RESUMEN

Collagen is a suitable material for regenerative medicine because it is characterized by its good biocompatibility. However, due to its fibrillar structure, it cannot organize itself into three-dimensional porous structures without additional modification. The introduction of synthetic monomer elements into the collagen macromolecules is a technique used to form three-dimensional, collagen-based, branched, and crosslinked structures. New types of graft copolymers made from cod collagen with a butyl acrylate and vinyl butyl ether copolymer in aqueous dispersion were obtained in the presence of triethylborane by a radical mechanism. The process of graft copolymer formation proceeded as usual by radical initiation, through radicals formed during triethylborane oxidation by oxygen residues, collagen borination, and reversible inhibition with the participation of a boroxyl radical. The characteristics of the graft copolymers were determined using methods of physical and chemical analysis (GPC, SEM, IR spectroscopy, etc.), while the cytotoxicity was assessed using the MTT assay method. It is shown that the grafting of alternating blocks of butyl acrylate and vinyl butyl ether to the protein macromolecules results in changes in the morphological pattern of the graft co-polymer in comparison with native collagen. This is manifested in the development of consolidations around the collagen fibers of the structural matrices, with the co-polymer cellular structure consisting of interpenetrating pores of unequal size. Additionally, it is important that the graft co-polymer solutions are not toxic at a certain concentration. The above properties confirm the promising nature of the technique's application as the basis for producing new materials for regenerative medicine.

RESUMEN

Triethylaluminum Al(C2H5)3, TEA, and triethylborane, B(C2H5)3, TEB, are transparent, colorless, pyrophoric liquids with boiling points of approximately 190 °C and 95 °C, respectively. Upon contact with ambient air, TEA, TEB, as well as their mixtures and solutions, in hydrocarbon solvents, ignite. They can also violently react with water. TEA and TEB can be used as hypergolic rocket propellants and incendiary compositions. In this manuscript, a novel scheme of the heterogeneous interaction of gaseous oxygen with liquid TEA/TEB microdroplets accompanied by the release of light hydrocarbon radicals into the gas phase is used for calculating the self-ignition of a spatially homogeneous mixture of fuel microdroplets in ambient air at normal pressure and temperature (NPT) conditions. In the primary initiation step, TEA and TEB react with oxygen, producing an ethyl radical, which can initiate an autoxidation chain. The ignition delay is shown to decrease with the decrease in the droplet size. Preliminary experiments on the self-ignition of pulsed and continuous TEA-TEB sprays in ambient air at NPT conditions are used for estimating the Arrhenius parameters of the rate-limiting reaction. Experiments confirm that the self-ignition delay of TEA-TEB sprays decreases with the injection pressure and provide the data for estimating the activation energy of the rate-limiting reaction, which appears to be close to 2 kcal/mol.

RESUMEN

A photocontrolled reversible addition-fragmentation chain transfer (RAFT) process is developed by initiating polymerization through a 1,3-diaminopropane-triethylborane (DAPTB)-diphenyl iodonium salt (Ph2 I+ ) complex (DAPTB/Ph2 I+ ) under ambient temperature and atmospheric conditions. Upon demand, this air-stable DAPTB/Ph2 I+ complex is photolyzed to liberate a reactive triethylborane that consumes atmospheric oxygen and generates ethyl radicals, which initiate and mediate RAFT polymerization. Controlled RAFT polymerization is thus achieved without any prior deoxygenation using a novel RAFT chain transfer agent, BP-FSBC, which contains both benzophenone and sulfonyl fluoride moieties. Furthermore, the kinetics of polymerization reveal that the reaction process is rapid, and well-defined polymers are produced by a 61% conversion of 2-hydroxyethyl acrylate (HEA) within 7 min and 77% conversion of N,N-dimethylacrylamide (DMA) within 10.5 min. The temporal and spatial control of this photopolymerization is also demonstrated by an "on/off" switch of UV irradiation and a painting-on-a-surface approach, respectively. In addition, active chain ends are demonstrated by preparing block copolymers by chain extension and click sulfur(VI)-fluoride exchange postreaction using RAFT-derived macrochain transfer agents.

Asunto(s)

RESUMEN

The anionic ring-opening copolymerization (ROCOP) of epoxides, namely of ethylene oxide (EO), with anhydrides (AH) generally produces strictly alternating copolymers. With triethylborane (TEB)-assisted ROCOP of EO with AH, statistical copolymers of high molar mass including ether and ester units could be obtained. In the presence of TEB, the reactivity ratio of EO (rEO), which is normally equal to 0 in its absence, could be progressively raised to values lower than 1 or higher than 1. Conditions were even found to obtain rEO equal or close to 1. Samples of P(EO-co-ester) with minimal compositional drift could be synthesized; upon basic degradation of their ester linkages, these samples afforded poly(ethylene oxide) (PEO) diol samples of narrow molar mass distribution. In other cases where rEO were lower or higher than 1, the PEO diol samples eventually isolated after degradation exhibited a broader distribution of molar masses because of the compositional drift of initial P(EO-co-ester) samples.

RESUMEN

In this investigation, a metal-free process was developed that enables the synthesis of poly(propylene carbonate) (PPC) diols/polyols by copolymerization of CO2 with propylene epoxide (PO) under environmentally friendly and cost-effective conditions. This process implies the recycling of triethylborane and of ammonium salts that both enter in the composition of the initiators used to copolymerize CO2 and PO. In complement to the above approach, a polymeric support, poly(diallyl dimethylammonium chloride), was synthesized and modified to carry ammonium carboxylate salts along its chain. The prepared polymeric initiator was utilized to copolymerize CO2 with PO under heterogeneous conditions. Not only were the polymerization results similar to the samples obtained under homogeneous conditions, but the polymer substrate could easily be recovered by simple filtration. The integrity of the polycarbonate diols/polyols and the recycling process were followed by 1 H and 11 B NMR spectroscopy, gel permeation chromatography, and matrix assisted laser desorption ionization time of flight (MALDI-TOF) MS.

RESUMEN

A practical and efficient palladium-catalyzed direct allylation of ß-dicarbonyl compounds with both cyclic and acyclic Morita-Baylis-Hillman (MBH) alcohols, using Et3B as a Lewis acid promoter, is described herein. A wide range of the corresponding functionalized allylated derivatives have been obtained in good yields and with high selectivity.

RESUMEN

A new mild C-C bond forming cyclization approach of catechol derivatives is reported. This approach relies on an initial dearomatization step using lead (IV) acetate followed by a carefully controlled radical cyclization step, which under the reaction conditions also facilitates rearomatization. Triethylborane is the key to the success of this reaction as it enables the reaction to proceed at low temperatures and is also believed to aid rearomatization. The amount and ratio of triethylborane and reducing agent (tributyltinhydride) that is employed as well as the concentration the reaction is run at are all essential to the success of this new approach.

RESUMEN

Triethylborane (TEB) was found to be a mild, efficient, and acid catalyst in electrophilic substitution reaction of indoles with aldehydes compounds to afford the corresponding bis(indolyl)methanes. Vibrindole A (5) and bis(indolyl)methanes derivatives 16 and 18 were synthesized using this methodology. Compound 16 is an intermediary in the synthesis of the natural bisindoles arsindoline B (2) and streptindole (6). The structure of vibrindole A (5) was unequivocally confirmed by a single crystal X-ray diffraction analysis.