聚乳酸组织工程支架结构的精密调控

采用糖球模板法结合热致相分离技术,制备了孔径尺寸、内连通度及孔隙率高度可控的左旋聚乳酸(PLLA)支架材料,并通过扫描电镜(SEM)、红外光谱(FTIR)以及示差扫描量热法(DSC)对其空间结构及性能进行了系统研究.支架材料孔径从50μm到800μm及内连通孔径从10μm到200μm连续可调,微观孔壁结构根据不同溶剂可形成各异的微纳米结构.支架的制备对PLLA化学结构无显著影响,但相分离过程会不同程度地降低PLLA的结晶度.     

Salt effects on macrophase separations in non‐stoichiometric mixtures of oppositely charged macromolecules: Theory and experiment

In the field of biological applications, polyelectrolyte complexes are proposed to encapsulate bioactive compounds, to deliver drugs, and also to transfect genes into cells under the name of polyplexes. Complex formation is obtained by addition of a polycation solution into a polyanion solution or vice‐versa. This work proposes a theoretical approach to describe complex formation in the case of non‐stoichiometric mixtures of oppositely charged macroions having different degrees of ionization and different degrees of polymerization under different salt conditions. In a second part, comparison was made with experimental data collected when a weak polybase, namely poly(l ‐lysine) under its bromide form was added stepwise to solutions of various polyanions under their sodium salt form, namely poly(l ‐lysine citramide imide), poly(l ‐lysine citramide), and poly(β‐malic acid), the latter lacking hydroxyl groups attached to the main chain. The stability of stroichiometric complexes made of poly(l ‐lysine) and poly(l ‐lysine citramide) having different molecular masses is discussed. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1717–1730     

Monitoring the Thiol/Thiophenol Molecule-Modulated Plasmon-Mediated Silver Oxidation with Dark-Field Optical Microscopy

Surface plasmon can trigger or accelerate many photochemical reactions, especially useful in energy and environmental industries. Recently, molecular adsorption has proven effective in modulating plasmon-mediated photochemistry, however the realized chemical reactions are limited and the underlying mechanism is still unclear. Herein, by using in situ dark-field optical microscopy, the plasmon-mediated oxidative etching of silver nanoparticles (Ag NPs), a typical hot-hole-driven reaction, is monitored continuously and quantitatively. The presence of thiol or thiophenol molecules is found essential in the silver oxidation. In addition, the rate of silver oxidation is modulated by the choice of different thiol or thiophenol molecules. Compared with the molecules having electron donating groups, the ones having electron accepting groups accelerate the silver oxidation dramatically. The thiol/thiophenol modulation is attributed to the modulation of the charge separation between the Ag NPs and the adsorbed thiol or thiophenol molecules. This work demonstrates the great potential of molecular adsorption in modulating the plasmon-mediated photochemistry, which will pave a new way for developing highly efficient plasmonic photocatalysts.     

Assembly of ϵ-Keggin Polyoxometalate from Molecular Crystal to Zeolitic Octahedral Metal Oxide

Zeolitic octahedral metal oxides are inorganic crystalline microporous materials with adsorption and redox properties. New ϵ-Keggin nickel molybdate–based zeolitic octahedral metal oxides have been synthesized. ³¹P NMR spectroscopy shows that reduction of Mo^VI-based molybdates forms an ϵ-Keggin polyoxometalate that immediately transfers to the solid phase. Investigation of the formation process indicates that a low Ni concentration, insoluble reducing agent, and long synthesis time are the critical factors for obtaining the zeolite octahedral metal oxides rather than the ϵ-Keggin polyoxometalate molecule. The synthesized zeolitic nickel molybdate with Na⁺ is used as the adsorbent, which effectively separates C₂ hydrocarbon mixtures.     

Eco-friendly solution processing of all-polymer solar cells: Recent advances and future perspective

All-polymer solar cells (all-PSCs) exhibit great potentials in commercial applications. All-PSCs have observed steady performance gains with power conversion efficiency now reaching over 17% in the open literature. However, the current processing of all-PSCs relies predominantly on toxic, chlorinated solvents in moisture-free environments, representing a significant barrier for their commercialization due to the added costs to handle and dispose of such solvents. There is thus an urgent need for safe, environmentally benign, and sustainable ink-based processing methods to produce all-PSC devices reliably and reproducibly in ambient air. In this perspective, fundamental insights on the interplay between all-polymer blend morphologies and eco-friendly solvents are provided. Also, we discuss the recent successes of the green processing methods to manipulate the photoactive morphologies for high-efficiency all-PSCs. In the end, we provide an outlook on future challenges and opportunities of eco-friendly solvents processed all-PSCs for large-scale manufacturing.     

具有高安全性和有效性的Ⅱ期两阶段临床试验

Ⅱ期临床试验的主要目的是对药物治疗的安全性和有效性进行评估.针对具有高安全性的Ⅱ期两阶段临床试验,给出小样本量下关于安全性和有效性的精确检验方法,并证明最大Ⅰ类错误概率与Ⅱ类错误概率分别在原假设和备择假设的边界处达到.在期望样本量最小原则下,给出最优两阶段设计的构造方法和常用设计表,供实际应用选用.     

Phase stability and temperature effect in ScX (X=S,Se and Te) compounds

Based on first-principles calculations, the structural stability and temperature effect in ScX (X=S, Se and Te) compounds are studied with three typical structures of B1 (NaCl-type), hcp (NiAs-type) and β-hcp (inverse Li₂O₂-type). Their dynamic stability has been verified using phonon mode analysis and molecular dynamics simulations. From the total energy calculations, we find that the most stable ground state structures are B1 for ScS, and hcp for ScSe and ScTe, respectively. Moreover, structural stabilities at finite temperature are studied with the combination of phonon dependent dynamics analysis and first-principles calculations, which reveals a phase transition from hcp to B1 in ScSe around 230 K and a phase transition from hcp to β-hcp in ScTe around 460 K, in accordance with experimental findings. The energy barrier and pathway along the phase transformation from hcp to β-hcp ScTe are also calculated and analyzed by the solid-state nudged elastic band method.