-
Journal of the American Chemical Society Jun 2024Near-infrared luminescent rare-earth organic complexes have attracted intensive attention in the field of optical waveguide amplification. However, their optical gains...
Near-infrared luminescent rare-earth organic complexes have attracted intensive attention in the field of optical waveguide amplification. However, their optical gains were commonly less than 4 dB/cm due to limited doping concentrations. Herein, two one-dimensional (1D) Nd coordination chains, namely, [Nd(TTA)(DBTDPO)] () and [Nd(TTA)(DPEPO)] (), bridged by phosphine oxide ligands were developed for the neodymium-doped waveguide amplifier. Despite its P-P distance being similar to DBTDPO, the different P═O orientation of DPEPO renders markedly shorter intra- and interchain Nd-Nd distances for in comparison to . Furthermore, the weaker intermolecular interactions alleviate the quenching effect for . Therefore, can provide more locally concentrated and radiative Nd ions, leading to a larger Nd-characteristic 1.06 μm emission intensity and duration than . Based on embedded and evanescent-field waveguide structures, achieves state-of-the-art gain maxima of 5.7 and 4.9 dB/cm as well as outstanding gain stability. These results indicate that controllable coordination assembly of lanthanide ions in multidimension provides a flexible approach to combine local high-density outputs and effective suppression of quenching.
PubMed: 38870413
DOI: 10.1021/jacs.4c02735 -
Dalton Transactions (Cambridge, England... Jun 2024Reaction of a sterically demanding iminophosphorano-phosphine, PhPCHPhPNAr* (here onwards referred to as PCPNAr*; Ar* = 2,6-dibenzhydryl-4-methylphenyl), (1) with...
Reaction of a sterically demanding iminophosphorano-phosphine, PhPCHPhPNAr* (here onwards referred to as PCPNAr*; Ar* = 2,6-dibenzhydryl-4-methylphenyl), (1) with [Ru(η--cymene)Cl] yielded three different types of complex, [RuCl{(η--cymene)(PCPNAr*)-κ-}] (2), [RuCl{(P(O)CPNAr*)(κ-,)(-η-arene)}] (3) and [RuCl{(POCPNAr*)(κ-,)(-η-arene)}] (4), depending on the reaction conditions CH activation, tethered η-arene coordination, -metallation or PN bond cleavage/rearrangement reactions. Interestingly, a similar reaction in CHCN in the presence of AgBF resulted in the insertion of CHCN into the PN bond to form a novel metallacycle [Ru(NCMe){(PCPN(CH)CNAr*)-κ-,,}][BF] (5) containing 4- and 5-membered rings an aza-Wittig type reaction. Complex 4 showed very good catalytic activity in the transfer hydrogenation of carbonyl compounds.
PubMed: 38869430
DOI: 10.1039/d4dt00940a -
Journal of Controlled Release :... Jun 2024Asthma is a chronic and heterogeneous disease affecting the lungs and respiratory tract. In particular, the neutrophil subtype of asthma was described as persistent,...
Asthma is a chronic and heterogeneous disease affecting the lungs and respiratory tract. In particular, the neutrophil subtype of asthma was described as persistent, more severe, and corticosteroid-resistant. Growing evidence suggested that nontypeable Haemophilus influenzae (NTHi) infection contributes to the development of neutrophilic asthma, exacerbating clinical symptoms and increasing the associated medical burden. In this work, arginine-grafted chitosan (CS-Arg) was ionically cross-linked with tris(2-carboxyethyl) phosphine (TCEP), and a highly-efficient antimicrobial agent, poly-ε-L-Lysine (ε-PLL), was incorporated to prepare ε-PLL/CS-Arg/TCEP (ECAT) composite nanogels. The results showed that ECAT nanogels exhibited highly effective inhibition against the proliferation of NTHi, Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli). In addition, ECAT nanogels could effectively inhibit the formation of mucins aggregates in vitro, suggesting that the nanogel might have the potential to destroy mucin in respiratory disease. Furthermore, in the ovalbumin (OVA)/NTHi-induced Balb/c mice model of neutrophilic asthma, the number of neutrophils in the alveolar lavage fluid and the percentage of inflammatory cells in the blood were effectively reduced by exposure to tower nebulized administration of ECAT nanogels, and reversing airway hyperresponsiveness (AHR) and reducing inflammation in neutrophilic asthma mice. In conclusion, the construction of ECAT nanogels was a feasible anti-infective and anti-inflammatory therapeutic strategy, which demonstrated strong potential in the clinical treatment of neutrophilic asthma.
PubMed: 38866241
DOI: 10.1016/j.jconrel.2024.06.024 -
Nanotechnology Jun 2024Significant efforts have been dedicated to designing porous organic cage compounds with geometric complexity and topological diversity. However, the use of these cage...
Significant efforts have been dedicated to designing porous organic cage compounds with geometric complexity and topological diversity. However, the use of these cage molecules as premade building units for constructing infinite cage-based superstructures remains unexplored. Here, we report the use of a panel-decorated phosphine organic cage as a special monomer to achieve supramolecular polymerization, resulting in cage-by-cage noncovalent polymers through the synergy of metal-coordination and intercage-dimerization. At a monomer concentration of 122 mM, the average degree of polymerization reaches 17, corresponding to a molecular weight of 26 kDa. The obtained cage-based supramolecular polymers can further hierarchically self-assemble into vesicular morphologies or one-dimensional nanofiber architectures. Selective control over the cosolvents can regulate their structural hierarchy and assembled morphology. This approach paves a new way for the construction of cage-based hierarchical assemblies and materials.
PubMed: 38865974
DOI: 10.1088/1361-6528/ad572c -
Inorganic Chemistry Jun 2024We report the synthesis and characterization of a series of BNP-incorporated borafluorenate heterocycles formed via thermolysis reactions of pyridylphosphine and...
We report the synthesis and characterization of a series of BNP-incorporated borafluorenate heterocycles formed via thermolysis reactions of pyridylphosphine and bis(phosphine)-coordinated borafluorene azides. The use of diphenyl-2-pyridylphosphine (PyPhP), trans-1,2-bis(diphenylphosphino)ethylene (PhP(H)C═C(H)PPh), and bis(diphenylphosphino)methane (PhPC(H)PPh) as stabilizing ligands resulted in Staudinger reactions to form complex heterocycles with four- (BNP, BNPC, PN) and five-membered (BNPC and BNPC) rings, which were successfully isolated and fully characterized by multinuclear NMR and X-ray crystallography. However, when bis(diphenylphosphino)benzene (PhP-Ph-PPh) was used as the ligand in a reaction with 9-bromo-9-borafluorene (BF-Br), due to the close proximity of the donor P atoms, the diphosphine-stabilized borafluoronium ion with an unusual borafluorene dibromide anion was formed. Reaction of the borafluoronium ion with trimethylsilyl azide left the cation intact, and the dibromide anion was substituted by a diazide. Density functional theory calculations were used to provide mechanistic insight into the formation of these new boracyclic compounds. This work highlights a new method in which donor phosphine ligands may be used to promote dimerization, cyclization, and ring contraction reactions to produce boracycles via Staudinger reactions.
PubMed: 38864676
DOI: 10.1021/acs.inorgchem.4c00854 -
Chemical Communications (Cambridge,... Jun 2024A novel phosphine-mediated α-umpolung/Wittig olefination/cyclization cascade process between -aminobenzaldehydes and Morita-Baylis-Hillman (MBH) carbonates has been...
A novel phosphine-mediated α-umpolung/Wittig olefination/cyclization cascade process between -aminobenzaldehydes and Morita-Baylis-Hillman (MBH) carbonates has been ingeniously developed. This protocol serves as a practical tool for the facile synthesis of a broad range of 2-vinylindolines in moderate to good yields under mild reaction conditions. The applicability of this method was demonstrated with gram-scale reaction and various transformations of the corresponding product.
PubMed: 38864654
DOI: 10.1039/d4cc01851f -
Chemistry, An Asian Journal Jun 2024The adducts 2M,R of general formula trans-[(L)M{R2P(CH2)2PR2}2{N2B(C6F5)3}] (L = ø or N2, M = Mo or W, R = Et or Ph), formed from Lewis acid-base pairing of B(C6F5)3 to...
The adducts 2M,R of general formula trans-[(L)M{R2P(CH2)2PR2}2{N2B(C6F5)3}] (L = ø or N2, M = Mo or W, R = Et or Ph), formed from Lewis acid-base pairing of B(C6F5)3 to a dinitrogen ligand of zero-valent group 6 bis(phosphine) complexes trans-[M{R2P(CH2)2PR2}2(N2)2] are shown to react with dihydrogen to afford hepta-coordinated bis(hydride) complexes [M(H)2{R2P(CH2)2PR2}{N2B(C6F5)3}] 3M,R which feature the rare ability to activate both dinitrogen and dihydrogen at a single metal center, except in the case where M = Mo and R = Ph for which fast precipitation of insoluble [Mo(H)4(dppe)2] (dppe = 1,2-bis(diphenylphosphino)ethane) occurs. The frustrated Lewis pair (FLP)-related reactivity of the B-N linkage in compounds 3W,R was explored and led to distal N functionalization without involvement of the hydride ligands. It is shown in one example that the resulting bis(hydride) diazenido compounds may also be obtained through a sequence involving first FLP-type N-functionalization followed by oxidative addition of H2. Those oily compounds were found to have limited stability in solution or in their isolated states. Finally, treatment of 3W,Et with the Lewis base N,N-dimethylaminopyridine (DMAP) affords the simple but unknown bis(hydride)-dinitrogen species [W(H)2(depe)2(N2)] 11Et (depe = 1,2-bis(diethylphosphino)ethane) which direct, selective formation from trans-[W(N2)2(depe)2] is not possible.
PubMed: 38864406
DOI: 10.1002/asia.202400451 -
Nanotechnology Jun 2024Breast cancer is one of the most basilisk cancers for women due to its high mortality rate which can be prevented drastically with early-stage detection. In this work,...
Breast cancer is one of the most basilisk cancers for women due to its high mortality rate which can be prevented drastically with early-stage detection. In this work, the adsorption mechanism of two volatile organic compounds that are present in the breath of breast cancer patients, 2-Methyloctane and 3, 3-Dimethylpentane, has been investigated on aluminum phosphide nanotubes (AlPNT) and gallium phosphide nanotubes (GaPNT) in order to understand their feasibility as sensor materials to diagnosis breast cancer at early stage. We have used the quantum mechanical approach by employing density functional theory using B3LYP-D3 hybrid potential for noncovalent interaction along with the LanL2DZ basis in the Gaussian 09 software package. The adsorption properties analyses suggest that GaPNT exhibits better sensing behavior as well as proclaims 12.6% greater adsorption energy for 2-Methyloctane and 9.4% greater adsorption energy for 3, 3-Dimethylpentane than AlPNT. Other structural and electric properties analyses satisfy this conclusion and suggest that GaPNT exhibits higher stability than AlPNT and could possibly be a potential candidate for developing biosensors to detect breast cancer at the preliminary stages.
Topics: Breast Neoplasms; Humans; Female; Nanotubes; Phosphines; Density Functional Theory; Adsorption; Gallium; Octanes; Volatile Organic Compounds; Biosensing Techniques
PubMed: 38861946
DOI: 10.1088/1361-6528/ad5681 -
The Journal of Organic Chemistry Jun 2024-Phosphinates represent a valuable class of organophosphorus building blocks and catalytic ligands. The existing synthetic approaches are generally associated with the...
-Phosphinates represent a valuable class of organophosphorus building blocks and catalytic ligands. The existing synthetic approaches are generally associated with the use of strong acids, the need for meticulous treatment of intermediates, and the limitation of only P-aryl introductions. Following a comprehensive investigation into the unexpected SiO-promoted hydrolysis observed during the chromatography workup of the crude R'P(OR) intermediates, we have developed an extremely simple and general synthetic route to -phosphinates from commercially available Grignard reagents and P(OR). An alternative approach involved the use of ClP(OR) in place of P(OR), which proved to be a valuable strategy for the preparation of sterically hindered ArMgBr substrates bearing bulky -substituted motifs. A library of 36 structurally diverse P-(cyclo)alkyl and P-(hetero)aryl -phosphinates was thus obtained in moderate to high yields using this practical protocol. Furthermore, the CuCl-mediated P(O)-H bond derivations were also examined, resulting in the formation of the corresponding EtOPhP(O)-X (X = O, N, S) compounds in nearly quantitative yields.
PubMed: 38861591
DOI: 10.1021/acs.joc.4c00760 -
The Journal of Organic Chemistry Jun 2024Despite the development of numerous advanced ligands for Pd-catalyzed Suzuki cross-coupling reaction, the potential of (oligo)peptides serving as ligands remains...
Despite the development of numerous advanced ligands for Pd-catalyzed Suzuki cross-coupling reaction, the potential of (oligo)peptides serving as ligands remains unexplored. This study demonstrates via density functional theory (DFT) modeling that (oligo)peptide ligands can drive superior activity compared to classic phosphines in these reactions. The utilization of natural amino acids such as Met, SeMet, and His leads to strong binding of the Pd center, thereby ensuring substantial stability of the system. The increasing sustainability and economic viability of (oligo)peptide synthesis open new prospects for applying Pd-(oligo)peptide systems as greener catalysts. The feasibility of engineering an artificial Pd-based enzyme for Suzuki cross-coupling is discussed, laying the groundwork for future innovations in catalytic systems.
Topics: Palladium; Catalysis; Peptides; Ligands; Molecular Structure; Density Functional Theory
PubMed: 38861408
DOI: 10.1021/acs.joc.4c00409