Search results for "counterion"
showing 10 items of 138 documents
Electronic Perspective on the Electrochemistry of Prussian Blue Films
2009
The derivative of the voltabsommetric scans, together with previous nano-electrogravimetric and X-ray diffraction results, allow different electrochemical processes to be distinguished during the Prussian blue (PB) voltammetric scan. Potassium, proton, and hydrated proton counterions involved in PB electrochemistry are related here to the electrochemical reactions of specific Fe sites. Potassium counterions show two different sites for their insertion: one located in the crystalline framework and another in ferrocyanide vacancies. From the monitoring of electroactive Fe sites, the covalent-exchange model is suggested as one of the first approaches to explain the origin of the PB magnetic or…
Multivalent ion-exchange model of biopolymer chromatography for mass overload conditions
1991
Abstract The simple model of multivalent ion-exchange biopolymer chromatography is analyzed on the basis of classical quasi-chemical temperature. The rigorous isotherm equation deduced from the stoichiometric displacement model (SDM) was used to stimulate the migration of a solute through the chromatographic column in the isocratic and gradient elution modes. The peak profiles generated for various sample sizes were compared with those obtained on the basis of a Langmuir isotherm. Peak tailing increases with the value of the exponent Z, defined as the ratio of the protein valency to the displacing counter-ion valency. For large Z the asymmetries due to the non-linearity of the isotherm are …
Counterion-mediated attraction and kinks on loops of semiflexible polyelectrolyte bundles.
2006
The formation of kinks in a loop of bundled polyelectrolyte filaments is analyzed in terms of the thermal fluctuations of charge density due to polyvalent counterions adsorbed on the polyelectrolyte filaments. It is found that the counterion-mediated attraction energy of filaments depends on their bending. By consideration of curvature elasticity energy and counterion-mediated attraction between polyelectrolyte filaments, the characteristic width of the kink and the number of kinks per loop is found to be in reasonable agreement with existing experimental data for rings of bundled actin filaments.
‘Interrupted’ diazotization of 3-aminoindoles and 3-aminopyrroles
2014
Abstract ‘Interrupted’ diazotization of 3-aminoindoles and 3-aminopyrroles, achieved by quenching with cold water immediately after the addition of nitrite, led, in good yields, to stable compounds whose structures were identified to be the diazonium species with nitrate as the counter ion, which show no saline character.
Structure and Yielding of Colloidal Silica Gels Varying the Range of Interparticle Interactions.
2016
The relationship between interaction range, structure, fluid-gel transition, and viscoelastic properties of silica dispersions at intermediate volume fraction, Φv ≈ 0.1 and in alkaline conditions, pH = 9 was investigated. For this purpose, rheological, physicochemical, and structural (synchrotron-SAXS) analyses were combined. The range of interaction and the aggregation state of the dispersions were tuned by adding either divalent counterions (Ca(2+)) or polycounterions (PDDA). With increasing calcium chloride concentration, a progressive aggregation was observed which precludes a fluid-gel transition at above 75 mM of calcium chloride. In this case, the aggregation mechanism is driven by s…
A study on the aminomercuration-nucleophilic demercuration of --1,5-cyclooctadiene; stereoselective synthesis of 2,6-disubstituted-9-aza bicyclo[3.3.…
1992
Abstract The aminomercuration of cis - cis -1,5-Cyclooctadiene with a series of mercury(II) salts followed by nucleophilic displacement of mercury by aromatic amines, water and nitrate ion has been studied. As a result, bicyclic triamines, aminoalcohols and nitrate esters have been obtained respectively in clean processes which occur under total stereoelectronic control by involvement of a tricyclic aziridium ion to afford a single stereoisomer in each case. The influence of the counter ion and the basicity of the amine on the tandem aminomercuration-demercuration is discussed.
Aggregation Processes and Formation of Silico-calco-alkaline Gels under High Ionic Strength
2002
This paper presents a systematic in situ study of the process of formation of silico-calco-alkaline gels starting from a liquid colloidal solution containing different alkaline ions and different calcium concentration until the final gel state. The combined use of X-ray and neutron small-angle scattering (SAS) and dynamical rheometry techniques lead to a consistent description of the structure of the aggregates and of the mechanisms of aggregation involved in gel formation. SAS results indicate that the aggregates are fractal objects, their structure strongly depending on calcium ion concentration. The differences in gelation kinetics for systems containing different alkaline ions were attr…
Synthesis of [5]Rotaxanes Containing Bi- and Tridentate Coordination Sites in the Axis
2010
A new example of a linear [5]rotaxane has been synthesized by using the traditional "gathering-and-threading" approach but based on an unusual axle incorporating a symmetrical bis(bidentate) chelating fragment built on a 4,7-phenanthroline core. The stoppering reaction is particularly noteworthy since, instead of using a trivial bulky stopper as precursor to the blocking group, two semistoppered copper-complexed [2]pseudorotaxanes (namely [2]semirotaxanes) are used, which leads to the desired [5]rotaxane in good yield. The efficiency of the method relies on the use of "click" chemistry, with its very mild conditions, and on the protection by a transition-metal (copper(I)) of the various coo…
Synthesis, crystal structures, and solid state quadratic nonlinear optical properties of a series of stilbazolium cations combined with gold cyanide …
2011
Three salts built up from (E)-4′-(dimethylamino)-stilbazolium (DMAS)H+, (E)-4′-(diethylamino)-stilbazolium (DEAS)H+, (E)-4′-{2-(methoxymethyl) pyrrolidinyl}-stilbazolium (MPS)H+, and gold cyanide as a counter-ion, are reported. The crystal structures have been solved for (DEAS)H+ Au(CN)2− (Cc space group), and for (MPS)H+ Au(CN)2− (P1 space group). The semi-empirical (ZINDO) calculated static hyperpolarizability (β0) of (MPS)H+ is equal to 147 × 10−30 cm5esu−1, in solid state, which is 25% higher than that of the cation of the well known (E)-4′-(dimethylamino)-methylstilbazolium tosylate (DAST). (MPS)H+ Au(CN)2− exhibits a unique crystal structure in which the cations are perfectly aligned.…
The influence of counterions and hydrophobic moieties on the thermostability of Langmuir-Blodgett multilayers
1994
Abstract Langmuir-Blodgett (LB) multilayers with various counterions and different organic moieties (one- and two-chain fatty acids, polymeric acid) are prepared to investigate on line temperature-dependent structural changes and desorption by small-angle X-ray scattering (SAXS), interference-enhanced reflection and Nomarsky microscopy. On temperature increase a sequence of phase transitions can be observed. A crystalline LB film melts to a fluid phase and eventually desorbs either from droplets or from a homogeneous film. The phase sequence depends on the counterion: nickel stearate and magnesium stearate melt while the layered structure is conserved; SAXS measurements reveal a continuous,…