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Keywords = direct electrochemistry

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24 pages, 6966 KB  
Review
Phenolic Antioxidants in Food: A Comparative Review of Chromatographic, Spectroscopic, and Electrochemical Detection Methods
by Yani Zhao, Qiongya Lu, Jinlan Tu, Zhouyuan Zhao and Bin Zou
Foods 2026, 15(18), 3270; https://doi.org/10.3390/foods15183270 - 16 Sep 2026
Viewed by 229
Abstract
The detection of phenolic antioxidants in food is essential for ensuring food safety. Chromatographic analysis, spectroscopic analysis, and electrochemical detection are three mainstream techniques widely applied for qualitative and quantitative analysis of antioxidants in complex matrices. However, existing reviews mostly focus on single [...] Read more.
The detection of phenolic antioxidants in food is essential for ensuring food safety. Chromatographic analysis, spectroscopic analysis, and electrochemical detection are three mainstream techniques widely applied for qualitative and quantitative analysis of antioxidants in complex matrices. However, existing reviews mostly focus on single techniques, lack systematic cross-platform comparisons. This paper reviews the classification of phenolic antioxidants, summarizes recent advances in each detection technique, and provides a horizontal comparison in terms of sensitivity, selectivity, analytical efficiency, cost, and applicable scenarios. Chromatography remains the gold standard for confirmatory analysis, spectroscopy is suitable for rapid screening, and electrochemistry shows unique potential for on-site real-time monitoring. Each technique has distinct advantages and limitations, and their integration represents a promising direction for comprehensive food safety monitoring. Future development trends, including intelligence, portability, and multi-technique integration, are also discussed to guide practical method selection for food-safety detection. Full article
(This article belongs to the Special Issue Intelligent Sensor Systems and Digital Technologies for Food Analysis)
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18 pages, 1444 KB  
Perspective
The Forgotten Allotrope: γ-Sulfur Stabilization in Carbon Matrices for Energy Storage Applications
by Marlena Bytniewska, Dimitrios A. Giannakoudakis and Mariusz Barczak
Materials 2026, 19(16), 3537; https://doi.org/10.3390/ma19163537 - 20 Aug 2026
Viewed by 399
Abstract
Lithium–sulfur (Li-S) batteries are widely regarded as one of the most promising candidates for next-generation electrochemical energy storage, owing to their very high theoretical energy density and reliance on abundant, low-cost elements. However, the practical deployment of Li-S technology remains severely constrained by [...] Read more.
Lithium–sulfur (Li-S) batteries are widely regarded as one of the most promising candidates for next-generation electrochemical energy storage, owing to their very high theoretical energy density and reliance on abundant, low-cost elements. However, the practical deployment of Li-S technology remains severely constrained by the polysulfide shuttle effect, originating from the dissolution, migration and parasitic redox cycling of lithium polysulfide intermediates, which leads to rapid capacity fading, low coulombic efficiency and incompatibility with industrial carbonate-based electrolytes. Recent reports on the formation and stabilization of γ-sulfur, a rare monoclinic allotrope, within porous carbon matrices have identified a prospective direction in sulfur electrochemistry, theoretically enabling polysulfide-free cycling and improved stability, also in conventional carbonate electrolytes. These findings challenge the long-held assumption that polysulfide formation is unavoidable in sulfur cathodes and suggest that control over sulfur allotropy and nanoconfinement, as well as carbon–sulfur chemistry, may unlock previously inaccessible performance and integration windows for metal–sulfur batteries, including most technologically advanced Li-S batteries. Based on recent studies, this Perspective article critically evaluates the evidence for γ-sulfur stabilization in carbon hosts, discusses the interplay between pore geometry, carbon surface chemistry and sulfur speciation, and finally identifies key knowledge gaps. Full article
(This article belongs to the Section Energy Materials)
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29 pages, 2260 KB  
Review
Bioleaching of Copper Sulfide Ores: From Microbial Mechanisms to Industrial Applications
by Zulaikha Abid and Yuandong Liu
Separations 2026, 13(8), 234; https://doi.org/10.3390/separations13080234 - 16 Aug 2026
Viewed by 522
Abstract
The global energy transition and rapid electrification are driving increased demand for copper. However, conventional pyrometallurgical and hydrometallurgical extraction routes are increasingly challenged by declining ore grades and stricter environmental regulations. Bioleaching involves the microbial catalysis of sulfide mineral dissolution and provides a [...] Read more.
The global energy transition and rapid electrification are driving increased demand for copper. However, conventional pyrometallurgical and hydrometallurgical extraction routes are increasingly challenged by declining ore grades and stricter environmental regulations. Bioleaching involves the microbial catalysis of sulfide mineral dissolution and provides a sustainable method for copper recovery from low-grade ores, tailings and secondary resources. This review provides a critical and integrated analysis of copper sulfide bioleaching, covering microbial diversity, molecular mechanisms, mineralogical controls, operational parameters, and industrial applications. This review also examines the functional roles of prominent acidophiles, including the functional roles of prominent acidophiles, including Acidithiobacillus spp., Leptospirillum spp. and thermophilic archaea, in the oxidation of iron and sulfur, mitigation of passivation, and metal solubilization. The molecular underpinnings of these processes are explored by investigating iron and sulfur oxidation gene networks (the rus operon and sox cluster), copper resistance systems (CopA, CusCBA) and biofilm formation pathways. The mineralogical controls on the behavior of chalcopyrite (refractory/passivating), chalcocite (highly reactive) and bornite (intermediate) are critically assessed. The synergistic effects of key operational parameters (temperature, pH, redox potential, aeration and particle size) on leaching kinetics and microbial community dynamics are investigated. The scalability, efficiency and environmental footprint of industrial applications such as heap, dump, stirred-tank and in situ bioleaching are discussed. Despite more than four decades of commercial development, several challenges remain, such as slow chalcopyrite dissolution, passivation, metal toxicity, and scale-up limitations. Emerging solutions such as synthetic microbial consortia, multi-omics technologies, artificial intelligence-assisted optimization, and digital twins are identified as transformative approaches for next-generation biomining. In this review, microbiology, mineralogy, electrochemistry, and process engineering are integrated to demonstrate that biotechnological leaching is among the most promising technologies for the sustainable production of copper and to identify future directions for its industrial application. Full article
(This article belongs to the Special Issue Separation Techniques in Recovery of Valuable Metal Resources)
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31 pages, 5687 KB  
Review
Deep Eutectic Solvents: A Comprehensive Landscape of Two Decades of Research, Emerging Frontiers, and Translational Challenges (2003–2025)
by Santiago Aparicio
Sustain. Chem. 2026, 7(3), 37; https://doi.org/10.3390/suschem7030037 - 20 Jul 2026
Cited by 1 | Viewed by 1477
Abstract
Deep eutectic solvents (DESs) have undergone a remarkable transformation over the past two decades, evolving from a laboratory curiosity into one of the most actively investigated solvent platforms in green chemistry. Yet, despite this rapid expansion, and although the field is well served [...] Read more.
Deep eutectic solvents (DESs) have undergone a remarkable transformation over the past two decades, evolving from a laboratory curiosity into one of the most actively investigated solvent platforms in green chemistry. Yet, despite this rapid expansion, and although the field is well served by numerous topical reviews, it still lacks a corpus-wide, cross-disciplinary synthesis capable of guiding strategic research priorities, identifying critical knowledge gaps, and informing policy and industrial investment decisions. The present work addresses this need through a thorough analysis of global DES research from 2003 to 2025, based on a deduplicated corpus of 17,757 publications retrieved from the Web of Science Core Collection and Scopus following PRISMA-adapted screening guidelines. The analysis maps temporal publication dynamics, geographic and institutional contributions, thematic evolution, journal landscape, component usage patterns, international collaboration networks, market projections, and alignment with the United Nations Sustainable Development Goals. The results document an exponential growth trajectory—from a single publication in 2004 to 3954 in 2025 (CAGR > 30%)—and reveal a clear thematic transition from early electrochemistry-dominated research toward extraction, pharmaceutical, and environmental applications, with machine-learning-assisted design and hydrophobic DES formulations emerging as the most dynamic current frontiers. China leads global output with 6819 publications (38.4%), while the United States and Malaysia achieve the highest citation-per-publication ratios among the leading nations (≈46.7 and ≈38.9, respectively, versus ≈27.6 for China), and Spain pairs a comparatively modest output with a high h-index, indicating that impact is large relative to volume. Type III DESs and NADESs collectively account for approximately 69% of the literature, with choline chloride present in 72% of reported formulations. The global DES market, valued at approximately USD 166 million in 2024, is projected to reach USD 370 million by 2030. Despite this progress, critical translational barriers persist: fewer than 0.3% of publications include techno-economic or life cycle assessment analysis, standardized characterization protocols remain absent, and toxicological datasets are systematically incomplete. This panoramic analysis is intended to serve as an evidence-based reference for researchers prioritizing future directions, for funding agencies assessing the maturity and needs of the field, and for industrial stakeholders evaluating the readiness of DES technologies for scale-up. Full article
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24 pages, 5330 KB  
Review
Reaction Mechanisms and Carbon Deposition Behavior in Methane Conversion via Solid Oxide Cells: A Review
by Hongyu Lu, Ziyi Yang, Xiaoyu Hu, Xianning Liu, Bin Wang, Zewei Lyu, Di Wu and Dongxu Cui
Coatings 2026, 16(7), 833; https://doi.org/10.3390/coatings16070833 - 14 Jul 2026
Viewed by 615
Abstract
Methane is an abundant energy carrier and carbon resource. However, its efficient utilization remains challenging because the strong C-H bonds in methane hinder low-temperature activation, whereas high-temperature conversion often leads to undesired side reactions and reduced product selectivity. Solid oxide cells (SOCs) provide [...] Read more.
Methane is an abundant energy carrier and carbon resource. However, its efficient utilization remains challenging because the strong C-H bonds in methane hinder low-temperature activation, whereas high-temperature conversion often leads to undesired side reactions and reduced product selectivity. Solid oxide cells (SOCs) provide a promising platform for methane conversion by integrating high-temperature electrochemistry, catalytic reactions, and ion transport within a single system, enabling efficient energy and chemical production. This review summarizes recent advances in SOC-based methane conversion through three representative pathways: direct electricity generation in methane-fueled solid oxide fuel cell (SOFC), syngas production via SOC-assisted methane reforming, and value-added C2 hydrocarbon synthesis through methane oxidative coupling in solid oxide electrolysis cell (SOEC). For methane-fueled SOFC, the relationships among fuel-electrode materials, microstructural characteristics, carbon deposition behavior, and electrochemical performance are discussed, together with current strategies for improving carbon resistance and operational stability. In methane reforming and upgrading processes, SOCs can regulate oxygen-ion transport, local reaction environments, and electrode reaction pathways, thereby enhancing methane conversion and product selectivity toward syngas, hydrogen, and C2 hydrocarbons. The roles of electrode design, catalyst development, and operating conditions in determining reaction performance are also highlighted. Finally, the major challenges facing SOC-based methane conversion are critically discussed. Future research directions involving advanced electrode materials, microstructure engineering, and multiscale modeling are proposed to support the development of efficient and durable SOC technologies for methane utilization. Full article
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28 pages, 1391 KB  
Review
Recent Advances in Nanomaterials for Pesticide Residue Detection: From Spectroscopic Analysis to Electrochemical Sensing
by Yue Niu, Mei Wang, Wei Lu, Bingliang Zhou, Xianghai Song and Quan Bu
Nanomaterials 2026, 16(13), 797; https://doi.org/10.3390/nano16130797 - 27 Jun 2026
Viewed by 847
Abstract
This review systematically summarizes the inherent characteristics and application superiorities of various nanomaterials, including metallic nanomaterials, metal oxides, carbon-based materials, metal–organic frameworks (MOFs), and quantum dots (QDs). State-of-the-art research progress is elaborated on the applications of these nanomaterials in multiple analytical techniques, such [...] Read more.
This review systematically summarizes the inherent characteristics and application superiorities of various nanomaterials, including metallic nanomaterials, metal oxides, carbon-based materials, metal–organic frameworks (MOFs), and quantum dots (QDs). State-of-the-art research progress is elaborated on the applications of these nanomaterials in multiple analytical techniques, such as surface-enhanced Raman spectroscopy (SERS), fluorescence spectroscopy, infrared spectroscopy, ultraviolet-visible spectroscopy, and electrochemistry. Furthermore, their pivotal functions in signal amplification, specific molecular recognition, and rapid analyte enrichment are thoroughly discussed. Additionally, this paper analyzes the prevailing challenges, including material heterogeneity, potential biosafety risks, poor anti-interference capacity against complex matrices, and the absence of unified industrial standardization. Future development directions are also proposed, involving green synthesis strategies, precise functional modification, portable intelligent detection, and simultaneous multi-component detection. This work aims to provide a reliable reference for further fundamental research and industrial translation of nanomaterials in the rapid and high-precision detection of pesticide residues. Full article
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24 pages, 1996 KB  
Review
Electrochemical Strategies for Lignin Valorization: Advancing Biomass Utilization
by Filemon Jalu Nusantara Putra, Aliyah Aliyah, Prihardi Kahar and Chiaki Ogino
Molecules 2026, 31(12), 2109; https://doi.org/10.3390/molecules31122109 - 15 Jun 2026
Viewed by 818
Abstract
Lignin is the most abundant renewable source of aromatic carbon, and yet it remains a mostly underutilized byproduct of the biorefinery and paper industries. Factors such as complexity and a heterogeneous structure make lignin recalcitrant to conventional valorization, the utility of which often [...] Read more.
Lignin is the most abundant renewable source of aromatic carbon, and yet it remains a mostly underutilized byproduct of the biorefinery and paper industries. Factors such as complexity and a heterogeneous structure make lignin recalcitrant to conventional valorization, the utility of which often requires harsh conditions and expensive catalysts. Electrochemical conversion has emerged as a highly promising, sustainable alternative due to the use of electricity produced by renewable sources to drive depolymerization under mild, ambient conditions. This review summarizes recent progress in this field and provides a comprehensive overview of the primary electrochemical pathways used to promote the valorization of lignin. Herein, we critically examine oxidative strategies that include both direct electrooxidation at the anode surface and indirect oxidation using redox mediators, and provide details of the key challenges of electrode deactivation and product overoxidation. We then discuss reductive strategies with a focus on electrocatalytic hydrogenolysis for C-O bond cleavage. Furthermore, we explore advanced integrated systems that combine electrochemistry with microbial, enzymatic, and photochemical processes to enhance selectivity and efficiency. Finally, this review addresses persistent challenges and offers future perspectives and suggests opportunities with an emphasis on the critical need for innovations in electrocatalyst design, green electrolytes, and integrated reactor engineering to unlock the full potential of lignin as a renewable feedstock for a circular carbon economy. Full article
(This article belongs to the Special Issue Lignin: New Insights in Chemistry)
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34 pages, 2232 KB  
Review
Supercapacitor Materials: Structure, Properties, and Applications for Energy Storage in Engineering Systems
by Lincoln Pinoski, Subin Antony Jose, Jacob Dowling, Nicholas Eastwood, Carly Farthing, Gavin Fisher and Pradeep L. Menezes
Materials 2026, 19(12), 2454; https://doi.org/10.3390/ma19122454 - 8 Jun 2026
Cited by 5 | Viewed by 1340
Abstract
The increasing global demand for high-performance, reliable, and sustainable energy storage systems has accelerated the development of supercapacitors as technologies capable of bridging the performance gap between conventional capacitors and batteries. Supercapacitors combine rapid charge–discharge capability, high power density, and exceptional cycle life [...] Read more.
The increasing global demand for high-performance, reliable, and sustainable energy storage systems has accelerated the development of supercapacitors as technologies capable of bridging the performance gap between conventional capacitors and batteries. Supercapacitors combine rapid charge–discharge capability, high power density, and exceptional cycle life through charge storage mechanisms based on ion adsorption and fast surface redox reactions at the electrode–electrolyte interface. This review examines the fundamental operating principles, charge storage mechanisms, electrode materials, mechanical and functional properties, fabrication methods, and engineering applications of modern supercapacitors. Carbon-based materials, metal oxides, conducting polymers, MXenes, sulfides, nitrides, borides, and emerging hybrid systems are critically compared in terms of capacitance, energy density, cycling stability, and mechanical robustness. Additionally, recent advances in scalable manufacturing approaches, including thin-film deposition and printing technologies, are discussed alongside key challenges such as limited energy density, interfacial instability, mechanical degradation, electrolyte compatibility, and large-scale processing. By consolidating recent developments across materials science, electrochemistry, and device engineering, this review provides insight into future directions for next-generation high-performance supercapacitor technologies. Full article
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28 pages, 1997 KB  
Review
Sensor Technologies in Medicine–Food Homology: A Comprehensive Review
by Yifan Qi, Shuwen Yan, Jianrong Chai, Tingrui Wang and Yuming Wang
Chemosensors 2026, 14(4), 95; https://doi.org/10.3390/chemosensors14040095 - 13 Apr 2026
Viewed by 1640
Abstract
Medicine–food homology (MFH) substances, which possess both medicinal and edible properties, have garnered widespread attention in the global health context of the new era. The MFH industry has experienced explosive growth and has gradually become a key supporting aspect of TCM modernization. However, [...] Read more.
Medicine–food homology (MFH) substances, which possess both medicinal and edible properties, have garnered widespread attention in the global health context of the new era. The MFH industry has experienced explosive growth and has gradually become a key supporting aspect of TCM modernization. However, due to the pollution of the modern environment, the content of pollutants in MFH products has been increasing, raising concerns regarding quality, safety, and efficacy control. Traditional quality-analysis technologies struggle to meet the needs of rapid on-site detection because of their dependence on large instruments and the complexity of operation. This dilemma has propelled advances in sensor technology. With its advantages of high sensitivity, real-time detection, and portability, sensor technology has become a key technical support for quality control and supervision in the field of MFH. In this review, we comprehensively categorize the mainstream sensor types used for analysis in the field of MFH, including intelligent sensors, optics, electrochemistry, biosensors, etc. This review outlines their research status, elaborates on their primary application directions and corresponding core technologies, discusses current challenges (including stability, interference, and cost), and presents future perspectives. Overall, sensor-based technologies offer a promising and scalable solution for the quality control of MFH products, addressing critical challenges such as stability, interference, and cost. With ongoing advances in intelligent sensing, optics, electrochemistry, and biosensing platforms, these methods are poised to play an increasingly vital role in ensuring the safety, efficacy, and quality consistency of MFH products amid growing environmental pressures. Full article
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34 pages, 4131 KB  
Review
Application of Single-Atom Nanozymes in the Detection of Small Biomolecules: A Review
by Wanyi Zhang, Rong Huang, Wenhui Luo, Xiaojing Si, Dongmei Deng and Liqiang Luo
Molecules 2026, 31(8), 1242; https://doi.org/10.3390/molecules31081242 - 9 Apr 2026
Cited by 4 | Viewed by 1300
Abstract
Single-atom nanozymes (SANs) with atomically dispersed metal sites show great potential in small biomolecule detection. This review first summarizes SAN synthesis (wet chemistry, atomic layer deposition, etc.), structural features (tunable coordination, metal-carrier interactions), and catalytic mechanisms (synergistic effects, d-band modulation). Afterwards, this review [...] Read more.
Single-atom nanozymes (SANs) with atomically dispersed metal sites show great potential in small biomolecule detection. This review first summarizes SAN synthesis (wet chemistry, atomic layer deposition, etc.), structural features (tunable coordination, metal-carrier interactions), and catalytic mechanisms (synergistic effects, d-band modulation). Afterwards, this review focuses on the applications of SANs in detecting small biomolecules, including glucose, glutathione, uric acid, ascorbic acid, hydrogen peroxide, and dopamine via colorimetry, fluorescence, and electrochemistry. Challenges such as matrix interference and stability, along with future directions in flexible electronics and clinical translation, are discussed, aiming to advance SAN-based detection technologies. Full article
(This article belongs to the Special Issue 30th Anniversary of Molecules—Recent Advances in Applied Chemistry)
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9 pages, 2041 KB  
Communication
Precursor-Directed Thermal Synthesis of Copper Catalysts for Tunable CO2 to CH4 and C2H4 Conversion at Industrial Current Densities
by Hunter B. Vibbert, Luqman Azhari, Nathan Rafisiman, Emma Olson, Bing Tan and Nicholas G. Pavlopoulos
Nanomaterials 2026, 16(6), 386; https://doi.org/10.3390/nano16060386 - 23 Mar 2026
Viewed by 612
Abstract
Scalable copper catalysts for electrochemical CO2 reduction have been prepared through precursor-directed thermal synthesis, enabling tunable conversion to CH4 and C2H4 at industrial current densities. Thermal treatment of distinct copper precursor salts was found to yield nanostructured catalysts [...] Read more.
Scalable copper catalysts for electrochemical CO2 reduction have been prepared through precursor-directed thermal synthesis, enabling tunable conversion to CH4 and C2H4 at industrial current densities. Thermal treatment of distinct copper precursor salts was found to yield nanostructured catalysts with composition- and morphology-dependent selectivity, and high Faradaic efficiencies under flow conditions. This simple, low-cost process demonstrates that precursor chemistry can control active phase formation and product distribution, providing a practical route toward scalable CO2 electroreduction. Full article
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20 pages, 4155 KB  
Review
Recent Advances in the High-Value Conversion of Alkenes Induced by Electrochemistry
by Xing’an Liang, Haolin Wang, Wei Xie, Zhenhua Liu and Dongmiao Qin
Molecules 2026, 31(6), 1027; https://doi.org/10.3390/molecules31061027 - 19 Mar 2026
Viewed by 1045
Abstract
Over the past few decades, electrosynthesis has advanced significantly, enabling numerous valuable transformations for synthetic chemists. Olefins are inexpensive, readily available industrial feedstocks extensively used in organic synthesis. Therefore, achieving high-value transformation of olefins is of great value. However, the use of stoichiometric [...] Read more.
Over the past few decades, electrosynthesis has advanced significantly, enabling numerous valuable transformations for synthetic chemists. Olefins are inexpensive, readily available industrial feedstocks extensively used in organic synthesis. Therefore, achieving high-value transformation of olefins is of great value. However, the use of stoichiometric oxidants and the generation of stoichiometric waste hinder its broader application. Utilizing electrochemistry to achieve high-value transformations of olefins represents a green, environmentally friendly, and sustainable strategy, since it eliminates the need for external oxidants. This review discusses recent advances in the high-value conversion of alkenes induced by electrochemistry. The article introduces two modes of electrochemical olefin transformation, discussing both synthetic applications and mechanistic studies. It highlights their advantages and suggests future directions to tackle the existing challenges in this synthetic domain. Full article
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4 pages, 165 KB  
Editorial
Electrochemistry of Organic and Organometallic Compounds
by Angel A. J. Torriero
Molecules 2026, 31(3), 535; https://doi.org/10.3390/molecules31030535 - 3 Feb 2026
Cited by 1 | Viewed by 695
Abstract
Electrochemistry occupies a distinctive position within modern chemistry by providing a direct and controllable link between molecular structure, redox behaviour, and functional performance [...] Full article
(This article belongs to the Special Issue Electrochemistry of Organic and Organometallic Compounds)
39 pages, 3073 KB  
Review
The Future of Green Chemistry: Evolution and Recent Trends in Deep Eutectic Solvents Research
by Veronika Jančíková and Michal Jablonský
Appl. Sci. 2026, 16(2), 654; https://doi.org/10.3390/app16020654 - 8 Jan 2026
Cited by 12 | Viewed by 4554
Abstract
Deep eutectic solvents are a sustainable and chemically tunable class of solvents formed by strong hydrogen bonding between a hydrogen bond acceptor and a hydrogen bond donor. Their extreme versatility has established deep eutectic solvents in ten key applied areas, including the green [...] Read more.
Deep eutectic solvents are a sustainable and chemically tunable class of solvents formed by strong hydrogen bonding between a hydrogen bond acceptor and a hydrogen bond donor. Their extreme versatility has established deep eutectic solvents in ten key applied areas, including the green extraction of bioactive compounds, CO2 capture, electrochemistry, and the catalytic media. Research is shifting towards highly innovative frontier trends, such as the role of deep eutectic solvents in dynamic covalent chemistry and as templates for advanced photocatalytic nanomaterials. Other innovative directions include artificial organelles for bioremediation, thermoacoustic deep eutectic solvents for smart drug delivery, and their use as multifunctional interfaces for 2D materials. The future of deep eutectic solvents lies in process engineering and scale-up, supported by computational chemistry, confirming their position as a central pillar of the circular economy. This trajectory marks the transition of deep eutectic solvents from laboratory curiosities to a scalable industrial reality. Full article
(This article belongs to the Special Issue Technical Advances in Biomass Conversion)
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42 pages, 1822 KB  
Review
Reversibility as a Design Principle in Inorganic, Organometallic and Organic Redox Mediators for Biosensors
by Angel A. J. Torriero
Inorganics 2026, 14(1), 10; https://doi.org/10.3390/inorganics14010010 - 26 Dec 2025
Cited by 3 | Viewed by 2352
Abstract
Redox mediators are central to electrochemical biosensors, enabling electron transfer between deeply buried enzymatic cofactors and electrode surfaces when direct electron transfer is kinetically inaccessible. Among all design parameters, the reversibility of mediator redox cycling remains the most decisive yet under-examined factor governing [...] Read more.
Redox mediators are central to electrochemical biosensors, enabling electron transfer between deeply buried enzymatic cofactors and electrode surfaces when direct electron transfer is kinetically inaccessible. Among all design parameters, the reversibility of mediator redox cycling remains the most decisive yet under-examined factor governing biosensor stability, drift and long-term reproducibility. This review establishes reversibility as a unifying framework grounded in inorganic and organometallic redox chemistry, with particular emphasis on coordination environments, ligand-field effects and outer-sphere electron-transfer pathways. Recent advances (2010–2025) in ruthenium and osmium polypyridyl complexes, cobalt macrocycles, hexacyanoferrates and Prussian Blue analogues are examined alongside ferrocene derivatives and other organometallic mediators, which together define the upper limits of reversible behaviour. Organic mediator families, including quinones, phenazines, indophenols, aminophenols and viologens, are discussed as mechanistic contrasts that highlight the structural and thermodynamic constraints that limit long-term cycling in aqueous media. Mechanistic indicators of reversibility, including peak separation, current ratios and heterogeneous electron-transfer rate constants, are linked to mediator architecture, coordination chemistry and immobilisation environment. By integrating molecular electrochemistry with applied sensor engineering, this review provides a mechanistically grounded basis for selecting or designing redox mediators that sustain efficient electron transfer, minimal fouling and calibration stability across diverse sensing platforms. Full article
(This article belongs to the Section Bioinorganic Chemistry)
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