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Enhanced photocurrent generation of a bio-photocathode based on photosystem I integrated in solvated redox polymers films nanostructured by SWCNTs
IF 4.8 2区 化学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-03-28 DOI: 10.1016/j.bioelechem.2025.108979
Yanling Yu , Xiaodong Su , Tong Xing , Xuelin Zhao , Zhou Zhang , Wanqing Zhang , Xinping Wang , Weining Zhao , Mei Li , Fangyuan Zhao
The most energetic light-induced charge-separation step in nature is driven by photosystem I (PSI), making this photosynthetic protein an attractive candidate for the development of semi-artificial energy conversion devices. Despite significant progress in semiconductor-free bio-photocathodes, the highest photocurrent density was only 322 ± 19 μA cm−2, achieved by integrating PSI within a pH-dependent poly(vinyl)imidazole Os(bispyridine)2Cl redox polymer (T Kothe et al., Chem. Eur. J., 2014, 20, 11029). This study presents a more efficient PSI-based bio-photocathode by incorporating single-walled carbon nanotubes (SWCNTs) into the redox hydrogel composed of the same Osmium-containing redox polymer. The nanostructured redox hydrogel film with SWCNTs serving as electric scaffolds significantly improves the stability, loading amount, and heterogeneous electron transfer rate, resulting in a substantial increase in photocurrent density exceeding 2 mA cm−2, the highest achieved in a semiconductor-free PSI based photocathode to date. Bioelectrodes constructed by pre-depositing SWCNTs on the electrode surface via covalent bonds outperform those formed by co-immobilizing SWCNTs with the redox hydrogel. The dependence of photocurrent on light intensity and the photocurrent spectrum action demonstrate that the photocurrent unequivocally arises from PSI charge separation. This research lays a promising foundation for the development of semi-artificial photoelectrochemical devices for light-to-energy conversion.
{"title":"Enhanced photocurrent generation of a bio-photocathode based on photosystem I integrated in solvated redox polymers films nanostructured by SWCNTs","authors":"Yanling Yu ,&nbsp;Xiaodong Su ,&nbsp;Tong Xing ,&nbsp;Xuelin Zhao ,&nbsp;Zhou Zhang ,&nbsp;Wanqing Zhang ,&nbsp;Xinping Wang ,&nbsp;Weining Zhao ,&nbsp;Mei Li ,&nbsp;Fangyuan Zhao","doi":"10.1016/j.bioelechem.2025.108979","DOIUrl":"10.1016/j.bioelechem.2025.108979","url":null,"abstract":"<div><div>The most energetic light-induced charge-separation step in nature is driven by photosystem I (PSI), making this photosynthetic protein an attractive candidate for the development of semi-artificial energy conversion devices. Despite significant progress in semiconductor-free bio-photocathodes, the highest photocurrent density was only 322 ± 19 μA cm<sup>−2</sup>, achieved by integrating PSI within a pH-dependent poly(vinyl)imidazole Os(bispyridine)<sub>2</sub>Cl redox polymer (T Kothe et al., <em>Chem. Eur. J.</em>, 2014, 20, 11029). This study presents a more efficient PSI-based bio-photocathode by incorporating single-walled carbon nanotubes (SWCNTs) into the redox hydrogel composed of the same Osmium-containing redox polymer. The nanostructured redox hydrogel film with SWCNTs serving as electric scaffolds significantly improves the stability, loading amount, and heterogeneous electron transfer rate, resulting in a substantial increase in photocurrent density exceeding 2 mA cm<sup>−2</sup>, the highest achieved in a semiconductor-free PSI based photocathode to date. Bioelectrodes constructed by pre-depositing SWCNTs on the electrode surface via covalent bonds outperform those formed by co-immobilizing SWCNTs with the redox hydrogel. The dependence of photocurrent on light intensity and the photocurrent spectrum action demonstrate that the photocurrent unequivocally arises from PSI charge separation. This research lays a promising foundation for the development of semi-artificial photoelectrochemical devices for light-to-energy conversion.</div></div>","PeriodicalId":252,"journal":{"name":"Bioelectrochemistry","volume":"165 ","pages":"Article 108979"},"PeriodicalIF":4.8,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143739244","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Investigation of acetate uptake kinetics of mature Geobacter sulfurreducens biofilms in continuous bioelectrochemical systems reveals unexpected challenges 对连续生物电化学系统中成熟的硫发生地杆菌生物膜吸收醋酸盐动力学的研究揭示了意想不到的挑战
IF 4.8 2区 化学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-03-28 DOI: 10.1016/j.bioelechem.2025.108978
Yvonne Schößow , Mareike Meyer , Oskar Zorc , Philip Haus , Benjamin Korth
Mature Geobacter sulfurreducens biofilms cultivated at two distinct anode potentials, representing unlimited and limited electron acceptor availability, were subjected to different acetate concentrations in a continuous reactor system. The Nernst-Michaelis-Menten equation, being modified to consider the conditions of a continuous stirred-tank reactor, was applied to analyze the acetate uptake kinetics. For the first time, the kinetics of pure G. sulfurreducens biofilms based on quantification of the acetate consumption were determined. Acetate uptake parameters (KM,Ac = 1.41 ± 0.42 mM, vmax,Ac = 1.10 ± 0.12 mmolAc h−1 gDW−1, n = 4) obtained from cultivation at 0.4 V (vs. SHE), showed significant differences compared to an approach that derived acetate uptake parameters from the current production. This deviation is likely related to the coulombic efficiency, which exhibited a dependence on the acetate concentration. The coulombic efficiency was 30–50 % for acetate concentrations <1 mM, and saturated at 78.6 ± 4.0 % for more than 2 mM acetate. Despite the Nernst-Michaelis-Menten equation being developed to cover limiting terminal electron acceptor conditions, its application to biofilms cultivated at −0.1 V yielded contradictory results indicating application limits. Considering the complexity and plasticity of acetate uptake kinetics together with the complex extracellular electron transfer machinery, Geobacter sulfurreducens biofilms are a model system that is shown to provide unexpected challenges and demanding highly controlled experimental conditions.
{"title":"Investigation of acetate uptake kinetics of mature Geobacter sulfurreducens biofilms in continuous bioelectrochemical systems reveals unexpected challenges","authors":"Yvonne Schößow ,&nbsp;Mareike Meyer ,&nbsp;Oskar Zorc ,&nbsp;Philip Haus ,&nbsp;Benjamin Korth","doi":"10.1016/j.bioelechem.2025.108978","DOIUrl":"10.1016/j.bioelechem.2025.108978","url":null,"abstract":"<div><div>Mature <em>Geobacter sulfurreducens</em> biofilms cultivated at two distinct anode potentials, representing unlimited and limited electron acceptor availability, were subjected to different acetate concentrations in a continuous reactor system. The Nernst-Michaelis-Menten equation, being modified to consider the conditions of a continuous stirred-tank reactor, was applied to analyze the acetate uptake kinetics. For the first time, the kinetics of pure <em>G. sulfurreducens</em> biofilms based on quantification of the acetate consumption were determined. Acetate uptake parameters (<span><math><msub><mi>K</mi><mrow><mi>M</mi><mo>,</mo><mi>Ac</mi></mrow></msub></math></span> = 1.41 ± 0.42 mM, <span><math><msub><mi>v</mi><mrow><mtext>max</mtext><mo>,</mo><mi>Ac</mi></mrow></msub></math></span> = 1.10 ± 0.12 mmolAc<sup>−</sup> h<sup>−1</sup> g<sub>DW</sub><sup>−1</sup>, <em>n</em> = 4) obtained from cultivation at 0.4 V (vs. SHE), showed significant differences compared to an approach that derived acetate uptake parameters from the current production. This deviation is likely related to the coulombic efficiency, which exhibited a dependence on the acetate concentration. The coulombic efficiency was 30–50 % for acetate concentrations &lt;1 mM, and saturated at 78.6 ± 4.0 % for more than 2 mM acetate. Despite the Nernst-Michaelis-Menten equation being developed to cover limiting terminal electron acceptor conditions, its application to biofilms cultivated at −0.1 V yielded contradictory results indicating application limits. Considering the complexity and plasticity of acetate uptake kinetics together with the complex extracellular electron transfer machinery, <em>Geobacter sulfurreducens</em> biofilms are a model system that is shown to provide unexpected challenges and demanding highly controlled experimental conditions.</div></div>","PeriodicalId":252,"journal":{"name":"Bioelectrochemistry","volume":"165 ","pages":"Article 108978"},"PeriodicalIF":4.8,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143817819","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
A novel conductometric biosensor based on hybrid organic/inorganic recognition element for determination of L-arginine
IF 4.8 2区 化学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-03-27 DOI: 10.1016/j.bioelechem.2025.108977
Svitlana Marchenko , Olga Saiapina , Yevheniia Nesterenko , Nadiia Shuvalova , Yaroslav Korpan , Nicole Jaffrezic-Renault , Sergei Dzyadevych
A highly accurate conductometric biosensor for determination of L-arginine (L-arg) in the real samples with the complex sample matrices was developed by co-immobilization of arginase, urease and the ammonium-sensitive zeolite clinoptilolite (Clt). The biosensors with different mutual arrangements of the enzyme component and zeolite on the sensitive surface of the gold interdigitated electrodes were studied and compared. The studies showed that the biosensor containing the primary layer of Clt deposited on the electrode surface followed by arginase and urease co-immobilized as the secondary layer has the most advantageous analytical characteristics compared to the biosensors based on other configurations of the bioselective membrane. In particular, for this biosensor they were as follows: sensitivity 9.61 ± 0.01 μS/mM, limit of detection 5 μM, linear range 0–280 μM and dynamic range 0–15 mM. The biosensor demonstrated high operational stability and storage stability. The effect of solution parameters (pH, ionic strength and buffer capacity) on the biosensor sensitivity was studied. Finally, we used the developed biosensor for quantification of L-arg in the food samples. The results of the biosensor analysis were compared with the control method (ion chromatography). The data of the biosensor method demonstrated high correlation with the reference data (R = 0.96).
{"title":"A novel conductometric biosensor based on hybrid organic/inorganic recognition element for determination of L-arginine","authors":"Svitlana Marchenko ,&nbsp;Olga Saiapina ,&nbsp;Yevheniia Nesterenko ,&nbsp;Nadiia Shuvalova ,&nbsp;Yaroslav Korpan ,&nbsp;Nicole Jaffrezic-Renault ,&nbsp;Sergei Dzyadevych","doi":"10.1016/j.bioelechem.2025.108977","DOIUrl":"10.1016/j.bioelechem.2025.108977","url":null,"abstract":"<div><div>A highly accurate conductometric biosensor for determination of L-arginine (L-arg) in the real samples with the complex sample matrices was developed by co-immobilization of arginase, urease and the ammonium-sensitive zeolite clinoptilolite (Clt). The biosensors with different mutual arrangements of the enzyme component and zeolite on the sensitive surface of the gold interdigitated electrodes were studied and compared. The studies showed that the biosensor containing the primary layer of Clt deposited on the electrode surface followed by arginase and urease co-immobilized as the secondary layer has the most advantageous analytical characteristics compared to the biosensors based on other configurations of the bioselective membrane. In particular, for this biosensor they were as follows: sensitivity 9.61 ± 0.01 μS/mM, limit of detection 5 μM, linear range 0–280 μM and dynamic range 0–15 mM. The biosensor demonstrated high operational stability and storage stability. The effect of solution parameters (pH, ionic strength and buffer capacity) on the biosensor sensitivity was studied. Finally, we used the developed biosensor for quantification of L-arg in the food samples. The results of the biosensor analysis were compared with the control method (ion chromatography). The data of the biosensor method demonstrated high correlation with the reference data (<em>R</em> = 0.96).</div></div>","PeriodicalId":252,"journal":{"name":"Bioelectrochemistry","volume":"165 ","pages":"Article 108977"},"PeriodicalIF":4.8,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143834116","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Interfacial extracellular electron uptake is linked to nitrate respiration in the marine heterotroph, Thalassospira xiamenensis SN3
IF 4.8 2区 化学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-03-26 DOI: 10.1016/j.bioelechem.2025.108976
Joshua D. Sackett , Gabriel P. Tonucci , Annette R. Rowe
Thalassospira species are ubiquitous marine bacteria with poorly understood ecology, and some have been implicated in iron corrosion. To better elucidate the mechanisms and ecological implications of extracellular electron transfer (EET) in oxidative processes, we conducted genomic and bioelectrochemical characterization of Thalassospira xiamenensis strain SN3, an obligate heterotroph isolated from coastal marine sediment cathode-oxidizing enrichments. Physiologic and genomic analyses indicate that SN3 lacks the capacity for lithoautotrophic growth and lacks homologs to genes canonically involved in EET. Bioelectrochemical characterization of SN3 cells shows that inward EET requires a terminal electron acceptor (respiration). Deletion of nitrate reductase catalytic subunit napA abolished current consumption and catalytic activity under nitrate-reducing conditions. Media exchange experiments demonstrate that inward EET in SN3 is facilitated by direct contact with the electrode, with a formal midpoint potential of −153 ± 16 mV vs. SHE. Through deletion of the formate dehydrogenase fdhABCD and electrochemical characterization of mutant cells, we show that inward EET is not a function of Fdh enzyme sorption to the electrode, as has been demonstrated for other organisms. This provides further evidence of a cell-mediated and contact-dependent EET mechanism. This work provides a foundation for investigating this metabolically versatile organism's yet uncharacterized mechanism of EET.
{"title":"Interfacial extracellular electron uptake is linked to nitrate respiration in the marine heterotroph, Thalassospira xiamenensis SN3","authors":"Joshua D. Sackett ,&nbsp;Gabriel P. Tonucci ,&nbsp;Annette R. Rowe","doi":"10.1016/j.bioelechem.2025.108976","DOIUrl":"10.1016/j.bioelechem.2025.108976","url":null,"abstract":"<div><div><em>Thalassospira</em> species are ubiquitous marine bacteria with poorly understood ecology, and some have been implicated in iron corrosion. To better elucidate the mechanisms and ecological implications of extracellular electron transfer (EET) in oxidative processes, we conducted genomic and bioelectrochemical characterization of <em>Thalassospira xiamenensis</em> strain SN3, an obligate heterotroph isolated from coastal marine sediment cathode-oxidizing enrichments. Physiologic and genomic analyses indicate that SN3 lacks the capacity for lithoautotrophic growth and lacks homologs to genes canonically involved in EET. Bioelectrochemical characterization of SN3 cells shows that inward EET requires a terminal electron acceptor (respiration). Deletion of nitrate reductase catalytic subunit <em>napA</em> abolished current consumption and catalytic activity under nitrate-reducing conditions. Media exchange experiments demonstrate that inward EET in SN3 is facilitated by direct contact with the electrode, with a formal midpoint potential of −153 ± 16 mV vs. SHE. Through deletion of the formate dehydrogenase <em>fdhABCD</em> and electrochemical characterization of mutant cells, we show that inward EET is not a function of Fdh enzyme sorption to the electrode, as has been demonstrated for other organisms. This provides further evidence of a cell-mediated and contact-dependent EET mechanism. This work provides a foundation for investigating this metabolically versatile organism's yet uncharacterized mechanism of EET.</div></div>","PeriodicalId":252,"journal":{"name":"Bioelectrochemistry","volume":"165 ","pages":"Article 108976"},"PeriodicalIF":4.8,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143748551","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Hybridization chain reaction and CRISPR/Cas12a-integrated biosensor for precise Ago2 detection
IF 4.8 2区 化学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-03-26 DOI: 10.1016/j.bioelechem.2025.108975
Qiang Tang , Jiayi Zhang , Jialuo Pang , Yingying Huang , Ying Guan , Yuanxun Gong , Qianli Tang , Kai Zhang , Xianjiu Liao
This study introduces an innovative electrochemiluminescence (ECL) biosensor for the highly sensitive and specific detection of Argonaute 2 (Ago2) activity. Ago2, a key enzyme in the RNA interference (RNAi) pathway, plays a crucial role in gene regulation, and its dysregulation is associated with diseases such as cancer and viral infections. The biosensor integrates hybridization chain reaction (HCR) amplification and the CRISPR/Cas12a system, leveraging a multi-stage signal amplification strategy. The detection mechanism begins with Ago2-mediated cleavage of a designed hairpin RNA (HP-RNA), releasing single-stranded RNA (ssRNA) that triggers HCR. This amplification step generates long DNA polymers, which serve as activators for the CRISPR/Cas12a system. Cas12a's collateral cleavage activity amplifies the signal further by cleaving a DNA reporter labeled with a ruthenium-based luminophore, enhancing the ECL output. This dual amplification strategy achieves exceptional sensitivity, with a detection limit of 0.126 aM. The biosensor demonstrates excellent specificity, distinguishing Ago2 from other Argonaute proteins, and maintains high reproducibility and stability, retaining 94 % of its signal after two weeks of storage. Real-world applicability was confirmed by accurately detecting Ago2 in spiked cell lysates, with recovery rates exceeding 100 %. The combination of HCR, CRISPR/Cas12a, and ECL establishes a robust platform for biomarker detection, offering superior sensitivity and adaptability for clinical diagnostics, disease monitoring, and therapeutic evaluation. This biosensor represents a significant advancement in the development of next-generation diagnostic tools.
{"title":"Hybridization chain reaction and CRISPR/Cas12a-integrated biosensor for precise Ago2 detection","authors":"Qiang Tang ,&nbsp;Jiayi Zhang ,&nbsp;Jialuo Pang ,&nbsp;Yingying Huang ,&nbsp;Ying Guan ,&nbsp;Yuanxun Gong ,&nbsp;Qianli Tang ,&nbsp;Kai Zhang ,&nbsp;Xianjiu Liao","doi":"10.1016/j.bioelechem.2025.108975","DOIUrl":"10.1016/j.bioelechem.2025.108975","url":null,"abstract":"<div><div>This study introduces an innovative electrochemiluminescence (ECL) biosensor for the highly sensitive and specific detection of Argonaute 2 (Ago2) activity. Ago2, a key enzyme in the RNA interference (RNAi) pathway, plays a crucial role in gene regulation, and its dysregulation is associated with diseases such as cancer and viral infections. The biosensor integrates hybridization chain reaction (HCR) amplification and the CRISPR/Cas12a system, leveraging a multi-stage signal amplification strategy. The detection mechanism begins with Ago2-mediated cleavage of a designed hairpin RNA (HP-RNA), releasing single-stranded RNA (ssRNA) that triggers HCR. This amplification step generates long DNA polymers, which serve as activators for the CRISPR/Cas12a system. Cas12a's collateral cleavage activity amplifies the signal further by cleaving a DNA reporter labeled with a ruthenium-based luminophore, enhancing the ECL output. This dual amplification strategy achieves exceptional sensitivity, with a detection limit of 0.126 aM. The biosensor demonstrates excellent specificity, distinguishing Ago2 from other Argonaute proteins, and maintains high reproducibility and stability, retaining 94 % of its signal after two weeks of storage. Real-world applicability was confirmed by accurately detecting Ago2 in spiked cell lysates, with recovery rates exceeding 100 %. The combination of HCR, CRISPR/Cas12a, and ECL establishes a robust platform for biomarker detection, offering superior sensitivity and adaptability for clinical diagnostics, disease monitoring, and therapeutic evaluation. This biosensor represents a significant advancement in the development of next-generation diagnostic tools.</div></div>","PeriodicalId":252,"journal":{"name":"Bioelectrochemistry","volume":"165 ","pages":"Article 108975"},"PeriodicalIF":4.8,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143725330","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
A high-sensitivity label-free electrochemical aptasensor for point-of-care measurements of low-density lipoprotein in plasma based on aptamer and MXene-CMCS-Hemin nanocomposites
IF 4.8 2区 化学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-03-20 DOI: 10.1016/j.bioelechem.2025.108972
Jintao Liang , Shuaikang Dong , Xiaohong Tan , Junyan Gong , Xuyang Chen , Zhide Zhou , Guiyin Li
Cardiovascular disease (CVD) remains a significant worldwide health challenge, with mortality rates rising rapidly. Low-density lipoprotein (LDL) is a crucial serum biomarker for the early diagnosis of CVD, which can significantly improve outcomes and reduce mortality. Herein, a label-free electrochemical aptasensor for rapid detection of LDL was developed based on the titanium carbide–carboxymethyl chitosan–hemin (MXene-CMCS-Hemin) nanocomposites as the electrochemical signal probe. Firstly, gold nanoparticles (Au NPs) were electrodeposited onto a screen-printed carbon electrode (SPCE) to form a conductive substrate. Subsequently, the MXene-CMCS-Hemin nanocomposites were anchored onto the Au NPs/SPCE surface. Then LDLApt was immobilized on the surface of MXene-CMCS-Hemin/Au NPs/SPCE to construct the electrochemical aptasensor. When LDL specifically bound with the LDLApt to form LDL-LDLApt complexes, hindering the electron transfer and reducing the Hemin oxidation current, LDL detection can be achieved via differential pulse voltammetry (DPV). Under optimal circumstances, the changes of Hemin's oxidation current showed a good linear response with LDL concentration in the range of 0.1–4.0 μmol/L with a detection limit of 0.095 μmol/L (S/N = 3). The aptasensor demonstrated good performance with the relative errors of 0.60 % to 6.58 % for the direct detection of LDL in human serum samples, which offers a novel tool for the clinical diagnosis of CVD.
{"title":"A high-sensitivity label-free electrochemical aptasensor for point-of-care measurements of low-density lipoprotein in plasma based on aptamer and MXene-CMCS-Hemin nanocomposites","authors":"Jintao Liang ,&nbsp;Shuaikang Dong ,&nbsp;Xiaohong Tan ,&nbsp;Junyan Gong ,&nbsp;Xuyang Chen ,&nbsp;Zhide Zhou ,&nbsp;Guiyin Li","doi":"10.1016/j.bioelechem.2025.108972","DOIUrl":"10.1016/j.bioelechem.2025.108972","url":null,"abstract":"<div><div>Cardiovascular disease (CVD) remains a significant worldwide health challenge, with mortality rates rising rapidly. Low-density lipoprotein (LDL) is a crucial serum biomarker for the early diagnosis of CVD, which can significantly improve outcomes and reduce mortality. Herein, a label-free electrochemical aptasensor for rapid detection of LDL was developed based on the titanium carbide–carboxymethyl chitosan–hemin (MXene-CMCS-Hemin) nanocomposites as the electrochemical signal probe. Firstly, gold nanoparticles (Au NPs) were electrodeposited onto a screen-printed carbon electrode (SPCE) to form a conductive substrate. Subsequently, the MXene-CMCS-Hemin nanocomposites were anchored onto the Au NPs/SPCE surface. Then LDL<sub>Apt</sub> was immobilized on the surface of MXene-CMCS-Hemin/Au NPs/SPCE to construct the electrochemical aptasensor. When LDL specifically bound with the LDL<sub>Apt</sub> to form LDL-LDL<sub>Apt</sub> complexes, hindering the electron transfer and reducing the Hemin oxidation current, LDL detection can be achieved via differential pulse voltammetry (DPV). Under optimal circumstances, the changes of Hemin's oxidation current showed a good linear response with LDL concentration in the range of 0.1–4.0 μmol/L with a detection limit of 0.095 μmol/L (S/N = 3). The aptasensor demonstrated good performance with the relative errors of 0.60 % to 6.58 % for the direct detection of LDL in human serum samples, which offers a novel tool for the clinical diagnosis of CVD.</div></div>","PeriodicalId":252,"journal":{"name":"Bioelectrochemistry","volume":"165 ","pages":"Article 108972"},"PeriodicalIF":4.8,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143696806","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
The unusual formaldehyde-induced activation of [NiFe]-hydrogenase: Implications from protein film electrochemistry and infrared spectroscopy
IF 4.8 2区 化学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-03-19 DOI: 10.1016/j.bioelechem.2025.108974
Lei Wan , Yanxin Gao , Serena DeBeer , Olaf Rüdiger
Here we investigate how formaldehyde (HCHO), a known strong inhibitor of [FeFe]‑hydrogenases and a mild inhibitor of [NiFe]‑hydrogenases, may exert more complex effects on this group of metalloenzymes, which reversibly catalyze the 2H+/H₂ reaction. We investigated the [NiFe]‑hydrogenase Hyd-2 from E. coli using protein film electrochemistry, a technique that enables the measurement of enzyme activity when the enzyme is adequately adsorbed on the electrode. The effect of HCHO on the electrocatalytic performance of Hyd-2 is highly dependent on the buffer pH and the direction of catalysis. During H₂ production, HCHO consistently acts as an inhibitor of Hyd-2. However, this effect is reversed in acidic pH values, where HCHO can mildly enhance the electrocatalytic H₂ oxidation by Hyd-2. FTIR investigations did not detect any new redox intermediate resulting from the inhibition or activation. Therefore, we propose that HCHO - a natural electrophile that can readily react with nucleophiles and proton acceptors - may facilitate the transfer protons during the rapid transformation of different redox species participating in the catalytic cycle of [NiFe]‑hydrogenases.
{"title":"The unusual formaldehyde-induced activation of [NiFe]-hydrogenase: Implications from protein film electrochemistry and infrared spectroscopy","authors":"Lei Wan ,&nbsp;Yanxin Gao ,&nbsp;Serena DeBeer ,&nbsp;Olaf Rüdiger","doi":"10.1016/j.bioelechem.2025.108974","DOIUrl":"10.1016/j.bioelechem.2025.108974","url":null,"abstract":"<div><div>Here we investigate how formaldehyde (HCHO), a known strong inhibitor of [FeFe]‑hydrogenases and a mild inhibitor of [NiFe]‑hydrogenases, may exert more complex effects on this group of metalloenzymes, which reversibly catalyze the 2H<sup>+</sup>/H₂ reaction. We investigated the [NiFe]‑hydrogenase Hyd-2 from <em>E. coli</em> using protein film electrochemistry, a technique that enables the measurement of enzyme activity when the enzyme is adequately adsorbed on the electrode. The effect of HCHO on the electrocatalytic performance of Hyd-2 is highly dependent on the buffer pH and the direction of catalysis. During H₂ production, HCHO consistently acts as an inhibitor of Hyd-2. However, this effect is reversed in acidic pH values, where HCHO can mildly enhance the electrocatalytic H₂ oxidation by Hyd-2. FTIR investigations did not detect any new redox intermediate resulting from the inhibition or activation. Therefore, we propose that HCHO - a natural electrophile that can readily react with nucleophiles and proton acceptors - may facilitate the transfer protons during the rapid transformation of different redox species participating in the catalytic cycle of [NiFe]‑hydrogenases.</div></div>","PeriodicalId":252,"journal":{"name":"Bioelectrochemistry","volume":"165 ","pages":"Article 108974"},"PeriodicalIF":4.8,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143704001","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Structural bioelectrochemistry of direct electron transfer-type multimeric dehydrogenases: Basic principle and rational strategies
IF 4.8 2区 化学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-03-17 DOI: 10.1016/j.bioelechem.2025.108973
Konatsu Ichikawa, Taiki Adachi, Keisei Sowa
Direct electron transfer (DET)-type bioelectrocatalysis, a coupled enzymatic and electrode reaction without redox mediators, provides insights into enzyme properties that facilitate the construction of efficient biomimetic devices. Because many DET-type multimeric dehydrogenases are membrane-bound proteins, obtaining the overall steric structures of these enzymes using conventional X-ray crystallography has proved difficult for many decades. Novel cryo-electron microscopy (cryo-EM) and single-particle image analysis have recently been developed that enable elucidation of the overall structure of membrane-bound DET-type multimeric dehydrogenases. In particular, “structural bioelectrochemistry,” a fusion of structural biology and bioelectrochemistry, has enabled rapid hypothesis testing via the analysis of three-dimensional (3D) structures using enzyme engineering and electrochemistry. This review outlines critical related studies in the last decade and the epoch-making breakthroughs leading to next-generation applications.
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引用次数: 0
Study on effect of electroporation combining high- and low-frequency harmonics
IF 4.8 2区 化学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-03-17 DOI: 10.1016/j.bioelechem.2025.108971
Borja López-Alonso , Tamara Polajžer , Matej Reberšek , Héctor Sarnago , Óscar Lucía , Damijan Miklavčič
The effects of electroporation are highly influenced by the shape of the applied waveform. This waveform shape can modify the transmitted energy and current flow patterns, impacting the electric field distribution, temperature rise among others. These interactions, along with their synergies with electroporation, are being explored across various industrial and research domains. For instance, in the biomedical field, high-frequency waveforms such as nanosecond pulses offer distinct advantages, while in the food industry, controlled temperature increases combined with electroporation are beneficial. However, in the medical field, the effects of combining high-frequency waveforms (in the MHz range) with low-frequency waveforms (in the kHz range commonly used in clinical electroporation) have not been thoroughly studied, though hypotheses have been proposed regarding their potential effects.
In this paper, proof of concept of the effect of the combination of two harmonics is presented using three different strategies to investigate new electroporation protocols. To support this study, a specialized electrical and thermal test bench was developed to control and evaluate the feasibility and potential of possible synergy between high- and low-frequency waveforms to electroporation using an in vitro model.
{"title":"Study on effect of electroporation combining high- and low-frequency harmonics","authors":"Borja López-Alonso ,&nbsp;Tamara Polajžer ,&nbsp;Matej Reberšek ,&nbsp;Héctor Sarnago ,&nbsp;Óscar Lucía ,&nbsp;Damijan Miklavčič","doi":"10.1016/j.bioelechem.2025.108971","DOIUrl":"10.1016/j.bioelechem.2025.108971","url":null,"abstract":"<div><div>The effects of electroporation are highly influenced by the shape of the applied waveform. This waveform shape can modify the transmitted energy and current flow patterns, impacting the electric field distribution, temperature rise among others. These interactions, along with their synergies with electroporation, are being explored across various industrial and research domains. For instance, in the biomedical field, high-frequency waveforms such as nanosecond pulses offer distinct advantages, while in the food industry, controlled temperature increases combined with electroporation are beneficial. However, in the medical field, the effects of combining high-frequency waveforms (in the MHz range) with low-frequency waveforms (in the kHz range commonly used in clinical electroporation) have not been thoroughly studied, though hypotheses have been proposed regarding their potential effects.</div><div>In this paper, proof of concept of the effect of the combination of two harmonics is presented using three different strategies to investigate new electroporation protocols. To support this study, a specialized electrical and thermal test bench was developed to control and evaluate the feasibility and potential of possible synergy between high- and low-frequency waveforms to electroporation using an <em>in vitro</em> model.</div></div>","PeriodicalId":252,"journal":{"name":"Bioelectrochemistry","volume":"165 ","pages":"Article 108971"},"PeriodicalIF":4.8,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143681019","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
An electrochemical biosensor using AuNPs-Ti3C2Tx and ARGET ATRP reactions as signal amplification strategies for ultra-sensitive detection of HER2 protein
IF 4.8 2区 化学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-03-15 DOI: 10.1016/j.bioelechem.2025.108970
Yanju Liu , Aozi Feng , Fengzhi Li , Liying Zhao , Qiyong Cai , Daoxiang Li , HuaixiaYang
Human epidermal growth factor receptor 2 (HER2) status is an important factor in evaluating the prognosis of breast cancer patients. Therefore, it is particularly important to develop a simple and sensitive method for the detection of HER2-positive breast cancer. Here, an ultra-sensitive electrochemical biosensor for detecting HER2-specific proteins was assembled using gold nanoparticles and Two-dimensional carbides (AuNPs-Ti3C2Tx) as a conducting substrate. The prepared AuNPs-Ti3C2Tx not only has good electrical conductivity and strong electrochemical signal output, but also provides a large number of active sites for the AuS bonds assembly aptamer. In addition, the antibodies-modified functionalized graphene oxide (GO) as a carrier platform, which provides an additional boost for the detection of trace targets with high sensitivity under optimal conditions. Afterwards,HER2 protein was detected by signal amplification effect of AuNPs-Ti3C2Tx and functionalized GO combined with Electron transfer activated regeneration catalyst atomic transfer radical polymerization (ARGET ATRP). In the range of 1 to 105 ng·mL−1, there was a good linear relationship between the HER2 concentration and the signal intensity, with a limit of detection of 0.19 pg·mL−1. Moreover, this method has good selectivity and stability, and then still maintains good detection performance and strong anti-interference ability in the complex environment of normal human serum, which is expected to be applied in clinical application.
{"title":"An electrochemical biosensor using AuNPs-Ti3C2Tx and ARGET ATRP reactions as signal amplification strategies for ultra-sensitive detection of HER2 protein","authors":"Yanju Liu ,&nbsp;Aozi Feng ,&nbsp;Fengzhi Li ,&nbsp;Liying Zhao ,&nbsp;Qiyong Cai ,&nbsp;Daoxiang Li ,&nbsp;HuaixiaYang","doi":"10.1016/j.bioelechem.2025.108970","DOIUrl":"10.1016/j.bioelechem.2025.108970","url":null,"abstract":"<div><div>Human epidermal growth factor receptor 2 (HER2) status is an important factor in evaluating the prognosis of breast cancer patients. Therefore, it is particularly important to develop a simple and sensitive method for the detection of HER2-positive breast cancer. Here, an ultra-sensitive electrochemical biosensor for detecting HER2-specific proteins was assembled using gold nanoparticles and Two-dimensional carbides (AuNPs-Ti<sub>3</sub>C<sub>2</sub>Tx) as a conducting substrate. The prepared AuNPs-Ti<sub>3</sub>C<sub>2</sub>Tx not only has good electrical conductivity and strong electrochemical signal output, but also provides a large number of active sites for the Au<img>S bonds assembly aptamer. In addition, the antibodies-modified functionalized graphene oxide (GO) as a carrier platform, which provides an additional boost for the detection of trace targets with high sensitivity under optimal conditions. Afterwards,HER2 protein was detected by signal amplification effect of AuNPs-Ti<sub>3</sub>C<sub>2</sub>Tx and functionalized GO combined with Electron transfer activated regeneration catalyst atomic transfer radical polymerization (ARGET ATRP). In the range of 1 to 10<sup>5</sup> ng·mL<sup>−1</sup>, there was a good linear relationship between the HER2 concentration and the signal intensity, with a limit of detection of 0.19 pg·mL<sup>−1</sup>. Moreover, this method has good selectivity and stability, and then still maintains good detection performance and strong anti-interference ability in the complex environment of normal human serum, which is expected to be applied in clinical application.</div></div>","PeriodicalId":252,"journal":{"name":"Bioelectrochemistry","volume":"165 ","pages":"Article 108970"},"PeriodicalIF":4.8,"publicationDate":"2025-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143681017","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
期刊
Bioelectrochemistry
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