Unified convergence analysis of a second-order method of multipliers for nonlinear conic programming

Science China Mathematics - In this paper, we accomplish the unified convergence analysis of a second-order method of multipliers (i.e., a second-order augmented Lagrangian method) for solving the...     

A Multiresponsive Functional AIEgen for Spatiotemporal Pattern Control and All-round Information Encryption

Functional materials with multi-responsive properties and good controllability are highly desired for developing bioinspired and intelligent multifunctional systems. Although some chromic molecules have been developed, it is still challenging to realize in situ multicolor fluorescence changes based on a single luminogen. Herein, we reported an aggregation-induced emission (AIE) luminogen called CPVCM, which can undergo a specific amination with primary amines to trigger luminescence change and photoarrangement under UV irradiation at the same active site. Detailed mechanistic insights were carried out to illustrate the reactivity and reaction pathways. Accordingly, multiple-colored images, a quick response code with dynamic colors, and an all-round information encryption system were demonstrated to show the properties of multiple controls and responses. It is believed that this work not only provides a strategy to develop multiresponsive luminogens but also develops an information encryption system based on luminescent materials.     

Atomically Dispersed Iron Regulating Electronic Structure of Iron Atom Clusters for Electrocatalytic H2O2 Production and Biomass Upgrading

The integration of highly active single atoms (SAs) and atom clusters (ACs) into an electrocatalyst is critically important for high-efficiency two-electron oxygen reduction reaction (2e⁻ ORR) to hydrogen peroxide (H₂O₂). Here we report a tandem impregnation-pyrolysis-etching strategy to fabricate the oxygen-coordinated Fe SAs and ACs anchored on bacterial cellulose-derived carbon (BCC) (FeSAs/ACs-BCC). As the electrocatalyst, FeSAs/ACs-BCC exhibits superior electrocatalytic activity and selectivity toward 2e⁻ ORR, affording an onset potential of 0.78 V (vs. RHE) and a high H₂O₂ selectivity of 96.5 % in 0.1 M KOH. In a flow cell reactor, the FeSAs/ACs-BCC also achieves high-efficiency H₂O₂ production with a yield rate of 12.51±0.18 mol g_cat⁻¹ h⁻¹ and a faradaic efficiency of 89.4 %±1.3 % at 150 mA cm⁻². Additionally, the feasibility of coupling the produced H₂O₂ and electro-Fenton process for the valorization of ethylene glycol was explored in detail. The theoretical calculations uncover that the oxygen-coordinated Fe SAs effectively regulate the electronic structure of Fe ACs which are the 2e⁻ ORR active sites, resulting in the optimal binding strength of *OOH intermediate for high-efficiency H₂O₂ production.     

Synthesis and Catalytic Study of Ruthenium Carbene Catalyst Containing a Zn‐Porphyrin Ligand

A ruthenium carbene complex containing a Zn‐porphyrin ligand has been developed. The complex was characterized by ¹H NMR, IR, HRMS and elemental analysis. The catalytic activity of the ruthenium carbene complex for olefin metathesis reactions was also investigated. The complex exhibited excellent performance for both ring‐closing and cross metathesis reactions at 35°C.     

Supramolecular Fluorescent Nanoparticles Constructed via Multiple Non‐Covalent Interactions for the Detection of Hydrogen Peroxide in Cancer Cells

Overabundance of hydrogen peroxide originating from environmental stress and/or genetic mutation can lead to pathological conditions. Thus, the highly sensitive detection of H₂O₂ is important. Herein, supramolecular fluorescent nanoparticles self‐assembled from fluorescein isothiocyanate modified β‐cyclodextrin (FITC‐β‐CD)/rhodamine B modified ferrocene (Fc‐RB) amphiphile were prepared through host–guest interaction between FITC‐β‐CD host and Fc‐RB guest for H₂O₂ detection in cancer cells. The self‐assembled nanoparticles based on a combination of multiple non‐covalent interactions in aqueous medium showed high sensitivity to H₂O₂ while maintaining stability under physiological condition. Owing to the fluorescence resonance energy transfer (FRET) effect, addition of H₂O₂ led to obvious fluorescence change of nanoparticles from red (RB) to green (FITC) in fluorescent experiments. In vitro study showed the fluorescent nanoparticles could be efficiently internalized by cancer cells and then disrupted by endogenous H₂O₂, accompanying with FRET from “on” to “off”. These supramolecular fluorescent nanoparticles constructed via multiple non‐covalent interactions are expected to have potential applications in diagnosis and imaging of diseases caused by oxidative stresses.     

Supramolecularly engineered phospholipids constructed by nucleobase molecular recognition: upgraded generation of phospholipids for drug delivery

Despite of great advances of phospholipids and liposomes in clinical therapy, very limited success has been achieved in the preparation of smart phospholipids and controlled-release liposomes for in vivo drug delivery and clinical trials. Here we report a supramolecular approach to synthesize novel supramolecularly engineered phospholipids based on complementary hydrogen bonding of nucleosides, which greatly reduces the need of tedious chemical synthesis, including reducing the strict requirements for multistep chemical reactions, and the purification of the intermediates and the amount of waste generated relative more traditional approaches. These upgraded phospholipids self-assemble into liposome-like bilayer structures in aqueous solution, exhibiting fast stimuli-responsive ability due to the hydrogen bonding connection. In vitro and in vivo evaluations show the resulted supramolecular liposomes from nucleoside phospholipids could effectively transport drug into tumor tissue, rapidly enter tumor cells, and controllably release their payload in response to an intracellular acidic environment, thus resulting in a much higher antitumor activity than conventional liposomes. The present supramolecularly engineered phospholipids represent an important evolution in comparison to conventional covalent-bonded phospholipid systems.     

生物正交反应在我国的研究进展

生物正交反应是指能够在生物体系中进行、且不会与天然生物化学过程相互干扰的一类化学反应. 这类反应的出现为科学家对生命进程的原位研究带来了革命性的技术, 已经成为化学生物学这一新兴交叉领域的核心方向之一. 自这一概念提出的近二十年里, 生物正交化学经历了反应类型由单一的“偶联反应”向成键偶联、断键剪切反应并重, 应用场景由简单的活细胞体系向更为复杂的生物活体升级的一系列发展历程. 同时, 在生命科学研究、医药研发、临床诊疗等多个领域展示出了广阔的应用前景. 我国化学生物学领域的学者们积极参与并推动了生物正交反应的快速发展, 在反应开发、体系优化和实际应用等方面开展了一系列原创工作, 取得了瞩目的成绩; 尤其是在“生物正交剪切反应”概念的提出与开发应用等方面产生了重要的国际影响. 本综述中, 分别按照金属介导、光介导和化学小分子介导的生物正交偶联反应以及生物正交剪切反应, 对近五年来我国学者在该领域的代表性成果进行系统介绍. 最后对生物正交反应的进一步发展与应用加以展望. 我们期待更多高效、兼容的生物正交反应得以发展, 并提出“遥控生物正交化学”的未来发展目标, 期待更多的化学家能够加入生物正交反应的开发拓展与应用探索当中.