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Scientific Reports Mar 2023Phosphine (PH) and ethyl formate (EF), the two popular fumigant disinfectants of stored product insect pests, are primarily evaluated for their knock down effects...
Phosphine (PH) and ethyl formate (EF), the two popular fumigant disinfectants of stored product insect pests, are primarily evaluated for their knock down effects without considering their post-fumigation sub-lethal activities. The sub-lethal activities (adult survivorship, fecundity, sterility and female sex pheromone production) of the fumigants were evaluated on a field-to-storage insect pest adzuki bean beetle, Callosobruchus chinensis (L.). The adults' survivorship and female fecundity, both were dose-dependently affected by sub-lethal PH and EF fumigation exposures. Hatchability of the eggs laid by fumigated female adults were also significantly affected. Gas-chromatography mass-spectrometry analysis of solid-phase micro-extraction from virgin fumigated C. cinensis females revealed that the PH LC (the lethal concentration required to kill the 25% of the population) fumigated female C. chinensis released significantly less amount of the pheromone components. In contrast, EF LC exposure did not affect the pheromone release. This study unveils the facts that the EF and PH fumigation have detrimental bioactivities against C. chinensis. Notably, this suggests to consider the sub-lethal EF and PH fumigation rather than the dose required to instantly kill all the C. chinensis individuals for disinfestation of stored adzuki bean.
Topics: Female; Animals; Sex Attractants; Pheromones; Survivorship; Fumigation; Coleoptera; Insecta; Phosphines; Fertility; Insecticides
PubMed: 36922539
DOI: 10.1038/s41598-023-30190-1 -
Scientific Reports Aug 2019The reaction of gold reagents [HAuCl•3HO], [AuCl(tht)], or cyclometalated gold(III) precursor, [C^NAuCl] with chiral ((R,R)-(-)-2,3-bis(t-butylmethylphosphino)...
The reaction of gold reagents [HAuCl•3HO], [AuCl(tht)], or cyclometalated gold(III) precursor, [C^NAuCl] with chiral ((R,R)-(-)-2,3-bis(t-butylmethylphosphino) quinoxaline) and non-chiral phosphine (1,2-Bis(diphenylphosphino)ethane, dppe) ligands lead to distorted Au(I), (1, 2, 4, 5) and novel cyclometalated Au(III) complexes (3, 6). These gold compounds were characterized by multinuclear NMR, microanalysis, mass spectrometry, and X-ray crystallography. The inherent electrochemical properties of the gold complexes were also studied by cyclic voltammetry and theoretical insight of the complexes was gained by density functional theory and TD-DFT calculations. The complexes effectively kill cancer cells with IC in the range of ~0.10-2.53 μΜ across K562, H460, and OVCAR8 cell lines. In addition, the retinal pigment epithelial cell line, RPE-Neo was used as a healthy cell line for comparison. Differential cellular uptake in cancer cells was observed for the compounds by measuring the intracellular accumulation of gold using ICP-OES. Furthermore, the compounds trigger early - late stage apoptosis through potential disruption of redox homeostasis. Complexes 1 and 3 induce predominant G1 cell cycle arrest. Results presented in this report suggest that stable gold-phosphine complexes with variable oxidation states hold promise in anticancer drug discovery and need further development.
Topics: Animals; Apoptosis; Cattle; Cell Cycle; Cell Death; Cell Line, Tumor; Cell Proliferation; Crystallography, X-Ray; Density Functional Theory; Electrochemistry; Electrodes; Endocytosis; Gold; Humans; Inhibitory Concentration 50; Magnetic Resonance Spectroscopy; Models, Molecular; Phosphines; Serum Albumin, Bovine; Serum Albumin, Human; Spectrophotometry, Ultraviolet; Temperature
PubMed: 31451718
DOI: 10.1038/s41598-019-48584-5 -
Nature Aug 2021The substitution of an alkyl electrophile by a nucleophile is a foundational reaction in organic chemistry that enables the efficient and convergent synthesis of organic...
The substitution of an alkyl electrophile by a nucleophile is a foundational reaction in organic chemistry that enables the efficient and convergent synthesis of organic molecules. Although there has been substantial recent progress in exploiting transition-metal catalysis to expand the scope of nucleophilic substitution reactions to include carbon nucleophiles, there has been limited progress in corresponding reactions with nitrogen nucleophiles. For many substitution reactions, the bond construction itself is not the only challenge, as there is a need to control stereochemistry at the same time. Here we describe a method for the enantioconvergent substitution of unactivated racemic alkyl electrophiles by a ubiquitous nitrogen-containing functional group, an amide. Our method uses a photoinduced catalyst system based on copper, an Earth-abundant metal. This process for asymmetric N-alkylation relies on three distinct ligands-a bisphosphine, a phenoxide and a chiral diamine. The ligands assemble in situ to form two distinct catalysts that act cooperatively: a copper/bisphosphine/phenoxide complex that serves as a photocatalyst, and a chiral copper/diamine complex that catalyses enantioselective C-N bond formation. Our study thus expands enantioselective N-substitution by alkyl electrophiles beyond activated electrophiles (those bearing at least one sp- or sp-hybridized substituent on the carbon undergoing substitution) to include unactivated electrophiles.
Topics: Amides; Bromides; Carbon; Catalysis; Copper; Cyclization; Diamines; Ligands; Nitrogen; Phosphines; Photochemistry
PubMed: 34182570
DOI: 10.1038/s41586-021-03730-w -
Molecules (Basel, Switzerland) Mar 2024A wide range of platinum(0)-η-()-1,2-ditosylethene complexes bearing isocyanide, phosphine and -heterocyclic carbene ancillary ligands have been prepared with high...
Platinum(0)-η-1,2-()ditosylethene Complexes Bearing Phosphine, Isocyanide and -Heterocyclic Carbene Ligands: Synthesis and Cytotoxicity towards Ovarian and Breast Cancer Cells.
A wide range of platinum(0)-η-()-1,2-ditosylethene complexes bearing isocyanide, phosphine and -heterocyclic carbene ancillary ligands have been prepared with high yields and selectivity. All the novel products underwent thorough characterization using spectroscopic techniques, including NMR and FT-IR analyses. Additionally, for some compounds, the solid-state structures were elucidated through X-ray diffractometry. The synthesized complexes were successively evaluated for their potential as anticancer agents against two ovarian cancer cell lines (A2780 and A2780) and one breast cancer cell line (MDA-MB-231). The majority of the compounds displayed promising cytotoxicity within the micromolar range against A2780 and MDA-MB-231 cells, with IC values comparable to or even surpassing those of cisplatin. However, only a subset of compounds was cytotoxic against cisplatin-resistant cancer cells (A2780). Furthermore, the assessment of antiproliferative activity on MRC-5 normal cells revealed certain compounds to exhibit in vitro selectivity. Notably, complexes , and showed low cytotoxicity towards normal cells (IC > 100 µM) while concurrently displaying potent cytotoxicity against cancer cells.
Topics: Female; Humans; Cisplatin; Platinum; Cell Line, Tumor; Cyanides; Breast Neoplasms; Spectroscopy, Fourier Transform Infrared; Ovarian Neoplasms; Coordination Complexes; Antineoplastic Agents; Ligands; Methane; Phosphines
PubMed: 38474631
DOI: 10.3390/molecules29051119 -
Journal of Labelled Compounds &... Nov 2022The synthesis of deuteriated tri-tert-butyl phosphine is reported. This synthesis is an adaptation of the known procedure for tri-tert-butyl phosphine via a Grignard...
The synthesis of deuteriated tri-tert-butyl phosphine is reported. This synthesis is an adaptation of the known procedure for tri-tert-butyl phosphine via a Grignard intermediate.
Topics: Molecular Structure; Phosphines
PubMed: 36041885
DOI: 10.1002/jlcr.4001 -
Inhalation Toxicology Sep 2017Phosphine (PH) is a toxidrome-spanning chemical that is widely used as an insecticide and rodenticide. Exposure to PH causes a host of target organ and systemic effects,...
Phosphine (PH) is a toxidrome-spanning chemical that is widely used as an insecticide and rodenticide. Exposure to PH causes a host of target organ and systemic effects, including oxidative stress, cardiopulmonary toxicity, seizure-like activity and overall metabolic disturbance. A custom dynamic inhalation gas exposure system was designed for the whole-body exposure of conscious male Sprague-Dawley rats (250-350 g) to PH. An integrated plethysmography system was used to collect respiratory parameters in real-time before, during and after PH exposure. At several time points post-exposure, rats were euthanized, and various organs were removed and analyzed to assess organ and systemic effects. The 24 h post-exposure LCt, determined by probit analysis, was 23,270 ppm × min (32,345 mg × min/m). PH exposure affects both pulmonary and cardiac function. Unlike typical pulmonary toxicants, PH induced net increases in respiration during exposure. Gross observations of the heart and lungs of exposed rats suggested pulmonary and cardiac tissue damage, but histopathological examination showed little to no observable pathologic changes in those organs. Gene expression studies indicated alterations in inflammatory processes, metabolic function and cell signaling, with particular focus in cardiac tissue. Transmission electron microscopy examination of cardiac tissue revealed ultrastructural damage to both tissue and mitochondria. Altogether, these data reveal that in untreated, un-anesthetized rats, PH inhalation induces acute cardiorespiratory toxicity and injury, leading to death and that it is characterized by a steep dose-response curve. Continued use of our interdisciplinary approach will permit more effective identification of therapeutic windows and development of rational medical countermeasures and countermeasure strategies.
Topics: Animals; Cardiotoxicity; Consciousness; Dose-Response Relationship, Drug; Gene Expression Regulation; Heart; Heart Diseases; Inhalation Exposure; Insecticides; Lethal Dose 50; Lung; Lung Diseases; Male; Myocardium; Phosphines; Rats, Sprague-Dawley; Risk Assessment; Rodenticides; Time Factors; Toxicity Tests, Acute
PubMed: 29251003
DOI: 10.1080/08958378.2017.1406564 -
Chemical Society Reviews Oct 2010Compared with simple ion receptors, which are able to bind either a cation or an anion, ion pair receptors bearing both a cation and an anion recognition site offer the... (Review)
Review
Compared with simple ion receptors, which are able to bind either a cation or an anion, ion pair receptors bearing both a cation and an anion recognition site offer the promise of binding ion pairs or pairs of ions strongly as the result of direct or indirect cooperative interactions between co-bound ions. This critical review focuses on the recent progress in the design of ion pair receptors and summarizes the various binding modes that have been used to accommodate ion pairs (110 references).
Topics: Calixarenes; Crystallography, X-Ray; Ions; Lewis Acids; Molecular Conformation; Oxides; Phosphines; Sulfoxides
PubMed: 20737073
DOI: 10.1039/c002694h -
Journal of the American Chemical Society Apr 2018Protein lysine crotonylation has emerged as an important post-translational modification (PTM) in the regulation of gene transcription through epigenetic mechanisms....
Protein lysine crotonylation has emerged as an important post-translational modification (PTM) in the regulation of gene transcription through epigenetic mechanisms. Here we introduce a chemical probe, based on a water-soluble phosphine warhead, which reacts with the crotonyl modification. We show that this reagent is complementary to antibody-based tools allowing detection of endogenous cellular proteins such as histones carrying the crotonylation PTM. The tool is also used to show that the histone acylation activity of the transcriptional coactivator, p300, can be activated by pre-existing lysine crotonylation through a positive feedback mechanism. This reagent provides a versatile and sensitive probe for the analysis of this PTM.
Topics: E1A-Associated p300 Protein; Histones; Humans; Lysine; Molecular Probes; Phosphines; Protein Processing, Post-Translational
PubMed: 29584949
DOI: 10.1021/jacs.7b13141 -
Chemphyschem : a European Journal of... Nov 2022Phosphinylidenes are an important class of organophosphorus compounds that can exhibit tautomerization between tricoordinated P(III) hydroxide (R R POH) and a...
Phosphinylidenes are an important class of organophosphorus compounds that can exhibit tautomerization between tricoordinated P(III) hydroxide (R R POH) and a pentacoordinated P(V) oxide (R R P(O)H) form. Herein we show, using the canonical variational transition state theory combined with multidimensional small-curvature tunneling approximation, the dominance of proton tunneling in the two-water-bridged tautomerizations of phosphinous acid and model phosphinylidenes comprising phosphosphinates, H-phosphonates, H-phosphinates and secondary phosphine oxides. Based on the studied system, the contribution of thermally-activated tunneling is predicted to speed up the semiclassical reaction rate by ca. threefold to as large as two orders of magnitude at 298.15 K in the gas phase. The large KIE and the concavity in the Arrhenius plots are further fingerprints of tunneling. The simulations also predicted that the rapid tunneling rate and short half-life span for the forward reaction, as opposed to the reverse reaction in fluorinated secondary phosphine oxides, would result in P(V) being elusive and only P(III) being isolable, which agrees with previous experiments where only P(III) was detected by IR and NMR spectroscopy. We also explored the role of solvent and predicted tunneling to be substantial.
Topics: Water; Phosphines; Protons; Oxides; Catalysis; Kinetics
PubMed: 35867911
DOI: 10.1002/cphc.202200396 -
Veterinary Medicine and Science Aug 2018Phosphine poisoning is rarely reported in poultry, and its diagnosis is a great challenge for veterinary toxicologists and pathologists. A case of phosphine toxicosis in...
Phosphine poisoning is rarely reported in poultry, and its diagnosis is a great challenge for veterinary toxicologists and pathologists. A case of phosphine toxicosis in local, free range chickens is reported. Fourteen dead chickens (age ≥6 months old) were presented to the veterinary clinic for necropsy. The history revealed that the chickens were normally fed with guinea corn grains, but were suspected to have been fed boiled rice laced with poison. The clinical signs observed were ruffled feathers, somnolence, anorexia and high mortality. The disease ran a 2-day course with mortality pattern of four chickens the first day, six overnight and 14 the following day. Necropsy findings showed generalized vascular congestion and haemorrhage in the lungs and visceral organs, with the crop and gizzard filled with guinea corn and rice grains and greenish-yellow faecal material in the intestinal lumen. The presence of widespread congestion and petechial haemorrhages on visceral organs with the microscopic pulmonary congestion, and diffuse intraparabronchial presence of air sac macrophages, strongly suggested an acute toxic cause of death. Chemical tests on the crop contents of the dead chickens were positive for phosphine gas. This report will contribute to a better understanding of the clinical signs and lesions presented in cases of acute phosphide rodenticide exposure in domestic chickens, with a brief review of the forensic literature.
Topics: Animals; Chickens; Female; Male; Nigeria; Phosphines; Poultry Diseases; Rodenticides
PubMed: 30698360
DOI: 10.1002/vms3.100