Hydrothermally stable mesoporous aluminosilicates with moderate acidity via degradation-assembly process and improved catalytic properties

Mesoporous aluminosilicates with hydrothermal stability and moderate acidity are synthesized via assembly of microporous zeolite precursors obtained by the degradation of zeolite NaY, denoted as “degradation-assembly” (DA) technique. By controlling the degradation degree of matrix NaY, precursors with larger spatial volume and stronger rigidity will be obtained. The characterization results showed that the walls of the mesophase in MDA (mesoporous aluminosilicate obtained by “DA” method) composed of the preformed zeolite Y building units and the moderate acidity was inherited from the introduced precursors. It was suggested that the more mature assembly units accounted for the increased acidity of MDA with more Al species retained in the framework of mesophases. The resulting aluminosilicates with simultaneously moderate acidity and hydrothermal stability showed superior catalytic properties when used in heavy oil catalytic cracking catalysts.     

Two micrometer fluorescence emission and energy transfer in Yb3+/Ho3+ co-doped lead silicate glass

Enhanced 2.0 μm and visible up-conversion emissions from Ho³⁺ via Yb³⁺ sensitization in lead silicate glasses have been obtained under the excitation of 980-nm laser diode. The possible energy transfer mechanism has been analyzed based on the photoemission spectroscopy and lifetime measurement. The lifetime of Ho³⁺: ⁵I₇ laser upper level has also been measured. Based on the absorption spectra, Judd–Ofelt parameters, spontaneous emission probability, the absorption, emission cross sections, and gain coefficients have been calculated and analyzed. The results indicate that the Yb³⁺/Ho³⁺ co-doped lead silicate glass has potential application in mid-infrared wavelengths.     

Properties and carbonization behavior of asphalt modified with the THF-soluble fraction of a coal liquefaction residue

This study focuses on the effects of the tetrahydrofuran-soluble fraction of direct coal liquefaction residue as a modifier to modify asphalt with formaldehyde. The properties and carbonization behavior of matrix asphalt and the modified asphalts were studied. The results indicate that the ductility properties of modified asphalts have been effectively improved. The morphology of modified asphalts without the addition of formaldehyde is a set of uniform distribution point, and it is converted from linear distribution to clustered distribution observed in fluorescence microscope images with the increase of the adding amount of formaldehyde.     

Copper(II)/Silver(I)‐Catalyzed Sequential Alkynylation and Annulation of Aliphatic Amides with Alkynyl Carboxylic Acids: Efficient Synthesis of Pyrrolidones

A highly efficient protocol for the synthesis of pyrrolidones by the copper‐catalyzed alkynylation/annulation of aliphatic amides with alkynyl carboxylic acids is discussed in this paper. A broad range of easily accessible alkynyl carboxylic acids were introduced at the β‐methyl group of aliphatic amides with the assistance of an 8‐aminoquinolyl auxiliary group via decarboxylation to achieve the subsequent cyclic C N bond formation within one hour. High selectivity of β‐methyl groups over methylene groups was observed, and the extension of this catalytic system to the activation of methylene C H bonds failed. The substrates with two different groups at the α‐position of the aliphatic amides lead to the formation of diastereoisomers which is determined by ¹H NMR spectroscopy. The initially produced products with Z‐configurations can be easily transformed to the corresponding products with E‐configurations by the treatment with dilute p‐toluenesulfonic acid after the reaction. This catalytic tandem decarboxylative cyclization provides a new opportunity for the direct functionalization of sp³ C H bonds.

     

Manganese(II)‐Mediated Domino Annulation Reaction of Vinyl Azides and 4‐Hydroxycoumarin: A Stereoselective Synthesis of Spirobenzofuranone‐lactams

A manganese(II) acetate‐catalyzed domino reaction of vinyl azides and 4‐hydroxycoumarin has been developed for the synthesis of polyfunctionalized spirofuranone‐lactams. A wide range of vinyl azides are capable of providing the desired spirofuranone‐lactams in good to excellent yields. The reaction was achieved via thermal decomposition of vinyl azides to 2H‐azirines, followed by an intramolecular nucleophilic attack and stereoselective cyclization. The mild reaction conditions and easy operation make this reaction advantageous for the synthesis of spirofuranone‐lactams.

     

Enantioselective Construction of Cyclic Enaminone‐Based 3‐Substituted 3‐Amino‐2‐oxindole Scaffolds via Catalytic Asymmetric Additions of Isatin‐Derived Imines

The first catalytic asymmetric construction of the cyclic enaminone‐based 3‐substituted 3‐amino‐2‐oxindole scaffold with potential bioactivity has been developed via chiral phosphoric acid‐catalyzed enantioselective addition reactions of cyclic enaminones to isatin‐derived imines, which afforded a series of cyclic enaminone‐based 3‐substituted 3‐amino‐2‐oxindoles in high yields and excellent enantioselectivities (up to 99% yield, 97% ee). The investigation of the reaction mechanism suggested that it was facilitated by a dual hydrogen‐bonding activation mode between the two substrates and the chiral phosphoric acid. Besides, this method could be utilized for a large‐scale synthesis with maintained enantioselectivity. This approach will not only offer a useful method for enantioselective construction of the cyclic enaminone‐based 3‐substituted 3‐amino‐2‐oxindole scaffold, but also enrich the research on catalytic asymmetric addition reactions of isatin‐derived imines by using electron‐rich olefins as nucleophiles. More importantly, a preliminary evaluation on the cytotoxicity of some selected products revealed that two of the enantio‐pure compounds exhibited moderate to strong cytotoxicity to A549, 786‐0, ECA109 and BT474 cancer cell lines.

     

磷化工"双废"联用工艺研究

以磷化工"双废"——磷石膏、磷尾矿为原料,通过硫酸循环酸浸磷尾矿,经盐酸分解磷尾矿、碳化磷石膏、转晶、酸化、析钙、析磷、浓缩、析镁等过程,得到了转化率为96.94％ 的CaCO 3,CaO质量分数为23.38％ 的二水石膏,MgO质量分数为8.27％、P2O5质量分数为23.89％、氮质量分数为6.83％ 的氮镁磷肥,氮质量分数为23.76％ 的氯化铵以及M g O质量分数为30.04％ 的碳酸镁等,所得产品均符合工业应用要求.讨论了循环酸浸过程中离子浓度的变化情况,为联合处理磷石膏、磷尾矿提供了新思路.     

Ru/SiO2 Catalyst for Highly Selective Hydrogenation of Dimethyl Malate to 1,2,4-Butanetriol at Low Temperatures in Aqueous Solvent

Catalysis Letters - Catalytic selective hydrogenation of esterified malic acid to produce 1,2,4-butanetriol (1,2,4-BT) using H2 as the reducing reagent suffers from the low 1,2,4-BT selectivity....     

Enhanced mechanical,thermal and dielectric properties of polyimide nanocomposites containing SiCp (SiCw) nanofillers for high energy-storage applications

Journal of Polymer Research - In this paper, we aimed to develop the nanocarrier based on poly (N-isopropyl acrylamide)—allyl acetoacetate grafted MoS2 nanosheets. The obtained polymer...