Construction of a (NNN)Ru-Incorporated Porous Organic Polymer with High Catalytic Activity for β-Alkylation of Secondary Alcohols with Primary Alcohols

Solid supports functionalized with molecular metal catalysts combine many of the advantages of heterogeneous and homogeneous catalysis. A (NNN)Ru-incorporated porous organic polymer (POP-bp/bbpRuCl3) exhibited high catalytic efficiency and broad functional group tolerance in the C–C cross-coupling of secondary and primary alcohols to give β-alkylated secondary alcohols. This catalyst demonstrated excellent durability during successive recycling without leaching of Ru which is ascribed to the strong binding of the pincer ligands to the metal ions.

Shallow and deep trap states of solvated electrons in methanol and their formation, electronic excitation, and relaxation dynamics

We present condensed-phase first-principles molecular dynamics simulations to elucidate the presence of different electron trapping sites in liquid methanol and their roles in the formation, electronic transitions, and relaxation of solvated electrons (e−met) in methanol. Excess electrons injected into liquid methanol are most likely trapped by methyl groups, but rapidly diffuse to more stable trapping sites with dangling OH bonds. After localization at the sites with one free OH bond (1OH trapping sites), reorientation of other methanol molecules increases the OH coordination number and the trap depth, and ultimately four OH bonds become coordinated with the excess electrons under thermal conditions. The simulation identified four distinct trapping states with different OH coordination numbers. The simulation results also revealed that electronic transitions of e−met are primarily due to charge transfer between electron trapping sites (cavities) formed by OH and methyl groups and that these transitions differ from hydrogenic electronic transitions involving aqueous solvated electrons (e−aq). Such charge transfer also explains the alkyl-chain-length dependence of the photoabsorption peak wavelength and the excited-state lifetime of solvated electrons in primary alcohols.

Genipap flour and its technological potential for food production and manufacturing

This research aimed to evaluate the technological potential of genipap flour (Genipa americana L.) in freeze drying and oven drying processes. The ripened genipap fruits were harvested and submitted to pulp extraction, which after dehydration in an oven and freeze drying, were crushed to obtain the flours. When analyzed by X-ray diffraction, the flours were amorphous, with indicative of starch. In addition, the presence of water, aromatics and primary alcohols was observed by infrared spectra (FTIR). In micrograph (SEM) FPJDE was less porous and starches were identified. For thermogravimetry (TGA) similar thermal events occurred, it was important to verify the thermal behavior, humidity and ash present in the food. In the mineral composition, potassium, magnesium, manganese, iron, phosphorus, copper, and calcium were present, the flours as a source of manganese and with a high content of iron, potassium, copper and magnesium. It was concluded that the flours present a quantity of nutrients and favorable technological characteristics such as: thermal stability, humidity below that established by law for the manufacture and production of food.

Fatty Alcohol Oxidase 3 (FAO3) and FAO4b as Mediators Connect the Alcohol- and Alkane-forming Pathways in Arabidopsis Stem Wax

Alcohol- and alkane-forming pathways in cuticular wax biosynthesis are well characterized in Arabidopsis. However, potential interactions between the two pathways remain unclear. Our study revealed that mutation of CER4, the key gene in the alcohol-forming pathway, also led to a deficiency in alkane-forming pathway in distal stems. To trace the connection between these two pathways, we characterized two homologs of fatty alcohol oxidase (FAO), FAO3 and FAO4b, which were highly expressed in distal stems and localized to the endoplasmic reticulum. The amounts of waxes from the alkane-forming pathway were significantly decreased in stems of fao4b, and much lower in fao3 fao4b, indicative of an overlapping function for both proteins in wax synthesis. Additionally, overexpression of FAO3 and FAO4b in Arabidopsis resulted in a dramatic reduction of primary alcohols and significant increase of aldehydes and related waxes. Moreover, expressing FAO3 or FAO4b led to significantly decreased amounts of C18 - C26 alcohols in yeast co-expressing CER4 and FAR1. Collectively, these findings demonstrate that FAO3 and FAO4b are functionally redundant in suppression of primary alcohols accumulation and contribution to aldehyde production, which provides a missing and long sought-after link between the two pathways in wax biosynthesis.

Reductive Hydroformylation of Isosorbide Diallyl Ether

Isosorbide and its functionalized derivatives have numerous applications as bio-sourced building blocks. In this context, the synthesis of diols from isosorbide diallyl ether by hydrohydroxymethylation reaction is of extreme interest. This hydrohydroxymethylation, which consists of carbon-carbon double bonds converting into primary alcohol functions, can be obtained by a hydroformylation reaction followed by a hydrogenation reaction. In this study, reductive hydroformylation was achieved using isosorbide diallyl ether as a substrate in a rhodium/amine catalytic system. The highest yield in bis-primary alcohols obtained was equal to 79%.