In this review, progress in the application of STM in electrocatalysis is systematically discussed. The construction of model electrocatalysts and electrocatalytic systems are summarized. Then, we present the STM investigation of electrocatalyst structures and surface processes related to electrocatalysis. Challenges and future developments in the field are discussed in the outlook.The last few years have seen huge growing interest in the heterogenisation of molecular catalysts since it allows combining the advantages of homogeneous and heterogeneous catalyses. Besides bringing recyclability, the immobilisation of the catalyst may increase its stability while allowing tuning its selectivity. In this respect, Metal-Organic Frameworks (MOFs) attract evergrowing interest as a platform for their confinement within their pores or channels. In this review, Cat@MOF composites wherein molecular catalysts (Cats) are immobilised into MOFs through non-covalent interactions with their host are reviewed thoroughly. Polyoxometalates (POMs) and other metal-based complexes as immobilised molecular species are covered. In the first part, the different synthetic methods and analytical tools are described. A critical analysis of the various physico-chemical methods available to characterise the Cat@MOF composites is provided - particular attention being paid toward their pertinence to the investigation of the content, the position and the stability of the catalyst within the MOF. Besides, the focus is on non-conventional techniques such as the Pair Distribution Function (PDF) method and a section is dedicated to the contribution of DFT calculations. In the second part, the applications of these materials in the fields of catalysis, including oxidation and reduction reactions, acid-base catalysis, and photo- and electrocatalysis, are detailed.Racemases and epimerases catalyse changes in the stereochemical configurations of chiral centres and are of interest as model enzymes and as biotechnological tools. They also occupy pivotal positions within metabolic pathways and, hence, many of them are important drug targets. This review summarises the catalytic mechanisms of PLP-dependent, enolase family and cofactor-independent racemases and epimerases operating by a deprotonation/reprotonation (1,1-proton transfer) mechanism and methods for measuring their catalytic activity. Strategies for inhibiting these enzymes are reviewed, as are specific examples of inhibitors. Rational design of inhibitors based on substrates has been extensively explored but there is considerable scope for development of transition-state mimics and covalent inhibitors and for the identification of inhibitors by high-throughput, fragment and virtual screening approaches. The increasing availability of enzyme structures obtained using X-ray crystallography will facilitate development of inhibitors by rational design and fragment screening, whilst protein models will facilitate development of transition-state mimics.Over the last three decades, photonic crystals (PhCs) have attracted intense interests thanks to their broad potential applications in optics and photonics. Generally, these structures can be fabricated via either "top-down" lithographic or "bottom-up" self-assembly approaches. The self-assembly approaches have attracted particular attention due to their low cost, simple fabrication processes, relative convenience of scaling up, and the ease of creating complex structures with nanometer precision. The self-assembled colloidal crystals (CCs), which are good candidates for PhCs, have offered unprecedented opportunities for photonics, optics, optoelectronics, sensing, energy harvesting, environmental remediation, pigments, and many other applications. The creation of high-quality CCs and their mass fabrication over large areas are the critical limiting factors for real-world applications. This paper reviews the state-of-the-art techniques in the self-assembly of colloidal particles for the fabrication of large-and highlight their novel real-world applications.Glutathione (GSH), the main redox buffer, has long been recognized as a pivotal modulator of tumor initiation, progression and metastasis. It is also implicated in the resistance of platinum-based chemotherapy and radiation therapy. https://www.selleckchem.com/products/OSI-906.html Therefore, depleting intracellular GSH was considered a potent solution to combating cancer. However, reducing GSH within cancer cells alone always failed to yield desirable therapeutic effects. In this regard, the convergence of GSH-scavenging agents with therapeutic drugs has thus been pursued in clinical practice. Unfortunately, the therapeutic outcomes are still unsatisfactory due to untargeted drug delivery. Advanced nanomedicine of synergistic GSH depletion and cancer treatment has attracted tremendous interest because they promise to deliver superior therapeutic benefits while alleviating life-threatening side effects. In the past five years, the authors and others have demonstrated that numerous nanomedicines, by simultaneously delivering GSH-depleting agents and therapeutic components, boost not only traditional chemotherapy and radiotherapy but also multifarious emerging treatment modalities, including photodynamic therapy, sonodynamic therapy, chemodynamic therapy, ferroptosis, and immunotherapy, to name a few, and achieved decent treatment outcomes in a large number of rodent tumor models. In this review, we summarize the most recent progress in engineering nanomedicine for GSH depletion-enhanced cancer therapies. Biosynthesis of GSH and various types of GSH-consuming strategies will be briefly introduced. The challenges and perspectives of leveraging nanomedicine for GSH consumption-augmented cancer therapies will be discussed at the end.We report a colorimetric sensor for the detection of Hg2+ ions utilizing surface-modified gold nanoparticles. Gold nanoparticles (GNPs) were synthesized by direct reduction and were subsequently functionalized using Schiff base ligands. Schiff base ligands as electron transfer agents have been frequently used for the determination of heavy metal ions. From the spectroscopic analysis, it was found that the mechanism could be defined as coordination between azomethine nitrogen and the carbonyl oxygen of the ligand with Hg2+ ions. The affinity of Hg2+ ions towards the bidentate Schiff base on the GNPs result from their self-aggregation and investigated to be a powerful asset for the development of Hg2+ ion-selective sensors, which is accompanied by a visible color change from pink to purple or can be detect by UV-Vis spectroscopy. The optimized structures and binding mechanisms were supported with a high correlation and agreement via spectroscopy and DFT calculations. These simple colorimetric tests can be extended for the rapid pre-screening of a wide variety of heavy metal ions for onsite detection and mitigation.
In this review, progress in the application of STM in electrocatalysis is systematically discussed. The construction of model electrocatalysts and electrocatalytic systems are summarized. Then, we present the STM investigation of electrocatalyst structures and surface processes related to electrocatalysis. Challenges and future developments in the field are discussed in the outlook.The last few years have seen huge growing interest in the heterogenisation of molecular catalysts since it allows combining the advantages of homogeneous and heterogeneous catalyses. Besides bringing recyclability, the immobilisation of the catalyst may increase its stability while allowing tuning its selectivity. In this respect, Metal-Organic Frameworks (MOFs) attract evergrowing interest as a platform for their confinement within their pores or channels. In this review, Cat@MOF composites wherein molecular catalysts (Cats) are immobilised into MOFs through non-covalent interactions with their host are reviewed thoroughly. Polyoxometalates (POMs) and other metal-based complexes as immobilised molecular species are covered. In the first part, the different synthetic methods and analytical tools are described. A critical analysis of the various physico-chemical methods available to characterise the Cat@MOF composites is provided - particular attention being paid toward their pertinence to the investigation of the content, the position and the stability of the catalyst within the MOF. Besides, the focus is on non-conventional techniques such as the Pair Distribution Function (PDF) method and a section is dedicated to the contribution of DFT calculations. In the second part, the applications of these materials in the fields of catalysis, including oxidation and reduction reactions, acid-base catalysis, and photo- and electrocatalysis, are detailed.Racemases and epimerases catalyse changes in the stereochemical configurations of chiral centres and are of interest as model enzymes and as biotechnological tools. They also occupy pivotal positions within metabolic pathways and, hence, many of them are important drug targets. This review summarises the catalytic mechanisms of PLP-dependent, enolase family and cofactor-independent racemases and epimerases operating by a deprotonation/reprotonation (1,1-proton transfer) mechanism and methods for measuring their catalytic activity. Strategies for inhibiting these enzymes are reviewed, as are specific examples of inhibitors. Rational design of inhibitors based on substrates has been extensively explored but there is considerable scope for development of transition-state mimics and covalent inhibitors and for the identification of inhibitors by high-throughput, fragment and virtual screening approaches. The increasing availability of enzyme structures obtained using X-ray crystallography will facilitate development of inhibitors by rational design and fragment screening, whilst protein models will facilitate development of transition-state mimics.Over the last three decades, photonic crystals (PhCs) have attracted intense interests thanks to their broad potential applications in optics and photonics. Generally, these structures can be fabricated via either "top-down" lithographic or "bottom-up" self-assembly approaches. The self-assembly approaches have attracted particular attention due to their low cost, simple fabrication processes, relative convenience of scaling up, and the ease of creating complex structures with nanometer precision. The self-assembled colloidal crystals (CCs), which are good candidates for PhCs, have offered unprecedented opportunities for photonics, optics, optoelectronics, sensing, energy harvesting, environmental remediation, pigments, and many other applications. The creation of high-quality CCs and their mass fabrication over large areas are the critical limiting factors for real-world applications. This paper reviews the state-of-the-art techniques in the self-assembly of colloidal particles for the fabrication of large-and highlight their novel real-world applications.Glutathione (GSH), the main redox buffer, has long been recognized as a pivotal modulator of tumor initiation, progression and metastasis. It is also implicated in the resistance of platinum-based chemotherapy and radiation therapy. https://www.selleckchem.com/products/OSI-906.html Therefore, depleting intracellular GSH was considered a potent solution to combating cancer. However, reducing GSH within cancer cells alone always failed to yield desirable therapeutic effects. In this regard, the convergence of GSH-scavenging agents with therapeutic drugs has thus been pursued in clinical practice. Unfortunately, the therapeutic outcomes are still unsatisfactory due to untargeted drug delivery. Advanced nanomedicine of synergistic GSH depletion and cancer treatment has attracted tremendous interest because they promise to deliver superior therapeutic benefits while alleviating life-threatening side effects. In the past five years, the authors and others have demonstrated that numerous nanomedicines, by simultaneously delivering GSH-depleting agents and therapeutic components, boost not only traditional chemotherapy and radiotherapy but also multifarious emerging treatment modalities, including photodynamic therapy, sonodynamic therapy, chemodynamic therapy, ferroptosis, and immunotherapy, to name a few, and achieved decent treatment outcomes in a large number of rodent tumor models. In this review, we summarize the most recent progress in engineering nanomedicine for GSH depletion-enhanced cancer therapies. Biosynthesis of GSH and various types of GSH-consuming strategies will be briefly introduced. The challenges and perspectives of leveraging nanomedicine for GSH consumption-augmented cancer therapies will be discussed at the end.We report a colorimetric sensor for the detection of Hg2+ ions utilizing surface-modified gold nanoparticles. Gold nanoparticles (GNPs) were synthesized by direct reduction and were subsequently functionalized using Schiff base ligands. Schiff base ligands as electron transfer agents have been frequently used for the determination of heavy metal ions. From the spectroscopic analysis, it was found that the mechanism could be defined as coordination between azomethine nitrogen and the carbonyl oxygen of the ligand with Hg2+ ions. The affinity of Hg2+ ions towards the bidentate Schiff base on the GNPs result from their self-aggregation and investigated to be a powerful asset for the development of Hg2+ ion-selective sensors, which is accompanied by a visible color change from pink to purple or can be detect by UV-Vis spectroscopy. The optimized structures and binding mechanisms were supported with a high correlation and agreement via spectroscopy and DFT calculations. These simple colorimetric tests can be extended for the rapid pre-screening of a wide variety of heavy metal ions for onsite detection and mitigation.
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