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Cytochrome P450 electrochemical biosensors transforming in vitro metabolism testing – Opportunities and challenges
IF 4.8 2区 化学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-01-21 DOI: 10.1016/j.bioelechem.2025.108913
Carina S.P. Vieira, Marcela A. Segundo, Alberto N. Araújo
The ability of the living world to flourish in the face of constant exposure to dangerous chemicals depends on the management ability of a widespread group of enzymes known as heme-thiolate monooxygenases or cytochrome P450 superfamily. About three-quarters of all reactions determining the metabolism of endogenous compounds, of those carried in foods, of taken drugs, or even of synthetic chemicals discarded into the environment depend on their catalytic performance. The chromatographic and (photo)luminometric methods routinely used as predictive and analytical tools in laboratories have significant drawbacks ranging from limited shelf-life of reagents, use of synthetic substrates, laborious and tedious procedures for highly sensitive detection. In this review, alternative electrochemical biosensors using the cytochrome P450 enzymes as bio-element are emphasized in their main aspects as well regarding their implementation and usefulness. Despite the various schemes proposed for the implementation, reports on real applications are scant for several reasons, including low reaction rates, broad substrate specificity, uncoupling reactions occurrence, and the need for expensive electron transfer partners to promote electron transfer. Finally, the prospect for future developments is introduced, focusing on integrating miniaturized systems with electrochemical techniques, alongside optimizing enzyme immobilization methods and electrode modifications to improve enzymatic stability and enhance sensor reliability. This progress represents a crucial step towards the creation of portable biosensors that mimic human physiological responses, supporting the precision medicine approach.
{"title":"Cytochrome P450 electrochemical biosensors transforming in vitro metabolism testing – Opportunities and challenges","authors":"Carina S.P. Vieira,&nbsp;Marcela A. Segundo,&nbsp;Alberto N. Araújo","doi":"10.1016/j.bioelechem.2025.108913","DOIUrl":"10.1016/j.bioelechem.2025.108913","url":null,"abstract":"<div><div>The ability of the living world to flourish in the face of constant exposure to dangerous chemicals depends on the management ability of a widespread group of enzymes known as heme-thiolate monooxygenases or cytochrome P450 superfamily. About three-quarters of all reactions determining the metabolism of endogenous compounds, of those carried in foods, of taken drugs, or even of synthetic chemicals discarded into the environment depend on their catalytic performance. The chromatographic and (photo)luminometric methods routinely used as predictive and analytical tools in laboratories have significant drawbacks ranging from limited shelf-life of reagents, use of synthetic substrates, laborious and tedious procedures for highly sensitive detection. In this review, alternative electrochemical biosensors using the cytochrome P450 enzymes as bio-element are emphasized in their main aspects as well regarding their implementation and usefulness. Despite the various schemes proposed for the implementation, reports on real applications are scant for several reasons, including low reaction rates, broad substrate specificity, uncoupling reactions occurrence, and the need for expensive electron transfer partners to promote electron transfer. Finally, the prospect for future developments is introduced, focusing on integrating miniaturized systems with electrochemical techniques, alongside optimizing enzyme immobilization methods and electrode modifications to improve enzymatic stability and enhance sensor reliability. This progress represents a crucial step towards the creation of portable biosensors that mimic human physiological responses, supporting the precision medicine approach.</div></div>","PeriodicalId":252,"journal":{"name":"Bioelectrochemistry","volume":"163 ","pages":"Article 108913"},"PeriodicalIF":4.8,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143035348","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
Real-time prediction of heparin concentration in blood extracorporeal circulation by relaxation time distribution (RTD)
IF 4.8 2区 化学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-01-20 DOI: 10.1016/j.bioelechem.2025.108912
Soichiro Ueno , Daisuke Kawashima , Katsuhiro Matsuura , Hiromichi Obara , Ryou Tanaka , Masahiro Takei
<div><div>Heparin concentration <span><math><mrow><mi>c</mi></mrow></math></span> in a blood extracorporeal circulation has been real-timely predicted based on the relaxation strength <span><math><mrow><msub><mrow><mi>Δ</mi><mi>ε</mi></mrow><mi>m</mi></msub></mrow></math></span> at relaxation frequency <span><math><mrow><msub><mi>f</mi><mi>m</mi></msub></mrow></math></span> extracted by relaxation time distribution (RTD). The simulated extracorporeal circulation was conducted to optimize the number of <span><math><mrow><msub><mrow><mi>Δ</mi><mi>ε</mi></mrow><mi>m</mi></msub></mrow></math></span> for the prediction of <em>c</em> using the porcine whole blood (WB) and low-leukocyte and −platelet blood (LLPB) under the condition of the gradual increment of <span><math><mrow><mi>c</mi></mrow></math></span> from 0 to 8 U/mL with constant flow rate and blood temperature. The experimental results show that among the three relaxation strengths <span><math><mrow><msub><mrow><mi>Δ</mi><mi>ε</mi></mrow><mn>1</mn></msub></mrow></math></span>, <span><math><mrow><msub><mrow><mi>Δ</mi><mi>ε</mi></mrow><mn>2</mn></msub></mrow></math></span> and <span><math><mrow><msub><mrow><mi>Δ</mi><mi>ε</mi></mrow><mn>3</mn></msub></mrow></math></span> (in ascending order of frequency), <span><math><mrow><msub><mrow><mi>Δ</mi><mi>ε</mi></mrow><mn>2</mn></msub></mrow></math></span> at <span><math><mrow><msub><mi>f</mi><mn>2</mn></msub></mrow></math></span> = 5.2 ∼ 6.2 MHz and <span><math><mrow><msub><mrow><mi>Δ</mi><mi>ε</mi></mrow><mn>3</mn></msub></mrow></math></span> at <span><math><mrow><msub><mi>f</mi><mn>3</mn></msub></mrow></math></span> = 42 ∼ 50 MHz were correlated to <span><math><mrow><mi>c</mi></mrow></math></span>. The <span><math><mrow><msub><mrow><mi>Δ</mi><mi>ε</mi></mrow><mn>3</mn></msub></mrow></math></span> was decreasing with increasing <span><math><mrow><mi>c</mi></mrow></math></span> in both cases, which was influenced by the plasma macromolecular concentrations, while the <span><math><mrow><msub><mrow><mi>Δ</mi><mi>ε</mi></mrow><mn>2</mn></msub></mrow></math></span> was increased with increasing <em>c</em> in WB case but was hardly changed in LLPB case because the <span><math><mrow><msub><mrow><mi>Δ</mi><mi>ε</mi></mrow><mn>2</mn></msub></mrow></math></span> is influenced by the blood cell concentrations and the shape changes of blood cell membranes. Heparin concentration <span><math><mrow><mi>c</mi></mrow></math></span> is estimated by the linear regression formula <span><math><mrow><msup><mrow><mi>c</mi></mrow><mrow><mi>P</mi><mi>R</mi><mi>E</mi></mrow></msup><mo>=</mo><msub><mi>a</mi><mn>1</mn></msub><msub><mrow><mo>(</mo><mi>Δ</mi><mi>ε</mi></mrow><mn>2</mn></msub><mo>-</mo><msubsup><mrow><mi>Δ</mi><mi>ε</mi></mrow><mrow><mn>2</mn></mrow><mrow><mi>c</mi><mo>=</mo><mn>0</mn></mrow></msubsup><mrow><mo>)</mo><mo>+</mo></mrow><msub><mi>a</mi><mn>2</mn></msub><mrow><mo>(</mo><msub><mrow><mi>Δ</mi><mi>ε</mi></mrow><mn>3</mn></msub><mo>-</mo><msubsup><mrow><
{"title":"Real-time prediction of heparin concentration in blood extracorporeal circulation by relaxation time distribution (RTD)","authors":"Soichiro Ueno ,&nbsp;Daisuke Kawashima ,&nbsp;Katsuhiro Matsuura ,&nbsp;Hiromichi Obara ,&nbsp;Ryou Tanaka ,&nbsp;Masahiro Takei","doi":"10.1016/j.bioelechem.2025.108912","DOIUrl":"10.1016/j.bioelechem.2025.108912","url":null,"abstract":"&lt;div&gt;&lt;div&gt;Heparin concentration &lt;span&gt;&lt;math&gt;&lt;mrow&gt;&lt;mi&gt;c&lt;/mi&gt;&lt;/mrow&gt;&lt;/math&gt;&lt;/span&gt; in a blood extracorporeal circulation has been real-timely predicted based on the relaxation strength &lt;span&gt;&lt;math&gt;&lt;mrow&gt;&lt;msub&gt;&lt;mrow&gt;&lt;mi&gt;Δ&lt;/mi&gt;&lt;mi&gt;ε&lt;/mi&gt;&lt;/mrow&gt;&lt;mi&gt;m&lt;/mi&gt;&lt;/msub&gt;&lt;/mrow&gt;&lt;/math&gt;&lt;/span&gt; at relaxation frequency &lt;span&gt;&lt;math&gt;&lt;mrow&gt;&lt;msub&gt;&lt;mi&gt;f&lt;/mi&gt;&lt;mi&gt;m&lt;/mi&gt;&lt;/msub&gt;&lt;/mrow&gt;&lt;/math&gt;&lt;/span&gt; extracted by relaxation time distribution (RTD). The simulated extracorporeal circulation was conducted to optimize the number of &lt;span&gt;&lt;math&gt;&lt;mrow&gt;&lt;msub&gt;&lt;mrow&gt;&lt;mi&gt;Δ&lt;/mi&gt;&lt;mi&gt;ε&lt;/mi&gt;&lt;/mrow&gt;&lt;mi&gt;m&lt;/mi&gt;&lt;/msub&gt;&lt;/mrow&gt;&lt;/math&gt;&lt;/span&gt; for the prediction of &lt;em&gt;c&lt;/em&gt; using the porcine whole blood (WB) and low-leukocyte and −platelet blood (LLPB) under the condition of the gradual increment of &lt;span&gt;&lt;math&gt;&lt;mrow&gt;&lt;mi&gt;c&lt;/mi&gt;&lt;/mrow&gt;&lt;/math&gt;&lt;/span&gt; from 0 to 8 U/mL with constant flow rate and blood temperature. The experimental results show that among the three relaxation strengths &lt;span&gt;&lt;math&gt;&lt;mrow&gt;&lt;msub&gt;&lt;mrow&gt;&lt;mi&gt;Δ&lt;/mi&gt;&lt;mi&gt;ε&lt;/mi&gt;&lt;/mrow&gt;&lt;mn&gt;1&lt;/mn&gt;&lt;/msub&gt;&lt;/mrow&gt;&lt;/math&gt;&lt;/span&gt;, &lt;span&gt;&lt;math&gt;&lt;mrow&gt;&lt;msub&gt;&lt;mrow&gt;&lt;mi&gt;Δ&lt;/mi&gt;&lt;mi&gt;ε&lt;/mi&gt;&lt;/mrow&gt;&lt;mn&gt;2&lt;/mn&gt;&lt;/msub&gt;&lt;/mrow&gt;&lt;/math&gt;&lt;/span&gt; and &lt;span&gt;&lt;math&gt;&lt;mrow&gt;&lt;msub&gt;&lt;mrow&gt;&lt;mi&gt;Δ&lt;/mi&gt;&lt;mi&gt;ε&lt;/mi&gt;&lt;/mrow&gt;&lt;mn&gt;3&lt;/mn&gt;&lt;/msub&gt;&lt;/mrow&gt;&lt;/math&gt;&lt;/span&gt; (in ascending order of frequency), &lt;span&gt;&lt;math&gt;&lt;mrow&gt;&lt;msub&gt;&lt;mrow&gt;&lt;mi&gt;Δ&lt;/mi&gt;&lt;mi&gt;ε&lt;/mi&gt;&lt;/mrow&gt;&lt;mn&gt;2&lt;/mn&gt;&lt;/msub&gt;&lt;/mrow&gt;&lt;/math&gt;&lt;/span&gt; at &lt;span&gt;&lt;math&gt;&lt;mrow&gt;&lt;msub&gt;&lt;mi&gt;f&lt;/mi&gt;&lt;mn&gt;2&lt;/mn&gt;&lt;/msub&gt;&lt;/mrow&gt;&lt;/math&gt;&lt;/span&gt; = 5.2 ∼ 6.2 MHz and &lt;span&gt;&lt;math&gt;&lt;mrow&gt;&lt;msub&gt;&lt;mrow&gt;&lt;mi&gt;Δ&lt;/mi&gt;&lt;mi&gt;ε&lt;/mi&gt;&lt;/mrow&gt;&lt;mn&gt;3&lt;/mn&gt;&lt;/msub&gt;&lt;/mrow&gt;&lt;/math&gt;&lt;/span&gt; at &lt;span&gt;&lt;math&gt;&lt;mrow&gt;&lt;msub&gt;&lt;mi&gt;f&lt;/mi&gt;&lt;mn&gt;3&lt;/mn&gt;&lt;/msub&gt;&lt;/mrow&gt;&lt;/math&gt;&lt;/span&gt; = 42 ∼ 50 MHz were correlated to &lt;span&gt;&lt;math&gt;&lt;mrow&gt;&lt;mi&gt;c&lt;/mi&gt;&lt;/mrow&gt;&lt;/math&gt;&lt;/span&gt;. The &lt;span&gt;&lt;math&gt;&lt;mrow&gt;&lt;msub&gt;&lt;mrow&gt;&lt;mi&gt;Δ&lt;/mi&gt;&lt;mi&gt;ε&lt;/mi&gt;&lt;/mrow&gt;&lt;mn&gt;3&lt;/mn&gt;&lt;/msub&gt;&lt;/mrow&gt;&lt;/math&gt;&lt;/span&gt; was decreasing with increasing &lt;span&gt;&lt;math&gt;&lt;mrow&gt;&lt;mi&gt;c&lt;/mi&gt;&lt;/mrow&gt;&lt;/math&gt;&lt;/span&gt; in both cases, which was influenced by the plasma macromolecular concentrations, while the &lt;span&gt;&lt;math&gt;&lt;mrow&gt;&lt;msub&gt;&lt;mrow&gt;&lt;mi&gt;Δ&lt;/mi&gt;&lt;mi&gt;ε&lt;/mi&gt;&lt;/mrow&gt;&lt;mn&gt;2&lt;/mn&gt;&lt;/msub&gt;&lt;/mrow&gt;&lt;/math&gt;&lt;/span&gt; was increased with increasing &lt;em&gt;c&lt;/em&gt; in WB case but was hardly changed in LLPB case because the &lt;span&gt;&lt;math&gt;&lt;mrow&gt;&lt;msub&gt;&lt;mrow&gt;&lt;mi&gt;Δ&lt;/mi&gt;&lt;mi&gt;ε&lt;/mi&gt;&lt;/mrow&gt;&lt;mn&gt;2&lt;/mn&gt;&lt;/msub&gt;&lt;/mrow&gt;&lt;/math&gt;&lt;/span&gt; is influenced by the blood cell concentrations and the shape changes of blood cell membranes. Heparin concentration &lt;span&gt;&lt;math&gt;&lt;mrow&gt;&lt;mi&gt;c&lt;/mi&gt;&lt;/mrow&gt;&lt;/math&gt;&lt;/span&gt; is estimated by the linear regression formula &lt;span&gt;&lt;math&gt;&lt;mrow&gt;&lt;msup&gt;&lt;mrow&gt;&lt;mi&gt;c&lt;/mi&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;mi&gt;P&lt;/mi&gt;&lt;mi&gt;R&lt;/mi&gt;&lt;mi&gt;E&lt;/mi&gt;&lt;/mrow&gt;&lt;/msup&gt;&lt;mo&gt;=&lt;/mo&gt;&lt;msub&gt;&lt;mi&gt;a&lt;/mi&gt;&lt;mn&gt;1&lt;/mn&gt;&lt;/msub&gt;&lt;msub&gt;&lt;mrow&gt;&lt;mo&gt;(&lt;/mo&gt;&lt;mi&gt;Δ&lt;/mi&gt;&lt;mi&gt;ε&lt;/mi&gt;&lt;/mrow&gt;&lt;mn&gt;2&lt;/mn&gt;&lt;/msub&gt;&lt;mo&gt;-&lt;/mo&gt;&lt;msubsup&gt;&lt;mrow&gt;&lt;mi&gt;Δ&lt;/mi&gt;&lt;mi&gt;ε&lt;/mi&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;mn&gt;2&lt;/mn&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;mi&gt;c&lt;/mi&gt;&lt;mo&gt;=&lt;/mo&gt;&lt;mn&gt;0&lt;/mn&gt;&lt;/mrow&gt;&lt;/msubsup&gt;&lt;mrow&gt;&lt;mo&gt;)&lt;/mo&gt;&lt;mo&gt;+&lt;/mo&gt;&lt;/mrow&gt;&lt;msub&gt;&lt;mi&gt;a&lt;/mi&gt;&lt;mn&gt;2&lt;/mn&gt;&lt;/msub&gt;&lt;mrow&gt;&lt;mo&gt;(&lt;/mo&gt;&lt;msub&gt;&lt;mrow&gt;&lt;mi&gt;Δ&lt;/mi&gt;&lt;mi&gt;ε&lt;/mi&gt;&lt;/mrow&gt;&lt;mn&gt;3&lt;/mn&gt;&lt;/msub&gt;&lt;mo&gt;-&lt;/mo&gt;&lt;msubsup&gt;&lt;mrow&gt;&lt;","PeriodicalId":252,"journal":{"name":"Bioelectrochemistry","volume":"163 ","pages":"Article 108912"},"PeriodicalIF":4.8,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143035352","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
Development of micro-nanostructured film with antibacterial, anticorrosive and thermal conductivity properties on copper surface
IF 4.8 2区 化学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-01-15 DOI: 10.1016/j.bioelechem.2025.108905
Li Lai, Muqiu Xia, Mengyu Fu, Yuanyuan Gao, Jiahao Sun, Guangzhou Liu, Shiqiang Chen
A micro-nano sharkskin like film (Cu-MNS-FA) was synthesized on copper surface through chemical etching followed by formate passivation, and its anticorrosive, antibacterial and thermal conductivity properties were investigated. Results show that after 7 d of exposure to nature, Pseudomonas aeruginosa and Desulfovibrio vulgaris seawater, the charge transfer resistance of Cu-MNS-FA is more than three times higher than that of unmodified copper. In particular, in D. vulgaris seawater, the Rct value of modified copper is 7 times higher than that of unmodified copper after the same exposure duration. The counts of sessile cells, specifically P. aeruginosa and D. vulgaris, on the surface of modified copper are reduced by > 88 % after 3 days of immersion. Furthermore, thermal conductivity remains 10 % higher than that of untreated copper after 7 d of immersion. This film improves the performance characteristics of copper in seawater heat exchange systems.
{"title":"Development of micro-nanostructured film with antibacterial, anticorrosive and thermal conductivity properties on copper surface","authors":"Li Lai,&nbsp;Muqiu Xia,&nbsp;Mengyu Fu,&nbsp;Yuanyuan Gao,&nbsp;Jiahao Sun,&nbsp;Guangzhou Liu,&nbsp;Shiqiang Chen","doi":"10.1016/j.bioelechem.2025.108905","DOIUrl":"10.1016/j.bioelechem.2025.108905","url":null,"abstract":"<div><div>A micro-nano sharkskin like film (Cu-MNS-FA) was synthesized on copper surface through chemical etching followed by formate passivation, and its anticorrosive, antibacterial and thermal conductivity properties were investigated. Results show that after 7 d of exposure to nature, <em>Pseudomonas aeruginosa</em> and <em>Desulfovibrio vulgaris</em> seawater, the charge transfer resistance of Cu-MNS-FA is more than three times higher than that of unmodified copper. In particular, in <em>D. vulgaris</em> seawater, the <em>R</em><sub>ct</sub> value of modified copper is 7 times higher than that of unmodified copper after the same exposure duration. The counts of sessile cells, specifically <em>P. aeruginosa</em> and <em>D. vulgaris</em>, on the surface of modified copper are reduced by &gt; 88 % after 3 days of immersion. Furthermore, thermal conductivity remains 10 % higher than that of untreated copper after 7 d of immersion. This film improves the performance characteristics of copper in seawater heat exchange systems.</div></div>","PeriodicalId":252,"journal":{"name":"Bioelectrochemistry","volume":"163 ","pages":"Article 108905"},"PeriodicalIF":4.8,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143027451","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
Print-Light-Synthesis of ruthenium oxide thin film electrodes for electrochemical sensing applications
IF 4.8 2区 化学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-01-15 DOI: 10.1016/j.bioelechem.2025.108909
Stefano Gianvittorio , Marco Malferrari , Horst Pick , Stefania Rapino , Andreas Lesch
Print-Light-Synthesis (PLS) combines the inkjet printing of a ruthenium precursor ink with the simultaneous photo-induced generation of ruthenium oxide films. During PLS, inkjet-printing generates on conductive as well as insulating substrates micrometer-thin reaction volumes that contain with high precision defined precursor loadings. Upon direct UV light irradiation, the Ru precursor converts to RuO2 while all other ink components escape in the gas phase. No post PLS processes are required, and the as-obtained RuO2 films can be immediately used as electrochemical devices. Two-dimensional RuO2 patterns with micrometric resolution and highly-controlled ruthenium loadings (few µg/cm2) are realized. Thin RuO2 films are generated on insulating substrates, such as polyimide, as well as individual RuO2 particles on conductive substrates, such as graphene layers. The RuO2 films are characterized by electron microscopy and spectroscopic techniques. The sensoristic applicability of the PLS-RuO2 electrodes is demonstrated by potentiometric pH sensing in cell cultures and amperometric detection of L-cysteine. For pH sensing the RuO2 film electrodes show Nernstian sensitivity. L-cysteine detection of RuO2-modified graphene electrodes showed an electrocatalytical effect and resulted in the possibility of selectively detecting L-Cysteine also in presence of the interfering compound uric acid.
{"title":"Print-Light-Synthesis of ruthenium oxide thin film electrodes for electrochemical sensing applications","authors":"Stefano Gianvittorio ,&nbsp;Marco Malferrari ,&nbsp;Horst Pick ,&nbsp;Stefania Rapino ,&nbsp;Andreas Lesch","doi":"10.1016/j.bioelechem.2025.108909","DOIUrl":"10.1016/j.bioelechem.2025.108909","url":null,"abstract":"<div><div>Print-Light-Synthesis (PLS) combines the inkjet printing of a ruthenium precursor ink with the simultaneous photo-induced generation of ruthenium oxide films. During PLS, inkjet-printing generates on conductive as well as insulating substrates micrometer-thin reaction volumes that contain with high precision defined precursor loadings. Upon direct UV light irradiation, the Ru precursor converts to RuO<sub>2</sub> while all other ink components escape in the gas phase. No post PLS processes are required, and the as-obtained RuO<sub>2</sub> films can be immediately used as electrochemical devices. Two-dimensional RuO<sub>2</sub> patterns with micrometric resolution and highly-controlled ruthenium loadings (few µg/cm<sup>2</sup>) are realized. Thin RuO<sub>2</sub> films are generated on insulating substrates, such as polyimide, as well as individual RuO<sub>2</sub> particles on conductive substrates, such as graphene layers. The RuO<sub>2</sub> films are characterized by electron microscopy and spectroscopic techniques. The sensoristic applicability of the PLS-RuO<sub>2</sub> electrodes is demonstrated by potentiometric pH sensing in cell cultures and amperometric detection of L-cysteine. For pH sensing the RuO<sub>2</sub> film electrodes show Nernstian sensitivity. L-cysteine detection of RuO<sub>2</sub>-modified graphene electrodes showed an electrocatalytical effect and resulted in the possibility of selectively detecting L-Cysteine also in presence of the interfering compound uric acid.</div></div>","PeriodicalId":252,"journal":{"name":"Bioelectrochemistry","volume":"163 ","pages":"Article 108909"},"PeriodicalIF":4.8,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143035350","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
Enhanced detection of Cystatin C for predicting adverse outcomes in gestational diabetes mellitus using a point-of-care immunosensor 利用即时免疫传感器增强胱抑素C检测,预测妊娠期糖尿病的不良结局。
IF 4.8 2区 化学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-01-13 DOI: 10.1016/j.bioelechem.2025.108907
Ya Jin , Yongmei Chen , Xiaoqin Li , Songjun Han , Lei Mou , Nan Li
Cystatin C (Cys-C) is emerging as a critical biomarker for assess gestational diabetes mellitus (GDM), a condition that significantly impacts maternal and fetal health. In this study, we developed a novel label-free electrochemical immunosensor designed for point-of-care applications, offering lower reagent consumption and rapid detection of Cys-C in pregnant women with GDM. Compared to traditional enzyme-linked immunosorbent assays (ELISA), the sensor demonstrates enhanced sensitivity, reduced reagent usage, and faster detection. In a cohort study involving 150 pregnant women with GDM and 150 healthy controls, serum Cys-C levels were analyzed using the developed sensor. Serum samples were collected and analyzed for Cys-C levels using our immunosensor. Serum Cys-C levels were significantly elevated in GDM patients compared to controls (P < 0.05), and higher levels were observed in GDM complicated by pregnancy-induced hypertension (PIH) and fetal growth restriction (FGR). Furthermore, elevated Cys-C levels were positively correlated with adverse pregnancy outcomes, including premature birth, fetal distress, and cesarean section (P < 0.05). This study underscores the potential of Cys-C as a reliable biomarker for GDM and highlights the advantages of our novel sensor for quick, accurate, and scalable GDM diagnosis and management.
妊娠期糖尿病(GDM)是一种严重影响母体和胎儿健康的疾病,胱抑素C (Cys-C)正成为评估妊娠期糖尿病(GDM)的关键生物标志物。在这项研究中,我们开发了一种新型的无标签电化学免疫传感器,设计用于护理点应用,提供更低的试剂消耗和快速检测GDM孕妇的Cys-C。与传统的酶联免疫吸附测定法(ELISA)相比,该传感器具有更高的灵敏度、更少的试剂使用量和更快的检测速度。在一项包括150名GDM孕妇和150名健康对照者的队列研究中,使用开发的传感器分析了血清Cys-C水平。使用我们的免疫传感器收集血清样本并分析Cys-C水平。GDM患者血清Cys-C水平显著高于对照组(P < 0.05),且GDM合并妊高征(PIH)和胎儿生长受限(FGR)患者血清Cys-C水平更高。此外,Cys-C水平升高与早产、胎儿窘迫、剖宫产等不良妊娠结局呈正相关(P < 0.05)。这项研究强调了Cys-C作为一种可靠的GDM生物标志物的潜力,并强调了我们的新型传感器在快速、准确和可扩展的GDM诊断和管理方面的优势。
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引用次数: 0
Conductive and flexible gold-coated polylactic acid nanofiber-based electrochemical aptasensor for monitoring cortisol level in sweat and saliva 用于监测汗液和唾液中皮质醇水平的导电柔性金包覆聚乳酸纳米纤维电化学适体传感器。
IF 4.8 2区 化学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-01-13 DOI: 10.1016/j.bioelechem.2025.108908
Mkliwa Koumbia, Takai Madoka
Conductive nanofibers can exhibit excellent mechanical properties such as flexibility, elasticity, porosity, large surface area-to-volume ratio, etc making them suitable for a wide range of applications including biosensor development. Their large surface area provides more active sites for immobilization of large amount of bioreceptors enabling more interaction sites with the target analytes, enhancing sensitivity and detection capabilities. However, engineering conductive nanofibers with such excellent properties is challenging limiting their effective deployment for intended applications. In this research, we propose a novel approach for easy fabrication of highly conductive and flexible nanofiber leveraging the electrospinning, electroless deposition and have applied it to cortisol monitoring; a common biomarker for stress which is often quantified through enzyme-linked immunoassays using blood or saliva samples. By adopting the nanofiber sheet as a transducer for aptamer immobilization and cortisol sensing our developed biosensor was able to detect cortisol in buffer, artificial saliva, and artificial sweat within five minutes, from 10 pg/mL to 10 µg/mL (27.59 pM to 27.59 µM) with a low detection limit of 1 pg/ml (2.76 pM). The Au-coated PLA nanofiber-based electrochemical biosensor’s flexibility allows for compact manufacturing, rendering it an optimal choice for integration into point-of-care testing and wearable systems.
导电纳米纤维具有优异的机械性能,如柔韧性、弹性、孔隙率、大表面积体积比等,适用于包括生物传感器开发在内的广泛应用。它们的大表面积为大量生物受体的固定化提供了更多的活性位点,使其与目标分析物有更多的相互作用位点,提高了灵敏度和检测能力。然而,具有如此优异性能的工程导电纳米纤维是一项挑战,限制了它们在预期应用中的有效部署。在这项研究中,我们提出了一种利用静电纺丝、化学沉积制备高导电性和柔性纳米纤维的新方法,并将其应用于皮质醇监测;一种常见的压力生物标志物,通常通过使用血液或唾液样本进行酶联免疫测定来量化。通过采用纳米纤维片作为适体固定和皮质醇传感的传感器,我们开发的生物传感器能够在5分钟内检测缓冲液,人工唾液和人工汗液中的皮质醇,检测范围从10 pg/mL到10µg/mL (27.59 pM到27.59µM),低检测限为1 pg/mL (2.76 pM)。基于au涂层PLA纳米纤维的电化学生物传感器的灵活性允许紧凑型制造,使其成为集成到护理点测试和可穿戴系统中的最佳选择。
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引用次数: 0
Optimized detection of calcium ion in serum using constant potential coulometry with metastable liquid–liquid contact doping enhanced PEDOT: PSS ink 亚稳液-液接触掺杂增强PEDOT: PSS墨水恒电位库仑法优化血清钙离子检测。
IF 4.8 2区 化学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-01-10 DOI: 10.1016/j.bioelechem.2025.108903
Suyun Wei , Jie Zhao , Shaojun Ke , Mingjia Zou , Qingze Han , Guofeng Cui
Highly stable calcium ion selective electrodes (Ca2+-ISEs) were developed by drop-casting a layer of poly(3,4-ethylenedioxythiophene): polystyrene sulfonate (PEDOT: PSS) as an ion-to-electron transfer layer onto Au electrode. The conductive PEDOT: PSS ink was prepared using a metastable liquid–liquid contact (MLLC) doping method, which induced phase separation, removed excess PSS, and significantly enhanced charge transfer kinetics and conductivity. The resulting Ca2+-ISEs exhibited excellent electrochemical performance. Potentiometric studies revealed a significant sensitivity of 33.1 ± 0.98 mV/decade (N = 3) with a high potential stability of 3.16 ± 2.53 μV/h. Importantly, Ca2+-ISEs combined with the constant potential coulometry method, the lower detection limit was optimized to 8.527 × 10−8 M (LOD = 3σ/s, N = 3). The performance of the Ca2+-ISE system was evaluated in inactivated fetal bovine serum using constant potential coulometry, demonstrating the highest measurement accuracy compared to potentiometric and chronoamperometric. The enhanced PEDOT: PSS-MLLC based Ca2+-ISEs combined with the constant potential coulometry method developed in this research demonstrate considerable potential for clinical applications in blood ion analysis.
通过在Au电极上滴铸一层聚(3,4-乙烯二氧噻吩):聚苯乙烯磺酸盐(PEDOT: PSS)作为离子-电子转移层,制备了高度稳定的钙离子选择性电极(Ca2+-ISEs)。采用亚稳液-液接触(MLLC)掺杂法制备了导电PEDOT: PSS油墨,诱导相分离,去除多余的PSS,显著提高了电荷转移动力学和电导率。得到的Ca2+- ise具有优异的电化学性能。电位测定结果表明,该方法灵敏度为33.1±0.98 mV/decade (N = 3),电位稳定性为3.16±2.53 μV/h。重要的是,Ca2+-ISE结合恒电位库仑法,优化了下限检测限为8.527 × 10-8 M (LOD = 3σ/s, N = 3)。用恒电位库仑法对Ca2+-ISE系统在灭活胎牛血清中的性能进行了评估,与电位法和计时安培法相比,显示出最高的测量精度。本研究开发的基于PEDOT: PSS-MLLC的增强型Ca2+-ISEs结合恒电位库伦法,在血液离子分析中具有相当大的临床应用潜力。
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引用次数: 0
Facile preparation of bifunctional monolayers through diazonium grafting and “click” postfunctionalization: A first step towards efficient aptasensing interfaces 通过重氮接枝和“点击”后功能化轻松制备双功能单层:迈向高效适配界面的第一步。
IF 4.8 2区 化学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-01-10 DOI: 10.1016/j.bioelechem.2025.108904
Andra Mihaela Onaş , Andreea Mădălina Pandele , Anamaria Hanganu , Ciprian Victor Florea , Horia Iovu , Matei D. Raicopol , Luisa Pilan
Herein, we present an efficient approach for developing electrochemical aptasensing interfaces, by “click” postfunctionalization of phenylethynyl-grafted glassy carbon substrates with mixed monolayers containing biorecognition elements and phosphorylcholine zwitterionic groups. Typically, controlling the composition of multicomponent surface layers by grafting from a mixture of aryldiazonium salts is challenging due to differences in their chemical reactivity. Our approach circumvents this issue by employing the electrochemical reduction of a single aryldiazonium salt containing a silyl-protected alkyne group followed by deprotection, to create phenylethynyl monolayers which can subsequently accommodate the concurrent immobilization of bioreceptors and zwitterionic groups through “click” postfunctionalization. We show that the surface ratio of the components in the bifunctional monolayers, estimated through XPS and electrochemical methods, can be accurately controlled by adjusting the mole ratio of the corresponding azide reagents in the “click” coupling solution. Moreover, electrochemical impedance spectroscopy and fluorescence microscopy investigations on bifunctional monolayers containing ssDNA and phosphorylcholine groups reveal that they effectively prevent nonspecific protein adsorption, while maintaining sufficiently low impedance to facilitate electrochemical detection. Finally, we demonstrate that proof of concept aptasensing interfaces based on binary layers containing a ferrocene-tagged cocaine/quinine aptamer and phosphorylcholine groups exhibit a trade-off between an improved analytical response and antifouling efficiency.
在此,我们提出了一种开发电化学适体感应界面的有效方法,通过将含有生物识别元素和磷胆碱两性离子基团的混合单层接枝苯乙基玻璃碳衬底“点击”后功能化。通常,通过接枝芳基重氮盐的混合物来控制多组分表面层的组成是具有挑战性的,因为它们的化学反应性存在差异。我们的方法通过电化学还原含有硅基保护的炔基的单一芳基重氮盐,然后进行去保护,来创建苯乙基单层,该单层随后可以通过“点击”后功能化来容纳生物受体和两性离子基团的同时固定,从而避免了这个问题。我们发现,通过XPS和电化学方法估计的双功能单层中组分的表面比可以通过调整相应叠氮化物试剂在“点击”耦合溶液中的摩尔比来精确控制。此外,电化学阻抗谱和荧光显微镜对含有ssDNA和磷胆碱基团的双功能单层的研究表明,它们有效地阻止了非特异性蛋白质的吸附,同时保持足够低的阻抗,便于电化学检测。最后,我们证明了概念证明,基于含有二铁标记的可卡因/奎宁适体和磷胆碱基团的二元层的适体感应界面在改进的分析响应和防污效率之间表现出权衡。
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引用次数: 0
Rapid and receptor-free Prussian blue electrochemical sensor for the detection of pathogenic bacteria in blood 快速无受体普鲁士蓝电化学传感器检测血液中致病菌。
IF 4.8 2区 化学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-01-09 DOI: 10.1016/j.bioelechem.2025.108902
Sriramprabha Ramasamy, Sekar Madhu, Jungil Choi
Bloodstream bacterial infections, a major health concern due to rising sepsis rates, require prompt, cost-effective diagnostics. Conventional methods, like CO2-based transduction, face challenges such as volatile metabolites, delayed gas-phase signaling, and the need for additional instruments, whereas electrochemical sensors provide rapid, sensitive, and efficient real-time detection. In this study, we developed a bioreceptor-free Prussian blue (PB) sensor platform for real-time bacterial growth monitoring in blood culture. PB thin films were electrodeposited onto a screen-printed carbon electrode (SPCE) via cyclic voltammetry (CV) technique under optimal conditions. The electrochemical performance of PB/SPCE was assessed using differential pulse voltammetry (DPV) against exoelectrogenic bacteria, including E. coli, P. aeruginosa, S. aureus, and E. faecalis. The proposed sensor exhibited surface-controlled electrochemical kinetics and bacteria-driven metal reduction from PB to Prussian white (PW), facilitated by extracellular electron transfer (EET). It showed significant sensitivity with an extensive detection range of 102–108 CFU/mL for E. coli and S. aureus, and 103–108 CFU/mL for P. aeruginosa and E. faecalis, with reliable detection limits. The sensor accessed the viability of the pathogen within 3 hrs, offering a rapid, efficient alternative to traditional, labor-intensive methods for blood-based diagnostics.
血液细菌感染是由于败血症率上升而引起的主要健康问题,需要及时、具有成本效益的诊断。传统的方法,如基于二氧化碳的转导,面临着诸如挥发性代谢物、延迟气相信号以及需要额外仪器等挑战,而电化学传感器提供了快速、敏感和高效的实时检测。在这项研究中,我们开发了一种无生物受体普鲁士蓝(PB)传感器平台,用于实时监测血液培养中的细菌生长。利用循环伏安法(CV)在最佳条件下将PB薄膜电沉积在丝网印刷碳电极(SPCE)上。采用差分脉冲伏安法(DPV)评价PB/SPCE对大肠杆菌、铜绿假单胞菌、金黄色葡萄球菌和粪肠杆菌等产电细菌的电化学性能。所提出的传感器具有表面控制的电化学动力学和细菌驱动的金属从PB还原到普鲁士白(PW),这是由细胞外电子转移(EET)促进的。该方法对大肠杆菌和金黄色葡萄球菌的检测范围为102 ~ 108 CFU/mL,对铜绿假单胞菌和粪肠杆菌的检测范围为103 ~ 108 CFU/mL,灵敏度显著,具有可靠的检出限。该传感器可在3小时内获取病原体的生存能力,为血液诊断提供了一种快速、有效的替代传统的劳动密集型方法。
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引用次数: 0
A carbon fiber modified with tin oxide/graphitic carbon nitride as an electrochemical indirect competitive immuno-sensor for ultrasensitive aflatoxin M1 detection 用氧化锡/氮化石墨碳修饰的碳纤维作为超灵敏黄曲霉毒素 M1 检测的电化学间接竞争免疫传感器。
IF 4.8 2区 化学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-01-09 DOI: 10.1016/j.bioelechem.2025.108898
Iram Naz , Muhammad Nasir , Mian Hasnain Nawaz , Silvana Andreescu , Akhtar Hayat , Farhat Jubeen
The importance of developing multifunctional nanomaterials for sensing technologies is increasing with the arrival of nanotechnology. In this study, we describe the introduction of novel nanoprobe electro-active material into the architecture of an electrochemical immuno-sensor. Based on the electrochemical immuno-sensor, functionalized tin oxide/graphitic carbon nitride nanocomposite (fSnO2/g-C3N4) was synthesized and then analyte specific anti-aflatoxin M1 monoclonal antibody (AFM1-ab) combined to form an electro-active nanoprobe (fSnO2/g-C3N4/AFM1-ab). First, aflatoxin M1 (AFM1) conjugated bovine serum albumin (BSA-AFM1) was electro-oxidized on the surface of carbon fiber (CF) followed by the consequent addition of nanoprobe. The formation of nanocomposite was substantiated through various characterization techniques, Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, X-ray diffraction (XRD), Thermogravimetric analysis (TGA) and Dynamic light scattering (DLS). Immuno-sensor fabrication was characterized via Field emission scanning electron microscopy (FE-SEM), optical microscope images, cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and differential pulse voltammetry (DPV). This immuno-sensor demonstrated good reproducibility, selectivity, specificity and sensitivity for AFM1 (LOD of 0.03 ng mL−1). Following spiking, this immuno-sensor produced good recovery values in the range of 94–96 % against real sample, such as milk. The development of sophisticated sensing methods for a range of analytes can greatly benefit from the widespread application of this innovative immuno-sensing approach.
随着纳米技术的发展,开发用于传感技术的多功能纳米材料的重要性日益增加。在这项研究中,我们描述了将新型纳米探针电活性材料引入电化学免疫传感器的结构中。在电化学免疫传感器的基础上,合成了功能化氧化锡/石墨氮化碳纳米复合材料(fSnO2/g-C3N4),并结合分析特异性抗黄曲霉毒素M1单克隆抗体(AFM1-ab)形成电活性纳米探针(fSnO2/g-C3N4/AFM1-ab)。首先,在碳纤维(CF)表面电氧化黄曲霉毒素M1 (AFM1)偶联牛血清白蛋白(BSA-AFM1),然后添加纳米探针。通过傅里叶变换红外光谱(FT-IR)、拉曼光谱、x射线衍射(XRD)、热重分析(TGA)和动态光散射(DLS)等表征技术证实了纳米复合材料的形成。通过场发射扫描电镜(FE-SEM)、光学显微镜图像、循环伏安法(CV)、电化学阻抗谱(EIS)和差分脉冲伏安法(DPV)对免疫传感器的制备进行了表征。该免疫传感器对AFM1具有良好的重现性、选择性、特异性和敏感性(LOD为0.03 ng mL-1)。在峰值之后,该免疫传感器对真实样品(如牛奶)产生了良好的回收率,范围为94- 96%。这种创新的免疫传感方法的广泛应用可以极大地受益于各种分析物的复杂传感方法的发展。
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Bioelectrochemistry
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