On the symmetry and topology of plasmonic eigenmodes in heptamer and hexamer nanocavities

Plasmonics is expected to play a key role in nanotechnology, leading to intriguing routes in many engineering and biological applications. Recently, it has been realized that toroidal resonances could be an alternative to electric and magnetic resonances, which have governed the innovation of plasmonic applications so far. In a previous contribution, we proved the existence of toroidal moments in an oligomeric void-plasmonic structure [1]. In this article, we investigate the role of topology and symmetry in decomposing the various dipolar, quadrupolar, and toroidal moments, using energy-filtering transmission electron microscopy supported by three-dimensional finite-difference time-domain method simulations. The consequences of changing the topology on the toroidal character are discussed by comparing results obtained from nanoholes forming heptamer and hexamer nanocavity systems that were drilled into a thin silver film.     

Explicit solutions of nonlinear wave equation systems

We apply the (G’/G)-expansion method to solve two systems of nonlinear differential equations and construct traveling wave solutions expressed in terms of hyperbolic functions, trigonometric functions, and rational functions with arbitrary parameters. We highlight the power of the (G’/G)-expansion method in providing generalized solitary wave solutions of different physical structures. It is shown that the (G’/G)-expansion method is very effective and provides a powerful mathematical tool to solve nonlinear differential equation systems in mathematical physics.     

Selectivity in the aggregates of the chiral organolithium N-Boc-2-lithiopiperidine with a chiral ligand: a DFT study

In this paper the aggregates of the chiral organolithium N-Boc-2-lithiopiperidine [Boc=CO₂C(CH₃)₃], which play an important role in the formation of chiral 2-substituted piperidines found in many alkaloid structures and medicinal compounds, have been investigated within the framework of Density Functional Theory (DFT) calculations. In the complex structures, the lithium atoms are tetra-coordinated, the diaminoalkoxide ligand is tridentate to one lithium atom and forms a chelate with the substrate which is stabilized by the solvent diethyl ether. The same type of bonding was observed for all the different ligand-bound structures; for ligands 6 and 7, which have bulky substituents, selectivity was in agreement with experiment. The results shed light on the microscopic structures of these species and suggest a potential ligand, 11, to yield high enantioselectivity.     

Iron(III) complex of a tridentate <Emphasis Type="Italic">NNN</Emphasis> type ligand: synthesis,X-ray structure,thermal analysis and voltammetric studies

A mononuclear iron(III) complex with 2,6-bis(3,4,5-trimethyl-N-pyrazolyl)pyridine (btmpp) has been synthesized, and characterized by X-ray crystallography, IR, UV–Vis and TGA–DTA methods. The Fe(III/II) couple was characterized by way of cyclic voltammetry using DMF solvent, where the complex was observed to have an irreversible behaviour.     

Allele-specific genotyping by using guanine and gold electrochemical oxidation signals

Electrochemical DNA biosensors have become strong candidates for DNA based analysis. Allele-specific genotyping is also one of the important research areas, where electrochemical approaches provide promising advances. Recently reported two methods based on electrochemical guanine and colloidal gold (Au) nanoparticle oxidation signals are reviewed and compared with the existing genotyping methods in this report.     

Exploiting the right side of the Ramachandran plot: substitution of glycines by D-alanine can significantly increase protein stability

A major goal of protein engineering is the enhancement of protein stability. Here we demonstrate a rational method for enhancing the stability of globular proteins by targeting glycine residues which adopt conformations with Phi > 0. Replacement of such a glycine by d-alanine can lead to a significant increase in stability. The approach is tested at three sites in two model proteins. NMR and CD indicated that the substitutions do not alter the structure. Replacement of glycine-24 of the N-terminal domain of L9 (NTL9) with d-Ala results in an increase in stability of 1.3 kcal mol-1, while replacement of glycine-34 of NTL9 leads to an increase of 1.9 kcal mol-1. Replacement of glycine-331 of the UBA domain with d-Ala leads to an increase in stability of 0.6 kcal mol-1.     

Highly Selective and Sensitive Voltammetric Sensor Based on Ruthenium Nanoparticle Anchored Calix[4]amidocrown‐5 Functionalized Reduced Graphene Oxide: Simultaneous Determination of Quercetin,Morin and Rutin in Grape Wine

In this report, ruthenium nanoparticles (RuNPs) and calix[4]amidocrown‐5 (C4A5) were synthesized and grafted onto the surface of reduced graphene oxide (RGO) nanocomposite (RuNPs/C4A5/RGO). The morphologies of the nanocomposites were characterized by transmission electron microscope, scanning electron microscope, atomic force microscope, electrochemical impedance spectroscopy and x‐ray photoelectron spectroscopy. The electrochemical experiments were performed by cyclic voltammetry, electrochemical impedance spectroscopy and square wave voltammetry. The simultaneous determination of quercetin, rutin and morin was performed on glassy carbon electrode modified with RuNPs/C4A5/RGO (RuNPs/C4A5/RGO/GCE). The linearity ranges and the detection limits of QR, RT and MR were 1.0×10^?10–1.0×10^?8 M and 2.0×10^?11 M respectively.     

Triethylamin-mediated addition of 2-aminoethanethiol hydrochloride to chalcones: Synthesis of 3-(2-aminoethylthio)-1-(aryl)-3-(thiophen-2-yl) propan-1-ones and 5,7-diaryl-2,3,6, 7-tetrahydro-1,4-thiazepines

The triethylamin-mediated addition of 2-aminoethanethiol hydrochloride to chalcone analogs was investigated. This addition, bearing a 2-thienyl group at the 3-position, gave the only addition adduct at room temperature in 3 h, whereas the chalcones bearing the 2-furyl group at the 1-position gave an addition-cyclization product (1, 4-thiazepine) in the same conditions. The effect of the groups to the reaction was investigated by changing the 1- and 3-position groups. The chalcones bearing the 2-thienyl group at the 1-position and the others afforded the mixture of products in different ratio at rt for 0.5–24 h. Moreover, the addition–cyclization products (1,4-thiazepine) were obtained under reflux conditions in 36 h. The structures of the synthesized compounds were elucidated by ¹H NMR, ¹³C NMR, infrared, and elemental analysis.     

Effect of trace metals on reactive crystallization of gypsum

The effect of Fe²⁺, Fe³⁺, and Cr³⁺ ions on crystallization of calcium sulfate dihydrate (gypsum) produced by the reaction between calcium hydroxide suspension and sulphuric acid solution was investigated at 3.5 pH and 65°C in the absence and presence of 2500 ppm citric acid concentration. Crystal size distributions, filtration rates, and morphology of gypsum were determined and discussed as a function of ion concentration. Average particle size of gypsum was not affected significantly by the presence of Fe²⁺, Fe³⁺, and Cr³⁺ ions individually. Variation of gypsum morphology depending on ion concentration affected the filtration characteristics. The presence of Fe³⁺ or Cr³⁺ ions besides 2500 ppm citric acid influenced both average particle size and filtration characteristics. The effect of citric acid on gypsum morphology was suppressed at high Fe³⁺ and Cr³⁺ ion concentrations. The change of morphology is related to the complex formation between Fe³⁺ or Cr³⁺ ions and citric acid at high ion concentrations. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Tailoring Electrochemical CO2 Reduction on Copper by Reactive Ionic Liquid and Native Hydrogen Bond Donors

Electrochemical CO₂ reduction (CO₂RR) on copper (Cu) shows promise for higher-value products beyond CO. However, challenges such as the limited CO₂ solubility, high overpotentials, and the competing hydrogen evolution reaction (HER) in aqueous electrolytes hinder the practical realization. We propose a functionalized ionic liquid (IL) which generates ion-CO₂ adducts and a hydrogen bond donor (HBD) upon CO₂ absorption to modulate CO₂RR on Cu in a non-aqueous electrolyte. As revealed by transient voltammetry, electrochemical impedance spectroscopy (EIS), and in situ surface-enhanced Raman spectroscopy (SERS) complemented with image charge augmented quantum-mechanical/molecular mechanics (IC-QM/MM) computations, a unique microenvironment is constructed. In this microenvironment, the catalytic activity is primarily governed by the IL and HBD concentrations; former controlling the double layer thickness and the latter modulating the local proton availability. This translates to ample CO₂ availability, reduced overpotential, and suppressed HER where C₄ products are obtained. This study deepens the understanding of electrolyte effects in CO₂RR and the role of IL ions towards electrocatalytic microenvironment design.