Highly effective and chemoselective hydrodeoxygenation of aromatic alcohols

Effective hydrodeoxygenation (HDO) of aromatic alcohols is very attractive in both conventional organic synthesis and upgrading of biomass-derived molecules, but the selectivity of this reaction is usually low because of the competitive hydrogenation of the unsaturated aromatic ring and the hydroxyl group. The high activity of noble metal-based catalysts often leads to undesired side reactions (e.g., saturation of the aromatic ring) and excessive hydrogen consumption. Non-noble metal-based catalysts suffer from unsatisfied activity and selectivity and often require harsh reaction conditions. Herein, for the first time, we report chemoselective HDO of various aromatic alcohols with excellent selectivity, using porous carbon–nitrogen hybrid material-supported Co catalysts. The C–OH bonds were selectively cleaved while leaving the aromatic moiety intact, and in most cases the yields of targeted compounds reached above 99% and the catalyst could be readily recycled. Nitrogen doping on the carbon skeleton of the catalyst support (C–N matrix) significantly improved the yield of the targeted product. The presence of large pores and a high surface area also improved the catalyst efficiency. This work opens the way for efficient and selective HDO reactions of aromatic alcohols using non-noble metal catalysts.

Porous carbon–nitrogen hybrid material-supported Co catalysts can effectively promote the chemoselective hydrodeoxygenation reaction of a various of aromatic alcohols in ethanol and hydrogen atmosphere, under relatively mild conditions.     

反应条件对钌基氨合成催化剂性能的影响

用氨合成催化剂性能评价装置,研究了反应温度、压力、空速和氢氮比对以活性炭为载体的钌基氨合成催化剂活性的影响。研究表明,低于400℃时,随着反应温度降低,催化剂的活性急剧降低。随着压力升高,催化剂活性增大。但钌催化剂具有较高的低压活性,适宜低压合成氨。随着空速的降低,催化剂的活性明显提高。在空速和压力一定的条件下,最佳氢氮比随反应温度而异,并且当空速较高或反应温度较低时,氢氮比的变化对催化剂活性的影响更加明显。     

Stereocontrolled enantioselective addition of diethylzinc to aldehydes using new chiral aminoalcohols

The new chiral β-aminoalcohols of indolinylmethanols ( 1 ) and their reduced derivatives ( 2 ) were synthesized from (S)-indoline-2-carboxylic acid. Both (R) and (S) enantiomers of the optically active secondary alcohols have been successfully obtained in high enantiomeric excess from the stereoselective addition of diethylzinc to the aldehydes catalyzed by the chiral aminoalcohols ( 1 and 2 ). The sense of the asymmetric induction and the degrees of enantioselectivities turned out to be highly dependent on the structure of the catalysts: The presence of the catalyst 1 afforded the (S)-configuration of the corresponding alcohols; on the other hand, the presence of 2 afforded the (R)-configuration of the alcohols in high enantiomeric selectivity.     

Structural Entropy of the Stochastic Block Models

With the rapid expansion of graphs and networks and the growing magnitude of data from all areas of science, effective treatment and compression schemes of context-dependent data is extremely desirable. A particularly interesting direction is to compress the data while keeping the “structural information” only and ignoring the concrete labelings. Under this direction, Choi and Szpankowski introduced the structures (unlabeled graphs) which allowed them to compute the structural entropy of the Erdős–Rényi random graph model. Moreover, they also provided an asymptotically optimal compression algorithm that (asymptotically) achieves this entropy limit and runs in expectation in linear time. In this paper, we consider the stochastic block models with an arbitrary number of parts. Indeed, we define a partitioned structural entropy for stochastic block models, which generalizes the structural entropy for unlabeled graphs and encodes the partition information as well. We then compute the partitioned structural entropy of the stochastic block models, and provide a compression scheme that asymptotically achieves this entropy limit.     

Complexation of poly(vinyl alcohol)–congo red aqueous solutions. 3. Dynamic light scattering study

Mesoscopic structures of poly(vinyl alcohol)(SINGLEBOND)Congo red (PVA(SINGLEBOND) CR) complexes in aqueous solutions were investigated in terms of dynamic light scattering (DLS) technique. The intensity-intensity time correlation function, g⁽²⁾(t), was analyzed with an equation including a single and a stretched exponential function. Two diffusion coefficients, D_f (fast) and D_s (slow) were evaluated. D_f was converted to the apparent correlation length, ξ_app, via the mode-mode coupling hypothesis. The estimated ξ_app was insensitive to the sol(SINGLEBOND)to(SINGLEBOND)gel transition but decreased with CR concentration. This change may be related to the electrostatic screening effect. On the other hand, D_s oscillates with increasing CR concentration at a specific PVA concentration range. This explains well the reentrant sol(SINGLEBOND)gel(SINGLEBOND)sol(SINGLEBOND)gel transition behavior observed in the PVA(SINGLEBOND)CR systems. D_s seems to represent the mobility of the PVA(SINGLEBOND)CR complexes, which annihilates at the gel point. © 1996 John Wiley & Sons, Inc.     

Catalytic hydrogenation of aromatic nitro compounds by non-noble metal complexes of chitosan

Silica-supported mono-metal (such as Ni, Cu) complexes and mixed metal (such as Cu/Zn, Cu/Cr) complexes of chitosan have been prepared. It is found that these non-noble metal complexes could be used as efficient catalysts for the hydrogenation of aromatic nitro compounds. The effects of type of metal, reaction temperature and pressure, solvent, nitrogen/metal molar ratio in the complex catalysts on the yields from nitrobenzene to aniline have been examined. It was also found that catalysts are active for the catalytic hydrogenation of other aromatic nitro compounds such as 2-nitroanisole, 2-nitroaniline, 2-nitrotoluene and 1-chloro-4-nitrobenzene.     

Synthesis and tautomerism of 2-aryl- and 2-heteroaryl derivatives of benzimidazole

Benzimidazoles containing furyl and thienyl substituents at C-2 were prepared by condensation of o-phenylenediamine and corresponding carboxylic acids in the presence of polyphosphoric acid. The 2-heteroarylbenzimidazoles showed tautomerism in dimethyl sulfoxide solution while 2-phenylbenzimidazole did not. The tautomerism appeared to be taking place by intermolecular relay of protons between stacked molecules.     

Reaction conducted under rather severe conditions for a colloidal catalyst - hydroformylation of propylene catalyzed by polymer-protected rhodium colloids

Hydroformylation of propylene has been conducted by a polymer-protected rhodium colloid catalyst with an activity of 130 mol butanal / g atom Rh·h. The neat colloid catalyst is stable enough for repeated use for 7 times lasting ∼50 h under the reaction condition (temperature: 363 K, pressure: 40 bar) with a total TON of 5,065 cycle / atom Rh.     

量子相变

量子相变是一种发生在绝对零度,由量子涨落而非热涨落导致的相变现象,满足著名的海森堡不确定关系。通过零温量子临界点的研究,可获知物质系统更广泛范围的行为,包括稀土磁性绝缘体,高温超导体和二维电子气体等。     

带有双X型铁心框架的超导MRI磁体的设计

文中对带有双X型铁心框架的MR I用高温和低温超导磁体的设计进行了介绍,包括项目的市场需求、磁体的基本参数和系统热负荷的预设计结果等。