Search results for "bonding"

Local Bonding Influence on the Band Edge and Band Gap Formation in Quaternary Chalcopyrites

2017

Quaternary chalcopyrites have shown to exhibit tunable band gaps with changing anion composition. Inspired by these observations, the underlying structural and electronic considerations are investigated using a combination of experimentally obtained structural data, molecular orbital considerations, and density functional theory. Within the solid solution Cu2ZnGeS4-x Se x , the anion bond alteration parameter changes, showing larger bond lengths for metal-selenium than for metal-sulfur bonds. The changing bonding interaction directly influences the valence and conduction band edges, which result from antibonding Cu-anion and Ge-anion interactions, respectively. The knowledge of the underlyi…

Conducting Polymers for Ammonia Sensing: Electrodeposition, Hybrid Materials and Heterojunctions

2017

International audience; Polyaniline (PANI) with electrodonating and electrowithdrawing substituents were electrodeposited and studied as sensing materials in resistors and heterojunctions. Whereas the dimethoxyaniline leads to a highly conductive material, the tetrafluoroaniline leads to a poor conducting polymer. However, this latter was used in heterojunctions, associated with a highly conductive material, the lutetium bisphthalocyanine LuPc2. Elsewhere, hybrid materials combining polypyrrole (PPy) with ionic macrocycles as counterions were also electrosynthesized and used as sensing material in resistors, for the detection of ammonia. They exhibit a higher sensitivity compared to PPy pre…

Uranocenium: Synthesis, Structure, and Chemical Bonding

2019

Abstraction of iodide from [(η5 -C5 i Pr5 )2 UI] (1) produced the cationic uranium(III) metallocene [(η5 -C5 i Pr5 )2 U]+ (2) as a salt of [B(C6 F5 )4 ]- . The structure of 2 consists of unsymmetrically bonded cyclopentadienyl ligands and a bending angle of 167.82° at uranium. Analysis of the bonding in 2 showed that the uranium 5f orbitals are strongly split and mixed with the ligand orbitals, thus leading to non-negligible covalent contributions to the bonding. Investigation of the dynamic magnetic properties of 2 revealed that the 5f covalency leads to partially quenched anisotropy and fast magnetic relaxation in zero applied magnetic field. Application of a magnetic field leads to domin…

Isolation of a perfectly linear uranium(II) metallocene

2020

Reduction of the uranium(III) metallocene [(eta(5)-(C5Pr5)-Pr-i)(2)UI] (1) with potassium graphite produces the "second-generation" uranocene [(eta(5)-(C5Pr5)-Pr-i)(2)U] (2), which contains uranium in the formal divalent oxidation state. The geometry of 2 is that of a perfectly linear bis(cyclopentadienyl) sandwich complex, with the ground-state valence electron configuration of uranium(II) revealed by electronic spectroscopy and density functional theory to be 5f(3) 6d(1). Appreciable covalent contributions to the metal-ligand bonds were determined from a computational study of 2, including participation from the uranium 5f and 6d orbitals. Whereas three unpaired electrons in 2 occupy orbi…

DENTIN/ENAMEL BONDING

2010

Atomically Precise Nanocluster Assemblies Encapsulating Plasmonic Gold Nanorods.

2018

The self-assembled structures of atomically precise, ligand-protected noble metal nanoclusters leading to encapsulation of plasmonic gold nanorods (GNRs) is presented. Unlike highly sophisticated DNA nanotechnology, this strategically simple hydrogen bonding-directed self-assembly of nanoclusters leads to octahedral nanocrystals encapsulating GNRs. Specifically, the p-mercaptobenzoic acid (pMBA)-protected atomically precise silver nanocluster, Na4 [Ag44 (pMBA)30 ], and pMBA-functionalized GNRs were used. High-resolution transmission and scanning transmission electron tomographic reconstructions suggest that the geometry of the GNR surface is responsible for directing the assembly of silver …

Programmable assembly of peptide amphiphile via noncovalent-to-covalent bond conversion

2017

Controlling the number of monomers in a supramolecular polymer has been a great challenge in programmable self-assembly of organic molecules. One approach has been to make use of frustrated growth of the supramolecular assembly by tuning the balance of attractive and repulsive intermolecular forces. We report here on the use of covalent bond formation among monomers, compensating for intermolecular electrostatic repulsion, as a mechanism to control the length of a supramolecular nanofiber formed by self-assembly of peptide amphiphiles. Circular dichroism spectroscopy in combination with dynamic light scattering, size-exclusion chromatography, and transmittance electron microscope analyses r…

A coupled plasticity-damage cohesive-frictional interface for low-cycle fatigue analysis

2022

A novel thermodynamically consistent cohesive-frictional model for the analysis of interface degradation and failure under either monotonic quasi-static loading or cyclic loading in low-cycle fatigue problems is proposed. Starting from the definition of a suitable Helmholtz energy density function, a phenomenological interface model is developed in the framework of plasticity and damage mechanics. In particular, a coupled plasticitydamage activation function is defined and employed together the consistent evolution rules to capture the evolution of damage and plasticity under the action of the external loads. Due to the specific features of such threshold and flow rules, the initiation and …

Ionic Transport through Chemically Functionalized Hydrogen Peroxide-Sensitive Asymmetric Nanopores

2015

We describe the fabrication of a chemical-sensitive nanofluidic device based on asymmetric nanopores whose transport characteristics can be modulated upon exposure to hydrogen peroxide (H2O2). We show experimentally and theoretically that the current-voltage curves provide a suitable method to monitor the H2O2-mediated change in pore surface characteristics from the electronic readouts. We demonstrate also that the single pore characteristics can be scaled to the case of a multipore membrane whose electric outputs can be readily controlled. Because H2O2 is an agent significant for medical diagnostics, the results should be useful for sensing nanofluidic devices.

Membrane potential of single asymmetric nanopores: Divalent cations and salt mixtures

2019

We study the electric potential difference (membrane potential) that arises across a single-pore membrane which separates two aqueous solutions at different salt concentrations. This potential difference is obtained here as the reversal potential of a conical nanopore, defined as the applied voltage needed to obtain a zero current through the membrane. To this end, different monovalent (LiCl, NaCl, KCl, and CsCl) and divalent (CaCl2, MgCl2, and BaCl2) cations are considered over a wide range of concentrations and salt mixtures for the two asymmetric nanostructure directionalities. The experimental data allows discussing fundamental questions on the interaction of the charges fixed to the po…