Heteroleptic (S^C)-cyclometallated gold(III) complexes as novel antiviral agents.

Despite the increasingly widespread clinical impact of adenovirus (HAdV) infections in healthy individuals and the associated high morbidity in immunosuppressed patients, particularly among the paediatric population, a specific treatment for this virus has yet to be developed. In this study, we report the anti-HAdV activity of sub-micromolar concentrations of four heteroleptic (C^S)-cycloaurated complexes bearing a single thiophosphinamide [, , and ] or thiophosphonamide [] chelating ligand and a dithiocarbamate moiety. In addition to their low cytotoxicity, the findings of mechanistic assays revealed that these molecules have antiviral activity by targeting stages of the viral replication cycle subsequent to DNA replication.

Crystal, Solution, and Computational Study of the Structure of Ortho-Lithium N,N-Diisopropyl-P,P-Diphenylphosphinothioic Amide.

The first crystal structure of an ortho-lithium phosphinothioic amide complexed with tetramethylethylenediamine 12 is reported. The complex consists of a spirane in which the spiro-lithium is N,N- and C,S-chelated by the diamine and organophosphorus ligands, respectively. The analogous ortho anion 14 obtained by Sn(IV)/Li transmetallation in THF has also been synthesized.

Solvent- and functional-group-assisted tautomerism of 3-alkyl substituted 5-(2-pyridyl)-1,2,4-triazoles in DMSO-water.

The tautomerism of a series of 5-alkyl substituted 3-(2-pyridyl)-1,2,4-triazoles in DMSO--containing water has been investigated by H, C and N NMR spectroscopy. The populations of the three possible regioisomers in the tautomeric equilibrium (A [3-alkyl-5-(2-pyridyl)-1], B [5-alkyl-3-(2-pyridyl)-1] and C [5-alkyl-3-(2-pyridyl)-4]) were determined. Isomers A (17-40%) and B (54-79%) are the major components and their ratio is insensitive to the substitution pattern, except for the unsubstituted and the methoxymethyl substituted derivatives.

Novel gold(III)-dithiocarbamate complex targeting bacterial thioredoxin reductase: antimicrobial activity, synergy, toxicity, and mechanistic insights.

Introduction: Antimicrobial resistance is a pressing global concern that has led to the search for new antibacterial agents with novel targets or non-traditional approaches. Recently, organogold compounds have emerged as a promising class of antibacterial agents. In this study, we present and characterize a (C^S)-cyclometallated Au(III) dithiocarbamate complex as a potential drug candidate.

Effect of culture conditions at lab-scale on metabolite composition and antibacterial and antibiofilm activities of Dunaliella tertiolecta.

Dunaliella tertiolecta RCC6 was cultivated indoors in glass bubble column photobioreactors operated under batch and semi-continuous regimens and using two different conditions of light and temperature. Biomass was harvested by centrifugation, frozen, and then lyophilized. The soluble material was obtained by sequential extraction of the lyophilized biomass with solvents with a gradient of polarity (hexane, ethyl acetate, and methanol) and its metabolic composition was investigated through nuclear magnetic resonance (NMR) spectroscopy.

Gold(III) Complexes Activity against Multidrug-Resistant Bacteria of Veterinary Significance.

The emergence and spread of multidrug-resistant bacteria are a global concern. The lack of new antibiotics in the pipeline points to the need for developing new strategies. In this sense, gold(III) complexes (G3Cs) could be a promising alternative due to their recently described antibacterial activity.

Synthesis of the cyanobacterial halometabolite Chlorosphaerolactylate B and demonstration of its antimicrobial effect and .

Chlorosphaerolactylate B, a newly discovered antimicrobial halometabolite from the cyanobacterium sp. LEGE 00249 has been synthesized in three steps by using 12-bromododecanoic acid as starting material. A total of 0.

A CS-Cyclometallated Gold(III) Complex as a Novel Antibacterial Candidate Against Drug-Resistant Bacteria.

The worldwide emergence and spread of infections caused by multidrug-resistant bacteria endangers the efficacy of current antibiotics in the clinical setting. The lack of new antibiotics in the pipeline points to the need of developing new strategies. Recently, gold-based drugs are being repurposed for antibacterial applications.

Microalgae and Cyanobacteria Strains as Producers of Lipids with Antibacterial and Antibiofilm Activity.

Lipids are one of the primary metabolites of microalgae and cyanobacteria, which enrich their utility in the pharmaceutical, feed, cosmetic, and chemistry sectors. This work describes the isolation, structural elucidation, and the antibiotic and antibiofilm activities of diverse lipids produced by different microalgae and cyanobacteria strains from two European collections (ACOI and LEGE-CC). Three microalgae strains and one cyanobacteria strain were selected for their antibacterial and/or antibiofilm activity after the screening of about 600 strains carried out under the NoMorFilm European project.

Unexpected metal-free synthesis of trifluoromethyl arenes tandem coupling of dicyanoalkenes and conjugated fluorinated sulfinyl imines.

A novel strategy for the synthesis of policyclic trifluoromethyl arenes has been devised. It involves a DBU-promoted tandem cycloaromatization reaction of dicyanoalkenes and fluorinated conjugated sulfinyl imines. This unprecedented transformation is a metal-free and air-tolerant process that takes place from readily available starting materials under mild reaction conditions.

Synthesis, crystal structures and magnetic properties of a P-stereogenic -(4-amino-tempo)phosphinic amide radical and its Cu complex.

The synthesis of phosphinic amides containing one 4-amino-TEMPO substituent at the ortho position has been achieved through copper(i) catalyzed cross-coupling reactions of ortho-iodophosphinic amides with 4-amino-TEMPO. The method has been extended to the preparation of the first example of a P-stereogenic ortho-(4-amino-tempo)phosphinic amide radical 10. The reaction of 10 with Cu(hfac)2 afforded the P-stereogenic CuII complex 19.

Chelation-Assisted Interrupted Copper(I)-Catalyzed Azide-Alkyne-Azide Domino Reactions: Synthesis of Fully Substituted 5-Triazenyl-1,2,3-triazoles.

We describe the synthesis of 1,4-(disubstituted)-5-triazenyl-1,2,3-triazoles through a ligand-free domino copper(I)-catalyzed azide-alkyne-azide process of chelating aryl azides bearing N-P═O, P═O, and SOH groups at the ortho position with a wide variety of acetylenes. DFT calculations reveal that Cu-chelation is a crucial factor in the interception of the CuAAC intermediate by the azide. The crystal structure of the catalytic species has been determined by X-ray diffraction.

Spiro[1,2]oxaphosphetanes of Nonstabilized and Semistabilized Phosphorus Ylide Derivatives: Synthesis and Kinetic and Computational Study of Their Thermolysis.

A series of tri- and tetrasubstituted spiro-oxaphosphetanes stabilized by -benzamide (BA) and -methyl -benzamide (MBA) ligands have been synthesized by the reaction of C,C-dilithiated phosphazenes with aldehydes and ketones. They include enantiopure products and the first example of an isolated oxaphosphetane having a phenyl substituent at C3 of the ring. Kinetic studies of their thermal decomposition showed that the process takes place irreversibly through a polar transition state (ρ = -0.

Chlorosphaerolactylates A-D: Natural Lactylates of Chlorinated Fatty Acids Isolated from the Cyanobacterium sp. LEGE 00249.

Four natural lactylates of chlorinated fatty acids, chlorosphaerolactylates A-D (-), were isolated from the methanolic extract of the cyanobacterium sp. LEGE 00249 through a combination of bioassay-guided and MS-guided approaches. Compounds - are esters of (mono-, di-, or tri)chlorinated lauric acid and lactic acid, whose structures were assigned on the basis of spectrometric and spectroscopic methods inclusive of 1D and 2D NMR experiments.

Synthesis, structural characterization and electrochemical and magnetic studies of M(hfac) (M = Cu, Co) and Nd(hfac) complexes of 4-amino-TEMPO.

Three mononuclear complexes [M(hfac)x(ATEMPO)y], where M = Cu (11) and Co (12), x = y = 2; M = Nd (13), x = 4, y = 1, and two polynuclear complexes [{Cu(hfac)2(ATEMPO)}n], where n = 2 (14) and 4 (15), were obtained by the reaction of M(hfac)x (M = CuII, CoII, NdIII; x = 2, 3) with 4-amino-TEMPO (4-amino-2,2,6,6-tetramethylpiperidin-N-oxyl) in good yields and their structural, electrochemical and magnetic properties were examined. In all cases, the radical is coordinated to the metal through the amino group, except 15, and the metal ions have an octahedral geometry, except 13. Different coordination architectures of the copper complexes were obtained as a function of the stoichiometry and solvents used.

[AMPK as a therapeutic target for metabolic syndrome].

The AMP-activated kinase (AMPK) is an important enzyme involved in the regulation of cell metabolism, whose activity is regulated by several mechanisms, mainly the increased concentration of AMP. This enzyme catalyze the phosphorylation of several regulatory proteins implicated in the metabolism of lipids and carbohydrates, upregulating their catabolism. Thus, the AMPK plays an important role in the pathophysiology of some diseases, such as metabolic syndrome and type 2 diabetes mellitus, which have a high prevalence among Mexican population.

Immobilized Gold Nanoparticles Prepared from Gold(III)-Containing Ionic Liquids on Silica: Application to the Sustainable Synthesis of Propargylamines.

A cycloaurated phosphinothioic amide gold(III) complex was supported on amorphous silica with the aid of an imidazolium ionic liquid (IL) physisorbed in the SiO₂ pores (SiO₂⁻IL) and covalently bonded to the SiO₂ (SiO₂@IL). Gold(0) nanoparticles (AuNPs) were formed in situ and subsequently immobilized on the SiO₂⁻IL/SiO₂@IL phase. The resulting catalytic systems Au⁻SiO₂⁻IL and Au⁻SiO₂@IL promoted the solvent-free A³ coupling reaction of alkynes, aldehydes, and amines in high yields under solvent-free conditions with very low catalyst loading and without the use of additives.

Synthesis of P-Stereogenic Benzoazaphosphole 1-Oxides via Alkynylation of P-Stereogenic ortho-Aurated and ortho-Iodo Phosphinic Amides.

An efficient methodology for the synthesis of P-stereogenic dihydrobenzoazaphosphole 1-oxides via intramolecular 5--dig alkyne hydroamination promoted by tetrabutylammonium fluoride is herein described. The required chiral -alkynylphosphinic amide starting materials were prepared in high yields under very mild reaction conditions through alkynylation of P-stereogenic (O^C)-cyclometalated (phosphinic amide)dichlorogold(III) complexes and Sonogashira cross-coupling of ortho-iodo P-stereogenic phosphinic amide.

Binuclear Lanthanide-Radical Complexes Featuring Two Centers with Different Magnetic and Luminescence Properties.

Binuclear complexes with general formula [Ln(hfac)(HO)(dppnTEMPO)] (Ln = Gd, Tb, and Dy) have been obtained using the paramagnetic ligand 1-piperidinyl-4-[(diphenylphosphinyl)amino]-2,2,6,6-tetramethyl (dppnTEMPO) as a bridge. One of the lanthanide ions is ferromagnetically coupled with the TEMPO moiety. Two of the complexes (Dy and Tb) show slow relaxation of the magnetization, and the non-magneto-equivalence of the two Ln ions was clearly observed.

Diastereoselective Ortho Lithiation of Phosphinimidic Amides: A Multinuclear Magnetic Resonance and Computational Study.

The structure of the dianion (S,R)-10 formed in the diastereoselective N,C dilithiation of the phosphinimidic amide (R)-PhP(═NCOMe)NHCH(Me)Ph (5; dr of 95:5) with tert-butyllithium in THF has been elucidated using multinuclear magnetic resonance methods, including 2D Li,X-HMQC (X = N, P) correlations. (S,R)-10 consists of a monomer in which C,N and N,O chelation of the lithium cations generates a system containing a five- and a six-membered metallacycle, respectively, sharing a P-N bond with the lithium atoms connected through the NCO moiety of the phosphazenyl group. Selective deprotonation of the pro-S P-phenyl ring of 5 was ascertained through NOE measurements.

Synthesis of P-stereogenic diarylphosphinic amides by directed lithiation: transformation into tertiary phosphine oxides via methanolysis, aryne chemistry and complexation behaviour toward zinc(ii).

The highly diastereoselective synthesis of P-stereogenic phosphinic amides via directed ortho lithiation (DoLi) of (SC)-P,P-diphenylphosphinic amides with t-BuLi followed by electrophilic quench reactions is described. Functionalised derivatives containing a wide variety of ortho substituents (Cl, Br, I, OH, N3, SiMe3, SnMe3, P(O)Ph2, Me, allyl, (t)BuOCO) have been prepared in high yields with diastereomeric ratios up to 98 : 2. The X-ray diffraction structure of the ortho-stannylated and ortho-iodo compounds showed that the pro-S P-phenyl ring was stereoselectively ortho-deprotonated by the organolithium base.

Derivatization of (quinolin-8-yl)phosphinimidic amides via ortho-lithiation revisited.

5The direct ortho-lithiation of N-H containing (quinolin-8-yl)phosphinimidic amides by reaction with 1 equiv. of n-BuLi described by Wang and co-workers has been re-examined. The multinuclear magnetic resonance ((1)H, (2)H, (7)Li, (13)C, (15)N and (31)P) study of the species formed in the monolithiation of N-(tert-butyl)-P,P-diphenyl-N'-(quinolin-8-yl)phosphinimidic amide 5 with n-BuLi in THF showed that proton abstraction occurred exclusively and quantitatively at the NH.

Differential response to environmental and nutritional factors of high-quality tomato varieties.

The effect of salinity and silicon treatments on the marketable quality of four Marmande tomato varieties was investigated through conventional quality attributes and (1)H HRMAS NMR spectroscopy. Following variations in ripening through the content of GABA deduced from NMR was crucial for understanding the effects of environmental and nutritional factors. NMR data also lead to a new taste index, which increases from December to January.

Synthesis, crystal structures and magnetic behaviour of four coordination compounds constructed with a phosphinic amide-TEMPO radical and [M(hfac)2] (M = Cu(II), Co(II) and Mn(II)).

In the present work we describe the synthesis, crystal structures and magnetic properties of four coordination compounds obtained by assembling a new phosphinic amide containing the TEMPO moiety, 1-piperidinyloxy-4-[(diphenylphosphinyl)amino]-2,2,6,6-tetramethyl radical (dppnTEMPO), with [M(hfac)2] building blocks (M = Cu(II), Co(II), Mn(II)). The crystal structures of the coordination compounds revealed the usefulness of the functionalized radical to provide discrete or extended architectures. In the copper compound () the ligand is coordinated through the oxygen atom of the NP[double bond, length as m-dash]O linkage to the metal, which exists in a square pyramidal or octahedral geometry.

Synthetic, structural, NMR and catalytic studies of phosphinic amide-phosphoryl chalcogenides (chalcogen = O, S, Se) as mixed-donor bidentate ligands in zinc chemistry.

ortho Substituted (diphenylphosphoryl)-, (diphenylphosphorothioyl)- and (diphenylphosphoroselenoyl)-phosphinic amides o-C6H4(P(X)Ph2)(P(O)N(i)Pr2) (X = O (20a), S (20b), Se (20c)) were synthesized by ortho directed lithiation of N,N-diisopropyl-P,P-diphenylphosphinic amide (Ph2P(O)N(i)Pr2) followed by trapping with Ph2PCl and subsequent oxidation of the o-(diphenylphosphine)phosphinic amide (19) with H2O2, S8 and Se. The reaction of the new mixed-donor bidentate ligands with zinc dichloride afforded the corresponding complexes [ZnCl2(P(X)Ph2)o-C6H4(P(O)N(i)Pr2)] (21a-c). The new compounds were structurally characterized in solution by nuclear magnetic resonance spectroscopy and in the solid-state by X-ray diffraction analysis of the ligand (20b) and the three complexes (21a-c).