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Bioluminescence-based electrochemical sensor for dual-mode direct hydrocarbon detection in saline water utilizing Photobacterium leiognathi and d-luciferin-modified au-SPE 利用光杆菌和d-荧光素修饰的au-SPE进行盐水中碳氢化合物双模直接检测的生物发光电化学传感器
IF 4.5 2区 化学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2026-01-24 DOI: 10.1016/j.bioelechem.2026.109233
Arash Rasti , Muhamad Afiq Aziz , Zaira Zaman Chowdhury , Sook Mei Khor
Early detection of hydrocarbon pollution in saline ecosystems faces challenges due to their complexity and the limitations of current detection methods. Salinity, temperature variations, the presence of other organic matter, and weathering processes hinder the effectiveness of traditional techniques, while the cost and complexity of some advanced detection technologies limit their widespread application. In this study, a gold screen-printed electrode (Au-SPE) modified with d-luciferin was developed to monitor the metabolic response of Photobacterium leiognathi to hexane and aromatic hydrocarbons in saline water and seawater. The sensor works by capturing adenosine triphosphate (ATP)-dependent electron release associated with bacterial bioluminescence, which varies according to the type of hydrocarbon. D-luciferin was immobilized on the Au-SPE via a self-assembled monolayer using ethylenediamine and EDC/NHS coupling to create a biocompatible interface. CV analysis revealed time-dependent shifts of anodic and cathodic peaks from −0.5 V to +0.5 V. The presence of aromatic hydrocarbons increased both bioluminescence light emission and current, indicating metabolic stimulation. In contrast, hexane suppressed bioluminescence and decreased current, indicating metabolic inhibition. These distinct responses enable rapid and selective differentiation between different types of hydrocarbons. The developed biosensor exhibits strong potential for real-time monitoring of oil contamination and assessing water quality in saline ecosystems.
盐化生态系统中烃类污染的早期检测由于其复杂性和现有检测方法的局限性而面临挑战。盐度、温度变化、其他有机物的存在和风化过程阻碍了传统技术的有效性,而一些先进探测技术的成本和复杂性限制了它们的广泛应用。本研究利用d-荧光素修饰的金丝网印刷电极(Au-SPE)来监测光杆菌在咸水和海水中对己烷和芳香烃的代谢反应。该传感器通过捕获与细菌生物发光相关的三磷酸腺苷(ATP)依赖的电子释放来工作,这种电子释放根据碳氢化合物的类型而变化。d -荧光素通过乙二胺和EDC/NHS偶联的自组装单层固定在Au-SPE上,形成生物相容性界面。CV分析显示阳极和阴极峰从−0.5 V到+0.5 V随时间变化。芳香烃的存在增加了生物发光发光和电流,表明代谢刺激。相反,己烷抑制生物发光并降低电流,表明代谢抑制。这些不同的反应使不同类型的碳氢化合物能够快速和选择性地区分。所开发的生物传感器在实时监测石油污染和评估咸水生态系统水质方面具有很强的潜力。
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引用次数: 0
Cu-enhanced microbiological corrosion resistance of CoNiV medium-entropy alloy cu增强CoNiV中熵合金的耐微生物腐蚀性能。
IF 4.5 2区 化学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2026-01-23 DOI: 10.1016/j.bioelechem.2026.109232
Zihao Wang , Xiaobao Zhou , Zuchuan Zhang , Lin Liu , Cong Li , Boxin Wei , Tangqing Wu
Microbiologically influenced corrosion (MIC) critically compromises the integrity of metal structures. This study investigates the effect of copper on the MIC behavior of CoNiV–Cux medium-entropy alloys (MEAs) in Desulfovibrio vulgaris environments. In sterile medium, increasing Cu reduced the combined film and charge transfer resistance, whereas in inoculated medium, the trend reversed. After 360 h, CoNiV–Cu10 MEA formed a protective oxide layer (δeff = 0.912 nm), three times thicker than CoNiV MEA. The corrosion current and passivation current were significantly lower in Cu-rich alloys under MIC. The apparently adverse effect of Cu in sterile conditions was associated with modifications in passive film defect chemistry and charge-transfer processes, whereas under MIC conditions, Cu addition enhanced passive film stability, suppressed microbial adhesion, and improved MIC resistance. These findings provide insight for designing Cu-alloyed MEAs with superior performance in MIC environments.
微生物影响腐蚀(MIC)严重危害金属结构的完整性。本文研究了铜对conv - cux中熵合金(MEAs)在普通脱硫弧菌环境中MIC行为的影响。在无菌培养基中,Cu的增加降低了组合膜和电荷传递电阻,而在接种培养基中则相反。360 h后,CoNiV- cu10 MEA形成保护氧化层(δeff = 0.912 nm),厚度为CoNiV MEA的3倍。在MIC作用下,富cu合金的腐蚀电流和钝化电流明显降低。Cu在无菌条件下的明显不利影响与钝化膜缺陷化学和电荷转移过程的改变有关,而在MIC条件下,Cu的加入增强了钝化膜的稳定性,抑制了微生物的粘附,并提高了MIC抗性。这些发现为在MIC环境中设计具有优异性能的cu合金mea提供了见解。
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引用次数: 0
Influence of synthesis temperature of eggshell-derived hydroxyapatite on biofilm formation and microbial fuel cell performance 蛋壳羟基磷灰石合成温度对生物膜形成和微生物燃料电池性能的影响
IF 4.5 2区 化学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2026-01-22 DOI: 10.1016/j.bioelechem.2026.109235
Vasumathi K. , Chin-Tsan Wang
Microbial fuel cells (MFCs) enable simultaneous wastewater treatment and bioelectricity generation, but their performance is often constrained by poor bacterial adhesion and slow anode electron transfer. Hydroxyapatite (HA) can address these limitations; however, most studies rely on commercial HA and rarely examine biowaste-derived sources or synthesis-route effects. In this study, eggshell-derived HA was synthesized via room-temperature precipitation (CHP) and hydrothermal treatment at 250 °C for 3 h (CHH), then blended with carbon to fabricate composite anodes. Dual-chamber MFCs inoculated with Shewanella putrefaciens were evaluated using electrochemical analyses (CV, EIS, polarization) and biofilm characterization (CFU counts, crystal violet staining, SEM). CHH achieved a peak power density of 0.164 W m−2, approximately 167% higher than bare carbon and 23–33% higher than carbon and CHP. CHP exhibited slightly lower peak power but superior sustained output over a wider current-density range, attributed to its low-crystallinity structure and rapid early colonization. The results demonstrate that HA nanostructure, governed by synthesis route, directly influences biofilm formation and electron transfer. Overall, eggshell-derived HA anodes significantly enhance MFC performance, establishing a clear synthesis–nanostructure–biofilm–performance relationship.
微生物燃料电池(mfc)能够同时进行废水处理和生物发电,但其性能往往受到细菌粘附性差和阳极电子转移缓慢的限制。羟基磷灰石(HA)可以解决这些限制;然而,大多数研究依赖于商业透明质酸,很少检查生物废物来源或合成途径的影响。在本研究中,通过室温沉淀(CHP)和250°C水热处理(CHH)合成蛋壳源HA,然后与碳混合制备复合阳极。采用电化学分析(CV、EIS、极化)和生物膜表征(CFU计数、结晶紫染色、扫描电镜)对接种了腐坏希瓦氏菌的双室mfc进行评价。CHH的峰值功率密度为0.164 W m−2,比裸碳高167%,比碳和CHP高23-33%。CHP的峰值功率略低,但由于其低结晶度结构和快速的早期定植,在较宽的电流密度范围内具有较好的持续输出。结果表明,透明质酸的纳米结构受合成路线的支配,直接影响生物膜的形成和电子的传递。总之,蛋壳衍生的HA阳极显著提高了MFC性能,建立了清晰的合成-纳米结构-生物膜-性能关系。
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引用次数: 0
The Nernst slope within the Association–Induction Hypothesis framework 联想-归纳假设框架内的能思特斜率
IF 4.5 2区 化学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2026-01-22 DOI: 10.1016/j.bioelechem.2026.109236
Anh L. Duong , Keito Kaida , Kaito Goto , Iori Kojima , Bernard Delalande , Hirohisa Tamagawa
The Goldman–Hodgkin–Katz (GHK) equation provides a quantitative description of the membrane potential, a quantity commonly ascribed to passive and active ion movements through channels and pumps in the plasma membrane. Consequently, the membrane potential is frequently viewed as a hallmark of living cells. In physiology, the Nernst equation is often treated as a simplified version of the GHK equation. The factor eψ/zkT (z: ion valency; ψ: membrane potential), termed the Nernst slope, serves as a key marker of the Nernst equation’s applicability and of cellular viability. Yet, nonliving systems can also develop potentials that exhibit the same characteristic slope, indicating that the Nernst slope is not necessarily a product of biological activity. An older, largely disregarded physiological model, the Association–Induction Hypothesis (AIH), explains membrane potential generation purely in terms of ion adsorption–desorption phenomena. Within the AIH framework, membrane potentials do not arise from ionic fluxes across the membrane but from equilibria that obey the law of mass action. In this study, we derive the Nernst slope using the AIH framework. This result suggests that the membrane potential may primarily reflect mass-action-determined equilibria rather than active physiological mechanisms.
戈德曼-霍奇金-卡茨(GHK)方程提供了膜电位的定量描述,这个量通常归因于通过质膜通道和泵的被动和主动离子运动。因此,膜电位经常被视为活细胞的标志。在生理学中,能斯特方程通常被视为GHK方程的简化版本。因子- eψ/zkT (z:离子价;ψ:膜电位)被称为能斯特斜率,是能斯特方程适用性和细胞活力的关键标志。然而,非生物系统也可以发展出具有相同特征斜率的电位,这表明能斯特斜率不一定是生物活动的产物。关联诱导假说(Association-Induction Hypothesis, AIH)是一种较老的、基本上被忽视的生理模型,它纯粹从离子吸附-解吸现象的角度来解释膜电位的产生。在AIH框架内,膜电位不是由穿过膜的离子通量产生的,而是由服从质量作用定律的平衡产生的。在本研究中,我们使用AIH框架推导了能斯特斜率。这一结果表明,膜电位可能主要反映质量-动作决定的平衡,而不是积极的生理机制。
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引用次数: 0
Electrochemical detection of thyroglobulin based upon biomimetic thyroid chemistry. 基于仿生甲状腺化学的甲状腺球蛋白电化学检测。
IF 4.5 2区 化学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2026-01-22 DOI: 10.1016/j.bioelechem.2026.109234
Bal-Ram Adhikari, Reem Elmahdy, Carlos A Ramirez, Jacek Lipkowski, Aicheng Chen

We report on a novel nature-inspired electrochemical platform for the sensitive detection of thyroglobulin (Tg), a critical biomarker for monitoring treatment efficacy in patients with differentiated thyroid cancer following thyroidectomy. Current Tg diagnostic strategies typically require multiple complex reactions that require various washing steps and stringent experimental protocols. For this study, we have successfully developed a lactoperoxidase (LPO) based Ag nanoparticles (AgNP) and reduced graphene oxide (rGO) nanohybrid platform, on which LPO was immobilized through the creation of a self-assembled monolayer (SAM) of mercaptopropionic acid (MPA) followed by EDC/NHS activation. Cyclic voltammetry (CV) was employed to characterize the electrochemical behaviours of the rGO-AgNP nanohybrid, prior to and following the formation of the self-assembled monolayer (SAM). Electrochemical impedance spectroscopy (EIS) was used to further investigate the behaviour of the rGO-AgNP nanohybrid, following the immobilization of LPO. Our study has shown that the developed biosensor demonstrated rapid, sensitive, and selective Tg detection over a broad linear range of 4.0-90.0 ng/mL with a low limit of detection of 0.75 ng/mL, highlighting its strong potential for biological and clinical applications.

我们报道了一种新的受自然启发的电化学平台,用于灵敏检测甲状腺球蛋白(Tg), Tg是监测分化型甲状腺癌患者甲状腺切除术后治疗效果的关键生物标志物。目前的Tg诊断策略通常需要多个复杂的反应,需要各种洗涤步骤和严格的实验方案。在这项研究中,我们成功开发了一种基于乳过氧化物酶(LPO)的银纳米颗粒(AgNP)和还原氧化石墨烯(rGO)纳米混合平台,通过创建巯基丙酸(MPA)的自组装单层(SAM),然后进行EDC/NHS活化,将LPO固定在该平台上。循环伏安法(CV)表征了rGO-AgNP纳米杂化物在形成自组装单层(SAM)之前和之后的电化学行为。利用电化学阻抗谱(EIS)进一步研究了固定化LPO后rGO-AgNP纳米杂化物的行为。我们的研究表明,开发的生物传感器在4.0-90.0 ng/mL的宽线性范围内具有快速,敏感和选择性的Tg检测,低检测限为0.75 ng/mL,突出了其在生物学和临床应用方面的强大潜力。
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引用次数: 0
Engineering a flat-lying three-stranded duplex probe for catalytic DNA circuit toward enhanced electrochemical biosensing 设计用于催化DNA电路的扁平三链双探针,以增强电化学生物传感
IF 4.5 2区 化学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2026-01-20 DOI: 10.1016/j.bioelechem.2026.109230
Xiaolin Zhang, Zhicheng Li, Fangfang Yang, Jieyu Zhang, Jing Yu, Li Wang, Shufeng Liu
Nucleic acid probe design and immobilization are fundamental to the high performance of biosensors. However, the dependence on elaborate fabrication processes or meticulous optimization of probe immobilization poses challenges to achieving reliable bioanalysis and high sensing efficiency. Herein, we report an effective strategy for constructing electrochemical DNA biosensor that leverages a catalytic DNA reaction on a uniquely designed three-stranded duplex (TSD) probe. The TSD probe is engineered with an internally positioned thiol group to adopt a favorable flat-lying immobilization orientation. Compared to conventional upright TSD probe, the flat-lying design facilitates a more accessible interface and more stable assembly density with reduced dependence on immobilization concentration. This flat-lying system demonstrated superior sensing performance, including a faster reaction rate (completed within 1.5 h vs. 2.5 h for upright probes) and a lower detection limit of 244 fM for target, which is about 40-fold better than the upright configuration. The sensor also demonstrated excellent selectivity against mismatched sequences, better reproducibility and was successfully applied for target detection in diluted serum. This work presents a novel and facile probe design and immobilization paradigm that eliminates the traditional need for complex density optimization, offering a robust sensing platform for highly sensitive and efficient DNA detection.
核酸探针的设计和固定是生物传感器高性能的基础。然而,依赖于复杂的制造工艺或精细的探针固定优化对实现可靠的生物分析和高传感效率提出了挑战。在此,我们报告了构建电化学DNA生物传感器的有效策略,该传感器利用独特设计的三链双链(TSD)探针上的催化DNA反应。TSD探针采用内部定位的硫醇基团设计,采用有利的平躺固定方向。与传统的直立式TSD探头相比,平面设计有助于更容易接近的界面和更稳定的组装密度,减少了对固定浓度的依赖。该平躺系统表现出优异的传感性能,包括更快的反应速度(在1.5小时内完成,而直立探针在2.5小时内完成)和较低的目标检测极限244 fM,比直立配置好约40倍。该传感器对不匹配序列具有良好的选择性,重现性好,成功应用于稀释血清中的靶标检测。这项工作提出了一种新颖而简便的探针设计和固定范例,消除了传统的复杂密度优化需求,为高灵敏度和高效率的DNA检测提供了一个强大的传感平台。
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引用次数: 0
Electrochemical sensing of organoferrocene ligand interaction with serum albumin in dimethyl sulfoxide media 二甲基亚砜介质中有机二茂二铁配体与血清白蛋白相互作用的电化学传感
IF 4.5 2区 化学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2026-01-20 DOI: 10.1016/j.bioelechem.2026.109231
Lucie Žaloudková , Vojtěch Hamala , Peter Šebest , Marek Zelinka , Hana Černocká , Jindřich Karban , Veronika Ostatná
Protein-ligand interactions are crucial for understanding biochemical reactions and pathways, as well as for the design of new therapeutics. In this work, we compare the electrochemical behavior of four neutral organoferrocene ligands that differ in the number of monosaccharide and ferrocene units. The presence of a carbohydrate moiety results in increased hydrophilicity, while ferrocene units increase hydrophobicity, which significantly influences interactions with the surface, as well as with serum albumin. The adsorption of di-ferrocene ligands on the electrode surface and to serum albumin is more pronounced than that of mono-ferrocenes. Additionally, di-ferrocene ligands require dissolution in organic solvents, such as dimethyl sulfoxide, which also influences ligand-electrode and ligand-protein affinities. The conclusions of our work highlight the importance of ligand nature in determining the dissociation constant and mutual interactions with proteins, including those where ligands bind non-specifically. Electrochemical methods are suitable for studying the interactions of hydrophobic ligands with proteins because the ligands are typically present at micromolar concentrations to ensure their solubility in water. In addition, these methods exhibit high sensitivity to subtle structural changes of the protein.
蛋白质-配体相互作用对于理解生化反应和途径以及新疗法的设计至关重要。在这项工作中,我们比较了四种中性有机二茂铁配体的电化学行为,这些配体的单糖和二茂铁单位的数量不同。碳水化合物部分的存在增加了亲水性,而二茂铁单元增加了疏水性,这显著影响了与表面以及与血清白蛋白的相互作用。二茂铁配体在电极表面和对血清白蛋白的吸附比单二茂铁配体更明显。此外,二茂铁配体需要溶解在有机溶剂中,如二甲基亚砜,这也会影响配体-电极和配体-蛋白质的亲和力。我们工作的结论强调了配体性质在确定解离常数和与蛋白质相互作用中的重要性,包括那些配体非特异性结合的蛋白质。电化学方法适合研究疏水配体与蛋白质的相互作用,因为配体通常以微摩尔浓度存在,以确保其在水中的溶解度。此外,这些方法对蛋白质的细微结构变化具有很高的灵敏度。
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引用次数: 0
Molecular structure-dependent bioelectrochemical decolorization of azo dyes 偶氮染料的分子结构依赖性生物电化学脱色
IF 4.5 2区 化学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2026-01-19 DOI: 10.1016/j.bioelechem.2026.109229
Hou-Yun Yang , Xiang Geng , Zhi-Dao Quan , Li Yu , Xian-Huai Huang , Wei-Hua Li , Tong-Zhan Xue , Yang Mu
Azo dyes, containing one or more azo bonds (–N=N–), are widely used but pose environmental and health risks due to their toxicity and resistance to degradation. Bioelectrochemical systems (BESs) offer a potential approach for their reductive degradation, yet the role of molecular structure in degradation remains unclear. In this study, nine representative azo dyes were examined to access how substituent type and position affect degradation kinetics and electron transfer under controlled cathodic potentials in BESs. Electron-withdrawing substituents (e.g., –SO3, –NO2) and o−/m- substitution enhanced azo bond cleavage, while p-substitution or steric hindered degradation. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) revealed that higher reduction currents and lower charge-transfer resistance correlated with faster degradation. Quantitative structure-activity relationship (QSAR) analysis identified that the –N=N– group and other molecular features such as atom count, are key determinants of azo dyes removal. Experimental and theoretical calculations showed that molecular structure regulates the electron transfer efficiency from electrode to dye by affecting the electron density and steric hindrance of the azo bond, thereby determining degradation kinetics. This study deepened the influence of the molecular structure on azo dyes bioelectrochemical removal, and provided optimized guidance for the treatment of wastewater containing azo dyes by BESs.
偶氮染料含有一个或多个偶氮键(- N=N -),被广泛使用,但由于其毒性和耐降解性而构成环境和健康风险。生物电化学系统(BESs)为其还原性降解提供了一种潜在的途径,但分子结构在降解中的作用尚不清楚。在本研究中,研究了9种具有代表性的偶氮染料,以了解取代基类型和位置如何影响BESs中受控阴极电位下的降解动力学和电子转移。吸电子取代基(如- so3−,- no2)和o−/m-取代促进偶氮键的裂解,而p-取代或位位取代阻碍降解。循环伏安法(CV)和电化学阻抗谱法(EIS)表明,较高的还原电流和较低的电荷转移电阻与较快的降解相关。定量构效关系(QSAR)分析表明- N=N -基团和其他分子特征,如原子数,是偶氮染料去除的关键决定因素。实验和理论计算表明,分子结构通过影响偶氮键的电子密度和位阻来调节从电极到染料的电子转移效率,从而决定降解动力学。本研究深化了分子结构对偶氮染料生物电化学去除的影响,为BESs处理含偶氮染料废水提供优化指导。
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引用次数: 0
Characterizing human endorphins with fast-scan cyclic voltammetry and carbon fiber microelectrodes 用快速扫描循环伏安法和碳纤维微电极表征人内啡肽。
IF 4.5 2区 化学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2026-01-14 DOI: 10.1016/j.bioelechem.2026.109226
Cam Abdullaeva , Daniel Coughlin , Nadiah Alyamni , Alexander G. Zestos
Endorphins are three proteins that belong to a family of neuropeptides that regulate pain perception, mood, and immune function by targeting opioid receptors. The biological role of ꞵ-endorphin is well studied, but α- and γ-endorphins are less understood. By creating more fast and reliable methods of detection, we can progress towards determining the physiological role of each endorphin. Carbon fiber microelectrodes (CFMEs) are promising sensors for biomolecule detection as they are small, cheap sensors that can target specific brain regions. Fast-scan cyclic voltammetry (FSCV) is an electroanalytical technique, often coupled with CFMEs, that has been used to measure a variety of neurotransmitters (NTs) and neuropeptides. This method is of interest due to its exceptionally high temporal resolution, but it is also relatively affordable, minimally invasive, and biocompatible. Because the endorphins contain tyrosine, they can be easily measured with FSCV using a modified sawhorse waveform (MSW). Endorphins were detected at as low as nanomolar concentrations with high stability, exhibiting a mixed adsorption- and diffusion-controlled mechanism, and can be co-detected with small molecule NTs such as dopamine (DA). ꞵ-Endorphins saturated the electrode quicker due to its bulkier size, and the CFME was found to be significantly more sensitive to α-endorphin than γ-endorphin. Finally, we detected endorphins in brain samples for proof of principle analysis of the assay.
内啡肽是属于神经肽家族的三种蛋白质,通过靶向阿片受体来调节疼痛感知、情绪和免疫功能。ꞵ-内啡肽的生物学作用研究得很好,但α-和γ-内啡肽了解较少。通过创造更快速、更可靠的检测方法,我们可以在确定每种内啡肽的生理作用方面取得进展。碳纤维微电极(CFMEs)是一种很有前途的生物分子检测传感器,因为它们体积小,价格便宜,可以瞄准特定的大脑区域。快速扫描循环伏安法(FSCV)是一种电分析技术,通常与CFMEs结合使用,已被用于测量各种神经递质(nt)和神经肽。这种方法因其极高的时间分辨率而引起人们的兴趣,但它也相对便宜,微创且具有生物相容性。因为内啡肽含有酪氨酸,所以它们可以很容易地用FSCV使用改进的锯木架波形(MSW)来测量。内啡肽可以在低至纳摩尔浓度下检测到,具有高稳定性,表现出混合的吸附和扩散控制机制,并且可以与小分子NTs(如多巴胺(DA))共同检测。ꞵ-内啡肽由于其体积较大而更快地饱和电极,并且发现CFME对α-内啡肽的敏感性明显高于γ-内啡肽。最后,我们在脑样品中检测到内啡肽,以证明该试验的原理分析。
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引用次数: 0
RNA aptamer-modified gold-plated carbon fiber microelectrodes for selective dopamine sensing RNA适体修饰的镀金碳纤维微电极选择性多巴胺传感。
IF 4.5 2区 化学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2026-01-14 DOI: 10.1016/j.bioelechem.2026.109225
Christian Meinert Bache , Michael E.J. López Mujica , Stepan Shipovskov , Andrew Ewing , Elena E. Ferapontova
Specific electroanalysis of neurotransmitters in the brain, bloodstream, cerebrospinal fluid (CSF), or at the cellular level critically depends on the availability of miniaturized electrodes for aptasensing. Yet, with electrode miniaturization, sensitivity of analysis and limits of detection (LOD) can be compromised. Here, we adapted the RNA-aptamer-based macroelectrode assay for dopamine to the microelectrode format, by using gold-plated carbon fiber microelectrodes (CFE), modified via thiol chemistry with cysteamine and an RNA aptamer, for specific dopamine detection. The sensitivity of analysis with gold-plated cylindrical microelectrodes improved 90-fold, to 9.75 μA μM−1 cm−2 (at +0.100 V) vs. 108 nA μM−1 cm−2 (at optimal +0.185 V) shown with gold disk macroelectrodes, with LOD being 60 and 100 nM, in PBS and in artificial CSF, respectively. Yet, epinephrine interfered at 0.1 V. At 0.05 V, the sensitivity dropped to 4.62 μA μM−1 cm−2 but the RNA-aptamer/cysteamine-modified CFEs demonstrated excellent selectivity for dopamine over epinephrine, norepinephrine, L-DOPA, DOPAC, and uric and ascorbic acids. These findings suggest a straightforward strategy for constructing biospecific aptamer-based microelectrodes. However, in matrices more complex than CSF, such as serum, dopamine oxidation was inhibited. Therefore, effective monitoring of dopamine levels in blood using aptamer microelectrodes will likely require the use of protective membranes.
脑、血流、脑脊液(CSF)或细胞水平的神经递质特异性电分析,严重依赖于适体感应的小型化电极的可用性。然而,随着电极的小型化,分析的灵敏度和检测限(LOD)可能会受到损害。在这里,我们将基于RNA适配体的多巴胺大电极检测方法调整为微电极形式,使用镀金碳纤维微电极(CFE),通过巯基化学与半胱胺和RNA适配体修饰,用于特异性多巴胺检测。在PBS和人工CSF中,镀金圆柱形微电极的灵敏度分别为9.75 μA μM-1 cm-2 (+0.100 V)和108 nA μM-1 cm-2(最优+0.185 V), LOD分别为60 nM和100 nM,提高了90倍。然而,肾上腺素在0.1 V时起干扰作用。在0.05 V下,灵敏度降至4.62 μA μM-1 cm-2,但rna适体/半胱氨酸修饰的CFEs对多巴胺的选择性优于肾上腺素、去甲肾上腺素、左旋多巴、多巴酸、尿酸和抗坏血酸。这些发现为构建生物特异性适配体微电极提供了一种简单的策略。然而,在比脑脊液更复杂的基质中,如血清,多巴胺氧化被抑制。因此,使用适体微电极有效监测血液中的多巴胺水平可能需要使用保护膜。
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引用次数: 0
期刊
Bioelectrochemistry
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