Search results for "Chemical engineering"
showing 10 items of 5892 documents
Electrochemical capacitance spectroscopy and capacitive relaxation of the changeover process in iron hexacyanoferrate molecular compound
2010
Abstract In this work it was proposed the use electrochemical capacitance spectroscopy (ECS) to evaluate the storage process during changeover in FeHCF compound. The approach is equivalent to electrochemical impedance spectroscopy (EIS) albeit from such analysis it was possible to focus attention on the capacitive and dielectric relaxation instead of the dispersive relaxation related to charge transfer. From such approach it was possible to obtain complementary information on the role played by [Fe 2+ (CN) 6 ] 4− vacancies during the changeover process. It was observed that Fe 3+ (NC) 5 OH − clusters located in these vacancies mediate an electronic and ionic coupled trapping/detrapping proc…
Effect of cationic polyamidoamine dendrimers on ionic transport through nanochannels
2021
Abstract The effect of polyamidoamine (PAMAM) dendrimers (generations G0–G3) on the ion transport properties of nanochannels (conical and cylindrical) is studied either by surface functionalization or by addition to the electrolyte solution. Surface functionalization with cationic dendrimers lead to inversion of the ion current rectification, indicating the anion selectivity of the modified nanochannels. This anion selectivity increases by immobilizing higher-generation dendrimers, as expected for an increase in the surface density of amino groups. However, compared to PAMAM G2, functionalization with PAMAM G3 results in higher cation and lower anion fluxes. Diffusion experiments of charged…
Adsorbed CO on group 10 metal fragments: A DFT study
2009
DFT calculations on the helicopter and cartwheel rotations of one CO molecule adsorbed at the bridge site on metal-surface fragments, characterized by two (M(8)) or three (M(14)) metal-atom layers (M = Ni, Pd, Pt) were performed by the B3LYP[LANL2DZ+6-31 g(d,p)] method, to rationalize the adsorption energetics and the steric hindrance characteristics of surface CO molecules. Potential Energy Surfaces were obtained, either fixing the C-O bond-length or allowing it to change. The behavior of the three metals, as obtained from the study of the configurational space characterizing the CO adsorption on the fragments was explained on the basis of the interaction energies involved in the different…
Li-ion diffusion in Li_{x}Nb_{9}PO_{25}$
2013
Abstract Wadsley–Roth phase Li x Nb 9 PO 25 has been studied as a potential candidate for anode material of Li-ion batteries. Its crystal structure, which consists of ReO 3 -type blocks of NbO 6 octahedra connected with PO 4 tetrahedra, provides a good stability and performance during Li + insertion/removal. Li-ion chemical diffusion coefficient ( D chem ) in Li x Nb 9 PO 25 was determined by means of potentiostatic intermittent titration technique and electrochemical impedance spectroscopy. Different data treatments (classical Warburg equation or the model of an electrode system with ohmic potential drop and/or slow kinetics of the interfacial Li + ion transfer across the electrode/electro…
Synthesis and Characterization of Fluorescent, Low-Symmetry Triphenylene Discotic Liquid Crystals: Tailoring of Mesomorphic and Optical Properties
1996
A series of monofunctionalized triphenylene-based discotic liquid crystals were synthesized starting from 2-hydroxy-3,6,7,10,11-pentakis(pentyloxy)triphenylene. These compounds are unique in that they possess a single electron-withdrawing group (and consequently a large dipole moment) connected directly to the polyaromatic core. All of the new liquid crystals show a significantly broader range of mesogenicity relative to the parent compound 2,3,6,7,10,11-hexakis(pentyloxy)triphenylene. Moreover, some of the new mesogens exhibit a more ordered mesophase relative to the hexagonal columnar phase (Dh) at lower temperatures. Monofunctionalization of the triphenylene core has a dramatic effect on…
Recent advances in steroidal supramolecular gels
2020
During the last decade or two the interest towards small molecules capable of self-assembly leading to gelation has increased intensively. The investigation of these supramolecular gels aims not only at understanding the fundamental processes underlying gel formation but also at development of new materials with a myriad of applications. Steroids are widely-spread natural products with a large and rigid steroidal nucleus combined with derivatizable functional groups leading to an adjustable polarity profile, which makes them attractive building blocks when designing novel low molecular weight gelators. Due to their unique properties, steroid-based supramolecular gels may find use in applica…
The effect of temperature on the internal dynamics of dansylated POPAM dendrimers
2011
The internal and rotational dynamics of the dansylated poly(propylene amine) dendrimers (POPAM) have been studied by time correlated single photon counting (TCSPC) and molecular dynamics (MD) simulations. The hydrodynamic volumes of the dendrimer generations from G1 to G4 were estimated by fluorescence anisotropy data. Experiments and simulations suggest that the volume and the shape of the dendrimers are temperature dependent. At low temperatures the dendrimer structure becomes more spacious and rigid and back-folding of the individual branches is slowed down. For the G3 and G4 generations the temperature effects are much stronger than for the smaller G1 and G2 generations, where back-fold…
Electrochemical behaviour of poly(neutral red) on an ITO electrode
1998
Abstract The formation of a radical cation, by electrochemical oxidation of the neutral red dye in acidic aqueous solution, is controlled by diffusion towards the electrode surface. This is the initiation step of the electrogeneration, potentiostatic or potentiodynamic, of poly(neutral red) films on an indium–tin oxide (ITO) electrode. The polymeric film is a redox semi-conductor, and shows a microporous membrane-like character. Its electrochemical behaviour depends on the generation process. The hydrogen ions play a double role: first as reactants at electrochemical and acid–base equilibrium, second as counterions of the electrons. The global process of the electron-hopping is limited by t…
Polyaminoacid–doxorubicin prodrug micelles as highly selective therapeutics for targeted cancer therapy
2016
An amphiphilic copolymer carrying high-dose doxorubicin (21% on a weight basis), PHEA–EDA–P,C–Doxo, was prepared by coupling doxorubicin with a biocompatible polyaminoacid through a pH-sensitive spacer. Additional derivatization with 4-pentynoic acid endows it with self-assembling properties by means of π–π stacking. These micelles can be triggered to promptly release drug in lysosomes (∼40% in 12 h) through pH-dependent micelle hydrolysis after uptake. In vitro tests on co-cultures of cancer (MDA-MB 231) and normal (HB-2) breast cells proved that the conjugate was selectively internalized into the former rather than normal cells, exploiting the caveolae-dependent endocytosis pathway, expla…
Understanding the local reactivity in polar organic reactions through electrophilic and nucleophilic Parr functions
2013
[EN] Building upon our recent studies devoted to the bonding changes in polar reactions [RSC Advances, 2012, 2, 1334 and Org. Biomol. Chem., 2012, 10, 3841], we propose herein two new electrophilic, P-k(+), and nucleophilic, P-k(-), Parr functions based on the spin density distribution at the radical anion and at the radical cation of a neutral molecule. These local functions allow for the characterisation of the most electrophilic and nucleophilic centres of molecules, and for the establishment of the regio- and chemoselectivity in polar reactions. The proposed Parr functions are compared with both, the Parr-Yang Fukui functions [J. Am. Chem. Soc. 1984, 106, 4049] based on frontier molecul…