Effectiveness of the suzuki-miyaura cross-coupling reaction for solid-phase peptide modification

The Suzuki-Miyaura (SM) cross-coupling reaction has recently become one of the most efficient methods for C-C bond construction opening a wide range of opportunities in organic synthesis. This study focused on the evaluation of the use of the SM reaction to modify peptides using a solid-phase synthesis approach, an avenue that was still not investigated intensively. We used as a peptide model [Ala (1,2,3), Leu (8)]Enk linked to a polystyrene support on which it was previously assembled. The aromatic residues Tyr (4) and Phe (7) of [Ala (1,2,3), Leu (8)]Enk were respectively substituted with p-iodo-Phe, and an SM-related strategy was developed. Results indicated that the reaction conditions involving K 3PO 4 or Na 2CO 3 (base), DMF (solvent), Pd(PPh 3) 4 (catalyst), and temperatures ranging from 50 to 80 degrees C during 20 h were found as optimal. Finally applying those optimal conditions, a series of [Ala (1,2,3), Leu (8)]Enk analogs modified at Tyr (4) or Phe (7) positions was synthesized using diverse boronic acid derivatives.     

Avoiding Carbothermal Reduction: Distillation of Alkoxysilanes from Biogenic,Green, and Sustainable Sources

The direct depolymerization of SiO₂ to distillable alkoxysilanes has been explored repeatedly without success for 85 years as an alternative to carbothermal reduction (1900 °C) to Si_met, followed by treatment with ROH. We report herein the base‐catalyzed depolymerization of SiO₂ with diols to form distillable spirocyclic alkoxysilanes and Si(OEt)₄. Thus, 2‐methyl‐2,4‐pentanediol, 2,2,4‐trimethyl‐1,3‐pentanediol, or ethylene glycol (EGH₂) react with silica sources, such as rice hull ash, in the presence of NaOH (10 %) to form H₂O and distillable spirocyclic alkoxysilanes [bis(2‐methyl‐2,4‐pentanediolato) silicate, bis(2,2,4‐trimethyl‐1,3‐pentanediolato) silicate or Si(eg)₂ polymer with 5–98 % conversion, as governed by surface area/crystallinity. Si(eg)₂ or bis(2‐methyl‐2,4‐pentanediolato) silicate reacted with EtOH and catalytic acid to give Si(OEt)₄ in 60 % yield, thus providing inexpensive routes to high‐purity precipitated or fumed silica and compounds with single Si−C bonds.     

Sufficient conditions for pseudo-Lipschitz property in convex semi-infinite vector optimization problems

This paper is devoted to the study of the pseudo-Lipschitz property of the efficient (Pareto) solution map for the perturbed convex semi-infinite vector optimization problem (CSVO). We establish sufficient conditions for the pseudo-Lipschitz property of the efficient solution map of (CSVO) under continuous perturbations of the right-hand side of the constraints and functional perturbations of the objective function. Examples are given to illustrate the obtained results.     

Avoiding Carbothermal Reduction: Distillation of Alkoxysilanes from Biogenic,Green, and Sustainable Sources

The direct depolymerization of SiO₂ to distillable alkoxysilanes has been explored repeatedly without success for 85 years as an alternative to carbothermal reduction (1900 °C) to Si_met, followed by treatment with ROH. We report herein the base‐catalyzed depolymerization of SiO₂ with diols to form distillable spirocyclic alkoxysilanes and Si(OEt)₄. Thus, 2‐methyl‐2,4‐pentanediol, 2,2,4‐trimethyl‐1,3‐pentanediol, or ethylene glycol (EGH₂) react with silica sources, such as rice hull ash, in the presence of NaOH (10 %) to form H₂O and distillable spirocyclic alkoxysilanes [bis(2‐methyl‐2,4‐pentanediolato) silicate, bis(2,2,4‐trimethyl‐1,3‐pentanediolato) silicate or Si(eg)₂ polymer with 5–98 % conversion, as governed by surface area/crystallinity. Si(eg)₂ or bis(2‐methyl‐2,4‐pentanediolato) silicate reacted with EtOH and catalytic acid to give Si(OEt)₄ in 60 % yield, thus providing inexpensive routes to high‐purity precipitated or fumed silica and compounds with single Si?C bonds.     

Controlling the Spontaneous Precipitation of Silver Nanoparticles in Sol-Gel Materials

The mechanisms responsible for spontaneous silver precipitation in silver-doped sol-gel materials are identified. The chemistry of the solvent phase is found to be the critical factor in controlling this phenomenon. The addition of HCl as catalyst leads to the formation of AgCl and subsequent formation of silver upon light exposure. Another factor leading to silver precipitation is the reducing capability of methanol radicals. Silver precipitation is inhibited by simply washing out the pore solvents by a solvent exchange method.