依诺沙星的检测,回收率为95.5%~105.0%。     

A Highly Selective Turn-On Fluorescent Chemosensor for Zinc Ion in Aqueous Media

In the paper, a novel rhodamine6G based fluorescent chemosensor bearing 3-carbaldehyde chromone was designed and synthesized. According to the fluorescence behavior toward several metal ions, it showed highly selectivity and sensitivity to Zn(II) over other commonly coexistent metal ions (Cu(II), Cd(II), Hg(II), Mg(II), K(I), Pb(II), Fe(III) and Cr(III)) in aqueous environment (pH?=?7.4). Meanwhile the binding constant between Zn(II) and chemosensor achieved 6.21?×?10¹¹ M^?1 in aqueous media. Moreover, according to the Job plot, 1:1 stoichiometry between Zn(II) and sensor was deduced in aqueous media (pH?=?7.4). The good selectivity and sensitivity in aqueous media effectively enhanced the application value of the fluorescent chemosensor for Zn(II).     

Mono and Trimethine Cyanines Cyan 40 and Cyan 2 as Probes for Highly Selective Fluorescent Detection of Non-canonical DNA Structures

Two of earlier reported dsDNA sensitive cyanine dyes??monomethine Cyan 40 and meso-substituted trimethine Cyan 2 were studied for their ability to interact with non-canonical DNA conformations. These dyes were characterized by spectral-luminescent methods in the presence of G-quadruplex, triplex and dsDNA motifs. We have demonstrated that Cyan 2 binds strongly and preferentially to triple- and quadruple-stranded DNA forms that results in a strong enhancement of the dye fluorescence, as compared to dsDNA, while Cyan 40 form fluorescent complexes preferentially only with the triplex form. Highly fluorescent complexes of Cyan 2 with DNA triplexes and G-quadruplexes and Cyan 40 with DNA triplexes are very stable and do not dissociate during gel electrophoresis, leading to preferential staining of the above DNA forms in gels. The data presented point to the intercalation mechanism of the Cyan 2 binding to G4-DNA, while the complexes of Cyan 40 and Cyan 2 with triplex DNA are believed to be formed via groove binding mode. The Cyan dyes can provide a highly sensitive method for detection and quantification of non-canonical structures in genome.