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Hemin
CHEMICAL ENGINEERING JOURNAL · 2025 · IF 13.2

Bidirectionally regulated catalytic performance of Hemin/oCNT based aptasensor via salt-induced charge screening for smartphone-assisted colorimetric detection of ATP

Tingsong Ye,Rongwei Cui,Xin Zhou,Yingying Huang,Xin Li,Sami Ramadan,Bing Li,Lizhou Xu,Danyang Li

The existing aptamer-regulated nanozymes for colorimetric detection primarily rely on unidirectional activity modulation. The role of salt ions in regulating nanozyme activity and the underlying mechanisms remain poorly understood, limiting their broader application. Herein, we report a novel bidirectional regulation strategy using a hemin-functionalized oxidized carbon nanotubes (Hemin/oCNT) nanozyme. Contrary to convertional approaches that seek to mitigate salt interference, we here leverage the salt-induced charge screening effect that high salt suppresses the peroxidase-like activity of Hemin/oCNT, yet paradoxically promotes aptamer binding to Hemin/oCNT. The formed aptamer/Hemin/oCNT complex exhibits restored and enhanced activity in high salt, attributed to improved dispersion, facilitated substrate (3,3′,5,5′-tetramethylbenzidine, TMB) adsorption and accelerated electron transfer. This bidirectional mechanism was harnessed to develop a one-step ‘mix-and-detect’ aptasensor for adenosine triphosphate (ATP). The assay achieves a wide linear range of 0.625–50 μM with a low detection limit of 300 nM (UV–vis). Furthermore, a smartphone-assisted dual mode (RGB/CMY, Red-Green-Blue/Cyan-Magenta-Yellow) platform was established, where the R channel achieved a superior detection limit of 190 nM, and the CMY mode possessed excellent precision analysis (RSD ≤ 2 %) owing to its signal stability. This sensor showed high selectivity for ATP and successful application in spiked diluted serum. This work represents a paradigm for designing high-performance biosensors by exploiting, rather than avoiding salt effects.

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SENSORS AND ACTUATORS B-CHEMICAL · 2014 · IF 3.84

A novel electrochemical biosensor based on hemin functionalized graphene oxide sheets for simultaneous determination of ascorbic acid, dopamine and uric acid

Hao Lin Zou,Bang Lin Li,Hong Qun Luo,Nian Bing Li

Graphene oxide (GO) has been demonstrated to be functionalized by hemin without any other reducing agents and the hemin functionalized graphene oxide (H-GO) hybrid nanomaterial was obtained under the condition of sonication, which could be ascribed to the π–π stacking and cation-π interactions between GO and hemin molecules. H-GO composite, characterized by scanning electron microscopy and UV–vis absorption spectroscopy, was used for preparation of the modified electrode considering its great electrocatalytic activity, large surface area, and abundant active sites. Due to the unique structure and excellent properties, H-GO modified glassy carbon electrode (GCE) showed high electrocatalytic activities for the oxidation of ascorbic acid, dopamine, and uric acid, achieving the simultaneous determination for those three different kinds of biomolecules with detection limits of 0.3, 0.17, and 0.17   μmol   L −1 ( S / N   =   3), respectively. In addition, the proposed biosensor exhibited high selectivity and good stability, which could be applied for the electrochemical determination in practical samples with satisfying results.

研究领域: 分析化学 · 生物医学工程
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BIOSENSORS & BIOELECTRONICS · 2018 · IF 8.173

Sandwich-type electrochemical immunosensor for sensitive detection of CEA based on the enhanced effects of Ag NPs@CS spaced Hemin/rGO

Chunyan Zhang,Shuan Zhang,Yilei Jia,Yueyun Li,Ping Wang,Qing Liu,Zhen Xu,Xinjin Li,Yunhui Dong

An ultrasensitive sandwich-type electrochemical immunosensor was designed by using gold nanoparticles (Au NPs) as the substrate material and microporous carbon spheres (CS) loading silver nanoparticles (Ag NPs) spaced Hemin/reduced graphene oxide (Hemin/rGO) porous composite materials (Ag NPs@CS-Hemin/rGO) as the detection antibodies (Ab 2 ) label for detecting carcinoembryonic antigen (CEA). The Au NPs with good electrical conductivity and biocompatibility could accelerate the electron transfer on the electrode interface and enhance the load capacity of capture antibodies (Ab 1 ). Hemin is peroxidase-like substance which has excellent catalytic ability for H 2 O 2 reduction but easy to molecular aggregation and oxidative self-destruction. Reduced graphene oxide (rGO) is a good supporting material for Hemin to mitigate this disadvantage. CS loading Ag NPs (Ag NPs@CS) as the spacer inserts into Hemin/rGO sheet can overcome the irreversible stacking of rGO, and form complex porous structure which exposes more active sites of Hemin. Moreover, Ag NPs loaded on CS also has catalytic ability for H 2 O 2 reduction. Thus the Ag NPs@CS-Hemin/rGO used as the Ab 2 label has a large working surface area and high utilization rate, which heightens the catalytic ability for H 2 O 2 reduction to amplify the current signal effectually. The current signal and the logarithm of CEA concentration presented a wide linear response range of 20 fg/mL to 200 ng/mL, and the detection limit of CEA was 6.7 fg/mL. Furthermore, the designed immunosensor exhibited a good reproducibility, selectivity and stability, which confirms a broad development prospect when applying it in early clinical detection.

研究领域: 生物医学工程 · 分析化学 · 纳米技术
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Food Bioscience · 2022 · IF 5.318

Soy protein isolate (SPI)-hemin complex nanoparticles as a novel water-soluble iron-fortifier: Fabrication, formation mechanism and in vitro bioavailability

Chao Fan,Jiang-lan Yuan,Jing Guo,Xu Kang

Hemin is recognized as a superior biological iron-fortifier in the prevention and treatment of iron deficiency anemia . Nevertheless, free hemin could have low bioavailability due to its insolubility in intestinal fluid after passing through the digestive tract, so hemin as a direct fortifier is not as effective as it should be. In this study, a novel hemin-delivery system with good water-solubility was developed by fabricating soy protein isolate (SPI)-hemin complex nanoparticles through pH-driven method, and the formation mechanism and bioavailability were also investigated. Hemin could bind to SPI and form nanoparticles with a diameter ranging from 100 to 300 nm in the process of pH dropping from 12.0 to 7.0, and thereby significantly improve the water-solubility of hemin. It was proved that the nanoparticles were produced mainly through hydrophobic interaction between SPI and hemin, and driven by entropy. The results from in vitro simulated gastrointestinal digestion experiments indicated that bioavailability of hemin was also significantly improved (P < 0.05), and the value in SPI-hemin nanoparticles reached nearly 80% at the concentrations of 1.0% (w/v) SPI and 0.25% (w/v) hemin. SPI-hemin nanoparticles could be an innovation for improving the solubility and bioavailability of hemin and an easily acceptable candidate for the design of novel iron-fortified foods.

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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES · 2021 · IF 6.953

Self-assembled recombinant camel serum albumin nanoparticles-encapsulated hemin with peroxidase-like activity for colorimetric detection of hydrogen peroxide and glucose

Jiarong Zhang,Qilan Xu,Wei Pei,Ling Cai,Xinyu Yu,Huijun Jiang,Jin Chen

The construction of enzyme mimics using protein protection layers possesses advantages of high biocompatibility and superior catalytic activity, which is desirable for biomedical applications including diseases diagnosis. Here, from E. coli expression system, recombinant protein of camel serum albumin (rCSA) from Camelus bactrianus was successfully obtained to encapsulate hemin via the self-assemble method without additional toxic organic reagents. As compared with that of horseradish peroxidase, the produced rCSA-hemin nanoparticles exhibited enhanced enzyme-mimicking activity and stability under harsh experimental conditions. Additionally, the steady-state kinetic analysis of rCSA-hemin in the solution revealed its higher affinity to the substrates. Therefore, a colorimetric detection method of H 2 O 2 and glucose was constructed with a linear range of 2.5–500 μM with an LOD of 2.39 and 2.42 μM, respectively, which was also applied for the determination of glucose in the serum samples with satisfying recovery ratio ranging from 101.1% to 112.1%. The constructed camel protein-derived nanozyme system of remarkable stability holds promising potentials for the versatile biomedical uses.

CAS / MDL: 9003-99-0 54827-17-7
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MICROCHIMICA ACTA · 2020 ·Vol. 187 ·期 2 ·1-11 · IF 6.232

Hemin@carbon dot hybrid nanozymes with peroxidase mimicking properties for dual (colorimetric and fluorometric) sensing of hydrogen peroxide, glucose and xanthine

Su Li,Cai Yexi,Wang Liang,Dong Wenpei,Mao Guojiang,Li Ye,Zhao Mingsheng,Ma Yanhua,Zhang Hua

The multifunctional hemin@carbon dot hybrid nanozymes (hemin@CD) with simultaneous peroxidase-like activity and fluorescence signalling property was prepared for the first time. Based on these properties, hemin@CD was applied to develop a dual-channel fluorescent probe for H 2 O 2 and H 2 O 2 -based biocatalytic systems. By virtue of the peroxidase-like activity, hemin@CD can catalyze the oxidative coupling of 4-aminoantipyrine with phenol in the presence of H 2 O 2 to form a pink-red quinoneimine dye with a maximum absorbance at 505 nm. Under the excitation wavelength of 480 nm, the green fluorescence of hemin@CD peaks at 540 nm and is quenched by the generated quinoneimine dye due to an inner filter effect, and also by H 2 O 2 because of dynamic quenching. Thus, a colorimetric and fluorimetric dual-channel optical probe for H 2 O 2 is obtained. Due to the glucose/xanthine transformations under formation of H 2 O 2 by the relevant oxidase catalysis, the probe can be applied for detection of glucose and xanthine. The colorimetric detection limits for H 2 O 2 , glucose and xanthine are 0.11, 0.15, 0.11 μM, and the and fluorimetric detection limits are 0.15, 0.15, 0.12 μM, respectively. Schematic representation of the colorimetric and fluorimetric dual probe for H 2 O 2 , glucose and xanthine based on the multifunctional emin@carbon dot) hybrid nanozymes with simultaneous peroxidase-like activity and fluorescence signalling property.

CAS / MDL: 83-07-8 108-95-2
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ACS Applied Nano Materials · 2021 · IF 5.097

WS2/Bi/BiOBr Nanostructures for Photoelectrochemical Sensing of 5-Formyluracil-2′-deoxyuridine-5′-triphosphate through Hemin/G-Quadruplex Double Signal Amplification

Qian Wang,Huanshun Yin,Jia Ding,Yunlei Zhou,Shiyun Ai

5-Formyluracil (5fU) is considered an important epigenetic modification agent involved in gene regulation, cell differentiation, and development. 5fU exists in many cells and tissues but is highly similar to the structure of 5-formylcytosine (5fC) and is less abundant in genome. Therefore, the development of a rapid, sensitive, and highly selective method to detect 5fU is desired. In this study, a photoelectrochemical biosensor based on WS2/Bi/BiOBr nanocomposites, black TiO2 (b-TiO2), and hemin/G-quadruplex was described, which was found to be highly sensitive and selective for 5-formyluracil-2′-deoxyuridine-5′-triphosphate (5fdUTP) detection. WS2/Bi/BiOBr was first employed as a photosensitive material, and 3,4-diaminobenzoic acid (DABA) was adopted as a 5fdUTP recognition and capture reagent, where DABA was captured by polyethylene polyamine through covalent reaction to form a stable amid bond. Then, a benzimidazole bond was formed between DABA and −CHO of 5fdUTP, and 5fdUTP was selectively captured on the electrode. Using b-TiO2 as a cross-linker, a guanine-rich ssDNA sequence was further immobilized on the electrode surface by covalent reaction with the 5fdUTP phosphate group. With the assistance of K+ and hemin, the hemin/G-quadruplex structure was formed on the electrode. The hemin molecules in the structure of hemin/G-quadruplex obviously enhanced the PEC response of the biosensor for detecting 5fdUTP, with a linear range of 0.005–500 nM and a detection limit of 1.53 pM (S/N = 3). In addition, this method exhibits optimistic selectivity. The precision and accuracy of this method were evaluated by studying the content of 5fdUTP in genome DNA of crop tissues with standard addition recovery experiments.

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MOLECULES · 2021 ·Vol. 26 ·期 16 ·5016 · IF 4.412

Smartphone-Assisted Colorimetric Detection of Glutathione and Glutathione Reductase Activity in Human Serum and Mouse Liver Using Hemin/G-Quadruplex DNAzyme

Yufen Lai,Mengyan Li,Xiaofei Liao,Li Zou

Abnormal levels of reduced glutathione (GSH) and glutathione reductase (GR) are usually related to a variety of diseases, so it is of great significance to determine the GSH concentration and GR activity. We herein develop a smartphone-assisted colorimetric biosensor for the detection of GSH and GR activity in human serum and mouse liver using hemin/G-quadruplex DNAzyme. Firstly, an obvious color change from colorless to green can be observed, owing to the high peroxidase-like activity of hemin/G-quadruplex DNAzyme toward 2,2′-azino-bis(3-ethylbenzothiozoline-6-sulfonic acid) (ABTS). With the addition of GSH or GR, the H2O2-mediated oxidation of ABTS catalyzed by hemin/G-quadruplex DNAzyme is significantly inhibited, resulting in remarkable color fading. Therefore, the detection of GSH and GR activity can be achieved by observing the color transition or measuring the absorbance at 420 nm. The detection limit was estimated to be as low as 0.1 μM and 10 μU/mL for GSH and GR, respectively. More interestingly, the RGB values of the sensing system can be identified by the smartphone application (APP, color collect), which makes it an ideal format for on-site determination and point-of-care testing (POCT). In addition, the proposed method shows excellent selectivity and acceptable applicability for the determination of GSH concentration and GR activity in human serum samples and mouse liver tissues, which might hold great application potential in clinical diagnosis and drug screening.Keywords:smartphone;colorimetric assay;glutathione;glutathione reductase;hemin/G-quadruplex DNAzyme

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SEPARATION AND PURIFICATION TECHNOLOGY · 2019 · IF 5.107

Enhanced catalytic degradation of bisphenol A by hemin-MOFs supported on boron nitride via the photo-assisted heterogeneous activation of persulfate

Qian Ke,Yanpeng Shi,Yixuan Liu,Feng Chen,Hao Wang,Xi-Lin Wu,Hongjun Lin,Jianrong Chen

The wide variety applications of Bisphenol A (BPA) have resulted in the world wide concerns because of its toxicity and estrogenic activity. Thus, it is critical to explore efficient method for the degradation of BPA. In this study, biomimetic metal-organic-frameworks (MOFs), composed of hemin as the organic linkage and copper ions as the nodes, supported on two-dimensional boron nitride (BN) have been fabricated via facile one-pot hydrothermal approach. The multifunctional Cu-hemin-MOFs/BN composites were applied to activate persulfate (PS) for the degradation of bisphenol A (BPA). Results showed that over 99% of BPA (40 mg/L) was degraded in 30 min under visible-light irradiation with a fast degradation kinetic (0.10 min −1 ). As compared with the traditional homogeneous catalysts, these Cu-hemin-MOFs based heterogeneous catalysts hold the advantages of high efficiency, easily separation, recycle and reuse without introducing secondary pollution. The BN not only acted as stabilizer to support the hemin-MOFs but also worked as adsorbents for the pre-concentration of the pollutants. Meanwhile, Cu-hemin-MOFs with dual active sites of the Fe and Cu were responsible for the PS activation, leading to the efficient degradation of BPA. Electron spin resonance (ESR) and radicals quenching experiments revealed the SO 4 – and OH were the main active radicals for the BPA oxidation. These findings indicated the synergistically combination of the hemin-MOFs with the 2D BN nanoplates endowed the composites with multifunctional properties, leading to the excellent catalytic activity for the oxidation of pollutants. This study provides new insights into the design and fabrication of novel MOF-based heterogeneous catalysts for the application in environmental remediation.

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MICROCHIMICA ACTA · 2018 ·Vol. 185 ·期 5 ·1-9 · IF 5.705

Exonuclease-assisted multicolor aptasensor for visual detection of ochratoxin A based on G-quadruplex-hemin DNAzyme-mediated etching of gold nanorod

Yu Xinhui,Lin Yaohui,Wang Xusheng,Xu Liangjun,Wang Zongwen,Fu FengFu

An exonuclease-assisted multicolor aptasensor was developed for the visual detection of ochratoxin A (OTA). It is based on the etching of gold nanorods (AuNRs) mediated by a G-quadruplex-hemin DNAzyme. A DNA sequence (AG4-OTA) was designed that comprises a hemin aptamer and an OTA aptamer. OTA binds to AG4-OTA to form an antiparallel G-quadruplex, which halts its digestion by exonuclease I (Exo I) from the 3′-end of AG4-OTA. Thus, the retained hemin aptamer can bind to hemin to form a G-quadruplex-hemin DNAzyme. This DNAzyme has peroxidase-like activity that catalyzes the oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB) by H 2 O 2 to produce its diimine derivative (TMB 2+ ) in acidic solution. TMB 2+ can etch the AuNRs by oxidizing Au(0) into Au(I). This results in the generation of rainbow-like colors and provides a multicolor platform for the visual detection of OTA. The assay is based on the use of a single isolated aptamer and possesses obvious advantages such as multi-color visual inspection, relatively high sensitivity and accuracy. It can be used to detect as little as 30 nM concentrations of OTA by visual observation and even 10 nM concentrations by spectrophotometry. The method was successfully applied to the determination of OTA in spiked beer where it gave recoveries of 101–108%, with a relative standard deviation (RSD, n  = 5) of <5%. Schematic of an exonuclease-assisted multicolor bioassay based on the G-quadruplex-hemin DNAzyme-mediated etching of gold nanorods (AuNRs). It enables visual detection of ochratoxin A (OTA) with a detection limit of 30 nM.

CAS / MDL: 13453-07-1
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BIOSENSORS & BIOELECTRONICS · 2014 · IF 6.451

Binding-induced and label-free colorimetric method for protein detection based on autonomous assembly of hemin/G-quadruplex DNAzyme amplification strategy

Hao Wu,Kai Zhang,Yaling Liu,Hongyong Wang,Jun Wu,Feifan Zhu,Pei Zou

In this work, a new binding-induced and label-free colorimetric method for protein detection has been developed on the basis of an autonomous assembly of hemin/G-quadruplex DNAzyme amplification strategy. The system consists of two proximity probes carrying two aptamer sequences as recognition elements for target, and two hairpin structures include three-fourths and one-fourth of the G-quadruplex sequences in inactive configuration as functional elements. In the presence of target protein, two proximity probes bind to the protein simultaneously, forming a stable DNA–protein complex. Then the complex triggers an autonomous cross-opening of the two functional hairpin structures, leading to the formation of numerous hemin/G-quadruplex DNAzymes. The resulting DNAzymes catalyze the oxidation of colorless 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS 2− ) to the green-colored ABTS •− with the presence of H 2 O 2 , thus providing the amplified colorimetric detection of target. Using human α-thrombin as the protein target, this binding-induced DNAzyme amplification colorimetric method affords high sensitivity with a detection limit of 1.9   pM. Furthermore, this method might be further extended to sensitive detection of other proteins by simply replacing recognition elements of proximity probes.

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SENSORS AND ACTUATORS B-CHEMICAL · 2016 · IF 4.758

Ultrasensitive and selective detection of isocarbophos pesticide based on target and random ssDNA triggered aggregation of hemin in polar organic solutions

Huayun Chen,Yuangen Wu,Wenping Yang,Shenshan Zhan,Shuyi Qiu,Pei Zhou

This paper reports a new assay platform that performed in polar organic solutions for ultrasensitive and highly selective detection of isocarbophos pesticide. The sensing system just contains hemin molecules and random ssDNAs. Free hemin molecules have a strong absorption peak at Soret band in polar organic solvents, and they can assemble into few small particles with random ssDNAs via their special π–π stacking interaction. However, the subsequent addition of isocarbophos into above sensing system can aggregate hemin molecules to form many larger particles, which result in a great decrease in absorbance value of sensing solution. UV/Vis absorption spectra and scanning probe microscope (SPM) were used to characterize hemin aggregation. Additionally, the effects of some parameters like type of solvents, hemin amount and random ssDNAs on the sensing platform were also investigated. The present assay platform has a detection limit as low as 0.2   μg/L, a dynamic range of 0.5–500   μg/L, and high selectivity over other competitive pesticides. Moreover, the assay platform also displays excellent stability and accuracy in the detection of spiked real samples, suggesting that such sensing platform will play an important role in biological and environmental detection.

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