壳聚糖基固体酸催化果糖合成5-羟甲基糠醛

以壳聚糖为原料,采用一步水热碳化和磺化法合成壳聚糖基固体酸材料(CASA),并将其用于催化无溶剂条件下果糖脱水合成5-羟甲基糠醛(5-HMF),考察了催化剂用量、反应温度、反应时间及催化剂循环利用次数对脱水反应的影响,并与甲壳素基固体酸材料(CISA)进行了催化性能比较。采用X射线衍射、扫描电镜、吡啶吸附红外光谱对CASA材料进行了结构和酸性质表征,建立了催化剂结构与性能的关系。结果表明,CASA材料含有大量的表面强Br?nsted酸性位点,因而其催化性能较CISA突出;当m(果糖)∶m(CASA)=6∶1、120℃反应5 h时,5-HMF的收率高达63.2%,且CASA可重复利用4次而无明显失活。     

Gold(I)‐Catalysed Cyclisation of Alkynoic Acids: Towards an Efficient and Eco‐Friendly Synthesis of γ‐, δ‐ and ϵ‐Lactones

The improved synthesis of γ‐, δ‐ and ϵ‐lactones using a dinuclear N‐heterocyclic carbene (NHC)‐gold(I) catalyst is reported. This solvent‐free process provides access to γ‐ and δ‐lactones in high regio‐ and stereoselectivity. Reactions were performed at low catalyst loadings and without the need for any additives. The use of a digold pre‐catalyst provides a new synthetic route to functionalised ϵ‐lactones, poorly accessible using previous methodologies.

     

Polyvinylpolypyrrolidone-Supported Chlorosulfonic Acid: An Efficient Catalyst for One-Pot Synthesis of Dihydropyrimidinones and Octahydroquinazolin-2,5-diones

Polyvinylpolypyrrolidone-supported chlorosulfonic acid has been successfully applied to perform one-pot reaction of arylaldehydes, urea, ethylacetoacetate, or cyclic 1,3-diketo compounds under solvent-free condition at 70°C to provide a series of dihydropyrimidinones and octahydroquinazolin-2,5-diones in good to excellent yields. The method offers several advantages such as high yield, short reaction time, simple workup, easy preparation, and reusability of the catalyst. The [PVPP-SO₃H]⁺Cl^? catalyst was characterized via Fourier transform infrared spectroscopy (FT-IR) and thermal gravimetric analysis (TGA). Moreover, the catalyst could be recycled several times without significant loss of its catalytic activity. Clean methodologies, easy work-up procedure, high yield, and simple preparation of the catalyst are some advantages of this article.     

绿色合成分子筛的研究进展

分子筛由于具有规则的孔道结构、适宜的酸性、良好的热和水热稳定性等特点,广泛应用于吸附、分离、离子交换及催化等领域。传统水热法制备分子筛因需要使用大量溶剂和有机模板剂,存在合成效率低、生产成本高、污染环境等一系列问题。近年来,随着"绿色化学"理念的深入人心,开发绿色、可持续的分子筛制备路线备受关注,逐渐成为该领域的研究热点。本文主要从水热法、离子热法、干胶法以及无溶剂法等几个方面,对国内外分子筛绿色合成的最新研究进展进行综述,并归纳比较上述合成方法的优缺点。最后,提出目前绿色合成分子筛过程中存在的问题,展望其未来发展前景。     

Benign and efficient preparation of thioethers by solvent-free S-alkylation of thiols with alkyl halides catalyzed by potassium fluoride on alumina

The preparation of thioethers by S-alkylation of various thiols with alkyl halides under solvent-free reaction conditions using potassium fluoride on alumina (KF/Al₂O₃) as a solid catalyst has been investigated in detail with respect to three different modes of reaction activation (ultrasound irradiation, microwave irradiation, and conventional heating) for obtaining maximum yield of the thioether. The importance of KF/Al₂O₃ as a particularly efficient catalyst was corroborated for all three modes of reaction activation, although the reaction time was found to be strongly dependent on the mode of activation. The yield of the thioethers was also found to depend on the amount of the solid catalyst relative to the equimolar amounts of the two reactants.     

Effect of extraction methods on kinetic,chemical composition and antibacterial activities of Tunisian Thymus vulgaris. L. essential oil

The present study aims to compare two innovative extraction techniques: microwave-assisted hydrodistillation (MAHD) and solvent-free microwave extraction (SFME) through traditional extraction techniques: hydrodistillation (HD) and steam distillation (SD) for their efficiency in the extraction of the volatile compounds from Tunisian Thymus vulgaris leaves; the kinetic, yield, composition and antibacterial activities of the essential oil were assessed in vitro. Results show that the essential oils extracted by microwaves were quantitatively (yield) similar to those obtained through the conventional methods, but qualitatively, essential oils analysed by gas chromatography–mass spectrometry (GC–MS) presented 17, 11, 11 and 8 compounds obtained through SFME, MAHD, SD and HD, respectively, mostly consisting of carvacrol (89.24–41.17%), followed by γ-terpinene (11.37–1.37%) and para-cymene (27.95–2.05%). The essential oils were screened for antibacterial activity against 5 microorganisms. All essential oils obtained by studied extraction methods showed the same resistance against Gram (?) and Gram (+) bacteria. The SFME method gave the best results: rapid kinetic of extraction (30 min vs. 35 min for MAHD, 120 min for SD, and 180 min for HD), less energy saving and cleanest process.     

Solvent-Free Fabrication of Tissue Engineering Scaffolds With Immiscible Polymer Blends

A completely organic solvent-free fabrication method is developed for tissue engineering scaffolds by gas foaming of immiscible polylactic acid (PLA) and sucrose blends, followed by water leaching. PLA scaffolds with above 90% porosity and 25–200 µm pore size were fabricated. The pore size and porosity was controlled with process parameters including extrusion temperature and foaming process parameters. Dynamic mechanical analysis showed that the extrusion temperature could be used to control the scaffold strength. Both unfoamed and foamed scaffolds were used to culture glioblastoma (GBM) cells M059 K. The results showed that the cells grew better in the foamed PLA scaffolds. The method presented in the paper is versatile and can be used to fabricate tissue engineering scaffolds without any residual organic solvents.     

承压罐体用无溶剂环氧重防腐涂料

罐体内部涂刷涂层是油田及气田通常采用的防腐蚀措施.我国相关部门专门制定了罐体内防腐蚀涂层性能标准,但是现有标准所规定的性能不能很好地体现承压罐体用涂层的要求.本工作采用自行设计的研究手段对承压罐体用无溶剂环氧重防腐蚀涂料的相关性能进行了研究,该研究手段能较好地体现涂层对承压罐体工况的适应性.该研究工作还表明,无溶剂环氧...     

无溶剂法合成高固含量水性聚氨酯

以混合二异氰酸酯[六亚甲基二异氰酸酯(HDI)/异佛尔酮二异氰酸酯(IPDI)]和聚己二酸丁二醇酯(PBA-2000)为基本原料、二羟甲基丁酸(DMBA)为亲水性单体[代替目前常用的二羟甲基丙酸(DMPA)]、三乙胺(TEA)为中和剂和乙二胺(EDA)为扩链剂,反应过程中不添加有机溶剂和催化剂,采用先乳化后扩链的预聚体分散法制备了固含量为50%左右的水性聚氨酯(WPU)。采用单因素试验法优选出制备WPU乳液的较佳工艺条件。结果表明:当R=n(-NCO)∶n(-OH)=1.88∶1、w(DMBA)=4.1%和n(EDA)∶n(-NCO)=0.37∶1时,WPU胶膜的强度(拉伸强度为23 MPa)和韧性(断裂伸长率为740%)俱佳。