Promoting the Phosphidation Process using an Oxygen Vacancy Precursor for Efficient Hydrogen Evolution Reaction

Based on previous works, most of the transition metal phosphides (TMPs) were directly prepared by decomposing NaH₂PO₂ with the precursors at high temperatures, which resulted in different degrees of phosphidation in the final product. Therefore, it is necessary to design an innovative approach to enhance the degree of phosphidation in the material using crystal defects. Here, oxygen-vacancy iron oxide/iron foam (Ov-Fe₂O₃/IF) was firstly prepared by generating oxygen vacancy in situ in an iron foam through heating in vacuum conditions. Subsequently, FeP/IF was formed by phosphating Ov-Fe₂O₃/IF. Under the effects of oxygen vacancies, oxygen-vacancy iron oxide could be completely phosphatized to produce more active sites on the surface of the material. This, in turn, could result in a catalyst with exceptional hydrogen evolution activity. Thus, the successful fabrication of FeP/IF demonstrated in this work provides an effective and feasible way for the preparation of other high-efficiency catalysts.     

田字形地震超材料甚低频宽带隙机理

在地球中传播的地震波主要有体波和表面波,而表面波中Rayleigh波对建筑物造成的破坏最为强烈。针对Rayleigh波的振动控制,提出一种田字形超材料结构。相比于传统的地震超材料,这种超材料屏障是由外部口字形框体内部嵌套十字形柱体组成,形成4个可填充区域,其外部框体采用部分埋入的方式,具有高强度、强稳定性、填充方式灵活的特点。应用有限元法计算了田字形超材料的能带结构和传输特性,并通过分析带隙边界处模态振型可知,带隙的打开是由于柱体的局域共振。结合带隙机理可知,柱体结构中土壤填充量不同可改变柱体的质量,形成不同的谐振频率,产生甚低频带隙。为进一步拓宽带隙,设计研究了正、负梯度的质量填充方式,均可得到3.3~13.1 Hz甚低频宽带隙,在谐振频率范围内两者的隔震方式分别为Rayleigh波彩虹捕获和Rayleigh波到体波的转化。最后,采用EI-Centro地震波对填充屏障进行了时程验证,加速度最大幅值衰减超过80%,为地震超材料在减震隔震方面应用提供了新的设计思路和方法。     

An Endoplasmic Reticulum Targeting Type I Photosensitizer for Effective Photodynamic Therapy against Hypoxic Tumor Cells

Organelle-targeted type I photodynamic therapy (PDT) shows great potential to overcome the hypoxic microenvironment in solid tumors. The endoplasmic reticulum (ER) is an indispensable organelle in cells with important biological functions. When the ER is damaged due to the production of reactive oxygen species (ROS), the accumulation of misfolded proteins will interfere with ER homeostasis, resulting in ER stress. Here, an ER-targeted benzophenothiazine-based photosensitizer NBS-ER was presented. ER targeting modification significantly reduced the dark toxicity and improved phototoxicity index (PI). NBS-ER could effectively produce O₂⁻⋅ with near-infrared irradiation, making its phototoxicity under hypoxia close to that under normoxia. Meanwhile, the photoinduced ROS triggered ER stress and induced apoptosis. In addition, NBS-ER possessed excellent photodynamic therapeutic effect in 4T1-tumor-bearing mice.     

Topological “interfacial” polymer chemistry: Dependency of polymer “shape” on surface morphology and stability of layer structures when heating organized molecular films of cyclic and linear block copolymers of n‐butyl acrylate‐ethylene oxide

The “topological polymer chemistry” of amphiphilic linear and cyclic block copolymers at an air/water interface was investigated. A cyclic copolymer and two linear copolymers (AB‐type diblock and ABA‐type triblock copolymers) synthesized from the same monomers were used in this study. Relatively stable monolayers of these three copolymers were observed to form at an air/water interface. Similar condensed‐phase temperature‐dependent behaviors were observed in surface pressure–area isotherms for these three monolayers. Molecular orientations at the air/water interface for the two linear block copolymers were similar to that of the cyclic block copolymer. Atomic force microscopic observations of transferred films for the three polymer types revealed the formation of monolayers with very similar morphologies at the mesoscopic scale at room temperature and constant compression speed. ABA‐type triblock linear copolymers adopted a fiber‐like surface morphology via two‐dimensional crystallization at low compression speeds. In contrast, the cyclic block copolymer formed a shapeless domain. Temperature‐controlled out‐of‐plane X‐ray diffraction (XRD) analysis of Langmuir–Blodgett (LB) films fabricated from both amphiphilic linear and cyclic block copolymers was performed to estimate the layer regularity at higher temperatures. Excellent heat‐resistant properties of organized molecular films created from the cyclic copolymer were confirmed. Both copolymer types showed clear diffraction peaks at room temperature, indicating the formation of highly ordered layer structures. However, the layer structures of the linear copolymers gradually disordered when heated. Conversely, the regularity of cyclic copolymer LB multilayers did not change with heating up to 50 °C. Higher‐order reflections (d₀₀₂, d₀₀₃) in the XRD patterns were also unchanged, indicative of a highly ordered structure. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 486–498     

Formation of Cr(VI) compounds during the thermal decomposition of amorphous chromium hydroxide

Chromium hydroxide (CH) was prepared by the reduction of purified sodium chromate using starch. CH was then used to prepare chromium oxide (Cr₂O₃). Results of thermogravimetric, X-ray diffraction, Fourier transform infrared spectroscopy, and chemical analyses suggested that a small amount of the initial Cr(VI) content speeds up the oxidation and reduction reactions, thereby promoting the purity and crystallization of Cr₂O₃. Cr(VI) in CH induced the evolution of CH and the formation of Cr(VI) containing compounds including CrO₃, NaCr(CrO₄)₂, Cr₃O₈, and Cr₅O₁₂ at low sintering temperature. Furthermore, homogeneous Cr₂O₃ nanoparticles with 99 % purity and particle size of 50 nm were obtained.     

Theoretical and experimental studies on a compact stretcher with large spectral bandwidth and high transmission efficiency

To ensure safe and effective amplification for the chirped pulse amplification laser facility, many factors such as pulse spectral width, pulse duration, grating parameters and incidence angle parameter are considered carefully in the design of the pulse stretcher. A compact four pass Offner stretcher design is given out. Experiment results show that the stretcher has broad spectral width, large stretching ratio and high transmission efficiency. By comparison, the calculated result of the dispersion effect on the pulse duration is completely consistent with the experiment result.