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NEW JOURNAL OF CHEMISTRY · 2021 ·Vol. 45 ·期 20 ·9066-9072 · IF 3.591

Label-free colorimetric detection of glutathione by autocatalytic oxidation of o-phenylenediamine based on Au3+ regulation and its application

Shaoguang Li,Huilin Liu,Xiaoying Zhang,Jiasong Cai,Kunlong Huang,Bing Chen,Liying Huang,Zhen Lin,Xinhua Lin,Hong Yao

A label-free, rapid, and highly sensitive colorimetric assay for the detection of glutathione (GSH) was developed. o-Phenylenediamine (OPD) can be selectively oxidized by Au3+ in phosphate buffer to produce light yellow 2,3-diaminophenazine. After the addition of GSH, the autocatalytic redox reaction between OPD and Au3+ can be effectively inhibited, resulting in a significant decrease in chroma and absorbance intensity. Reduced absorbance intensity can be used for the quantification of GSH. In addition, this method can achieve the discriminative detection of biothiols, such as cysteine and homocysteine. Based on these findings, a simple colorimetric assay was developed for the detection of GSH in the range of 1 nM to 1 mM with a low detection limit of 0.08 nM. More importantly, this procedure is simple, and the whole assay can be accomplished quickly within 15 min. Additionally, the proposed method was successfully used for the determination of GSH in biological fluids, such as serum samples.

研究领域: 分析化学 · 生物医学
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Small · 2024 ·Vol. 20 ·期 29 ·2310563 · IF 13

Formation and Fluorescent Mechanism of Multiple Color Emissive Carbon Dots from o-Phenylenediamine

Pengfei Li,Shanshan Xue,Lu Sun,Xiaobao Ma,Wenning Liu,Li An,Yichang Liu,Dan Qu,Zaicheng Sun

Carbon dots (CDs) have received considerable attention in many application areas owing to their unique optical properties and potential applications; however, the fluorescent mechanism is an obstacle to their applications. Herein, three-color emissive CDs are prepared from single o -phenylenediamine (oPD) by regulating the ratio of ethanol and dimethylformamide (DMF). Fluorescent mechanism of these CDs is proposed as molecular state fluorescence. Reaction intermediates are identified using liquid chromatrography–mass spectroscopy (LC–MS) and 1 H nuclear magnetic resonance (NMR) spectra. 1H-Benzo[d]imidazole (BI), 2,3-diaminophenazine (DAP), and 5,14-dihydroquinoxalino[2,3-b] phenazine (DHQP) are proposed to be the fluorophores of blue, green, and red emissive CDs by comparing their optical properties. As per the LC–MS and 1 H-NMR analysis, DHQP with red emission tends to form from DAP and oPD in pure ethanol. By adding DMF, BI formation is enhanced and DHQP formation is suppressed. The prepared CDs exhibit green emission with DAP. When the DMF amount is >50%, BI formation is considerably promoted, resulting in DAP formation being suppressed. BI with blue emission then turns into the fluorophore of CDs. This result provides us an improved understanding of the fluorescent mechanism of oPD-based CDs, which guides us in designing the structure and optical properties of CDs.

CAS / MDL: 68-12-2
研究领域: 材料科学 · 光学 · 化学
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Light-Science & Applications · 2022 ·Vol. 11 ·期 1 ·1-11 · IF 20.257

Formation and fluorescent mechanism of red emissive carbon dots from o-phenylenediamine and catechol system

Li Pengfei,Xue Shanshan,Sun Lu,Zong Xupeng,An Li,Qu Dan,Wang Xiayan,Sun Zaicheng

Carbon dots (CDs) as the advancing fluorescent carbon nanomaterial have superior potential and prospective. However, the ambiguous photoluminescence (PL) mechanism and intricate structure-function relationship become the greatest hindrances in the development and applications of CDs. Herein, red emissive CDs were synthesized in high yield from o -phenylenediamine (oPD) and catechol (CAT). The PL mechanism of the CDs is considered as the molecular state fluorophores because 5,14-dihydroquinoxalino[2,3-b] phenazine (DHQP) is separated and exhibits the same PL properties and behavior as the CDs. These include the peak position and shape of the PL emission and PL excitation and the emission dependence on pH and solvent polarity. Both of them display close PL lifetime decays. Based on these, we deduce that DHQP is the fluorophore of the red emissive CDs and the PL mechanism of CDs is similar to DHQP. During the PL emission of CDs, the electron of the molecule state can transfer to CDs. The formation process of DHQP is further confirmed by the reaction intermediates (phthalazine, dimers) and oPD. These findings provide insights into the PL mechanism of this type of CDs and may guide the further development of tunable CDs for tailored properties.

研究领域: 材料科学 · 化学
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Small · 2021 ·Vol. 17 ·期 47 ·2104083 · IF 13.281

Unveiling the Actual Catalytic Sites in Nanozyme-Catalyzed Oxidation of o-Phenylenediamine

Lu Cheng,Fengxia Wu,Haibo Bao,Fenghua Li,Guobao Xu,Yongjun Zhang,Wenxin Niu

Nanozymes have offered remarkable advantages over natural enzymes and found widespread applications including biosensors, immunoassays, nanomedicines, and environmental remediation. Oxidation of o -phenylenediamine (OPD) by nanozymes has been listed as a standard protocol for determining nanozyme activities. Given the complexity of OPD oxidation processes, however, the mechanism of nanozyme-catalyzed oxidation of OPD remains elusive. In this report, mechanistic studies of nanozyme-catalyzed oxidation of OPD are performed and a distinguishably different mechanism from that of natural enzymes is found. A combination of Fourier transform infrared spectroscopy, nuclear magnetic resonance, electrospray ionization mass spectrometry, and electron microscopic studies provides compelling evidence that polymerization of OPD occurs on the surface of several different nanozymes. The unexpected polymerization causes a dense coating layer of poly( o -phenylenediamine) (POPD) on nanozymes renders the intrinsic properties of nanozymes. Therefore, this fundamental discovery raise serious concerns using OPD-based colorimetric method for determining nanozyme activities. Without examining the surface change of nanozymes after catalytic reactions, the use of OPD-based colorimetric method for determining nanozyme activities is strongly discouraged. Furthermore, POPD is discovered as a new oxidase mimic, and this new mechanism also provides a general and robust method to coat nanomaterials with POPD polymers of enzyme-mimicking properties.

研究领域: 生物化学 · 纳米生物学 · 材料科学
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Journal of Inorganic and Organometallic Polymers and Materials · 2021 ·Vol. 31 ·期 11 ·4177-4187 · IF 3.543

Preparation of the Ratio-Fluorescence Probe Based on O-phenylenediamine for Selective and Sensitive Detection of Cu2+

Yang Wenming,Wu Changchun,Wang Ningwei,Song Guangsan,Ni Xiaoni,Huang Weihong

A fluorescent probe based on the functionalized carbon quantum dots (CQDs-OPD) was successfully synthesized for selective and sensitive detection of Cu 2+ . Using O-phenylenediamine (OPD) as the carbon resource and N,N-dimethylformamide (DMF) as the solvent, the CQDs-OPD was prepared by the hydrothermal method. The fluorescence mechanism of CQDs-OPD was studied by the intercept method. Furthermore, the probe was characterized by TEM, UV–Vis, FT-IR and Zeta potentiometric analysis, the fluorescent probe exhibits a good fluorescence properties and stability. The prepared ratio-fluorescent probe shows a good linear range from 0 to 25 μmol/L with a lower LOD of 40 nmol/L. Moreover, the probe also has been successfully applied to the detection of Cu 2+ in the real samples with the recovery rate of 96.92–97.80% and the RSD of less than 2.0%.

研究领域: 分析化学 · 环境科学
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SEPARATION AND PURIFICATION TECHNOLOGY · 2024 · IF 8.1

Foam fractionation for the separation and enrichment of trace m-phenylenediamine and o-phenylenediamine in solution

Wenxuan Li,Peifeng Li,Feiqiang He,Xiaoping Zhang,Yuling Zhu,Jianhua Ding

In this study, a foam fractionation technique was developed for the separation and enrichment of the trace m-phenylenediamine (MPD) and o-phenylenediamine (OPD) in solution. Firstly, a self-designed foam fractionation device was assembled and built, followed by a comprehensive characterization on gas types, foam fractionation column parameters, and porous sieve plate material used in the apparatus. Subsequently, the most crucial parameters for the separation and enrichment, such as surfactant species, solution pH, electrolyte categories, and gas flow rate, were identified and optimized. The mechanisms of key processes during foam fractionation under the influence of these parameters were thoroughly discussed. Other influencing factors, such as surfactant concentration, foam collection time, and solution volume in the fractionation column, were optimized using response surface methodology (RSM). Under these optimal conditions, maximal enrichment ratios of 138.2 and 85.5 were achieved for MPD and OPD, respectively. Finally, foam fractionation coupled with high-performance liquid chromatography (HPLC) was employed to detect MPD and OPD in the solution. The results demonstrated limits of detection (LOD) of 1.5 × 10 −2 μg/L and 1.5 μg/L for MPD and OPD, with relative standard deviation (RSD) values of 4.1 % and 3.9 %. When testing various actual samples, the recoveries were in the range from 92.0 % or greater in all cases. The method exhibited advantages of high sensitivity, precision, and accuracy, attributed to the high enrichment efficiency of foam fractionation. In conclusion, the foam fractionation method established in this study offers simplicity in apparatus, operational convenience, environmental friendliness (minimized use of organic solvents), and high enrichment efficiency. It proves valuable for the quantitative analysis of trace amounts of MPD and OPD in solution, presenting a novel approach for the detection of trace organic compounds in solutions.

CAS / MDL: 108-45-2
研究领域: 分析化学 · 环境科学
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Scientific Reports · 2025 ·Vol. 15 ·期 1 ·1-9 · IF 3.9

Ratiometric fluorescence nanoprobe based on nitrogen-doped carbon dots for Cu2+ and Fe3+ detection

Yang Chunlei,Xu Guiju,Hou Chenghao,Zhang Hongwei

Heavy metal ions pollution in environmental waters has an increasing impact on human health. As two common metal ions, copper ions (Cu 2+ ) and ferric ions (Fe 3+ ) widely exist in nature and play a vital role in life process. Therefore, it is significant to design sensitive and simple detection approaches for Cu 2+ and Fe 3+ . In our work, the ratiometric fluorescence analysis method (denoted as N-CDs/OPD) was established for Cu 2+ and Fe 3+ detection. The N-CDs exhibited a Cu 2+ and Fe 3+ fluorescence quenching response properties. The o-phenylenediamine (OPD) may be oxidized to 2,3-diaminophenazine (DAP) by Cu 2+ and Fe 3+ . With addition of Cu 2+ or Fe 3+ , the fluorescence of N-CDs (436 nm) was quenched and a new peak at 556 nm (DAP) appeared, which realized fluorescent ratiometric detection of Cu 2+ and Fe 3+ . The Cu 2+ concentration shows a good linear correlation versus fluorescence ratio (F 436 /F 556 ) in the range of 10 to 30 µM (R 2  = 0.9981) with detection limit (LOD) of 0.86 µM. In addition, a good linear relationship between fluorescence ratio (F 436 /F 556 ) and Fe 3+ concentration in the range of 20 to 80 µM (R 2  = 0.9880) with LOD of 7.12 µM. This nanoprobe realizes the detection of authentic samples successfully, which is expected to serve as a testing kit for analysis in water samples.

研究领域: 环境科学 · 分析化学
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MICROCHIMICA ACTA · 2019 ·Vol. 186 ·期 3 ·1-9 · IF 5.479

A novel signal amplification strategy based on the use of copper nanoclusters for ratiometric fluorimetric determination of o-phenylenediamine

Ma Yujun,Yu Ying,Lin Bixia,Zhang Li,Cao Yujuan,Guo Manli

Copper nanoclusters (CuNCs) were synthesized starting from glutathione and copper(II) nitrate. They show blue fluorescence peaking at 432 nm when excited at 334 nm. In the presence of o -phenylenediamine (OPD), the blue fluorescence is decreased, but a yellow fluorescence appears with a peak at 557 nm. UV-visible absorptiometry, fluorometry and fluorescence lifetime measurements were used to show that OPD is oxidized by the small fraction of copper(II) ions present in the CuNCs to form the oxidized form of o -phenylenediamine (oxOPD) which displays weak yellow fluorescence, while the blue fluorescence decreases. The ratio of fluorescences at 557 and 432 nm increases linearly in the 0.15 to 110 μg·L −1 OPD concentration range, and the detection limit is 93 ng·L −1 . Compared to the method based on the use of dissolved Cu(II), the employment of CuNCs reduces the detection limit by a factor of 40. The method was applied to the determination of OPD in spiked environmental water and industrial wastewater samples. Recoveries ranged from 96.8 to 100.3%. Schematic presentation of a ratiometric fluorometric method for detection of o-phenylenediamine (OPD) based on copper nanoclusters (CuNCs). OPD is oxidized by Cu 2+ present in CuNCs to form the oxidized form of o -phenylenediamine (oxOPD). FRET occurred between oxOPD and CuNCs, and the F 557 /F 432 value is amplified.

研究领域: 分析化学 · 环境科学 · 生物医学
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RSC Advances · 2021 ·Vol. 11 ·期 55 ·34525-34532 · IF 3.361

Ratiometric fluorescence assay based on carbon dots and Cu2+-catalyzed oxidation of O-phenylenediamine for the effective detection of deferasirox

Chen-Fang Miao,Xian-Zhong Guo,Xin-Tian Zhang,Yin-Ning Lin,Wen-Di Han,Zheng-Jun Huang,Shao-Huang Weng

The monitoring of deferasirox (DEF) has important clinical roles in patients who need iron excretion. However, analytical methods with practicability and simplicity are limited. Moreover, ratiometric fluorescence strategies based on Förster resonance energy transfer (FRET) from carbon dots (CDs) as a donor are rarely reported as a drug monitor. In this work, CDs with an appropriate emitting wavelength at 480 nm and excitation around 370 nm were prepared by hydrothermal approach and HCl post-treatment. O-Phenylenediamine (OPD) can be oxidized by Cu2+ to produce yellow fluorescent 2,3-diaminophenazine (oxOPD) in the system of Cu2+ and OPD (Cu–OPD). Correspondingly, a remarkable FRET from CDs to oxOPD in the system of CDs, Cu2+ and OPD (CDs–Cu–OPD) was fabricated with the quenching illustration of CDs, but emitting property of oxOPD. Attributed to the chelation ability of DEF on Cu2+, the inhibitory effects of DEF on the Cu2+-triggered oxidative capability reduced the FRET system by the decreased oxOPD. Thus, the recovered CDs at F480 and decreased oxOPD at F560 were found through a ratiometric mode by the addition of DEF in CDs–Cu–OPD for the DEF assay. The FRET behavior of CDs and oxOPD in CDs–Cu–OPD was proved clearly through the calculation of the association constant, binding constant, number of binding sites, and the distance between the donor and acceptor. Furthermore, this ratiometric method exhibited promising analytical performance for DEF with the application in real samples. The implementation of this work expands the application field of CDs and OPD oxidation in drug monitoring, and even other biological analyses through ratiometric strategy.

研究领域: 分析化学 · 药物分析 · 生物医学
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NEW JOURNAL OF CHEMISTRY · 2019 ·Vol. 43 ·期 9 ·3707-3712 · IF 3.069

A convenient fluorescent assay for quinolones based on their inhibition towards the oxidase-like activity of Cu2+

Shuyun Zhu,Han Cao,Xiaolu Yan,Jing Sun,Jiayi Qiu,Xiaoqing Qu,Ya-Nan Zuo,Xiao Wang,Xian-En Zhao

In this work, we proposed a convenient fluorescent assay for the detection of quinolones based on their inhibition towards the oxidation of o-phenylenediamine (OPD) by copper ions (Cu2+). Free Cu2+ can oxidize OPD into fluorescent 2,3-diaminophenzine followed by the formation of copper nanoparticles (CuNPs), which would further catalyze the oxidation of OPD. When quinolones were added, their strong binding affinity to Cu2+ inhibited the oxidase-like activity of Cu2+. So, the fluorescence intensity of the Cu2+–OPD system decreased obviously. The determination of quinolones can be achieved by using this fluorimetric assay without the use of complicated instruments and protocols. As demonstrated, this assay offered a highly sensitive readout for quinolones including nalidixic acid, cinoxacin, ciprofloxacin, and moxifloxacin in the linear ranges of 1.0–100 nM, 0.5–100 nM, 1.0–100 nM, and 0.1–100 nM, respectively. In addition, the developed assay was successfully applied to the direct analysis of quinolones in real amples.

CAS / MDL: 95-54-5
研究领域: 分析化学 · 药物分析 · 生物化学
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TALANTA · 2020 · IF 5.339

o-Phenylenediamine/gold nanocluster-based nanoplatform for ratiometric fluorescence detection of alkaline phosphatase activity

Xue Han,Zhen Meng,Lian Xia,Fengli Qu,Rong-Mei Kong

This study demonstrates a novel and convenient ratiometric fluorescent method for the detection of alkaline phosphatase (ALP) activity. Amino-functionalized mesoporous silica nanoparticle-gold nanoclusters (MSN-AuNCs) nanocomposites were integrated with o-phenylenediamine (OPD) to form a ratiometric fluorescence nanoplatform. The presence of ALP induced the generation of quinoxaline (QX) derivative which called 3-(dihydroxyethyl)furo[3,4-b]quinoxaline-1-one (DFQ) with strong fluorescence emission at 450 nm, while the orange-red fluorescence of MSN-AuNCs at 580 nm was slightly quenched. Meanwhile, an obvious fluorescence color change from orange-red to purple and finally to blue can be observed by naked eyes with the increasing of ALP concentration. Therefore, employing the fluorescence emission of DFQ at 450 nm as the reporter signal and the fluorescence emission of MSN-AuNCs at 580 nm as a reference signal, a sensitive ratiometric detection method for ALP was developed. Quantitative detection of ALP activity in the linear range from 0.2 to 80 U/L with a detection limit of 0.1 U/L can be realized in this way, which endows the assay with high sensitivity enough for practical detection of ALP in human serum samples.

研究领域: 生物化学 · 纳米医学 · 分析化学
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SPECTROSCOPY LETTERS · 2019 · IF 1.081

Analysis of the binding mechanism between o-phenylenediamine and bovine hemoglobin by molecular spectroscopy and molecular modeling methods

Jian-Li Liu,Yu-Chi Kong,Jing-Yi Miao,Yong-Lin He,Ruo-Chen Bi,Yin He,Xiang-Yu Cao

This study was aimed to reveal the binding mechanism between bovine hemoglobin and o-phenylenediamine by using molecular spectroscopy techniques and molecular modeling methods. The experimental results revealed that the fluorescence quenching mechanism was a combined dynamic and static quenching. The binding constant was (1.17 ± 0.02)×104 L/mol, and only a single binding site exists. The binding distance was 2.46 nm. The binding process was a spontaneous reaction, dominated by hydrophobic forces. The molecular docking simulations have also confirmed the results of the spectroscopic methods. The results reported here may significantly help understanding the interaction mechanism of o-phenylenediamine and hemoglobin.

CAS / MDL: 95-54-5
研究领域: 生物化学 · 分子生物学
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