Hydrogen-bonded polymer multilayers probed by neutron reflectivity

We present a neutron reflectivity study of the internal structure of multilayers made of a weak polyelectrolyte and a neutral component where interactions between adjacent layers are controlled by hydrogen-bonding. We found the degree of interpenetration of polymer layers expressed as the interlayer roughness to be strongly correlated with the strength of intermolecular interactions between the adjacent layers. In addition, polymer layers become more diffuse with a distance from the substrate. Our results demonstrate that hydrogen-bonded films exhibit a close correlation between their structure and properties, which is essential for various applications.     

Isotachophoretic determination of hydrosulfite and metabisulfite in technical samples

A method for determination of metabisulfite and hydrosulfite in poultice and decolorant by isotachophoresis was developed. Metabisulfite and hydrosulfite are ionizable oxoanions of sulfur of similar character that can easily be oxidized to sulfates. To protect the analytes from oxidation the solid samples were dissolved in a 1% (w/v) solution of formaldehyde. Hydrosulfite and metabisulfite present in the samples were transformed by the reaction with formaldehyde to stable compounds, hydroxymethanesulfinate and hydroxymethanesulfonate that were determined isotachophoretically without any pretreatment except for sample filtering and degassing. A capillary of 0.4 mm i.d. and 100 mm effective length made of fluorinated ethylene-propylene copolymer was filled with an electrolyte system consisting of 10 mmol L⁻¹ HCl + 11 mmol L⁻¹ imidazole, 0.15% (w/v) hydroxyethylcellulose, pH 6.0 (leading electrolyte) and 5 mmol L⁻¹ benzoic acid + 6 mmol L⁻¹ imidazole, pH 6.5 (terminating electrolyte). Separation was performed at a driving current of 80 μA and for detection current was decreased to 30 μA. Using contactless conductivity detection, the calibration curves in the tested concentration range up to 2.5 mmol L⁻¹ were linear for both metabisulfite and hydrosulfite complexes. The concentration detection limits for metabisulfite and hydrosulfite were 2.9 and 3.4 μmol L⁻¹, respectively. For 1 mmol L⁻¹ concentration, values of R.S.D. (n = 6) were 2.6% for hydrosulfite and 0.8% for metabisulfite. Isotachophoretic determination took about 20 min. The elaborated isotachophoretic procedure is simple to perform, sufficiently sensitive and accurate. In addition to this, low cost of analyses makes the method an alternative procedure to methods used so far for the determination of oxoanions of sulfur.     

Influence of aggregation on interaction of lipophilic, water-insoluble azaphthalocyanines with DOPC vesicles

Dioleoylphosphatidylcholine unilamellar vesicles made by extrusion technique (LUVETs) were studied as the delivery system for lipophilic water-insoluble potential photosensitizers for photodynamic therapy (PDT). Two azaphthalocyanines (AzaPcs) with hydrophobic substituents only and two also possessing two charged amino groups were introduced into the study. All compounds are insoluble in water and form aggregates in PBS with tetrahydrofuran as cosolvent. The size of these aggregates depends on the concentration of AzaPc in solution. AzaPcs with tert-butyl substituents were found to be incorporated into the lipid bilayer of vesicles in the monomeric form even at high concentrations. The stability of LUVETs with incorporated AzaPc was excellent for at least 4 weeks. Therefore, they are suitable for use as a delivery system for these water-insoluble photosensitizers. Very low amount of AzaPc with n-octyl substituents incorporated into LUVETs due to its stronger self-aggregation. Values of binding constants determined for all AzaPcs showed inverse order than expected from their lipophilicities. However, the binding constants followed the order of the strength of aggregation forces. Aggregation of AzaPcs in water medium plays a very important role in the interaction of AzaPcs with LUVETs.     

Detection enhancement in nano-channels using micro-machined silicon groove

The present paper reports on an experimental study of the possibility to use a micro-machined detection groove to enhance the detection sensitivity in flat-rectangular nano-channels for ultra-rapid liquid chromatography separations. Transversally running detection grooves with three different axial widths (respectively, 2, 4 and 6mum) and one depth (4.75mum) were tested in glass and silicon channels for the whole range of detectable fluorescein isothiocyanate isomer I, FITC, concentrations. The groove with the most square-like cross-section (i.e., 4mum wide and 4.75mum deep) yielded the best combination of detection gain and minimal additional band broadening. In a 1cm long channel, the effective plate loss caused by the 4mum wide groove would only be of the order of 20%, while the gain in S/N-ratio was of the order of a factor of 5. The detection groove concept yields larger gains in silicon channel substrates than in glass channel substrates, due to the larger stray light losses occurring in the latter.     

Hydrogen-bonding networks from first-principles: exploring the guanidine crystal

Hydrogen bonding is among the most important interactions in molecular crystals, and examples are abundant. As a consequence of such interactions, many molecules crystallize in complex but intriguing structures, in contrast to the relatively simple packing principles of metallic or ionic solids. In this work, we present a computational approach based on plane-wave density-functional theory (DFT) and supercell techniques, aiming to understand and quantify hydrogen-bonded networks in the solid state and in two-, one-, and zero-dimensional fragments derived from the molecular crystal. With such methodology at hand, we investigate guanidine, a fitting example of a molecular crystal and an important compound for inorganic and organic chemistry alike. On the basis of our computations, we discuss the initially proposed layered structure of guanidine and identify both stabilizing and destabilizing cooperative interactions in the three crystalline dimensions.     

Quadrupolar ordering of phospholipid molecules in narrow necks of phospholipid vesicles

Shapes of phospholipid vesicles that involve narrow neck(s) were studied theoretically. It is taken into account that phospholipid molecules are intrinsically anisotropic with respect to the membrane normal and that they exhibit quadrupolar orientational ordering according to the difference between the local principal membrane curvatures. Direct interactions between oriented molecules were considered within a linear approximation of the energy coupling with the deviatoric field. The equilibrium shapes of axisymmetric closed vesicles were studied by minimization of the free energy of the phospholipid bilayer membrane under relevant geometrical constraints. The variational problem was stated by a system of Euler-Lagrange differential equations that revealed a singularity in the derivative of the meridian curvature at points where the effect of the orientational ordering exactly counterbalances the effect of the isotropic bending. The system of Euler-Lagrange differential equations was solved numerically to yield consistently related equilibrium orientational distribution of the phospholipid molecules and vesicle shape. According to our estimation of the model constants the formation of the neck is promoted if direct interactions between the oriented molecules are taken into account. It was shown that the energy of the equilibrium shapes is considerably affected by the quadrupolar ordering of phospholipid molecules.     

On the Darboux transformation. I

Automorphisms of the family of all Sturm-Liouville equationsy=qy are investigated. The classical Darboux transformation arises as a particular case of a general results.