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Cu2(V2O7)-rGO Engineered Sensor for the Electrochemical Determination of Antipsychotic drug, Pimozide 用于电化学检测抗精神病药物匹莫齐特的 Cu2(V2O7)-rGO 工程传感器
IF 2.7 4区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2024-09-27 DOI: 10.1007/s12678-024-00895-6
Karuna Korgaonkar, Naveenkumar P. Agadi, J. Seetharamappa

A unique and irregular form distorted Cu2(V2O7) sphere with crumbled sheets of rGO nanocomposite was developed as a sensor over a glassy carbon electrode (GCE). It showed a higher sensitivity for an antipsychotic drug, pimozide (PMZ). Voltammetric techniques were used to investigate the electrochemical behavior of PMZ. The formation of Cu2(V2O7)-rGO nanocomposite was confirmed by X-ray diffraction analysis. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) were used to examine the surface morphology and its properties. Cyclic voltammetric studies revealed that PMZ displayed intense electrocatalytic activity and exhibited an electro-oxidation peak at the modified electrode. The modified electrode possessed unique qualities such as fast electron transfer ability, repeatability, and reproducibility. The proposed differential pulse voltammetric (DPV) and square wave voltammetric (SWV) methods showed linearity in the concentration range of 5.12 × 10−9 M to 3.06 × 10−4 M and 1.02 × 10−9 M to 5.30 × 10−4 M, respectively. The limit of detection (LOD) was calculated to be 1.70 × 10−10 M and 8.52 × 10−11 M, while the limit of quantification (LOQ) was found to be 5.66 × 10−10 M and 2.84 × 10−10 M, respectively, for DPV and SWV methods. The developed methods were successfully applied for the determination of PMZ in pharmaceutical formulations and human urine samples.

Graphical Abstract

研究人员在玻璃碳电极(GCE)上开发了一种独特的不规则变形 Cu2(V2O7)球体,球体上有碎裂的 rGO 纳米复合材料片,作为传感器。它对抗抑郁药物匹莫齐特(PMZ)具有更高的灵敏度。研究人员采用伏安法研究了匹莫齐(PMZ)的电化学行为。X 射线衍射分析证实了 Cu2(V2O7)-rGO 纳米复合材料的形成。扫描电子显微镜(SEM)和原子力显微镜(AFM)用于研究其表面形貌及其特性。循环伏安研究表明,PMZ 具有很强的电催化活性,并在修饰电极上出现了电氧化峰。改性电极具有快速电子传递能力、可重复性和再现性等独特品质。所提出的微分脉冲伏安法(DPV)和方波伏安法(SWV)分别在 5.12 × 10-9 M 至 3.06 × 10-4 M 和 1.02 × 10-9 M 至 5.30 × 10-4 M 的浓度范围内呈线性关系。经计算,DPV 和 SWV 方法的检出限(LOD)分别为 1.70 × 10-10 M 和 8.52 × 10-11 M,定量限(LOQ)分别为 5.66 × 10-10 M 和 2.84 × 10-10 M。所建立的方法成功地应用于药物制剂和人体尿样中PMZ的测定。 图文摘要
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引用次数: 0
Green Synthesis of Cobalt Oxide Decorated Chitosan Substrates for Electrochemical Detection of Nitrite and Hydrogen Evolution Reactions 用于亚硝酸盐和氢进化反应电化学检测的氧化钴装饰壳聚糖基底的绿色合成技术
IF 2.7 4区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2024-09-26 DOI: 10.1007/s12678-024-00889-4
Mahmoud A. Hefnawy, Rewaida Abdel-Gaber, Sobhi M. Gomha, Magdi E. A. Zaki, Shymaa S. Medany

The Co2O3-Chitosan composite (Co@Chitosan) nanoparticles were synthesized through a green approach. The composite under investigation was characterized by various analytical methods, including scanning electron microscopy (SEM), transmitted electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and atomic force microscope (AFM) confirming the preparation step. The modified composite’s performance was evaluated for its potential applications in nitrite sensing and hydrogen production by utilizing diverse electrochemical methodologies. The Co2O3-Chitosan that has been modified exhibits a linear detection range of 0.25–100 µM and a limit of detection (LOD) of 0.117 µM with a response time of approximately 5 s using the amperometry technique. Furthermore, the utilization of Co2O3-Chitosan composite as a proficient catalyst for hydrogen generation in an alkaline environment was implemented. The electrode exhibited enduring stability in fuel generation and heightened energy safeguarding. The current density of the electrode was observed to attain a value of (upeta) 50 at − 0.55 and − 0.43 V (versus RHE) for Co2O3 and Co@Chitosan, respectively. The study investigated the durability of electrodes during extended periods of constant potential chronoamperometry lasting 6 h. The Co2O3 and Co@Chitosan exhibited a reduction in initial current by 11% and 7%, respectively.

Graphical Abstract

通过绿色方法合成了 Co2O3-壳聚糖复合纳米粒子(Co@壳聚糖)。通过扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X 射线光电子能谱(XPS)和原子力显微镜(AFM)等多种分析方法对所研究的复合材料进行了表征,确认了制备步骤。通过采用不同的电化学方法,对改性复合材料在亚硝酸盐传感和制氢方面的潜在应用进行了性能评估。使用安培计技术,经修饰的 Co2O3-Citosan 的线性检测范围为 0.25-100 µM,检测限 (LOD) 为 0.117 µM,响应时间约为 5 秒。此外,还将 Co2O3-Citosan 复合材料用作在碱性环境中制氢的高效催化剂。该电极在燃料生成方面表现出持久的稳定性和更高的能量保障。据观察,Co2O3 和 Co@ 壳聚糖电极的电流密度分别在 - 0.55 和 - 0.43 V(相对于 RHE)时达到 50。该研究调查了电极在持续 6 小时的恒电位计时法中的耐用性。Co2O3 和 Co@ 壳聚糖的初始电流分别降低了 11% 和 7%。
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引用次数: 0
Manganese Oxide Applications in Sulfonamides Electrochemical, Thermal and Optical Sensors: A Short Review 氧化锰在磺胺电化学、热学和光学传感器中的应用:简评
IF 2.7 4区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2024-09-25 DOI: 10.1007/s12678-024-00890-x
Pheladi L. Mokaba, Nolwazi T. Gazu, Marang L. Makinita, Nomcebo H. Mthombeni, Pinkie Ntola, Usisipho Feleni

In recent years, the development of highly sensitive and selective electrochemical sensors has been a pivotal area of research, driven by the growing demand for environmental monitoring and industrial process control. Among various materials investigated for sensor applications, manganese oxide (MnO2) nanoparticles have garnered significant attention due to their excellent electrochemical properties, environmental friendliness, and natural abundance. Critical analyses of the synthesis of MnO2 using different techniques such as hydrothermal method, chemical precipitation, and sol–gel process which allows for the fine-tuning of particle size and morphology while enhancing the electrochemical sensing capabilities have been reviewed. The review also provides a comprehensive overview of the recent advancement evaluation of manganese oxide-based electrodes for detecting sulfonamides and other analytes in water across diverse matrices. This paper sets the stage for a comprehensive exploration of the synthesis methods and application areas of MnO2 nanoparticles in electrochemical sensors, highlighting their role in advancing sensor technology and their impact on various sectors.

Graphical Abstract

近年来,在环境监测和工业过程控制需求不断增长的推动下,高灵敏度和高选择性电化学传感器的开发已成为一个关键的研究领域。在研究的各种传感器应用材料中,纳米氧化锰(MnO2)颗粒因其优异的电化学特性、环境友好性和天然丰富性而备受关注。本综述对采用水热法、化学沉淀法和溶胶-凝胶法等不同技术合成 MnO2 的关键技术进行了分析,这些技术可对颗粒大小和形态进行微调,同时增强电化学传感能力。综述还全面概述了最近对基于氧化锰的电极在不同基质的水中检测磺胺类药物和其他分析物的进展评估。本文为全面探讨电化学传感器中二氧化锰纳米粒子的合成方法和应用领域奠定了基础,突出了它们在推动传感器技术发展方面的作用及其对各行各业的影响。
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引用次数: 0
An Ultrasensitive Dopamine Electrochemical Sensor Based on PVP/rGO-MWCNT Composites 基于 PVP/rGO-MWCNT 复合材料的超灵敏多巴胺电化学传感器
IF 2.7 4区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2024-09-20 DOI: 10.1007/s12678-024-00894-7
Yixuan Jiang, Dandan Luo, Saiwen Liu, Jin Zhang, Wei Meng, Chao Chen

Dopamine (DA) is a neurotransmitter secreted by the brain that plays a variety of roles in the central nervous system. An imbalance in dopamine can cause a range of disease symptoms and negative effects, such as Parkinson’s disease and arrhythmia. Detecting DA accurately and rapidly is therefore crucial for medical diagnosis and disease prevention. In this study, PVP and rGO-MWCNTs were encapsulated via a hydrothermal method to form a composite material. The composite was then characterized by scanning electron microscopy (SEM). The three materials were combined, and on this basis, a new DA electrochemical sensor was constructed. Notably, the high specific surface area and high conductivity of the rGO-MWCNTs cooperate with the amphiphilic and stable dispersion of PVP, which further improves the electrocatalytic activity of the sensor for DA. Under optimal conditions, the DA content is detected within a wide range and has a low detection limit, which can be explained by the electrochemical redox process of the sensor. In addition, the sensor shows satisfactory recovery and accuracy in detecting the DA content in real human serum samples via the standard addition method.

多巴胺(DA)是大脑分泌的一种神经递质,在中枢神经系统中发挥着多种作用。多巴胺失衡可导致一系列疾病症状和负面影响,如帕金森病和心律失常。因此,准确、快速地检测多巴胺对医疗诊断和疾病预防至关重要。在本研究中,通过水热法将 PVP 和 rGO-MWCNTs 包裹成一种复合材料。然后用扫描电子显微镜(SEM)对该复合材料进行表征。在此基础上,构建了一种新型 DA 电化学传感器。值得注意的是,rGO-MWCNTs 的高比表面积和高电导率与 PVP 的两亲性和稳定分散性相互配合,进一步提高了传感器对 DA 的电催化活性。在最佳条件下,DA 含量的检测范围广,检测限低,这可以用传感器的电化学氧化还原过程来解释。此外,通过标准添加法检测真实人体血清样品中的 DA 含量时,该传感器显示出令人满意的回收率和准确性。
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引用次数: 0
Electrochemical Conversion of Triclosan as a Greener Alternative to Chemical Oxidation 电化学转化三氯生作为化学氧化的绿色替代品
IF 2.7 4区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2024-09-20 DOI: 10.1007/s12678-024-00892-9
Tyra Lewis, Stephanie Gao, Deanna Haas, Sanela Martic

Triclosan, like many other aromatic halides, plays an important role industrially and inevitably ends up in the environment. Chemical treatments have effectively mitigated the presence of such chemicals, through using harsh oxidizing treatments, which are not without issues. A milder and greener alternative, such as an electrochemical method, is needed for the mitigation of compounds, such as triclosan. Herein, we evaluated triclosan treatment via electrochemical cycling and compared it to a traditional chemical oxidative process. Cyclic voltammetry was carried out using a three-electrode cell containing glassy carbon, silver wire, and platinum wire in organic solvent. Electrochemical cycling revealed 6 × greater triclosan conversion compared to traditional chemical oxidation reaction, as monitored by UV–Vis spectroscopy. In terms of reaction product selectivity, the chemical and electrochemical reactions yielded the oxidized triclosan and an ether cleavage product, dichlorophenol, as determined by gas chromatography–mass spectrometry. Of note, the chemical oxidation yielded the chlorinated re-dimerization side product, which was not observed during electrochemical cycling, which is beneficial, as such products have to be degraded again. Overall, our findings indicate that electrochemical methods offer significant advantages over traditional organic methods, such as product selectivity, relative conversion, and greener operation. In addition, electrochemical approaches offer tunability, such as electrode material, electrolyte, solvent, potential, or current applied, all of which may be integrated into a more efficient environmental application.

Graphical Abstract

三氯生和许多其他芳香族卤化物一样,在工业中发挥着重要作用,并不可避免地最终进入环境。化学处理方法通过使用苛刻的氧化处理来有效缓解此类化学物质的存在,但这种方法并非没有问题。我们需要一种更温和、更环保的替代方法,如电化学方法,来减轻三氯生等化合物的危害。在此,我们评估了通过电化学循环处理三氯生的方法,并将其与传统的化学氧化工艺进行了比较。循环伏安法是在有机溶剂中使用包含玻璃碳、银丝和铂丝的三电极电池进行的。通过紫外可见光谱监测,电化学循环显示三氯生的转化率是传统化学氧化反应的 6 倍。从反应产物的选择性来看,化学反应和电化学反应都产生了氧化的三氯生和醚裂解产物二氯苯酚(通过气相色谱-质谱法测定)。值得注意的是,化学氧化产生的氯化再二聚化副产物在电化学循环过程中没有观察到,这是有益的,因为这类产品必须再次降解。总之,我们的研究结果表明,与传统的有机方法相比,电化学方法具有显著的优势,如产品选择性、相对转化率和更环保的操作。此外,电化学方法还具有可调性,如电极材料、电解质、溶剂、电位或所应用的电流,所有这些都可以整合到更高效的环境应用中。
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引用次数: 0
Exfoliated 2-D Graphitic Carbon Nitride Nanosheets for Electrochemical Detection of the Antiviral Drug Valganciclovir 用于电化学检测抗病毒药物缬更昔洛韦的剥离二维氮化石墨碳纳米片
IF 2.7 4区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2024-08-27 DOI: 10.1007/s12678-024-00887-6
Madasu Sreenivasulu, Shweta J. Malode, Abdullah N. Alodhayb, Nagaraj P. Shetti

The research focuses on creating an innovative graphitic carbon nitride electrochemical sensor (g-C3N4) for the precise and sensitive detection of the antiviral medication valganciclovir (VCR), also known as Valcyte. VCR is an antiviral medication used to treat diseases, including CMV retinitis, and to protect transplant patients against CMV infection by stopping the virus from spreading. This drug is typically given to patients with weak immune systems, HIV/AIDS, and organ transplants. Though VCR provides numerous benefits, it must be administered with caution as it can cause allergic reactions and renal damage. A modified carbon paste electrode called g-C3N4/CPE has demonstrated remarkable electrocatalytic activity in oxidizing varying levels of chlorine radiation. Various methods were employed to characterize the created g-C3N4, including field emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HR-TEM), X-ray diffraction (XRD), and Raman and Fourier transform infrared (FT-IR). The sensor has a detection range of 1 to 16 µM, which makes it more sensitive than traditional drug detection techniques. It can detect as low as 0.88 × 10−8 M under ideal experimental conditions. The sensor’s ability to identify VCR using g-C3N4 was tested using amperometric i-t curve analysis. The EIS (electrochemical impedance spectroscopy) was employed to investigate the electrochemical features of many electrodes. The comparable Rct values were 3114 Ω, 13,770 Ω, and 3794 Ω for g-C3N4/CPE, bare GCE, and bare CPE, respectively. During the test, various commonly used interferents and drugs were introduced to the VCR solution to examine the influence of foreign interferents on the outcomes. Various electrokinetic factors were examined to explore the electrochemical behavior of VCR. Environmental monitoring, drug analysis, and clinical diagnostics benefited from successfully using the generated g-C3N4/CPE. Additionally, it can play a vital role in creating new and efficient methods for antiviral drug VCR determination.

Graphical Abstract

这项研究的重点是创建一种创新的石墨氮化碳电化学传感器(g-C3N4),用于精确灵敏地检测抗病毒药物缬更昔洛韦(VCR),也称为 Valcyte。VCR 是一种抗病毒药物,用于治疗包括 CMV 视网膜炎在内的疾病,并通过阻止病毒传播来保护移植患者免受 CMV 感染。这种药物通常用于免疫系统较弱的患者、艾滋病毒/艾滋病患者和器官移植患者。虽然 VCR 有很多好处,但必须谨慎使用,因为它会引起过敏反应和肾脏损伤。一种名为 g-C3N4/CPE 的改性碳浆电极在氧化不同程度的氯辐射时表现出显著的电催化活性。研究人员采用了多种方法对所制备的 g-C3N4 进行表征,包括场发射扫描电子显微镜 (FE-SEM)、高分辨率透射电子显微镜 (HR-TEM)、X 射线衍射 (XRD)、拉曼光谱和傅立叶变换红外光谱 (FT-IR)。该传感器的检测范围为 1 至 16 µM,比传统的药物检测技术更加灵敏。在理想的实验条件下,它可以检测到 0.88 × 10-8 M 的低浓度。使用安培 i-t 曲线分析法测试了传感器利用 g-C3N4 识别 VCR 的能力。EIS (电化学阻抗光谱)被用来研究许多电极的电化学特征。g-C3N4/CPE 、裸 GCE 和裸 CPE 的可比 Rct 值分别为 3114 Ω、13,770 Ω 和 3794 Ω。在测试过程中,向 VCR 溶液中引入了各种常用干扰物和药物,以考察外来干扰物对测试结果的影响。研究了各种电动因素,以探索 VCR 的电化学行为。成功使用所生成的 g-C3N4/CPE 将有助于环境监测、药物分析和临床诊断。此外,它还能在创建新型高效的抗病毒药物 VCR 检测方法方面发挥重要作用。
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引用次数: 0
Simultaneous Measurement of Uric Acid, Guanine, and Adenine Using AgNP@Mn-MOFs Composite-Based Electrochemical Sensor at Trace Level: Application to Blood, Urine, and DNA Sample Matrices 利用基于 AgNP@Mn-MOFs 复合材料的痕量级电化学传感器同时测量尿酸、鸟嘌呤和腺嘌呤:在血液、尿液和 DNA 样品基质中的应用
IF 2.7 4区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2024-08-26 DOI: 10.1007/s12678-024-00885-8
Supritha K. M., Pandurangappa M.

A composite containing silver nanoparticles embedded Mn-MOFs has been synthesized using a simple solvothermal route. The composite-modified electrode has been utilized in the simultaneous measurement of purine base pairs of DNA [guanine (GU), adenine (AD)] and uric acid (UA). The morphology of the composite has been studied by scanning electron microscopy which revealed that the Ag nanoparticles homogeneously get distributed over the layers of Mn-MOFs. The thermal stability of the composite has been studied by thermogravimetric analysis. BET adsorption–desorption isotherm study revealed the large surface area and mesoporous nature of the composite. The electrochemical behavior of the composite material has been studied through impedance spectroscopy, cyclic voltammetry (CV), and square wave voltammetry (SWV) techniques to decipher the redox nature of it towards the target analytes like GU, AD, and UA. Each of these analytes has displayed a distinct catalytic oxidative signal with well-resolved peaks during their simultaneous measurement. The linearity obtained for UA, GU, and AD by square wave voltammetry is in the concentration range of 0.5–280 µM with a limit of detection of 64.49, 78.84, and 125.33 nM, respectively. The composite-modified electrode has been successfully applied to real sample matrices like human serum, urine, and commercially available fish sperm DNA samples. The fabricated sensor showed very good responses to these analytes from real sample matrices with prolonged stability and reproducibility.

Graphical Abstract

我们采用简单的溶热法合成了一种嵌入 Mn-MOFs 的银纳米粒子复合材料。复合材料修饰的电极被用于同时测量 DNA 的嘌呤碱基对(鸟嘌呤 (GU) 和腺嘌呤 (AD))和尿酸 (UA)。通过扫描电子显微镜对复合材料的形态进行了研究,结果表明银纳米粒子均匀地分布在 Mn-MOFs 层上。通过热重分析研究了复合材料的热稳定性。BET 吸附-解吸等温线研究显示了复合材料的大表面积和介孔性质。通过阻抗光谱、循环伏安法(CV)和方波伏安法(SWV)技术对复合材料的电化学行为进行了研究,以破译它对 GU、AD 和 UA 等目标分析物的氧化还原性质。在同时测量过程中,每种分析物都显示出明显的催化氧化信号,峰值分明。用方波伏安法测量 UA、GU 和 AD 的线性范围为 0.5-280 µM,检测限分别为 64.49、78.84 和 125.33 nM。复合修饰电极已成功应用于实际样品基质,如人血清、尿液和市售鱼类精子 DNA 样品。所制造的传感器对真实样品基质中的这些分析物显示出非常好的响应,并且具有长期的稳定性和可重复性。
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引用次数: 0
Hofmann-Type Coordination Polymer-Derived Nickel Phosphide Nanoplates for Electrocatalytic Oxidation and Determination of Insulin 用于电催化氧化和胰岛素测定的霍夫曼型配位聚合物衍生磷化镍纳米板
IF 2.7 4区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2024-08-24 DOI: 10.1007/s12678-024-00888-5
Mahmoud Roushani, Hadi Hosseini, Kowsar Maleki, Farzaneh Mohammadi

It is of key importance to design efficient insulin electrocatalysts based on nonprecious noble metal-free. However, the design of advanced nanostructured based metal phosphides is scarcely reported. In this work, for the first time, a novel insulin sensor based on Ni2P electrode materials with nanoplate structure was designed. In this regard, Hofmann-type coordination polymers (HCPs) based on Ni(H2O)2[Ni(CN)4]·H2O (Ni–Ni HCP) were prepared and used as precursors to the preparation of Ni2P. The unique layer structure of Ni–Ni HCP precursors can lead to the preparation of Ni2P nanoplates with large surface areas, high availability of active catalytic centers, and abundant interior space for fast diffusion and boosted reaction kinetics. The electrochemical results showed that the Ni2P nanoplates offer excellent capability toward insulin oxidation in 0.1 M NaOH electrolyte solution. Moreover, a proper linear relationship was obtained between insulin concentrations and the current responses in the range of 10 to 100 pM with the detection limit of 3 pM and with good capability for the determination of insulin in the human blood serum sample. This work offers a rational method for the structure engineering of Ni2P nanoplates using HCP precursors, which can lead to the fabrication of high-performance insulin sensor.

Graphical Abstract

设计基于非贵金属的高效胰岛素电催化剂至关重要。然而,先进的基于纳米结构的金属磷化物的设计却鲜有报道。在这项工作中,首次设计了一种基于纳米板结构 Ni2P 电极材料的新型胰岛素传感器。为此,研究人员制备了基于 Ni(H2O)2[Ni(CN)4]-H2O 的霍夫曼型配位聚合物(HCP)(Ni-Ni HCP),并将其用作制备 Ni2P 的前驱体。Ni-Ni HCP 前驱体独特的层状结构可制备出具有大表面积、高活性催化中心可用性和丰富内部空间的 Ni2P 纳米板,从而快速扩散并提高反应动力学。电化学结果表明,Ni2P 纳米板在 0.1 M NaOH 电解质溶液中具有出色的胰岛素氧化能力。此外,在 10 至 100 pM 范围内,胰岛素浓度与电流响应之间呈适当的线性关系,检测限为 3 pM,具有良好的测定人血清样品中胰岛素的能力。这项工作为利用 HCP 前驱体进行 Ni2P 纳米板结构工程提供了一种合理的方法,从而可以制备高性能的胰岛素传感器。
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引用次数: 0
In Situ Synthesized Gold-Conjugated Hemoglobin-Cu3 (PO4)2 Hybrid Nanopetals for Enhanced Electrochemical Detection of H2O2 用于增强 H2O2 电化学检测的原位合成金共轭血红蛋白-Cu3 (PO4)2 混合纳米金属
IF 2.7 4区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2024-08-17 DOI: 10.1007/s12678-024-00886-7
Mallesh Santhosh, Tusan Park

In situ synthesis of novel hybrid organic–inorganic nanopetals (HNPs) of Copper (Cu2+) and gold-conjugated hemoglobin (Au@Hb) is reported. The presence of Au within the protein matrix prevents the formation of a flower-like assembly of the formed nanopetals of Au@Hb and Cu2+ via the co-precipitation method. Morphological, chemical, and electrocatalytic activities of in situ synthesized Au@Hb-Cu HNPs were examined systematically. The hybrid nanopetal (Au@Hb-Cu HNP)-modified screen-printed PET electrodes show enhanced electrocatalytic activity toward the oxidation of H2O2 compared to electrodes modified with Hb-copper hybrid nanoflowers (Hb-Cu HNFs) without Au conjugation. The proposed biosensor exhibits excellent electrochemical performance with broad linear responses over a H2O2 concentration ranging from 5 to 1000 µM (R2 = 0.99) and showed a lower detection limit of 1.46 µM at 0.30 V vs. pseudo Ag/AgCl. Enhanced electrochemical performance is attributed to heterogeneous active sites over hybrid nanopetal surfaces. Moreover, the hybrid nanopetal–modified electrodes showed excellent stability and anti-interference performance in the presence of ascorbic acid, uric acid, fructose, and glucose. These results demonstrate that Au@Hb-Cu HNPs offer a better and more promising alternative for the electrochemical detection of H2O2 sensitively.

Graphical Abstract

报告了铜(Cu2+)和金共轭血红蛋白(Au@Hb)原位合成新型有机-无机杂化纳米金属(HNPs)的过程。蛋白质基质中金的存在阻止了通过共沉淀法形成的 Au@Hb 和 Cu2+ 纳米金属的花状组装。研究人员系统地考察了原位合成的 Au@Hb-Cu HNPs 的形态、化学和电催化活性。与不添加金的铅铜杂化纳米花(Hb-Cu HNFs)修饰的电极相比,杂化纳米金属(Au@Hb-Cu HNP)修饰的丝网印刷 PET 电极对 H2O2 的氧化具有更强的电催化活性。所提出的生物传感器具有优异的电化学性能,在 H2O2 浓度为 5 到 1000 µM 的范围内具有广泛的线性响应(R2 = 0.99),在 0.30 V 电压下与假银/氯化银相比,检测限低至 1.46 µM。电化学性能的增强归功于混合纳米金属表面的异质活性位点。此外,混合纳米金属修饰的电极在抗坏血酸、尿酸、果糖和葡萄糖存在下表现出优异的稳定性和抗干扰性能。这些结果表明,Au@Hb-Cu HNPs 为电化学灵敏检测 H2O2 提供了一种更好、更有前景的替代方法。
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引用次数: 0
A Theoretical Inquest of Atomically Injected Ni-Atom over Graphene and Analogous Substrates for Hydrogen Evolution Reaction 石墨烯和类似基底上原子注入镍原子进行氢气进化反应的理论探索
IF 2.7 4区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2024-08-03 DOI: 10.1007/s12678-024-00884-9
Hemang P. Tanna, Prafulla K. Jha

A rational catalyst for electrocatalytic hydrogen evolution reaction (HER) is a long-standing challenge that researchers are confronted with. In view of this, tiny particles of transition metals (TMs) spread over a substrate acting as an active site for the reaction, scientifically known as single-atom catalysts is seen as an efficacious way for designing an efficient catalyst. Herein, we comprehensively investigated catalytic activity of Ni-atoms spread over various kinds of two-dimensional (2D) substrates like graphene, AlC, AlN, h-BN, BeO, and MgO (Ni@2D) towards HER using density functional theory calculations. All the considered 2D substrates have various inequivalent anchoring sites like top, hollow, bridge, and vacancy sites for Ni-atoms. So, there are total 34 anchoring sites, and we computed binding energy (E(_b)) of Ni-atom over all the sites. Having large number of configurations, we first applied a screener on stability of Ni@2D and only considered those configurations for which the E(_b) value is <(-)3.00 eV for further calculations. Out of 34, 17 configurations were falling in this range. Further, we computed the differential Gibbs free energy of H-adsorption ((Delta)G(_H)) and generated volcano plot between (Delta)G(_H) and exchange current density ((i_0)) as a prime indicators of HER activity. Then, we screened these configurations based on (Delta)G(_H) values that (|Delta)G(_H|) (le) to 0.5 eV, and out of 17, 10 systems were falling in this region. At last, we examined complete reaction profile of HER via Volmer-Heyrovsky (VH) and Volmer-Tafel (VT) mechanisms over the remaining 10 configurations, and the lowest activation energy for HER are 0.12 eV and 0.21 eV for Ni@AlN and 0.28 eV and 0.36 eV for Ni@h-BN via VT and VH mechanism, respectively. Our findings show Ni@AlN and Ni@h-BN could be a non-noble TM candidate for eco-operational HER catalyst.

摘要 为电催化氢进化反应(HER)寻找合理的催化剂是研究人员长期面临的挑战。有鉴于此,将过渡金属(TMs)的微小颗粒铺在基底上作为反应的活性位点(科学上称为单原子催化剂)被认为是设计高效催化剂的有效方法。在此,我们利用密度泛函理论计算全面研究了分布在石墨烯、AlC、AlN、h-BN、BeO 和 MgO 等各种二维(2D)基底上的镍原子(Ni@2D)对 HER 的催化活性。所有考虑的二维基底都有各种不等价的锚定位点,如顶部、空心、桥和镍原子的空缺位点。因此,总共有 34 个锚定位点,我们计算了所有位点上镍原子的结合能(E (_b ()))。由于存在大量的构型,我们首先对 Ni@2D 的稳定性进行了筛选,只考虑那些 E (_b )值为 3.00 eV 的构型进行进一步的计算。在 34 个构型中,有 17 个构型属于这一范围。此外,我们还计算了H-吸附的差分吉布斯自由能((Delta)G(_H)),并生成了(Delta)G(_H)和交换电流密度((i_0))之间的火山图,作为HER活性的主要指标。然后,我们根据 (Delta)G(_H) (le) 到 0.5 eV 的值((|Delta)G(_H|) (le))对这些配置进行了筛选,在 17 个系统中,有 10 个系统属于这一区域。最后,我们通过Volmer-Heyrovsky(VH)和Volmer-Tafel(VT)机制考察了其余10种构型的HER的完整反应曲线,通过VT和VH机制,Ni@AlN的HER最低活化能分别为0.12 eV和0.21 eV,Ni@h-BN的最低活化能分别为0.28 eV和0.36 eV。我们的研究结果表明,Ni@AlN和Ni@h-BN可以作为生态操作型HER催化剂的非贵金属候选材料。
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Electrocatalysis
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