Topics in Current Chemistry最新文献

Solar-driven photocatalysis mediated by semiconductors has been rapidly developed as a green and sustainable technology for environmental remediation. Continuous efforts have been devoted to novel semiconducting photocatalysts to boost the efficiency of the photocatalytic system. However, controversy has widely existed in materials characterization and photocatalytic activity evaluation. This review overviews the recent advances in characterization methodology and photocatalytic activity evaluation of solar-driven catalysts (SDCs) for environmental remediation. After a general and brief introduction of different SDCs, the compositional, structural, and optical characterizations of SDCs are summarized. Moreover, the characterization methods and challenges in the doped and coupled SDCs are discussed. Finally, the challenges in the evaluation of current evaluation methods for the photocatalytic activity of SDCs are highlighted.

Glycopolymer materials have emerged as a significant biopolymer class that has piqued the scientific community's attention due to their potential applications. Recently, they have been found to be a unique synthetic biomaterial; glycopolymer materials have also been used for various applications, including direct therapeutic methods, medical adhesives, drug/gene delivery systems, and biosensor applications. Therefore, for the next stage of biomaterial research, it is essential to understand current breakthroughs in glycopolymer-based materials research. This review discusses the most widely utilized synthetic methodologies for glycopolymer-based materials, their properties based on structure–function interactions, and the significance of these materials in biosensing applications, among other topics. When creating glycopolymer materials, contemporary polymerization methods allow precise control over molecular weight, molecular weight distribution, chemical activity, and polymer architecture. This review concludes with a discussion of the challenges and complexities of glycopolymer-based biosensors, in addition to their potential applications in the future.

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Cyclometalated Ir(III) complexes exhibit strong phosphorescence emission with lifetime of submicroseconds to several microseconds at room temperature. Their synthetic versatility enables broad control of physical properties, such as charge and lipophilicity, as well as emission colors. These favorable properties have motivated the use of Ir(III) complexes in luminescent bioimaging applications. This review examines the recent progress in the development of phosphorescent biolabels and sensors based on Ir(III) complexes. It begins with a brief introduction about the basic principles of the syntheses and photophysical processes of cyclometalated Ir(III) complexes. Focus is placed on illustrating the broad imaging utility of Ir(III) complexes. Phosphorescent labels illuminating intracellular organelles, including mitochondria, lysosomes, and cell membranes, are summarized. Ir(III) complexes capable of visualization of tumor spheroids and parasites are also introduced. Facile chemical modification of the cyclometalating ligands endows the Ir(III) complexes with strong sensing ability. Sensors of temperature, pH, CO₂, metal ions, anions, biosulfur species, reactive oxygen species, peptides, and viscosity have recently been added to the molecular imaging tools. This diverse utility demonstrates the potential of phosphorescent Ir(III) complexes toward bioimaging applications.

Cyclometalated iridium(III) (Ir(III)) complexes exhibit excellent photophysical properties that include large Stokes shift, high emission quantum yields, and microsecond-order emission lifetimes, due to low-lying metal-to-ligand charge transfer (spin-forbidden singlet–triplet (³MLCT) transition). As a result, analogs have been applied for research not only in the material sciences, such as the development of organic light-emitting diodes (OLEDs), but also for photocatalysts, bioimaging probes, and anticancer reagents. Although a variety of methods for the synthesis and the applications of functionalized cyclometalated iridium complexes have been reported, functional groups are generally introduced to the ligands prior to the complexation with Ir salts. Therefore, it is difficult to introduce thermally unstable functional groups such as peptides and sugars due to the harsh reaction conditions such as the high temperatures used in the complexation with Ir salts. In this review, the functionalization of Ir complexes after the formation of cyclometalated Ir complexes and their biological and material applications are described. These methods are referred to as “post-complexation functionalization (PCF).” In this review, applications of PCF to the design and synthesis of Ir(III) complexes that exhibit blue –red and white color emissions, luminescence pH probes, luminescent probes of cancer cells, compounds that induce cell death in cancer cells, and luminescent complexes that have long emission lifetimes are summarized.

The molecules possessing triazine and tetrazine moieties belong to a special class of heterocyclic compounds. Both triazines and tetrazines are building blocks and have provided a new dimension to the design of biologically important organic molecules. Several of their derivatives with fine-tuned electronic properties have been identified as multifunctional, adaptable, switchable, remarkably antifungal, anticancer, antiviral, antitumor, cardiotonic, anti-HIV, analgesic, anti-protozoal, etc. The objective of this review is to comprehensively describe the recent developments in synthesis, coordination properties, and various applications of triazine and tetrazine molecules. The rich literature demonstrates various synthetic routes for a variety of triazines and tetrazines through microwave-assisted, solid-phase, metal-based, [4+2] cycloaddition, and multicomponent one-pot reactions. Synthetic approaches contain linear, angular, and fused triazine and tetrazine heterocycles through a combinatorial method. Notably, the triazines and tetrazines undergo a variety of organic transformations, including electrophilic addition, coupling, nucleophilic displacement, and intramolecular cyclization. The mechanistic aspects of these heterocycles are discussed in a detailed way. The bioorthogonal application of these polyazines with various strained alkenes and alkynes provides a new prospect for investigations in chemical biology. This review systematically encapsulates the recent developments and challenges in the synthesis and possible potential applications of various triazine and tetrazine systems.

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Conjugated polymers (CPs) have been recently widely investigated for their properties and their applications in different fields including photocatalysis. Among the family of CPs, polypyrrole (PPy) has been the most extensively studied owing to its good environmental stability, high electrical conductivity, superior redox properties and easy synthesis. Besides, nanostructured polypyrrole-based nanomaterials are a type of active organic materials for photocatalysis, which is one of their emerging applications. Nanostructuration of polypyrrole can reduce the electron-hole recombination because of short charge transfer distances and reactant adsorption, and product desorption can be enhanced owing to the high surface area offered by nanostructures. This review summarizes synthesis of different nanostructures based on π-conjugated polymer polypyrrole and the latest developments for photocatalytic applications, including degradation of organic pollutants and hydrogen generation.

In recent years, photoactive proteins such as rhodopsins have become a common target for cutting-edge research in the field of optogenetics. Alongside wet-lab research, computational methods are also developing rapidly to provide the necessary tools to analyze and rationalize experimental results and, most of all, drive the design of novel systems. The Automatic Rhodopsin Modeling (ARM) protocol is focused on providing exactly the necessary computational tools to study rhodopsins, those being either natural or resulting from mutations. The code has evolved along the years to finally provide results that are reproducible by any user, accurate and reliable so as to replicate experimental trends. Furthermore, the code is efficient in terms of necessary computing resources and time, and scalable in terms of both number of concurrent calculations as well as features. In this review, we will show how the code underlying ARM achieved each of these properties.

This review article discusses historical and contemporary research studies of asymmetric allylic oxidation of olefins using homogeneous and heterogeneous copper complexes of various kinds of oxazoline-based ligands, until the end of 2021. It is revealed that this strategy is a powerful method to form a new stereogenic center bearing an oxygen substituent adjacent to an unchanged C=C bond. Enantioselectivities as well as chemical yields, and also the reactivity, are strongly dependent on the type of substrate, oxidant, the copper salt and its oxidation state, ligand structure, temperature, nature of the solvent, and additives such as phenylhydrazine and porous materials.

To analyze chemical reaction dynamics based on a reaction path network, we have developed the “Reaction Space Projector” (ReSPer) method with the aid of the dimensionality reduction method. This program has two functions: the construction of a reduced-dimensionality reaction space from a molecular structure dataset, and the projection of dynamic trajectories into the low-dimensional reaction space. In this paper, we apply ReSPer to isomerization and bifurcation reactions of the Au₅ cluster and succeed in analyzing dynamic reaction routes involved in multiple elementary reaction processes, constructing complicated networks (called “closed islands”) of nuclear permutation-inversion (NPI) isomerization reactions, and elucidating dynamic behaviors in bifurcation reactions with reference to bundles of trajectories. Interestingly, in the second application, we find a correspondence between the contribution ratios in the ability to visualize and the symmetry of the morphology of closed islands. In addition, the third application suggests the existence of boundaries that determine the selectivity in bifurcation reactions, which was discussed in the phase space. The ReSPer program is a versatile and robust tool to clarify dynamic reaction mechanisms based on the reduced-dimensionality reaction space without prior knowledge of target reactions.

Domesticating solar energy by exploiting photovoltaic technology has become a quintessential strategy for future global energy production. Since 2015, non-fullerene organic solar cells (NF-OSC) have attracted a great deal of attention owing to the marvellous properties of non-fullerene acceptors (NFA) such as structural versability, broad absorption, suitable energy levels, tunable charge transport and morphology, leading to remarkable accomplishments in power conversion efficiency (PCE) from 1% to nearly 20%. One class of materials is provided by the fused ring aromatic indacenodithiophene (IDT) and its derivatives, which are emerging continuously as promising next-generation building blocks to construct high performance photovoltaic materials. Encouraging PCEs of more than 15% have been achieved in their binary NF-OSCs, while careful device engineering and proper amalgamation of a third component have led to PCEs of almost 18% in ternary devices. This review surveys recent developments in the area of IDT-based materials for photovoltaic applications. Different strategies to develop efficient IDT-based NFA and factors influencing the bandgaps, molecular energy levels, charge transport properties, and film morphologies, as well as the photovoltaic performance of these materials, are discussed.

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