Single Particle-Based Confocal Laser Scanning Microscopy for Visual Detection of Copper Ions in Confined Space

Main observation and conclusion A single particle-based confocal laser scanning microscopy was developed for the visual detection of copper ions in confined spa...     

Atomic-scale simulations for lithium dendrite growth driven by strain gradient

Dendrite formation is a major obstacle, e.g., capacity loss and short circuit,to the next-generation high-energy-density lithium(Li)-metal batteries. The development of successful Li dendrite mitigation strategies is impeded by an insu?cient understanding in Li dendrite growth mechanisms. The Li-plating-induced internal stress in Li-metal and its e?ects on dendrite growth have been widely studied, but the underlying microcosmic mechanism is elusive. In the present study, the role of the plating-...     

Regulating the assembly and expansion of the silver cluster from the Ag37 to Ag46 nanowheel driven by heteroanions

Precise control over the shape and size of metal nanoclusters through anion template-driven self-assembly is one of the key scientific goals in the nanocluster community, however, it is still not understood comprehensively. In this work, we report the controllable synthesis and atomically precise structures of silver nanowheels Ag37 and Ag46, using homo (Cl⁻ ions) and heteroanion (Cl⁻ and CrO₄²⁻ ions) template strategies, along with macrocyclic p-phenyl-thiacalix[4]arene and small ⁱPrS⁻ ligands. Structural analyses revealed that in Ag37, Cl⁻ ions serve as both local and global templates, whereas CrO₄²⁻ ions function as local and Cl⁻ ions as global templates in Ag46, resulting in a pentagonal nanowheel (Ag37) and a hexagonal (Ag46) nanowheel. The larger ionic size and more negative charges of CrO₄²⁻ ions than Cl⁻ ions offer more coordination sites for the silver atoms and are believed to be the key factors that drive the nanowheel core to expand significantly. Also, by taking advantage of the deep cavity of thiacalix[4]arene with an extended phenyl group, Ag46 has been used as a host material for dye adsorption depending on the charge and size of organic dyes. The successful use of heteroanions to control the expansion of well-defined silver nanowheels fills the knowledge gap in understanding the directing role of heteroanions in dictating the shape and size of nanoclusters at the atomic level.

A heteroanion self-assembly strategy for regulating the shape and expanding the size of the silver cluster from Ag₃₇ to Ag₄₆ with a macrocyclic (p-phenyl-thiacalix[4]arene) ligand has been presented.     

Two birds one stone: β-fluoropyrrolyl-cysteine SNAr chemistry enabling functional porphyrin bioconjugation

Bioconjugation, a synthetic tool that endows small molecules with biocompatibility and target specificity through covalent attachment of a biomolecule, holds promise for next-generation diagnosis or therapy. Besides the establishment of chemical bonding, such chemical modification concurrently allows alteration of the physicochemical properties of small molecules, but this has been paid less attention in designing novel bioconjugates. Here, we report a “two birds one stone” methodology for irreversible porphyrin bioconjugation based on β-fluoropyrrolyl-cysteine S_NAr chemistry, in which the β-fluorine of porphyrin is selectively replaced by a cysteine in either peptides or proteins to generate novel β-peptidyl/proteic porphyrins. Notably, due to the distinct electronic nature between fluorine and sulfur, such replacement makes the Q band red-shift to the near-infrared region (NIR, >700 nm). This facilitates intersystem crossing (ISC) to enhance the triplet population and thus singlet oxygen production. This new methodology features water tolerance, a fast reaction time (15 min), good chemo-selectivity, and broad substrate scope, including various peptides and proteins under mild conditions. To demonstrate its potential, we applied porphyrin β-bioconjugates in several scenarios, including (1) cytosolic delivery of functional proteins, (2) metabolic glycan labeling, (3) caspase-3 detection, and (4) tumor-targeting phototheranostics.

This work demonstrates ‘two birds one stone’ β-fluoropyrrolyl-cysteine SNAr chemistry. This methodology not only achieves porphyrin peptide/protein conjugates but also induces attractive porphyrinic photophysical properties to facilitate promising biological applications.     

新型掺碳二氧化硅-薄膜体声波谐振器结构及其仿真验证

一定厚度的低声阻抗支撑层可以在薄膜体声波谐振器(FBAR)与衬底之间形成声学隔离层,防止声波泄漏到衬底当中。掺碳二氧化硅(CDO)是一种低声阻抗材料,对FBAR具有较好的温度补偿效果,可以作为FBAR与衬底之间的声学隔离层,从而构成一种新型的CDO-FBAR。为了分析CDO-FBAR与通孔型FBAR相比性能是否退化,以及CDO声学隔离层所需厚度,采用多物理场耦合仿真软件分析了CDO-FBAR和通孔型FBAR的谐振频率、Q值、有效机电耦合系数和S参数,并提取了CDO-FBAR纵向振动位移。分析结果表明：CDO-FBAR的谐振频率整体向下漂移;CDO声学隔离层导致S参数的寄生干扰;由于声学损耗增加,Q值略有降低,其中并联谐振点处的Q值降幅更大;有效机电耦合系数略有降低;声波传播到声学隔离层中9 m处就完全衰减,即只需要9 m厚的CDO声学隔离层就能在FBAR与衬底之间形成有效的声学隔离。由此,仿真验证了这种新颖的CDO-FBAR结构的可行性。     

Purification Process and In Vitro and In Vivo Bioactivity Evaluation of Pectolinarin and Linarin from Cirsium japonicum

Pectolinarin and linarin are two major flavone O-glycosides of Cirsium japonicum, which has been used for thousands of years in traditional Chinese medicine. Pharmacological research on pectolinarin and linarin is meaningful and necessary. Here, a process for the purification of pectolinarin and linarin from C. japonicum was established using macroporous resin enrichment followed by prep-HPLC separation. The results show the purity of pectolinarin and linarin reached 97.39% and 96.65%, respectively. The in vitro bioactivities result shows the ORAC values of pectolinarin and linarin are 4543 and 1441 µmol TE/g, respectively, meanwhile their inhibition rate of BSA-MGO-derived AGEs is 63.58% and 19.31% at 2 mg/mL, which is 56.03% and 30.73% in the BSA-fructose system, respectively. The COX-2 inhibition rate at 50 µg/mL of linarin and pectolinarin reached 55.35% and 40.40%, respectively. Furthermore, the in vivo bioassay combining of histopathologic evaluation and biochemical analysis of liver glutamic oxaloacetic transaminase, serum creatinine and TNF-α show pectolinarin can alleviate lipopolysaccharide (LPS)-induced acute liver and kidney injury in mice. Metabolomics analysis shows that pectolinarin attenuates LPS-challenged liver and kidney stress through regulating the arachidonic acid metabolism and glutathione synthesis pathways. Collectively, our work presents a solid process for pectolinarin and linarin purification and has discovered a promising natural therapeutic agent—pectolinarin.     

Fluorination of Terminal Groups Promoting Electron Transfer in Small Molecular Acceptors of Bulk Heterojunction Films

The fluorination strategy is one of the most efficient and popular molecular modification methods to develop new materials for organic photovoltaic (OPV) cells. For OPV materials, it is a broad agreement that fluorination can reduce the energy level and change the morphology of active layers. To explore the effect of fluorination on small molecule acceptors, we selected two non-fullerene acceptors (NFA) based bulk heterojunction (BHJ) films, involving PM6:Y6 and PM6:Y5 as model systems. The electron mobilities of the PM6:Y5 and PM6:Y6 BHJ films are 5.76 × 10⁻⁷ cm²V⁻¹s⁻¹ and 5.02 × 10⁻⁵ cm²V⁻¹s⁻¹ from the space-charge-limited current (SCLC) measurements. Through molecular dynamics (MD) simulation, it is observed that halogen bonds can be formed between Y6 dimers, which can provide external channels for electron carrier transfer. Meanwhile, the “A-to-A” type J-aggregates are more likely to be generated between Y6 molecules, and the π–π stacking can be also enhanced, thus increasing the charge transfer rate and electron mobility between Y6 molecules.     

Efficient Degradation of Tetracycline Antibiotics by Engineered Myoglobin with High Peroxidase Activity

Tetracyclines are one class of widely used antibiotics. Meanwhile, due to abuse and improper disposal, they are often detected in wastewater, which causes a series of environmental problems and poses a threat to human health and safety. As an efficient and environmentally friendly method, enzymatic catalysis has attracted much attention. In previous studies, we have designed an efficient peroxidase (F43Y/P88W/F138W Mb, termed YWW Mb) based on the protein scaffold of myoglobin (Mb), an O₂ carrier, by modifying the heme active center and introducing two Trp residues. In this study, we further applied it to degrade the tetracycline antibiotics. Both UV-Vis and HPLC studies showed that the triple mutant YWW Mb was able to catalyze the degradation of tetracycline, oxytetracycline, doxycycline, and chlortetracycline effectively, with a degradation rate of ~100%, ~98%, ~94%, and ~90%, respectively, within 5 min by using H₂O₂ as an oxidant. These activities are much higher than those of wild-type Mb and other heme enzymes such as manganese peroxidase. As further analyzed by UPLC-ESI-MS, we identified multiple degradation products and thus proposed possible degradation mechanisms. In addition, the toxicity of the products was analyzed by using in vitro antibacterial experiments of E. coli. Therefore, this study indicates that the engineered heme enzyme has potential applications for environmental remediation by degradation of tetracycline antibiotics.     

Metal–Organic Frameworks–Based Memristors: Materials,Devices, and Applications

Facing the explosive growth of data, a number of new micro-nano devices with simple structure, low power consumption, and size scalability have emerged in recent years, such as neuromorphic computing based on memristor. The selection of resistive switching layer materials is extremely important for fabricating of high performance memristors. As an organic-inorganic hybrid material, metal-organic frameworks (MOFs) have the advantages of both inorganic and organic materials, which makes the memristors using it as a resistive switching layer show the characteristics of fast erasing speed, outstanding cycling stability, conspicuous mechanical flexibility, good biocompatibility, etc. Herein, the recent advances of MOFs-based memristors in materials, devices, and applications are summarized, especially the potential applications of MOFs-based memristors in data storage and neuromorphic computing. There also are discussions and analyses of the challenges of the current research to provide valuable insights for the development of MOFs-based memristors.     

非均质Cosserat连续体细-宏观均匀化条件

基于平均场理论的多尺度模拟关键问题之一是给定恰当的代表性体积单元(RVE)的边界条件,以使均匀化过程满足Hill-Mandel细宏观能量等价条件,也即Hill宏观均匀化条件.对于非均质Cosserat连续体,已有的研究工作只能得到合理的混合平动位移-偶应力表征元边界条件,常用的一致平动位移-转角以及周期边界条件等均不能使用,给计算均匀化算法推导和实施带来了困难,也阻碍了多尺度分析方法的进一步发展与应用.为此,论文在推导和建立一个新的Hill定理版本基础上,不仅成功地给定了多种强形式表征元边界条件,而且构造出了合理的弱形式周期边界条件,这些条件既满足细宏观能量等价也符合一阶平均场理论基本假定,可在均匀化方法中推广与应用.