Acetylated galactopyranosyl N-heterocyclic monocarbene complexes of Silver(I) as novel anti-proliferative agents in a rhabdomyosarcoma cell line.

Herein, four silver(I) complexes bearing acetylated d-galactopyranoside-based N-heterocyclic carbene ligands were synthesized and fully characterized by elemental analysis, NMR, and X-ray photoelectron spectroscopy. All complexes were obtained with an anomeric ß-configuration and as monocarbene species. In this study, we investigated the biological effects of the silver(I) complexes 2a-d on the human rhabdomyosarcoma cell line, RD. Our results show concentration-dependent effects on cell density, growth inhibition, and activation of key signaling pathways such as Akt 1/2, ERK 1/2, and p38-MAPK, indicating their potential as anticancer agents. Notably, at 35.5 µM, the complexes induced mitochondrial network disruption, as observed with 2b and 2c, whereas with 2a, this disruption was accompanied by nuclear content release. These results provide insight into the utility of carbohydrate incorporated NHC complexes of silver(I) as new agents in cancer therapy.

Rational design of galactopyranoside-substituted N-heterocyclic carbene palladium(ii) complexes. Stable and efficient catalyst for C-C coupling in aqueous media.

Following a rational design, three novel palladium(ii) complexes bearing galactopyranoside-based N-heterocyclic carbene ligands have been synthesized via transmetalation of the corresponding Ag(i) complexes. Palladium(ii) complexes have been characterized by NMR, FT-IR and elemental analysis. Catalytic studies, using the Stille and Suzuki-Miyaura cross-coupling reactions as model C-C coupling, reveal that the complexes are active and reusable. The best results in terms of TON values were achieved in aqueous medium using either the in situ deacetylation of the catalyst or the previously deacetylated catalyst. The catalytic condition using in situ deacetylation was more efficient because it avoids an additional deprotection step.

Galactopyranoside-Substituted N-Heterocyclic Carbene Gold(I) Complexes: Synthesis, Stability, and Catalytic Applications to Alkyne Hydration.

A series of novel gold(I) complexes bearing galactopyranoside-based N-heterocyclic carbene ligands have been synthesized via transmetalation of the corresponding Ag(I) complex. Gold(I) complexes have been characterized by NMR, Fourier transform infrared (FTIR), and elemental analysis. An exhaustive NMR analysis shows that the complexes are not stable when hydroxyl groups are deprotected. Catalytic studies, using the alkyne hydration as a model reaction, indicate that the synthesized complexes are active and reusable.

The use of ultrasound in the South Cone region. Advances in organic and inorganic synthesis and in analytical methods.

In organic and inorganic synthesis and in analytical methods, an external conventional heat source is usually applied to carry out a chemical reaction at a high temperature, or an extraction procedure. In the last decades, the use of ultrasound as an alternative energy source has become an interesting field of research in these topics in the South Cone region (Argentina, Chile, Uruguay, Southern Brazil and Paraguay). For this reason, the present review, covering the period 2009 to mid-2021, is a compilation of ultrasound-assisted synthetic and analytical methodologies.

Fast and easily obtained information about mobilizable metals from sediment samples. Extraction assisted by benzothiophene-based ionic liquids.

A fast and easy method for trace metal extraction on sediments was developed in our laboratories. Three new stable S-metylbenzothiophenium salts were employed along with microwaves to modify the BCR protocol to obtain the concentration of metals of the first two fractions in only one step. The optimum conditions were obtained with 0.125 g of sediment irradiated at 250 W for 30 s at 120 °C, in 5 ml of an aqueous mixture of 10 mM of 1,2-dimethylbenzothiophenium tetrafluoroborate and 0.5 M of hydroxylamine chlorhydrate at pH 2. The method validation was carried out employing BCR 701. The extracted metals were determined by ICP OES. A student's paired t-test was applied with the reference method, giving satisfactory results.

Water-soluble gold nanoparticles: recyclable catalysts for the reduction of aromatic nitro compounds in water.

A structure/catalytic activity study of water-soluble gold nanoparticles, stabilized by zwitterionic ligands derived from imidazolium salts, in the reduction of aromatic nitro compounds in pure water at different temperature, as well as their recyclability, was performed. Our studies indicate that the nanoparticles synthesized by an easy, fast and reproducible process, need a short characteristic induction time to restructure the surfaces and make them active. The differences observed in the catalytic activity of the nanoparticles, determined by using the typical Langmuir-Hinshelwood model, are strongly based on the degree of coverage and spatial arrangement of the imidazolium salts on them. Finally, we demonstrate that gold nanoparticles stabilized by non-traditional ligands can be an excellent choice for nitro compound degradation.

Formation of S-alkyl thiophenium ionic liquids: mechanistic rationale and structural relationships.

The quaternization of thiophenes through S-alkylation reactions with iodoalkanes in the presence of silver salts opens the door to a new family of room-temperature ionic liquids, yet relatively unexplored in terms of chemical reactivity and applications. This computational study provides a mechanistic rationale that accounts for their formation. The results are consistent with the calculated energy barriers of the corresponding transition structures. Calculations indicate that the geometry at the sulfur atom goes from flat to tetrahedral during salt formation, and the electron delocalization of thiophene is greatly reduced, if not lost, as inferred from aromaticity indexes. Moreover, the rationale explains the influence of polarizable anions on S-alkylation and why alkyl substitution at the α-position of thiophenes gives rise to more stable species than unsubstituted derivatives.

Gold nanoparticles stabilized with sulphonated imidazolium salts in water and reverse micelles.

Herein we describe the synthesis of gold nanoparticles (Au-NPs) in presence of sulphonated imidazolium salts [1,3-bis(2,6-diisopropyl-4-sodiumsulfonatophenyl)imidazolium (L1), 1-mesityl-3-(3-sulfonatopropyl)imidazolium (L2) and 1-(3-sulfonatopropyl)imidazolium (L3)] in water and in a confinement environment created by reverse micelles (RMs). The Au-NPs were characterized-with an excellent agreement between different techniques-by UV-vis spectroscopy, transmission electron microscopy (TEM), dynamic light scattering (DLS) and zeta potential. In homogeneous media, the Au-NPs interact with the imidazolium ring and the sulphonate groups were directed away from the NPs' surface. This fact is responsible for the Au-NPs' stability-over three months-in water. Based on the obtained zeta potential values we assume the degree of coverage of the Au-NPs by the imidazolium salts. In n-heptane/sodium 1,4-bis (2-ethylhexyl) sulfosuccinate (AOT)/water RMs, the Au-NPs formed in presence of sulphonated imidazolium salts present different patterns depending on the ligand used as stabilizer. Interestingly, the Au-NPs are more stable in time when the salts are present in AOT RMs (three weeks) in comparison with the same RMs system but in absence of ligands (less than an hour). Clearly, the sulphonated imidazolium salts are very effective Au-NPs stabilizers in a different medium and this generates a plus to be able to use them for multiple purposes.

Synthesis and behavior of novel sulfonated water-soluble N-heterocyclic carbene (η(4)-diene) platinum(0) complexes.

A series of water-soluble (NHC)Pt(0)(dvtms) and (NHC)Pt(0)(AE) complexes containing different sulfonated NHC ligands (dvtms = divinyltetramethyldisiloxane and AE = diallyl ether) are reported. The dvtms compounds have been found to be quite robust and to display some conformational rigidity, whereas their AE counterparts are less stable and more flexible. The catalytic evaluation of these complexes in the hydrosilylation of alkynes in water revealed no benefits in favor of the complexes containing the more labile spectator diene (AE), and a fairly regular catalytic behavior for all complexes that restricts the location of the sulfonate group to the proximity of the metal site.

Probing the microenvironment of unimicelles constituted of amphiphilic hyperbranched polyethyleneimine using 1-methyl-8-oxyquinolinium betaine.

In this work, the microenvironment of the core of different unimicelles of hyperbranched polyethyleneimine (HPEI) capped with different aliphatic chains (stearate, palmitate, and laurate) dissolved in toluene has been investigated. To achieve this goal we have used 1-methyl-8-oxyquinolinium betaine (QB) as a molecular probe due to its solvatochromic behavior to monitor the micropolarity and hydrogen bond donor ability of the unimicelle cores. QB shows that the micropolarity and the hydrogen bond donor capability of the polar core of reverse unimicellar media are very different than toluene and similar to the one obtained with traditional surfactants that form reverse micellar media but at a very low unimicelle concentration. Particularly, our results show that the hydrogen bonding ability of the core is the driving force for QB to partition toward the unimicellar media.

Antibacterial properties of water-soluble gold(I) N-heterocyclic carbene complexes.

The antibacterial properties of water-soluble gold(I) complexes [1-methyl-3-(3-sulfonatopropyl)imidazol-2-ylidene]gold(I) chloride (C1), [1-mesityl-3-(3-sulfonatopropyl)imidazol-2-ylidene]gold(I) chloride (C2), [1-(2,6-diisopropylphenyl)-3-(3-sulfonatopropyl)imidazol-2-ylidene]gold(I) chloride (C3) and [1,3-bis(2,6-diisopropyl-4-sodiumsulfonatophenyl)imidazol-2-ylidene]gold(I) chloride (C4) and the respective ligands were assessed by agar diffusion and broth macrodilution methods against Gram-positives Staphylococcus aureus, Enterococcus faecalis and Micrococcus luteus and the Gram-negative bacteria Yersinia ruckeri, Pseudomonas aeruginosa and Escherichia coli. Viability after treatments was determined by direct plate count. The bactericidal activity displayed by C1 and C3 was comparable to that of AgNO3.

Ultrasound-assisted synthesis of unsymmetrical biaryls by Stille cross-coupling reactions.

We describe herein an efficient method for the synthesis of unsymmetrically-substituted biphenyls using a sonochemical variation of the Stille coupling, whose results have also been compared with the conventional silent reaction. Ultrasound significantly enhances this useful organometallic transformation affording products in higher yields and in shorter reaction times than non-irradiated reactions. The scope has been explored with a selection of arylstannanes as precursors and, remarkably, no by-products resulting from homo-coupling could be detected.

Selective synthetic routes to sterically hindered unsymmetrical diaryl ketones via arylstannanes.

Bulky arylstannanes and bulky aroyl chlorides are good reaction partners for the synthesis of two-, three-, and even four-ortho-substituted benzophenones, in good to excellent isolated yields (47-91%). Three simple and direct routes, with differential advantages, are proposed: (i) a catalyst-free protocol, in o-dichlorobenzene (ODCB) at 180 °C; (ii) a room temperature protocol, using AlCl(3) (0.5 equiv), in dichloromethane (DCM); and (iii) a solvent-free, indium-promoted procedure. A radical mechanism is proposed for the indium-mediated reactions.

Efficient catalyst-free bi- and triaroylation of aromatic rings in a single step.

The exceptional leaving group ability of the trimethylstannyl group in electrophilic aromatic substitutions makes possible the synthesis, in a single step, of bi- and triaroylarenes through the catalyst-free, regioselective reaction of bi- and tristannylarenes with different aroyl halides in o-dichlorobenzene as solvent. Specific di- and triketones are obtained in good to excellent yields (45-83%).