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TALANTA · 2025 · IF 6.1

Remote and in-situ monitoring of plasmon-induced catalysis reaction by fiber SERS probes

Lianyu Bao,Fei Zhou,Ye Liu,Botian Wang,Rang Chu,Qingmao Zhang,Hongcheng Wang

Monitoring chemical reaction processes is of great significance in the study of the reaction mechanisms, and the optimization or control of reaction conditions. In this work, we demonstrate a novel monitoring method of chemical reactions using fiber SERS probes. The high-performance fiber SERS probes are prepared by the laser-induced evaporation self-assembly method (LIESAM), where lots of Au-nanorod clusters are deposited on the fiber facet for providing large SERS enhancement factor and good hot electron catalytic property. The remote and in-situ monitoring of chemical reactions is achieved through simply dipping the probes into the reaction solution. Taking the classic reduction reaction from 4-nitrothiophenol (4-NTP) to 4-aminothiophenol (4-ATP) by sodium borohydride (NaBH 4 ) as an example, the time-resolved SERS spectra collected by probes clearly reflect the reduction procedure of the disappearance of 4-NTP, the formation of intermediate product 4,4′-dimercaptoazobenzene (4,4′-DMAB) and the emergence of the final product 4-ATP. In addition, a new Raman peak at 1366 cm −1 is observed when the 4-NTP is reduced in an H 2 atmosphere generated by the hydrolysis of NaBH 4 , corresponding the formation of a new intermediate product 4-nitrosothiophenol (4-NSTP). Also, the monitoring of the oxidation reaction from 4-ATP to 4,4′-DMAB is demonstrated using fiber SERS probes. Considering that all the SERS spectra are acquired with a portable Raman spectrometer and the fiber has a very low transmission loss, this work provides a good platform for remote, on-site and in situ monitoring of chemical reactions in liquid environments and thus finds important applications in scientific research and industrial scenarios.

研究领域: 化学 · 材料科学
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Nano Research · 2023 ·Vol. 16 ·期 11 ·12697-12705 · IF 9.9

Plasmonic nanostructures acting as a light-driven O2-sensitive nitroreductase mimic for enhanced photochemical oxidation of para-aminothiophenol

Gao Xinshuang,Zheng Jia-jia,Li Hanbo,Cai Rui,Gao Xingfa,Wu Xiaochun

Nanozymes, as a novel form of enzyme mimics, have garnered considerable interest. Despite overcoming the main disadvantages of their natural analogs, they still face challenges such as restricted mimic types and low substrate specificity. Herein, we introduce a reactive ligand modification strategy to diversify enzyme mimic types. Specifically, we have utilized helical plasmonic nanorods (HPNRs) modified with para -nitrothiophenol (4-NTP) to create an oxygen-sensitive nitroreductase (NTR) with light-controllability. HPNRs act as a light-adjustable source of nicotinamide adenine dinucleotide/nicotinamide adenine dinucleotide phosphate (NAD(P)H), providing photon-generated energetic electrons to adsorbed 4-NTP molecules. In the presence of O 2 , the activated 4-NTP transfers the captured electron to the adsorbed O 2 , mimicking the electron transfer process in its natural counterpart. This enhanced O 2 activation notably boosts the oxidative coupling of para -aminothiophenol (4-ATP). Density functional theory (DFT) calculations reveal that hot electrons injected into the lowest unoccupied molecular orbital (LUMO) energy level of 4-NTP can be transferred to that of molecular oxygen. In conclusion, our findings underline the potential of the reactive ligand modification strategy in developing new types of enzyme reactions, which opens up promising avenues for the enhancement and diversification of nanozyme functionalities.

CAS / MDL: 299-11-6 7757-82-6
研究领域: 生物化学 · 纳米生物学 · 催化科学
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MATERIALS LETTERS · 2020 · IF 3.204

Carbon-dot-based colorimetric turn-on probe for selectively detecting thiophenols

Shengrui Zhang,Qin Wang,Zhifeng Liu,Jin Liu,Jiufu Lu

A colorimetric turn-on probe was developed for the selective naked-eye determination of thiophenols by using yellow-emissive carbon dots (Y-CDs) as the colorimetric reporter and 2, 4-dinitrobenzenesulfonamide (DNBS) group as the recognition unit. The surfaces of Y-CDs were covalently coated with 2, 4-dinitrobenzenesulfonyl chloride to afford the 2, 4-dinitrobenzene- functionalized carbon dots ( CD-DNBS ) as a novel probe for detecting thiophenols. CD-DNBS was nearly colorless. Upon addition of thiophenol , the DNBS moiety of CD-DNBS could be readily cleaved via nucleophilic substitution reactions, leading to a dramatic increase in absorbance at 400 nm. The established detection probe displays a high selectivity towards thiophenol over biothiols and other biologically related species.

研究领域: 分析化学 · 生物化学
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JOURNAL OF SEPARATION SCIENCE · 2017 ·Vol. 40 ·期 12 ·2528-2540 · IF 2.557

3-(2-Bromoacetamido)-N-(9-ethyl-9H)-carbazol fluorescent probe and its application for the determination of thiophenols in rubber products by HPLC with fluorescence detection and atmospheric chemical ionization mass spectrometry identification

Jinmao You,Kun Dou,Cuihua Song,Guoliang Li,Zhiwei Sun,Shijuan Zhang,Guang Chen,Xianen Zhao,Na Hu,Wu Zhou

A rapid, sensitive, and selective precolumn derivatization method for the simultaneous determination of eight thiophenols using 3-(2-bromoacetamido)- N -(9-ethyl-9 H )-carbazol as a labeling reagent by high-performance liquid chromatography with fluorescence detection has been developed. The labeling reagent reacted with thiophenols at 50°C for 50 min in aqueous acetonitrile in the presence of borate buffer (0.10 mol/L, pH 11.2) to give high yields of thiophenol derivatives. The derivatives were identified by online postcolumn mass spectrometry. The collision-induced dissociation spectra for thiophenol derivatives gave the corresponding specific fragment ions at m/z 251.3, 223.3, 210.9, 195.8, and 181.9. At the same time, derivatives exhibited intense fluorescence with an excitation maximum at λ ex = 276 nm and an emission maximum at λ em = 385 nm. Excellent linear responses were observed for all analytes over the range of 0.033–6.66 μmol/L with correlation coefficients of more than 0.9997. Detection limits were in the range of 0.94–5.77 μg/L with relative standard deviations of less than 4.54%. The feasibility of derivatization allowed the development of a rapid and highly sensitive method for the quantitative analysis of trace levels of thiophenols from some rubber products. The average recoveries ( n = 3) were in the range of 87.21–101.12%.

研究领域: 分析化学 · 环境科学
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JOURNAL OF FOOD COMPOSITION AND ANALYSIS · 2024 · IF 4

A turn-on fluorescent probe for the detection of hydrogen sulfide and thiophenol in water and beer samples

Jia-Rui Xu,Yi Zheng,Tian-Zhen Liu,Bao-Xiang Zhao,Kai-Ming Wang

Hydrogen sulfide (H 2 S) and thiophenol (PhSH) are toxic pollutants that can affect the quality and safety of food and water. It is of importance to detect these analytes. However, developing fluorescent probes that can selectively discriminate H 2 S and PhSH is challenging due to their similar reactivity. In this work, we reported a dual-functional probe N -(4-(benzo[ d ]thiazol-2-yl)phenyl)− 2,4-dinitrobenzenesulfonamide ( NBT ) that could synchronously and selectively respond to H 2 S and PhSH in different solvents. NBT exhibited high selectivity, a low detection limit (82.66 nM for H 2 S, 21.44 nM for PhSH), and a wide linear range (5–70 μM for H 2 S, 5–35 μM for PhSH). Therefore, NBT was successfully applied to detect H 2 S and PhSH in water and beer samples with excellent recovery and precision. This probe provides a simple and effective method for the simultaneous and quantitative detection of H 2 S and PhSH in water and beer samples without the need for sophisticated instruments.

CAS / MDL: 6278-73-5 207683-19-0
研究领域: 分析化学 · 环境科学 · 食品科学
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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2023 · IF 4.4

ESIPT-based fluorescent enhanced probes prompted by methylated β-cyclodextrin for the detection of thiophenols

Hai-Yan Peng,Gang Zhang,Ru Sun,Yu-Jie Xu,Jian-Feng Ge

Thiophenol and its derivatives are compounds with high toxicity to organisms and environmental pollution, so it is necessary to detect the level of thiophenols in the environment and biological samples. The probes 1a-b were obtained by introducing the 2,4-dinitrophenyl ether group into diethylcoumarin–salicylaldehyde based compounds. And they can form host-guest compounds with methylated β-cyclodextrin (M-β-CD), the association constants of inclusion complexes are 49.2 M −1 , 125 M −1 respectively. The fluorescence intensities of probes 1a-b at 600 nm ( 1a ) and 670 nm ( 1b ) increased significantly in thiophenols detection. Meanwhile, with the addition of M-β-CD, the hydrophobic cavity of M-β-CD significantly increased the fluorescence intensity of probes 1a-b , thus the detection limits of probes 1a-b to thiophenols were reduced from 410 nM, 365 nM to 62 nM, 33 nM respectively. Whereas, the good selectivity and short response time of probes 1a-b towards thiophenols was not affected in the presence of M-β-CD. Moreover, probes 1a-b were used for further water sample detection and HeLa cell imaging experiments due to their good response to thiophenols and the results suggested that probes 1a-b had the potential to detect the content of thiophenols in water samples and living cells.

CAS / MDL: 67-64-1
研究领域: 分析化学 · 环境科学 · 生物医学
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ACS Sensors · 2022 · IF 9.618

High-Throughput Surface-Enhanced Raman Scattering for Screening Chemical Sensor Candidates Enabled by Bipolar Electrochemistry

Sanjun Fan,Xinyu Wang,Yingling Li,Xiaofeng Chen,Haotian Chen,Zachary D. Schultz,Zheng Li

A variety of hydrothermal or electrochemical methods have been explored to prepare noble metal nanostructures as surface-enhanced Raman scattering (SERS) substrates. However, most of those metallic nanoarrays are structurally homogeneous, which makes it laborious to select the high-performance substrates for particular Raman sensing purposes. Here, a high-throughput SERS imaging strategy is demonstrated for the first time for screening chemical sensors with sub-nanomolar sensitivities. Bipolar electrochemistry was applied to generate Au or Au–Ag gradient nanoarrays with diverse chemical compositions, morphologies, and particle dimensions ranging from several nanometers to micrometers. The selected “hot-spots” on the Au–Ag alloy nanoarray exhibited a 660-fold enhancement in SERS intensity compared to those on the pure Au gradient nanoarray. The SERS screening of 4-aminothiophenol, 4-nitrothiophenol, and 4-mercaptobenzoic acid was carried out that provided a limit of detection (LOD) between 1 and 5 pM. The distinctive LODs among three thiophenolic Raman probes are ascribed to the differences in the affinity of the probe to the alloy, orientation of the metal–ligand monolayer, or plasmonic environment of the nanoarray surface. As a continuous, rapid, and cost-effective manner to fabricate transitional nanostructures and screen out SERS responsive sites, this method not only facilitates controllable synthesis of noble metal nanoarrays but has the potential to provide an alternative tool for ultrasensitive chemical sensing on a wide range of bimetallic substrates.

CAS / MDL: 64-17-5 7761-88-8
研究领域: 分析化学 · 材料科学 · 电化学 · 纳米技术 · 光谱学
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ANALYTICAL CHEMISTRY · 2012 · IF 5.856

Reaction-Based Fluorescent Probe for Selective Discrimination of Thiophenols over Aliphaticthiols and Its Application in Water Samples

Zheng Wang,De-Man Han,Wen-Ping Jia,Qi-Zhong Zhou,Wei-Ping Deng

The development of highly sensitive and selective detection techniques for the discrimination of relevant toxic benzenethiols and biologically active aliphatic thiols is of considerable importance in the fields of chemical, biological, and environmental sciences. In this article, we describe a new design of reaction-based fluorescent probe for discrimination of thiophenols over aliphaticthiols through intramolecular charge transfer pathways using N-butyl-4-amino-1,8-naphthalimide as a fluorophore, the strongly electron-withdrawing 2,4-dinitrobenzenesulfonamide group as a recognition unit, and 2,3-dihydroimidazo-[1,2-a] pyridine moiety as a linker. This rational design not only affords finely tunable spectroscopic properties by adding 2,3-dihydroimidazo-[1,2-a] pyridine moiety but also provides the chance to regulate the selectivity and sensitivity of the probe due to the formation of a new type of potentially reversible sulfonamide bond through 4-dimethylaminopyridine-like resonance. The developed probe displayed high off/on signal ratios, good selectivity, and sensitivity with a detection limit of 20 nM and a relative standard deviation of 1.7% for 11 replicate detections of 0.33 μM thiophenol and was successfully applied to the determination of thiophenols in water samples with quantitative recovery (from 94% to 97%) demonstrating its application prospect for thiophenols sensing in environmental and biological sciences.

研究领域: 化学科学 · 环境科学 · 生物科学
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CHINESE JOURNAL OF CATALYSIS · 2024 · IF 15.7

Near-unity photocatalytic dehydrocoupling of thiophenols into disulfides and hydrogen using coupled CdS Nanorods and Ni-containing polyoxometalate

Mengzhen Ren,Tianfu Liu,Yuanyuan Dong,Zheng Li,Jiaxin Yang,Zhenheng Diao,Hongjin Lv,Guo-Yu Yang

ABSTRACT Simultaneously harnessing the photogenerated electrons and holes to convert thiols into the value-added disulfides with the concomitant formation of H 2 represents a highly promising strategy for maximizing the conversion of solar energy into chemical energy. Herein, we report an effective catalytic system comprising CdS nanorods (NRs) and Ni-containing polyoxometalate (Na 6 K 4 [Ni 4 (H 2 O) 2 (PW 9 O 34 ) 2 ] (Ni 4 P 2 )) (Ni 4 P 2 /CdS), which exhibited efficient photocatalytic activities towards the near-unity dehydrocoupling of 4-methoxythiophenol (4-MTP) into disulfide and H 2 evolution. The photooxidative dehydrocoupling of 4-MTP can be finished after 4 h photocatalysis , leading to 98.39% conversion of 4-MTP with the yield of disulfide and H 2 reaching 24.45 and 25.96 μmol, respectively. The Ni 4 P 2 /CdS catalytic system also showed good photocatalytic recycling stability. Comprehensive experimental and characterization results indicated that the synergistic cooperation between CdS NRs and Ni 4 P 2 facilitated the separation and migration of the photogenerated electron-hole pairs, thereby improving the photocatalytic dehydrocoupling of 4-MTP to disulfide coupling with hydrogen production .

研究领域: 化学 · 材料科学 · 催化 · 太阳能转换
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JOURNAL OF MOLECULAR STRUCTURE · 2024 · IF 4

A naphthimide based fluorescent probe for the detection of thiophenols and its application in actual water and food

Di Zhang,Ran Duan,Xiaohua Zhou,Zhiwei Ma,Jiacheng Shi,He Chen,Jie Guo,Man Li,Tieliang Wang,Xujin Wu

Thiophenol (PhSH) and its derivatives are widely employed as common industrial raw materials, while they also pose high toxicity for animals and aquatic organisms. Herein, a novel fluorescent probe P1 was constructed, based on photo-induced electron transfer (PET) mechanism, using naphthimide as the fluorophore and 7-nitrobenzoxadiazole as the recognizing group. Probe P1 exhibited an “Off-On” fluorescence recognition response to PhSH by nucleophilic substitution reaction. The probe displayed advantageous properties for the recognition of PhSH, including a chromogenic response, high selectivity, fast response (< 90 s), and a large Stokes shift (150 nm). In addition, probe P1 exhibited a good linear response to PhSH within the range of 0–9 μM, and the limit of detection (LOD) is 21 nM. Furthermore, probe P1 has been successfully applied for the efficient and rapid PhSH detection in environmental water and actual food samples.

研究领域: 分析化学 · 环境科学 · 食品安全
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Scientific Reports · 2016 ·Vol. 6 ·期 1 ·1-5 · IF 5.228

The discovery of the hydrogen bond from p-Nitrothiophenol by Raman spectroscopy: Guideline for the thioalcohol molecule recognition tool

Ling Yun,Xie Wen Chang,Liu Guo Kun,Yan Run Wen,Wu De Yin,Tang Jing

Inter- and intra- molecular hydrogen bonding plays important role in determining molecular structure, physical and chemical properties, which may be easily ignored for molecules with a non-typical hydrogen bonding structure. We demonstrated in this paper that the hydrogen bonding is responsible for the different Raman spectra in solid and solution states of p-Nitrothiophenol (PNTP). The consistence of the theoretical calculation and experiment reveals that the intermolecular hydrogen bonding yields an octatomic ring structure (8) of PNTP in the solid state, confirmed by the characteristic S-H---O stretching vibration mode at 2550 cm −1 ; when it comes to the solution state, the breakage of hydrogen bond of S-H---O induced the S-H stretching vibration at 2590 cm −1 . Our findings may provide a simple and fast method for identifying the intermolecular hydrogen bonding.

研究领域: 化学 · 光谱学 · 分子生物学
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TALANTA · 2018 · IF 4.244

Ultrasensitive detection of thiophenol based on a water-soluble pyrenyl probe

Zhiyi Yao,Wenqi Ge,Mingwei Guo,Keren Xiao,Yadong Qiao,Zhong Cao,Hai-Chen Wu

We report a simple pyrene-based fluorescent probe , sodium 8-(2,4-dinitrophenoxy)pyrene-1,3,6-trisulfonate (HPTS-DNP), for the ultrasensitive and visual detection of thiophenol in 100% aqueous media. The sensing mechanism of this method is based on nucleophilic aromatic substitution on HPTS-DNP caused by thiophenol to afford a highly fluorescent product, 8-hydroxypyrene-1,3,6-trisulfonic acid trisodium salt (HPTS). The extremely low fluorescence background of HPTS-DNP and high quantum yield of HPTS ensure the superior sensing performance toward thiophenol, including rapid responses, off-on detection mode and excellent sensitivity. The detection limit is as low as 0.49 nmol L −1 according to the measurements with a spectrofluorimeter. This probe also features good selectivity (response ratio of thiophenol to interferents >30), precision (2.93%) and accuracy (102%). This approach could be applied for monitoring the thiophenol concentrations in environmental water samples. HPTS-DNP also showed good cell permeation capacity and low cellular cytotoxicity, indicating further application in bioimaging studies.

研究领域: 分析化学 · 环境科学 · 生物医学
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