Current trends in structural development and modification strategies for metal-organic frameworks (MOFs) towards photocatalytic H2 production: A review

Photocatalytic H₂ generation using semiconductor photocatalysts is considered as a cost-effective and eco-friendly technology for solar to energy conversion; however, the present photocatalysts have been recognized to depict low efficiency. Currently, porous coordination polymers known as metal-organic frameworks (MOFs) constituting flexible and modifiable porous structure and having excess active sites are considered to be appropriate for photocatalytic H₂ production. This review highlights current progress in structural development of MOF materials along with modification strategies for enhanced photoactivity. Initially, the review discusses the photocatalytic H₂ production mechanism with the concepts of thermodynamics and mass transfer with particular focus on MOFs. Elaboration of the structural categories of MOFs into Type I, Type II, Type III and classification of MOFs for H₂ generation into transition metal based, post-transition metal based, noble-metal based and hetero-metal based has been systematically discussed. The review also critically deliberate various modification approaches of band engineering, improvement of charge separation, efficient irradiation utilization and overall efficiency of MOFs including metal modification, heterojunction formation, Z-scheme formation, by introducing electron mediator, and dye based composites. Also, the MOF synthesized derivatives for photocatalytic H₂ generation are elaborated. Finally, future perspectives of MOFs for H₂ generation and approaches for efficiency improvement have been suggested.     

Influence of Al3+ doping for V5+ on the structural,optical, thermal and electrical properties of V2-xAlxO5-δ (x=0–0.20) ceramics

This paper reports an investigation on the structure-properties correlation of trivalent metal oxide (Al₂O₃)-doped V₂O₅ ceramics synthesized by the melt-quench technique. XRD patterns confirmed a single orthorhombic V₂O₅ phase formation with increasing strain on the doping of Al₂O₃ in place of V₂O₅ in the samples estimated by Williamson-Hall analysis. FTIR and Raman investigations revealed a structural change as [VO₅] polyhedra converts into [VO₄] polyhedra on the doping of Al₂O₃ into V₂O₅. The optical band gap was found in a wide semiconductor range as confirmed by UV–visible spectroscopy analysis. The thermal and conductivity behavior of the prepared samples were studied using thermal gravimetric analysis (TGA) and impedance analyzer, respectively. All the prepared ceramics exhibit good DC conductivity (0.22–0.36 Sm^-1) at 400 ?C. These materials can be considered for intermediate temperature solid oxide fuel cell (IT-SOFC)/battery applications due to their good conductivity and good thermal stability.     

{X,Y}-Cyclacene Graphs with Next Nearest Neighbor Interactions

Eigensolutions of {X( = C,B,N),Y( = C,B,N)}-cyclacene graphs with next nearest neighbor (nnn) interactions have been obtained in analytical forms by adapting n-fold rotational symmetry followed by two-fold rotational symmetry (or a plane of symmetry). Expressions of eigensolution indicate the subspectral relationship among such cyclacenes with an even number of hexagonal rings e.g., eigenvalues of {X,Y}-di-cyclacene are found in the eigenspectra of all such even cyclacenes. Total π-electron energies and highest occupied molecular orbital and lowest unoccupied molecular orbital (HOMO–LUMO) gaps are calculated using the analytical expressions obtained and are found to vary negligibly with the variation of nnn interactions in such cyclacenes. Total π-electron energy is found to increase due to increase in restriction intensity of nnn interactions, whereas the HOMO–LUMO gap of polyacenecs having the even number of hexagonal rings and with one electron at each site (atom) decreases with increase in the restriction intensity since such systems contain degenerate half-filled HOMO (bonding or nonbonding) that are much more vulnerable for perturbations imposed through nnn interactions.     

How Cells Communicate with Each Other in the Tumor Microenvironment: Suggestions to Design Novel Therapeutic Strategies in Cancer Disease

Connexin- and pannexin (Panx)-formed hemichannels (HCs) and gap junctions (GJs) operate an interaction with the extracellular matrix and GJ intercellular communication (GJIC), and on account of this they are involved in cancer onset and progression towards invasiveness and metastatization. When we deal with cancer, it is not correct to omit the immune system, as well as neglecting its role in resisting or succumbing to formation and progression of incipient neoplasia until the formation of micrometastasis, nevertheless what really occurs in the tumor microenvironment (TME), which are the main players and which are the tumor or body allies, is still unclear. The goal of this article is to discuss how the pivotal players act, which can enhance or contrast cancer progression during two important process: “Activating Invasion and Metastasis” and the “Avoiding Immune Destruction”, with a particular emphasis on the interplay among GJIC, Panx-HCs, and the purinergic system in the TME without disregarding the inflammasome and cytokines thereof derived. In particular, the complex and contrasting roles of Panx1/P2X7R signalosome in tumor facilitation and/or inhibition is discussed in regard to the early/late phases of the carcinogenesis. Finally, considering this complex interplay in the TME between cancer cells, stromal cells, immune cells, and focusing on their means of communication, we should be capable of revealing harmful messages that help the cancer growth and transform them in body allies, thus designing novel therapeutic strategies to fight cancer in a personalized manner.     

Optical Properties of One-dimensional Three-component Photonic Band Gap Structure

1　IntroductionMaterialswithPhotonicBandGaps (PBG’s)havebeenwidelystudiedboththeoreticallyandex perimentallyinthepastfew years[1～ 4] .Theexis tenceofgaps,which prohibitthepropagationofelectromagnetic (EM )wavesinacertainrangeoffrequencies,canhavesignificantimpactsbothinsci enceandtechnology .Manypracticalapplicationsofthesestructureshavebeensuggestedanddemon strated ,suchasPhotonicCrystal (PC)microcavi ties[5] ,infraredPC[6] ,PClens[7] ,suppressingspontaneousemission ,manipulatinglight…     

Improving narrow bandgap a-SiGe:H alloys grown by hot-wire chemical vapor deposition

We have improved the electronic properties of narrow-bandgap (Tauc gap below 1.5 eV) amorphous-silicon germanium alloys (a-SiGe:H) grown by hot-wire chemical vapor deposition (HWCVD) by lowering the substrate temperature and deposition rate. Prior to this work, we were unable to grow a-SiGe:H alloys with bandgaps below 1.5 eV that had photo-to-dark conductivity ratios comparable with our plasma-enhanced CVD (PECVD) grown materials [B.P. Nelson et al., Mater. Res. Soc. Symp. 507 (1998) 447]. Decreasing the filament diameter from our standard configuration of 0.5 mm to 0.38 or 0.25 mm provides first big improvements in the photoresponse of these alloys. Lowering the substrate temperature from our previous optimal temperatures (T_sub starting at 435 °C) to at 250 °C provides additional photo-to-dark conductivity ratio increasing by two orders of magnitude for growth conditions containing 20–30% GeH₄ in the gas phase (relative to the total GeH₄+SiH₄ flow).     

Gap modulation in MCu[Q1−xQ′x]F (M=Ba, Sr; Q, Q′=S, Se, Te) and related materials

BaCuQF (Q=S, Se, Te) materials exhibit band gaps that allow transmission of much of the visible spectrum. BaCuSF is transparent in thin-film form with a band gap of 3.1 eV. Band gap estimates for powders of the solid solution series BaCuS_1−xSe_xF were obtained from wavelength-dependent diffuse-reflectance measurements using an integrating sphere. The band gap can be tuned by the substitution of Se for S to 2.9 eV for BaCuSeF. The decrease scales almost linearly with the increase in the volume of the tetragonal unit cell, which is determined primarily by the expansion of the a lattice parameter; the overall volume increase is 7.0% from x=0 to 1. Further reduction of the band gap is observed in BaCuSe_1−xTe_xF solid solutions, where a unit cell volume increase of 5.5% produces a band gap of 2.7 eV in BaCuSe_0.5Te_0.5F. Powders and films of BaCuSF exhibit strong red luminescence under ultraviolet excitation, which is suppressed by K doping. Additional tuning of band gap and electrical properties (the materials are p-type conductors) can be achieved by replacing Ba with Sr.     

基于聚类算法实现信号盲分类

本文解决了信号处理、工业控制等领域存在的非平稳信号盲分类问题。在聚类中广泛应用的K-Means算法及其它基于中心的聚类算法有两个共同的缺陷-需要预先确定类数目且随机初始化中心引起性能不稳定。本文提出的算法较好地解决了这两个问题，提高了算法稳定性，实现了非平稳信号盲分类。提取非平稳信号的小波系数作为聚类的样本空间，分析聚类结果的统计偏差以估计类的数目，采用调和均值准则进行分类。最后给出的仿真结果表明本文提出的方法较传统的K-Means算法明显降低分类错误率。     

异质谷间转移电子器件的计算机模拟

使用弛豫时间近似求出了描述两能谷间电子交换的方程。在此基础上建立了双能谷电子的连续性方程和油松方程。对具体的ＧａＡｓ／ＡｌｘＧａ１－ｘＡｓ异质谷间转移电子器件结构求解了这些方程组，得到了直流工作时器件内的电场分布、双能谷中载流子的布居以及两个能谷的电流分布。这些结果正好和常规Ｇｕｎｎ器件相反，说明了两种器件的不同工作机理。最后通过对低Ａｌ组份势垒结构的计算说明了Ｘ谷电子注入对器件工作的重要作用。     

Importance of out-of-plane dispersion of the excitation spectrum of superconducting bilayers with Josephson coupling

We study the effect of Josephson coupling between adjacent superconducting layers on the BCS energy spectrum. We find that the interference between the gap functions of two layers can lead to vanishing condensation energy for perpendicular momenta corresponding to the formation of standing waves. We therefore predict a conventional energy spectrum for large interlayer spacings, if the gap of the single layers has no nodes, and in all cases a gapless spectrum for small spacings. Within the experimental error, our numerical results account for the low-temperature dependence of the penetration depth reported in Nd_1.85Ce_0.15CuO₄ and YBa₂Cu₃O_6.9.