3DOM InVO4-supported chromia with good performance for the visible-light-driven photodegradation of rhodamine B

Three-dimensionally ordered macroporous (3DOM) monoclinic InVO₄ and its supported chromia (yCrO_x/3DOM InVO₄, y denotes as the weight percentage of Cr₂O₃, y = 5, 10, 15, and 20 wt%) photocatalysts were fabricated using the ascorbic acid-assisted polymethyl methacrylate-templating and incipient wetness impregnation methods, respectively. Physicochemical properties of the materials were characterized by means of a number of analytical techniques. Photocatalytic activities of the samples were evaluated for the degradation of rhodamine B (RhB) in the presence of H₂O₂ under visible-light illumination. Compared to 3DOM InVO₄ and 15CrO_x/bulk InVO₄, yCrO_x/3DOM InVO₄ showed much better visible-light-driven photocatalytic performance for RhB degradation, with the 15CrO_x/3DOM InVO₄ sample performing the best. It is concluded that the CrO_x loading, higher surface area and surface oxygen vacancy density and lower bandgap energy as well as the better quality of 3DOM structure were responsible for the good photocatalytic performance of 15CrO_x/3DOM InVO₄ for the degradation of RhB.     

Synthesis of β-amino-α-trifluoromethyl alcohols and their applications in organic synthesis

A comprehensive overview on methods applied for syntheses of β-amino-α-trifluoromethyl alcohols, including stereocontrolled variants, is presented. In addition, reported cases of the exploration of β-amino-α-trifluoromethyl alcohols for the preparation of trifluoromethylated peptidomimetics and other biologically active, fluorinated compounds are discussed. Attractive opportunities for their applications as organocatalysts are also presented.     

Crystal packing of 8,9,10,12-tetrafluoro-<Emphasis Type="Italic">o</Emphasis>-carborane: H...F versus H...H contacts

Detailed study of the crystal packing of 8,9,10,12-tetrafluoro-o-carborane by the topological analysis of the electron density distribution function was performed and the competing between the F...H and H...H interactions in the crystal was investigated.     

Surface chemistry of alkyl and perfluoro ethers: a FTIR and ab initio study of adsorption and decomposition of CF3OCF3 on an Al2O3 surface

The adsorption and thermal decomposition of perfluorodimethyl ether, (CF₃)₂O, on a high-surface-area Al₂O₃ surface was investigated by FTIR under both vacuum and pressure conditions. IR spectra in the 4000-1050 cm⁻¹ range were collected and the spectral assignments were assisted by quantum chemical ab initio calculations. The spectral evidence indicated that (CF₃)₂O decomposed to form adsorbed fluoroformate, FCOO (ads). Increases of temperature (up to 525 K) caused the FCOO (ads) to convert to hydrogen formate, HCOO (ads). Surface hydroxyl groups participated in the decomposition of (CF₃)₂O and the conversion of FCOO (ads) to HCOO (ads). A decomposition mechanism is proposed.     

钯催化烯丙基磺酰胺的分子内胺氟化反应

报道了钯催化的非活性烯烃的胺氟化反应,在酸性添加剂HOAc的作用下,反应以较好的收率和区域选择性地得到6-endo环合产物,实现了氟代的环状磺胺类产物的有效合成.     

含氟高分子基因载体

阳离子高分子被广泛应用为非病毒类基因载体,但这类高分子材料的转染效率与细胞毒性之间通常存在"恶性"关联,即获得高转染效率时往往会伴随严重的细胞毒性.如何制备兼具高效、低毒特点的高分子载体是成功实施基因治疗的关键.含氟高分子是一类具有独特理化性质的高分子,能够在低电荷密度条件下与核酸形成稳定的复合物,从而实现高效、低毒的基因转染.含氟功能基团可帮助阳离子高分子改善复合物稳定性、细胞内吞、内涵体逃逸、胞内核酸释放等多个环节,从而赋予了含氟高分子在基因递送过程中的氟效应.该专论系统地总结了含氟高分子基因载体的研究,介绍了含氟高分子的基因递送性能、作用机理以及在基因治疗、基因编辑中的应用,并对含氟高分子载体的未来发展进行了展望.     

Synthesis of dihydrofurans containing trifluoromethyl ketone and heterocycles by radical cyclization of fluorinated 1,3-dicarbonyl compounds with 2-thienyl and 2-furyl substituted alkenes

Manganese(III) acetate based radical cyclization of various fluorinated 1,3-dicarbonyl compounds with 2-thienyl and 2-furyl substituted alkenes produced 3-trifluoroacetyl and 2-trifluoromethyl-dihydrofurans in good yields. The radical cyclizations of 2-methyl-5-[(E)-2-phenylvinyl]furan 2b and 2-[(E)-2-phenylvinyl]thiophene 2c led to the formations of 5-(5-methyl-2-furyl)-4,5-dihydrofuran and 5-(2-thienyl)-4,5-dihydrofuran, respectively. In the reactions of 1,3-dicarbonyls with alkenes, 2-thienyl substituted alkenes formed 4,5-dihydrofurans in higher yields than 2-furyl substituted alkenes.     

Efficient synthesis of fluorinated α- and β-amino nitriles from fluoroalkylated α,β-unsaturated imines

A simple and efficient synthesis of fluoroalkylated α-amino nitrile (4) derivatives by regioselective 1,2-addition of trimethylsilyl cyanide to fluoroalkylated α,β-unsaturated imines (1) is described. Fluoroalkylated β-amino nitriles (7) are also prepared by regioselective 1,2-addition of α-carbanions derived from acetonitrile to fluoroalkylated α,β-unsaturated imines (1). Fluoroalkylated α-(4) and β-amino nitriles (7) are also prepared through an ‘one pot’ procedure by reaction of enaminophosphonate 2 with BuLi, addition of aldehydes and subsequent addition of either trimethylsilyl cyanide or α-carbanion derived from acetonitrile. Basic hydrolysis of α-(4) and β-amino nitriles (7) gives fluoroalkylated α-(5) and β-amino acids (8).     

Heat-resistant and soluble fluorinated poly(amide imide)s based on non-coplanar ortho-linked diimide-dicarboxylic acid

A series of novel fluorinated heat-resistant poly(amide imide)s (PAIS) based on non-coplanar diimide-diacid monomer (DIDA) were synthesized and characterized. The poly(amide imide)s were obtained in high yields and possessed inherent viscosities in the range of 0.47-0.91 dL g⁻¹. All of the polymers were amorphous in nature, showed outstanding solubility and could be readily soluble in common organic solvents such as N,N-dimethylacetamide, N-methyl-2-pyrrolidinoned, dimethyl sulfoxide, N,N-dimethylformamide, pyridine and tetrahydrofuran. Glass transition temperatures were in the range of 221-263 °C, as determined by differential scanning calorimetry. Degradation temperatures for 10% weight loss occurred all above 520 °C and char yields was more than 50% at 700 °C in nitrogen atmosphere. Moreover, these PAIs possessed low refractive indexes (n = 1.58-1.59), birefringence (Δn = 0.008-0.013), and dielectric constants (? ≈ 2.5) due to the trifluoromethyl pendent groups and ortho-catenated aromatic rings that interrupt chain packing and increase free volume.     

预聚物复合助稳定剂条件下含氟丙烯酸酯共聚物的细乳液聚合

以甲基丙烯酸三氟乙酯(TFMA)、苯乙烯(St)和丙烯酸丁酯(BA)为共聚单体,在十二烷基硫酸钠(SDS)/磺酸盐型阴离子氟表面活性剂(S100)/辛基苯基聚氧乙烯醚(OP-10)组成的乳化体系中,采用预聚物和十六醇(HDL)共同组成的复合助稳定剂,对细乳液聚合制备St/BA/TFMA三元共聚物的过程进行了研究.通过F...