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Chemical Reviews Jun 2021Bioorthogonal phosphines were introduced in the context of the Staudinger ligation over 20 years ago. Since that time, phosphine probes have been used in myriad... (Review)
Review
Bioorthogonal phosphines were introduced in the context of the Staudinger ligation over 20 years ago. Since that time, phosphine probes have been used in myriad applications to tag azide-functionalized biomolecules. The Staudinger ligation also paved the way for the development of other phosphorus-based chemistries, many of which are widely employed in biological experiments. Several reviews have highlighted early achievements in the design and application of bioorthogonal phosphines. This review summarizes more recent advances in the field. We discuss innovations in classic Staudinger-like transformations that have enabled new biological pursuits. We also highlight relative newcomers to the bioorthogonal stage, including the cyclopropenone-phosphine ligation and the phospha-Michael reaction. The review concludes with chemoselective reactions involving phosphite and phosphonite ligations. For each transformation, we describe the overall mechanism and scope. We also showcase efforts to fine-tune the reagents for specific functions. We further describe recent applications of the chemistries in biological settings. Collectively, these examples underscore the versatility and breadth of bioorthogonal phosphine reagents.
Topics: Azides; Benzene Derivatives; Cycloaddition Reaction; Phosphines
PubMed: 34101453
DOI: 10.1021/acs.chemrev.1c00014 -
Nature Chemistry Sep 2022
Topics: Phosphines; Xanthenes
PubMed: 36028622
DOI: 10.1038/s41557-022-01031-x -
ChemistryOpen Aug 2020Bioorthogonal reactions including the bioorthogonal ligations and cleavages have become an active field of research in chemical biology, and they play important roles in... (Review)
Review
Bioorthogonal reactions including the bioorthogonal ligations and cleavages have become an active field of research in chemical biology, and they play important roles in chemical modification and functional regulation of biomolecules. This review summarizes the developments and applications of the representative bioorthogonal reactions including the Staudinger reactions, the metal-mediated bioorthogonal reactions, the strain-promoted cycloadditions, the inverse electron demand Diels-Alder reactions, the light-triggered bioorthogonal reactions, and the reactions of chloroquinoxalines and -dithiophenols.
Topics: Alkynes; Azides; Catalysis; Cycloaddition Reaction; Heterocyclic Compounds, 1-Ring; Light; Metals, Heavy; Phosphines; Photolysis; Quinoxalines; Sulfhydryl Compounds
PubMed: 32817809
DOI: 10.1002/open.202000128 -
Chemistry (Weinheim An Der Bergstrasse,... Dec 2022By applying the potassium salts of cyclopentadienyl-phosphine ligands LK to CoCl , the corresponding cobalt chlorides (1, LCo Cl) were prepared. By reducing complexes 1...
By applying the potassium salts of cyclopentadienyl-phosphine ligands LK to CoCl , the corresponding cobalt chlorides (1, LCo Cl) were prepared. By reducing complexes 1 with KHBEt under a N atmosphere, bridging end-on complexes, LCo -N -Co L (2 a and 2 b), were successfully obtained. N -labeled [ N ]-2 a was prepared under N / N exchange in THF solution. LCo -N -Co L complex 2 a could react with P molecules to release N and generate a Co-P -Co moiety 4. Further reduction of complex 2 b led to cleavage of a P-C bond in the cyclopentadienyl-phosphine ligand to provide novel μ-PCy -bridged Co -N complex 5. DFT calculations confirmed the experimental observations.
Topics: Models, Molecular; Nitrogen; Phosphines; Cobalt; Ligands
PubMed: 36259370
DOI: 10.1002/chem.202202803 -
Fa Yi Xue Za Zhi Apr 2022To study the distribution of total phosphine in phosphine poisoning victims and summarize the characteristics of phosphine poisoning cases.
OBJECTIVES
To study the distribution of total phosphine in phosphine poisoning victims and summarize the characteristics of phosphine poisoning cases.
METHODS
The phosphine and its metabolites in the biological samples of 29 victims in 16 phosphine poisoning cases were qualified and quantified by headspace gas chromatography-mass spectrometry.
RESULTS
Five victims among 29 were poisoned by ingestion of aluminium phosphide and 24 by inhalation of phosphine gas. Phosphine metabolites were detected in the biological samples of 23 victims, and the concentrations of total phosphine in blood ranged 0.5-34.0 μg/mL. The total concentration of phosphine in liver tissue was up to 71.0 μg/g. Phosphine was not detected in the blood of the other six survived victims, which may be related to the small amount of phosphine exposure and the delay in blood sampling.
CONCLUSIONS
The total concentration of phosphine in blood and tissues caused by aluminum phosphine ingestion is higher than that caused by phosphine gas inhalation. The death cases of phosphine inhalation are characterized by long exposure time, repeated exposures and age susceptibility.
Topics: Aluminum Compounds; Gas Chromatography-Mass Spectrometry; Humans; Liver; Phosphines; Poisoning
PubMed: 35899515
DOI: 10.12116/j.issn.1004-5619.2020.300901 -
Molecules (Basel, Switzerland) May 2022α-Aminophosphonates, -phosphinates, and -phosphine oxides are a group of organophosphorus compounds that were investigated as extraction agents for rare earth (RE)... (Review)
Review
α-Aminophosphonates, -phosphinates, and -phosphine oxides are a group of organophosphorus compounds that were investigated as extraction agents for rare earth (RE) metals and actinoids for the first time in the 1960s. However, more systematic investigations of their extraction properties towards REs and actinoids were not started until the 2010s. Indeed, recent studies have shown that these α-amino-functionalized compounds can outperform the commercial organophosphorus extraction agents in RE separations. They have also proven to be very efficient extraction and precipitation agents for recovering Th and U from RE concentrates. These actinoids coexist with REs in some of the commercially important RE-containing minerals. The efficient separation and purification of REs is becoming more and more important every year as these elements have a pivotal role in many existing technologies. If one also considers the facile synthesis of α-amino-functionalized organophosphorus extractants and precipitation agents, it is expected that they will be increasingly utilized in the extraction chemistry of REs and actinoids in the future. This review collates α-aminophosphonates, -phosphinates, and -phosphine oxides that have been utilized in the separation chemistry of REs and actinoids, including their most relevant synthetic routes and molecular properties. Their extraction and precipitation properties towards REs and actinoids are also discussed.
Topics: Actinoid Series Elements; Metals, Rare Earth; Organophosphonates; Oxides; Phosphines; Thorium; Uranium
PubMed: 35684403
DOI: 10.3390/molecules27113465 -
Archives of Environmental &... 2022The aim is to assess the prevalence and knowledge on acute occupational exposure to phosphine in the shipping industry. We followed PRISMA guidelines for scoping review.... (Review)
Review
The aim is to assess the prevalence and knowledge on acute occupational exposure to phosphine in the shipping industry. We followed PRISMA guidelines for scoping review. We searched in 4 databases without language and date restrictions for scientific articles in peer-reviewed and gray literature. We found 13 peer-reviewed articles and 63 articles in gray literature. These covered 56 incidents from 1963 to 2019 for a total of 254 victims and 22 fatalities. There is an increase in the number of reported cases over the last 20 years. Neurologic and gastrointestinal symptoms are predominant, and hospitalization is needed in 80% of cases. Our review underlined the principal risk as gas exposure through leaks between holds and the ventilation system. Further studies on the knowledge and the prevention in order to improve good practices onboard, prevent the risk of fire explosion, and a global reporting system of new cases are recommended.
Topics: Naval Medicine; Occupational Exposure; Phosphines; Ships
PubMed: 34657582
DOI: 10.1080/19338244.2021.1990829 -
Journal of the American Chemical Society Dec 2022Phosphine ligands are the most important class of ligands for cross-coupling reactions due to their unique electronic and steric properties. However, metalloproteins...
Phosphine ligands are the most important class of ligands for cross-coupling reactions due to their unique electronic and steric properties. However, metalloproteins generally rely on nitrogen, sulfur, or oxygen ligands. Here, we report the genetic incorporation of P3BF, which contains a biocompatible borane-protected phosphine, into proteins. This step is followed by a straightforward one-pot strategy to perform deboronation and palladium coordination in aqueous and aerobic conditions. The genetically encoded phosphine ligand P3BF should significantly expand our ability to design functional metalloproteins.
Topics: Metalloproteins; Ligands; Phosphines; Palladium
PubMed: 36417425
DOI: 10.1021/jacs.2c09683 -
Nanotechnology Aug 2019The latest advances concerning ultra-small gold nanoparticles (≤2 nm) commonly known as gold nanoclusters (AuNCs) are reviewed and discussed in the context of... (Review)
Review
The latest advances concerning ultra-small gold nanoparticles (≤2 nm) commonly known as gold nanoclusters (AuNCs) are reviewed and discussed in the context of biological and biomedical applications (labeling, delivery, imaging and therapy). A great diversity of synthetic methods has been developed and optimized aiming to improve the chemical structures and physicochemical properties of the resulting AuNCs. The main synthetic approaches were surveyed with emphasis on methods leading to water-soluble AuNCs since aqueous solutions are the preferred media for biological applications. The most representative and recent experimental results are discussed in relationship to their potential for biomedical applications.
Topics: Animals; Antineoplastic Agents; Disease Models, Animal; Drug Compounding; Drug Delivery Systems; Fluorescent Dyes; Gold; Humans; Metal Nanoparticles; Molecular Imaging; Neoplasms; Particle Size; Phosphines; Radiation-Sensitizing Agents; Solubility; Staining and Labeling; Sulfhydryl Compounds; Water
PubMed: 31071693
DOI: 10.1088/1361-6528/ab2088 -
Molecules (Basel, Switzerland) Jul 2022A Knoevenagel based redox-reaction promoted by intramolecular phosphine sources is presented for the first time. The influence of different diketones, aldehydes, bases...
A Knoevenagel based redox-reaction promoted by intramolecular phosphine sources is presented for the first time. The influence of different diketones, aldehydes, bases and acids was investigated. The effects of different substituents were evaluated based on their electronical influence on the diketone structure. With the obtained results a mechanism is proposed, giving information about transition states formed during the reaction, which can lead to different products. This type of an internal redox transformation with a phosphine oxide moiety remaining in the molecule after the redox reaction represents a new type of reaction.
Topics: Catalysis; Ketones; Oxidation-Reduction; Phosphines; Stereoisomerism
PubMed: 35956825
DOI: 10.3390/molecules27154875