Search results for "SOLVENT"
showing 10 items of 1395 documents
Frozen or dynamic? : An atomistic simulation perspective on the timescales of electrochemical reactions
2023
Electrochemical systems span a wide range of timescales, and several recent works have put forth the idea that the reaction environment should remain frozen and out of equilibrium during electrochemical electron or proton transfer reactions. Furthermore, simplified treatments of the electrochemical interface model the solvent and ions as frozen molecules. However, the claims and practices of a frozen environment strongly clash with most theoretical and simulation approaches developed to study electrochemical reaction rates. It has also been suggested that the electrode potential should not be fixed when simulating reaction rates due to conductivity limitations, which indicates constant pote…
Combined Use of Structure Analysis, Studies of Molecular Association in Solution, and Molecular Modelling to Understand the Different Propensities of…
2021
The arrangement of hydroxyl groups in the benzene ring has a significant effect on the propensity of dihydroxybenzoic acids (diOHBAs) to form different solid phases when crystallized from solution. All six diOHBAs were categorized into distinctive groups according to the solid phases obtained when crystallized from selected solvents. A combined study using crystal structure and molecule electrostatic potential surface analysis, as well as an exploration of molecular association in solution using spectroscopic methods and molecular dynamics simulations were used to determine the possible mechanism of how the location of the phenolic hydroxyl groups affect the diversity of solid phases formed…
Effect of different processing techniques and presence of antioxidant on the chitosan film performance
2022
In the last two decades, the naturally occurring polysaccharides have gained great attention because of their potential applications in different sectors, for example, from food to biomedical sectors. Chitosan is a cationic polysaccharide with good transparency, and currently, it has been considered also as suitable material for the formulation film and coating in cultural heritage protection. In this work, the chitosan films (Ch), with and without natural antioxidant such as citric acid (CA), are formulated considering two different processing techniques: (i) conventional solvent casting and (ii) compression molding, that is an unconventional method for this polysaccharide, giving the poss…
Chasing Weak Forces: Hierarchically Assembled Helicates as a Probe for the Evaluation of the Energetics of Weak Interactions.
2017
London dispersion forces are the weakest interactions between molecules. Because of this, their influence on chemical processes is often low, but can definitely not be ignored, and even becomes important in cases of molecules with large contact surfaces. Hierarchically assembled dinuclear titanium(IV) helicates represent a rare example in which the direct observation of London dispersion forces is possible in solution even in the presence of strong cohesive solvent effects. Hereby, the dispersion forces do not unlimitedly support the formation of the dimeric complexes. Although they have some favorable enthalpic contribution to the dimerization of the monomeric complex units, large flexible…
Substituent effects on the mechanism changeover in a multipathway reaction: A model for the behavior of biological systems?
2009
By studying the rearrangement in dioxane/water of a series of (Z)-arylhydrazones of 5-amino-3- benzoyl-1,2,4-oxadiazole (1a-k) into the relevant (2-aryl-5-phenyl-2H-1,2,3-triazol-4-yl)ureas (2a-k) in a wide range of pS + (an operational scale of proton concentration in the mixed solvent used; dioxane/water, 1:1, v:v), the occurrence of three different reaction pathways (specific-acid- catalyzed, uncatalyzed, and general-base-catalyzed) for the relevant SNi process has been recently enlightened. The significantly different substituent effects on the three pathways cause some crossovers in the log kA,R versus pS + plots. Both the pS + value at which the crossover occurs and the width of the u…
Polaroid-Type Operators
2018
In this chapter we introduce the classes of polaroid-type operators, i.e., those operators T ∈ L(X) for which the isolated points of the spectrum σ(T) are poles of the resolvent, or the isolated points of the approximate point spectrum σap(T) are left poles of the resolvent. We also consider the class of all hereditarily polaroid operators, i.e., those operators T ∈ L(X) for which all the restrictions to closed invariant subspaces are polaroid. The class of polaroid operators, as well as the class of hereditarily polaroid operators, is very large. We shall see that every generalized scalar operator is hereditarily polaroid, and this implies that many classes of operators acting on Hilbert s…
A route to simple nonionic surfactants
2016
AbstractA method for the synthesis of nonionic surfactants – N-alkyl-O-(2-hydroxyethyl) carbamates is proposed by acylation of fatty amines with ethylene carbonate without any solvent or catalyst. The surface tension of the prepared surfactants was measured, toxicity and biodegradability were determined for the surfactant with n-dodecyl as a hydrophobic group and N-monosubstituted amide and hydroxyl groups for their hydrophilic part.
Fluorinated heterocyclic compounds: an assay on the photochemistry of some fluorinated 1-oxa-2-azoles: an expedient route to fluorinated heterocycles
2004
Abstract Photoinduced heterocyclic rearrangements of ON bond-containing azoles have been claimed in the synthesis of target fluorinated heterocyclic compounds. In this context, the photochemical behavior of some fluorinated 1,2,4-oxadiazoles has been investigated. Irradiations of 3-amino-5-perfluoroalkyl-1,2,4-oxadiazoles at λ =313 nm in methanol gave open-chain products arising from a reaction of the nucleophilic solvent with either the first formed ring-photolytic species or with a nitrilimine moiety generated from it. Differently, irradiations in methanol with the presence of triethylamine (TEA) followed competing phototransposition pathways leading to the ring-isomers 2-amino-5-perfluo…
New Insights into Segmental Packing, Chain Dynamics and Thermomechanical Performance of Aliphatic Polyurea Composites: Comparison between Silica Oxid…
2021
Polyurea (PU) is intrinsically reinforced by its microphase-separated morphology, giving its excellent mechanical properties. In this study, it is shown how a high-index PU formulation applies easy diffusion of hard segments into the soft phase of the PU matrix and tune its chain mobility. Moreover, the interaction of micro (>100 nm), nano (<100 nm) fillers with the microdomains and their thermomechanical properties are unraveled. Herein, nanosilica oxide (NS) and micro titanium (III) oxide (Ti2O3) are incorporated at low loadings into a solvent-free two-component aliphatic PU via insitu polymerization. While NS achieves an interfacial interaction with urea groups and forms a tight ha…