基于1,1'-联-2-萘酚衍生物的手性荧光传感器

具有光活性的1,1′-联-2-萘酚（BINOL）衍生物是近年来研究较多的C2轴不对称芳香化合物,不仅具有很强的手性诱导作用,而且在适合结构基团修饰下能产生很强的荧光,可作为一类有效而灵敏的荧光化学传感器。在与手性胺、氨基醇、氨基酸、α-羟基羧酸、手性醇和单糖等手性有机化合物作用时,该荧光化学传感器在不同识别位点接受客体分子、通过光诱导电子转移（PET）及电子交换能量转移（EET）等引起共轭高分子内能级发生变化,使得所有这些相互作用十分灵敏地在其发光强度和能量上反映出来,具体表现在化学传感器荧光增强与减弱或发射波长的变化上。本文总结了近年来1,1′-联-2-萘酚衍生物的荧光化学传感器在手性异构体识别领域的最新研究进展。     

跨膜Ca~(2+)梯度通过磷脂酰胆碱调节肌质网Ca~(2+)-ATP酶

将纯化的肌质网Ca~(2+)-ATP酶重组在具有或不具有跨膜Ca~(2+)梯度的脂质体上,研究了磷脂(特别是磷脂酰胆碱)在跨膜Ca~(2+)梯度对肌质网Ca~(2+)-ATP酶功能调节中的作用。结果表明:(1)高浓度的(Ca~(2+)对与不同磷脂保温的去脂Ca~(2+)-ATP酶都产生抑制,但对与PC保温的Ca~(2+)-ATP酶抑制最大。(2)当存在一个正向跨膜Ca~(2+)梯度时(酶活性中心一侧Ca~(2+)浓度较低,类似生理条件),它只对与中性磷脂PC:PE重组的Ca~(2+)-ATP酶产生抑制,且PC:PE(摩尔比)为1:1时,抑制程度最大。如以酸性磷脂PS或PG替代PC则均无明显抑制。(3)比较不同脂肪酸侧链的PC的作用表明,当DOPC或DPPC存在时均有明显抑制作用,而DMPC则几乎不表现抑制作用。(4)若Ca~(2+)梯度逆转,则无论是与酸性磷脂或中性磷脂重组的肌质网Ca~(2+)-ATP酶都会被抑制。     

基于手性联萘酚高分子对汞离子的荧光传感器

手性联萘酚高分子由单体(R)-3,3′-二炔基-6,6′-二正丁基-2,2′-联萘酚(R-M-1)和对苯二叠氮(M-1)通过CuAAC反应得到,通过1HNMR、13CNMR、FTIR、旋光度、GPC、热分析、荧光光谱等方法对单体和高分子进行了结构表征和性能测试。该高分子是通过"Click"反应得到的手性联萘酚高分子,本文探讨了手性高分子传感器对各种金属离子的荧光传感性质,结果表明,与其他离子如K+、Mg2+、Pb2+、Co2+、Ni2+、Ag+、Cd2+、Cu2+、Zn2+等相比,Hg2+几乎使高分子荧光完全淬灭。这表明,以三氮唑基团作为连接基团和识别位点的高分子可作为有效识别Hg2+的荧光化学传感器。     

大麦根细胞质膜存在H~+/Ca~(2+)反向传递系统

在发现大麦根细胞质膜上存在不需Mg~(2+)和需Mg~(2+)两个Ca~(2+)转运过程的基础上,进一步研究了这两个过程的转运机制,发现需Mg~(2+)的Ca~(2+)转运过程依赖于跨膜H~+梯度。无论以ATP为能源的、还是人为造成的跨膜H~+梯度,都可驱动跨膜Ca~(2+)转运;跨膜Ca~(2+)转运过程伴随着H~+梯度的消减。不需Mg~(2+)的转运过程则与跨膜H~+梯度无关。这些结果指出,大麦根细胞质膜上除了Ca~(2+)-ATP酶这一初级Ca~(2+)转运系统外,还存在一个以跨膜H~+梯度为能源的次级Ca~(2+)转运系统,即H~+/Ca~(2+)反向传递系统。     

基于联萘酚的水溶性手性大环荧光传感器的合成与晶体结构

以R-联萘酚、氯氰胺、间苯二胺、1,2二苯基乙二胺、乙二胺为原料合成了3个水溶性手性大环荧光传感器;利用核磁共振(1 H NMR和13 C NMR)、质谱、红外光谱验证了合成产物的结构,利用元素分析仪测定了其组成,并利用X射线衍射分析确定了单晶R-3的晶体结构.结果表明,R-3属于单斜晶系,P2(1)/n空间群,晶胞参数为:a=1.128 6nm,b=1.566 1nm,c=2.293 9nm,β=90°,Z=4,Dc=1.328g.cm-3,F(000)=1 684.     

跨膜Ca~(2+)梯度对重组腺苷酸环化酶活力及构象的影响

本文将分离并部分纯化的腺苷酸环化酶催化亚基(ACc)重组于具有或不具有跨膜Ca~(2+)梯度的大豆磷脂脂质体上.酶活性的测试结果表明,酶活性中心一侧Ca~(2+)浓度低于另一侧(500倍)的脂酶体(类似生理条件)酶活性最高;在Ca~(2+)浓度梯度相反的情况下酶活性最低.外加Ca~(2+)载体A23187消除脂酶体两侧的Ca~(2+)梯度可导致前者酶活力降低而后者酶活力升高.不具有Ca~(2+)浓度梯度的脂酶体酶活性介于上述两种脂酶体之间. 蛋白内源荧光及KI对其淬灭效率的测试结果均反映上述几种脂酶体中ACc构象的差异.     

基于咔唑衍生物的荧光化学传感器的合成及其对金属离子的选择性识别性能

以咔唑为原料合成了2个荧光化学传感器,所得化合物的组成和结构经元素分析以及质谱、红外光谱、核磁共振氢谱验证.通过在25℃下进行荧光光谱滴定,研究了传感器在体积比为1∶1的二甲基亚砜/水缓冲溶液[三羟甲基氨基甲烷盐酸盐(Tris-HCl),pH=7.4]中对Cu2+和Fe3+的选择性识别作用.结果表明,所合成的传感器与Cu2+和Fe3+形成1∶1的配合物并导致荧光猝灭,并对Cu2+离子和Fe3+离子具有较高的选择性识别和荧光传感性能.     

Hg~(2+)荧光传感器的设计及合成(英文)

设计合成了一种新颖的基于萘荧光基团的Hg2+荧光传感器.通过荧光光谱滴定实验研究了其对Hg2+、Li+、Na+、K+、Zn2+、Co2+、Ni 2+、Cu2+、Fe2+、Mn2+、Cr3+和Fe3+等金属离子的选择性识别能力.结果表明,该传感器在生理pH=7.4的H2O-DMSO中对Hg2+表现出较高的选择性,并且形成1∶1的配合物;主客体相互作用荧光猝灭的络合常数为(9.07±0.41)×104.     

联噻唑衍生物荧光猝灭汞离子传感器的研究

合成了一种新的荧光体4,4'-叔丁基-2,2'-联噻唑(DtBBT),并将其PVC敏感膜用于Hg(Ⅱ)的检测.实验表明,Hg(Ⅱ)对DtBBT的荧光具有猝灭作用,当HS(Ⅱ)浓度为1.0×10-9～1.0×10-5mol/L时,体系荧光猝灭度与Hg(Ⅱ)的浓度呈线性关系,据此建立了测定痕量Hg(Ⅱ)的高灵敏、高选择性方法,并用于河水中Hg(Ⅱ)的测定,获得了满意的结果.     

化学计量学-荧光分析法同时测定萘、1-萘酚和2-萘酚

根据正交信号校正(OSC)、小波包变换(WPT)及偏最小二乘法(PLS)的算法原理,编制了名为POSC-WPTPLS的程序,结合荧光分析法快速、灵敏、选择性较好的优点,将该程序用于同时测定荧光光谱严重重叠的萘、1-萘酚和2-萘酚多组分体系,并将3种化学计量学方法(OSC-WPT-PLS、WPT-PLS和PLS)进行比较...     

A highly selective fluorescent chemosensor for Pb2+

A new fluorescent sensor based on rhodamine B for Pb2+ was synthesized. The new fluorescent sensor showed an extreme selectivity for Pb2+ over other metal ions examined in acetonitrile. Upon the addition of Pb2+, an overall emission change of 100-fold was observed, and the selectivity was calculated to be 200 times that of Zn2+. The signal transduction occurs via of reversible CHEF (chelation-enhanced fluorescence) with this inherent quenching metal ion.     

Dual-signaling fluorescent chemosensor based on bisthiazole derivatives

A new bisthiazole chemosensor (3) with phenolic substituents at the position 2 of the thiazole rings was prepared. The chemosensor 3 acts as a potential dual-function fluorescence chemosensor with Cu²⁺ and Zn²⁺ ions causing complete quenching and ratiometric change of fluorescence, respectively. The mechanism of fluorescence was based on the cation-induced inhibition of excited-state intramolecular proton transfer (ESIPT).     

A sugar-quinoline fluorescent chemosensor for selective detection of Hg2+ ion in natural water

A selective and sensitive fluorescent sensor for detection of Hg2+ in natural water was achieved by incorporating the well-known fluorophore quinoline group and a water-soluble D-glucosamine group within one molecule.     

A highly selective and sensitive fluorescent chemosensor for Zn^2＋

A new selective Zn^2＋ fluorescent chemosensor, o-vanillin-4-ethoxybenzoylhydrazone （1）, was designed and prepared. Free 1 mainly displayed very weak fluorescence at 480 nm upon excitation at 403 nm. It displayed high selectivity for Zn^2＋ and had a 518- fold fluorescent enhancement upon binding of Zn^2＋, while the other cation ions had only little influence on the fluorescence of 1. Mechanism of enhancement of l＇s fluorescence by Zn^2＋ was briefly discussed.     

A highly selective ratiometric fluorescent chemosensor for Zn2+ ion based on a polyimine macrocycle

A new ratiometric fluorescent chemosensor based on a polyimine macrocycle ligand 1 has been synthesized. The chemosensor can exhibit a pronounced fluorescence response and high selectivity to Zn²⁺ ion over other 15 metal ions, including Cd²⁺. Sensor 1 appears an emission peak at 370 nm. Upon the addition of Zn²⁺ ion, the typical emission peak for 1 at 370 nm is obviously quenched, but a new emission peak at around 470 nm appears and shows a large enhancement due to the formation of a 1:1 Zn²⁺-1 complex. In addition, there is a good linear relationship between the fluorescence ratio I_470nm/I_370nm and the concentration of Zn²⁺, which makes a ratiometric assay of Zn²⁺ ion possible.     

A metal–organic gel‐based fluorescent chemosensor for selective Al3+ detection

As an important metal element, aluminium has a significant impact on the environment and human health, and thus the detection of Al³⁺ has become the subject of much research. We synthesized a Ni(II)‐based metal–organic gel (Ni‐MOG), which can serve as an Al³⁺ fluorescence sensor with high selectivity and sensitivity, the limit of detection being calculated to be 0.5 μM. In addition, a composite film was further fabricated by hybridization of this Ni‐MOG with poly(vinyl alcohol). The composite film produced a rapid fluorescence response to Al³⁺ solutions at concentrations above 5 × 10^?5 M in 5 min. The Ni‐MOG composite film can also be successfully applied for the sensitive detection of Al³⁺ in real samples of tap water and seawater. The effective detection of Al³⁺ described in this contribution provides a new insight into water quality monitoring and has promising application value.     

A novel "turn-on" fluorescent chemosensor for the selective detection of Al3+ based on aggregation-induced emission

A water-soluble, 'turn-on' fluorescent chemosensor based on aggregation-induced emission (AIE) has been developed. It exhibits rapid response, excellent selectivity, and sensitivity to Al(3+).     

Highly sensitive and selective fluorescent chemosensor for Ag+ based on a coumarin-Se2N chelating conjugate

A highly sensitive and selective fluorescent chemosensor SC1 for Ag(+) based on a coumarin-Se(2)N chelating conjugate has been synthesized and characterized. Due to inhibiting a photoinduced electron transfer (PET) quenching pathway, a fluorescent enhancement factor of 4-fold is observed under the binding of the Ag(+) cation to the chemosensor SC1 with a detection limit down to the 10(-8) M range.     

A "turn-on" fluorescent Hg2+ chemosensor based on Ferrier carbocyclization

A "turn-on" fluorescent chemosensor with excellent selectivity and satisfactory sensitivity on Hg(2+) detection in 100% water media has been established employing a carbohydrate based Ferrier carbocyclization reaction. The probe has also presented satisfactory results for the imaging of Hg(2+) ions in cells and organisms.     

Highly selective fluorescent chemosensor for Na~+ based on pyrene-modified calix[4]arene derivative

A novel calix[4]arene derivative with pyrene fluorophores at the upper rim and tetraester ionophores at the lower rim was synthesized in six steps,and its structure was proved by NMR and ESI-MS spectro-scopies. Furthermore,the chemosensing behavior of the host compound for alkali and alkaline earth metal ions was investigated by fluorescence spectroscopy. The obtained results show that the calix-arene host can selectively bind sodium ion with the complexation stability constant of 2190 mol-1.L. The complexa...