Electroanalysis

电分析
  • 文章类型: Journal Article
    开发了一种基于导电聚吡咯掺杂碳量子点(QD)的纳米杂化修饰玻碳电极,并用于电化学检测抗组织转谷氨酰胺酶(anti-tTG)抗体。为了提高聚吡咯的导电性,载波移动性,和载流子浓度,测试了四种类型的碳纳米颗粒。此外,通过与N-羟基琥珀酰亚胺(NHS)/N-(3-二甲基氨基丙基)-N'-乙基碳二亚胺盐酸盐(EDC)交联,用PAMAM树枝状聚合物和转谷氨酰胺酶2蛋白对掺杂有QD的聚吡咯修饰的电极进行官能化。通过电化学测量(差分脉冲伏安法(DPV),阻抗谱,和X射线光电子能谱(XPS))。通过扫描电子显微镜(SEM)观察其表面特性,傅里叶变换红外(FTIR)光谱,和接触角测量。所得修饰电极具有良好的稳定性和重复性。DPV在-0.1和0.6V之间(与Ag/AgCl3MKCl参比电极)用于评估抗体与抗原(转谷氨酰胺酶2蛋白)相互作用后发生的电化学变化,检测限为0.79U/mL。如果不使用二级标签,由于这些修饰的电极特征,可以在低浓度下检测(抗tTG)抗体。
    A nanohybrid-modified glassy carbon electrode based on conducting polypyrrole doped with carbon quantum dots (QDs) was developed and used for the electrochemical detection of anti-tissue transglutaminase (anti-tTG) antibodies. To improve the polypyrrole conductivity, carrier mobility, and carrier concentration, four types of carbon nanoparticles were tested. Furthermore, a polypyrrole-modified electrode doped with QDs was functionalized with a PAMAM dendrimer and transglutaminase 2 protein by cross-linking with N-hydroxysuccinimide (NHS)/N-(3-dimethylaminopropyl)-N\'-ethylcarbodiimide hydrochloride (EDC). The steps of electrode surface modification were surveyed via electrochemical measurements (differential pulse voltammetry (DPV), impedance spectroscopy, and X-ray photoelectron spectroscopy (XPS)). The surface characteristics were observed by scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, and contact angle measurements. The obtained modified electrode exhibited good stability and repeatability. DPV between - 0.1 and 0.6 V (vs. Ag/AgCl 3 M KCl reference electrode) was used to evaluate the electrochemical alterations that occur after the antibody interacts with the antigen (transglutaminase 2 protein), for which the limit of detection was 0.79 U/mL. Without the use of a secondary label, (anti-tTG) antibodies may be detected at low concentrations because of these modified electrode features.
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  • 文章类型: Journal Article
    可3D打印的复合材料已成为用于设计和制造电化学传感器的有吸引力的选择。然而,为了确保电极/电解质界面处的正确电荷转移动力学,通常需要激活,该步骤包括去除聚合物以揭示导电纳米填料。在这项工作中,我们提出了一种新的有效方法,用于使用微波辐射活化由填充炭黑(CB-PLA)的聚乳酸组成的复合材料。用于化学实验室的微波合成器(CEM,马修斯,NC,美国)被用于此目的,确定CB-PLA电极的适当活化时间是在70°C和100W的微波功率下15分钟。80W厨房微波炉的有用性也首次提出,并讨论了作为CB-PLA电极活化更可持续的方法。已经确定在厨房微波炉中10分钟足以激活电极。通过电化学技术测定微波活化电极的电化学性质,并使用扫描电子显微镜(SEM)对其形貌进行了表征,拉曼光谱,和接触角测量。这项研究证实,在微波活化过程中,PLA分解以露出导电炭黑填料。我们提供了3D打印的厨房微波炉激活的实用性的概念验证,在电解质水溶液中对乙酰氨基酚电分析中的独立式电化学电池(FSEC)。我们建立了使用伏安法检测对乙酰氨基酚的线性令人满意的极限,范围从1.9μM到1mM,检测限(LOD)为1.31μM。
    3D-printable composites have become an attractive option used for the design and manufacture of electrochemical sensors. However, to ensure proper charge-transfer kinetics at the electrode/electrolyte interface, activation is often required, with this step consisting of polymer removal to reveal the conductive nanofiller. In this work, we present a novel effective method for the activation of composites consisting of poly(lactic acid) filled with carbon black (CB-PLA) using microwave radiation. A microwave synthesizer used in chemical laboratories (CEM, Matthews, NC, USA) was used for this purpose, establishing that the appropriate activation time for CB-PLA electrodes is 15 min at 70 °C with a microwave power of 100 W. However, the usefulness of an 80 W kitchen microwave oven is also presented for the first time and discussed as a more sustainable approach to CB-PLA electrode activation. It has been established that 10 min in a kitchen microwave oven is adequate to activate the electrode. The electrochemical properties of the microwave-activated electrodes were determined by electrochemical techniques, and their topography was characterized using scanning electron microscopy (SEM), Raman spectroscopy, and contact-angle measurements. This study confirms that during microwave activation, PLAs decompose to uncover the conductive carbon-black filler. We deliver a proof-of-concept of the utility of kitchen microwave-oven activation of a 3D-printed, free-standing electrochemical cell (FSEC) in paracetamol electroanalysis in aqueous electrolyte solution. We established satisfactory limits of linearity for paracetamol detection using voltammetry, ranging from 1.9 μM to 1 mM, with a detection limit (LOD) of 1.31 μM.
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  • 文章类型: Journal Article
    在液体活检的时代,microRNAs成为癌症早期诊断和预后的有希望的候选者。为疾病的发展提供有价值的见解。在所有现有的分析方法中,即使传统的方法如核酸扩增方法具有高灵敏度的优点,它们不能在现场使用,虽然传感器可能不太敏感,尽管他们的便携性。为了提高现有电分析系统的分析性能,我们演示了一个简单的色谱纸基磁盘如何合理地提高灵敏度,取决于预浓缩循环的数量。通过使用与所选miRNA互补的亚甲基蓝(MB)修饰的单链序列(ssDNA)修饰纸质电极,开发了用于miRNA检测的纸质电化学平台。即与肺癌相关的miR-224。检测限约为。在加标的人血清样品中已获得0.6nM。为了进一步提高灵敏度,采用外部色谱蜡样纸基圆盘预浓缩样品,这已经在标准和血清溶液中得到了证明。对于每个解决方案,三个miR-224水平已经被预浓缩,获得令人满意的约降低检测限。使用简单且可持续的程序50μM。这种方法在分析和生物分析化学领域开辟了广阔的可能性,不仅可用于电化学,还可用于其他检测和转导结构。
    In the era of liquid biopsy, microRNAs emerge as promising candidates for the early diagnosis and prognosis of cancer, offering valuable insights into the disease\'s development. Among all the existing analytical approaches, even if traditional approaches such as the nucleic acid amplification ones have the advantages to be highly sensitive, they cannot be used at the point-of-care, while sensors might be poorly sensitive despite their portability. In order to improve the analytical performance of existing electroanalytical systems, we demonstrate how a simple chromatographic paper-based disk might be useful to rationally improve the sensitivity, depending on the number of preconcentration cycles. A paper-based electrochemical platform for miRNA detection has been developed by modifying a paper-based electrode with a methylene blue (MB)-modified single-stranded sequence (ssDNA) complementary to the chosen miRNA, namely miR-224 that is associated with lung cancer. A detection limit of ca. 0.6 nM has been obtained in spiked human serum samples. To further enhance the sensitivity, an external chromatographic wax-patterned paper-based disk has been adopted to preconcentrate the sample, and this has been demonstrated both in standard and in serum solutions. For each solution, three miR-224 levels have been preconcentrated, obtaining a satisfactory lowering detection limit of ca. 50 pM using a simple and sustainable procedure. This approach opens wide possibilities in the field of analytical and bioanalytical chemistry, being useful not only for electrochemistry but also for other architectures of detection and transduction.
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  • 文章类型: Journal Article
    描述了由二维导电材料(Ag@MXene)和防污环状多功能肽(CP)共同构建的传感界面。虽然Ag@MXene的大表面积加载更多的CP探针,CP与Ag@MXene结合以形成污垢屏障并确保靶向序列的结构刚性。这种策略协同地增强了生物传感器的灵敏度和抗污染性。SPR结果表明,CP与靶标的结合亲和力比防污直链多功能肽(SP)与靶标的结合亲和力高6.23倍。在10mg/mLBSA电化学污染试验中,Ag@MXene+CP(CP与Ag@MXene组合的复合传感界面)的抗污性是裸电极的30倍。设计的电化学传感器在0.1至50ng/mL的PD-L1浓度下具有良好的选择性和宽的动态响应范围。最低检测限为24.54pg/mL(S/N=3)。具有相当大的比表面积的防污二维材料,结合非直链防污多功能肽,为研究电化学传感器的灵敏度和防污性能提供了广泛的范围。
    A sensing interface co-constructed from the two-dimensional conductive material (Ag@MXene) and an antifouling cyclic multifunctional peptide (CP) is described. While the large surface area of Ag@MXene loads more CP probes, CP binds to Ag@MXene to form a fouling barrier and ensure the structural rigidity of the targeting sequence. This strategy synergistically enhances the biosensor\'s sensitivity and resistance to contamination. The SPR results showed that the binding affinity of the CP to the target was 6.23 times higher than that of the antifouling straight-chain multifunctional peptide (SP) to the target. In the 10 mg/mL BSA electrochemical fouling test, the fouling resistance of Ag@MXene + CP (composite sensing interface of CP combined with Ag@MXene) was 30 times higher than that of the bare electrode. The designed electrochemical sensor exhibited good selectivity and wide dynamic response range at PD-L1 concentrations from 0.1 to 50 ng/mL. The lowest detection limit was 24.54 pg/mL (S/N = 3). Antifouling 2D materials with a substantial specific surface area, coupled with non-straight chain antifouling multifunctional peptides, offer a wide scope for investigating the sensitivity and antifouling properties of electrochemical sensors.
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  • 文章类型: Journal Article
    生产,优化,物理化学,和用回收的聚乳酸(rPLA)制成的低成本导电添加剂制造长丝的电分析表征,蓖麻油,炭黑,报道了石墨(CB-G/PLA)。通过优化炭黑和石墨负载,电导率的最佳比例,材料成本低,并且发现可印刷性为60%炭黑至40%石墨。发现具有10重量%蓖麻油的rPLA内的最大组成是35重量%的总纳米碳负载,其产生的价格低于每个电极0.01英镑,同时仍提供优异的低温柔性和可再现印刷。由这种灯丝生产的添加剂制造的电极提供了优异的电化学性能,具有异质电子(电荷)转移速率常数,k0计算为(2.6±0.1)×10-3cms-1,而商业PLA基准为(0.46±0.03)×10-3cms-1。将添加剂制造的电极应用于β-雌二醇的测定,灵敏度为400nAµM-1,定量极限为70nM,检测限为21nM,这与文献中的其他报道相比非常好。然后将该系统应用于检测四个真实水样中的β-雌二醇,包括水龙头,瓶装,河,湖水,其中回收率在95和109%之间。由于能够以较低的材料成本(每克0.06英镑)制造高性能长丝,并通过使用更可持续的材料,如回收聚合物,生物增塑剂,和天然存在的石墨,未来,增材制造将在电分析武器库中占有永久的地位。
    The production, optimisation, physicochemical, and electroanalytical characterisation of a low-cost electrically conductive additive manufacturing filament made with recycled poly(lactic acid) (rPLA), castor oil, carbon black, and graphite (CB-G/PLA) is reported. Through optimising the carbon black and graphite loading, the best ratio for conductivity, low material cost, and printability was found to be 60% carbon black to 40% graphite. The maximum composition within the rPLA with 10 wt% castor oil was found to be an overall nanocarbon loading of 35 wt% which produced a price of less than £0.01 per electrode whilst still offering excellent low-temperature flexibility and reproducible printing. The additive manufactured electrodes produced from this filament offered excellent electrochemical performance, with a heterogeneous electron (charge) transfer rate constant, k0 calculated to be (2.6 ± 0.1) × 10-3 cm s-1 compared to (0.46 ± 0.03) × 10-3 cm s-1 for the commercial PLA benchmark. The additive manufactured electrodes were applied to the determination of β-estradiol, achieving a sensitivity of 400 nA µM-1, a limit of quantification of 70 nM, and a limit of detection of 21 nM, which compared excellently to other reports in the literature. The system was then applied to the detection of ß-estradiol within four real water samples, including tap, bottled, river, and lake water, where recoveries between 95 and 109% were obtained. Due to the ability to create high-performance filament at a low material cost (£0.06 per gram) and through the use of more sustainable materials such as recycled polymers, bio-based plasticisers, and naturally occurring graphite, additive manufacturing will have a permanent place within the electroanalysis arsenal in the future.
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  • 文章类型: Journal Article
    新烟碱,作为增长最快的一类杀虫剂,目前占全球农药市场的25%以上。它们在控制对农田构成威胁的各种害虫方面的有效性,家庭院子/花园,不能否认高尔夫球场果岭。然而,新烟碱的广泛使用导致传粉者等非靶标生物的显着下降,昆虫,和鸟。此外,潜在的慢性,这些化合物对人体健康的亚致死效应在很大程度上仍是未知的。为了解决这些紧迫的问题,探索和了解电化学传感器在检测新烟碱残留方面的能力至关重要。令人惊讶的是,尽管这个话题越来越重要,目前文献中没有全面的评论文章。因此,我们提出的综述旨在通过全面分析使用电化学方法测定新烟碱来弥补这一差距.在这篇评论文章中,我们将深入研究电化学分析的各个方面,包括电极材料的影响,采用的技术,和使用不同类型的电极机构。通过综合和分析该领域的现有研究,我们的审查将为研究人员提供有价值的见解和指导,科学家,和政策制定者一样。
    Neonicotinoids, as the fastest-growing class of insecticides, currently account for over 25% of the global pesticide market. Their effectiveness in controlling a wide range of pests that pose a threat to croplands, home yards/gardens, and golf course greens cannot be denied. However, the extensive use of neonicotinoids has resulted in significant declines in nontarget organisms such as pollinators, insects, and birds. Furthermore, the potential chronic, sublethal effects of these compounds on human health remain largely unknown. To address these pressing issues, it is crucial to explore and understand the capabilities of electrochemical sensors in detecting neonicotinoid residues. Surprisingly, despite the increasing importance of this topic, no comprehensive review article currently exists in the literature. Therefore, our proposed review aims to bridge this gap by providing a thorough analysis of the use of electrochemical methods for neonicotinoid determination. In this review article, we will delve into various aspects of electrochemical analysis, including the influence of electrode materials, employed techniques, and the different types of electrode mechanisms utilized. By synthesizing and analysing the existing research in this field, our review will offer valuable insights and guidance to researchers, scientists, and policymakers alike.
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  • 文章类型: Journal Article
    本文介绍了一种低成本的一次性传感器,用于非酒精和酒精饮料中的没食子酸(GA)检测,使用丝网印刷电池(SPC),其工作电极(在石墨中)用电合成分子印迹聚吡咯(eMIP)修饰。我们对电化学过程的初步表征表明,没食子酸(GA)在约+0.3V的电势下经历不可逆氧化。峰值电势不受eMIP膜的存在和高达20%的醇百分比(乙醇)的影响。GA测定基于利用其氧化峰的差分脉冲伏安法(DPV)分析。分析方法的校准数据和品质因数(LOD,LOQ,和线性范围)进行计算。为了验证传感器在实际矩阵中应用GA的可行性,分析了一些非酒精和酒精饮料。然后将结果与文献中报道的结果以及通过Folin-Ciocalteu方法测定的总多酚含量进行比较。在所有情况下,GA的浓度与以前在文献中发现的饮料的浓度一致。值得注意的是,该值始终低于总多酚含量,展示了传感器在区分目标分子与其他多酚存在的选择性。
    This paper presents a low-cost disposable sensor for gallic acid (GA) detection in non-alcoholic and alcoholic beverages using a screen-printed cell (SPC) whose working electrode (in graphite) is modified with electrosynthesized molecularly imprinted polypyrrole (eMIP). Our preliminary characterization of the electrochemical process shows that gallic acid (GA) undergoes irreversible oxidation at potentials of about +0.3 V. The peak potential is not affected by the presence of the eMIP film and alcohol percentages (ethanol) up to 20%. The GA determination is based on a differential pulse voltammetry (DPV) analysis leveraging its oxidation peak. The calibration data and the figures of merit of the analytical method (LOD, LOQ, and linear range) are calculated. To validate the feasibility of the sensor\'s application for the dosing of GA in real matrices, some non-alcoholic and alcoholic beverages are analyzed. The results are then compared with those reported in the literature and with the total polyphenol content determined by the Folin-Ciocalteu method. In all cases, the concentrations of GA align with those previously found in the literature for the beverages examined. Notably, the values are consistently lower than the total polyphenol content, demonstrating the sensor\'s selectivity in discriminating the target molecule from other polyphenols present.
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  • 文章类型: Journal Article
    该综述讨论了用于分析药物与DNA相互作用的电化学方法。电分析方法基于DNA分子中杂环含氮碱基的电化学氧化电位和最大氧化电流幅度的相互作用引起的变化的记录。可以基于杂环含氮碱基的电氧化电位向更负(阴极)或正(阳极)值的变化来鉴定DNA-药物相互作用的机制。药物嵌入DNA会将电化学氧化电位转移到正值,表明热力学上不利的过程,阻碍了DNA中含氮碱基的氧化。向负值的电势偏移表明静电相互作用,例如,DNA小沟中的药物结合,因为这个过程不会干扰碱的电化学氧化。DNA碱基电化学氧化强度的浓度依赖性降低允许量化相互作用的类型并计算结合常数。
    The review discusses electrochemical methods for analysis of drug interactions with DNA. The electroanalysis method is based on the registration of interaction-induced changes in the electrochemical oxidation potential of heterocyclic nitrogenous bases in the DNA molecule and in the maximum oxidation current amplitude. The mechanisms of DNA-drug interactions can be identified based on the shift in the electrooxidation potential of heterocyclic nitrogenous bases toward more negative (cathodic) or positive (anodic) values. Drug intercalation into DNA shifts the electrochemical oxidation potential to positive values, indicating thermodynamically unfavorable process that hinders oxidation of nitrogenous bases in DNA. The potential shift toward the negative values indicates electrostatic interactions, e.g., drug binding in the DNA minor groove, since this process does not interfere with the electrochemical oxidation of bases. The concentration-dependent decrease in the intensity of electrochemical oxidation of DNA bases allows to quantify the type of interaction and calculate the binding constants.
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  • 文章类型: Journal Article
    改进用于测定有机/无机化合物的新颖且有效的生物传感器是用于生物医学科学的临床诊断和研究的分析化学中的挑战。基于电化学酶的生物传感器是商业上成功的生物传感器组之一,由于其低成本而使其极具吸引力,高选择性,和敏感性。核/壳纳米颗粒由于其独特的物理化学性质和可调的表面特性而成为开发基于酶的电化学生物传感器的通用平台。本研究全面回顾了核/壳纳米颗粒用于开发基于酶的电化学生物传感器的最新趋势和进展。此外,根据首选的电化学技术,对2007年至2023年在该领域进行的研究进行了统计评估。综述了近年来核壳纳米粒子在酶基电化学生物传感器中的应用,食物污染物,和临床生物标志物。此外,该综述强调了最近的创新和策略,以提高基于酶的电化学生物传感器的性能,使用核/壳纳米粒子。这些包括具有特定功能的纳米材料的整合,例如亲水特性,化学和热稳定性,电导率,生物相容性,和催化活性,以及新型混合纳米结构和多功能纳米复合材料的开发。
    Improving novel and efficient biosensors for determining organic/inorganic compounds is a challenge in analytical chemistry for clinical diagnosis and research in biomedical sciences. Electrochemical enzyme-based biosensors are one of the commercially successful groups of biosensors that make them highly appealing because of their low cost, high selectivity, and sensitivity. Core/shell nanoparticles have emerged as versatile platforms for developing enzyme-based electrochemical biosensors due to their unique physicochemical properties and tunable surface characteristics. This study provides a comprehensive review of recent trends and advancements in the utilization of core/shell nanoparticles for the development of enzyme-based electrochemical biosensors. Moreover, a statistical evaluation of the studies carried out in this field between 2007 and 2023 is made according to the preferred electrochemical techniques. The recent applications of core/shell nanoparticles in enzyme-based electrochemical biosensors were summarized to quantify environmental pollutants, food contaminants, and clinical biomarkers. Additionally, the review highlights recent innovations and strategies to improve the performance of enzyme-based electrochemical biosensors using core/shell nanoparticles. These include the integration of nanomaterials with specific functions such as hydrophilic character, chemical and thermal stability, conductivity, biocompatibility, and catalytic activity, as well as the development of new hybrid nanostructures and multifunctional nanocomposites.
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  • 文章类型: Journal Article
    双氯芬酸(DCF)是一种具有镇痛和解热特性的非甾体抗炎药。它用于治疗类风湿性关节炎疼痛,骨关节炎,和急性肌肉疼痛的情况下,可以口服给药,局部或静脉内。由于它的广泛使用,亲水性,稳定性和降解不良(食物链中的生物积累),DCF是一种新兴的化学污染物,可对生态系统造成不利影响。考虑到药物制剂中DCF的消耗及其对环境的负面影响,新敏感的发展,选择性,便宜,快,现场应用需要具有在线能力的分析设备。
    这篇简短的评论试图涵盖与使用纳米材料作为电化学测定药物制剂中DCF的催化剂有关的最新进展,生物流体和环境样品。
    本文旨在证明电化学传感器如何代表DCF分析的常规方法的可靠替代品。
    手稿重点介绍了用于DCF检测的电化学传感器的开发进展。我们分析了许多最近的论文(主要是自2019年以来)关于为定量测定DCF而开发的传感器,指示检测极限,线性范围,稳定性,再现性,和分析应用。概述了与传感器设计和未来前景相关的当前挑战。
    UNASSIGNED: Diclofenac (DCF) is a non-steroidal anti-inflammatory drug possessing analgesic and antipyretic properties. It is used for the treatment of rheumatoid arthritis pain, osteoarthritis, and acute muscle pain conditions and can be administrated orally, topically or intravenously. Because of its widespread use, hydrophilicity, stability and poor degradation (bioaccumulation in the food chain), DCF is an emerging chemical contaminant that can cause adverse effects in the ecosystems. Taking into account the consumption of DCF in pharmaceutical formulations and its negative impact on the environment, the development of new sensitive, selective, cheap, fast, and online capable analytical devices is needed for on-site applications.
    UNASSIGNED: This brief review attempts to cover the recent developments related to the use of nanomaterials as catalysts for electrochemical determination of DCF in pharmaceutical formulations, biological fluids and environmental samples.
    UNASSIGNED: The article aims to prove how electrochemical sensors represent reliable alternatives to conventional methods for DCF analysis.
    UNASSIGNED: The manuscript highlights the progress in the development of electrochemical sensors for DCF detection. We have analyzed numerous recent papers (mainly since 2019) on sensors developed for the quantitative determination of DCF, indicating the limit of detection, linear range, stability, reproducibility, and analytical applications. Current challenges related to the sensor design and future perspectives are outlined.
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