Topics in Current Chemistry最新文献

Organic dyes, porphyrins and inorganic complexes containing imidazole (IM) motifs have been demonstrated as a new class of sensitizers in dye-sensitized solar cells (DSSCs). Particularly, the amphoteric nature of IM-based motifs allows them to be used as donors (D), auxiliary donors (D_A), linker/branch (π), or acceptors (A) in D–π–A-based organic dyes and porphyrins and also employed as cyclometalated heteroleptic and ancillary ligands in the Ru(II) and Ir(III) complexes for DSSCs. It is noteworthy that the introduction of IM chromophores in the dyes of D–π–A configuration can improve the light-harvesting properties and prohibit the charge recombination reactions due to the extension of the π-conjugated structures and hydrophobic nature. Similarly, in the case of inorganic complexes, the presence of IM motifs as ligands can improve the light-harvesting ability, give facilely tuned HOMO and LUMO energy levels, increase the charge recombination resistance and photostability. This results in enhanced photocurrent (J_SC) and photovoltage (V_OC) and consequently solar-to-power conversion efficiency (η) of DSSC devices based on Ru(II) and Ir(III) complexes. Considering the interesting DSSC applications of IM-derived molecules, in this review, we therefore comprehensively discuss their photophysical, electrochemical and photovoltaic properties reported so far and establish their structure–activity relationship to further advance the η of DSSCs. To the best of our knowledge, there is no such a review interpreting the importance of molecules possessing IM-motifs for DSSC applications to date.

Graphical Abstract

Fluorescence microscopy is a key tool in the biological sciences, which finds use as a routine laboratory technique (e.g., epifluorescence microscope) or more advanced confocal, two-photon, and super-resolution applications. Through continued developments in microscopy, and other analytical methods, the importance of lipids as constituents of subcellular organelles, signalling or regulating molecules continues to emerge. The increasing recognition of the importance of lipids to fundamental cell biology (in health and disease) has prompted the development of protocols and techniques to image the distribution of lipids in cells and tissues. A diverse suite of spectroscopic and microscopy tools are continuously being developed and explored to add to the “toolbox” to study lipid biology. A relatively recent breakthrough in this field has been the development and subsequent application of metal-based luminescent complexes for imaging lipids in biological systems. These metal-based compounds appear to offer advantages with respect to their tunability of the photophysical properties, in addition to capabilities centred around selectively targeting specific lipid structures or classes of lipids. The presence of the metal centre also opens the path to alternative imaging modalities that might not be applicable to traditional organic fluorophores. This review examines the current progress and developments in metal-based luminescent complexes to study lipids, in addition to exploring potential new avenues and challenges for the field to take.

Near-infrared (NIR, 700–1700 nm) luminescent imaging is an emerging bioimaging technology with low photon scattering, minimal autofluorescence, deep tissue penetration, and high spatiotemporal resolution that has shown fascinating promise for NIR imaging-guided theranostics. In recent progress, NIR luminescent metal complexes have attracted substantially increased research attention owing to their intrinsic merits, including small size, anti-photobleaching, long lifetime, and metal-centered NIR emission. In the past decade, scientists have contributed to the advancement of NIR metal complexes involving efforts to improve photophysical properties, biocompatibility, specificity, pharmacokinetics, in vivo visualization, and attempts to exploit new ligand platforms. Herein, we summarize recent progress and provide future perspectives for NIR metal complexes, including d-block transition metals and f-block lanthanides (Ln) as NIR optical molecular probes for bioassays.

Photocatalytic reforming of biomass has emerged as an area of significant interest within the last decade. The number of papers published in the literature has been steadily increasing with keywords such as ‘hydrogen’ and ‘visible’ becoming prominent research topics. There are likely two primary drivers behind this, the first of which is that biomass represents a more sustainable photocatalytic feedstock for reforming to value-added products and energy. The second is the transition towards achieving net zero emission targets, which has increased focus on the development of technologies that could play a role in future energy systems. Therefore, this review provides a perspective on not only the current state of the research but also a future outlook on the potential roadmap for photocatalytic reforming of biomass. Producing energy via photocatalytic biomass reforming is very desirable due to the ambient operating conditions and potential to utilise renewable energy (e.g., solar) with a wide variety of biomass resources. As both interest and development within this field continues to grow, however, there are challenges being identified that are paramount to further advancement. In reviewing both the literature and trajectory of the field, research priorities can be identified and utilised to facilitate fundamental research alongside whole systems evaluation. Moreover, this would underpin the enhancement of photocatalytic technology with a view towards improving the technology readiness level and promoting engagement between academia and industry.

Metal complex luminophores have seen dramatic expansion in application as imaging probes over the past decade. This has been enabled by growing understanding of methods to promote their cell permeation and intracellular targeting. Amongst the successful approaches that have been applied in this regard is peptide-facilitated delivery. Cell-permeating or signal peptides can be readily conjugated to metal complex luminophores and have shown excellent response in carrying such cargo through the cell membrane. In this article, we describe the rationale behind applying metal complexes as probes and sensors in cell imaging and outline the advantages to be gained by applying peptides as the carrier for complex luminophores. We describe some of the progress that has been made in applying peptides in metal complex peptide-driven conjugates as a strategy for cell permeation and targeting of transition metal luminophores. Finally, we provide key examples of their application and outline areas for future progress.

Luminescence chemosensors are one of the most useful tools for the determination and imaging of small biomolecules and ions in situ in real time. Based on the unique photo-physical/-chemical properties of ruthenium(II) (Ru(II)) complexes, the development of Ru(II) complex-based chemosensors has attracted increasing attention in recent years, and thus many Ru(II) complexes have been designed and synthesized for the detection of ions and small biomolecules in biological and environmental samples. In this work, we summarize the research advances in the development of Ru(II) complex-based chemosensors for the determination of ions and small biomolecules, including anions, metal ions, reactive biomolecules and amino acids, with a particular focus on binding/reaction-based chemosensors for the investigation of intracellular analytes’ evolution through luminescence analysis and imaging. The advances, challenges and future research directions in the development of Ru(II) complex-based chemosensors are also discussed.

With the ever-increasing demand for energy in the world, the tendency to use renewable energies has been growing rapidly. Sunlight, as an inexhaustible energy source, and the oceans, as one of the most valuable treasures on Earth, are available for free. Simultaneous exploitation of these two sources of energy and matter (sunlight and oceans) in one configuration can provide a sustainable solution for future energy supply. Among the various types of such energy storage and conversion systems, solar rechargeable seawater batteries (SRSBs) can meet this need by storing the chemical energy of seawater by receiving solar energy. SRSBs consist of two compartments: a closed compartment including a sodium metal anode in an organic liquid electrolyte, and an open compartment containing a semiconductor photoelectrode immersed in seawater, which are separated from each other by a ceramic solid electrolyte membrane. In this complex system, the photoelectrode is irradiated by sunlight, whereby electrons are excited and reach the Na metal anode after passing though the external circuit. The ceramic solid electrolyte harvests only sodium ions from seawater and transfers them to the anodic part, where the transferred ions are reduced to sodium metal atoms. At the same time, an oxygen evolution reaction takes place at the cathodic part. In this way, the battery is charged. The use of a photoelectrode in the charging process significantly increases the voltage efficiency of SRSBs to more than 90%, whereas a cell with only the seawater compartment (without a photoelectrode) will not deliver satisfactory performance. Therefore, to achieve very high efficiencies, designing an accurate system with the best components is absolutely necessary. This review focuses on the working principle of SRSBs, at the same time explaining the effect of key components on the performance and stability of SRSBs. The role of the semiconductor photoelectrode in improving the voltage efficiency of SRSBs is also described in detail, and finally strategies proposed to overcome obstacles to the commercialization of SRSBs are introduced.

Direct reductive N-methylation of inexpensive and readily available nitro compounds as raw material feedstocks is more attractive and straightforward compared with conventional N-methylation of amines to prepare biologically and pharmaceutically important N-methylated amine derivatives. This strategy for synthesis of N-methylamines avoids prepreparation of NH-free amines and therefore significantly shortens the separation and purification steps. In recent years, numerous methylating agents and catalytic systems have been reported for this appealing transformation. Thus, it is an appropriate time to summarize such advances. This review elaborates on the most important discoveries and advances in this research arena, with special emphasis on the mechanistic aspect of reactions that may provide new insights into catalyst improvement.

Fischer glycosylation is typically the chemical reaction of a monosaccharide and an alcohol in presence of an acidic catalyst to afford glycosides in pyranosidic and furanosidic forms. This reaction is still applied today for the synthesis of specialized glycosides, and optimization and modification of the method have continued since its discovery by Emil Fischer in the 1890s. This review presents advancements in Fischer glycosylation described in literature of the past 15 years and its implementation in modern chemical methods.