宽体液腔Janus-Helmholtz换能器

本文使用有限元方法对宽体液腔Janus-Helmholtz(JH)换能器进行了仿真分析,得出了壳体宽度拓展增量对JH换能器工作性能的影响规律。使用三维建模的方式,分析了连接部分对换能器性能的影响及宽体壳体的的模态,证明了三维建模的必要性。依据仿真优化结构设计了一款宽体液腔JH换能器并进行了湖上测试。最终测试结果与仿真结果有很好的一致性,相较直筒JH换能器其谐振频率降低300Hz,发射电压响应最高可达144dB。     

Identifying the viscoelastic properties of soft matter from the indentation response of a hard film-soft substrate system

The indentation technique is widely used in measuring the mechanical properties of soft matter at the microscale or nanoscale,but still faces challenges by these unique properties as well as the consequent strong surface adhesion, including the strong nonlinear effect, unclear judgment of the contact point, difficulties in estimating the contact area, and the risk of the indenter piercing the sample. Here we propose a two-step method to solve these problems: lay a hard film on a soft matter, and obtain the viscoelastic properties of this soft matter through the indentation response of this composite structure. We first establish a theoretical indentation model of the hard film-soft substrate system based on the theory of plates, elastic-viscoelastic correspondence principle and Boltzmann superposition principle. To verify the correctness of this method, we measure the mechanical properties of the methyl vinyl silicone rubber(MVSR) covered by a Cu nanofilm. Finally, we test the effectiveness and error sensitivity of this method with the finite element method(FEM). The results show that our method can accurately measure the mechanical properties of soft matter, while effectively circumventing the problems of the traditional indentation technique.     

Unprecedented Oxidative Addition and Metal‐Only Lewis Pair Chemistry of Antimony Trihalides

Reaction of the zero‐valent platinum complex [Pt(PCy₃)₂] with SbF₃ generates the cationic diplatinum stibenium complex [{(Cy₃P)₂Pt}₂(μ‐SbF₂)]⁺, the first unsupported metal‐only Lewis pair containing an antimony‐centered Lewis acid. In contrast, SbCl₃ undergoes oxidative addition to [Pt(PCy₃)₂], resulting in the dihalostibanyl complex trans‐[PtCl(SbCl₂)(PCy₃)₂], the first example of oxidative addition of an antimony–halide bond to a transition metal.     

New fabrication approach to develop a high birefringence photo-crosslinked film based on a sulfur-containing liquid crystalline molecule with large temperature dependence of birefringence

ABSTRACT

We present a new fabrication approach to achieve a high birefringence film by means of photopolymerization based on an alkylthio-containing rod-like liquid crystalline molecule exhibiting large temperature dependence of birefringence. We designed a new reactive mesogen having alkylthio linkages (BPM–S). It was found that BPM–S had a larger increment of birefringence with decreasing temperature, relative to commercially available alkoxy analog LC242. This result could be thought to be due to enhanced intermolecular attractive interaction for an alkylthio mesogen implied by the proximity of laterally neighboring molecules and cybotactic nematic tendency based on wide-angle X-ray measurement. The uniaxially-aligned photo-polymerized film for BPM–S showed higher birefringence than that for LC 242.     

Group 6 Oxyfluoro-Anion Salts of [XeF5]+ and [Xe2F11]+: Syntheses and Structures of [XeF5][M2O2F9] (M=Mo,W), [Xe2F11][M′OF5] (M′=Cr,Mo, W), [XeF5][HF2]⋅CrOF4, and [XeF5][WOF5]⋅XeOF4

The reactions of the fluoride-ion donor, XeF₆, with the fluoride-ion acceptors, M′OF₄ (M′=Cr, Mo, W), yield [XeF₅]⁺ and [Xe₂F₁₁]⁺ salts of [M′OF₅]⁻ and [M₂O₂F₉]⁻ (M=Mo, W). Xenon hexafluoride and MOF₄ react in anhydrous hydrogen fluoride (aHF) to give equilibrium mixtures of [Xe₂F₁₁]⁺, [XeF₅]⁺, [(HF)_nF]⁻, [MOF₅]⁻, and [M₂O₂F₉]⁻ from which the title salts were crystallized. The [XeF₅][CrOF₅] and [Xe₂F₁₁][CrOF₅] salts could not be formed from mixtures of CrOF₄ and XeF₆ in aHF at low temperature (LT) owing to the low fluoride-ion affinity of CrOF₄, but yielded [XeF₅][HF₂]⋅CrOF₄ instead. In contrast, MoOF₄ and WOF₄ are sufficiently Lewis acidic to abstract F⁻ ion from [(HF)_nF]⁻ in aHF to give the [MOF₅]⁻ and [M₂O₂F₉]⁻ salts of [XeF₅]⁺ and [Xe₂F₁₁]⁺. To circumvent [(HF)_nF]⁻ formation, [Xe₂F₁₁][CrOF₅] was synthesized at LT in CF₂ClCF₂Cl solvent. The salts were characterized by LT Raman spectroscopy and LT single-crystal X-ray diffraction, which provided the first X-ray crystal structure of the [CrOF₅]⁻ anion and high-precision geometric parameters for [MOF₅]⁻ and [M₂O₂F₉]⁻. Hydrolysis of [Xe₂F₁₁][WOF₅] by water contaminant in HF solvent yielded [XeF₅][WOF₅]⋅XeOF₄. Quantum-chemical calculations were carried out for M′OF₄, [M′OF₅]⁻, [M′₂O₂F₉]⁻, {[Xe₂F₁₁][CrOF₅]}₂, [Xe₂F₁₁][MOF₅], and {[XeF₅][M₂O₂F₉]}₂ to obtain their gas-phase geometries and vibrational frequencies to aid in their vibrational mode assignments and to assess chemical bonding.     

Unravelling the Time Scale of Conformational Plasticity and Allostery in Glycan Recognition by Human Galectin-1

The interaction of human galectin-1 with a variety of oligosaccharides, from di-(N-acetyllactosamine) to tetra-saccharides (blood B type-II antigen) has been scrutinized by using a combined approach of different NMR experiments, molecular dynamics (MD) simulations, and isothermal titration calorimetry. Ligand- and receptor-based NMR experiments assisted by computational methods allowed proposing three-dimensional structures for the different complexes, which explained the lack of enthalpy gain when increasing the chemical complexity of the glycan. Interestingly, and independently of the glycan ligand, the entropy term does not oppose the binding event, a rather unusual feature for protein-sugar interactions. CLEANEX-PM and relaxation dispersion experiments revealed that sugar binding affected residues far from the binding site and described significant changes in the dynamics of the protein. In particular, motions in the microsecond-millisecond timescale in residues at the protein dimer interface were identified in the presence of high affinity ligands. The dynamic process was further explored by extensive MD simulations, which provided additional support for the existence of allostery in glycan recognition by human galectin-1.     

Cyclic Bis-alkylidene Complexes of Titanium and Zirconium: Synthesis,Characterization, and Reaction

Transition-metal alkylidenes have exhibited wide applications in organometallic chemistry and synthetic organic chemistry, however, cyclic Schrock-carbene-like bis-alkylidenes of group 4 metals with a four-electron donor from an alkylidene have not been reported. Herein, the synthesis and characterization of five-membered cyclic bis-alkylidenes of titanium ( 4 a , b ) and zirconium ( 5 a , b ) are reported, as the first well-defined group 4 metallacyclopentatrienes, by two-electron reduction of their corresponding titana- and zirconacyclopentadienes. DFT analyses of 4 a show a four-electron donor (σ-donation and π-donation) from an alkylidene carbon to the metal center. The reaction of 4 a with N,N′-diisopropylcarbodiimide (DIC) leads to the [2+2]-cycloaddition product 6 . Compound 4 a reacted with CO, affording the oxycyclopentadienyl titanium complex 7 . These reactivities demonstrate the multiple metal–carbon bond character. The reactions of 4 a or 5 a with cyclooctatetraene (COT) or azobenzene afforded sandwich titanium complex 8 or diphenylhydrazine-coordinated zirconacyclopentadiene 9 , respectively, which exhibit two-electron reductive ability.     

TEMPO-mediated radical polymerization in the synthesis of poly(methyl methacrylate) macromonomer

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形状记忆合金椭圆孔口问题的有限单元法

基于Lagoudas形状记忆合金(SMA)三维本构模型,假设材料为各向同性,推导了SMA平面应力状态的增量型本构方程,继而编写了ABAQUS用户自定义材料(UMAT)子程序,研究了在双向拉伸情况下,外载荷、温度、椭圆孔口长短轴之比对超弹性SMA椭圆孔口板中应力诱发马氏体相变区的影响。数值结果表明:应力诱发马氏体相变首先发生在椭圆孔口长轴端点部位,在外加载荷作用下逐渐扩展到板内,并由内向外形成马氏体相区、相变混合区和奥氏体相区;SMA板内应力诱发马氏体完全相变区面积与施加外载荷成正相关,与温度成负相关;随着椭圆孔口长短轴之比增大,SMA板内应力诱发马氏体完全相变区面积呈现出先减小后增大的趋势;拉应力差值相同时,相较于拉应力沿椭圆孔口长轴方向较大的情况,当拉应力沿椭圆孔口短轴方向较大时,SMA板内完全相变区面积较大,椭圆孔口周边应力集中现象更明显。