Molecular fragments and the hybrid basis

A method of performing ab initio calculations of the electronic structure of fragments within a larger molecule is reported. The method uses the self-consistent group formalism of McWeeny together with the systematic use of a hybrid atomic orbital basis. The mutual compatibility of these two ideas is stressed and results are given for model calculations on fragments in saturated hydrocarbon chains and rings. © 1996 John Wiley & Sons, Inc.     

On the hamiltonicity of a planar graph and its vertex-deleted subgraphs

Tutte proved that every planar 4-connected graph is hamiltonian. Thomassen showed that the same conclusion holds for the superclass of planar graphs with minimum degree at least 4 in which all vertex-deleted subgraphs are hamiltonian. We here prove that if in a planar $n$-vertex graph with minimum degree at least 4 at least $n-5$ vertex-deleted subgraphs are hamiltonian, then the graph contains two hamiltonian cycles, but that for every there exists a nonhamiltonian polyhedral $n$-vertex graph with minimum degree at least 4 containing $cn$ hamiltonian vertex-deleted subgraphs. Furthermore, we study the hamiltonicity of planar triangulations and their vertex-deleted subgraphs as well as Bondy's meta-conjecture, and prove that a polyhedral graph with minimum degree at least 4 in which all vertex-deleted subgraphs are traceable, must itself be traceable.     

Side-Chain Chemistry Governs Hierarchical Order of Charge-Complementary β-sheet Peptide Coassemblies

Self-assembly of proteinaceous biomolecules into functional materials with ordered structures that span length scales is common in nature yet remains a challenge with designer peptides under ambient conditions. This report demonstrates how charged side-chain chemistry affects the hierarchical co-assembly of a family of charge-complementary β-sheet-forming peptide pairs known as CATCH(X+/Y−) at physiologic pH and ionic strength in water. In a concentration-dependent manner, the CATCH(6K+) (Ac-KQKFKFKFKQK-Am) and CATCH(6D−) (Ac-DQDFDFDFDQD-Am) pair formed either β-sheet-rich microspheres or β-sheet-rich gels with a micron-scale plate-like morphology, which were not observed with other CATCH(X+/Y−) pairs. This hierarchical order was disrupted by replacing D with E, which increased fibril twisting. Replacing K with R, or mutating the N- and C-terminal amino acids in CATCH(6K+) and CATCH(6D−) to Qs, increased observed co-assembly kinetics, which also disrupted hierarchical order. Due to the ambient assembly conditions, active CATCH(6K+)-green fluorescent protein fusions could be incorporated into the β-sheet plates and microspheres formed by the CATCH(6K+/6D−) pair, demonstrating the potential to endow functionality.     

Conformational analysis of siloxane-based enzyme-mimic precursors[1]

The conformational flexibility of six hybrid organodisiloxane oligomers were studied using the Low Mode-Monte Carlo conformational search method with the MM2* force field and the Generalized Born/Surface Area continuum solvent model for water. These systems have enzyme-like properties as synthetic acyltransferases and contain aminopyridine groups in various states of protonation. An ensemble of low energy structures was generated and used to investigate the dependence of molecular shape and flexibility on protonation, which plays an important role in catalyst solubility and self-association. The results as measured by the number of unique conformations, end-to-end or longest intramolecular distance and radius of gyration of the conformational point cloud indicate that the number of protonated pyridines plays a significant role in the overall molecular shape. A similar study was also carried out on various POSS-substitutive organodisiloxane oligomers.     

Eco-friendly Synthesis of Silver Nanoparticles and its Application in Hydrogen Photogeneration and Nanoplasmonic Biosensing

Environmentally friendly methods for silver nanoparticles (AgNPs) synthesis without the use of hazardous chemicals have recently drawn attention. In this work, AgNPs have been synthesized by microwave irradiation using only honey solutions or aqueous fresh pink radish extracts. The concentrations of honey, radish extract, AgNO₃ and pH were varied. AgNPs presented mean sizes between 7.0 and 12.8 nm and were stable up to 120 days. The AgNPs were employed as co-catalyst (TiO₂@AgNPs) to increase the hydrogen photogeneration under UV-vis and only visible light irradiation, when compared to pristine TiO₂ NPs. The prepared photocatalyst also showed hydrogen generation under visible light. Additionally, AgNPs were used to assemble a nanoplasmonic biosensor for the biodetection of extremely low concentrations of streptavidin, owing to its specific binding to biotin. It is shown here that green AgNPs are versatile nanomaterials, thus being potential candidates for hydrogen photogeneration and biosensing applications.     

High-Throughput Optimization of Photochemical Reactions using Segmented-Flow Nanoelectrospray-Ionization Mass Spectrometry**

Within the realm of drug discovery, high-throughput experimentation techniques enable the rapid optimization of reactions and expedited generation of drug compound libraries for biological and pharmacokinetic evaluation. Herein we report the development of a segmented flow mass spectrometry-based platform to enable the rapid exploration of photoredox reactions for early-stage drug discovery. Specifically, microwell plate-based photochemical reaction screens were reformatted to segmented flow format to enable delivery to nanoelectrospray ionization-mass spectrometry analysis. This approach was demonstrated for the late-stage modification of complex drug scaffolds, as well as the subsequent structure–activity relationship evaluation of synthesized analogs. This technology is anticipated to expand the robust capabilities of photoredox catalysis in drug discovery by enabling high-throughput library diversification.