泡沫铝率相关性能的有限元模拟

构建了三维随机分布球形泡孔模型,模拟开、闭孔混合结构泡沫铝材料的微细观结构,并通过有限元方法计算了10~104 s-1应变率范围内、孔隙率35%~65%泡沫铝材料的率相关性以及应变率和相对密度变化对泡沫铝动态压缩力学性能的影响。研究表明:中、低应变率下,泡沫铝材料率相关性能主要取决于基体材料的应变率敏感性;高应变率下,泡沫铝材料率相关性能受基体材料的应变率敏感性以及微结构惯性联合作用,且相对密度较低泡沫铝材料的微结构惯性效应更显著。     

Graft polymerization of 2-hydroxyethyl methacrylate via ATRP with poly(acrylonitrile-co-p-chloromethyl styrene) as a macroinitiator

Amphiphilic graft copolymers are excellent additives for the development of antifouling membranes by nonsolvent induced phase separation. We report a convenient approach to the synthesis of novel graft copolymers with hydrophobic polyacrylonitrile (PAN) backbones and hydrophilic poly(2-hydroxyethyl methacrylate) (PHEMA) side chains. Atom transfer radical polymerization (ATRP) of 2-hydroxyethyl methacrylate was carried out with poly(acrylonitrile-co-p-chloromethyl styrene) (PAN-co-PCMS) as a macroinitiator in the presence of CuCl/2,2’-bipyridine at 50 °C in dimethyl sulfoxide. Kinetics of the graft polymerization was also evaluated. The synthesis of poly(acrylonitrile-co-p-chloromethyl styrene-g-2-hydroxyethyl methacrylate) (PAN-co-(PCMS-g-PHEMA)) can be relatively controlled when CMS (the ATRP sites) unit in the macroinitiator is around 5 mol%. Both the macroinitiators and graft copolymers were characterized by FTIR, NMR and GPC. The surface morphology and wettability of the copolymer films were studied by AFM and water contact angle measurement, respectively. We demonstrate that phase segregation between the PAN-co-PCMS backbones and the PHEMA side chains takes place and the surface hydrophilicity of the graft copolymers increases with the length of the PHEMA side chains. Because these amphiphilic graft copolymers can be synthesized in mass, they will be useful as latent additives for the fabrication of advanced PAN separation membranes.     

Synthesis and biological evaluation of lycorine derivatives as dual inhibitors of human acetylcholinesterase and butyrylcholinesterase

ABSTRACT: BACKGROUND: Alzheimer's disease (AD) is a neurologically degenerative disorder that affects more than 20 million people worldwide. The selective butyrylcholinesterase (BChE) inhibitors and bivalent cholinesterase (ChE) inhibitors represent new treatments for AD. FINDINGS: A series of lycorine derivatives (1--10) were synthesized and evaluated for anti-cholinesterase activity. Result showed that the novel compound 2-O-tert-butyldimethylsilyl-1-O-(methylthio)methyllycorine (7) was a dual inhibitor of human acetylcholinesterase (hAChE) and butyrylcholinesterase (hBChE) with IC50 values of 11.40 [PLUS-MINUS SIGN] 0.66 muM and 4.17 [PLUS-MINUS SIGN] 0.29 muM, respectively. The structure-activity relationships indicated that (i) the 1-O-(methylthio)methyl substituent in lycorine was better than the 1-O-acetyl group for the inhibition of cholinesterase; (ii) the acylated or etherified derivatives of lycorine and lycorin-2-one were more potent against hBChE than hAChE; and (iii) the oxidation of lycorine at C-2 decreases the activity. CONCLUSION: Acylated or etherified derivatives of lycorine are potential dual inhibitors of hBChE and hAChE. Hence, further study on the modification of lycorine for ChE inhibition is necessary.     

Alcohol‐Processable Organic Amorphous Electrolytes as an Effective Electron‐Injection Layer for Organic Light‐Emitting Diodes

A new series of monoammonium‐based organic electrolytes with the tetrafluoroborate (BF₄^?) counteranion have been synthesized. Replacing the pendant ethyl groups in the fluorenyl unit with 4‐ethoxyphenyl groups dramatically improves both solubility and morphological stability. The characterization of the alcohol‐processable amorphous ionic compounds as an electron‐injection layer in organic light‐emitting diodes (OLEDs) reveals that the organic electrolyte that comprises a rigid linear‐conjugated unit provides better device performance, with respect to its counterpart containing a branched bulky moiety. The capability of these compounds to facilitate electron injection from air‐stable aluminum metal is preliminarily discussed on the basis of the investigations of the electron‐only devices and photovoltaic experiments.     

Mn（OAc）2/Schiff base as a new efficient catalyst system for the Henry reaction of nitroalkanes with aldehydes

A series of novel Schiff bases bearing triazole structure were synthesized and characterized by IR and NMR.Mn（OAc）₂/Schiff base efficiently catalyzed Henry reaction of nitroalkanes with aldehydes to produce the corresponding products of β-nitroalcohols, under mild conditions with high yields（up to 99%）.A reaction mechanism is proposed based on the experimental results.     

A Highly Reactive and Sinter-Resistant Catalytic System Based on Platinum Nanoparticles Embedded in the Inner Surfaces of CeO(2) Hollow Fibers

Ceria (CeO(2) ) hollow fibers with Pt nanoparticles (Pt?NPs) embedded in their inner surfaces were prepared by sequentially depositing Pt?NPs and CeO(2) sheaths on electrospun fibers of polystyrene, followed by calcination in air at 400?°C. Despite a relatively low Pt loading in this system, the turnover frequency for CO oxidation was 2-3 orders of magnitude higher than those of other systems, and the reactivity was also stable up to 700?°C.     

Self-supported interconnected Pt nanoassemblies as highly stable electrocatalysts for low-temperature fuel cells

In it for the long haul: Clusters of Pt nanowires (3D Pt nanoassemblies, Pt?NA) serve as an electrocatalyst for low-temperature fuel cells. These Pt nanoassemblies exhibit remarkably high stability following thousands of voltage cycles and good catalytic activity, when compared with a commercial Pt?catalyst and 20?%?wt Pt?catalyst supported on carbon black (20?% Pt/CB).     

Hydrogenation properties of KSi and NaSi Zintl phases

The recently reported KSi-KSiH(3) system can store 4.3 wt% of hydrogen reversibly with slow kinetics of several hours for complete absorption at 373 K and complete desorption at 473 K. From the kinetics measured at different temperatures, the Arrhenius plots give activation energies (E(a)) of 56.0 ± 5.7 kJ mol(-1) and 121 ± 17 kJ mol(-1) for the absorption and desorption processes, respectively. Ball-milling with 10 wt% of carbon strongly improves the kinetics of the system, i.e. specifically the initial rate of absorption becomes about one order of magnitude faster than that of pristine KSi. However, this fast absorption causes a disproportionation into KH and K(8)Si(46), instead of forming the KSiH(3) hydride from a slow absorption. This disproportionation, due to the formation of stable KH, leads to a total loss of reversibility. In a similar situation, when the pristine Zintl NaSi phase absorbs hydrogen, it likewise disproportionates into NaH and Na(8)Si(46), indicating a very poorly reversible reaction.     

Evolutionary divergence of sedoheptulose 7-phosphate cyclases leads to several distinct cyclic products

Sedoheptulose 7-phosphate cyclases are enzymes that utilize the pentose phosphate pathway intermediate, sedoheptulose 7-phosphate, to generate cyclic precursors of many bioactive natural products, such as the antidiabetic drug acarbose, the crop protectant validamycin, and the natural sunscreens mycosporine-like amino acids. These proteins are phylogenetically related to the dehydroquinate (DHQ) synthases from the shikimate pathway and are part of the more recently recognized superfamily of sugar phosphate cyclases, which includes DHQ synthases, aminoDHQ synthases, and 2-deoxy-scyllo-inosose synthases. Through genome mining and biochemical studies, we identified yet another subset of DHQS-like proteins in the actinomycete Actinosynnema mirum and the myxobacterium Stigmatella aurantiaca DW4/3-1. These enzymes catalyze the conversion of sedoheptulose 7-phosphate to 2-epi-valiolone, which is predicted to be an alternative precursor for aminocyclitol biosynthesis. Comparative bioinformatics and biochemical analyses of these proteins with 2-epi-5-epi-valiolone synthases (EEVS) and desmethyl-4-deoxygadusol synthases (DDGS) provided further insights into their genetic diversity, conserved amino acid sequences, and plausible catalytic mechanisms. The results further highlight the uniquely diverse DHQS-like sugar phosphate cyclases, which may provide new tools for chemoenzymatic, stereospecific synthesis of various cyclic molecules.