Chelating Metal Ions in a Metal-Organic Framework for Constructing a Biomimetic Catalyst Through Post-modification

Crystal engineering, as a burgeoning technology, has been widely used to construct metalloporphyrins biomimetic catalysts. Herein, a bimetallic metal-organic framework (MOF) was constructed by 4-(4-carboxyphenyl)-1,2,4-triazole ligand, Co²⁺ and Zr⁴⁺ metal ions by solvothermal reaction(named PFC-88). A N,N-chelation site was found between the two adjacent ligands in PFC-88, consequently a porphyrin-like structure was obtained through chelating Fe³⁺ in this site by post-modification, named PFC-88-Fe. The result of a single crystal X-ray technology verified that Fe ions were successfully metalated in the N,N-chelation site of PFC-88, which is assisted by the X-ray absorption near-edge structure(XANES) spectra. An o-phenylenediamine oxidation reaction was applied to assessing the catalytic activity of PFC-88-Fe, in which the absorbance increases of phenazine-2,3-diamine at λ=418 nm were recorded by absorption spectroscopy in kinetic mode, exhibiting the application potential as a biomimetic catalyst.     

First-principles study on structural,electronic and ferroelectric properties of Bi2VO5.5 compound

A first-principles investigation of the origin of ferroelectricity in the Aurivillius compound Bi₂VO_5.5 is presented. Calculations with the density functional theory, in conjunction with the modern theory of polarization, allowed us to study the structural, electronic, and polar properties of two configurations built with oxygen vacancies, causing a charge imbalance and a subsequent displacement of the ions, generating two maximum polarizations, one of 14.75 μC/cm² and one of 4.31 μC/cm² along [011] direction. Electron localization function schemes were used to identify the asymmetry of charges in (001), (010) and (100) planes. The results obtained in this study establish that the origin of ferroelectricity is due to the displacement of the ions caused by oxygen vacancies and the asymmetric distribution of the isolated pair of Bi ions. On the other hand, the bandgap calculations and the results of P_s establish that Bi₂VO_5.5 is a candidate ferro-photovoltaic material.     

Conformational change-modulated spin transport at single-molecule level in carbon systems

Controlling the spin transport at the single-molecule level, especially without the use of ferromagnetic contacts, becomes a focus of research in spintronics. Inspired by the progress on atomic-level molecular synthesis, through first-principles calculations, we investigate the spin-dependent electronic transport of graphene nanoflakes with side-bonded functional groups, contacted by atomic carbon chain electrodes. It is found that, by rotating the functional group, the spin polarization of the transmission at the Fermi level could be switched between completely polarized and unpolarized states. Moreover, the transition between spin-up and spin-down polarized states can also be achieved, operating as a dual-spin filter. Further analysis shows that, it is the spin-dependent shift of density of states, caused by the rotation, that triggers the shift of transmission peaks, and then results in the variation of spin polarization. Such a feature is found to be robust to the length of the nanoflake and the electrode material, showing great application potential. Those findings may throw light on the development of spintronic devices.     

Electronic structures of CO adsorbed Pt-skin surface on Pt–Co and Pt–Ni alloys

By using angle resolved photoemission spectroscopy, we investigate the electronic structures of Pt-skin layer of Pt–Co and Pt–Ni alloys with CO molecules on the surface. Measured Fermi surface maps and band dispersions reflect the signatures of chemical bonding between Pt-skin layer and CO molecules. Furthermore, the degree of chemical bonding strength of CO molecules, estimated from the energy shift of the participating bands, is found to be reduced on both Pt bimetallic alloys. Our results show how the surface band structure of Pt bimetallic alloys is modified with molecular orbitals of CO molecules on the surface, revealing the important role of the electronic structure in the determination of chemical properties of bimetallic alloys.     

Supramolecular Arrangement and DFT analysis of Zinc(II) Schiff Bases: An Insight towards the Influence of Compartmental Ligands on Binding Interaction with Protein

We report, for the first time, a detailed crystallographic study of the supramolecular arrangement for a set of zinc(II) Schiff base complexes containing the ligand 2,6-bis((E)-((2-(dimethylamino)ethyl)imino)methyl)-4-R-phenol], where R=methyl/tert-butyl/chloro. The supramolecular study acts as a pre-screening tool for selecting the compartmental ligand R of the Schiff base for effective binding with a targeted protein, bovine serum albumin (BSA). The most stable hexagonal arrangement of the complex [Zn − Me] (R=Me) stabilises the ligand with the highest FMO energy gap (ΔE=4.22 eV) and lowest number of conformations during binding with BSA. In contrast, formation of unstable 3D columnar vertebra for [Zn − Cl] (R=Cl) tend to activate the system with lowest FMO gap (3.75 eV) with highest spontaneity factor in molecular docking. Molecular docking analyses reported in terms of 2D LigPlot+ identified site A, a cleft of domains IB, IIIA and IIIB, as the most probable protein binding site of BSA. Arg144, Glu424, Ser428, Ile455 and Lys114 form the most probable interactions irrespective of the type of compartmental ligands R of the Schiff base whereas Arg185, Glu519, His145, Ile522 act as the differentiating residues with ΔG=−7.3 kcal mol⁻¹.     

黄绿色葡萄石的矿物学特征及谱学研究

葡萄石可以以板状、片状、葡萄状、肾状、放射状或块状集合体的形式产出,因其美丽的外观和特殊的晶体结构,近年来受到了学者的广泛关注。本文通过电子探针、粉晶X射线衍射仪、傅里叶变换红外光谱仪、显微拉曼光谱仪、紫外可见分光光度计等仪器对黄绿色葡萄石的成分、结构及谱学特征进行了分析与探讨。葡萄石的主要致色元素为Fe,且Fe³⁺经常取代Al³⁺占据八面体配位,Fe²⁺经常取代Ca²⁺存在于空隙中。电子探针数据表明:Fe与Al的含量变化整体呈现负相关关系,Fe与Ca的含量变化也整体呈现负相关关系,Fe含量相对较高的样品其黄绿色调加深。XRD图谱和拉曼光谱的结果表明:在葡萄石中绿帘石以包裹体的形式存在。红外光谱和拉曼光谱表明葡萄石中存在硅氧四面体和铝氧八面体两种架构,紫外可见吸收光谱揭示了葡萄石的致色机理。本文对葡萄石的矿物学特征及谱学特征进行系统分析,为后续葡萄石的进一步研究提供思路与实验数据。     

Asymmetric Total Syntheses,Stereostructures, and Cytotoxicities of Marine Bromotriterpenoids Aplysiol B (Laurenmariannol) and Saiyacenol A

There are marine cytotoxic bromotriterpenoids, named the thyrsiferol family that are structurally characterized by some tetrahydropyran (THP) and tetrahydrofuran (THF) rings. The thyrsiferol family belongs to natural products that are often difficult to determine their stereostructures even by the current, highly advanced spectroscopic methods, especially in acyclic systems including stereogenic tetrasubstituted carbon centers. In such cases, it is effective to predict and synthesize the possible stereostructures. Herein, to elucidate ambiguous stereostructures and unassigned absolute configurations of aplysiol B, laurenmariannol, and saiyacenol A, members of the thyrsiferol family, we carried out their asymmetric chemical syntheses featuring 6-exo and 5-exo oxacyclizations of epoxy alcohol precursors and 6-endo bromoetherification of a bishomoallylic alcohol. In this paper, we report total assignments of their stereostructures through their asymmetric chemical syntheses and also their preliminary cytotoxic activities against some tumor cells. These results could not have been achieved without depending on asymmetric total synthesis.     

Diffusion Model of a Non-Integer Order PIγ Controller with TCP/UDP Streams

In this article, a way to employ the diffusion approximation to model interplay between TCP and UDP flows is presented. In order to control traffic congestion, an environment of IP routers applying AQM (Active Queue Management) algorithms has been introduced. Furthermore, the impact of the fractional controller PIγ and its parameters on the transport protocols is investigated. The controller has been elaborated in accordance with the control theory. The TCP and UDP flows are transmitted simultaneously and are mutually independent. Only the TCP is controlled by the AQM algorithm. Our diffusion model allows a single TCP or UDP flow to start or end at any time, which distinguishes it from those previously described in the literature.