Search results for "solvation"
showing 10 items of 157 documents
Atomistic Simulations of Functional Au_{144}(SR)_{60} Gold Nanoparticles in Aqueous Environment
2012
Charged monolayer-protected gold nanoparticles (AuNPs) have been studied in aqueous solution by performing atomistic molecular dynamics simulations at physiological temperature (310 K). Particular attention has been paid to electrostatic properties that modulate the formation of a complex comprised of the nanoparticle together with surrounding ions and water. We focus on Au-144 nanoparticles that comprise a nearly spherical Au core (diameter similar to 2 nm), a passivating Au-S interface, and functionalized alkanethiol chains. Cationic and anionic AuNPs have been modeled with amine and carboxyl terminal groups and Cl-/Na+ counterions, respectively. The radial distribution functions show tha…
Understanding Noncovalent Interactions of Small Molecules with Carbon Nanotubes
2017
We combine experimental methods, density functional theory (DFT) calculations, and molecular dynamics (MD) simulations in the quantitative analysis of noncovalent interactions between (6,5)-enriched single-walled carbon nanotubes (SWNTs), as hosts, and a set of pyrene derivatives with different electronic properties and surface areas, as guests. The experiments and calculations were carried out in two solvents with markedly different polarities, namely 1,1',2,2'-tetrachloroethane (TCE) and N,N-dimethylformamide (DMF). Our results show that dispersion forces govern the supramolecular association of small molecules with (6,5)-SWNTs, with negligible contributions from ground-state charge-trans…
Modelling small angle neutron scattering data from polymers in supercritical fluids
2000
In this paper we report a SANS investigation of micelle formation by fluorocarbon-hydrocarbon block copolymers in supercritical CO2(scCO2) at 313K. A sharp unimer-micelle transition is obtained due to the tuning of the solvating ability of scCO2 by profiling pressure. At high pressure the copolymer is in a monomeric state with a random coil structure. By lowering the pressure aggregates are formed with the hydrocarbon segments forming the core and the fluorocarbon segments forming the corona of spherical aggregates. This aggregate-unimer transition is driven by the gradual penetration of CO2 molecules toward the core of the aggregate and is critically related to the density of the solvent, …
Spectrophotometric determination of binding constants between some aminocyclodextrins and nitrobenzene derivatives at various pH values
2002
Abstract The inclusion capacity of three modified cyclodextrins—namely mono-(6- N , N -dimethylamino-6-deoxy)- ( 3 ), mono-6-(2-aminoethyl)-amino-6-deoxy- ( 4 ) and mono-6-(2- N , N -dimethylaminoethyl)-amino-6-deoxy- ( 5 ) β-cyclodextrin, with six para -substituted nitrobenzenes ( A – F ) has been investigated at three different pH values. Molecular interactions in inclusion complexes have also been investigated by means of molecular mechanics (MM2/QD) models. The desolvation of the cyclodextrin is the most important factor in determining the binding ability of the various hosts. However, for a given host, electrostatic and van der Waals interactions and the formation of a hydrogen bond be…
Binding properties of mono-(6-deoxy-6-amino)-β-cyclodextrin towards p-nitroaniline derivatives: a polarimetric study
2009
Abstract Polarimetry was used in order to investigate the formation of supramolecular complexes between mono-6-amino-β-cyclodextrin and various p-nitroaniline derivatives at two different pH values. Comparison with the behaviour of native β-cyclodextrin gave us the opportunity to consider the effect exerted by the presence of charged groups, having different solvation requirements, on the binding equilibrium. Data offer some support to the hypothesis of ‘dynamic co-inclusion’ of solvent molecules within the host–guest complex.
Free energy of solvation of solutes and their partition coefficients in methanol-water binary mixtures
2001
A method is presented that permits semiquantitative estimation of the partitioning of any solute between any two media. The method is adapted to the simulation of multicomponent solvents. As an example, the free energies of solvation ΔG solv,aq o in methanol-water binary mixtures and the partition coefficientsP for organic solvent—aqueous solvent were calculated. The organic solvents studied were 1-octanol, cyclohexane and chloroform. Linear relationships were observed between the relative dielectric constant and the volume fraction of methanol in mixtures with water. The four hydrocarbon models studied were hexane, cyclohexane, hexatriene and benzene. The results are in agreement with calc…
Solvation chemistry of water-soluble thiol-protected gold nanocluster Au102 from DOSY NMR spectroscopy and DFT calculations
2014
The hydrodynamic diameter of Aum(pMBA)n [(m, n) = (102, 44) and (144, 60)] clusters in aqueous media was determined via DOSY NMR spectroscopy. The apparent size of the same (n, m) cluster depends on the counter ion of the deprotonated pMBA− ligand as explained by the competing ion-pair strength and hydrogen bonding interactions studied in DFT calculations. The choice of the counter ion affects the surface chemistry and molecular structure at the organic/water interface, which is relevant for biological applications.
Photoiodocarboxylation of Activated C═C Double Bonds with CO2 and Lithium Iodide
2018
The photolysis at 254 nm of lithium iodide and olefins 1 carrying an electron-withdrawing Z-substituent in CO2-saturated (1 bar) anhydrous acetonitrile at room temperature produces the atom efficient and transition metal-free photoiodocarboxylation of the C═C double bond. The reaction proceeds well for terminal olefins 1 to form the new C-I and C-C σ-bonds at the α and β-positions of the Z-substituent, respectively, and is strongly inhibited by polar protic solvents or additives. The experimental results suggest that the reaction channels through the radical anion [CO2•-] in acetonitrile, yet involves different intermediates in aqueous medium. The stabilizing ion-quadrupole and electron don…
Equilibrium swelling and solvation studies on crosslinked polyacrylamides
2004
Polyacrylamide (PA) crosslinked with four different crosslinking agents, triethyleneglycol dimethacrylate (TEGDMA), N,N′-methylene bisacrylamide (NNMBA), hexanediol dimethacrylate (HDDMA) and divinylbenzene (DVB), with mole percents ranging from 5 to 20, was prepared by solution polymerization and subjected to swelling and solvation studies. Solubility parameters and cohesive energy density were determined from swelling studies. Molecular weight between crosslinks for these systems were determined by Flory–Rehner analysis. There is a discontinuous volume change for 10% NNMBA and HDDMA crosslinked PA, 15% TEGDMA crosslinked PA and 10 and 15% DVB crosslinked PA in solvent mixtures of acetic a…
A procedure for predicting sorption equilibrium in ternary polymer systems from Flory–Huggins binary interaction parameters and the inversion point o…
1989
A procedure has been developed, based on the Flory–Huggins theory as generalized by Pouchlý, which permits the calculation of preferential (λ) and total (Y) sorption coefficients from previous information on the binary interaction parameters, χ, χ, and g12(ϕ10) and on the mixture composition at which the sign of λ inverts. The expressions obtained were applied to 10 cosolvent polymer systems for which experimental values of λ and Y are known. Practically in all the studied systems, the theoretical predictions are in fair accordance with the experimental data.