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ACS Omega Jan 2023A fast, mild, and efficient catalyst-free approach has been developed for the synthesis of chromonyl-substituted α-aminophosphine oxides by the three-component reaction...
A fast, mild, and efficient catalyst-free approach has been developed for the synthesis of chromonyl-substituted α-aminophosphine oxides by the three-component reaction of 3-formyl-6-methylchromone, primary amines, and secondary phosphine oxides at ambient temperature. Carrying out the reaction with aliphatic amines or aminoalcohols at a higher temperature (80 °C), phosphinoyl-functionalized 3-aminomethylene chromanones were formed instead of the corresponding chromonyl-substituted α-aminophosphine oxides. No reaction occurred when 3-formyl-6-methylchromone and secondary phosphine oxides were reacted with aromatic amines in the absence of any catalyst. Applying a basic catalyst, the formation of the phosphinoyl-functionalized 3-aminomethylene chromanones was observed; however, the reaction was not complete. Detailed experimental and quantum chemical studies were performed to study the transformation. Moreover, the cytotoxicity of phosphinoyl-functionalized 3-aminomethylene chromanones was also investigated in three different cell lines, such as human lung adenocarcinoma (A549), mouse fibroblast (NIH/3T3), and human promyelocytic leukemia (HL60) cells. Several derivatives showed modest activity against the human promyelocytic leukemia (HL60) cell line.
PubMed: 36687078
DOI: 10.1021/acsomega.2c07333 -
European Journal of Medicinal Chemistry Nov 2021Given the increasing reports of well-defined bimetallic molecular complexes as potential anticancer agents in the last decades, along with the prevalence of platinum in... (Review)
Review
Given the increasing reports of well-defined bimetallic molecular complexes as potential anticancer agents in the last decades, along with the prevalence of platinum in anticancer therapy, we report here a detailed survey of bimetallic platinum and palladium complexes investigated as potential anticancer agents. Specifically, we will concentrate on the synthesis, characterisation and biological (anticancer) studies of a sub-class of these agents, namely homo and heterobimetallic complexes bearing a bridging phosphane ligand of the type: [LM(μ-RP(CH)PR)ML] (where M is platinum or palladium, M is any other transition metal, R = alkyl or aryl substituents, L or L are co-ligands, n = 1-6). We will review the in vitro and in vivo activities and any mechanistic anticancer studies of these complexes with a view of trying to delineate patterns in biological activity and structure-activity relationships (SAR). We do not include the review of bimetallic complexes in this class that have not undergone any anticancer testing, nor those that have been involved in other biological investigations unrelated to cancer studies.
Topics: Animals; Antineoplastic Agents; Cell Survival; Coordination Complexes; Humans; Ligands; Palladium; Phosphines; Platinum; Structure-Activity Relationship
PubMed: 34214843
DOI: 10.1016/j.ejmech.2021.113651 -
Toxics Jan 2023Limited availability of fish metabolic pathways for PFAS may lead to risk assessments with inherent uncertainties based only upon the parent chemical or the assumption...
Limited availability of fish metabolic pathways for PFAS may lead to risk assessments with inherent uncertainties based only upon the parent chemical or the assumption that the biodegradation or mammalian metabolism map data will serve as an adequate surrogate. A rapid and transparent process, utilizing a recently created database of systematically collected information for fish, mammals, poultry, plant, earthworm, sediment, sludge, bacteria, and fungus using data evaluation tools in the previously described metabolism pathway software system MetaPath, is presented. The fish metabolism maps for 10 PFAS, heptadecafluorooctyl(tridecafluorohexyl)phosphinic acid (C6/C8 PFPiA), bis(perfluorooctyl)phosphinic acid (C8/C8 PFPiA), 2-[(6-chloro-1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexyl)oxy]-1,1,2,2-tetrafluoroethanesulfonic acid (6:2 Cl-PFESA), -Ethylperfluorooctane-1-sulfonamide (Sulfuramid; N-EtFOSA), -Ethyl Perfluorooctane Sulfonamido Ethanol phosphate diester (SAmPAP), Perfluorooctanesulfonamide (FOSA), 8:2 Fluorotelomer phosphate diester (8:2 diPAP), 8:2 fluorotelomer alcohol (8:2 FTOH), 10:2 fluorotelomer alcohol (10:2 FTOH), and 6:2 fluorotelomer sulfonamide alkylbetaine (6:2 FTAB), were compared across multiple species and systems. The approach demonstrates how comparisons of metabolic maps across species are aided by considering the sample matrix in which metabolites were quantified for each species, differences in analytical methods used to identify metabolites in each study, and the relative amounts of metabolites quantified. Overall, the pathways appear to be well conserved across species and systems. For PFAS lacking a fish metabolism study, a composite map consisting of all available maps would serve as the best basis for metabolite prediction. This emphasizes the importance and utility of collating metabolism into a searchable database such as that created in this effort.
PubMed: 36668800
DOI: 10.3390/toxics11010074 -
ACS Omega Dec 2020Hydrogenation of ester to alcohol is an essential reaction in organic chemistry due to its importance in the production of a wide range of bulk and fine chemicals. There... (Review)
Review
Hydrogenation of ester to alcohol is an essential reaction in organic chemistry due to its importance in the production of a wide range of bulk and fine chemicals. There are a number of homogeneous and heterogeneous catalyst systems reported in the literature for this useful reaction. Mostly, phosphine-based bifunctional catalysts, owing to their ability to show metal-ligand cooperation during catalytic reactions, are extensively used in these reactions. However, phosphine-based catalysts are difficult to synthesize and are also highly air- and moisture-sensitive, restricting broad applications. In contrast, N-heterocyclic carbenes (NHCs) can be easily synthesized, and their steric and electronic attributes can be fine-tuned easily. In recent times, many phosphine ligands have been replaced by potent σ-donor NHCs, and the resulting bifunctional metal-ligand systems are proven to be very efficient in several important catalytic reactions. This mini-review focuses the recent advances mainly on bifunctional metal-NHC complexes utilized as (pre)catalysts in ester hydrogenation reactions.
PubMed: 33324787
DOI: 10.1021/acsomega.0c04819 -
Molecules (Basel, Switzerland) Dec 2023Tris(hetaryl)substituted phosphines and their chalcogenides are promising polydentate ligands for the design of metal complexes. An experimental and theoretical...
Tris(hetaryl)substituted phosphines and their chalcogenides are promising polydentate ligands for the design of metal complexes. An experimental and theoretical conformational analysis of tris[2-(4-pyridyl)ethyl]phosphine, tris[2-(2-pyridyl)ethyl]phosphine, and their chalcogenides was carried out by the methods of dipole moments, IR spectroscopy and DFT B3PW91/6-311++G(df,p) calculations. In solution, these compounds exist as an equilibrium of mainly non-eclipsed (synclinal or antiperiplanar) forms with a predominance of a symmetrical conformer having a -orientation of the C-C bonds of pyridylethyl substituents relative to the P=X bond (X = lone pair, O, S, Se) and a -orientation of the pyridyl rings relative to the zigzag ethylene bridges. Regardless of the presence and nature of the chalcogen atom (oxygen, sulfur, or selenium) in the studied molecules with many axes of internal rotation, steric factors-the different position of the nitrogen atoms in the pyridyl rings and the configuration of ethylene bridges-determine the realization and spatial structure of preferred conformers.
PubMed: 38202693
DOI: 10.3390/molecules29010110 -
Acta Crystallographica. Section E,... Feb 2021Palladium 2-di-cyclo-hexyl-phosphanyl-2',6'-diisopropoxybiphenyl (Pd-RuPhos) catalysts demonstrate high catalytic activity for Negishi cross-couplings of sterically...
Palladium 2-di-cyclo-hexyl-phosphanyl-2',6'-diisopropoxybiphenyl (Pd-RuPhos) catalysts demonstrate high catalytic activity for Negishi cross-couplings of sterically hindered aryl halides, for Suzuki-Miyaura cross-couplings of tosyl-ated olefins, and for Buchwald-Hartwig amination of sterically hindered amines. The solid-state structure of the free RuPhos ligand, CHOP, is reported herein for the first time. RuPhos crystallizes in a triclinic cell containing two independent mol-ecules of the phosphine without any lattice solvent. Pertinent bond metrics and comparisons to other phosphine ligands are presented. The structure of RuPhos will be of assistance in the use of this ligand in the design of cross-coupling catalysts.
PubMed: 33614148
DOI: 10.1107/S2056989021000542 -
Scientific Reports May 2023The use of metal phosphides, particularly aluminum phosphide, poses a significant threat to human safety and results in high mortality rates. This study aimed to...
The use of metal phosphides, particularly aluminum phosphide, poses a significant threat to human safety and results in high mortality rates. This study aimed to determine mortality patterns and predictive factors for acute zinc and aluminum phosphide poisoning cases that were admitted to Menoufia University Poison and Dependence Control Center from 2017 to 2021. Statistical analysis revealed that poisoning was more common among females (59.7%), aged between 10 and 20 years, and from rural regions. Most cases were students, and most poisonings were the result of suicidal intentions (78.6%). A new hybrid model named Bayesian Optimization-Relevance Vector Machine (BO-RVM) was proposed to forecast fatal poisoning. The model achieved an overall accuracy of 97%, with high positive predictive value (PPV) and negative predictive value (NPV) values of 100% and 96%, respectively. The sensitivity was 89.3%, while the specificity was 100%. The F1 score was 94.3%, indicating a good balance between precision and recall. These results suggest that the model performs well in identifying both positive and negative cases. Additionally, the BO-RVM model has a fast and accurate processing time of 379.9595 s, making it a promising tool for various applications. The study underscores the need for public health policies to restrict the availability and use of phosphides in Egypt and adopt effective treatment methods for phosphide-poisoned patients. Clinical suspicion, positive silver nitrate test for phosphine, and analysis of cholinesterase levels are useful in diagnosing metal phosphide poisoning, which can cause various symptoms.
Topics: Female; Humans; Child; Adolescent; Young Adult; Adult; Aluminum; Bayes Theorem; Phosphines; Aluminum Compounds; Poisons; Heavy Metal Poisoning; Poisoning; Pesticides
PubMed: 37217491
DOI: 10.1038/s41598-023-34489-x -
Molecules (Basel, Switzerland) Mar 2023Organoruthenium pyrithione (1-hydroxypyridine-2-thione) complexes have been shown in our recent studies to be a promising family of compounds for development of new...
Organoruthenium pyrithione (1-hydroxypyridine-2-thione) complexes have been shown in our recent studies to be a promising family of compounds for development of new anticancer drugs. The complex [(η--cymene)Ru(pyrithionato)(pta)]PF contains phosphine ligand pta (1,3,5-triaza-7-phosphaadamantane) as a functionality that improves the stability of the complex and its aqueous solubility. Here, we report our efforts to find pta alternatives and discover new structural elements to improve the biological properties of ruthenium anticancer drugs. The pta ligand was replaced by a selection of phosphine, phosphite, and arsine ligands to identify new functionalities, leading to improvement in inhibitory potency towards enzyme glutathione -transferase. In addition, cytotoxicity in breast, bone, and colon cancers was investigated.
Topics: Ruthenium; Ruthenium Compounds; Phosphines; Antineoplastic Agents; Organometallic Compounds; Coordination Complexes; Cell Line, Tumor
PubMed: 36985471
DOI: 10.3390/molecules28062499 -
Nanomaterials (Basel, Switzerland) May 2023Solution-processed cadmium telluride (CdTe) nanocrystal (NC) solar cells offer the advantages of low cost, low consumption of materials and large-scale production via a...
Solution-processed cadmium telluride (CdTe) nanocrystal (NC) solar cells offer the advantages of low cost, low consumption of materials and large-scale production via a roll-to-roll manufacture process. Undecorated CdTe NC solar cells, however, tend to show inferior performance due to the abundant crystal boundaries within the active CdTe NC layer. The introduction of hole transport layer (HTL) is effective for promoting the performance of CdTe NC solar cells. Although high-performance CdTe NC solar cells have been realized by adopting organic HTLs, the contact resistance between active layer and the electrode is still a large problem due to the parasitic resistance of HTLs. Here, we developed a simple phosphine-doping technique via a solution process under ambient conditions using triphenylphosphine (TPP) as a phosphine source. This doping technique effectively promoted the power conversion efficiency (PCE) of devices to 5.41% and enabled the device to have extraordinary stability, showing a superior performance compared with the control device. Characterizations suggested that the introduction of the phosphine dopant led to higher carrier concentration, hole mobility and a longer lifetime of the carriers. Our work presents a new and simple phosphine-doping strategy for further improving the performance of CdTe NC solar cells.
PubMed: 37299669
DOI: 10.3390/nano13111766 -
Molecules (Basel, Switzerland) Mar 2020Phosphine resistance is a worldwide issue threatening the grain industry. The cuticles of insects are covered with a layer of lipids, which protect insect bodies from...
Preliminary Study on the Differences in Hydrocarbons Between Phosphine-Susceptible and -Resistant Strains of (Fabricius) and (Herbst) Using Direct Immersion Solid-Phase Microextraction Coupled with GC-MS.
Phosphine resistance is a worldwide issue threatening the grain industry. The cuticles of insects are covered with a layer of lipids, which protect insect bodies from the harmful effects of pesticides. The main components of the cuticular lipids are hydrocarbon compounds. In this research, phosphine-resistant and -susceptible strains of two main stored-grain insects, and , were tested to determine the possible role of their cuticular hydrocarbons in phosphine resistance. Direct immersion solid-phase microextraction followed by gas chromatography-mass spectrometry (GC-MS) was applied to extract and analyze the cuticular hydrocarbons. The results showed significant differences between the resistant and susceptible strains regarding the cuticular hydrocarbons that were investigated. The resistant insects of both species contained higher amounts than the susceptible insects for the majority of the hydrocarbons, sixteen from cuticular extraction and nineteen from the homogenized body extraction for and eighteen from cuticular extraction and twenty-one from the homogenized body extraction for . 3-methylnonacosane and 2-methylheptacosane had the highest significant difference between the susceptible and resistant strains of from the cuticle and the homogenized body, respectively. Unknown5 from the cuticle and 3-methylhentriacontane from the homogenized body recorded the highest significant differences in . The higher hydrocarbon content is a key factor in eliminating phosphine from entering resistant insect bodies, acting as a barrier between insects and the surrounding phosphine environment.
Topics: Alkanes; Animals; Coleoptera; Complex Mixtures; Edible Grain; Gas Chromatography-Mass Spectrometry; Insecticide Resistance; Insecticides; Integumentary System; Phosphines; Solid Phase Microextraction; Tribolium; Triticum
PubMed: 32235326
DOI: 10.3390/molecules25071565