Desarrollo de nuevos catalizadores quirales de bisfosfina/diamina-Ru para la hidrogenación asimétrica de la acetofenona

El trabajo que aquí se presenta se enfocó al desarrollo de catalizadores quirales del tipo bisfosfina/diamina-Ru útiles en la hidrogenación asimétrica de la acetofenona. Los alcoholes secundarios quirales productos de la hidrogenación asimétrica son de gran interés en la elaboración de agroquímicos, perfumería y fármacos. En los compuestos de coordinación sintetizados, se incorporó una diamina que formaba un anillo quelato de 7 miembros con Ru en lugar del comúnmente utilizado anillo quelato de 5 miembros, un área de gran interés recientemente. Adicionalmente, en las diaminas empleadas, la naturaleza de la quiralidad es conferida por un impedimento de rotación ó quiralidad axial. Esta naturaleza de quiralidad ha sido escasamente estudiada, ya que en la mayoría de los ligantes de diamina la quiralidad se debe a un átomo estereogénico. Se realizaron pruebas catalíticas a diferentes concentraciones de base, sustrato y catalizador, así como también, se adicionaron dos bases (t-BuOK y KOH). Los perfiles de conversión y exceso enantiomérico contra tiempo estuvieron influenciados por estas modificaciones. Los experimentos permitieron observar la función de cada ligante en el catalizador. El ligante de diamina modificaba principalmente la conversión hacia el alcohol secundario, y el ligante de bisfosfina tuvo más impacto sobre los valores de exceso enantiomérico. Un perfil típico del comportamiento de la conversión a lo largo del tiempo consistió de una zona inicial de rápido aumento, seguido de una etapa de poco incremento y terminando con aumentos pequeños o nulos. Dicho comportamiento en gráficas similares ha sido atribuido en otros trabajos a desactivación, y por consiguiente, se aplicó un modelo cinético que la considera para así obtener los parámetros involucrados. La estructura de los catalizadores se determinó mediante espectroscopía en el Infrarrojo y Resonancia Magnética Nuclear de 31P. Con la ayuda de Infrarrojo se obtuvo evidencia de la conservación de los grupos de diaminas y bisfosfinas, además de que se encontraban unidos al Ru. La Resonancia magnética Nuclear de 31P arrojó información acerca del modo en que se acomodaron los ligantes y se pudo constatar de manera adecuada la formación del compuesto hexacoordinado de Ru

Chiral Catalyst Deactivation during the Asymmetric Hydrogenation of Acetophenone

Asymmetric hydrogenation in solution catalyzed by chiral catalysts is a powerful tool to obtain chiral secondary alcohols. It is possible to reach conversions and enantiomeric excesses close to 99%, but that frequently requires the use of non-optimal amounts of catalysts or long reaction times. That is in part caused by the lack of kinetic information needed for the design of large-scale reactors, including few reported details about catalyst deactivation. In this work, we present a kinetic model for the asymmetric hydrogenation in solution of acetophenone, a prochiral substrate, catalyzed by different bisphosphine-diamine Ru complexes. The experimental data was fitted with a first order model that includes first order deactivation of the catalyst and the presence of residual activity. The fit of the experimental data is very good, and an analysis of the kinetic and deactivation parameters gives further insight into the role of each ligand present in the Ru catalysts. This is the first report of a kinetic analysis of homogenous complexes’ catalysis including an analysis of their deactivation

Environment-Friendly Approach toward the Treatment of Raw Agricultural Wastewater and River Water via Flocculation Using Chitosan and Bean Straw Flour as Bioflocculants

International audienc

Preparation of Surgical Thread from a Bioplastic Based on Nopal Mucilage

Currently, natural materials represent a sustainable option for the manufacture of biopolymers with numerous industrial applications and characteristics comparable with synthetic materials. Nopal mucilage (NM) is an excellent natural resource for the synthesis of bioplastics (BPs). In the present research, the fabrication of biopolymers by using NM is addressed. Changes in the plasticizer (sorbitol and cellulose) concentration, in addition to the implementation of two sources of starch (corn starch (CS) and potato starch (PS)) to obtain the surgical thread, were analyzed. The NM extracted was close to 14% with ethanol. During the characterization of the extract, properties such as moisture, humidity, viscosity, and functional groups, among others, were determined. In the CS and PS analysis, different structures of the polymeric chains were observed. BP degradation with different solvents was performed. Additionally, the addition of sorbitol and cellulose for the BP mixtures presenting the highest resistance to solvent degradation and less solubility to water was conducted. The obtained thread had a uniform diameter, good elasticity, and low capillarity compared to other prototypes reported in the literature

A Comprehensive Study of Coke Deposits on a Pt-Sn/SBA-16 Catalyst during the Dehydrogenation of Propane

Catalytic propane dehydrogenation is an attractive method to produce propylene while avoiding the issues of its traditional synthesis via naphtha steam cracking of naphtha. In this contribution, a series of Pt-Sn/SBA-16 catalysts were synthesized and evaluated for this purpose. Bimetallic Pt-Sn catalysts were more active than catalysts containing only Pt. The catalyst with the best performance was assessed at different reaction times of 0, 60, 180, and 300 min. The evolution of coke deposits was also studied. Thermogravimetric analysis demonstrated the presence of two types of coke on the catalyst surface at low and high temperature, respectively. Raman results showed an increased coke’s crystal size from 60 to 180 min on stream, and from 180 to 300 min under reaction, Raman suggested a reduction in the crystal size of coke. Also transmission electron microscopy confirmed a more evident agglomeration of metallic particles with reaction times higher than 180 min. These results are consistent with the phenomena called “coke migration” and the cause is often explained by coke movement near the particle to the support; it can also be explained due to sintering of the metallic particle, which we propose as a more suitable explanation

A Comprehensive Study of Coke Deposits on a Pt-Sn/SBA-16 Catalyst during the Dehydrogenation of Propane

Catalytic propane dehydrogenation is an attractive method to produce propylene while avoiding the issues of its traditional synthesis via naphtha steam cracking of naphtha. In this contribution, a series of Pt-Sn/SBA-16 catalysts were synthesized and evaluated for this purpose. Bimetallic Pt-Sn catalysts were more active than catalysts containing only Pt. The catalyst with the best performance was assessed at different reaction times of 0, 60, 180, and 300 min. The evolution of coke deposits was also studied. Thermogravimetric analysis demonstrated the presence of two types of coke on the catalyst surface at low and high temperature, respectively. Raman results showed an increased coke’s crystal size from 60 to 180 min on stream, and from 180 to 300 min under reaction, Raman suggested a reduction in the crystal size of coke. Also transmission electron microscopy confirmed a more evident agglomeration of metallic particles with reaction times higher than 180 min. These results are consistent with the phenomena called “coke migration” and the cause is often explained by coke movement near the particle to the support; it can also be explained due to sintering of the metallic particle, which we propose as a more suitable explanation

Chitosan as an Outstanding Polysaccharide Improving Health-Commodities of Humans and Environmental Protection

Public health, production and preservation of food, development of environmentally friendly (cosmeto-)textiles and plastics, synthesis processes using green technology, and improvement of water quality, among other domains, can be controlled with the help of chitosan. It has been demonstrated that this biopolymer exhibits advantageous properties, such as biocompatibility, biodegradability, antimicrobial effect, mucoadhesive properties, film-forming capacity, elicitor of plant defenses, coagulant-flocculant ability, synergistic effect and adjuvant along with other substances and materials. In part, its versatility is attributed to the presence of ionizable and reactive primary amino groups that provide strong chemical interactions with small inorganic and organic substances, macromolecules, ions, and cell membranes/walls. Hence, chitosan has been used either to create new materials or to modify the properties of conventional materials applied on an industrial scale. Considering the relevance of strategic topics around the world, this review integrates recent studies and key background information constructed by different researchers designing chitosan-based materials with potential applications in the aforementioned concerns

Chitosan as an Outstanding Polysaccharide Improving Health-Commodities of Humans and Environmental Protection

Public health, production and preservation of food, development of environmentally friendly (cosmeto-)textiles and plastics, synthesis processes using green technology, and improvement of water quality, among other domains, can be controlled with the help of chitosan. It has been demonstrated that this biopolymer exhibits advantageous properties, such as biocompatibility, biodegradability, antimicrobial effect, mucoadhesive properties, film-forming capacity, elicitor of plant defenses, coagulant-flocculant ability, synergistic effect and adjuvant along with other substances and materials. In part, its versatility is attributed to the presence of ionizable and reactive primary amino groups that provide strong chemical interactions with small inorganic and organic substances, macromolecules, ions, and cell membranes/walls. Hence, chitosan has been used either to create new materials or to modify the properties of conventional materials applied on an industrial scale. Considering the relevance of strategic topics around the world, this review integrates recent studies and key background information constructed by different researchers designing chitosan-based materials with potential applications in the aforementioned concerns