scholarly journals Exploring Electron-Sink Behaviors of Molecular Assemblies

2021 ◽  
Author(s):  
Yume Mai
Keyword(s):  
Metal Carbonyl ◽  
Redox Mediators ◽  
Organometallic Complex ◽  
Molecular Assemblies ◽  
Electrode Surfaces ◽  
Synthetic Strategy ◽  
Mesoscopic Structure ◽  
Large Clusters ◽  
Electron Sink ◽  
The Relationship

Metal carbonyl clusters, such as the [Ni32C6(CO)36]6- anion, have been documented to display electron-sink phenomena. However, such large clusters suffer from inefficient yields due to their demanding and unreliable synthesis routes. To approach this obstacle, we investigated the electrochemical properties of Fe2(μ-PPh2)2(CO)6, an organometallic complex known to experience a reversible two-electron transfer process. In this work, we report a modular synthetic strategy for expanding the electron-sink capacity of molecular assemblies by installing Fe2(μ-PPh2)2(CO)6 redox mediators to arylisocyanide ligands. Specifically, the coordination of three Fe2(μ-PPh2)2(CO)6 subunits to a trifunctional arylisocyanide ligand produces an electron-sink ensemble that can accommodate six electrons, exceeding the precedent benchmark [Ni32C6(CO)36]6- anion. The redox mediators store electrons within quantized unoccupied frontier orbitals and act as individual quantum capacitors. Ultimately, we propose to modify the electrode surfaces with these redox mediators to examine the relationship between the electrode’s mesoscopic structure and its macroscopic capacitance.

The fine structure of the Kolmogoroff–Avrami theorem

1979 ◽  
Vol 57 (11) ◽  
pp. 1304-1318 ◽  
Author(s):  
Arthur Smith ◽  
Stephen Fletcher
Keyword(s):  
Fine Structure ◽  
Phase Changes ◽  
Avrami Equation ◽  
Convex Polygons ◽  
Step Method ◽  
Electrode Surfaces ◽  
Instantaneous Nucleation ◽  
Single Nucleus ◽  
Coverage Function ◽  
The Relationship

The fundamental processes underlying phase changes at electrode surfaces are often described in terms of the Kolmogoroff–Avrami theorem.Some aspects of the 'fine structure' of this theorem are considered. Particular attention is paid to the case of two-dimensional nucleation and growth under the influence of an applied electrode potential (equivalent to supersaturation). A probabilistic analysis is presented for circularly-symmetric nuclei which obviates the need for concepts such as 'overlap' between emergent nuclei. The concept of a 'collision front' is introduced which is defined as the line of contact along which neighbouring nuclei collide. It is shown that for instantaneous nucleation (potentiostatic double step method) the extended set of collision fronts constitutes a net composed of irregular convex polygons. The properties of this net are investigated in some detail. In particular, the extent of applicability of the Kolmogoroff–Avrami equation is delineated, the distribution of collisional polygons is calculated, and an approximate treatment for the variance of the surface coverage function is presented. The general approach exposes clearly the relationship between the single nucleus and the multinuclear situations.

Redox Behavior of [H6-nNi38Pt6(CO)48]n-(n= 4−6) Anions:  A Series of Metal Carbonyl Clusters Displaying Electron-Sink Features

1999 ◽  
Vol 38 (16) ◽  
pp. 3721-3724 ◽  
Author(s):  
Fabrizia Fabrizi de Biani ◽  
Cristina Femoni ◽  
Maria Carmela Iapalucci ◽  
Giuliano Longoni ◽  
Piero Zanello ◽  
...  
Keyword(s):  
Metal Carbonyl ◽  
Redox Behavior ◽  
Carbonyl Clusters ◽  
Metal Carbonyl Clusters ◽  
Electron Sink

scholarly journals Chemical synthesis of erythropoietin glycoforms for insights into the relationship between glycosylation pattern and bioactivity

2016 ◽  
Vol 2 (1) ◽  
pp. e1500678 ◽  
Author(s):  
Masumi Murakami ◽  
Tatsuto Kiuchi ◽  
Mika Nishihara ◽  
Katsunari Tezuka ◽  
Ryo Okamoto ◽  
...  
Keyword(s):  
Biological Activity ◽  
Chemical Synthesis ◽  
Glycosylation Pattern ◽  
Chemical Ligation ◽  
Homogeneous Form ◽  
Synthetic Strategy ◽  
Coupling Strategy ◽  
The Relationship

The role of sialyloligosaccharides on the surface of secreted glycoproteins is still unclear because of the difficulty in the preparation of sialylglycoproteins in a homogeneous form. We selected erythropoietin (EPO) as a target molecule and designed an efficient synthetic strategy for the chemical synthesis of a homogeneous form of five EPO glycoforms varying in glycosylation position and the number of human-type biantennary sialyloligosaccharides. A segment coupling strategy performed by native chemical ligation using six peptide segments including glycopeptides yielded homogeneous EPO glycopeptides, and folding experiments of these glycopeptides afforded the correctly folded EPO glycoforms. In an in vivo erythropoiesis assay in mice, all of the EPO glycoforms displayed biological activity, in particular the EPO bearing three sialyloligosaccharides, which exhibited the highest activity. Furthermore, we observed that the hydrophilicity and biological activity of the EPO glycoforms varied depending on the glycosylation pattern. This knowledge will pave the way for the development of homogeneous biologics by chemical synthesis.

High electrocatalytic activity of W18O49 nanowires for cobalt complex and ferrocenium redox mediators

RSC Advances ◽  
2014 ◽  
Vol 4 (79) ◽  
pp. 42190-42196 ◽  
Author(s):  
Huawei Zhou ◽  
Yantao Shi ◽  
Qingshun Dong ◽  
Liang Wang ◽  
Hong Zhang ◽  
...  
Keyword(s):  
Electrocatalytic Activity ◽  
Rational Design ◽  
Catalytic Properties ◽  
Cobalt Complex ◽  
Redox Mediators ◽  
Catalytic Processes ◽  
The Relationship

Understanding the relationship between the surface of electrocatalysts and the catalytic properties of different redox mediators is beneficial to the rational design of efficient catalysts for use in practical catalytic processes.

Electron-Sink Features of Homoleptic Transition-Metal Carbonyl Clusters

2008 ◽  
pp. 1137-1158 ◽  
Author(s):  
Giuliano Longoni ◽  
Cristina Femoni ◽  
Maria Carmela Iapalucci ◽  
Piero Zanello
Keyword(s):  
Transition Metal ◽  
Metal Carbonyl ◽  
Carbonyl Clusters ◽  
Metal Carbonyl Clusters ◽  
Electron Sink

A Brief Review of Transparent Wood: Synthetic Strategy, Functionalization, and Applications

2021 ◽  
Vol 18 ◽  
Author(s):  
Caichao Wan ◽  
Xinyi Liu ◽  
Qiongtao Huang ◽  
Wenjie Cheng ◽  
Jiahui Su ◽  
...  
Keyword(s):  
Renewable Resources ◽  
Building Materials ◽  
Channel Structure ◽  
Wall Structure ◽  
Human Beings ◽  
Environmental Friendliness ◽  
Synthetic Strategy ◽  
Research Activities ◽  
Cellular Wall ◽  
The Relationship

: Severe pressure from energy consumption and serious pollution from non-renewable resources have urged human beings to develop green and energy-efficient materials. Transparent wood, consisting of original wood channel structure filled with resins, has favorable environmental friendliness and high transparency and haze, which holds huge potential in various important fields. Herein, a brief review of the current research activities centering on the development of transparent wood is provided. This review begins with an introduction to the background of transparent wood. Next, the cellular wall structure of wood and the synthetic strategy of transparent wood (including decolorization and impregnation) are summarized. Furthermore, the functionalization of transparent wood through doping nanomaterials or modifying resins is highlighted, and the relationship between the physicochemical properties and the potential uses (like optoelectronics, building materials, and furniture decoration) of transparent wood are clarified. Finally, a brief overview of the prospects and challenges for transparent wood is provided.

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