Search results for "counterion"
showing 10 items of 138 documents
Synthesis of polyvinyl acetate-graft-poly-2-oxazolines
1994
Poly(vinyl acetate-co-vinyl chloroformate) (1) was synthesized via phosgenation of poly(vinyl acetate-co-vinyl alcohol). It was shown that (1) is capable of initiating the polymerization of 2-phenyl-2-oxazoline and 2-methyl-2-oxazoline, when the counter ion is exchanged using potassium iodide. Polyvinyl acetate-graft-poly-2-phenyl-2-oxazoline and polyvinyl acetate-graft-poly-2-methyl-2-oxazoline are obtained in the grafting reaction.
Assembling Magnetic Blocks: A Strategy to Control the Nuclearity and Magnetic Properties of Polynuclear Complexes
1996
Synthetic strategies dealing with the polymerization of either di-μ-hydroxocopper(II) complexes or 2,2′-bipyrimidine (bpym)-containing first row transition metal ions allow the preparation of polynuclear compounds whose structures and magnetic properties are presented here. The influence of structural and chemical parameters on the magnitude of the singlet-triplet energy gap (J) in di-μ-hydroxocopper(II) complexes [LCu(OH)2CuL]2+ with L = 2,2′-bipyridine (bpy) and bpym is analyzed and discussed. Special attention is devoted to nature of the counterion which allows the preparation of hydroxo-bridge copper(II) cubane and double cubane type complexes where all the intramolecular magnetic inter…
Electrospray ion mobility mass spectrometry of positively charged sodium bis[2-ethythexyl)sulfosuccinate aggregates.
2014
Collision cross-sections (CCS) of positively singly and multiply charged aggregates of the surfactant sodium bis(2-ethylhexyl)sulfosuccinate (AOTNa) in the gas phase have been measured by quadrupole ion mobility time-of-flight mass spectrometry. Calibration of the observed drift times to the CCS of the AOTNa non-covalent aggregates was achieved by collecting, under the same experimental conditions, the drift times of a range of singly and multiply charged polyalanine peptides whose CCS had been obtained by conventional ion mobility spectrometry. Together with an obvious increase of the aggregate cross-section with the aggregation number, it was found that the aggregate cross-section increa…
Physicochemical Properties of Copper(II) Bis(2-ethylhexyl) Sulfosuccinate Reversed Micelles
1998
Abstract Measurements of some physicochemical properties (density, viscosity, conductance, UV–vis spectra, IR spectra) of the water/copper(II) bis(2-ethylhexyl) sulfosuccinate (Cu(DEHSS) 2 )/CCl 4 microemulsions, at a fixed surfactant molal concentration ([Cu (DEHSS) 2 ] = 0.05003 mol kg −1 ), as function of the molar ratio R ( R = [water]/[DEHSS − ]) have been performed at 25°C. Information on some structural and dynamical properties of the water-containing Cu(DEHSS) 2 reversed micelles and of their evolution with R are derived from the experimental results. The comparison with the same properties of water-containing sodium bis(2-ethylhexyl) sulfosuccinate reversed micelles allows to evide…
Intrinsic Viscosities of Polymer Blends: Sensitive Probes of Specific Interactions between the Counterions of Polyelectrolytes and Uncharged Macromol…
2018
In joint dilute aqueous solutions of pullulan (PUL) and poly(sodium 4-styrenesulfonate) (PSS-Na) the Na+ ions of the polyelectrolyte interact so favorably with the monomeric units of PUL that isolated coils containing both types of macromolecules are formed upon dilution. When water is replaced against a 1 M solution of NaCl, this effect dies out because of the large surplus of Na+ ions. On the other hand, if the water contains increasing amounts of the respective counterpolymer instead of NaCl, the formation of mixed isolated coils is fostered, where a further diminution of the intrinsic viscosities is caused by the lower the solvent quality. The molar mass of PSS-Na plays an important rol…
Self-assembly and anion encapsulation properties of cavitand-based coordination cages.
2001
Two novel classes of cavitand-based coordination cages 7a--j and 8a--d have been synthesized via self-assembly procedures. The main factors controlling cage self-assembly (CSA) have been identified in (i) a P--M--P angle close to 90 degrees between the chelating ligand and the metal precursor, (ii) Pd and Pt as metal centers, (iii) a weakly coordinated counterion, and (iv) preorganization of the tetradentate cavitand ligand. Calorimetric measurements and dynamic (1)H and (19)F NMR experiments indicated that CSA is entropy driven. The temperature range of the equilibrium cage-oligomers is determined by the level of preorganization of the cavitand component. The crystal structure of cage 7d r…
The effect of TMEDA on the kinetics of the anionic polymerization of methyl methacrylate in tetrahydrofuran using lithium as counterion
2000
The kinetics of the anionic polymerization of methyl methacrylate in presence of N,N,N', -tetramethylethylenediamine (TMEDA) in THF are investigated using 1,1-diphenyl-hexyllithium as initiator in a temperature range between -20°C and 0°C in a flow-tube reactor. The rate constants of propagation determined in the presence of TMEDA are compared to those obtained in the absence of a chelating agent. For propagation, the reaction order with respect to active centers is found to be 0.5 in both cases which indicates that the chelation of the lithium cation does not effectively perturb the aggregation of the enolate ion pair. Both the rate constants of propagation via non-aggregated ion pairs, k …
Phase Trapping in Multistep Spin Crossover Compound
2020
The dimeric motif is the smallest unit for two interacting spin centers allowing for systematic investigations of cooperative interactions. As spin transition compounds, dinuclear complexes are of particular interest, since they potentially reveal a two-step spin crossover (SCO), switching between the high spin-high spin [HS-HS], the high spin-low spin [HS-LS], and the low spin-low spin [LS-LS] states. Herein, we report the synthesis and characterization of six dinuclear iron(II) complexes [FeII2(μ2-L1)2](BF4)4 (C1), [FeII2(μ2-L1)2](ClO4)4 (C2), [FeII2(μ2-L1)2](F3CSO3)4 (C3), [FeII2(μ2-L2)2](BF4)4 (C4), [FeII2(μ2-L2)2](BF4)4 (C5), and [FeII2(μ2-L2)2](BF4)4 (C6), based on the 1,3,4-thiadiazo…
Ion size effects on the current efficiency of narrow charged pores
2001
Abstract The effects of ion size on the current efficiency (CE) of charged membranes with narrow pores are studied theoretically. The CE is a measure of the membrane permselectivity defined as the ratio between the counterion flux and the sum of the counterion and coion fluxes when an electric potential difference is applied between the two solutions bathing the membrane. It is studied here as a function of two relevant experimental parameters: the ratio between the ionic radius and the pore radius, and the ratio between the external salt concentration and the membrane fixed charge concentration. The ratio of the CE values corresponding to the point and finite size ions is also calculated a…
Counterion-Mediated Crossing of the Cyanine Limit in Crystals and Fluid Solution: Bond Length Alternation and Spectral Broadening Unveiled by Quantum…
2020
Absorption spectra of cyanine⊕·Br⊖ salts show a remarkable solvent dependence in non/polar solvents, exhibiting narrow, sharp band shapes in dichloromethane but broad features in toluene; this chan...