Search results for "Theoretical Chemistry"
showing 10 items of 8456 documents
Modeling of surface vs. bulk ionic conductivity in fixed charge membranes
2003
A two-region model for describing the conductivity of porous fixed charge membranes is proposed. In the surface region, the conductivity is due to the mobile positive ions (counterions) around the negative fixed charges. In the pore center region, the conductive properties resemble those of the external electrolyte solution because the fixed charges are assumed to be effectively neutralized by the counterions in the surface region. Activation energies and surface diffusion coefficients are estimated by assuming that the counterion jump from a fixed charge group is the rate limiting process for surface transport. The barrier energy for this jump is calculated using a simple electrostatic mod…
Precatalyst or dosing-device? The [Pd2{μ-(C6H4) PPh2}2{μ-O2C(C6H5)}2] complex anchored on a carboxypolystyrene polymer as an effective supplier of pa…
2020
Abstract A new catalyst has been synthesized from the precursor [Pd2{μ-(C6H4) PPh2}2 {μ-O2C(C6H5)}2] immobilized on a carboxypolystyrene polymer that exhibits an excellent dispersion of the Pd (II) centers, reusability, and catalytic activity in front of phenyl bromides. The activity of this new material was studied in detail for the Suzuki-Miyaura reaction and compared to that of Pd nanoparticles (NPs) supported on UVM-7 (a mesoporous silica), and Pd NPs stabilized with polyvinylpirrolydone. The homogeneous/heterogeneous character of the catalytic process was determined from the results of the hot-filtration, centrifugation, poisoning, three phases tests, and from differential sensitivity …
A DFT study on the NHC catalysed Michael addition of enols to α,β-unsaturated acyl-azoliums. A base catalysed C–C bond-formation step
2013
The NHC catalysed nucleophilic additions of enols to α,β-unsaturated acyl-azolium intermediates have been investigated using DFT methods at the MPWB1K/6-31G** computational level. In the direct and the conjugate additions, formation of a hydrogen bond (HB) with the carboxyl oxygen is not sufficient to favour the C-C bond formation as a consequence of the low nucleophilic character of enols. Interestingly, when enols form a HB with the chloride counterion, the activation energies associated with the conjugate addition decrease as a consequence of the increased nucleophilic character of enols and the increased electrophilic character of the 'acyl-azolium + Cl' ion pair. Analysis of the DFT re…
Synthesis, characterization and antimicrobial activity of palladium(II) complexes with some alkyl derivates of thiosalicylic acids: Crystal structure…
2012
Abstract S-Alkyl (R = benzyl, methyl, ethyl, propyl and butyl) derivatives of thiosalicylic acid and the corresponding palladium(II) complexes were prepared and their structures were proposed on the basis of infrared, 1H and 13C NMR spectroscopy. The cis geometrical configurations of the isolated complexes were proposed on the basis of an X-ray structural study of the bis(S-benzyl-thiosalicylate)–palladium(II), [Pd(S-bz-thiosal)2] complex. Antimicrobial activity of the tested compounds was evaluated by determining the minimum inhibitory concentration (MIC) and minimum microbicidal concentration (MMC) in relation to 26 species of microorganisms. The tested ligands, with a few exceptions, sho…
Enantioselective transport of amino acid through supported chiral liquid membranes
1993
Abstract Two chiral alcohols, nopol and (2S)-(−)-methyl-1-butanol, immobilized in the pores of a polyethylene film were used for the anantioselective transport of amino acid hydrochloride. The degree of stereoselectivity of the permeation process varied from 0.39 to 1.52 depending on both the type of the chiral membrane phase and the properties of the amino acid. The evaluation of the membrane ability to separate stereoisomers was performed by the step-by-step analysis by considering the effect of amino acids' hydrophobicity, polarity and degree of chirality. For the purpose of this paper, the chirality measure was introduced. It was demonstrated that the enantioselectivity was affected mai…
Stereoselective glycosylation of Alcohols and Silyl Ethers Using Glycosyl Fluorides and Boron Trifluoride Etherate
1985
The stereoselective glycosylation of alcohols and their silyl ethers has been achieved using O-alkyl-, O-acyl-, and acetal-protected glycosyl fluorides of the pyranose and furanose series and boron trifluoride etherate in CH2Cl2.
Structural Characterization of Surfactant-Coated Bimetallic Cobalt/Nickel Nanoclusters by XPS, EXAFS, WAXS, and SAXS
2011
Cobalt nickel bimetallic nanoparticles were synthesized by changing the sequence of the chemical reduction of Co(II) and Ni(II) ions confined in the core of bis(2-ethylhexyl)phosphate (2)., and Ni(DEHP)(2). The reduction was carried out by mixing, sequentially or contemporaneously, fixed amounts of n-heptane solution of Co(DEHP)2 and Ni(DEHP)2 micelles with a solution of sodium borohydride in ethanol at a fixed (reductant)/(total metal) molar ratio. This procedure involves the rapid formation of surfactant-coated nanoparticles, indicated as Co/Ni (Co after Ni), Ni/Co (Ni after Co), and Co + Ni (simultaneous), followed by their slow separation as nanostructures embedded in a sodium bis(2-eth…
Study of the role of sulfur functionalities in humic acids for uranium(VI) complexation
2009
Humic substances influence the speciation and migration behavior of toxic and radiotoxic metal ions, such as actinides, in the environment. Depending on their origin, humic substances contain different amounts of sulfur ranging from 0.1 to 3.6% and 0.5 to 1.43% in soil and aquatic humic substances, respectively [1]. Reduced, intermediately oxidized and highly oxidized sulfur functionalities occur in humic substances [1]. Although sulfur functionalities occur in small concentrations, they can play an important role in the complexation of selected metal ions. Knowledge about the impact of sulfur functionalities on the metal ion complexation by humic substances and their significance compared …
Hydrogen Bonding in Amorphous Alkaline Earth Carbonates
2018
Amorphous intermediates play a crucial role during the crystallization of alkaline earth carbonates. We synthesized amorphous carbonates of magnesium, calcium, strontium, and barium from methanolic solution. The local environment of water and the strength of hydrogen bonding in these hydrated modifications were probed with Fourier transform IR spectroscopy,
The CdCl2 effects on synthetic DNAs encaged in the nanodomains of a cationic water-in-oil microemulsion
2011
The present work is dedicated to the study of the interactions of CdCl(2) with the synthetic polynucleotides polyAT and polyGC confined in the nanoscopic aqueous compartment of the water-in-oil microemulsion CTAB/pentanol/hexane/water, with the goal to mimic in vitro the situation met by the nucleic acids in vivo. In biological structures, in fact, very long strings of nucleic acids are segregated into very small compartments having a radius exceedingly smaller than the length of the encapsulated macromolecule. For comparison, the behaviour of polyGC was also studied in aqueous solutions of matched composition. The conformational and thermal stabilities of both polynucleotides enclosed in t…