scholarly journals Substructural Approach for Assessing the Stability of Higher Fullerenes

2021 ◽  
Vol 22 (7) ◽  
pp. 3760
Author(s):  
Ayrat R. Khamatgalimov ◽  
Valeri I. Kovalenko
Keyword(s):  
Electronic Structure ◽  
Detailed Analysis ◽  
Fullerene Molecule ◽  
Structural Features ◽  
Higher Fullerenes ◽  
Substructure Approach ◽  
The Stability

This review describes the most significant published results devoted to the study of the nature of the higher fullerenes stability, revealing of correlations between the structural features of higher fullerene molecules and the possibility of their producing. A formalization of the substructure approach to assessing the stability of higher fullerenes is proposed, which is based on a detailed analysis of the main structural features of fullerene molecules. The developed substructure approach, together with the stability of the substructures constituting the fullerene molecule, helps to understand deeper the features of the electronic structure of fullerenes.

Performance of Electronic Structure Methods for the Description of Hückel-Möbius Interconversions in Extended π-Systems

2019 ◽  
Author(s):  
Tatiana Woller ◽  
Ambar Banerjee ◽  
Nitai Sylvetsky ◽  
Xavier Deraet ◽  
Frank De Proft ◽  
...  
Keyword(s):  
Electronic Structure ◽  
Basis Set ◽  
Dft Methods ◽  
Molecular Switching ◽  
Wide Range ◽  
Electronic Structure Methods ◽  
Explicitly Correlated ◽  
Relative Errors ◽  
The Stability ◽  
Basis Set Expansion

<p>Expanded porphyrins provide a versatile route to molecular switching devices due to their ability to shift between several π-conjugation topologies encoding distinct properties. Taking into account its size and huge conformational flexibility, DFT remains the workhorse for modeling such extended macrocycles. Nevertheless, the stability of Hückel and Möbius conformers depends on a complex interplay of different factors, such as hydrogen bonding, p···p stacking, steric effects, ring strain and electron delocalization. As a consequence, the selection of an exchange-correlation functional for describing the energy profile of topological switches is very difficult. For these reasons, we have examined the performance of a variety of wavefunction methods and density functionals for describing the thermochemistry and kinetics of topology interconversions across a wide range of macrocycles. Especially for hexa- and heptaphyrins, the Möbius structures have a pronouncedly stronger degree of static correlation than the Hückel and figure-eight structures, and as a result the relative energies of singly-twisted structures are a challenging test for electronic structure methods. Comparison of limited orbital space full CI calculations with CCSD(T) calculations within the same active spaces shows that post-CCSD(T) correlation contributions to relative energies are very minor. At the same time, relative energies are weakly sensitive to further basis set expansion, as proven by the minor energy differences between MP2/cc-pVDZ and explicitly correlated MP2-F12/cc-pVDZ-F12 calculations. Hence, our CCSD(T) reference values are reasonably well-converged in both 1-particle and n-particle spaces. While conventional MP2 and MP3 yield very poor results, SCS-MP2 and particularly SOS-MP2 and SCS-MP3 agree to better than 1 kcal mol<sup>-1</sup> with the CCSD(T) relative energies. Regarding DFT methods, only M06-2X provides relative errors close to chemical accuracy with a RMSD of 1.2 kcal mol<sup>-1</sup>. While the original DSD-PBEP86 double hybrid performs fairly poorly for these extended p-systems, the errors drop down to 2 kcal mol<sup>-1</sup> for the revised revDSD-PBEP86-NL, again showing that same-spin MP2-like correlation has a detrimental impact on performance like the SOS-MP2 results. </p>

Structurally-modified subphthalocyanines: molecular design towards realization of expected properties from the electronic structure and structural features of subphthalocyanine

2014 ◽  
Vol 50 (53) ◽  
pp. 6949-6966 ◽  
Author(s):  
Soji Shimizu ◽  
Nagao Kobayashi
Keyword(s):  
Electronic Structure ◽  
Molecular Design ◽  
Structural Features ◽  
Feature Article ◽  
System 2

This feature article summarizes recent contributions of the authors in the synthesis of structurally-modified subphthalocyanines, which covers (1) modification of the conjugated system, (2) core-modification, and (3) exterior-modification.

FABRICATION OF NANOPOROUS CHITOSAN MEMBRANES

NANO ◽  
2010 ◽  
Vol 05 (01) ◽  
pp. 53-60 ◽  
Author(s):  
XIAOLIANG WANG ◽  
XIANG LI ◽  
ELEANOR STRIDE ◽  
MOHAN EDIRISINGHE
Keyword(s):  
Low Frequency ◽  
Drug Carriers ◽  
Structural Features ◽  
Wound Dressings ◽  
Ftir Analysis ◽  
Tissue Engineering Scaffolds ◽  
Nanoscale Structures ◽  
Low Frequency Ultrasound ◽  
Chitosan Membranes ◽  
The Stability

Naturally derived biopolymers have been widely used for biomedical applications such as drug carriers, wound dressings, and tissue engineering scaffolds. Chitosan is a typical polysaccharide of great interest due to its biocompatibility and film-formability. Chitosan membranes with controllable porous structures also have significant potential in membrane chromatography. Thus, the processing of membranes with porous nanoscale structures is of great importance, but it is also challenging and this has limited the application of these membranes to date. In this study, with the aid of a carefully selected surfactant, polyethyleneglycol stearate-40, chitosan membranes with a well controlled nanoscale structure were successfully prepared. Additional control over the membrane structure was obtained by exposing the suspension to high intensity, low frequency ultrasound. It was found that the concentration of chitosan/surfactant ratio and the ultrasound exposure conditions affect the structural features of the membranes. The stability of nanopores in the membrane was improved by intensive ultrasonication. Furthermore, the stability of the blended suspensions and the intermolecular interactions between chitosan and the surfactant were investigated using scanning electron microscope and Fourier transform infrared spectroscopy (FTIR) analysis, respectively. Hydrogen bonds and possible reaction sites for molecular interactions in the two polymers were also confirmed by FTIR analysis.

Can boron form coordination complexes with diffuse electrons? Evidence for linked solvated electron precursors

2022 ◽  
Author(s):  
Zachary Jordan ◽  
Shahriar N. Khan ◽  
Benjamin A. Jackson ◽  
Evangelos Miliordos
Keyword(s):  
Electronic Structure ◽  
Density Functional ◽  
Molecular System ◽  
Hydrocarbon Chain ◽  
Solvated Electron ◽  
Excitation Energies ◽  
Functional Theory ◽  
Boron Complexes ◽  
The Stability ◽  
First Time

Abstract Density functional theory and ab initio multi-reference calculations are performed to examine the stability and electronic structure of boron complexes that host diffuse electrons in their periphery. Such complexes (solvated electron precursors or SEPs) have been experimentally identified and studied theoretically for several s- and d-block metals. For the first time, we demonstrate that a p-block metalloid element can form a stable SEP when appropriate ligands are chosen. We show that three ammonia and one methyl ligands can displace two of the three boron valence electrons to a peripheral 1s-type orbital. The shell model for these outer electrons is identical to previous SEP systems (1s, 1p, 1d, 2s). Further, we preformed the first examination of a molecular system consisting of two SEPs bridged by a hydrocarbon chain. The electronic structure of these dimers is very similar to that of traditional diatomic molecules forming bonding and anti-bonding σ and π orbitals. Their ground state electronic structure resembles that of two He atoms, and our results indicate that the excitation energies are nearly independent of the chain length for four carbon atoms or longer. These findings pave the way for the development of novel materials similar to expanded metals and electrides.

scholarly journals Surface-Tension-Confined Channel with Biomimetic Microstructures for Unidirectional Liquid Spreading

Micromachines ◽  
2020 ◽  
Vol 11 (11) ◽  
pp. 978
Author(s):  
Yi Zhang ◽  
Yang Gan ◽  
Liwen Zhang ◽  
Deyuan Zhang ◽  
Huawei Chen
Keyword(s):  
Surface Tension ◽  
Underlying Mechanism ◽  
Structural Features ◽  
Liquid Motion ◽  
Water Separation ◽  
Lab On Chip ◽  
Liquid Spreading ◽  
Oil Water Separation ◽  
On Chip ◽  
The Stability

Unidirectional liquid spreading without energy input is of significant interest for the broad applications in diverse fields such as water harvesting, drop transfer, oil–water separation and microfluidic devices. However, the controllability of liquid motion and the simplification of manufacturing process remain challenges. Inspired by the peristome of Nepenthes alata, a surface-tension-confined (STC) channel with biomimetic microcavities was fabricated facilely through UV exposure photolithography and partial plasma treatment. Perfect asymmetric liquid spreading was achieved by combination of microcavities and hydrophobic boundary, and the stability of pinning effect was demonstrated. The influences of structural features of microcavities on both liquid spreading and liquid pinning were investigated and the underlying mechanism was revealed. We also demonstrated the spontaneous unidirectional transport of liquid in 3D space and on tilting slope. In addition, through changing pits arrangement and wettability pattern, complex liquid motion paths and microreactors were realized. This work will open a new way for liquid manipulation and lab-on-chip applications.

Crystallographic analysis and biochemical applications of a novel penicillin-binding protein/β-lactamase homologue from a metagenomic library

2014 ◽  
Vol 70 (9) ◽  
pp. 2455-2466 ◽  
Author(s):  
Tri Duc Ngo ◽  
Bum Han Ryu ◽  
Hansol Ju ◽  
Eun Jin Jang ◽  
Kyeong Kyu Kim ◽  
...  
Keyword(s):  
Metagenomic Library ◽  
Structural Features ◽  
Crystallographic Analysis ◽  
Penicillin Binding Protein ◽  
Hydrophobic Residues ◽  
Penicillin Binding Proteins ◽  
Hydrophobic Compounds ◽  
Nitrophenyl Phosphate ◽  
Biophysical Studies ◽  
The Stability

Interest in penicillin-binding proteins and β-lactamases (the PBP-βL family) is increasing owing to their biological and clinical significance. In this study, the crystal structure of Est-Y29, a metagenomic homologue of the PBP-βL family, was determined at 1.7 Å resolution. In addition, complex structures of Est-Y29 with 4-nitrophenyl phosphate (4NP) and with diethyl phosphonate (DEP) at 2.0 Å resolution were also elucidated. Structural analyses showed that Est-Y29 is composed of two domains: a β-lactamase fold and an insertion domain. A deep hydrophobic patch between these domains defines a wide active site, and a nucleophilic serine (Ser58) residue is located in a groove defined primarily by hydrophobic residues between the two domains. In addition, three hydrophobic motifs, which make up the substrate-binding site, allow this enzyme to hydrolyze a wide variety of hydrophobic compounds, including fish and olive oils. Furthermore, cross-linked Est-Y29 aggregates (CLEA-Est-Y29) significantly increase the stability of the enzyme as well as its potential for extensive reuse in various deactivating conditions. The structural features of Est-Y29, together with biochemical and biophysical studies, could provide a molecular basis for understanding the properties and regulatory mechanisms of the PBP-βL family and their potential for use in industrial biocatalysts.

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