The structures of the complexes formed between N-methylol ethanone （model molecule of ceramide） and azacyclopentane-2-one （the model molecule of azone） have been fully optimized at the B3LYP/6-311＋＋G＊＊ level. ...The structures of the complexes formed between N-methylol ethanone （model molecule of ceramide） and azacyclopentane-2-one （the model molecule of azone） have been fully optimized at the B3LYP/6-311＋＋G＊＊ level. The intermolecular hydrogen bonding interaction energies have been calculated by using the B3LYP/6-311＋＋G＊＊, B3LYP/6-311＋＋G（2df,2p）, MP2（full）/6-311 ＋＋G＊＊ and MP2（full）/6-311 ＋＋G（2df,2p） methods, respectively. The results show that strong O-H…O=C, N-H…O=C and C-H…O=C hydrogen bonds could exist between azacyclopentane-2-one and N-methylol ethanone. The formation of the complexes might change the conformation of ceramide molecule and thus cause better percutaneous permeation for the drugs. This is perhaps the origin of the permeation enhances the activity of azone for medicament, as is in accordance with the experimental results. The hydrogen-bonding interactions follow the order of （a） 〉 （c） 〉 （b） 〉 （d） 〉 （g） ≈ （e） ≈ （i） 〉 （h） 〉 （f）. The analyses of frequency, NBO, AIM and electron density shift are used to further reveal the nature of the complex formation. In the range of 263.0- 328.0 K, the complex is formed via an exothermic reaction, and the solvent with lower temperature and dielectric constant is favorable to this process.展开更多
Global energy issues and the reliance on hydrocarbon resources have resulted in the reduction of petroleum sources, and the focus of the chemical industries has shifted to substitute raw material sources. The major ra...Global energy issues and the reliance on hydrocarbon resources have resulted in the reduction of petroleum sources, and the focus of the chemical industries has shifted to substitute raw material sources. The major raw materials used in wood adhesives, such as hydrocarbons like polyvinyl acetate, would be gradually replaced by renewable natural polymers. Currently, polyvinyl alcohol has the limitation of petroleum origin, which is non-economical and it will be replaced by biopolymers. Conventionally available wood adhesive emulsions are colloid-like polyvinyl alcohol stabilized. Starch, being a naturally available polymer, has gained interest from researchers for replacing polyvinyl alcohol as a stabilizer. New research on sustainable, economical, biodegradable, renewable, and environmentally friendly starch grafted polyvinyl acetate emulsion that was synthesized by the graft polymerization of vinyl acetate monomer onto starch. However, starch grafted polyvinyl acetate emulsion-based adhesive’s properties, such as poor water resistance, weak adhesion, delayed drying rate and delayed setting speed, have resulted in limitations in its application as a wood adhesive. A detailed review of starch grafting on vinyl acetate and comonomers like acrylamides, and acrylic acid, and the addition of nano-fillers to enhance the water resistance and performance properties of sustainable adhesives has been explained.展开更多
文摘The structures of the complexes formed between N-methylol ethanone （model molecule of ceramide） and azacyclopentane-2-one （the model molecule of azone） have been fully optimized at the B3LYP/6-311＋＋G＊＊ level. The intermolecular hydrogen bonding interaction energies have been calculated by using the B3LYP/6-311＋＋G＊＊, B3LYP/6-311＋＋G（2df,2p）, MP2（full）/6-311 ＋＋G＊＊ and MP2（full）/6-311 ＋＋G（2df,2p） methods, respectively. The results show that strong O-H…O=C, N-H…O=C and C-H…O=C hydrogen bonds could exist between azacyclopentane-2-one and N-methylol ethanone. The formation of the complexes might change the conformation of ceramide molecule and thus cause better percutaneous permeation for the drugs. This is perhaps the origin of the permeation enhances the activity of azone for medicament, as is in accordance with the experimental results. The hydrogen-bonding interactions follow the order of （a） 〉 （c） 〉 （b） 〉 （d） 〉 （g） ≈ （e） ≈ （i） 〉 （h） 〉 （f）. The analyses of frequency, NBO, AIM and electron density shift are used to further reveal the nature of the complex formation. In the range of 263.0- 328.0 K, the complex is formed via an exothermic reaction, and the solvent with lower temperature and dielectric constant is favorable to this process.
文摘Global energy issues and the reliance on hydrocarbon resources have resulted in the reduction of petroleum sources, and the focus of the chemical industries has shifted to substitute raw material sources. The major raw materials used in wood adhesives, such as hydrocarbons like polyvinyl acetate, would be gradually replaced by renewable natural polymers. Currently, polyvinyl alcohol has the limitation of petroleum origin, which is non-economical and it will be replaced by biopolymers. Conventionally available wood adhesive emulsions are colloid-like polyvinyl alcohol stabilized. Starch, being a naturally available polymer, has gained interest from researchers for replacing polyvinyl alcohol as a stabilizer. New research on sustainable, economical, biodegradable, renewable, and environmentally friendly starch grafted polyvinyl acetate emulsion that was synthesized by the graft polymerization of vinyl acetate monomer onto starch. However, starch grafted polyvinyl acetate emulsion-based adhesive’s properties, such as poor water resistance, weak adhesion, delayed drying rate and delayed setting speed, have resulted in limitations in its application as a wood adhesive. A detailed review of starch grafting on vinyl acetate and comonomers like acrylamides, and acrylic acid, and the addition of nano-fillers to enhance the water resistance and performance properties of sustainable adhesives has been explained.
