氰基亚胺与亚甲基二氢苯并呋喃二酮类化合物的[3+2]环加成反应:螺吡唑类化合物的合成

采用具有环外双键的二氢苯并呋喃二酮类化合物和氰基亚胺的[3+2]环加成反应,在温和条件下,以高产率(78%~94%)和高非对映选择性(>20∶1dr)构建了一系列具有螺环结构的吡唑类化合物.     

Cooperative effect of Fe and Ti species over Fe–Ti–Ox catalysts on the catalytic hydrolysis performance of hydrogen cyanide

FeO_x, TiO₂, and Fe–Ti–O_x catalysts were synthesized and used in the catalytic hydrolysis of hydrogen cyanide (HCN). Nearly 100% HCN conversion was achieved at 250 °C over the Fe–Ti–O_x catalyst. TiO₂ rutile was detected over TiO₂, but not over Fe–Ti–O_x, which suggested that the interaction between Fe and Ti species could inhibit the TiO₂ phase transition. Furthermore, the interaction between Fe and Ti species over Fe–Ti–O_x could promote the selectivity of NH₃ and CO. The mechanism of hydrolysis of HCN over FeO_x, TiO₂, and Fe–Ti–O_x can be given as follows: HCN + H₂O → methanamide → ammonium formate → formic acid → H₂O + CO.     

Synthesis,characterization, and thermal properties of novel silicon 1,1,3,3-tetramethylguanidinate derivatives and use as single-source chemical vapor deposition precursors

A series of chemical vapor deposition (CVD) precursors have been synthesized by a single-step reaction of 1,1,3,3-tetramethylguanidine and a variety of silicon chlorides. The structures of the 1,1,3,3-tetramethylguanidinate-based compounds were verified by ¹H NMR, ¹³C NMR, XPS, EI-MS, and elemental analysis. The thermal stability, transport behavior, and vapor pressures of these compounds were evaluated by simultaneous thermal analyses (STA). These compounds are highly stable and those in liquid form are very volatile. Silicon carbonitride (SiCN) thin films were prepared by using bis (tetramethylguanidine)-dimethyl-silane as the precursor in helicon wave plasma chemical vapor deposition (HWP-CVD). The properties of the films were investigated by SEM, AFM, and XPS. The results showed that the films have good uniformities, low friction coefficient, and high hardness, enabling the films for fabrication of semiconductor devices.     

Effectively promoted catalytic activity by adjusting calcination temperature of Ce-Fe-Ox catalyst for NH3-SCR

A series of Ce-Fe-O_x catalysts prepared by the different calcination temperatures (marked as CF-X, where X represented calcination temperature) were used to the selectivity catalytic reduction of NO_x by NH₃. The results explained the relationship between calcination temperature and the sulfate species over Ce-Fe-O_x, and then investigated the surface acidity and catalytic performance. The large amounts of sulfate species were formed over CF-450 and CF-550 while it was decomposed with further the increasing of calcination temperature, which resulted in the loss of surface acidity, causing a decrease in the catalytic activity over Ce-Fe-O_x. Thereby, the CF-450 catalyst showed the best catalytic activity and over 90% NO_x conversion was obtained at 244–450 °C. Besides, the favored pore structure, more Fe³⁺ active species, higher Ce³⁺ concentration and the abundance of chemical adsorbed oxygen species, as well as the surface acid sites, would together contribute to the excellent catalytic activity of CF-450 catalyst.     

Click and count: specific detection of acid ceramidase activity in live cells

The use of intact cells in medical research offers a number of advantages over employing cell-free systems. In diagnostics, cells isolated from liquid biopsies can be directly used, speeding up the time of analysis and diminishing the risk of protein degradation by sample manipulation. In drug discovery, studies in live cells take into account aspects neglected in cell-free systems, such as uptake, metabolization, and subcellular concentration by compartmentalization of potential drug candidates. Therefore, probes for studies in cellulo are of paramount importance. Acid ceramidase (AC) is a lysosomal enzyme that hydrolyses ceramides into sphingoid bases and fatty acids. The essential role of this enzyme in the outburst and progress of several diseases, some of them still incurable, is well sustained. Despite the great clinical relevance of AC as a biomarker and therapeutic target, the specific monitoring of AC activity in live cells has remained elusive due to the concomitant existence of neutral and alkaline ceramidases. In this work, we report that 1-deoxydihydroceramides are exclusively hydrolysed by AC. Using N-octanoyl-18-azidodeoxysphinganine as a probe and a BODIPY-substituted bicyclononyne, we show the click-reliant predominant staining of lysosomes, with extra-lysosomal labeling also occurring in some cells. Importantly, using pharmacological and genetic tools together with high resolution mass spectrometry, we demonstrate that both lysosomal and extra-lysosomal staining are AC-dependent. These findings are translated into the specific flow cytometry monitoring of AC activity in intact cells, which fills an important gap in the field of diseases linked to altered AC activity.

The use of intact cells in medical research offers a number of advantages over employing cell-free systems.     

Daphnane Diterpenoids of Trigonostemon thyrsoideus

Chemistry of Natural Compounds -     

DG polynomial algebras and their homological properties

In this paper, we introduce and study differential graded(DG for short) polynomial algebras. In brief, a DG polynomial algebra A is a connected cochain DG algebra such that its underlying graded algebra A~# is a polynomial algebra K[x_1, x_2,..., x_n] with |xi| = 1 for any i ∈ {1, 2,..., n}. We describe all possible differential structures on DG polynomial algebras, compute their DG automorphism groups, study their isomorphism problems, and show that they are all homologically smooth and Gorenstein DG algebras. Furthermore, it is proved that the DG polynomial algebra A is a Calabi-Yau DG algebra when its differential ?_A≠ 0 and the trivial DG polynomial algebra(A, 0) is Calabi-Yau if and only if n is an odd integer.     

Proof of Sun’s conjectures on super congruences and the divisibility of certain binomial sums

The Ramanujan Journal - In this paper, we study the vanishing properties of Fourier coefficients of rth powers of the Dedekind eta function. We give a certain type of classification of this...     

Topotactic Conversion of Alkali-Treated Intergrown Germanosilicate CIT-13 into Single-Crystalline ECNU-21 Zeolite as Shape-Selective Catalyst for Ethylene Oxide Hydration

The conversion of the alkali-treated intergrowth germanosilicate CIT-13 into the single-crystalline high-silica ECNU-21 (named after East China Normal University) zeolite, with a novel topology and a highly crystalline zeolite framework, has been realized through a creative top-down strategy involving a mild alkaline-induced multistep process consisting of structural degradation and reconstruction. Instead of acid treatment, hydrolysis in aqueous ammonia solution not only readily cleaved the chemically weak Ge(Si)−O−Ge bonds located within the interlayer double four ring (D4R) units of CIT-13, but also cleaved the metastable Si−O−Si bonds therein. This led to extensive removal of the D4R units, and also generated silanol groups on adjacent silica-rich layers, which then condensed to form a novel daughter structure upon calcination. Individual oxygen bridges in the reassembled ECNU-21 replaced the germanium-rich D4R units in CIT-13, thereby eliminating the original intergrowth phenomenon along the b axis. With an ordered crystalline structure of 10-ring (R) channels as well as suitable germanium-related Lewis acid sites, ECNU-21 serves as a stable solid Lewis acid catalyst for the shape-selective hydration of ethylene oxide (EO) to ethylene glycol (EG) at greatly reduced H₂O/EO ratios and reaction temperature in comparison with the noncatalytic industrial process.     

Size effect of lead-free halide double perovskite on luminescence property

Lead-free halide double perovskites have gathered wide scientific interest since they are environmentally friendly and stable.However,compared to the lead perovskites,their optoelectronic properties are compromised.Herein we report a series of bulk lead-free mixed Bi-In halide double perovskites:Cs_2AgBi_(1-x)In_xCl_6(0x1).The Cs_2AgBi_(0.125)In_(0.875)Cl_6breaks the parity-forbidden transition and retains direct band gap structure,having warm-white light emission,with photoluminescence quantum efficiency(PLQE)of 70.3%,much higher than the PLQE of reported lead perovskite materials.Its exciton self-trapping dynamics is investigated.Meanwhile,the Cs_2AgBi_(0.125)In_(0.875)Cl_6nanocrystals and Cs_2AgBi_(0.125)In_(0.875)Cl_6microcrystals can be synthesized by modified hot injection and rapid cooling crystallization,respectively.The size effect of Cs_2AgBi_(0.125)In_(0.875)Cl_6is studied on the photoluminescence(PL)property.Additionally,the bulk material exhibits excellent stability on exposure to light,humidity and air for more than 3 months.It is a promising candidate as highly efficient warm white-light emitting material for road lighting.