Tuning of emission by effect of local symmetry in BaLaLiWO6:Dy3+/Eu3+ for WLEDs

The luminescence center energy transfer, crystal field strength, and covalency are limited by the crystal structure of the host and subsequently affect the luminescence efficiency, color, and intensity. Here, we report an excellent red phosphor BaLaLiWO₆:0.40Eu³⁺ and the dependence between symmetry and luminous performance. A model for changing symmetry is drawn by analyzing the Coulomb potential and structure for the application of a double-perovskite phosphor BLLWO: Dy³⁺, Eu³⁺ in white light LEDs. The addition of Dy³⁺/Eu³⁺ makes the W-O bond formed by the B-site and oxygen ion longer and the Li-O bond shorter, and the difference between the eight octahedral around the A-site is reduced, increasing the symmetry of the A-site. Local symmetry was successfully modulated by changing the Eu³⁺ concentration to control the Y/B ratio of Dy³⁺ and the R/O ratio of Eu³⁺ and smoothly achieved (0.382, 0.373) warm white light color coordinate. The phosphor has excellent thermal stability and still has 92.3% intensity at 475 K. The above results show that the wavelength composition of the luminescence is tunable by changing the symmetry of the environment in which the doped ions are located. It applies to single hosts for the regulation of white light emission.     

Charge Transportation and Chirality in Liquid Crystalline Helical Network Phases of Achiral BTBT-Derived Polycatenar Molecules

First examples of multichain (polycatenar) compounds, based on the π-conjugated [1]benzothieno[3,2-b]benzothiophene unit are designed, synthesized, and their soft self-assembly and charge carrier mobility are investigated. These compounds, terminated by the new fan-shaped 2-brominated 3,4,5-trialkoxybenzoate moiety, form bicontinuous cubic liquid crystalline (LC) phases with helical network structure over extremely wide temperature ranges (>200 K), including ambient temperature. Compounds with short chains show an achiral cubic phase with the double network, which upon increasing the chain length, is at first replaced by a tetragonal 3D phase and then by a mirror symmetry is broken triple network cubic phase. In the networks, the capability of bypassing defects provides enhanced charge carrier mobility compared to imperfectly aligned columnar phases, and the charge transportation is non-dispersive, as only rarely observed for LC materials. At the transition to a semicrystalline helical network phase, the conductivity is further enhanced by almost one order of magnitude. In addition, a mirror symmetry broken isotropic liquid phase is formed beside the 3D phases, which upon chain elongation is removed and replaced by a hexagonal columnar LC phase.     

Repeated low-velocity impact responses of SiC particle reinforced Al metal-matrix composites

This study aimed to investigate experimentally the repeated low-velocity impact behaviors of SiC reinforced aluminum 6061 metal-matrix composites for different volume fractions and energy levels. In addition, the hardness variations were measured by the Vickers hardness tests from the impacted and impact-free cross-sections of the particle reinforced metal-matrix composites. Low-velocity impact tests were applied to composite samples manufactured by powder metallurgy (in 10, 20, and 30% volume fractions) at two total energy levels (15 and 60 J as single) and in repetitions equal to the sum of these energy levels (5 + 5 + 5 and 20 + 20 + 20 J as repeated). As a result, in increasing the impact number for all volume fractions, the total contact time was shortened and the peak contact force increased, whereas both the permanent central deflection and the absorbed energies reduced. Hence, these variations obtained under repeated impacts (5 + 5 + 5 and 20 + 20 + 20 J) revealed that metal-matrix composites showed a tougher behavior with an increase in the impact numbers from 1st to 3rd, particularly because of the strain hardening effect. Furthermore, an increase in volume fraction from 10 to 30% resulted in an increase in the impact strength under all repeated and single impacts despite changing deformation and damage mechanisms due to increasing the strain hardening effect and particle fractures. The hardness was affected by the volume fraction and increased as the volume fraction increased in both the impacted and impact-free zones. The repeated impact increased the impacted zone hardness more than the single impact for all volume fractions. Additionally, the hardness of the impacted zone under 20 + 20 + 20 J repeated impact was measured as the highest value in the 30% volume fraction. Therefore, metal-matrix composites can behave harder with the strain hardening effect under repeated impacts.     

在轨维修后端模块接口机构的研究

在轨维修可以大大的延长空间科学仪器的使用寿命,节省大量的经济成本。为了实现空间望远镜后端模块的在轨操作和更换,设计了一套与之对应的接口机构,能够解决在轨快速定位与安装。根据321运动学定位准则,详细介绍了该接口机构的内部组成和工作原理;然后把该接口机构与后端模块进行组件级有限元仿真,仿真结果表明一阶模态远高于整机基频可以有效地避免发射时候的共振;设计了一套平面内的工装来模拟后端模块,利用等效质量法对整个机构进行重力卸载;搭建实验平台,利用激光跟踪仪来测量整个后端模块的重复定位安装精度,实验数据表明,X,Y,Z 3个方向的重复平移定位误差分别为±5.58μm,±3.24μm及±3.63μm,优于总体指标±10μm;热实验结果表明整个机构可以完全释放由于温度变化产生的形变,具有很高的热稳定性;使入射光线和靶面的相对位置持续稳定,保证了较高的成像质量。为其他空间在轨维护装置提供强有力的参考价值。     

Characterizing pathological imperfections in macromolecular crystals: lattice disorders and modulations

Macromolecular crystal structure determination can be complicated or brought to a halt by crystal imperfections. These issues motivated us to write up what we affectionately call ‘The Definitive Hitchhiker’s Guide to Pathological Macromolecular Crystals: Lattice Disorders and Modulations’. Perhaps the most challenging imperfections are lattice order–disorder phenomena and positional modulations. Many of these types of crystals have been solved, and progress has been made on the more challenging forms. Diagnostic tools and how to solve many of these problem crystal structures are reviewed. New avenues are provided for approaching the solution of incommensurately modulated crystals. There are a good number of case studies in the literature of lattice order–disorder phenomena and crystallographic modulations that make it timely to write a review. This review concludes with a projected pathway for solving incommensurately modulated crystals, personal views of future directions and needs of the crystallographic community.     

What is a crystal to the new chemical crystallographer,after that first,automated structure analysis?

This educational review postulates the importance of maintaining an adequate level of crystallographic education among structure-dependent scientists whose interests are not primarily in crystallography, at a time when automation and validation have made it possible to obtain high-quality structure analyses in many cases with a minimum of crystallographic background. The topics addressed are intended to form a second round of crystallographic education for a novice user whose first round involved hands-on experience with structure solution and an introduction to elementary concepts. The specific topics, chosen for their relevance as basic knowledge and their lack of emphasis in many formal treatments, are (1) crystallographic reference frames and the utility of the reciprocal cell in geometrical calculations; (2) the relationship between the two concepts that constitute our model of the crystal, namely the unit cell and the lattice; (3) the manner in which an atom is represented in concept and in practice; (4) the importance of interleaved symmetry elements required by the presence of additional symmetry on a lattice; (5) the harnessing of the natural properties of the crystalline state for the potential manipulation of properties of synthetic crystals; and (6) useful terminology for navigating a crystal structure.     

Symmetry Breaking in Monometallic Nanocrystals toward Broadband and Direct Electron Transfer Enhanced Plasmonic Photocatalysis

Metallic nanocrystals manifest themselves as fascinating light absorbers for applications in plasmon-enhanced photocatalysis and solar energy harvesting. The essential challenges lie in harvesting the full-spectrum solar light and harnessing the plasmon-induced hot carriers at the metal–acceptor interface. To this end, a cooperative overpotential and underpotential deposition strategy is proposed to mitigate both the challenges. Specifically, by utilizing both ionic additive and thiol passivator to introduce symmetry-breaking growth over gold icosahedral nanocrystals, the microscopic origin can be attributed to the site-specific nucleation of stacking faults and dislocations. By adopting asymmetric crystal shape and unique surface facets, such nanocrystals attain high activity toward photocatalytic ammonia borane hydrolysis, arising from combined broadband plasmonic properties and enhanced direct transfer of hot electrons across the metal–adsorbate interface.     

单曲柄双摇杆无相差扑翼驱动机构的设计与仿真

在具有二级减速齿轮的单曲柄双摇杆机构上,通过加入Watt直线机构,建立三维扑翼飞行器模型,保证了左右拍动完全对称,提高了扑动的紧凑性和稳定性。Adams仿真分析表明左右扑翼角度和角速度完全一致,提高了运动对称性,验证了该优化方法的正确性和可行性。     

Excited-state absorption of meso-tetrasulfonatophenyl porphyrin: Effects of pH and micelles

The influence of the environment on the excited state transitions of meso-tetrakis(p-sulfonatophenyl) porphyrin (TPPS) is reported. TPPS was investigated in protonated and non-protonated forms, and in the presence of the cationic cetyltrimethylammonium bromide (CTAB) micelles. The singlet excited-state absorption spectra were measured by using the white-light continuum Z-scan technique and the triplet–triplet absorption spectra were acquired employing an association of laser flash photolysis and Z-scan techniques. Our results show that the perseveration of the molecular symmetry, upon excitation, depends on the state of multiplicity of the molecules, as well as on the environment and structural characteristics of the porphyrin. Additionally, it was observed that for excited molecules, the ring distortion caused by the protonation of porphyrin ring has great influence on the changes observed for the symmetry and vibronic structure. The results clearly show that the porphyrin investigated is a promising candidate for optical limiting applications for all investigated environments.