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1.
Hyperhomocysteinemia is an established risk factor for atherosclerosis and vascular disease. Therefore, designing a hyperhomocysteinemia specific probe is of great significance for the early warning of cardiovascular diseases. However, developing probes that can efficiently and specifically recognize homocysteine (Hcy) remains a tremendous challenge. Therefore, we designed an Hcy-specific fluorescent probe (HSFP) with excellent selectivity and anti-interference capability. Interestingly, this probe can automatically “off–on” in water solution, but the fluorescence of HSFP remains “off” when Hcy is present in the solution. The spectroscopic data demonstrated that the fluorescence of HSFP attenuated 13.8 folds toward Hcy in water without interference from other biothiols and amino acids. Furthermore, HSFP can sensitively reflect the change of Hcy content in cells. Therefore, HSFP was further applied to detect hyperhomocysteinemia in vivo with high efficiency. In summary, we have developed an Hcy-specific fluorescent probe to efficiently detect Hcy in vivo and in vitro, which may contribute to basic or clinical research.An Hcy-specific fluorescent probe (HSFP) with excellent selectivity and anti-interference capability was developed for the detection of hyperhomocysteinemia. 相似文献
2.
Peipei Deng Yongyan Pei Mengling Liu Wenzhu Song Mengru Wang Feng Wang Chunxian Wu Li Xu 《RSC advances》2021,11(13):7610
The detection of mitochondrial Cu2+ and cysteine is very important for investigating cellular functions or dysfunctions. In this study, we designed a novel cyclometalated iridium(iii) luminescence chemosensor Ir bearing a bidentate chelating pyrazolyl-pyridine ligand as a copper-specific receptor. The biocompatible and photostable Ir complex exhibited not only mitochondria-targeting properties but also an “on–off–on” type phosphorescence change for the reversible dual detection of Cu2+ and cysteine. Ir had a highly sensitive (detection limit = 20 nM) and selective sensor performance for Cu2+ in aqueous solution due to the formation of a non-phosphorescent Ir–Cu(ii) ensemble through 1 : 1 binding. According to the displacement approach, Ir was released from the Ir–Cu(ii) ensemble accompanied with “turn-on” phosphorescence in the presence of 0–10 μM cysteine, with a low detection limit of 54 nM. This “on–off–on” process could be accomplished within 30 s and repeated at least five times without significant loss of signal strength. Moreover, benefiting from its good permeability, low cytotoxicity, high efficiency, and anti-interference properties, Ir was found to be suitable for imaging and detecting mitochondrial Cu2+ and cysteine in living cells and zebrafish.An iridium(iii) complex-based mitochondria targeting phosphorescent probe for selectively detecting Cu2+ and Cys in aqueous solution, living cells and zebrafish has been developed. 相似文献
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A new photochromic diarylethene derivative with a 4-methylphenol unit has been designed and synthesized. It displayed distinct photochromism and fluorescent ‘‘turn on’’ features to Mg2+ in acetonitrile solution. With the addition of Mg2+, there was an obvious increase of fluorescent emission intensity at 552 nm, accompanied by a clear change of fluorescent color from dark purple to green. Meantime, the 1 : 1 stoichiometry between the derivative and Mg2+ was verified by Job''s plot and HRMS. Furthermore, the sensor was successfully applied in the detection of Mg2+ in practical samples. Moreover, based on the multiple-responsive fluorescence switching behaviors, it also could be used to construct a molecular logic circuit with UV/vis lights and Mg2+/EDTA as input signals and the emission at 552 nm as the output signal.A new photochromic diarylethene derivative with a 4-methylphenol unit has been designed and synthesized. 相似文献
5.
Herein, we report novel “off–on” fluorescent sensing of organophosphate pesticides using a carbon dot (CD)–Au(iii) complex/acetylcholinesterase (AChE) system. The above sensor utilizes the quenching of CD fluorescence by Au(iii) and its subsequent recovery by thiocholine, which is generated by AChE-catalyzed hydrolysis of acetylthiocholine (ATCh) and effectively scavenges Au(iii). In the presence of organophosphates, the catalytic activity of AChE is inhibited, allowing these species to be quantified based on the decreased recovery of CD fluorescence intensity. The developed sensor was used to analyze a real pesticide-spiked sample (4.48 μM), achieving a recovery of 99.85% and exhibiting a linear response range of 0.45–44.80 μM.Herein, we report novel “off–on” fluorescent sensing of organophosphate pesticides using a carbon dot (CD)–Au(iii) complex/acetylcholinesterase (AChE) system. 相似文献
6.
ZhaoGuo Hong Chu Zheng Bi Luo Xin You HeDong Bian Hong Liang ZhenFeng Chen FuPing Huang 《RSC advances》2020,10(11):6297
Based on 1,2-dimethoxyphenyl (veratrole, open) and 1,2-methylenedioxyphenyl (pepper ring, close)-derived pyridine–triazole analogues, two groups of copper(ii) complexes, namely, Group I(C1–C3) and Group II(C4–C6) were synthesized and fully characterized. All ligands and complexes were tested in vitro by MTT assays on seven tumour cell lines (T24, Hep-G2, Sk-Ov-3, MGC-803, HeLa, A549 and NCI-H460) and one normal liver cell line (HL-7702). Surprisingly, the pepper-ring-derived complexes (C4–C6) showed significantly enhanced cytotoxicity compared with the 1,2-bimethoxyphenyl ring-derived complexes (C1–C3) and the standard anticancer drug cisplatin. Cellular uptake assays indicated that the Cu accumulation was consistent with cytotoxicity. In addition, flow cytometry and western blot analysis showed that the apoptosis of the leading complex C4 may be induced by the Bcl-2 family-mediated proteins through the mitochondrial dysfunction pathway. Furthermore, UV-vis and fluorescence spectroscopy assays revealed that C4 has stronger insertion-binding interactions with CT-DNA than C1 and the fluorescence of C1 and C4 with BSA is mainly quenched by static quenching.The pepper ring-modified complexes (Group II, C4–C6) exhibited significant antitumor activity than veratrole-modified complexes (Group I, C1–C3) towards several cancer cells with IC50 ranging from 3.45 to 8.59 μM. 相似文献
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In this paper, 5,10,15,20-(4-sulphonatophenyl) porphyrin (TSPP) was synthesized by a facile route and used as a fluorescent probe to construct a sensor system based on the high water solubility and high quantum yield. It was found that when riboflavin (RF) was introduced into the TSPP solution, the fluorescence intensity of TSPP decreased for the peaks at 645 nm and 700 nm based on the principle of the electrostatic attractions and hydrophobic interactions between TSPP and riboflavin. When the fluorescence emission peak of riboflavin appeared at 550 nm, the fluorescence sensor system changed from the “on” state to the “off” state. When sulfur ions (S2−) were further introduced into the TSPP–riboflavin system, the fluorescence intensity of riboflavin was further decreased based on the specific reaction between S2− and riboflavin. However, the fluorescence signal of TSPP was restored and the fluorescence sensing system changed from the “off” state to the “on” state. Therefore, TSPP was used as a fluorescent probe to construct an “on–off–on” fluorescent sensing system, the linear range of S2− detected by this system is 5.0 × 10−9 to 3.6 × 10−5 M, and the detection limit (LOD) is 1.1 × 10−9 M. The sensing system has higher accuracy and sensitivity, and it can be successfully used in the sensing of S2− in real samples.In this paper, 5,10,15,20-(4-sulphonatophenyl) porphyrin (TSPP) was synthesized by a facile route and used as a fluorescent probe to construct a sensor system based on the high water solubility and high quantum yield. 相似文献
8.
In this work, a novel sensor, (E)-N′-(3-(tert-butyl)-2-hydroxybenzylidene)thiophene-2-carbohydrazide (1), based on salicylaldehyde and thiophene hydrazide moieties was designed and synthesized. The single-crystal structure of 1 was achieved and studied for understanding its functional properties. The interaction and recognition abilities of 1 with different metal ions were investigated. Sensor 1 showed excellent “turn-on” fluorescence with highly selective and specific recognition ability in the presence of gallium ions (Ga3+) in an aqueous solution. The sensing behavior of 1 with Ga3+ was also studied by photophysical experiments, ESI-MS analysis, and 1H NMR titration. The limit of detection (LOD) and limit of quantification (LOQ) of 1 for the detection of Ga3+ in an aqueous solution were calculated as 58 nM, and 192 nM, respectively. DFT calculations were carried out to optimize the configuration of 1 and 1–Ga3+ complexes and rationalize the photophysical experimental data. Highly selective test strips based on sensor 1 were developed for Ga3+ detection. Sensor 1 was also used to detect Ga3+ in actual water samples, and a considerable recovery rate was obtained.In this work, a highly selective water-soluble “turn-on” fluorescent sensor for gallium ion recognition was reported. 相似文献
9.
In this update, we developed a mild, efficient and practical method using fluorosulfuryl imidazolium salt A as an environment friendly promoter for conversion of oximes to nitriles or amides via β-elimination or Beckmann rearrangement in almost quantitative yield in 10 minutes. The target products were generated in gram-scale and could be collected through crystallization without silica gel column purification in excellent yield.In this update, we developed a mild, efficient and practical method using stable “F–SO2+” donor A as an environment friendly promoter for conversion of oximes to nitriles or amides via β-elimination or Beckmann rearrangement in excellent yields.Nitriles and amides are important classes of organonitrogen compounds. Nitrile and amide play an important role in organic synthesis and are core structures of many agrochemicals, bioactive drugs, natural products, fine chemicals and functional materials.1,2 Examples include tecovirimat (1), an antiviral indicated for the treatment of smallpox,3 which is also effective in treating monkeypox infections;4 PF-07321332 (2), which is a nitrile inhibitor of the SARS-CoV-2 main protease;5 P5TCN-2F, a polythiophene organic solar cells (OSCs) (3), revealed that the cyano-group leads to high-efficiency OSCs and improved polymer crystallinity (Scheme 1).6Open in a separate windowScheme 1Selected examples for valuable nitriles and amides.Owing to their widespread applications, there has been a push in recent decades to develop a more efficient, mild, Rosenmund–von Braun and safe approach to nitriles and amides. Sandmeyer and Braun reactions,7 formal acid–nitrile exchange,8 transition-metal-catalyzed cyanation of halides,9 and direct C–H cyanation are examples of traditional cyanide-based processes to nitriles (Scheme 2a(1)).10 Meanwhile, many cyanide-free synthetic methods have been developed, such as amide dehydration,11 primary amine hydrogenation,12 and cyanation with other nitrogen sources.13 Amides are commonly formed by reacting carboxylic acid or its derivatives with amines via condensation or transition metal-catalyzed coupling (Scheme 2a(2)).14 Aside from that, other protocols to amides have been reported, including carbonylative hydroamidation,15 nitrile hydrolysis,16 nitro-reduction amidation,17 and N-arylation of activated amides.18 The aforementioned strategies, however, were limited to toxic reagents, expensive transition-metal catalysts, complex reaction systems, and harsh conditions, especially when two or more components are used as raw materials, which may result in low atom utilization and more by-products. As a result, developing a solution to the aforementioned difficulties is critical.Open in a separate windowScheme 2Strategies for preparation of nitriles and amides.Oximes are simple and easily accessible class of chemical,18 particularly aldoximes and ketoximes, which could be converted to nitriles and amides efficiently by β-elimination and Beckman rearrangement,19 respectively (Scheme 2b). Various catalysts have been devised in recent years to facilitate the heterolysis of nitrogen–oxygen bond in order to achieve this transformation, but there are still certain drawbacks. Such as o-NosylOXY,20 required microwave irradiation and high temperature. In 2020, Xu reported that HCl·DMPU assisted conversion of aldehydes into nitriles while HCl–DMPU is a solution emitting fumes.21 Recently, Ding, Qin and Fokin groups reported rapid and mild SO2F2-promoted dehydration of oxime.22 However, the use of a greenhouse gas SO2F2 is not safe as it may leak out in operation.23 Although the organoselenium-catalyzed dehydration of aldoximes can produce nitriles under environment friendly conditions, it required for hours up to days.24 To some extends, those disadvantages restrict its wide applications.In 2018, Dong and Sharpless reported a fluorosulfuryl imidazolium salt A, which showned unprecedented reactivity, selectivity, and scope as an “F–SO2+” donor and is a far more reactive fluorosulfurylating agent than SO2F2.25 Subsequently, it was developed for the crucial precursor of diazotransfer reagent, which enables the preparation of azides from primary amines.26 Moreover, fluorosulfuryl imidazolium salt A provides a practical and efficient process to prepare unsymmetrical sulfamides via Sulfur(vi)–Fluoride Exchange (SuFEx) click chemistry.27 Most recently, Liao and Wang groups reported that fluorosulfuryl imidazolium salt could produce SO2F radical and enabled fluorosulfonylation of olefins.28Inspired by the wide application of fluorosulfuryl imidazolium salt and its unprecedented reactivity, and upon viewing the limitations of the preparation of nitriles and amides from oximes, we tried to apply fluorosulfuryl imidazolium salt A for the β-elimination of aldoximes and Beckmann rearrangement of ketoximes after our continuous efforts on the utilization of SO2F2-promoted transformations.29 As predicted, the alkylated imidazolium species served as good leaving groups and delivers the “F–SO2+” fragment,27,30 and aldoximes or ketoximes would react with “F–SO2+”, with the assistance of the base, to generate the corresponding sulfonyl ester, and further produce the nitriles or amides via β-elimination or Beckmann rearrangement. As predicted, aldoximes or ketoximes would react with fluorosulfuryl imidazolium salt A, with the assistance of the base, to generate the corresponding sulfonyl ester, and futher produce the nitriles or amides via β-elimination or Beckmann rearrangement (Scheme 2c). When 4-bromobenzaldehyde oxime (1d) or acetophenone oxime (3a) were used as model substrates, 4-bromobenzonitrile (2d) or N-phenylacetamide (4a) were obtained in 98% yields under the optimal reaction conditions (the more details please see ESI Tables S1 and S2†).Having established the optimal reaction conditions, we examined the scope and generality of this protocol from aryl aldoximes into nitriles. As shown in