新型荧光探针罗丹明肉桂酰胺的合成及其用于荧光分光光度法测定汞

以罗丹明B和肉桂酸为主要反应物,制备了新型荧光探针罗丹明肉桂酰胺,并采用红外光谱、核磁和质谱对荧光探针的结构进行了表征。在含30%（φ）乙醇的pH 7.0 HEPES缓冲溶液中,荧光探针与Hg²⁺形成1比1的络合物,通过测定在发射波长584 nm处的荧光强度,与汞的浓度在1.0×10^-6mol·L^-1以内呈线性关系,方法的检出限（3s）为7.4×10^-9mol·L^-1。试验结果表明:该荧光探针对Hg²⁺具有很好的选择性,不受其他金属离子的干扰。     

基于氮化碳量子点/罗丹明B系统检测汞离子的比率荧光探针

通过一步水热法,以柠檬酸和尿素为原料,制备了蓝色氮化碳量子点(CNQDs),并对CNQDs的粒径分布、元素组成、形貌结构及表面官能团进行了表征,考察了CNQDs的光谱性质。以CNQDs为母体与罗丹明B(RhB)构成比率荧光探针CNQDs/RhB,基于CNQDs/RhB(447 nm/581 nm)的荧光强度比值F₀=(F₄₄₇/F₅₈₁)的变化情况对汞离子(Hg²⁺)进行定量测定,具有高选择性和灵敏性。结果显示,该探针对Hg²⁺的检测线性范围为2～40μmol/L,检出限为1.95μmol/L。常见的阴离子和阳离子对CNQDs/Rh B检测Hg²⁺基本无影响,并对该比率型荧光探针的检测机制进行了探究。最后,将该探针应用于实际水样中Hg²⁺的检测,说明该探针具有潜在的应用价值。通过研究,对Hg²⁺的检测提供了新的思路,也预示了该荧光探针在水环境检测方面具有广阔的应用前景。     

一种萘酰亚胺-罗丹明衍生物的合成、聚集诱导荧光增强及其双通道荧光探针性能

合成了一种萘酰亚胺-罗丹明新型荧光探针N,N'-罗丹明内酰乙氨基-4-吡啶乙烯基-1,8-萘酰亚胺(PNRh),并通过核磁氢谱、核磁碳谱及高分辨质谱结构表征.测定了PNRh的固体、乙醇和水的混合溶液中的荧光光谱,实验发现暗室中紫外灯下固体PNRh发出亮黄色荧光,最大发射波长为592 nm.在乙醇和水的混合溶液中,随着含水量的增加,荧光逐渐增强,当含水量达到100%时,荧光强度最大,溶液则由微弱的蓝色荧光变为暗红色的荧光.研究了荧光分子PNRh对金属离子Hg2+和Cr3+的选择性识别.实验发现PNRh具有聚集诱导荧光增强的性质,可实现对Hg2+和Cr3+的比率和双通道识别,是一种优良的Hg2+和Cr3+检测荧光探针.     

检测汞离子的比色-荧光双通道探针的设计合成及应用

以7-羟基吩恶嗪酮(试卤灵)为荧光团、硫代甲酸苯酯为汞离子(Hg²⁺)识别基团,经一步简单有机合成反应,制备了比色-荧光双通道探针NMP。采用核磁共振氢谱(¹H NMR)、核磁共振碳谱(¹³C NMR)和高分辨率质谱(HRMS)表征了探针结构,利用吸收光谱和荧光发射光谱测试了探针对Hg²⁺的选择性和灵敏度。光谱测试结果表明,探针对Hg²⁺具有较好的选择性和检测灵敏度,检出限(3σ)为17 nmol/L。反应溶液由淡黄色变为紫红色,可对溶液中Hg²⁺进行比色检测,并可用于实际水样中Hg²⁺的检测。采用CCK-8法测试了探针的细胞毒性,结果表明,在探针浓度低于10μmol/L时,细胞存活率高于90%。共聚焦荧光显微成像结果表明,探针具有较好的细胞通透性,可对细胞内Hg²⁺进行荧光成像。     

基于小分子的汞离子荧光探针*

汞离子（Hg²⁺）作为一种极具生理毒性的化学物质,其检测方法在传感领域得到了广泛的研究。荧光探针由于具有高效灵敏、快速便捷检测等优点而成为Hg²⁺检测的重要手段之一。通过Hg²⁺与探针特征的结合位点作用,引起其光物理性质的变化,从而实现对Hg²⁺的高选择性识别。本文综述了近年来小分子Hg²⁺荧光探针的研究进展。文中着重总结了Hg²⁺荧光探针分子的设计原理、检测机制及应用方法;评述了这些化合物的结构和检测性能之间的关系;最后展望了Hg²⁺荧光探针的研究和发展方向。     

基于牛血清白蛋白功能化金纳米棒的荧光探针测定Hg2+

建立了一种以牛血清白蛋白功能化的金纳米棒(BSA-Cys-GNRs)为荧光探针检测Hg²⁺的新方法。以半胱氨酸作为连接臂成功将牛血清白蛋白修饰在金纳米棒表面,通过紫外可见吸收光谱、荧光光谱、红外光谱和荧光倒置显微镜等多种分析方法对材料进行表征。研究发现,在295nm波长光激发下,BSA-Cys-GNRs探针在338nm显示强荧光,而Hg²⁺能够有效地猝灭BSA-Cys-GNRs的荧光。对一系列影响猝灭效果的因素进行考察,得出pH 4.0、孵育时间5.0min为最佳检测条件。Mn²⁺、K⁺、Ni²⁺、Na⁺、Cr³⁺、Cd²⁺、Mg²⁺、Cu²⁺、Ca²⁺、Al³⁺和Zn²⁺对BSA-Cys-GNRs的荧光信号没有明显的影响。当Hg²⁺的浓度为0.04444~8.888μmol·L^-1时,荧光猝灭效率与Hg²⁺的浓度之间存在良好的线性关系,检测限为8.08nmol·L^-1。将该方法用于环境水样中Hg²⁺的检测,回收率为98.9%~105.0%。     

一种罗丹明6G类“Off-On”型Fe3+比色荧光探针

设计合成了一种基于罗丹明6G的新型比色荧光探针(RG),并通过核磁共振氢谱、碳谱和质谱进行了表征。该探针在pH=6的Tris-HCl缓冲溶液中可与Fe³⁺作用,溶液由无色变为粉红色,在530nm处产生强吸收,同时在557nm处发射强荧光。通过金属离子选择性实验,发现探针RG对Fe³⁺有高选择性;此外,探针溶液530nm的吸光度和557nm的荧光强度与Fe³⁺浓度呈良好的线性关系,检出限分别为1.26和3.87μmol/L。Job’s曲线分析表明探针分子与Fe³⁺的反应摩尔比为1∶1。此外,以乙二胺四乙酸为络合剂实现了探针分子的重复使用。该探针可用于实际水样中Fe³⁺的精准检测。     

三芳胺类荧光探针合成及对化妆品中Hg2+的检测

基于汞离子促进硫代缩醛脱保护作用,设计合成了一种三芳胺类荧光探针N-(1,1′-联苯-4-基)-N-(4-(双(乙基硫代)-甲基)苯基)-9,9-二甲基-9H-芴-2-胺(简称L),并采用核磁共振、红外光谱及高分辨质谱对其结构表征。荧光发射光谱表明,在乙腈(ACN)/4-羟乙基哌嗪乙磺酸(HEPES)(V∶V=9∶1,HEPES 10mmol·L^-1,pH=7.4)缓冲溶液中,探针可实现对Hg²⁺的“turn-off”检测,检测过程具有响应时间短、离子选择性好、抗共存金属离子干扰性强等优点。在0～20μmol·L^-1范围内,Hg²⁺浓度与荧光强度呈现良好线性关系,探针对Hg²⁺检测极限低至1.57×10^-8 mol·L^-1,可实现Hg²⁺的痕量检测。将探针L应用于化妆品中Hg²⁺检测,加标回收率96.3%～101.7%,相对标准偏差0.52%～2.76%,准确度较高,具有良好的应用前景。     

喹啉酮-香豆素类Hg2+比色荧光探针的合成及应用

设计合成了新型喹啉酮-香豆素类比色荧光探针7-二乙氨基-3-[3-(7-二乙氨基)香豆素基-3-氧代丙烯基]喹啉-2-酮(QCO), 用于检测水溶液中的Hg²⁺. 探针QCO对Hg²⁺表现出高选择性和强抗干扰性. 此外, Hg²⁺引起探针QCO溶液的颜色变化明显, 可裸眼识别. 比色法中, 吸收值比(A₅₀₀/A₃₈₀)与Hg²⁺浓度呈良好的线性关系, 其检出限为2.62×10^-8 mol/L. 荧光法中, 探针QCO对Hg²⁺的检出限为5.42×10^-8 mol/L. 经等摩尔变化( Job’s Plot)法、 质谱及红外光谱验证, 探针QCO与Hg²⁺形成络合比为1∶1(摩尔比)的络合物. 硅胶板实验和加标回收率实验结果表明, 探针QCO可用于检测实际水样中的Hg²⁺.     

基于蒽酰亚胺基团的新型Fe3+和Hg2+化学敏感器

含蒽酰亚胺基团的化合物N-(2-(6-氨基吡啶))-9-蒽酰亚胺(L¹)对Fe³⁺表现出灵敏的荧光增强响应.L¹的衍生物N,N-’(2,6-吡啶基)-二(9-蒽酰亚胺)(L²)对Hg²⁺在紫外-可见吸收光谱和荧光光谱上显示了良好的识别性.即使在其它金属阳离子存在下,L¹和L²分别对于Fe³⁺和Hg²⁺仍然表现出较好的选择性.     

FRET-based sensor for imaging chromium(III) in living cells

On the basis of fluorescent resonance energy transfer from 1,8-naphthalimide to rhodamine, a fluorophore dyad (FD8) containing rhodamine and a naphthalimide moiety was synthesized as a Cr3+-selective fluorescent probe for monitoring Cr3+ in living cells with ratiometric fluorescent methods.     

Highly selective ratiometric fluorescent sensing for Hg(2+) and Au(3+), respectively, in aqueous media

A nonsulfur probe based on a 1,8-naphthalimide and alkyne conjugate for the ratiometric fluorescent sensing for Hg(2+) and Au(3+) through the tuning of pH in different aqueous solutions is described. This work provides a novel reaction-based approach for selective recognition of these two ions with significant change of fluorescence color and constitutes the first ratiometric case for Au(3+).     

A highly selective colorimetric and ratiometric two-photon fluorescent probe for fluoride ion detection

A naphthalimide-based highly selective colorimetric and ratiometric fluorescent probe for the fluoride ion displayed both one- and two-photon ratiometric changes. Upon reaction with the F(-) (TBA(+) and Na(+) salts) anion in CH(3)CN as well as in aqueous buffer solution, probe 1 shows dramatic color changes from colorless to jade-green and remarkable ratiometric fluorescence enhancements signals. These properties are mechanistically ascribed to a fluoride-triggered Si-O bond cleavage that resulted in a green fluorescent 4-amino-1,8-naphthalimide.     

Dansyl-anthracene dyads for ratiometric fluorescence recognition of Cu2+

Dansyl-anthracene dyads 1 and 2 in CH(3)CN-H(2)O (7:3) selectively recognize Cu(2+) ions amongst alkali, alkaline earth and other heavy metal ions using both absorbance and fluorescence spectroscopy. In absorbance, the addition of Cu(2+) to the solution of dyads 1 or 2 results in appearance of broad absorption band from 200 nm to 725 nm for dyad 1 and from 200 nm to 520 nm for dyad 2. This is associated with color change from colorless to blue (for 1) and fluorescent green (for 2). This bathochromic shift of the spectrum could be assigned to internal charge transfer from sulfonamide nitrogen to anthracene moiety. In fluorescence, under similar conditions dyads 1 and 2 on addition of Cu(2+) selectively quench fluorescence due to dansyl moiety between 520-570 nm (for 1)/555-650 nm (for 2) with simultaneous fluorescence enhancement at 470 nm and 505 nm for dyads 1 and 2, respectively. Hence these dyads provide opportunity for ratiometric analysis of 1-50 μM Cu(2+). The other metal ions viz. Fe(3+), Co(2+), Ni(2+), Cd(2+), Zn(2+), Hg(2+), Ag(+), Pb(2+), Li(+), Na(+), K(+), Mg(2+), Ca(2+), Ba(2+) do not interfere in the estimation of Cu(2+) except Cr(3+) in case of dyad 1. The coordination of dimethylamino group of dansyl unit with Cu(2+) causes quenching of fluorescence due to dansyl moiety between 520-600 nm and also restricts the photoinduced electron transfer from dimethylamino to anthracene moiety to release fluorescence between 450-510 nm. This simultaneous quenching and release of fluorescence respectively due to dansyl and anthracene moieties emulates into Cu(2+) induced ratiometric change.     

New Hg2+ and Cu2+ selective chromo- and fluoroionophore based on a bichromophoric azine

[graph: see text] A new probe, 1,4-bis(1-pyrenyl)-2,3-diaza-1,3-butadiene, selectively senses Hg2+ and Cu2+ through two different channels: the yellow-deep-pink color change and the enhancement of the fluorescence with the red shift of the excimer emission, which can visually be discernible by a green fluorescence in the presence of Hg2+ and an orange fluorescence in the presence of Cu2+.     

Development of a ratiometric fluorescent zinc ion probe in near-infrared region, based on tricarbocyanine chromophore

Novel ratiometric fluorescent probes for Zn2+ in the near-infrared region, based on a tricarbocyanine chromophore, have been designed, synthesized, and evaluated. Upon addition of Zn2+, a 44 nm red shift of the absorption maximum was observed, which indicates that this probe could work as a ratiometric probe for Zn2+. This change is due to the difference in the electron-donating ability of the amine substituent before and after reaction with Zn2+. This fluorescence modulation of amine-substituted tricarbocyanines should be applicable to dual-wavelength measurement of various biomolecules or enzyme activities.     

A ratiometric fluorescent probe for the detection of hypochlorous acid in living cells and zebra fish with along wavelength emission

A ratiometric fluorescence probe, NClO, for the rapid and selective detection of HClO had been designed and synthesized based on a 1,8-naphthalimide derivative. Probe NClO displayed a red emission(λ_(max)= 615 nm). In the presence of HClO, the solution of probe NClO gave off a strong green fluorescence(λ_(em), _(max)= 520 nm) with a rapid response(within seconds). This probe had been applied to image HClO in living cells and zebra fish.     

新型双发色团固体激光染料薄膜的光稳定性研究

利用UV-Vis吸收光谱仪和光化学反应器研究了新型双发色团固体激光染料薄膜的光降解动力学.研究结果表明:双发色团固体激光染料薄膜的光褪色反应遵循假一级动力学衰减.在PRNAM系列共聚物(N-烯丙基-若丹明1、N-[(2-丙烯酸基)乙基]-1,8-萘酰亚胺和甲基丙烯酸甲酯的共聚物)中萘酰亚胺基团通过聚合物碳链与若丹明基团的氮原子相连;而在PRNM系列共聚物(若丹明1的烯丙基酯、N-[(2-丙烯酸基)乙基]-1,8-萘酰亚胺和甲基丙烯酸甲酯的共聚物)中则是与若丹明基团的酯基相连.PRNAM系列共聚物的光稳定性优于PRNM和PRM(若丹明1的烯丙基酯和甲基丙烯酸甲酯的共聚物)系列的光稳定性.     

Fluorescence turn-on chemosensor for Hg~(2+) based on a rhodamine derivative and its application in bioimaging

A fluorescence turn-on chemosensor based on rhodamine B derivative (FD10) has been developed as a highly sensitive chemosensor for Hg2+. A prominent fluorescence enhancement was measured in the presence of Hg2+, which was in agreement with the changes in the absorption spectrum. Furthermore, by means of laser scanning fluorescence microscopy experiments, it was demonstrated that FD10 was cell-permeable and could be used as a fluorescent probe for monitoring Hg2+ in living cells.     

半青蓝素修饰汞离子探针的比色传感行为

合成了以半青蓝素为发光基团,分别以Se2N和S2N为结合位点的比色传感器3a和3b,通过紫外-可见光谱研究了它们对各种金属离子的化学传感行为. 结果表明,与含有S原子的主体分子3b相比,含有Se杂原子的主体3a对Hg2+具有较好的识别作用.向主体3a的乙腈水溶液中加入Hg2+后,其吸收光谱在410 nm处出现了一个新的吸收峰,同时溶液颜色由玫瑰红色变为桔黄色. 因此,化合物3a有望成为一种用于检测Hg2+的新型化学传感器.