Directed Evolution of a Cp*RhIII-Linked Biohybrid Catalyst Based on a Screening Platform with Affinity Purification

Directed evolution of Cp*Rh^III-linked nitrobindin (NB), a biohybrid catalyst, was performed based on an in vitro screening approach. A key aspect of this effort was the establishment of a high-throughput screening (HTS) platform that involves an affinity purification step employing a starch-agarose resin for a maltose binding protein (MBP) tag. The HTS platform enables efficient preparation of the purified MBP-tagged biohybrid catalysts in a 96-well format and eliminates background influence of the host E. coli cells. Three rounds of directed evolution and screening of more than 4000 clones yielded a Cp*Rh^III-linked NB(T98H/L100K/K127E) variant with a 4.9-fold enhanced activity for the cycloaddition of acetophenone oximes with alkynes. It is confirmed that this HTS platform for directed evolution provides an efficient strategy for generating highly active biohybrid catalysts incorporating a synthetic metal cofactor.     

Effect of Mn2+ doping on the lattice and the microwave dielectric properties of MgTa2O6 ceramics

A series of Mn²⁺-doped Mg_1-xMn_xTa₂O₆ (x = 0.02, 0.04, 0.06, 0.08, 0.10, 0.12) ceramics were synthesized by solid-state reaction method. The influence of introducing Mn–O bonds as a partial replacement for Mg–O bonds on the lattice and microwave dielectric properties was systematically investigated. XRD and Rietveld refinement confirm that Mn²⁺ occupies the 2a Wyckoff position and forms a pure trirutile phase. Moreover, based on the chemical bond theory, the dielectric constant is mainly affected by the ionicity of the Ta–O bond. The lattice and dielectric properties remain relatively stable with Mn²⁺ doping below 0.1, but excessive Mn²⁺ doping leads to pronounced distortion of the lattice, which is not beneficial for lattice stability and microwave dielectric properties. Introducing an appropriate amount of Mn–O bonds with high bond dissociation energy facilitates MgO6 octahedron stability, which improves the thermal stability of the lattice. Accordingly, the microwave dielectric properties for 0.06 Mn²⁺-doped MgTa₂O₆ ceramics were determined: ε_r = 28, Q × f = 105,000 GHz (at 7.5 GHz), τ_f = 19.5 ppm/^°C.     

高强不锈钢绞线网与ECC黏结-滑移关系模型

高强不锈钢绞线网与ECC的黏结是二者协同工作的基础，且黏结 滑移关系模型是其黏结性能的综合反映，故通过对17组51个高强不锈钢绞网增强ECC薄板试件进行单边拉拔试验，研究横向钢绞线间距、纵向钢绞线直径和相对锚固长度等因素对钢绞线网在ECC中黏结性能的影响规律。试验结果表明，横向钢绞线的设置可使黏结破坏由脆性破坏转变为延性破坏；高强不锈钢绞线网与ECC的黏结滑移曲线可分为5个阶段，分别为上升段、微降段、延性强化段、下降段和残余段。基于试验结果，对钢绞线网在ECC中的黏结破坏特征和黏结 滑移机理进行分析，在相关黏结-滑移关系模型的基础上，提出钢绞线网与ECC的黏结 滑移关系模型，并进行模型参数分析。所提模型及模型参数计算公式与试验结果吻合良好，能较好地反映钢绞线网与ECC的界面黏结滑移特征。     

In-situ preparation of cross-linked hybrid anion exchange membrane of quaternized poly (styrene-b-isobutylene-b-styrene) covalently bonded with graphene

Introducing graphene into polymer matrix is an effective way to enhance performances of anion exchange membrane (AEM). However, utilizing the advantages of graphene by physical approach is limited due to the weak interface interaction between graphene and polymer matrix. Herein, we report an effective strategy to covalently bond graphene with polymer matrix to improve the interface interaction and further to improve the properties of AEM. A series of cross-linked quaternized graphene-based hybrid AEM were fabricated by covalently bonding poly (vinylbenzyl chloride) grafted graphene (GN-g-PVBC) copolymer with chloromethyl functionalized poly (styrene-b-isobutylene-b-styrene) (SIBS) through the cross-linker (N,N,N′,N′-tetramethyl-1,6-hexanediamine) by in-situ synthetic approach. The interface interaction between graphene and QSIBS is greatly enhanced according to micromorphology characterization of the hybrid membrane. The cross-linked quaternized hybrid AEM containing 0.55 wt% of GN-g-PVBC exhibits obviously improved dynamical mechanical properties (storage modulus: 418 MPa), ion conductivity (1.81 × 10² S cm^?1), methanol barrier property (5.19 × 10^?7 cm² s^?1), selectivity (3.49 × 10⁴ S s cm^?3) at 60 °C and especially a comparably excellent chemical stability to that of Nafion 115 due to the enhanced interface interaction between graphene and the polymer matrix.     

Casting methods for the production of rotationally symmetric copper bimetals

ABSTRACT

Multiple-material products are characterised by a complex property profile which is achieved by combining the particular advantages of at least two different materials. Bimetal casting is an energy- and material-efficient technology for the production of multi-metallic objects. This paper describes the development of a semi-continuous casting process for the formation of a rotationally symmetric bimetal with a cohesive bonding character at the interface of a copper–tin alloy (CuSn6) and pure copper (Cu99.5). Initial experiments are conducted by static casting to evaluate the thermal process window. Based on the results of the initial experiments, a vertical semi-continuous compound casting process is developed. A stable cohesive bond between the joining partners is accomplished by forming a solid solution at the interface.

This paper is part of a Thematic Issue on Copper and its Alloys.     

Ab initio calculations of the NO2 fission for CL-20 conformers

NO₂ fission is regarded to be the most important initial decomposition process of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20). In this study, four CL-20 conformers based on the ε-CL-20 were obtained after the optimization at m062x/cc-pvtz level, and the bond length, bond order and bond dissociation energy of the N-N bonds were examined to investigate the stability of these bonds. In addition, the rate constants and activation energy of the NO₂ fission were evaluated using the microcanonical variational transition state theory (μVT). The calculation results have shown that N-N bonds in the case of pseudo-equatorial and axial of nitro groups are the most stable and the least stable, respectively, by evaluating the bond length, bond order and minimum energy path (MEP). The NO₂ fission rate constants are affected by not only the stability of N-N bonds but also the repulsion forces from the other nitro groups, and the fission process for pseudo-equatorial positioning of nitro groups is easier to be accelerated due to the increase of the repulsion forces. The decomposition of CL-20 conformer may mainly originate from the fission of the pseudo-equatorial positioning of nitro groups, especially for CL-20 III conformer because of the significant low activation energy.     

不锈钢酸洗污泥对烧结黏结相与平衡相的影响

 不锈钢酸洗污泥安全填埋占用土地且难以消除对环境的危害，将酸洗污泥作为烧结配料使用有望回收其中铁、铬、镍等金属，并充分利用其中的熔剂组分，实现酸洗污泥在冶金企业的闭路资源化利用。铁矿粉配加酸洗污泥烧结黏结相强度试验表明，随着酸洗污泥配加比例的增加，黏结相强度先增加后减小，且随着碱度的增加整体减小，当酸洗污泥配加比例为10%时，试样中赤铁矿、磁铁矿质量分数最大，枪晶石质量分数较小，在碱度为1.5时于1 280 ℃焙烧4 min，试样的黏结相强度最大可达15.12 kN。平衡相烧结试验表明，配加酸洗污泥能改善烧结矿质量，铁矿粉配加10%的酸洗污泥，碱度为1.5，1 300 ℃烧结240 min后，烧结矿的矿相组成和微观结构最好，综合性能最佳。     

Chemical bond characteristics and infrared reflectivity spectrum of a novel microwave dielectric ceramic CaIn2O4 with near-zero τf

Orthorhombic-structured CaIn₂O₄ ceramics with a space group Pca2₁ were synthesized via a solid-state reaction method. A high relative density (95.6 %) and excellent microwave dielectric properties (ε_r ～11.28, Qf = 74,200 GHz, τ_f ～ ?4.6 ppm/°C) were obtained when the ceramics were sintered at 1375 °C for 6 h. The dielectric properties were investigated on the basis of the Phillips–Van Vechten–Levine chemical bond theory. Results indicated that the dielectric properties were mainly determined by the Inbond">O bonds in the CaIn₂O₄ ceramics. These bonds contributed more (74.65 %) to the dielectric constant than the Cabond">O bonds (25.35 %). Furthermore, the intrinsic dielectric properties of the CaIn₂O₄ ceramics were investigated via infrared reflectivity spectroscopy. The extrapolated microwave dielectric properties were ε_r ～10.12 and Qf = 112,200 GHz. Results indicated that ion polarization is the main contributor to the dielectric constant in microwave frequency ranges.     

Group and group-interaction contribution method for estimating the melting temperatures of deep eutectic solvents

Deep eutectic solvents (DESs) are mixtures of two or more components that have lower melting temperatures compared to their constituting components. DESs possess many advantages, for example, low volatility, low flammability, and low toxicity, which make them promising alternatives to traditional organic solvents. The melting temperature, one of the important physical properties, is of essential importance for industrial applications. In this work, a group and group-interaction contribution method was proposed to estimate the melting temperatures of DESs using an extensive database (1528 DESs, 1541 data points). The average absolute relative deviation (%AARD) between the estimated and experimental values of the melting temperature was 5.67% for binary DESs. Subsequently, this method was also extended to estimate the melting temperature of ternary DESs, with the AARD of 6.13%. The results indicate the high accuracy and broad applicability of the method and pave the way for the rational design of task-specific DESs.     

Mechanistic study of the effect of Ca–Sn co-doping on the microwave dielectric properties and magnetic properties of YIG

To investigate the crystal structure, electrical properties, and magnetic properties of Ca–Sn co-doped Y_3-xCa_xFe_5-xSn_xO₁₂ (x = 0.00–0.25 in steps of 0.05), solid-state reaction experiments, first principles calculations, and complex crystal bonding theoretical calculations were performed. The relative permittivity (ε_r) is strongly correlated with the average bond ionicity when Ca²⁺ is added. Furthermore, appropriate Sn⁴⁺ substitution significantly lowers the dielectric loss (tanδ_ε) associated with the lattice energy. The right amount of Ca–Sn co-doping can change the saturation magnetization (4πM_S) and improve the microscopic morphology of YIG, lowering the ferromagnetic resonance linewidth (ΔH) of YIG. The optimized microwave dielectric and magnetic properties are as follows: ε_r = 14.7, tanδ_ε = 4.15 × 10^?4, 4πM_S = 1680 G, and ΔH = 53 Oe for Y_2.8Ca_0.2Fe_4.8Sn_0.2O₁₂ sintered for 6 h at 1425 °C. Based on this material, a simple 3D model of a strip-line circulator with an insertion loss of less than 0.3 dB at each port and isolation greater than 20 dB in the 10–12 GHz range was developed, indicating the potential of the material for microwave high-frequency components such as circulators.