Separation of a CaCl2-HCl Model Mixture on Neutral Nanoporous Hypercrosslinked Polystyrene under Static and Dynamic Conditions

The distribution of CaCl₂ and HCl (separately and in a mixture) between the aqueous and nanoporous hypercrosslinked polystyrene sorbent phases was studied under static conditions. It was shown that virtually the whole pore volume of the sorbent was accessible to HCl, whereas CaCl₂ was largely excluded from small pores. It was found that the distribution isotherms of the electrolytes between the phases changed significantly in going from the pure electrolytes to their mixture. Under dynamic (chromatographic) conditions, the elution profiles of CaCl₂ and HCl (separately and in a mixture) were studied. It was shown that the components of the mixture competed for the pore space of the sorbent: small HCl molecules were displaced from large pores and the interstitial space into small pores inaccessible to CaCl₂. (This is why the retention of HCl in the chromatography column significantly increased as the concentration of the mixture grew; that is, both the efficiency and selectivity of separation increased as the column became loaded heavier.) It was found that the degree of hydration of ions decreased as the concentration of the solution increased.     

Functionalization of magnetic nanoparticles with amphiphilic block copolymers: self-assembled thermoresponsive submicrometer particles

For the first time the four block copolymers derived from 1-alkyl[2-(acryloyloxy)ethyl]dimethylammonium bromides with hexyl (ADA) or cetyl (ADHA) groups and 2-hydroxyethylacrylate (HEA) or N-isopropylacrylamide (NIPAM) were synthesized and employed for functionalization of monodisperse iron oxide nanoparticles (NPs). The polyADA (pADA) or polyADHA (pADHA) block consists of long hydrophobic tails (C(6) or C(16)) connected to a positively charged quaternary ammonium group, making this block amphiphilic. The second block was either fully hydrophilic (pHEA) or thermoresponsive (pNIPAM). The dependence of the NP coating on the length of the hydrophobic tail in the amphiphilic block, the composition of the hydrophilic block, and the NP sizes have been studied. Unusual self-assembling of iron oxide NPs into well-defined composite submicrometer particles was observed for pADHA-b-pNIPAM in the wide range of concentrations (at the pADHA repeating unit concentrations of 0.065 × 10(-2)-2.91 × 10(-2) mmol/mL per 1 mg/mL NPs) but only two concentrations, 1.62 × 10(-2) and 1.94 × 10(-2) mmol/mL, led to regular spherical particles. The thermoresponsive behavior of these composite particles was tested using ζ-potential and dynamic light scattering measurements, while the morphology of particles was characterized by transmission electron microscopy. Coating of NPs with pADHA-b-pHEA results in the formation of individually coated NPs. The different composite particle morphologies are explained by different properties of pHEA and pNIPAM. It is demonstrated that the composite particles based on pADHA-b-pNIPAM are responsive to a magnetic field and can be recommended as magnetic stoppers in biorelated membrane separations. The incorporation of Pd species in submicrometer particles makes them promising candidates for catalytic applications as magnetically recoverable catalysts with a high magnetic response.     

Different types of hydrogen bonds in 2-substituted pyrroles and 1-vinyl pyrroles as monitored by (1)H, (13)C and (15)N NMR spectroscopy and ab initio calculations

According to the (1)H, (13)C and (15)N NMR spectroscopic data and ab initio calculations, the strong N--H...O intramolecular hydrogen bond in the Z-isomers of 2-(2-acylethenyl)pyrroles causes the decrease in the absolute size of the (1)J(N,H) coupling constant by 2 Hz in CDCl(3) and by 4.5 Hz in DMSO-d(6), the deshielding of the proton and nitrogen by 5-6 and 15 ppm, respectively, and the lengthening of the N--H link by 0.025 A. The N--H...N intramolecular hydrogen bond in the 2(2'-pyridyl)pyrrole leads to the increase of the (1)J(N,H) coupling constant by 3 Hz, the deshielding of the proton by 1.5 ppm and the lengthening of the N--H link by 0.004 A. The C--H...N intramolecular hydrogen bond in the 1-vinyl-2-(2'-pyridyl)-pyrrole results in the increase of the (1)J(C,H) coupling constant by 5 Hz, the deshielding of the proton by 1 ppm and the shortening of the C--H link by 0.003 A. Different behavior of the coupling constants and length of the covalent links under the hydrogen bond influence originate from the different nature of the hydrogen bonding (predominantly covalent or electrostatic), which depends in turn on the geometry of the hydrogen bridge. The Fermi-contact mechanism only is responsible for the increase of the coupling constant in the case of the predominantly electrostatic hydrogen bonding, whereas both Fermi-contact and paramagnetic spin-orbital mechanisms bring about the decrease of coupling constant in the case of the predominantly covalent hydrogen bonding.     

New monomers and polymers via Diels-Alder cycloaddition

The series of new bis(naphthalic anhydrides) was prepared through Diels-Alder cycloaddition. The Diels-Alder cycloaddition was used as a synthetic route to new phenylated monomers as well as to polymers. All polymers synthesized revealed to be soluble in a wide range of organic solvents such as toluene, THF, chloroform, and displayed high thermostability. Therefore, they can be processed easily and are promising candidates for advanced coating systems as well as for electrooptical applications.