Glycerol Boosted Rh-Catalyzed Hydroaminomethylation Reaction: A Mechanistic Insight.

We report a Rh-catalyzed hydroaminomethylation reaction of terminal alkenes in glycerol that proceeds efficiently under mild conditions to produce the corresponding amines in relatively high selectivity towards linear amines, moderate to excellent yields by using a low catalyst loading (1 mol % [Rh], 2 mol % phosphine) and relative low pressure (H2 /CO, 1:1, total pressure 10 bar). This work sheds light on the importance of glycerol in enabling enamine reduction via hydrogen transfer. Moreover, evidence for the crucial role of Rh as chemoselective catalyst in the condensation step has been obtained for the first time in the frame of the hydroaminomethylation reaction by precluding deleterious aldol condensation reactions. The hydroaminomethylation proceeds under a molecular regime; the outcome of catalytically active species into metal-based nanoparticles renders the catalytic system inactive.

Musa paradisiaca L. peel extract-bioinspired anisotropic nano-silver with the multipurpose of hydrogenation eco-catalyst and antimicrobial resistance.

In an effort to pursue a green synthesis approach, the biosynthesis of nano-silver (nAg) using plant extracts has garnered significant attention, particularly for its antimicrobial resistance and medical applications, which have been the focus of numerous studies. However, there remains a gap in surface catalytic studies, especially regarding the hydrogenation of 4-nitrophenol. While some studies have addressed catalytic kinetics, thermodynamic aspects have been largely overlooked, leaving the catalytic mechanisms of biosynthesized nAg unclear. In this context, the present work offers a straightforward, eco-friendly, and efficient protocol to obtain nano-silver inspired by Musa paradisiaca L. peel extract. This nAg serves multiple purposes, including antimicrobial resistance and as an eco-catalyst for hydrogenation. Predominantly consisting of zero-valent silver with anisotropic polyhedral shapes, mainly decahedra with an edge length of 50 nm, this nAg demonstrated effective antimicrobial action against both S. aureus and E. coli bacteria. More importantly, both kinetic and thermodynamic studies on the hydrogenation of 4-nitrophenol to 4-aminophenol catalyzed by this bio-inspired nAg revealed that the rate-limiting step is not diffusion-limited. Instead, the adsorbed hydrogen and 4-nitrophenolate react together via electron transfer on the surface of the nAg. The activation energy of 26.24 kJ mol-1 indicates a highly efficient eco-catalyst for such hydrogenation processes.

Thiol-Surface-Engineered Cellulose Nanocrystals in Favor of Copper Ion Uptake.

Cellulose, the most abundant natural polymer on earth, has recently gained attention for a large spectrum of applications. At a nanoscale, nanocelluloses (mainly involving cellulose nanocrystals or cellulose nanofibrils) possess many predominant features, such as highly thermal and mechanical stability, renewability, biodegradability and non-toxicity. More importantly, the surface modification of such nanocelluloses can be efficiently obtained based on the native surface hydroxyl groups, acting as metal ions chelators. Taking into account this fact, in the present work, the sequential process involving chemical hydrolysis of cellulose and autocatalytic esterification using thioglycolic acid was performed to obtain thiol-functionalized cellulose nanocrystals. The change in chemical compositions was attributed to thiol-functionalized groups and explored via the degree of substitution using a back titration method, X-ray powder diffraction, Fourier-transform infrared spectroscopy and thermogravimetric analysis. Cellulose nanocrystals were spherical in shape and ca. 50 nm in diameter as observed via transmission electron microscopy. The adsorption behavior of such a nanomaterial toward divalent copper ions from an aqueous solution was also assessed via isotherm and kinetic studies, elucidating a chemisorption mechanism (ion exchange, metal chelation and electrostatic force) and processing its operational parameters. In contrast to an inactive configure of unmodified cellulose, the maximum adsorption capacity of thiol-functionalized cellulose nanocrystals toward divalent copper ions from an aqueous solution was 4.244 mg g-1 at a pH of 5 and at room temperature.

Cellulose nanocrystals isolated from corn leaf: straightforward immobilization of silver nanoparticles as a reduction catalyst.

As the most abundant natural biopolymer on earth, celluloses have long-term emerged as a capable platform for diverse purposes. In the context of metal nanoparticles applied to catalysis, the alternatives to traditional catalyst supports by using biomass-derived renewable materials, likely nanocelluloses, have been paid a great effort, in spite of being less exploited. In this study, cellulose nanocrystals were isolated from corn leaf via chemical treatment involving alkalizing, bleaching and acid hydrolysis. The crystallinity of obtained cellulose was evaluated in each step, focusing on the effects of reactant concentration and reaction time. Cellulose nanocrystals were characterized by powder X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), evidencing the presence of cellulose nanospheres (crystallinity index of 67.3% in comparison with 38.4% from untreated raw material) in the size range of 50 nm. Without using any additional surfactants or stabilizers, silver nanoparticles (AgNPs) well-dispersed on the surface of cellulose nanocrystals (silver content of 5.1 wt%) could be obtained by a simple chemical reduction using NaBH4 at room temperature. The catalytic activity was evaluated in the selective reductions of 4-nitrophenol towards 4-aminophenol and methyl orange towards aromatic amine derivatives in water at room temperature. The effects of catalyst amount and reaction time were also studied in both reduction processes, showing near-quantitative conversions within 5 minutes and obeying the pseudo-first-order kinetics, with the apparent kinetic rate constants of 8.9 × 10-3 s-1 (4-nitrophenol) and 13.6 × 10-3 s-1 (methyl orange). The chemical structure of the catalytic system was found to be highly stable during reaction and no metal leaching was detected in reaction medium, evidencing adaptability of cellulose nanocrystals in immobilizing noble metal nanoparticles.

Green Orange Peel-Mediated Bioinspired Synthesis of Nanoselenium and Its Antibacterial Activity against Methicillin-Resistant Staphylococcus aureus.

In this study, green orange peel (GOP) was feasibly evidenced in preparing selenium nanoparticles (SeNPs). Acting as reducing agents, polyphenolic compounds were extracted from GOP at the optimal extraction conditions (at 70 °C for 1.5 h, mass ratio of dried orange peel/distilled water of 5/100). The formation of SeNPs was observed at the wavelength range of 250-300 nm by ultraviolet-visible spectroscopy (UV-vis), and their highest yield could be reached at the following conditions: volume ratio of extract/selenious acid solution (V Ext/V Se) of 40/10, synthesis duration of 4 h, selenious acid concentration (C Se) of 80 mM, and reaction temperature of 120 °C. The highly crystalline structure of SeNPs in the hexagonal phase was characterized by powder X-ray diffraction (XRD) with a lattice parameter of 4.3 Å; meanwhile, their spheres with an average crystal size of 18.3 nm were estimated by high-resolution transmission electron microscope (HR-TEM). The rationale of bioreducing agents extracted from green orange peel for the formation of SeNPs was also recognized by Fourier-transform infrared spectroscopy (FT-IR). The antibacterial investigation of the SeNP sample was assessed against antibiotic-resistant bacteria, typically methicillin-resistant Staphylococcus aureus (MRSA), by executing the zone of inhibition and the minimum inhibitory concentration (MIC) tests. The SeNP sample demonstrated excellent antibacterial activity with an average diameter of inhibition zones of 20.0 ± 0.7 mm and an MIC of 4.94 µg/L. A comparison of the physicochemical properties of SeNPs synthesized from GOP extract by the hydrothermal method with SeNP products from other green reducing agents and other methods as well as its antibacterial activity compared with other nanoparticles and some antibiotics was conducted to highlight the superiority of GOP-mediated green-synthesized SeNPs.

Palladium and Copper: Advantageous Nanocatalysts for Multi-Step Transformations.

Metal nanoparticles have been deeply studied in the last few decades due to their attractive physical and chemical properties, finding a wide range of applications in several fields. Among them, well-defined nano-structures can combine the main advantages of heterogeneous and homogeneous catalysts. Especially, catalyzed multi-step processes for the production of added-value chemicals represent straightforward synthetic methodologies, including tandem and sequential reactions that avoid the purification of intermediate compounds. In particular, palladium- and copper-based nanocatalysts are often applied, becoming a current strategy in the sustainable synthesis of fine chemicals. The rational tailoring of nanosized materials involving both those immobilized on solid supports and liquid phases and their applications in organic synthesis are herein reviewed.