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1.
Small molecular biothiols, cysteine (Cys), homocysteine (Hcy) and glutathione (GSH), play important roles in organisms, and their concentration levels are indicative of some human diseases. Herein we report an organic dye-conjugated β-diketonate-Eu3+ complex, [Eu(NBD-keto)3(DPBT)] (NBD-keto: 7-nitro-2,1,3-benzoxadiazole (NBD)-conjugated to 1,1,1,2,2-pentafluoro-5-phenyl-3,5-pentanedionate through a “O” ether bond; DPBT: 2-(N,N-diethylanilin-4-yl)-4,6-bis(3,5-dimethylpyrazol-1-yl)-1,3,5-triazine), which acts as a unique luminescent probe for detecting and discriminating biothiols. [Eu(NBD-keto)3(DPBT)] itself is not luminescent due to intramolecular interactions between NBD and β-diketonate-Eu3+ moieties. Upon reaction with biothiols, the β-diketonate-Eu3+ complex [Eu(keto)3(DPBT)] is generated, which emits long-lived red emission at 610 nm. Meanwhile, three biothiol-substituted NBD derivatives that exhibit different luminescence behaviors, green emissive (short-lived) NBD-NR (R=Cys or Hcy) at 540 nm and non-luminescent NBD-SR (R=GSH), are also generated. These luminescence response behaviors allow time-gated and steady-state luminescence modes to be combined for detecting total biothiols and discriminating GSH and Cys/Hcy. Using this probe, the quantitative detection and discrimination of GSH and Cys/Hcy in lysis solutions of HeLa cells were realized, which revealed the potential of the probe for biomedical applications. 相似文献
2.
Zhen Li Zhao Wei Feng Xu Yin Huan Li Tian Jian Lu Yong Mei Chen Gui Jiang Zhou 《Macromolecular rapid communications》2012,33(14):1191-1196
Novel phosphorescent hydrogels have been explored by immobilizing an IrIII metal complex into the matrices of hydrogels. FTIR spectra demonstrate that the IrIII–PNaAMPS hydrogel is achieved by irreversible incorporation of positively charged [Ir(ppy)2(dmbpy)]Cl (ppy = 2‐phenylpyrine, dmbpy = 4,4′‐dimethyl‐2,2′‐bipyridine) into negatively charged poly(2‐acrylamido‐2‐methylpropane sulfonic acid sodium) (PNaAMPS) hydrogel via electrostatic interaction. The photoluminescent spectra indicate that the IrIII–PNaAMPS hydrogel exhibits stable phosphorescence. In vitro cultivation of human retinal pigment epithelial cells demonstrates the cytocompatibility of the IrIII–PNaAMPS hydrogel. This work herein represents a facile pathway for fabrication of phosphorescent hydrogels. 相似文献
3.
A highly water soluble fluorescent probe was developed for sensitive and selective detection of biothiols with a red emission and a large Stokes shift. The probe was successfully applied to detect biothiols both in aqueous solution and in living cells. 相似文献
4.
《结构化学》2019,38(10)
Biothiols such as cysteine(Cys), homocysteine(Hcy) and glutathione(GSH) act as critical roles in maintaining biological redox homeostasis, which is crucial for a plenty of physiological and pathological processes. Therefore, the detection of biothiols is very important and beneficial for many applications. Herein, we have designed and developed a new crystal dimethyl 4-(2,4-dinitrophenylsulfonyloxy)pyridine-2,6-dicarboxylate(P) with 2,4-dinitrobenzene-1-sulfonyl(DNBS) pendant for light-up and detection of biothiols(Cys was selected as the analyte model). The fluorescence "off-on" switch is triggered by the cleavage of DNBS unit by the interaction with biothiols via nucleophilic aromatic substitution reaction. The turn-on fluorescent probe exhibited excellent selectivity and sensitivity toward biothiols. 相似文献
5.
Cyclometalated Mono‐ and Dinuclear IrIII Complexes with “Click”‐Derived Triazoles and Mesoionic Carbenes 下载免费PDF全文
Dr. Ramananda Maity Stephan Hohloch Prof. Dr. Cheng‐Yong Su Margarethe van der Meer Prof. Dr. Biprajit Sarkar 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(32):9952-9961
Orthometalation at IrIII centers is usually facile, and such orthometalated complexes often display intriguing electronic and catalytic properties. By using a central phenyl ring as C?H activation sites, we present here mono‐ and dinuclear IrIII complexes with “click”‐derived 1,2,3‐triazole and 1,2,3‐triazol‐5‐ylidene ligands, in which the wingtip phenyl groups in the aforementioned ligands are additionally orthometalated and bind as carbanionic donors to the IrIII centers. Structural characterization of the complexes reveal a piano stool‐type of coordination around the metal centers with the “click”‐derived ligands bound either with C^N or C^C donor sets to the IrIII centers. Furthermore, whereas bond localization is observed within the 1,2,3‐triazole ligands, a more delocalized situation is found in their 1,2,3‐triazol‐5‐ylidene counterparts. All complexes were subjected to catalytic tests for the transfer hydrogenation of benzaldehyde and acetophenone. The dinuclear complexes turned out to be more active than their mononuclear counterparts. We present here the first examples of stable, isomer‐pure, dinuclear cyclometalated IrIII complexes with poly‐mesoionic‐carbene ligands. 相似文献
6.
Protein Labelling with Versatile Phosphorescent Metal Complexes for Live Cell Luminescence Imaging 下载免费PDF全文
Timothy U. Connell Janine. L. James Prof. Anthony R. White Prof. Paul S. Donnelly 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(40):14146-14155
To take advantage of the luminescent properties of d6 transition metal complexes to label proteins, versatile bifunctional ligands were prepared. Ligands that contain a 1,2,3‐triazole heterocycle were synthesised using CuI catalysed azide–alkyne cycloaddition “click” chemistry and were used to form phosphorescent IrIII and RuII complexes. Their emission properties were readily tuned, by changing either the metal ion or the co‐ligands. The complexes were tethered to the metalloprotein transferrin using several conjugation strategies. The IrIII/RuII–protein conjugates could be visualised in cancer cells using live cell imaging for extended periods without significant photobleaching. These versatile phosphorescent protein‐labelling agents could be widely applied to other proteins and biomolecules and are useful alternatives to conventional organic fluorophores for several applications. 相似文献
7.
A Multi‐signal Fluorescent Probe with Multiple Binding Sites for Simultaneous Sensing of Cysteine,Homocysteine, and Glutathione 下载免费PDF全文
Guo‐xing Yin Ting‐ting Niu Ya‐bing Gan Ting Yu Dr. Peng Yin Prof. Hai‐min Chen Prof. You‐yu Zhang Prof. Hai‐tao Li Prof. Shou‐zhuo Yao 《Angewandte Chemie (International ed. in English)》2018,57(18):4991-4994
A novel fluorescent probe was developed by integrating chlorinated coumarin and benzothiazolylacetonitrile and exploited for simultaneous detection of cysteine (Cys), homocysteine (Hcy), and glutathione (GSH). Featuring four binding sites and different reaction mechanisms for different biothiols, this probe exhibited rapid fluorescence turn‐on for distinguishing Cys, Hcy, and GSH with 108‐, 128‐, 30‐fold fluorescence increases at 457, 559, 529 nm, respectively, across different excitation wavelengths. Furthermore, the probe was successfully applied to the fluorescence imaging of endogenous Cys and GSH and exogenous Cys, Hcy, and GSH in living cells. 相似文献
8.
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2018,130(18):5085-5088
A novel fluorescent probe was developed by integrating chlorinated coumarin and benzothiazolylacetonitrile and exploited for simultaneous detection of cysteine (Cys), homocysteine (Hcy), and glutathione (GSH). Featuring four binding sites and different reaction mechanisms for different biothiols, this probe exhibited rapid fluorescence turn‐on for distinguishing Cys, Hcy, and GSH with 108‐, 128‐, 30‐fold fluorescence increases at 457, 559, 529 nm, respectively, across different excitation wavelengths. Furthermore, the probe was successfully applied to the fluorescence imaging of endogenous Cys and GSH and exogenous Cys, Hcy, and GSH in living cells. 相似文献
9.
ükriye Nihan Karuk Elmas Ibrahim Berk Gunay Abdurrahman Karagoz Aykut Bostanci Gkhan Sadi Ibrahim Yilmaz 《Electroanalysis》2020,32(4):775-780
The selective and sensitive detection of biothiols; cysteine (Cys), homocysteine (Hcy) and glutathione (GSH) in aqueous solutions is of considerable importance because of their pivotal roles in maintaining the reducing environment in the cells. This study describes a strategy for the determination of biothiols based on the PDI/Met‐Hg2+complex platform. We designed and fabricated methionine modified perylene diimide molecule as a selective sensing probe for Hg2+ ions in aqueous solutions ( PDI/Met‐Hg 2+). The complex between perylene bisimide derivative ( PDI/Met) and Hg2+ was investigated and it demonstrated turn‐on fluorescence response for the detection of the biological thiols. Besides, PDI/Met displayed fluorescence quenching response in the presence of mercury ions and the emission intensity of PDI/Met‐Hg2+ was recovered after transferring biothiols (Cys, Hcy, and GSH). Thus, PDI/Met could be utilized as a fluorescent chemosensor for the sequential recognition of mercury ions and biological thiols. 相似文献
10.
Rational Design of an Ultrasensitive and Highly Selective Chemodosimeter by a Dual Quenching Mechanism for Cysteine Based on a Facile Michael‐Transcyclization Cascade Reaction 下载免费PDF全文
Xiangmin Li Yongjun Zheng Hongjuan Tong Rui Qian Dr. Lin Zhou Prof. Dr. Guixia Liu Prof. Dr. Yun Tang Prof. Dr. Hao Li Prof. Dr. Kaiyan Lou Prof. Dr. Wei Wang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(27):9247-9256
Differentiation of biologically important thiols, such as cysteine (Cys), homocysteine (Hcy), and glutathione (GSH) is still a challenging task. Herein, we present a novel fluorescent chemodosimeter capable of selectively detecting Cys over other biothiols including Hcy and GSH and other amino acids by a facile thiol‐Michael addition/transcyclization rearrangement cascade click process. The unique transcyclization step is critical for the selectivity as a result of the kinetically favorable formation of a six‐membered ring with the Cys Michael adduct. Moreover, the probe adopts a distinctive dual quenching mechanism—photoinduced electron transfer (PET) and photoinduced intramolecular charge transfer (ICT) to deliver a drastic turn‐on fluorescence response only at the Cys‐selective transcylization step. The judicious selection of strong electron‐withdrawing naphthalimide fluorophore with maleimide group enhances the electrophilicity and thus reactivity for the cascade process leading to fast detection and ultrasensitivity with a detection limit of 2.0 nm (S/N=3). The probe has demonstrated its practical utility potential in Cys imaging in live cells. 相似文献
11.
Shujuan Liu Weili Qiao Guoyi Cao Yang Chen Yun Ma Yanqin Huang Xiangmei Liu Wenjuan Xu Qiang Zhao Wei Huang 《Macromolecular rapid communications》2013,34(1):81-86
Homocysteine (Hcy) and cysteine (Cys) are two important kinds of amino acids in human bodies. Herein, we synthesized an iridium(III) complex‐functionalized poly(N‐isopropylacrylamide) and its hydrogel, which could be used as the excellent phosphorescent bioprobe for sensing Hcy and Cys. Their detection can be realized in aqueous system through the variations in absorption and photoluminescence spectra. Furthermore, living cell imaging experiments demonstrate that the phosphorescent bioprobe is membrane permeable and can monitor the changes of Hcy and Cys within living cells. In addition, the probe is also thermoresponsive, and its photoluminescence intensified with increasing temperature. These results suggests that this bioprobe has promising application in biomedical fields. 相似文献
12.
Yan Zheng Peng Hou Yu Li Jingwen Sun Hongxia Cui Haiyan Zhang Song Chen 《Molecules (Basel, Switzerland)》2021,26(8)
Due to the redox properties closely related to numerous physiological and pathological processes, biothiols, including cysteine (Cys), homocysteine (Hcy) and glutathione (GSH), have received considerable attention in biological science. On account of the important physiological roles of these biothiols, it is of profound significance to develop sensitive and selective detection of biothiols to understand their biological profiles. In this work, we reported an efficient fluorescent probe, PHPQ-SH, for detecting biothiols in vitro and vivo, based on the phenothiazine-HPQ skeleton, with DNBS (2,4-dinitrobenzenesulfonate) as the response unit. Probe PHPQ-SH exhibited brilliant sensing performances toward thiols, including a large Stokes shift (138 nm), excellent sensitivity (for GSH, LOD = 18.3 nM), remarkable fluorescence enhancement (163-fold), low cytotoxicity, rapid response (8 min), and extraordinary selectivity. Finally, the probe PHPQ-SH illustrated herein was capable of responding and visualizing biothiols in MCF-7 cells and zebrafish. 相似文献
13.
《Tetrahedron》2019,75(36):130477
Two fluorescein derivatives containing 2,4-dinitrobenzenesulfonyl group have been developed as fluorescent probes to detect the biothiols (Cys, Hcy and GSH) in aqueous solution. Probes 1 and 2 can distinguish these biothiols in the presence of other amino acids. While probe 1 can recognize the biothiols in PBS/DMSO (v:v = 95:5, pH = 7.40) solution, notably probe 2 could be used in PBS buffer solution (pH = 7.40). The detection limit of Cys for probe 2 reached at 0.021 μM in aqueous solution, which was lower than the intracellular concentration of Cys. In the recognition process, a reaction between the probes and the biothiols occurred, in which the S–O bond was cleaved to remove 2, 4-dinitrobenzenesulfonyl group. The data of 1H NMR, MS and DFT/TD-DFT calculation further confirmed the detection mechanism. Moreover, two probes were successfully applied to the HeLa cell imaging. 相似文献
14.
A Solution‐Processable Donor–Acceptor Compound Containing Boron(III) Centers for Small‐Molecule‐Based High‐Performance Ternary Electronic Memory Devices 下载免费PDF全文
Dr. Chun‐Ting Poon Dr. Di Wu Dr. Wai Han Lam Prof. Dr. Vivian Wing‐Wah Yam 《Angewandte Chemie (International ed. in English)》2015,54(36):10569-10573
A novel small‐molecule boron(III)‐containing donor–acceptor compound has been synthesized and employed in the fabrication of solution‐processable electronic resistive memory devices. High ternary memory performances with low turn‐on (VTh1=2.0 V) and distinct threshold voltages (VTh2=3.3 V), small reading bias (1.0 V), and long retention time (>104 seconds) with a large ON/OFF ratio of each state (current ratio of “OFF”, “ON1”, and “ON2”=1:103:106) have been demonstrated, suggestive of its potential application in high‐density data storage. The present design strategy provides new insight in the future design of memory devices with multi‐level transition states. 相似文献
15.
Are Triphenylamine‐Functionalized or Carbazole‐Functionalized Iridium Complexes the More Effective Phosphorescent Materials? A Theoretical Perspective 下载免费PDF全文
Dr. Yan Li Lu‐Yi Zou Prof. Dr. Ai‐Min Ren Dr. Ming‐Shuo Ma Jian‐Xun Fan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(16):4671-4680
The ground and excited states, charge injection/transport, and phosphorescence properties of eleven carbazole‐ and triphenylamine‐functionalized IrIII complexes were investigated by using the DFT method. By analyzing the spin–orbit coupling (SOC) matrix elements, radiative decay rate constants kr, and the electronic structures and energies at the ${{\rm{S}}_{\rm{0}}^{{\rm{opt}}} }$ and ${{\rm{T}}_{\rm{1}}^{{\rm{opt}}} }$ states, it was possible to rationalize the order of the experimental phosphorescence quantum yields of a series of IrIII complexes and to predict that [Ir(Nph‐2‐Cz‐tz)3] has a higher phosphorescence quantum yield than [Ir(TPA‐tz)3] (TPA=triphenylamine, tz=thiazolyl, Cz=carbazole, Nph=N‐phenyl). Carbazole‐functionalized IrIII complexes were shown to be efficient phosphorescent materials that have not only fast but also balanced electron/hole‐transport performance as well as high phosphorescence quantum yields. The phosphorescence emission spectra can be modulated by modifying or replacing a pyridyl substituent. 相似文献
16.
Qingsong Liu Changli Zhang Xiaoqing Wang Shuwen Gong Weijiang He Zhipeng Liu 《化学:亚洲杂志》2016,11(2):202-206
Due to the similar structure and reactivity of cysteine (Cys), homocysteine (Hcy) and glutathione (GSH), the simultaneous discrimination of Cys over Hcy and GSH by a single fluorescent sensor is still a great challenge. In this work, a benzothiazole‐pyimidine‐based boron difluoride complex ( BPB ) was developed as a new fluorescent sensor for Cys. The sensor exhibits a highly selective “turn‐on” response to cysteine over Hcy, GSH and other amino acids in aqueous solution at physiological pH. The observed pseudo‐first‐order rate constant for the reaction of BPB with Cys was calculated to be about 0.062 min−1. The detection limit of this sensor for Cys was determined to be 332 nm, and bioimaging of exogenous Cys by this sensor was successfully applied in living cells, thus indicating that this sensor holds great potential for biological applications. 相似文献
17.
Giulia Lavarda Daiki Shimizu Toms Torres Atsuhiro Osuka 《Angewandte Chemie (International ed. in English)》2020,59(8):3127-3130
Peripherally metalated porphyrinoids are promising functional π‐systems displaying characteristic optical, electronic, and catalytic properties. In this work, 5‐(2‐pyridyl)‐ and 5,10,15‐tri(2‐pyridyl)‐BIII‐subporphyrins were prepared and used to produce cyclometalated subporphyrins by reactions with [Cp*IrCl2]2, which proceeded through an efficient C?H activation to give the corresponding mono‐ and tri‐IrIII complexes, respectively. While the mono‐IrIII complex was obtained as a diastereomeric mixture, a C3‐symmetric tri‐IrIII complex with the three Cp*‐units all at the concave side was predominantly obtained in a high yield of 90 %, which displays weak NIR phosphorescence even at room temperature in degassed CH2Cl2, differently from the mono‐IrIII complexes. 相似文献
18.
《中国化学快报》2021,32(9):2873-2876
The development of fluorescent probes enabling to distinguish Cys, Hcy and GSH has always been a considerable challenge, in particular the distinction of Hcy and other two biothiols, because Hcy has a very similar structure with Cys and a relatively lower concentration in living organisms. In this work, a special o-dialdehyde fluorescent probe, quinoline-2,3-dicarboxaldehyde (QDA), has been synthesized and demonstrated superior performance in differentiating detection of Hcy and GSH, which is different from the previous reported o-dialdehyde probes specifically detecting GSH. Furthermore, the probe can selectively distinguish Hcy and GSH from different signal channels in living cells and zebrafish, meaning it has great potential in biological applications. This finding will provide a novel idea for the design of fluorescent probes to distinguish biothiols. 相似文献
19.
Xuecong Li Dr. Prerna Yadav Prof. Dr. Bernhard Spingler Prof. Dr. Felix Zelder 《ChemistryOpen》2022,11(6):e202200106
Homocysteine (Hcy) is a sulfur-containing α-amino acid that differs by one methylene (CH2) subunit from homologous cysteine (Cys). Elevated levels of Hcy are diagnostic markers of cardiovascular disease and other medical conditions. We present a new CuII-salicylidene glycinato complex 1 for the selective fluorometric detection of Hcy in water. In the presence of this analyte, the non-fluorescent copper-complex demetallates and disassembles into its building blocks. This process liberates a 3-chloro-5-sulfosalicylaldehyde signaling unit and is accompanied by a 51-fold turn-on fluorescence at 485 nm (λex=350 nm). Out of twenty proteinogenic amino acids, only histidine (12-fold turn-on fluorescence) and Cys (8-fold turn-on fluorescence) trigger some disassembly of probe 1 . In comparison with important pioneering work on the detection of biothiols, this study strikingly demonstrates that structural modifications of chelate core structures steer substrate selectivity of metal-based probes. Importantly, probe 1 has proven suitable for the detection of Hcy in artificial urine. 相似文献
20.
Encapsulation and Enhanced Luminescence Properties of IrIII Complexes within a Hexameric Self‐Assembled Capsule 下载免费PDF全文
Dr. Shinnosuke Horiuchi Hirotaka Tanaka Prof. Dr. Eri Sakuda Prof. Dr. Yasuhiro Arikawa Prof. Dr. Keisuke Umakoshi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(49):17533-17537
Encapsulation and luminescence studies of [Ir(ppy)2(bpy)]Cl (ppy=2‐phenylpyridinate, bpy=2,2′‐bipyridine) within a hexameric resorcinarene capsule are reported. One IrIII complex cation was encapsulated within the capsule, as demonstrated by NMR and dynamic light scattering (DLS) studies. The emission color of the IrIII complex was drastically changed from orange to yellow by encapsulation, in contrast with the lack of significant changes in the absorption spectrum. The hexameric capsule effectively hampers the non‐radiative pathway to increase both the luminescence quantum yield and the exited state lifetime. The luminescent properties of the encapsulated IrIII complex depend on the ratio of IrIII complex to the resorcinarene monomer as well as the concentration of resorcinarene monomer owing to the reversible process of self‐assembly of the hexameric capsule. Quenching experiments revealed that the IrIII complex in the capsule was effectively separated from quenchers. 相似文献