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Chemistry (Weinheim An Der Bergstrasse,... Mar 2024Phosphinidenes are heavy congeners of nitrenes that have been broadly used as in situ reagents in synthetic phosphorus chemistry and also serve as versatile ligands in...
Phosphinidenes are heavy congeners of nitrenes that have been broadly used as in situ reagents in synthetic phosphorus chemistry and also serve as versatile ligands in coordination with transition metals. However, the detection of free phosphinidenes is largely challenged by their high reactivity and also the lack of suitable synthetic methods, rendering the knowledge about the fundamental properties of this class of low-valent phosphorus compounds limited. Recently, an increasing number of free phosphinidenes bearing prototype structural and bonding properties have been prepared for the first time, thus enabling the exploration of their distinct reactivity from the nitrene analogues. This Concept article will discuss the experimental approaches for the generation of the highly unstable phosphinidenes and highlight their distinct reactivity from the nitrogen analogues so as to stimuate future studies about their potential applications in phosphorus chemistry.
PubMed: 38108540
DOI: 10.1002/chem.202303283 -
Angewandte Chemie (International Ed. in... Apr 2024This review discusses recent advances in light-driven radiochemistry for three key isotopes: fluorine-18, carbon-11, and zirconium-89, and their applications in positron... (Review)
Review
This review discusses recent advances in light-driven radiochemistry for three key isotopes: fluorine-18, carbon-11, and zirconium-89, and their applications in positron emission tomography (PET). In the case of fluorine-18, the predominant approach involves the use of cyclotron-produced [F]fluoride or reagents derived thereof. Light serves to activate either the substrate or the fluorine-18 labeled reagent. Advancements in carbon-11 photo-mediated radiochemistry have been leveraged for the radiolabeling of small molecules, achieving various transformations, including C-methylation, C-carboxylation, C-carbonylation, and C-cyanation. Contrastingly, zirconium-89 photo-mediated radiochemistry differs from fluorine-18 and carbon-11 approaches. In these cases, light facilitates a postlabeling click reaction, which has proven valuable for the labeling of large biomolecules such as monoclonal antibodies (mAbs). New technological developments, such as the incorporation of photoreactors in commercial radiosynthesizers, illustrate the commitment the field is making in embracing photochemistry. Taken together, these advances in photo-mediated radiochemistry enable radiochemists to apply new retrosynthetic strategies in accessing novel PET radiotracers.
Topics: Radiochemistry; Fluorine Radioisotopes; Positron-Emission Tomography; Radiopharmaceuticals; Carbon Radioisotopes; Radioisotopes; Zirconium
PubMed: 38135665
DOI: 10.1002/anie.202317136 -
Chemistry (Weinheim An Der Bergstrasse,... Jun 20241,2,4-triazolo-[4,3-a]pyrazine was prepared via a two-step electrochemical, photochemical process. First, a 5-substituted tetrazole is electrochemically coupled to...
1,2,4-triazolo-[4,3-a]pyrazine was prepared via a two-step electrochemical, photochemical process. First, a 5-substituted tetrazole is electrochemically coupled to 2,6-dimethoxypyrazine to yield 1,5- and 2,5- disubstituted tetrazoles. Subsequent photochemical excitation of the 2,5-disubstituted tetrazole species using an ultraviolet lamp releases nitrogen gas and produces a short-lived nitrilimine intermediate. Subsequent cyclization of the nitrilimine intermediate yields a 1,2,4-triazolo-[4,3-a]pyrazine backbone. The scope of this reaction was explored using various tetrazoles and pyrazines. Materials produced were identified using chemical analytical techniques and computationally studied for potential application as an insensitive energetic material.
PubMed: 38570880
DOI: 10.1002/chem.202400661 -
Advanced Science (Weinheim,... Nov 2023Photoinduced reversible deactivation radical polymerization (photo-RDRP) or photoinduced controlled/living radical polymerization has emerged as a versatile and powerful... (Review)
Review
Photoinduced reversible deactivation radical polymerization (photo-RDRP) or photoinduced controlled/living radical polymerization has emerged as a versatile and powerful technique for preparing functional and advanced polymer materials under mild conditions by harnessing light energy. While UV and visible light (λ = 400-700 nm) are extensively employed in photo-RDRP, the utilization of near-infrared (NIR) wavelengths (λ = 700-2500 nm) beyond the visible region remains relatively unexplored. NIR light possesses unique properties, including enhanced light penetration, reduced light scattering, and low biomolecule absorption, thereby providing opportunities for applying photo-RDRP in the fields of manufacturing and medicine. This comprehensive review categorizes all known NIR light-induced RDRP (NIR-RDRP) systems into four mechanism-based types: mediation by upconversion nanoparticles, mediation by photocatalysts, photothermal conversion, and two-photon absorption. The distinct photoinitiation pathways associated with each mechanism are discussed. Furthermore, this review highlights the diverse applications of NIR-RDRP reported to date, including 3D printing, polymer brush fabrication, drug delivery, nanoparticle synthesis, and hydrogel formation. By presenting these applications, the review underscores the exceptional capabilities of NIR-RDRP and offers guidance for developing high-performance and versatile photopolymerization systems. Exploiting the unique properties of NIR light unlocks new opportunities for synthesizing functional and advanced polymer materials.
PubMed: 37750445
DOI: 10.1002/advs.202304942 -
Angewandte Chemie (International Ed. in... Mar 2024Ruthenium(II) complexes with chelating polypyridine ligands are among the most frequently investigated compounds in photophysics and photochemistry, owing to their... (Review)
Review
Ruthenium(II) complexes with chelating polypyridine ligands are among the most frequently investigated compounds in photophysics and photochemistry, owing to their favorable luminescence and photoredox properties. Equally good photoluminescence performance and attractive photocatalytic behavior is now achievable with isoelectronic molybdenum(0) complexes. The zero-valent oxidation state of molybdenum is stabilized by carbonyl or isocyanide ligands, and metal-to-ligand charge transfer (MLCT) excited states analogous to those in ruthenium(II) complexes can be established. Microsecond MLCT excited-state lifetimes and photoluminescence quantum yields up to 0.2 have been achieved in solution at room temperature, and the emission wavelength has become tunable over a large range. The molybdenum(0) complexes are stronger photoreductants than ruthenium(II) polypyridines and can therefore perform more challenging chemical reductions. The triplet nature of their luminescent MLCT states allows sensitization of photon upconversion via triplet-triplet annihilation, to convert low-energy input radiation into higher-energy output fluorescence. This review summarizes the current state of the art concerning luminescent molybdenum(0) complexes and highlights their application potential. Molybdenum is roughly 140 times more abundant and far cheaper than ruthenium, hence this research is relevant in the greater context of finding more sustainable alternatives to using precious and rare transition metals in photophysics and photochemistry.
PubMed: 37885363
DOI: 10.1002/anie.202314475 -
Science Advances Oct 2023Transparent silica glass is one of the most essential materials used in society and industry, owing to its exceptional optical, thermal, and chemical properties....
Transparent silica glass is one of the most essential materials used in society and industry, owing to its exceptional optical, thermal, and chemical properties. However, glass is extremely difficult to shape, especially into complex and miniaturized structures. Recent advances in three-dimensional (3D) printing have allowed for the creation of glass structures, but these methods involve time-consuming and high-temperature processes. Here, we report a photochemistry-based strategy for making glass structures of micrometer size under mild conditions. Our technique uses a photocurable polydimethylsiloxane resin that is 3D printed into complex structures and converted to silica glass via deep ultraviolet (DUV) irradiation in an ozone environment. The unique DUV-ozone conversion process for silica microstructures is low temperature (~220°C) and fast (<5 hours). The printed silica glass is highly transparent with smooth surface, comparable to commercial fused silica glass. This work enables the creation of arbitrary structures in silica glass through photochemistry and opens opportunities in unexplored territories for glass processing techniques.
PubMed: 37792949
DOI: 10.1126/sciadv.adi2958 -
Biophysical Reviews Aug 2023Proteins are the most abundant biomolecules in living organisms and tissues and are also present in many natural and processed foods and beverages, as well as in... (Review)
Review
Proteins are the most abundant biomolecules in living organisms and tissues and are also present in many natural and processed foods and beverages, as well as in pharmaceuticals and therapeutics. When exposed to UV-visible light, proteins containing endogenous or exogenous chromophores can undergo direct and indirect photochemical processes, resulting in protein modifications including oxidation of residues, cross-linking, proteolysis, covalent binding to molecules and interfaces, and conformational changes. When these modifications occur in an uncontrolled manner in a physiological context, they can lead to biological dysfunctions that ultimately result in cell death. However, rational design strategies involving light-activated protein modification have proven to be a valuable tool for the modulation of protein function or even for the construction of new biomaterials. This mini-review describes the fundamentals of photochemical processes in proteins and explores some of their emerging biomedical and nanobiotechnological applications, such as photodynamic therapy (PDT), photobonding for wound healing, photobioprinting, photoimmobilization of biosensors and enzymes for sensing, and biocatalysis, among others.
PubMed: 37681095
DOI: 10.1007/s12551-023-01081-6 -
National Science Review Aug 2023The recently constructed vacuum ultraviolet (VUV) free electron laser (FEL) at the Dalian Coherent Light Source (DCLS) is yielding a wealth of new and exquisitely... (Review)
Review
The recently constructed vacuum ultraviolet (VUV) free electron laser (FEL) at the Dalian Coherent Light Source (DCLS) is yielding a wealth of new and exquisitely detailed information about the photofragmentation dynamics of many small gas-phase molecules. This Review focuses particular attention on five triatomic molecules-HO, HS, CO, OCS and CS. Each shows excitation wavelength-dependent dissociation dynamics, yielding photofragments that populate a range of electronic and (in the case of diatomic fragments) vibrational and rotational quantum states, which can be characterized by different translational spectroscopy methods. The photodissociation of an isolated molecule from a well-defined initial quantum state provides a lens through which one can investigate how and why chemical reactions occur, and provides numerous opportunities for fruitful, synergistic collaborations with high-level quantum chemists. The chosen molecules, their photofragments and the subsequent chemical reaction networks to which they can contribute are all crucial in planetary atmospheres and in interstellar and circumstellar environments. The aims of this Review are 3-fold: to highlight new photochemical insights enabled by the VUV-FEL at the DCLS, notably the recently recognized central atom elimination process that is shown to contribute in all of these triatomic molecules; to highlight some of the potential implications of this rich photochemistry to our understanding of interstellar chemistry and molecular evolution within the universe; and to highlight other and future research directions in areas related to chemical reaction dynamics and astrochemistry that will be enabled by increased access to VUV-FEL sources.
PubMed: 37771464
DOI: 10.1093/nsr/nwad158 -
Marine Drugs Jul 2023In this perspective, we showcase the benefits of continuous flow chemistry and photochemistry and how these valuable tools have contributed to the synthesis of organic... (Review)
Review
In this perspective, we showcase the benefits of continuous flow chemistry and photochemistry and how these valuable tools have contributed to the synthesis of organic scaffolds from the marine environment. These technologies have not only facilitated previously described synthetic pathways, but also opened new opportunities in the preparation of novel organic molecules with remarkable pharmacological properties which can be used in drug discovery programs.
Topics: Drug Discovery; Technology; Chemistry, Pharmaceutical
PubMed: 37504932
DOI: 10.3390/md21070402 -
Photochemistry and Photobiology 2024
PubMed: 38225762
DOI: 10.1111/php.13900