利用空间位阻和氢溢流协同作用促进5-羟甲基糠醛选择性加氢制备5-甲基糠醛

化学工业生产中，用氢气为还原剂，通过选择性加氢可以制备多种重要化学品。5-羟甲基糠醛是重要的生物质基平台化合物，而5-甲基糠醛是用途广泛的化学品。由5-羟甲基糠醛加氢得到5-甲基糠醛是一条非常理想的路径，但是选择性活化C-OH非常困难。本文设计并制备了Pt@PVP/Nb₂O₅(PVP: 聚乙烯吡咯烷酮)催化剂，该催化体系巧妙地结合了位阻效应、氢溢流和催化剂界面的电子效应，系统研究了该催化剂对5-羟甲基糠醛选择性加氢制备5-甲基糠醛催化性能，在最优条件下，5-甲基糠醛的选择性可达92%。利用密度泛函理论计算研究了5-羟甲基糠醛选择性加氢制备5-甲基糠醛反应路径。     

High Uptake of ReO4− and CO2 Conversion by a Radiation‐Resistant Thorium–Nickle [Th48Ni6] Nanocage‐Based Metal–Organic Framework

Assembled from [Th₄₈Ni₆] nanocages, the first transition‐metal (TM)‐thorium metal–organic framework (MOF, 1 ) has been synthesized and structurally characterized. 1 exhibits high solvent and acid/base stability, and resistance to 400 kGy β irradiation. Notably, 1 captures ReO₄^? (an analogue of radioactive ⁹⁹TcO₄^?, a key species in nuclear wastes) with a maximum capacity of 807 mg g^?1, falling among the largest values known to date. Furthermore, 1 can enrich methylene blue (MB) and can also serve as an effective and recyclable catalyst for CO₂ fixation with epoxides; there is no significant loss of catalytic activity after 10 cycles. Theoretical studies with nucleus‐independent chemical shifts and natural bond orbital analysis reveal that the [Th₆O₈] clusters in 1 have a unique stable electronic structure with (d–p)π aromaticity, partially rationalising 1 ′s stability.     

EXPERIMENTAL RESEARCH ON FAILURE AND ENERGY DISSIPATION CHRACTERISTICS OF THE SANDSTONE1)

通过三轴卸荷试验,探究了不同路径下卸荷速率对砂岩力学特性及破坏过程中的能量耗散的影响。试验结果表明在全过程应力-应变曲线的弹性阶段,轴向变形起主导作用,弹塑性阶段,环向应变的增加值大于轴向应变增加值。在围压卸荷阶段,卸荷速率越小,卸荷阶段的应变折合柔度越大,此时岩样的变形不充分,呈现明显的脆性破坏。恒主应力差路径下的耗散能大于恒轴压路径下的耗散能的35%,卸荷速率越大,岩样的弹性应变能越小。     

Ab initio investigation of possible lower-energy candidate structure for cationic water cluster (H2O) 12+ via particle swarm optimization method

Detecting the underlying performance of hydrated electrons and hydroxyl radicals in the cationic water cluster can greatly help to understand the inter reaction mechanism in the liquid water and aqueous solutions. Based on our previous (H₂O)₁₀⁺ research, we have paid attention to more problems of larger cationic clusters in this work, including the existence of hemibonded type, long-range correction functions, and hydrogen-bonded site analyses. The lower-energy structures of the cationic water cluster (H₂O)₁₂⁺ have been comprehensively explored, and more experienced functions are introduced to check the ground state and vibration spectrum. Unlike the configuration regularity of neutral (H₂O)₁₂ clusters and small cationic water clusters, those new-found structures for (H₂O)₁₂⁺ are inclined to adopt three dimension (3D) cage-like structures and the H₂O-OH₂ structure appears in the higher energy isomer. The calculation reveals that the lowest stable isomer is the 3D cage structure W14 predicted at MP2 level, which has not been reported yet. In the thermal simulation, structure transition from the cage-like to the ring-like occurs at T?>?≈256 K, and the two dimension (2D) ring-like structure occupies a dominant position at high temperature range. The infrared spectra explain that the difference of the spectra between the 2D net structures and 3D cage-structures is mainly caused by the weight fluctuation of single acceptor-single donor (AD), double acceptor-single donor (AAD), and single acceptor-double donor (ADD) sites in these isomers. This further gives a similarity relation between (H₂O)₁₂⁺ and H⁺(H₂O)₁₂ clusters in the shape of the network and spectral characteristics. By molecular orbitals and topological analysis, we find that the lone pair orbital on hydroxyl radical dominates the reactivity and stability of cationic system. The present research may be helpful for exploring the evolution law of the larger cationic water clusters in the future.

     

Miktoarm star‐shaped poly(lactic acid) copolymer: Synthesis and stereocomplex crystallization behavior

The miktoarm star‐shaped poly(lactic acid) (PLA) copolymer, (PLLA)₂‐core‐(PDLA)₂, was synthesized via stepwise ring‐opening polymerization of lactide with dibromoneopentyl glycol as the starting material. ¹H NMR and FTIR spectroscopy proved the feasibility of synthetic route and the successful preparation of star‐shaped PLA copolymers. The results of FTIR spectroscopy and XRD showed that the stereocomplex structure of the copolymer could be more perfect after solvent dissolution treatment. Effect of chain architectures on crystallization was investigated by studying the nonisothermal and isothermal crystallization of the miktoarm star‐shaped PLA copolymer and other stereocomplexes. Nonisothermal differential scanning calorimetry and polarizing optical microscopy tests indicated that (PLLA)₂‐core‐(PDLA)₂ exhibited the fastest formation of a stereocomplex in a dynamic test due to its special structure. In isothermal crystallization tests, the copolymer exhibited the fast crystal growth rate and the most perfect crystal morphology. The results reveal that the unique molecular structure has an important influence on the crystallization of the miktoarm star‐shaped PLA copolymer. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 814–826     

Comparative in vivo constituents and pharmacokinetic study in rats after oral administration of ultrafine granular powder and traditional decoction slices of Chinese Salvia

Salvia miltiorrhiza, one of the most well‐known herbal medicines, is commonly used for the treatment of coronary heart diseases in China. Besides traditional decoction slices (TDS), another relatively new product of S. miltiorrhiza, ultrafine granular powder (UGP; D90 < 45 μm), is also increasingly being used. In this paper, a UHPLC‐LTQ‐Orbitrap MS technique was developed for a metabolite profile study after oral administration of UGP and TDS of S. miltiorrhiza. The results showed that the number of in vivo absorbed compounds from UGP was much greater than that from TDS, and different types of products from S. miltiorrhiza will have different metabolic processes in vivo. Furthermore, a UHPLC‐Q‐Trap MS/MS method for simultaneously determining four tanshinones (tanshinone IIA, dihydrotanshinone I, tanshinone I and cryptotanshinone) was established and applied to assess the pharmacokinetics of the two types of products. All of the analytes displayed significant higher area under the concentration–time curve and peak concentration after oral administration of UGP than after TDS, indicating that ultrafine powder product could improve the bioavailability and absorption of cryptotanshinon,tanshinone II A,dihydrotanshinonE I and tanshinone I in vivo. The present study provides scientific information for further exploration of the pharmacology of these two types of S. miltiorrhiza and offers a reference for clinical administration of S. miltiorrhiza.     

A coefficient identification problem for a mathematical model related to ductal carcinoma in situ

We consider a coefficient identification problem for a mathematical model with free boundary related to ductal carcinoma in situ (DCIS). This inverse problem aims to determine the nutrient consumption rate from additional measurement data at a boundary point. We first obtain a global‐in‐time uniqueness of our inverse problem. Then based on the optimization method, we present a regularization algorithm to recover the nutrient consumption rate. Finally, our numerical experiment shows the effectiveness of the proposed numerical method.     

Side-on-End-on Coordination of Dinitrogen on a Polynuclear Vanadium Nitride Cluster Anion [V5N5]−

The side-on-end-on coordination of N₂ can be very important to activate and functionalize this very stable molecule. However, such coordination has rarely been reported. This study reports a gas-phase species (a polynuclear vanadium nitride cluster anion [V₅N₅]⁻) that can capture N₂ efficiently (12 %), and the quantum chemistry modelling suggests an unusual side-on-end-on coordination. The cluster anions were generated by laser ablation and the reaction with N₂ has been characterized by mass spectrometry, photoelectron imaging spectroscopy, and density functional theory calculations. The back-donation interactions between the localized d–d bonding orbitals on the low-coordinated dual metal (V) sites and the antibonding π* orbitals of N₂ are the driving forces to adsorb N₂ with a high binding energy (about 2.0 eV).