Operando XAFS on Hydrated Calcium Vanadium Bronze Cathode for Aqueous Zn-ion Storage

Multivalent ion storage and aqueous electrochemical systems continue to build interest for energy application. The Zn-ion system with 2 electron transfer and an ideal metal anode is a strong candidate but is still at the early stage of development. Using both in situ near-edge (XANES) and X-ray absorption fine structure spectroscopy, EXAFS, a nanostructured cathode material, Ca_xV₂O₅-H₂O (CVO), was probed at the V-K absorption edge. This operando study reveals the local electronic and geometric structure changes for CVO during galvanostatic cycling as the active material in an aqueous Zn-ion cell. The XANES data provides a fine resolution to track the evolution of the vanadium oxidative state and near-neighbor coordination sphere showing subtle shifts and delocalized charge. The Zn-ion influence on the V-K absorption edge is visualized using a difference technique called Δμ. Coupled with theoretical calculations and modelling, the extended region extracted local bonding information further confirms excellent electronic and structural reversibility of this vanadium oxide bronze in an aqueous Zn-ion electrochemical cell.     

药物化学中的大分子效应※

药物种类按照分子量来划分可以分为小分子药物(自然提取或化学合成的)和大分子药物(生物制剂). 尽管目前小分子药物仍然是市场的主流, 但其研发增速趋缓, 而大分子药物在药物研发中的地位日渐突显, 并被预期在未来药物市场中占据越来越高的份额. 除了生物制剂大分子药物, 将小分子药物与天然或合成大分子结合制备得到的化学合成大分子药物, 近年来受到药物研究者们越来越多的关注. 由于大分子具有丰富的骨架结构及空间构架, 其所特有的骨架效应、多价效应, 以及通过分子组装而产生的聚集效应和靶向效应等, 能够为药物化学的设计带来更多新的可能. 有鉴于此, 本综述将简略介绍药物化学设计中的大分子效应, 重点讨论合成大分子的骨架效应、多价效应、聚集效应和靶向效应等为药物化学设计所带来的新性能. 通过对药物化学中大分子效应所带来的优势、问题和重要研究进展的探讨, 以期能够推动化学合成大分子药物的发展, 为药物化学设计提供新的思路.     

Multivalent ions and biomolecules: Attempting a comprehensive perspective

Ions are ubiquitous in nature. They play a key role for many biological processes on the molecular scale, from molecular interactions, to mechanical properties, to folding, to self-organisation and assembly, to reaction equilibria, to signalling, to energy and material transport, to recognition etc. Going beyond monovalent ions to multivalent ions, the effects of the ions are frequently not only stronger (due to the obviously higher charge), but qualitatively different. A typical example is the process of binding of multivalent ions, such as Ca²⁺, to a macromolecule and the consequences of this ion binding such as compaction, collapse, potential charge inversion and precipitation of the macromolecule. Here we review these effects and phenomena induced by multivalent ions for biological (macro)molecules, from the “atomistic/molecular” local picture of (potentially specific) interactions to the more global picture of phase behaviour including, e. g., crystallisation, phase separation, oligomerisation etc. Rather than attempting an encyclopedic list of systems, we rather aim for an embracing discussion using typical case studies. We try to cover predominantly three main classes: proteins, nucleic acids, and amphiphilic molecules including interface effects. We do not cover in detail, but make some comparisons to, ion channels, colloidal systems, and synthetic polymers. While there are obvious differences in the behaviour of, and the relevance of multivalent ions for, the three main classes of systems, we also point out analogies. Our attempt of a comprehensive discussion is guided by the idea that there are not only important differences and specific phenomena with regard to the effects of multivalent ions on the main systems, but also important similarities. We hope to bridge physico-chemical mechanisms, concepts of soft matter, and biological observations and connect the different communities further.     

Oligomeric guanidine synthesis assisted by TFA-sensitive arylsulfonylthiourea

Through arylsulfonyl activation of thiourea, efficient synthesis of oligomeric guanidines can be achieved in either solution or solid-phase. Incorporation of TFA-sensitive arylsulfonyl groups, such as Pbf, during the synthesis greatly simplifies deprotection procedures for obtaining the final oligomeric guanidine products.     

A Universal Organic Cathode for Ultrafast Lithium and Multivalent Metal Batteries

Low‐cost multivalent battery chemistries (Mg²⁺, Al³⁺) have been extensively investigated for large‐scale energy storage applications. However, their commercialization is plagued by the poor power density and cycle life of cathodes. A universal polyimides@CNT (PI@CNT) cathode is now presented that can reversibly store various cations with different valences (Li⁺, Mg²⁺, Al³⁺) at an extremely fast rate. The ion‐coordination charge storage mechanism of PI@CNT is systemically investigated. Full cells using PI@CNT cathodes and corresponding metal anodes exhibit long cycle life (>10000 cycles), fast kinetics (>20 C), and wide operating temperature range (?40 to 50 °C), making the low‐cost industrial polyimides universal cathodes for different multivalent metal batteries. The stable ion‐coordinated mechanism opens a new foundation for the development of high‐energy and high‐power multivalent batteries.     

CERTAIN SUFFICIENT CONDITIONS FOR STARLIKENESS AND CONVEXITY OF MEROMORPHICALLY MULTIVALENT FUNCTIONS

In this paper we derive certain suffcient conditions for starlikeness and con-vexity of orderαof meromorphically multivalent functions in the punctured unit disk.     

Anchoring of histidine-tagged proteins to molecular printboards: self-assembly, thermodynamic modeling, and patterning

In this paper the multivalent binding of hexahistidine (His6)-tagged proteins to beta-cyclodextrin (beta-CD) self-assembled monolayers (SAMs) by using the nickel(II) complex of a hetero-divalent orthogonal adamantyl nitrilotriacetate linker (4) is described. Nonspecific interactions were suppressed by using monovalent adamantyl-hexa(ethylene glycol) derivative 3. With the mono-His6-tagged maltose binding protein (His6-MBP), thermodynamic modeling based on surface plasmon resonance (SPR) titration data showed that the MBP molecules in solution were linked, on average, to Ni.4 in 1:1 stoichiometry. On the surface, however, the majority of His(6)-MBP was complexed to surface-immobilized beta-CDs through three Ni.4 complexes. This difference is explained by the high effective beta-CD concentration at the surface and is a new example of supramolecular interfacial expression. In a similar adsorption scheme, SPR proved that the alpha-proteasome could be attached to beta-CD SAMs in a specific manner. Patterning through microcontact printing of (His6)4-DsRed-fluorescent timer (DsRed-FT), which is a tetrameric, visible autofluorescent protein, was carried out in the presence of Ni.4 Fluorescence measurements showed that the (His6)4-DsRed-FT is bound strongly through Ni.4 to the molecular printboard.     

Estimating vaccine coverage by using computer algebra

Email: altmannd{at}rki.deEmail: altmann{at}mathematik.hu-berlin.de The approach of N Gay for estimating the coverage of a multivalentvaccine from antibody prevalence data in certain age cohortsis complemented by using computer aided elimination theory ofvariables. Hereby, Gay's usage of numerical approximation canbe replaced by exact formulae which are surprisingly nice, too.