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Microneedle-Based Glucose Biosensors: A Critical Review of Materials, Fabrication Strategies, and Clinical Translation 基于微针的葡萄糖生物传感器:材料、制造策略和临床转化的重要回顾
IF 2.6 3区 化学 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2026-08-31 DOI: 10.1002/elan.70202
Gayatri Pathade, Abhijeet Raut, Atul Sherje

Diabetes mellitus is a common metabolic disease that requires frequent and accurate glucose monitoring to prevent serious complications and improve outcomes of treatment. Traditional glucose-monitoring methods like finger pricking and injectable insulin delivery are invasive, painful, and often inconvenient for long-term use which can adversely affect patient compliance. In addition, the poor permeability of the stratum corneum limits the effectiveness of many conventional transdermal systems, highlighting the need for minimally invasive and patient-friendly alternatives. Microneedle-based biosensors have attracted considerable interest as promising platforms for continuous glucose monitoring, since they can penetrate the outer layer of skin with minor pain and directly access the interstitial fluid to detect glucose in real time. Microneedle design, materials, fabrication technologies, and sensing strategies have been substantially advanced. However, most of the existing reviews discuss these aspects individually and have limited coverage on the synergistic effects of the microneedle structure, material property, fabrication strategy, and sensing mechanism on the biosensor performance and clinical applicability. This review focuses on the recent advances of microneedle-based glucose biosensors including different microneedle architectures, fabrication techniques, material systems, and sensing mechanisms such as enzymatic, nonenzymatic, colorimetric, fluorescence-based, and surface-enhanced Raman scattering (SERS)–based systems. The effects of microneedle design mechanical properties on sensing efficiency, biocompatibility, and patient comfort are discussed in detail. Current challenges such as biofouling, long-term stability, manufacturing complexity, and wearable integration are also discussed. Overall, microneedle-based biosensors are promising for minimally invasive and personalized management of diabetes.

糖尿病是一种常见的代谢性疾病,需要频繁和准确的血糖监测,以防止严重并发症和改善治疗效果。传统的血糖监测方法,如手指穿刺和注射胰岛素,是侵入性的,痛苦的,并且通常不方便长期使用,这可能会对患者的依从性产生不利影响。此外,角质层的渗透性差限制了许多传统透皮系统的有效性,强调了对微创和患者友好的替代方案的需求。基于微针的生物传感器作为有前景的连续血糖监测平台已经引起了相当大的兴趣,因为它们可以在轻微疼痛的情况下穿透皮肤外层,并直接进入间质液来实时检测葡萄糖。微针的设计、材料、制造技术和传感策略都有了长足的进步。然而,现有的综述大多是单独讨论这些方面,对微针结构、材料特性、制造策略和传感机制对生物传感器性能和临床适用性的协同作用的报道有限。本文综述了基于微针的葡萄糖生物传感器的最新进展,包括不同的微针结构、制造技术、材料系统和传感机制,如酶、非酶、比色、荧光和基于表面增强拉曼散射(SERS)的系统。详细讨论了微针设计力学性能对传感效率、生物相容性和患者舒适度的影响。还讨论了当前面临的挑战,如生物污染、长期稳定性、制造复杂性和可穿戴集成。总的来说,基于微针的生物传感器有望实现糖尿病的微创和个性化管理。
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引用次数: 0
Microneedle-Based Glucose Biosensors: A Critical Review of Materials, Fabrication Strategies, and Clinical Translation 基于微针的葡萄糖生物传感器:材料、制造策略和临床转化的重要回顾
IF 2.6 3区 化学 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2026-08-31 DOI: 10.1002/elan.70202
Gayatri Pathade, Abhijeet Raut, Atul Sherje

Diabetes mellitus is a common metabolic disease that requires frequent and accurate glucose monitoring to prevent serious complications and improve outcomes of treatment. Traditional glucose-monitoring methods like finger pricking and injectable insulin delivery are invasive, painful, and often inconvenient for long-term use which can adversely affect patient compliance. In addition, the poor permeability of the stratum corneum limits the effectiveness of many conventional transdermal systems, highlighting the need for minimally invasive and patient-friendly alternatives. Microneedle-based biosensors have attracted considerable interest as promising platforms for continuous glucose monitoring, since they can penetrate the outer layer of skin with minor pain and directly access the interstitial fluid to detect glucose in real time. Microneedle design, materials, fabrication technologies, and sensing strategies have been substantially advanced. However, most of the existing reviews discuss these aspects individually and have limited coverage on the synergistic effects of the microneedle structure, material property, fabrication strategy, and sensing mechanism on the biosensor performance and clinical applicability. This review focuses on the recent advances of microneedle-based glucose biosensors including different microneedle architectures, fabrication techniques, material systems, and sensing mechanisms such as enzymatic, nonenzymatic, colorimetric, fluorescence-based, and surface-enhanced Raman scattering (SERS)–based systems. The effects of microneedle design mechanical properties on sensing efficiency, biocompatibility, and patient comfort are discussed in detail. Current challenges such as biofouling, long-term stability, manufacturing complexity, and wearable integration are also discussed. Overall, microneedle-based biosensors are promising for minimally invasive and personalized management of diabetes.

糖尿病是一种常见的代谢性疾病,需要频繁和准确的血糖监测,以防止严重并发症和改善治疗效果。传统的血糖监测方法,如手指穿刺和注射胰岛素,是侵入性的,痛苦的,并且通常不方便长期使用,这可能会对患者的依从性产生不利影响。此外,角质层的渗透性差限制了许多传统透皮系统的有效性,强调了对微创和患者友好的替代方案的需求。基于微针的生物传感器作为有前景的连续血糖监测平台已经引起了相当大的兴趣,因为它们可以在轻微疼痛的情况下穿透皮肤外层,并直接进入间质液来实时检测葡萄糖。微针的设计、材料、制造技术和传感策略都有了长足的进步。然而,现有的综述大多是单独讨论这些方面,对微针结构、材料特性、制造策略和传感机制对生物传感器性能和临床适用性的协同作用的报道有限。本文综述了基于微针的葡萄糖生物传感器的最新进展,包括不同的微针结构、制造技术、材料系统和传感机制,如酶、非酶、比色、荧光和基于表面增强拉曼散射(SERS)的系统。详细讨论了微针设计力学性能对传感效率、生物相容性和患者舒适度的影响。还讨论了当前面临的挑战,如生物污染、长期稳定性、制造复杂性和可穿戴集成。总的来说,基于微针的生物传感器有望实现糖尿病的微创和个性化管理。
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引用次数: 0
A Portable Multifrequency Electrochemical Response Analyzer for Comparative Electrolyte Characterization 一种用于比较电解质表征的便携式多频电化学响应分析仪
IF 2.6 3区 化学 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2026-08-30 DOI: 10.1002/elan.70205
Nikhil Gogawale, Avdhut Kadam, Prabhakar Kadam, Santosh Kamble, Tukaram Dongale, Ganesh Nhivekar

A portable multifrequency electrochemical response analyzer was developed on an ESP32 microcontroller platform for comparative impedance-sensitive characterization of aqueous electrolytes. The instrument employs PWM square-wave excitation (1–15 kHz), a two-electrode stainless steel probe, and RC signal conditioning with 12-bit analog-to-digital converter (ADC) sampling. Response values are determined via a voltage-divider relationship between electrolyte impedance and the conditioning network, yielding comparative measurements in arbitrary units. Analysis of strong electrolytes (HCl, NaOH, KOH, NaCl) and weak electrolyte (CH3COOH) at 0.001–1 M revealed monotonically increasing responses with excitation frequency (gain ratio 14.8–23.6). Strong electrolytes exhibited moderate frequency dependence consistent with complete ionization, whereas acetic acid showed markedly higher absolute responses and enhanced interfacial polarization due to partial ionization, enabling quantitative class-level discrimination. Repeatability at 0.1 M NaCl (n = 5) yielded CV < 2.1% across all frequencies. The analyzer offers a small, cost-effective screening platform for portable electrochemical characterization in resource-constrained environments, made WiFi enabled with real-time visualization and CSV data export, enabling use in environmental assessment, process monitoring, and analytical screening.

在ESP32微控制器平台上开发了一种便携式多频电化学响应分析仪,用于比较阻抗敏感表征水溶液电解质。该仪器采用PWM方波激励(1-15 kHz),双电极不锈钢探头,并采用12位模数转换器(ADC)采样的RC信号调理。响应值是通过电解液阻抗和调理网络之间的分压器关系确定的,产生任意单位的比较测量。强电解质(HCl, NaOH, KOH, NaCl)和弱电解质(CH3COOH)在0.001-1 M下的响应随着激励频率(增益比14.8-23.6)的增加而单调增加。强电解质表现出与完全电离一致的中度频率依赖性,而乙酸表现出明显更高的绝对响应,并且由于部分电离而增强了界面极化,从而实现了定量的类水平区分。在0.1 M NaCl (n = 5)下,所有频率的重复性CV <均为2.1%。该分析仪为资源受限环境下的便携式电化学表征提供了一个小型、经济高效的筛选平台,支持WiFi实时可视化和CSV数据导出,可用于环境评估、过程监控和分析筛选。
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引用次数: 0
A Portable Multifrequency Electrochemical Response Analyzer for Comparative Electrolyte Characterization 一种用于比较电解质表征的便携式多频电化学响应分析仪
IF 2.6 3区 化学 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2026-08-30 DOI: 10.1002/elan.70205
Nikhil Gogawale, Avdhut Kadam, Prabhakar Kadam, Santosh Kamble, Tukaram Dongale, Ganesh Nhivekar

A portable multifrequency electrochemical response analyzer was developed on an ESP32 microcontroller platform for comparative impedance-sensitive characterization of aqueous electrolytes. The instrument employs PWM square-wave excitation (1–15 kHz), a two-electrode stainless steel probe, and RC signal conditioning with 12-bit analog-to-digital converter (ADC) sampling. Response values are determined via a voltage-divider relationship between electrolyte impedance and the conditioning network, yielding comparative measurements in arbitrary units. Analysis of strong electrolytes (HCl, NaOH, KOH, NaCl) and weak electrolyte (CH3COOH) at 0.001–1 M revealed monotonically increasing responses with excitation frequency (gain ratio 14.8–23.6). Strong electrolytes exhibited moderate frequency dependence consistent with complete ionization, whereas acetic acid showed markedly higher absolute responses and enhanced interfacial polarization due to partial ionization, enabling quantitative class-level discrimination. Repeatability at 0.1 M NaCl (n = 5) yielded CV < 2.1% across all frequencies. The analyzer offers a small, cost-effective screening platform for portable electrochemical characterization in resource-constrained environments, made WiFi enabled with real-time visualization and CSV data export, enabling use in environmental assessment, process monitoring, and analytical screening.

在ESP32微控制器平台上开发了一种便携式多频电化学响应分析仪,用于比较阻抗敏感表征水溶液电解质。该仪器采用PWM方波激励(1-15 kHz),双电极不锈钢探头,并采用12位模数转换器(ADC)采样的RC信号调理。响应值是通过电解液阻抗和调理网络之间的分压器关系确定的,产生任意单位的比较测量。强电解质(HCl, NaOH, KOH, NaCl)和弱电解质(CH3COOH)在0.001-1 M下的响应随着激励频率(增益比14.8-23.6)的增加而单调增加。强电解质表现出与完全电离一致的中度频率依赖性,而乙酸表现出明显更高的绝对响应,并且由于部分电离而增强了界面极化,从而实现了定量的类水平区分。在0.1 M NaCl (n = 5)下,所有频率的重复性CV <均为2.1%。该分析仪为资源受限环境下的便携式电化学表征提供了一个小型、经济高效的筛选平台,支持WiFi实时可视化和CSV数据导出,可用于环境评估、过程监控和分析筛选。
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引用次数: 0
Synergistic Integration of Carbon Quantum Dots and Zeolitic Imidazolate Framework-8 for Advanced Electrochemical Biosensing of Dopamine 碳量子点和沸石咪唑酸框架-8协同集成用于多巴胺的高级电化学生物传感
IF 2.6 3区 化学 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2026-08-27 DOI: 10.1002/elan.70206
Ngaira Mandela, Tobias Topisia

Dopamine is a key catecholaminergic neurotransmitter, and its precise determination in biological fluids is essential for studying neurological dysfunction and developing diagnostic approaches. This study reports a thermally optimized carbon quantum dot-embedded zeolitic imidazolate framework-8 (CDs@ZIF-8) nanocomposite as an electrochemical sensing platform for ultrasensitive dopamine detection. Carbon quantum dots were synthesized via a hydrothermal route using L-proline and o-phenylenediamine as carbon and nitrogen precursors and subsequently integrated into the ZIF-8 framework through pH-regulated electrostatic impregnation. Structural characterization confirmed the successful incorporation of CDs while preserving the sodalite-type crystalline structure of ZIF-8. The introduction of CDs significantly improved the electrochemical properties of ZIF-8 by reducing the charge transfer resistance from approximately 510 to 55 Ω and enhancing dopamine oxidation performance through improved electron transport and increased accessible active sites. Temperature optimization identified 30 °C as the optimal sensing condition, enabling the CDs@ZIF-8-modified glassy carbon electrode to achieve a wide linear detection range from 0.05 to 180 μM, a sensitivity of 0.2156 μA μM−1, and a detection limit of 18 nM (S/N = 3). The sensor exhibited high selectivity against common interfering substances, excellent storage stability with 93.8% signal retention after 10 days, and reliable analytical performance in fetal bovine serum samples with recoveries of 97.1%–104.8%. The developed CDs@ZIF-8 platform provides an effective strategy for improving metal–organic framework-based electrochemical sensing systems and demonstrates potential for dopamine monitoring in complex biological matrices.

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引用次数: 0
Synergistic Integration of Carbon Quantum Dots and Zeolitic Imidazolate Framework-8 for Advanced Electrochemical Biosensing of Dopamine 碳量子点和沸石咪唑酸框架-8协同集成用于多巴胺的高级电化学生物传感
IF 2.6 3区 化学 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2026-08-27 DOI: 10.1002/elan.70206
Ngaira Mandela, Tobias Topisia

Dopamine is a key catecholaminergic neurotransmitter, and its precise determination in biological fluids is essential for studying neurological dysfunction and developing diagnostic approaches. This study reports a thermally optimized carbon quantum dot-embedded zeolitic imidazolate framework-8 (CDs@ZIF-8) nanocomposite as an electrochemical sensing platform for ultrasensitive dopamine detection. Carbon quantum dots were synthesized via a hydrothermal route using L-proline and o-phenylenediamine as carbon and nitrogen precursors and subsequently integrated into the ZIF-8 framework through pH-regulated electrostatic impregnation. Structural characterization confirmed the successful incorporation of CDs while preserving the sodalite-type crystalline structure of ZIF-8. The introduction of CDs significantly improved the electrochemical properties of ZIF-8 by reducing the charge transfer resistance from approximately 510 to 55 Ω and enhancing dopamine oxidation performance through improved electron transport and increased accessible active sites. Temperature optimization identified 30 °C as the optimal sensing condition, enabling the CDs@ZIF-8-modified glassy carbon electrode to achieve a wide linear detection range from 0.05 to 180 μM, a sensitivity of 0.2156 μA μM−1, and a detection limit of 18 nM (S/N = 3). The sensor exhibited high selectivity against common interfering substances, excellent storage stability with 93.8% signal retention after 10 days, and reliable analytical performance in fetal bovine serum samples with recoveries of 97.1%–104.8%. The developed CDs@ZIF-8 platform provides an effective strategy for improving metal–organic framework-based electrochemical sensing systems and demonstrates potential for dopamine monitoring in complex biological matrices.

{"title":"Synergistic Integration of Carbon Quantum Dots and Zeolitic Imidazolate Framework-8 for Advanced Electrochemical Biosensing of Dopamine","authors":"Ngaira Mandela,&nbsp;Tobias Topisia","doi":"10.1002/elan.70206","DOIUrl":"https://doi.org/10.1002/elan.70206","url":null,"abstract":"<p>Dopamine is a key catecholaminergic neurotransmitter, and its precise determination in biological fluids is essential for studying neurological dysfunction and developing diagnostic approaches. This study reports a thermally optimized carbon quantum dot-embedded zeolitic imidazolate framework-8 (CDs@ZIF-8) nanocomposite as an electrochemical sensing platform for ultrasensitive dopamine detection. Carbon quantum dots were synthesized via a hydrothermal route using L-proline and o-phenylenediamine as carbon and nitrogen precursors and subsequently integrated into the ZIF-8 framework through pH-regulated electrostatic impregnation. Structural characterization confirmed the successful incorporation of CDs while preserving the sodalite-type crystalline structure of ZIF-8. The introduction of CDs significantly improved the electrochemical properties of ZIF-8 by reducing the charge transfer resistance from approximately 510 to 55 Ω and enhancing dopamine oxidation performance through improved electron transport and increased accessible active sites. Temperature optimization identified 30 °C as the optimal sensing condition, enabling the CDs@ZIF-8-modified glassy carbon electrode to achieve a wide linear detection range from 0.05 to 180 μM, a sensitivity of 0.2156 μA μM<sup>−1</sup>, and a detection limit of 18 nM (<i>S</i>/<i>N</i> = 3). The sensor exhibited high selectivity against common interfering substances, excellent storage stability with 93.8% signal retention after 10 days, and reliable analytical performance in fetal bovine serum samples with recoveries of 97.1%–104.8%. The developed CDs@ZIF-8 platform provides an effective strategy for improving metal–organic framework-based electrochemical sensing systems and demonstrates potential for dopamine monitoring in complex biological matrices.</p>","PeriodicalId":162,"journal":{"name":"Electroanalysis","volume":"38 9","pages":""},"PeriodicalIF":2.6,"publicationDate":"2026-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148848970","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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
Electrochemical Oxidation of 2,5-Dihydroxybenzoic Acid in the Presence of p-Toluenesulfinic Acid: Formation of a Novel Disulfone Derivative and Experimental–Theoretical Comparison With Other Hydroquinone Derivatives 2,5-二羟基苯甲酸在对甲苯亚磺酸存在下的电化学氧化:一种新型二砜衍生物的形成及与其他对苯二酚衍生物的实验-理论比较
IF 2.6 3区 化学 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2026-08-24 DOI: 10.1002/elan.70213
Hadi Beiginejad, Morteza Vatanparast, Fahimeh Varmaghani

The electrochemical oxidation of 2,5-dihydroxybenzoic acid (2,5-DHBA) in the presence of p-toluenesulfinic acid (TSA) was investigated by cyclic voltammetry and controlled-potential coulometry. The results revealed an ECEC mechanism, leading to the formation of a new disulfone derivative. In contrast, investigation of five other hydroquinone derivatives under identical conditions revealed that their electrochemical oxidation in the presence of the nucleophile follows an EC mechanism. To clarify the origin of this mechanistic difference, density functional theory (DFT) calculations were performed using various functionals in combination with CPCM and SMD solvation models. Comparison of calculated oxidation free energies (ΔGtot) with experimental voltammetric data identified the M06-2X-D3/6-311++G(d,p)/SMD level as the most reliable method, providing excellent agreement with experiment. The results demonstrated that the total change in Gibbs free energy of the electrochemical oxidation of the species is the key factor governing the reaction pathway. Products whose ΔGtot are higher than those of the corresponding starting materials do not undergo further oxidation under the experimental conditions, resulting in an EC mechanism. In contrast, species with lower ΔGtot values are susceptible to further oxidation, leading to an ECEC mechanism.

采用循环伏安法和控制电位库仑法研究了2,5-二羟基苯甲酸(2,5- dhba)在对甲苯磺酸(TSA)存在下的电化学氧化反应。结果揭示了ECEC机制,导致新的二砜衍生物的形成。相比之下,在相同条件下对其他五种对苯二酚衍生物的研究表明,它们在亲核试剂存在下的电化学氧化遵循EC机制。为了澄清这种机制差异的起源,密度泛函理论(DFT)计算使用各种泛函结合CPCM和SMD溶剂化模型。将计算的氧化自由能(ΔGtot)与实验伏安数据进行比较,确定M06-2X-D3/6-311++G(d,p)/SMD水平是最可靠的方法,与实验结果吻合良好。结果表明,物质的电化学氧化过程中吉布斯自由能的总变化是控制反应途径的关键因素。ΔGtot高于相应起始原料的产物在实验条件下不会进一步氧化,产生EC机制。相反,ΔGtot值较低的物种容易进一步氧化,导致ECEC机制。
{"title":"Electrochemical Oxidation of 2,5-Dihydroxybenzoic Acid in the Presence of p-Toluenesulfinic Acid: Formation of a Novel Disulfone Derivative and Experimental–Theoretical Comparison With Other Hydroquinone Derivatives","authors":"Hadi Beiginejad,&nbsp;Morteza Vatanparast,&nbsp;Fahimeh Varmaghani","doi":"10.1002/elan.70213","DOIUrl":"https://doi.org/10.1002/elan.70213","url":null,"abstract":"<p>The electrochemical oxidation of 2,5-dihydroxybenzoic acid (2,5-DHBA) in the presence of <i>p</i>-toluenesulfinic acid (TSA) was investigated by cyclic voltammetry and controlled-potential coulometry. The results revealed an <i>ECEC</i> mechanism, leading to the formation of a new disulfone derivative. In contrast, investigation of five other hydroquinone derivatives under identical conditions revealed that their electrochemical oxidation in the presence of the nucleophile follows an <i>EC</i> mechanism. To clarify the origin of this mechanistic difference, density functional theory (DFT) calculations were performed using various functionals in combination with CPCM and SMD solvation models. Comparison of calculated oxidation free energies (Δ<i>G</i><sub>tot</sub>) with experimental voltammetric data identified the M06-2X-D3/6-311++G(d,p)/SMD level as the most reliable method, providing excellent agreement with experiment. The results demonstrated that the total change in Gibbs free energy of the electrochemical oxidation of the species is the key factor governing the reaction pathway. Products whose Δ<i>G</i><sub>tot</sub> are higher than those of the corresponding starting materials do not undergo further oxidation under the experimental conditions, resulting in an <i>EC</i> mechanism. In contrast, species with lower Δ<i>G</i><sub>tot</sub> values are susceptible to further oxidation, leading to an <i>ECEC</i> mechanism.</p>","PeriodicalId":162,"journal":{"name":"Electroanalysis","volume":"38 9","pages":""},"PeriodicalIF":2.6,"publicationDate":"2026-08-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148807705","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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
Electrochemical Oxidation of 2,5-Dihydroxybenzoic Acid in the Presence of p-Toluenesulfinic Acid: Formation of a Novel Disulfone Derivative and Experimental–Theoretical Comparison With Other Hydroquinone Derivatives 2,5-二羟基苯甲酸在对甲苯亚磺酸存在下的电化学氧化:一种新型二砜衍生物的形成及与其他对苯二酚衍生物的实验-理论比较
IF 2.6 3区 化学 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2026-08-24 DOI: 10.1002/elan.70213
Hadi Beiginejad, Morteza Vatanparast, Fahimeh Varmaghani

The electrochemical oxidation of 2,5-dihydroxybenzoic acid (2,5-DHBA) in the presence of p-toluenesulfinic acid (TSA) was investigated by cyclic voltammetry and controlled-potential coulometry. The results revealed an ECEC mechanism, leading to the formation of a new disulfone derivative. In contrast, investigation of five other hydroquinone derivatives under identical conditions revealed that their electrochemical oxidation in the presence of the nucleophile follows an EC mechanism. To clarify the origin of this mechanistic difference, density functional theory (DFT) calculations were performed using various functionals in combination with CPCM and SMD solvation models. Comparison of calculated oxidation free energies (ΔGtot) with experimental voltammetric data identified the M06-2X-D3/6-311++G(d,p)/SMD level as the most reliable method, providing excellent agreement with experiment. The results demonstrated that the total change in Gibbs free energy of the electrochemical oxidation of the species is the key factor governing the reaction pathway. Products whose ΔGtot are higher than those of the corresponding starting materials do not undergo further oxidation under the experimental conditions, resulting in an EC mechanism. In contrast, species with lower ΔGtot values are susceptible to further oxidation, leading to an ECEC mechanism.

采用循环伏安法和控制电位库仑法研究了2,5-二羟基苯甲酸(2,5- dhba)在对甲苯磺酸(TSA)存在下的电化学氧化反应。结果揭示了ECEC机制,导致新的二砜衍生物的形成。相比之下,在相同条件下对其他五种对苯二酚衍生物的研究表明,它们在亲核试剂存在下的电化学氧化遵循EC机制。为了澄清这种机制差异的起源,密度泛函理论(DFT)计算使用各种泛函结合CPCM和SMD溶剂化模型。将计算的氧化自由能(ΔGtot)与实验伏安数据进行比较,确定M06-2X-D3/6-311++G(d,p)/SMD水平是最可靠的方法,与实验结果吻合良好。结果表明,物质的电化学氧化过程中吉布斯自由能的总变化是控制反应途径的关键因素。ΔGtot高于相应起始原料的产物在实验条件下不会进一步氧化,产生EC机制。相反,ΔGtot值较低的物种容易进一步氧化,导致ECEC机制。
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引用次数: 0
Thermal Safety of Lithium-Ion Batteries With Ionic Liquid ([Bmim]TF2N)-Based Binary Electrolytes 离子液体([Bmim]TF2N)基二元电解质锂离子电池的热安全性
IF 2.6 3区 化学 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2026-08-23 DOI: 10.1002/elan.70215
Xuhai Pan, Tianwei Huang, Yucheng Zhu, Zhixiang Chen, Yahong Liu, Min Hua

Large-scaleapplicationof lithium-ion batteries has been hampered by thermal safety issues associated with organic electrolytes based on carbonates. The development of flame-resistant or noncombustible electrolytes is therefore essential. Recently, researchers have shown increasing interest in novel ionic liquid-based electrolytes. However, pure ionic liquids are unsuitable as electrolyte solvents. 1-Butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([Bmim]TF2N) is a favorable candidate for binary electrolytes owing to its higher conductivity and lower viscosity. Herein, a series of experiments was conducted on binary electrolytes composed of [Bmim]TF2N and carbonate-based electrolytes (1 M LiPF6 in EC/DMC/EMC, 1:1:1 v/v/v). The results revealed that the [Bmim]TF2N binary electrolyte outperformed the carbonate electrolyte.The [Bmim]TF2N-containing electrolytes exhibited higher total ionic conductivity than the carbonate-based electrolyte under the tested conditions. The binary electrolytes exhibited 6.61% and 11.63% greater flame-retardant efficiencies than the carbonate electrolytes when the [Bmim]TF2N concentrations were 20% ([Bmim]TF2N-20%) and 40% ([Bmim]TF2N-40%), respectively. After 100 cycles, LiFePO4 batteries employing [Bmim]TF2N-20% and [Bmim]TF2N-40% delivered capacities of 141.8 and 141.4 mAh g−1, respectively, with corresponding capacity retention rates that were 3.52% and 4.4% higher than those of the carbonate batteries (132.5 mAh g−1). Furthermore, among all the electrolytes tested, the [Bmim]TF2N-20% binary electrolyte exhibited the highest charge/discharge capacity under high-rate cycling conditions.

{"title":"Thermal Safety of Lithium-Ion Batteries With Ionic Liquid ([Bmim]TF2N)-Based Binary Electrolytes","authors":"Xuhai Pan,&nbsp;Tianwei Huang,&nbsp;Yucheng Zhu,&nbsp;Zhixiang Chen,&nbsp;Yahong Liu,&nbsp;Min Hua","doi":"10.1002/elan.70215","DOIUrl":"https://doi.org/10.1002/elan.70215","url":null,"abstract":"<p>Large-scaleapplicationof lithium-ion batteries has been hampered by thermal safety issues associated with organic electrolytes based on carbonates. The development of flame-resistant or noncombustible electrolytes is therefore essential. Recently, researchers have shown increasing interest in novel ionic liquid-based electrolytes. However, pure ionic liquids are unsuitable as electrolyte solvents. 1-Butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([Bmim]TF<sub>2</sub>N) is a favorable candidate for binary electrolytes owing to its higher conductivity and lower viscosity. Herein, a series of experiments was conducted on binary electrolytes composed of [Bmim]TF<sub>2</sub>N and carbonate-based electrolytes (1 M LiPF<sub>6</sub> in EC/DMC/EMC, 1:1:1 v/v/v). The results revealed that the [Bmim]TF<sub>2</sub>N binary electrolyte outperformed the carbonate electrolyte.The [Bmim]TF<sub>2</sub>N-containing electrolytes exhibited higher total ionic conductivity than the carbonate-based electrolyte under the tested conditions. The binary electrolytes exhibited 6.61% and 11.63% greater flame-retardant efficiencies than the carbonate electrolytes when the [Bmim]TF<sub>2</sub>N concentrations were 20% ([Bmim]TF<sub>2</sub>N-20%) and 40% ([Bmim]TF<sub>2</sub>N-40%), respectively. After 100 cycles, LiFePO<sub>4</sub> batteries employing [Bmim]TF<sub>2</sub>N-20% and [Bmim]TF<sub>2</sub>N-40% delivered capacities of 141.8 and 141.4 mAh g<sup>−1</sup>, respectively, with corresponding capacity retention rates that were 3.52% and 4.4% higher than those of the carbonate batteries (132.5 mAh g<sup>−1</sup>). Furthermore, among all the electrolytes tested, the [Bmim]TF<sub>2</sub>N-20% binary electrolyte exhibited the highest charge/discharge capacity under high-rate cycling conditions.</p>","PeriodicalId":162,"journal":{"name":"Electroanalysis","volume":"38 8","pages":""},"PeriodicalIF":2.6,"publicationDate":"2026-08-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148848714","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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
Thermal Safety of Lithium-Ion Batteries With Ionic Liquid ([Bmim]TF2N)-Based Binary Electrolytes 离子液体([Bmim]TF2N)基二元电解质锂离子电池的热安全性
IF 2.6 3区 化学 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2026-08-23 DOI: 10.1002/elan.70215
Xuhai Pan, Tianwei Huang, Yucheng Zhu, Zhixiang Chen, Yahong Liu, Min Hua

Large-scaleapplicationof lithium-ion batteries has been hampered by thermal safety issues associated with organic electrolytes based on carbonates. The development of flame-resistant or noncombustible electrolytes is therefore essential. Recently, researchers have shown increasing interest in novel ionic liquid-based electrolytes. However, pure ionic liquids are unsuitable as electrolyte solvents. 1-Butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([Bmim]TF2N) is a favorable candidate for binary electrolytes owing to its higher conductivity and lower viscosity. Herein, a series of experiments was conducted on binary electrolytes composed of [Bmim]TF2N and carbonate-based electrolytes (1 M LiPF6 in EC/DMC/EMC, 1:1:1 v/v/v). The results revealed that the [Bmim]TF2N binary electrolyte outperformed the carbonate electrolyte.The [Bmim]TF2N-containing electrolytes exhibited higher total ionic conductivity than the carbonate-based electrolyte under the tested conditions. The binary electrolytes exhibited 6.61% and 11.63% greater flame-retardant efficiencies than the carbonate electrolytes when the [Bmim]TF2N concentrations were 20% ([Bmim]TF2N-20%) and 40% ([Bmim]TF2N-40%), respectively. After 100 cycles, LiFePO4 batteries employing [Bmim]TF2N-20% and [Bmim]TF2N-40% delivered capacities of 141.8 and 141.4 mAh g−1, respectively, with corresponding capacity retention rates that were 3.52% and 4.4% higher than those of the carbonate batteries (132.5 mAh g−1). Furthermore, among all the electrolytes tested, the [Bmim]TF2N-20% binary electrolyte exhibited the highest charge/discharge capacity under high-rate cycling conditions.

{"title":"Thermal Safety of Lithium-Ion Batteries With Ionic Liquid ([Bmim]TF2N)-Based Binary Electrolytes","authors":"Xuhai Pan,&nbsp;Tianwei Huang,&nbsp;Yucheng Zhu,&nbsp;Zhixiang Chen,&nbsp;Yahong Liu,&nbsp;Min Hua","doi":"10.1002/elan.70215","DOIUrl":"https://doi.org/10.1002/elan.70215","url":null,"abstract":"<p>Large-scaleapplicationof lithium-ion batteries has been hampered by thermal safety issues associated with organic electrolytes based on carbonates. The development of flame-resistant or noncombustible electrolytes is therefore essential. Recently, researchers have shown increasing interest in novel ionic liquid-based electrolytes. However, pure ionic liquids are unsuitable as electrolyte solvents. 1-Butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([Bmim]TF<sub>2</sub>N) is a favorable candidate for binary electrolytes owing to its higher conductivity and lower viscosity. Herein, a series of experiments was conducted on binary electrolytes composed of [Bmim]TF<sub>2</sub>N and carbonate-based electrolytes (1 M LiPF<sub>6</sub> in EC/DMC/EMC, 1:1:1 v/v/v). The results revealed that the [Bmim]TF<sub>2</sub>N binary electrolyte outperformed the carbonate electrolyte.The [Bmim]TF<sub>2</sub>N-containing electrolytes exhibited higher total ionic conductivity than the carbonate-based electrolyte under the tested conditions. The binary electrolytes exhibited 6.61% and 11.63% greater flame-retardant efficiencies than the carbonate electrolytes when the [Bmim]TF<sub>2</sub>N concentrations were 20% ([Bmim]TF<sub>2</sub>N-20%) and 40% ([Bmim]TF<sub>2</sub>N-40%), respectively. After 100 cycles, LiFePO<sub>4</sub> batteries employing [Bmim]TF<sub>2</sub>N-20% and [Bmim]TF<sub>2</sub>N-40% delivered capacities of 141.8 and 141.4 mAh g<sup>−1</sup>, respectively, with corresponding capacity retention rates that were 3.52% and 4.4% higher than those of the carbonate batteries (132.5 mAh g<sup>−1</sup>). Furthermore, among all the electrolytes tested, the [Bmim]TF<sub>2</sub>N-20% binary electrolyte exhibited the highest charge/discharge capacity under high-rate cycling conditions.</p>","PeriodicalId":162,"journal":{"name":"Electroanalysis","volume":"38 8","pages":""},"PeriodicalIF":2.6,"publicationDate":"2026-08-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148848636","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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
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