Form selection of concomitant polymorphs: A case study informed by crystallization kinetics modeling

Molecular mechanisms and process kinetics of crystallizing concomitant polymorphs remain poorly understood. Solvent-mediated phase transformation and concomitant crystallization are difficult to be distinguished in practice, as multiple forms can be detected at the same time. Herein, we developed a population balance model to simulate a concomitant crystallization process of two polymorphs of tolfenamic acid. Our kinetic modeling aims to understand concomitant crystallization and help guide form selection of such a molecular system. Crystallization kinetics of ethanolic solutions were uncovered from induction time measurements, as well as seeded and unseeded crystallization experiments. Experimental and simulation results demonstrate that the stable form I crystallizes concomitantly with the metastable form II. The faster growing form II results in an intermediate decline in the composition of form I in crystallized samples, a characteristic feature of the concomitantly crystallized system. A four-quadrant scheme of attainable polymorph outcome was simulated under various crystallization conditions.     

Ferroelectric domain structure and atomic-scale phase distribution in a Pb(Mg1/3Nb2/3)O3-PbTiO3 single crystal

Lead-based relaxor ferroelectric crystals, such as Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃, are promising for functional applications due to their outstanding ferroelectric properties. Revealing ferroelectric domain structure and phase distribution at the nanoscale are important to understand the basic theory of ferroelectricity and promote their practical applications. In this study, the ferroelectric domain structure and atomic-scale phase distribution in a Pb(Mg_1/3Nb_2/3)O₃ - 35 at.% PbTiO₃ single crystal in the region of morphotropic phase boundary are systematically investigated by a combination of optical microscopy, scanning electron microscopy, and aberration-corrected transmission electron microscopy. It is found that 90° and 180° coarse domains are formed simultaneously in the ferroelectric single crystal. Moreover, there are tweed-like nano-domains formed inside each coarse single domain. Through careful investigations of distribution of stress and tetragonality, it is revealed that the tweed-like nano-domains are composed of nano-sized rhombohedral (R), monoclinic (M), and tetragonal (T) phases. The nano-scale T, M, R phases have the best, moderate, and lowest ferroelectricity, respectively.     

Double pyrovanadates CaMgV2O7: Formation mechanism,phase structure,and thermodynamic properties

A double pyrovanadate CaMgV₂O₇ sample was synthesized via a facile solid-state route under an air atmosphere. The nonequilibrium formation pathways of the CaMgV₂O₇ were investigated via powder X-ray diffraction. A multistep reactions path (metavanadates–pyrovanadates–double pyrovanadate CaMgV₂O₇) was proposed to describe the formation of the CaMgV₂O₇ considering the thermodynamic and kinetic factors. The cell unit parameters of the CaMgV₂O₇ sample indicated the crystallization according to a monoclinic system with space group P12/c1(14), and the lattice parameters of a = 6.756 Å, b = 14.495 Å, c = 11.253 Å, β = 99.12, and V = 108.806 Å³. X-ray photoelectron spectroscopy also confirmed the +5 oxidation state vanadium in CaMgV₂O₇. The endothermic effects at 1033 and 1143 K were related to the incongruent melting and liquidus temperatures of CaMgV₂O₇, respectively. The comprehensive thermodynamic properties of CaMgV₂O₇ were established in both low- and high-temperature regions, utilizing a physical property measurement system and multi-high-temperature calorimetry (96 lines). The heat capacity (200 J mol K⁻¹) and entropy (198 J mol K⁻¹) at 298.15 K were computed based on the low-temperature heat capacity values, and the enthalpy of formation at 298.15 K was also estimated. The fitted high-temperature capacity can be used to obtain the changes in the enthalpy, entropy, and Gibbs free energy. This study is part of building a reliable thermodynamic database of the CaO–MgO–V₂O₅ system.     

Rayleigh-Type Wave in A Rotated Piezoelectric Crystal Imperfectly Bonded on a Dielectric Substrate

Propagation characteristics of Rayleigh-type wave in a piezoelectric layered system are theoretically investigated. The piezoelectric layer is considered as a cubic crystal with finite thickness rotated about Y-axis and is imperfectly bonded onto a semi-infinite dielectric substrate. The imperfect interface between the two constituents is assumed to be mechanically compliant and dielectrically weakly conducting. The exact dispersion relations for electrically open or shorted boundary conditions are obtained. The numerical results show that the phase velocity of Rayleigh-type wave is symmetric with respect to the cut orientation of 45。 and can achieve the maximum propagation speed in this orientation. The mechanical imperfection plays an important role in the dispersion relations, further the normal imperfection can produce a significant reduction of phase velocity comparing with the tangential imperfection. Comparing with the mechanical imperfection the electrical imperfection makes a relatively small reduction of phase velocity of Rayleigh-type wave. The obtained results can provide some fundamentals for understanding of piezoelectric semiconductor and for design and application of piezoelectric surface acoustic wave devices.     

基于飞秒激光制备的光子晶体光纤Fabry-Perot温度传感器

提出并设计了一种基于飞秒激光在光子晶体光纤(photonic crystal fiber,PCF)中制备光纤法布里-珀罗(Fabry-Perot,F-P)传感器的方法。采用飞秒脉冲激光作为加工光源,结合放大倍率100×的物镜以及三维加工平台在PCF侧面采用逐线刻写方式进行加工。通过对飞秒激光光斑在光纤上的聚焦位置以及刻写功率进行优化,在PCF上刻写了深度均为80 μm、间隔为800 μm的两条划线,实现了周期为0.98 nm的全光纤F-P结构制备；实验中,对传感器在40~120 ℃温度范围内的光谱特性进行了测试与分析,每隔10 ℃进行一次数据采集,随着温度逐渐增加波长向长波方向漂移,通过对该采样点数据进行线性拟合,得到该测试点的波长温度灵敏度为9.73 pm/℃,拟合线性度为0.997。     

碳基采暖电热材料研究进展

近几年,由于节能与环保的需求,电取暖的方式得到大力的推广,电热材料的研究与应用受到人们广泛的重视。非金属碳基电热材料是新型的节能型电热采暖材料,本文重点对影响非金属碳基电热材料中的炭黑基电热材料、碳纤维基电热材料、碳晶电热材料电热性能的因素及相关应用进行了综述。     

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.     

A Structural Rationale for N-Methylbicuculline Acting as a Promiscuous Competitive Antagonist of Inhibitory Pentameric Ligand-Gated Ion Channels

Bicuculline, a valued chemical tool in neurosciences research, is a competitive antagonist of specific GABA_A receptors and affects other pentameric ligand-gated ion channels including the glycine, nicotinic acetylcholine and 5-hydroxytryptamine type 3 receptors. We used a fluorescence-quenching assay and isothermal titration calorimetry to record low-micromolar dissociation constants for N-methylbicuculline interacting with acetylcholine-binding protein and an engineered version called glycine-binding protein (GBP), which provides a surrogate for the heteromeric interface of the extracellular domain of the glycine receptor (GlyR). The 2.4 Å resolution crystal structure of the GBP:N-methylbicuculline complex, sequence and structural alignments reveal similarities and differences between GlyR and the GABA_A receptor–bicuculline interactions. N-methylbicuculline displays a similar conformation in different structures, but adopts distinct orientations enforced by interactions and steric blocks with key residues and plasticity in the binding sites. These features explain the promiscuous activity of bicuculline against the principal inhibitory pentameric ligand-gated ion channels in the CNS.     

基于拓扑单向波导的电磁诱导透明效应研究

为了研究电磁诱导透明效应在拓扑单向波导中的表现，设计了一种基于磁性光子晶体的耦合谐振腔波导。通过对谐振腔位置的调控实现了具有单向性质的电磁诱导透明效应，并利用有限时域差分仿真证明了电磁诱导透明效应在单向拓扑波导中的相关特性。该研究可为拓扑波导中实现光延迟、光开关等提供参考。     

Crystal-field engineering of ultrabroadband mid-infrared emission in Co2+-doped nano-chalcogenide glass composites

Tunable and ultrabroadband mid-infrared (MIR) emissions in the range of 2.5–4.5 μm are firstly reported from Co²⁺-doped nano-chalcogenide (ChG) glass composites. The composites embedded with a variety of binary (ZnS, CdS, ZnSe) and ternary (ZnCdS, ZnSSe) ChG nanocrystals (NCs) can be readily obtained by a simple one-step thermal annealing method. They are highly transparent in the near- and mid-infrared wavelength region. Low-cost and commercially available Er³⁺-doped fiber lasers can be used as the excitation source. By crystal-field engineering of the embedded NCs through cation- or anion-substitution, the emission properties of Co²⁺ including its emission peak wavelength and bandwidth can be tailored in a broad spectral range. The phenomena can be accounted for by crystal-field theory. Such nano-ChG composites, perfectly filling the 3–4 μm spectral gap between the oscillations of Cr²⁺ and Fe²⁺ doped IIVI ChG crystals, may find important MIR photonic applications (e.g., gas sensing), or can be used directly as an efficient pump source for Fe²⁺: IIVI crystals which are suffering from lack of pump sources.