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Organic & Biomolecular Chemistry Apr 2022Thiols are a functional group commonly used for selective reactions in a biochemical setting because of their high nucleophilicity. Phosphorus nucleophiles can undergo...
Thiols are a functional group commonly used for selective reactions in a biochemical setting because of their high nucleophilicity. Phosphorus nucleophiles can undergo some similar reactions to thiols, but remain underexploited in this setting. In this work we show that phosphine nucleophiles react cleanly and quickly with a dehydroalanine electrophile, itself generated from cysteine, to give a stable adduct in a peptide context. NMR reveals the product to be a phosphonium ion and indicates some backbone conformational constraint, possibly arising from transient carbonyl coordination. The reaction proceeded quickly, with a pseudo-first order rate constant of 0.126 min at 1 mM peptide (80% conversion in 10 min), and with no detectable side products on the peptide. A broad peptide sequence scope and water-soluble phosphines with alkyl as well as aromatic groups were all shown to react efficiently. Phosphine addition proved to be efficient on nisin as a model Dha-containing biologically-derived peptide and on an mRNA-displayed peptide, as well as on TCEP-modified agarose for peptide capture from solution. This reaction thus presents a promising approach for modification of peptides for cargo attachment or altered physical properties in peptide discovery.
Topics: Alanine; Amino Acid Sequence; Phosphines; Sulfhydryl Compounds
PubMed: 35353113
DOI: 10.1039/d2ob00410k -
Scientific Reports Feb 2021Phosphine is the most commonly used gas for fumigation for durable commodities globally, but there is still inadequate information regarding its efficacy in conjunction...
Phosphine is the most commonly used gas for fumigation for durable commodities globally, but there is still inadequate information regarding its efficacy in conjunction with proper concentration monitoring. In a series of bioassays, insect mortality after specific exposure intervals to phosphine in selected species was examined, as well as the appearance of the so called "sweet spot". The species that were tested were: Oryzaephilus surinamensis (L.), Tribolium castaneum (Herbst), Sitophilus oryzae (L.) and Rhyzopertha dominica (F.) with populations that had different levels of phosphine resistance. Evaluation was conducted by using the Phosphine Tolerance Test (PTT), with exposure of the adult stage for 15, 30, 60, 90, 150 and 300 min at 3000 ppm. At the end of these intervals (separate bioassays for each time interval), the insects were transferred to Petri dishes, in which recovery was recorded at different time intervals (2 h, 1, 2 and 7 days). The majority of susceptible populations of all species were instantly immobilized even in the shortest exposure period (15 min), in contrast with resistant populations that were active even after 300 min. After exposure to phosphine, populations and exposure time affected mortality of susceptible populations, whereas resistant populations recovered regardless of species and exposure time. Additional bioassays at the concentrations of 500, 1000, 2000 and 3000 ppm for 1, 3, 5, 20, 30 and 40 h showed the presence of the "sweet spot", i.e., decrease of mortality with the increase of concentration. In fact, for most of the tested species, the "sweet spot" appeared in 1000 and 2000 ppm at a 5-h exposure time, regardless of the level of resistance to phosphine. This observation is particularly important both in terms of the assessment of resistance and in the context of non-linear recovery at elevated concentrations, indicating the occurrence of strong hormetic reversals in phosphine efficacy.
Topics: Animals; Food Parasitology; Fumigation; Insecticide Resistance; Insecticides; Phosphines; Toxicity Tests; Tribolium; Weevils
PubMed: 33594183
DOI: 10.1038/s41598-021-83463-y -
Drug Metabolism Letters 2021Due to its easy availability, rapid and severe toxicity, and no specific antidote, aluminum phosphide has emerged as a lethal toxin, commonly used for suicidal intent in... (Review)
Review
Due to its easy availability, rapid and severe toxicity, and no specific antidote, aluminum phosphide has emerged as a lethal toxin, commonly used for suicidal intent in agricultural communities. Despite various advances in medicine, this compound's toxicity is poorly understood, and it still has a very high case fatality rate with no definitive treatment options available. This review aims to understand the mechanism of toxicity, clinical toxidrome of acute aluminum phosphide poisoning, and the available therapeutic options, including recent advances. A literature review was performed searching PubMed, EMBASE Ovid, and Cochrane Library, using the following search items: ("aluminum phosphide poisoning" OR "aluminum phosphide poisoning toxicity" OR "aluminum phosphide ingestion") AND ("management" OR "therapy" OR "treatment"). Selected articles were discussed amongst all the authors to shape this review. High case fatality rate and lack of any specific antidote are persisting challenges. Therapeutic measures need to be implemented from all fronts - reducing easy access to the poison, developing less toxic alternatives for use as a pesticide, and more studies directed at developing an effective reversal agent for phosphine. The advent of promising agents like glucose-insulin-potassium infusion and lipid emulsion is a new ray of hope in the complete recovery in this fatal poisoning. The need of the hour is to find an agent that rapidly and effectively reverses aluminum phosphide's toxic effects. Large multicenter controlled trials are required to establish the role of glucose-insulin-potassium and lipid emulsion.
Topics: Aluminum Compounds; Antidotes; Glucose; Humans; Multicenter Studies as Topic; Pesticides; Phosphines
PubMed: 34818996
DOI: 10.2174/1872312814666210813115625 -
Proceedings of the Japan Academy.... 2021Metal-catalyzed asymmetric synthesis is one of the most important methods for the economical and environmentally benign production of useful optically active compounds.... (Review)
Review
Metal-catalyzed asymmetric synthesis is one of the most important methods for the economical and environmentally benign production of useful optically active compounds. The success of the asymmetric transformations is significantly dependent on the structure and electronic properties of the chiral ligands coordinating to the center metals, and hence the development of highly efficient ligands, especially chiral phosphine ligands, has long been an important research subject in this field. This review article describes the synthesis and applications of P-chiral phosphine ligands possessing chiral centers at the phosphorus atoms. Rationally designed P-chiral phosphine ligands are synthesized by the use of phosphine-boranes as the intermediates. Conformationally rigid and electron-rich P-chiral phosphine ligands exhibit excellent enantioselectivity and high catalytic activity in various transition-metal-catalyzed asymmetric reactions. Recent mechanistic studies of rhodium-catalyzed asymmetric hydrogenation are also described.
Topics: Hydrogenation; Ligands; Phosphines; Rhodium
PubMed: 34759073
DOI: 10.2183/pjab.97.026 -
Chembiochem : a European Journal of... Sep 2022The synthesis, characterisation, and evaluation of the in vitro cytotoxicity of five maleonitriledithiolate-based ruthenium metal complexes bearing various phosphine...
The synthesis, characterisation, and evaluation of the in vitro cytotoxicity of five maleonitriledithiolate-based ruthenium metal complexes bearing various phosphine ligands towards two ovarian cancer cell lines (A2780 and A2780cisR), one non-small-cell lung cancer cell line (H460) and one normal prostate cell line (PNT2) are presented herein. These 18-electron complexes were designed with four water-soluble phosphine ligands to increase the water-solubility character of the corresponding electron-deficient ruthenium complex which showed great in vitro promises, and triphenylphosphine for comparison. The complexes with triphenylphosphine-3,3',3''-trisulfonic acid and triphenylphosphine present similar cytotoxicity compared to the 16-electron precursor, with equal cytotoxicity to both A2780 and A2780cisR. Hints at the mechanism of action suggest an apoptotic pathway based on reactive oxygen species (ROS) production. No toxicity was observed in preliminary in vivo pilot studies for these two complexes in subcutaneous A2780 and A2780cisR xenograft models, with some evidence of tumour growth delay.
Topics: Antineoplastic Agents; Carcinoma, Non-Small-Cell Lung; Cell Line, Tumor; Coordination Complexes; Drug Screening Assays, Antitumor; Female; Humans; Ligands; Lung Neoplasms; Organophosphorus Compounds; Ovarian Neoplasms; Phosphines; Reactive Oxygen Species; Ruthenium; Water
PubMed: 35838006
DOI: 10.1002/cbic.202200259 -
Inorganic Chemistry Oct 2022Twelve tri(-carbazolyl)phosphine gold(I) complexes, bearing both protonated and deuterated aryl phosphorous triamide-type ligands, have been synthesized and...
Twelve tri(-carbazolyl)phosphine gold(I) complexes, bearing both protonated and deuterated aryl phosphorous triamide-type ligands, have been synthesized and characterized. An elusive Au-H(D) interaction between the H(D) atoms of the tri(-carbazolyl)phosphine ligand at the H-1(D-1) position of the carbazolyl ring and the central gold atom was observed. Complexes / bearing the dibrominated tri(-carbazolyl)phosphine ligand exhibit isotopic polymorphism, in which two dramatically different crystal-packing modes between the protonated and deuterated forms occur. The catalytic potential of these complexes has been showcased in the gold(I)-catalyzed glycosylation with glycosyl -alkynylbenzoates as donors, with TON being up to 27 000.
Topics: Gold; Ligands; Phosphines; Catalysis
PubMed: 36219576
DOI: 10.1021/acs.inorgchem.2c02902 -
Chemical Communications (Cambridge,... Oct 2022A phosphine-free Ir(III)-NHC-based efficient catalytic system is developed for integrated CO capture with tetramethylguanidine as a capturing agent and conversion to...
A phosphine-free Ir(III)-NHC-based efficient catalytic system is developed for integrated CO capture with tetramethylguanidine as a capturing agent and conversion to formate with H gas, conducting both the steps in water, affording product yield up to 85% and TON up to 19 171 in just 12 h. In the segment of "integrated CO-capture and conversion to formate", this system represents not only the first phosphine-free module, but also one of the few best known homogeneous catalysts.
Topics: Amines; Carbon Dioxide; Formates; Phosphines; Water
PubMed: 36156031
DOI: 10.1039/d2cc03861g -
Molecules (Basel, Switzerland) May 2021Phosphinic and phosphonic acids are useful intermediates and biologically active compounds which may be prepared from their esters, phosphinates and phosphonates,... (Review)
Review
Phosphinic and phosphonic acids are useful intermediates and biologically active compounds which may be prepared from their esters, phosphinates and phosphonates, respectively, by hydrolysis or dealkylation. The hydrolysis may take place both under acidic and basic conditions, but the C-O bond may also be cleaved by trimethylsilyl halides. The hydrolysis of -esters is a challenging task because, in most cases, the optimized reaction conditions have not yet been explored. Despite the importance of the hydrolysis of -esters, this field has not yet been fully surveyed. In order to fill this gap, examples of acidic and alkaline hydrolysis, as well as the dealkylation of phosphinates and phosphonates, are summarized in this review.
PubMed: 34064764
DOI: 10.3390/molecules26102840 -
Bioorganic Chemistry Mar 2023Tertiary phosphine oxides, phosphine sulfides, and phosphine selenides containing pyridine, imidazole, and pyrazole groups have been synthesized via the reaction of...
Tertiary phosphine oxides, phosphine sulfides, and phosphine selenides containing pyridine, imidazole, and pyrazole groups have been synthesized via the reaction of elemental phosphorus or secondary phosphine oxides with functional pyridines, imidazoles, and pyrazoles. Alkyl tris(2-pyridylethyl)phosphonium iodide and bromide are also obtained by quaternization of the corresponding phosphine. Antimicrobial activity of the synthesized compounds, including nitrogen-containing heterocycles, phosphorus, selenium, and sulfur, with respect to Enterococcus durans, Bacillus subtilis, Escherichia coli, Pseudomonas aeruginosa microorganisms is evaluated. It is found that phosphine chalcogenides bearing imidazole (14, 19), pyrazole (13), and pyridine fragments (5, 9) and phosphonium salts (11, 12) can be considered as new promising antibacterial agents. For some synthesized compounds, LC is determined. Phosphine oxide with methylpyrazole fragments (13) and phosphonium salts (11, 12) show strong profile of antimicrobial activity, and cytotoxic effect of phosphonium bromide having a long chain radical (12) is by order of magnitude higher than that of cisplatin. We believe that the results obtained may contribute to the development of highly effective agents for the treatment and prevention of bacterial infections and cancers.
Topics: Cytostatic Agents; Phosphorus; Bromides; Salts; Anti-Infective Agents; Anti-Bacterial Agents; Pyrazoles; Pyridines; Imidazoles; Oxides; Microbial Sensitivity Tests
PubMed: 36702003
DOI: 10.1016/j.bioorg.2023.106363 -
Annual Review of Entomology Jan 2020Development of resistance in major grain insect pest species to the key fumigant phosphine (hydrogen phosphide) across the globe has put the viability and sustainability... (Review)
Review
Development of resistance in major grain insect pest species to the key fumigant phosphine (hydrogen phosphide) across the globe has put the viability and sustainability of phosphine in jeopardy. The resistance problem has been aggravated over the past two decades, due mostly to the lack of suitable alternatives matching the major attributes of phosphine, including its low price, ease of application, proven effectiveness against a broad pest spectrum, compatibility with most storage conditions, and international acceptance as a residue-free treatment. In this review, we critically analyze the published literature in the area of phosphine resistance with special emphasis on the methods available for detection of resistance, the genetic basis of resistance development, key management strategies, and research gaps that need to be addressed.
Topics: Animals; Food Parasitology; Fumigation; Insect Control; Insecta; Insecticide Resistance; Insecticides; Phosphines
PubMed: 31610132
DOI: 10.1146/annurev-ento-011019-025047