Encrypting Chemical Reactivity in Protein Sequences toward Information‐Coded Reactions†

Controlling chemical reactivity has been the central theme in chemistry. Herein, we review the recent progress on the development of genetically encoded protein coupling reactions and their potential applications. The chemical reactivity is encoded in the protein sequences. The information is read out by folding and molecular recognition between two reactive components and subsequently translated into chemical bonding via autocatalysis. It has emerged as a unique way to tune the chemical reactivity and is regarded as one type of information‐coded reactions. Not only has it received many applications such as protein topology engineering, bioconjugation, biomaterials and synthetic biology, but also its principle may be extended beyond protein chemistry to enable new modes of supramolecular interactions that promote chemical bonding and that are simultaneously reinforced by covalent bonds.     

First systematic investigation of C-H...Cl hydrogen bonding using inorganic supramolecular synthons: lamellar, stitched stair-case, linked-ladder, and helical structures

Using a group of six neutral M(II)Cl(2)-containing coordination compounds as building blocks, the first systematic investigation of C-H...Cl hydrogen-bonding interactions was performed. Single-crystal X-ray structural analyses of four new compounds (pseudo-tetrahedral Co(II) and Zn(II); distorted trigonal bipyramidal Zn(II)) authenticate the metal coordination geometry. To provide a unified view of the presence of noncovalent interactions in this class of compounds, we have re-examined the packing diagram of two previously reported compounds (a distorted square-pyramidal Cu(II) complex and a trans-octahedral Co(II) complex). The organic ligands of our choice comprise bidentate/tridentate pyrazolylmethylpyridines and an unsymmetrical tridentate pyridylalkylamine. This systematic investigation has allowed us to demonstrate the existence of versatile C-H...Cl(2)M interactions and to report the successful application of such units as inorganic supramolecular synthons. Additional noncovalent interactions such as C-H...O and O-H...Cl hydrogen bonding and pi-pi stacking interactions have also been identified. Formation of novel supramolecular architectures has been revealed: 2D lamellar (p-cyclophane) and 3D lamellar, 3D "stitched staircase" (due to additional hydrogen-bonding interactions by water tetramers, with an average O-O bond length in the tetramer unit of 2.926 A, acting as "molecular clips" between staircases), 3D linked ladder, and single-stranded 1D helix.     

Probabilistic approach to homoclinic chaos

Three-dimensional systems possessing a homoclinic orbit associated to a saddle focus with eigenvalues ±i, – and giving rise to homoclinic chaos when the Shil'nikov condition < is satisfied are studied. The 2D Poincaré map and its 1D contractions capturing the essential features of the flow are given. At homoclinicity, these 1D maps are found to be piecewise linear. This property allows one to reduce the Frobenius—Perron equation to a master equation whose solution is analytically known. The probabilistic properties such as the time autocorrelation function of the state variablex are explicitly derived.     

新工科环境下“EDA技术”课程改革的探索

高校新工科人才培养的要求是培养一大批多样化、创新型卓越工程科技人才。针对培养要求切实做出积极的改革,首先重构EDA技术课程的教学时间,由线上和线下两部分组成。线上课要求完成课程视频学习、单元测验、讨论和期末测试;线下课堂要求完成见面课项目设计、实验课和期末考试。通过线上线下课堂教学的结合,加强过程性考核手段,完善学生学习评价机制。     

傅里叶变换差分求和性质的案例教学法

连续时间信号的傅里叶变换性质是信号与系统课程中一项非常重要的内容,但学生往往将注意力集中在性质的理论推导和具体表达形式上,忽略了性质背后的物理意义和具体的工程应用。本文以音乐的幅度谱、雷达动目标显示和图像平滑处理为例,介绍如何从物理意义和工程实践两个方面加深对傅里叶变换微积分性质的理解。     

Surface Control and Electrical Tuning of MXene Electrode for Flexible Self-Powered Human–Machine Interaction

MXene materials emerge as promising candidates for energy harvesting and storage application. In this study, the effect of the surface chemistry on the work function of MXenes, which determines the performance of MXene-based triboelectric nanogenerator (TENG), is elucidated. First-principles calculations reveal that the surface functional group greatly influences MXene work function:  OH termination reduces the work function with respect to that of bare surface, while  F and  Cl increase it. Then, work functions are experimentally determined by Kelvin probe force microscopy. The MXene prepared by gentle etching at 40 °C for 48 h (GE_40/48) has the largest work function. Furthermore, an electron-cloud potential-well model is established to explain the mechanism of electron emission-dominated charge transfer and assemble a triboelectric device to verify experimentally its conclusions. It is found that GE_40/48 has the best performance with a 281 V open-circuit voltage, 9.7 µA short-current current, and storing 1.019 µC of charge, which is consistent with the model. Last, a patterned TENG is demonstrated for self-powered human–machine interaction application. This finding enhances the understanding of the inherent mechanism between the surface structure and the output performance of MXene-based TENG, which can be applied to other TENG based on 2D materials.     

Interfacial Proton Supply/Filtration Regulates the Dynamics of Electrocatalytic Nitrogen Reduction Reaction: A Perspective

As a promising energy carrier, ammonia synthesis by electrocatalytic nitrogen reduction reaction (eNRR) is a promising green and low-carbon ammonia synthesis strategy that can replace the traditional Haber–Bosch process. However, the development of eNRR processes is mainly severely constrained by competitive hydrogen evolution reaction (HER), and the corresponding strategies to inhibit this adverse side reaction to obtain high eNRR selectivity are still limited. In addition, for this complex reaction involving gas–liquid–solid three-phase interface and proton/electron transfer, it is great significance to analyze and summarize the existing inhibition HER strategies from the viewpoint of dynamics. In view of this, this work reviews proton supply/filtration regulation strategy in catalytic system, allowing a systematic survey of the literature focusing on interface membrane regulation (inorganic membrane and organic membrane), electrolyte regulation (metal-mediated strategy and electrolyte ion regulation strategy) and system device design (electrode structure design and electrolytic cell device design). Constructive catalytic system design guidance is also suggested to inhibit hydrogen evolution and improve NH₃ selectivity, aiming for scalable and economically feasible applications.     

Balancing MXene Surface Termination and Interlayer Spacing Enables Superior Microwave Absorption

Surface chemistry and interlayer engineering determines the electrical properties of 2D MXene. However, it remains challenging to regulate the surface and interfacial chemistry of MXene simultaneously. Herein, simultaneous modulation of Ti₃C₂T_x MXene surface termination and layer spacing by alkali treatment are achieved. The electrical and electromagnetic properties of Ti₃C₂T_x are investigated in detail with respect to KOH and ammonia concentration dependence. A high concentration of KOH caused the Ti₃C₂T_x layer spacing to expand to 13.7 Å and the surface O/F ratio to increase to 33.84. Because of its weaker ionization effect, ammonia provides finer tuning compared to the drastic intercalation of KOH with a thorough sweeping of the F-containing groups. Ti₃C₂T_x is enriched with conductive -OH termination after ammonia treatment, which achieves an effective balance with the increased interlayer resistance. Therefore, NH₃H₂O-Ti₃C₂T_x achieves broad-band impedance matching and exhibits an efficient microwave loss of −49.1 dB at a low thickness of 1.7 mm, with an effective frequency bandwidth of 3.9 GHz. The results herein optimize the electrical properties of Ti₃C₂T_x using surface and interfacial chemistry to achieve broad microwave absorption, providing a framework for enhancing the electromagnetic wave loss of intrinsic MXene.     

Defect Engineering of MOF-Based Membrane for Gas Separation

Metal–organic frameworks (MOFs) are highly versatile materials that have been identified as promising candidates for membrane-based gas separation applications due to their uniformly narrow pore windows and virtually unlimited structural and chemical features. Defect engineering of MOFs has opened new opportunities for manipulating MOF structures, providing a simple yet efficient approach for enhancing membrane separation. However, the utilization of this strategy to tailor membrane microstructures and enhance separation performance is still in its infancy. Thus, this summary aims to provide a guideline for tailoring defective MOF-based membranes. Recent developments in defect engineering of MOF-based membranes will be discussed, including the synthesis strategies for defective MOFs, the effects of defects on the gas adsorption properties, gas transport mechanisms, and recently reported defective MOF-based membranes. Furthermore, the emerging challenges and future prospects will be outlined. Overall, defect engineering offers an exciting opportunity to improve the performance of MOF-based gas membranes. However, there is still a long way to go to fully understand the influence of defects on MOF properties and optimize the design of MOF-based membranes for specific gas separation applications. Nonetheless, continued research in this field holds great promise for the development of next-generation membrane-based gas separation technologies.