RESUMO
This review summarizes the results of the author's basic research on organic electrochemistry conducted at Gifu Pharmaceutical University over about 40 years. After completing graduate school, the author became a research associate in Prof. Tanekazu Kubota's laboratory and started research on molecular spectroscopy in 1983. After Prof. Kubota retired in 1989, the author continued investigations in the field of organic electrochemistry as an independent researcher. At that time, a research environment in which ab initio molecular orbital calculations can be used as an analytical tool for experimental research was developed, and the author commenced research on organic electrochemistry combined with quantum chemical calculations as a lifework. The author's research topics were basic research on the molecular theory of redox potentials of organic molecules, molecular design of functional molecules, intermolecular interactions of organic molecules involving electron transfers and electron transfer systems composed of bioactive quinones, and analytical application research based on the basic electrochemistry. In this review article, the essence of the research results is introduced while reflecting on the existing situation at the time of the research. The author concludes the review by expressing gratitude to all colleagues for supporting the research in the author's laboratory.
Assuntos
Química Analítica , Eletroquímica , Transporte de Elétrons , Teoria Quântica , Animais , Química Analítica/tendências , Química Orgânica/tendências , Eletroquímica/tendências , Humanos , Modelos Moleculares , QuinonasRESUMO
The valorization of CO2 to valuable products via microbial electrosynthesis (MES) is a technology transcending the disciplines of microbiology, (electro)chemistry, and engineering, bringing opportunities and challenges. As the field looks to the future, further emphasis is expected to be placed on engineering efficient reactors for biocatalysts, to thrive and overcome factors which may be limiting performance. Meanwhile, ample opportunities exist to take the lessons learned in traditional and adjacent electrochemical fields to shortcut learning curves. As the technology transitions into the next decade, research into robust and adaptable biocatalysts will then be necessary as reactors shape into larger and more efficient configurations, as well as presenting more extreme temperature, salinity, and pressure conditions.
Assuntos
Dióxido de Carbono , Eletroquímica , Dióxido de Carbono/metabolismo , Eletroquímica/tendências , Eletrodos , Microbiota/fisiologiaRESUMO
In this review, the roles of room temperature ionic liquids (RTILs) and RTIL based solvent systems as proposed alternatives for conventional organic electrolyte solutions are described. Ionic liquids are introduced as well as the relevant properties for their use in electrochemistry (reduction of ohmic losses), such as diffusive molecular motion and ionic conductivity. We have restricted ourselves to provide a survey on the latest, most representative developments and progress made in the use of ionic liquids as electrolytes, in particular achieved by the cyclic voltammetry technique. Thus, the present review comprises literature from 2015 onward covering the different aspects of RTILs, from the knowledge of these media to the use of their properties for electrochemical processes. Out of the scope of this review are heat transfer applications, medical or biological applications, and multiphasic reactions.
Assuntos
Líquidos Iônicos/química , Compostos de Amônio/química , Fenômenos Químicos , Condutividade Elétrica , Técnicas Eletroquímicas/tendências , Eletroquímica/tendências , Eletrólitos/química , Imidazóis/química , Estrutura Molecular , Compostos Organofosforados/química , Pirrolidinas/química , Solventes/química , Compostos de Sulfônio/química , Temperatura , ViscosidadeRESUMO
The innovation of nanoparticles assumes a critical part of encouraging and giving open doors and conceivable outcomes to the headway of new era devices utilized as a part of biosensing. The focused on the quick and legitimate detecting of specific biomolecules using functionalized gold nanoparticles (Au NPs), and carbon nanotubes (CNTs) has turned into a noteworthy research enthusiasm for the most recent decade. Sensors created with gold nanoparticles or carbon nanotubes or in some cases by utilizing both are relied upon to change the very establishments of detecting and distinguishing various analytes. In this review, we will examine the current utilization of functionalized AuNPs and CNTs with other synthetic mixes for the creation of biosensor prompting to the location of particular analytes with low discovery cutoff and quick reaction.
Assuntos
Técnicas Biossensoriais/métodos , Técnicas Biossensoriais/tendências , Eletroquímica/tendências , Ouro/química , Nanopartículas Metálicas/química , Nanotubos de Carbono/química , Técnicas Biossensoriais/instrumentaçãoRESUMO
We introduce dual kinetic chronoamperometry, in which reciprocal relations are established between the kinetic curves of electrochemical reactions that start from symmetrical initial conditions. We have performed numerical and experimental studies in which the kinetic curves of the electron-transfer processes are analyzed for a reversible first order reaction. Experimental tests were done with the ferrocyanide/ferricyanide system in which the concentrations of each component could be measured separately using the platinum disk/gold ring electrode. It is shown that the proper ratio of the transient kinetic curves obtained from cathodic and anodic mass transfer limited regions give thermodynamic time invariances related to the reaction quotient of the bulk concentrations. Therefore, thermodynamic time invariances can be observed at any time using the dual kinetic curves for reversible reactions. The technique provides a unique possibility to extract the non-steady state trajectory starting from one initial condition based only on the equilibrium constant and the trajectory which starts from the symmetrical initial condition. The results could impact battery technology by predicting the concentrations and currents of the underlying non-steady state processes in a wide domain from thermodynamic principles and limited kinetic information.
Assuntos
Eletroquímica/tendências , Transporte de Elétrons , Termodinâmica , Eletrodos , Concentração de Íons de Hidrogênio , Cinética , Modelos BiológicosRESUMO
This review shows the recent advances and state of the art in paper-based analytical devices (PADs) through the analysis of their integration with microfluidics and LOC micro- and nanotechnologies, electrochemical/optical detection and electronic devices as the convergence of various knowledge areas. The important role of the paper design/architecture in the improvement of the performance of sensor devices is discussed. The discussion is fundamentally based on µPADs as the new generation of paper-based (bio)sensors. Data about the scientific publication ranking of PADs, illustrating their increase as an experimental research topic in the past years, are supplied. In addition, an analysis of the simultaneous evolution of PADs in academic lab research and industrial commercialization highlighting the parallelism of the technological transfer from academia to industry is displayed. A general overview of the market behaviour, the leading industries in the sector and their commercialized devices is given. Finally, personal opinions of the authors about future perspectives and tendencies in the design and fabrication technology of PADs are disclosed.
Assuntos
Pesquisa Biomédica/métodos , Desenho de Equipamento , Pesquisa Interdisciplinar , Dispositivos Lab-On-A-Chip/tendências , Papel , Animais , Pesquisa Biomédica/instrumentação , Pesquisa Biomédica/tendências , Celulose/química , Colódio/química , Eletroquímica/instrumentação , Eletroquímica/métodos , Eletroquímica/tendências , Desenho de Equipamento/tendências , Humanos , Proteínas Imobilizadas/metabolismo , Pesquisa Interdisciplinar/tendências , Microquímica/instrumentação , Microquímica/métodos , Microquímica/tendências , Microfluídica/instrumentação , Microfluídica/métodos , Microfluídica/tendências , Nanotecnologia/instrumentação , Nanotecnologia/métodos , Nanotecnologia/tendências , Óptica e Fotônica/instrumentação , Óptica e Fotônica/métodos , Óptica e Fotônica/tendências , Testes Imediatos/tendênciasRESUMO
A novel electrochemically controlled release method for nitric oxide (NO) (based on electrochemical reduction of nitrite ions) is combined with an amperometric oxygen sensor within a dual lumen catheter configuration for the continuous in vivo sensing of the partial pressure of oxygen (PO2) in blood. The on-demand electrochemical NO generation/release method is shown to be fully compatible with amperometric PO2 sensing. The performance of the sensors is evaluated in rabbit veins and pig arteries for 7 and 21 h, respectively. Overall, the NO releasing sensors measure both venous and arterial PO2 values more accurately with an average deviation of -2 ± 11% and good correlation (R(2) = 0.97) with in vitro blood measurements, whereas the corresponding control sensors without NO release show an average deviation of -31 ± 28% and poor correlation (R(2) = 0.43) at time points >4 h after implantation in veins and >6 h in arteries. The NO releasing sensors induce less thrombus formation on the catheter surface in both veins and arteries (p < 0.05). This electrochemical NO generation/release method could offer a new and attractive means to improve the biocompatibility and performance of implantable chemical sensors.
Assuntos
Técnicas Biossensoriais/métodos , Monitorização Fisiológica/métodos , Óxido Nítrico/química , Oxigênio/análise , Animais , Eletroquímica/tendências , Óxido Nítrico/sangue , Coelhos , SuínosRESUMO
Microbial electrochemical technologies (METs) are emerging green processes producing useful products from renewable sources without causing environmental pollution and treating wastes. The separator, an important part of METs that greatly affects the latter's performance, is commonly made of Nafion proton exchange membrane (PEM). However, many problems have been identified associated with the Nafion PEM such as high cost of membrane, significant oxygen and substrate crossovers, and transport of cations other than protons protons and biofouling. A variety of materials have been offered as alternative separators such as ion-exchange membranes, salt bridges, glass fibers, composite membranes and porous materials. It has been claimed that low cost porous materials perform better than PEM. These include J-cloth, nylon filter, glass fiber mat, non-woven cloth, earthen pot and ceramics that enable non-ion selective charge transfer. This paper provides an up-to-date review on porous separators and plots directions for future studies.
Assuntos
Fontes de Energia Bioelétrica/tendências , Eletroquímica/instrumentação , Eletroquímica/tendências , Membranas Artificiais , PorosidadeRESUMO
The results from a final-year undergraduate project led to an $876M sale of a spin-out company 19 years later: the 1977 communication from Mark Eddowes and Allen Hill seeded the rich field of protein electrochemistry, the technology that underpins commercial glucose biosensors.
Assuntos
Eletroquímica/tendências , Proteínas/química , Técnicas Biossensoriais , Técnicas Eletroquímicas , Eletrodos , Transporte de Elétrons , Enzimas/química , Enzimas/metabolismo , Glucose/análise , Proteínas/metabolismoRESUMO
Screen-printed electrodes (SPEs), which are used as economical electrochemical substrates, have gone through significant improvements over the past few decades with respect to both their format and their printing materials. Because of their advantageous material properties, such as disposability, simplicity, and rapid responses, SPEs have been successfully utilised for the rapid in situ analysis of environmental pollutants. This critical review describes the basic fabrication principles, the configuration designs of SPEs and the hybrid analytical techniques based on SPEs. We mainly overview the electrochemical applications of SPEs in environmental analysis over the past 3 years, including the determination of organic compounds, heavy metals and gas pollutants.
Assuntos
Eletroquímica/tendências , Eletrodos , Monitoramento Ambiental , Poluentes Ambientais/química , Impressão , Poluentes Ambientais/análise , Análise em MicrossériesRESUMO
Electrospinning is the most versatile technology in use today, for the generation of polymer nanoscale fibers. The nano materials generated using this technology have a large surface area and are highly porous making it very useful in many applications in diverse fields such as energy storage, healthcare, biotechnology, environmental engineering, defense and security. The production of the fibers and the morphology can be easily controlled by modifications to the processing parameters. The relatively high production rate and simplicity of the setup makes electrospinning highly attractive. This review summarizes the effect of various processing parameters on the effective generation of nanofibers. By simple modifications to the electric field inside the electrospinning chamber the fiber collection can be easily controlled. In addition, the various applications of electrospun fibers in electronic devices, environmental sensors and filters, energy storage, and in biomedicine such as in tissue engineering, drug delivery and enzyme encapsulation are examined and the current research in each field is also explored in this review.
Assuntos
Cristalização/métodos , Eletroquímica/tendências , Previsões , Nanoestruturas/química , Nanoestruturas/ultraestrutura , Nanotecnologia/tendências , Substâncias Macromoleculares/química , Conformação Molecular , Tamanho da Partícula , Rotação , Propriedades de SuperfícieRESUMO
Physical electrochemistry has undergone a remarkable evolution over the last few decades, integrating advanced techniques and theory from solid state and surface physics. Single-crystal electrode surfaces have been a core notion, opening for scanning tunnelling microscopy directly in aqueous electrolyte (in situ STM). Interfacial electrochemistry of metalloproteins is presently going through a similar transition. Electrochemical surfaces with thiol-based promoter molecular monolayers (SAMs) as biomolecular electrochemical environments and the biomolecules themselves have been mapped with unprecedented resolution, opening a new area of single-molecule bioelectrochemistry. We consider first in situ STM of small redox molecules, followed by in situ STM of thiol-based SAMs as molecular views of bioelectrochemical environments. We then address electron transfer metalloproteins, and multi-centre metalloenzymes including applied single-biomolecular perspectives based on metalloprotein/metallic nanoparticle hybrids.
Assuntos
Eletroquímica/métodos , Transporte de Elétrons , Metaloproteínas/química , Conformação Proteica , Eletroquímica/tendências , Ouro/química , Nanopartículas Metálicas/química , Metaloproteínas/metabolismo , Microscopia de Força Atômica/métodos , Microscopia de Tunelamento/métodos , Modelos Moleculares , Reprodutibilidade dos TestesRESUMO
Similar to its popular older cousins of fullerene and carbon nanotubes (CNTs), the latest form of nanocarbon, graphene, is inspiring intensive research efforts in its own right. As an atomically thin layer of sp(2)-hybridized carbon, graphene possesses spectacular electronic, optical, magnetic, thermal and mechanical properties, which make it an exciting material in a variety of important applications. In this review, we present the current advances in the field of graphene electroanalytical chemistry, including the modern methods of graphene production, and graphene functionalization. Electrochemical (bio) sensing developments using graphene and graphene-based materials are summarized in more detail, and we also speculate on their future and discuss potential progress for their applications in electroanalytical chemistry.
Assuntos
Técnicas de Química Analítica/métodos , Eletroquímica/métodos , Grafite/química , Nanoestruturas/química , Técnicas de Química Analítica/tendências , Eletroquímica/tendências , NanotecnologiaRESUMO
Nanotechnology assists in the development of biocomposite nanofibrous scaffolds that can react positively to changes in the immediate cellular environment and stimulate specific regenerative events at molecular level to generate healthy tissues. Recently, electrospinning has gained huge momentum with greater accessibility of fabrication of composite, controlled and oriented nanofibers with sufficient porosity required for effective tissue regeneration. Current developments include the fabrication of nanofibrous scaffolds which can provide chemical, mechanical and biological signals to respond to the environmental stimuli. These nanofibers are fabricated by simple coating, blending of polymers/bioactive molecules or by surface modification methods. For obtaining optimized surface functionality, with specially designed architectures for the nanofibers (multi-layered, core-shell, aligned), electrospinning process has been modified and simultaneous 'electrospin-electrospraying' process is one of the most lately introduced technique in this perspective. Properties such as porosity, biodegradation and mechanical properties of composite electrospun nanofibers along with their utilization for nerve, cardiac, bone, skin, vascular and cartilage tissue engineering are discussed in this review. In order to locally deliver electrical stimulus and provide a physical template for cell proliferations, and to gain an external control on the level and duration of stimulation, electrically conducting polymeric nanofibers are also fabricated by electrospinning. Electrospun polypyrrole (PPy) and polyaniline (PAN) based scaffolds are the most extensively studied composite substrates for nerve and cardiac tissue engineering with or without electrical stimulations, and are discussed here. However, the major focus of ongoing and future research in regenerative medicine is to effectively exploit the pluripotent potential of Mesenchymal Stem Cell (MSC) differentiation on composite nanofibrous scaffolds for repair of organs.
Assuntos
Eletroquímica/tendências , Regeneração Tecidual Guiada/tendências , Nanofibras/química , Nanofibras/uso terapêutico , Nanotecnologia/tendências , Engenharia Tecidual/tendências , Animais , Humanos , Nanofibras/ultraestruturaRESUMO
Graphene, a 2D nanomaterial that possesses spectacular physical, chemical and thermal properties, has caused immense excitement amongst scientists since its freestanding form was isolated in 2004. With research into graphene rife, it promises enhancements and vast applicability within many industrial aspects. Furthermore, graphene possesses a vast array of unique and highly desirable electrochemical properties, and it is this application that offers the most enthralling and spectacular journey. We present a review of the current literature concerning the electrochemical applications and advancements of graphene, starting with its use as a sensor substrate through to applications in energy production and storage, depicting the truly remarkable journey of a material that has just come of age.
Assuntos
Eletroquímica/instrumentação , Eletroquímica/métodos , Grafite/química , Técnicas Biossensoriais/instrumentação , Técnicas Biossensoriais/métodos , Eletroquímica/tendências , Eletrodos , Modelos Moleculares , Tamanho da PartículaRESUMO
Biomolecule-nanoparticle (or carbon nanotube) hybrid systems provide new materials that combine the unique optical, electronic, or catalytic properties of the nanoelements with the recognition or biocatalytic functions of biomolecules. This article summarizes recent applications of biomolecule-nanoparticle (or carbon nanotubes) hybrid systems for sensing, synthesis of nanostructures, and for the fabrication of nanoscale devices. The use of metallic nanoparticles for the electrical contacting of redox enzymes with electrodes, and as catalytic labels for the development of electrochemical biosensors is discussed. Similarly, biomolecule-quantum dot hybrid systems are implemented for optical biosensing, and for monitoring intracellular metabolic processes. Also, the self-assembly of biomolecule-metal nanoparticle hybrids into nanostructures and functional nanodevices is presented. The future perspectives of the field are addressed by discussing future challenges and highlighting different potential applications.
Assuntos
Técnicas Biossensoriais/tendências , DNA/química , Nanoestruturas/química , Nanotecnologia/tendências , Proteínas/química , Animais , Técnicas Biossensoriais/métodos , Avaliação Pré-Clínica de Medicamentos/métodos , Avaliação Pré-Clínica de Medicamentos/tendências , Eletroquímica/métodos , Eletroquímica/tendências , Células HeLa , Humanos , Nanoestruturas/ultraestrutura , Nanotecnologia/métodos , Pontos QuânticosRESUMO
Advances in functional materials for energy conversion and storage technologies are crucial in addressing the global challenge of green sustainable energy. This article aims to demonstrate the valuable role that modern modelling techniques now play in providing deeper fundamental insight into novel materials for rechargeable lithium batteries and solid oxide fuel cells. Recent work is illustrated by studies on important topical materials encompassing transition-metal phosphates and silicates for lithium battery electrodes, and apatite-type silicates for fuel cell electrolytes.
Assuntos
Fontes Geradoras de Energia , Lítio/química , Apatitas/química , Biocombustíveis , Conservação dos Recursos Naturais , Fontes de Energia Elétrica , Eletricidade , Eletroquímica/métodos , Eletroquímica/tendências , Eletrodos , Íons , Modelos TeóricosRESUMO
With the emergence of nanotechnology, researchers become more interested in studying the unique properties of nanoscale materials. Electrospinning, an electrostatic fiber fabrication technique has evinced more interest and attention in recent years due to its versatility and potential for applications in diverse fields. The notable applications include in tissue engineering, biosensors, filtration, wound dressings, drug delivery, and enzyme immobilization. The nanoscale fibers are generated by the application of strong electric field on polymer solution or melt. The non-wovens nanofibrous mats produced by this technique mimics extracellular matrix components much closely as compared to the conventional techniques. The sub-micron range spun fibers produced by this process, offer various advantages like high surface area to volume ratio, tunable porosity and the ability to manipulate nanofiber composition in order to get desired properties and function. Over the years, more than 200 polymers have been electrospun for various applications and the number is still increasing gradually with time. With these in perspectives, we aim to present in this review, an overview of the electrospinning technique with its promising advantages and potential applications. We have discussed the electrospinning theory, spinnable polymers, parameters (solution and processing), which significantly affect the fiber morphology, solvent properties and melt electrospinning (alternative to solution electrospinning). Finally, we have focused on varied applications of electrospun fibers in different fields and concluded with the future prospects of this efficient technology.