Quantum chemical study on HKrC5N, HXeC5N, and related rare gas compounds.

The recent identification of HRgC5N (Rg = Kr, Xe) in a cryogenic matrix calls for an in-depth theoretical study on these compounds. Here we present the results of CCSD(T), MP2, and DFT calculations concerning the molecular structure, stability, and vibrational spectroscopy. The procedure combining CCSD(T) calculations for variable H-Rg distances with the anharmonic description of the corresponding stretching vibration, based on a Morse-type potential energy function, was proposed and has led to good agreement between computational and experimental values for H-Rg stretching frequencies, at relatively low computational costs. High Raman scattering activity of HRgC5N and of its isomers, predicted at the DFT level, gives some prospects for the detection of these molecules with a method alternative to the IR absorption spectroscopy.

Atomic force microscopy evidence for conformational changes of fibronectin adsorbed on unmodified and sulfonated polystyrene surfaces.

The effect of polystyrene surface polarity on the conformation of adsorbed fibronectin (FN) has been studied with atomic force microscopy. We demonstrated that bare sulfonated and nonsulfonated polystyrene surfaces featured similar topographies. After the FN adsorption, direct comparison of both types of substrata revealed drastically different topographies, roughness values, and also cell-adhesive properties. This was interpreted in terms of FN conformational changes induced by the surface polarity. At high-solute FN concentrations the multilayer FN adsorption took place resulting, for the sulfonated substratum, in an increase of surface roughness, whereas for the nonsulfonated one the roughness was approximately stable. Conversely, the FN conformation characteristic for the first saturative layer tended to be conserved in the consecutive layers, as evidenced by height histograms. The height of individual FN molecules indicated, consonantly with the derived thickness of the adsorbed protein layer (the latter value being 1.4 nm and 0.6 nm, respectively, for an unmodified and sulfonated polystyrene surface), that molecules are flattened on polar surfaces and more compact on nonsulfonated ones. It was also demonstrated that the FN adsorption and conformation on polymeric substrata, and hence the resultant cell-adhesive properties, depended on the chemistry of the original surface rather than on its topography. Our results also demonstrated the ability of surface polarity to influence the protein conformation and its associated biological activity.

The C3N- anion: first detection of its electronic luminescence in rare gas solids.

The 193 nm laser irradiation of cyanoacetylene (HCCCN) that was isolated in rare gas solids led to a long-lived luminescence (origin at 3.58 eV), which was assigned to the a (3)Sigma(+)-X (1)Sigma(+) system of cyanoacetylide (CCCN(-)). The identification, which involved (15)N and (2)H isotopic substitution studies, is based on vibronic spacings in the phosphorescence spectrum (compared to previous infrared absorption measurements and to theoretical results regarding CCCN(-) vibrational frequencies), as well as on a BD(T)/cc-pVTZ prediction for the singlet-triplet energy gap in this anion (3.61 eV). The same emission was also generated from KrHC(3)N mixtures subjected to a glow electric discharge immediately before the solidification (cold-window-radial-discharge technique).

Theoretical prediction and the first IR matrix observation of several L-cysteine molecule conformers.

For the first time the argon-matrix low-temperature IR spectra of cysteine are recorded. They reveal a quite complicated spectral pattern, which can also be reproduced in the N2 matrix. Assignment of the observed spectra is undertaken on the basis of comparison of the experimental and calculated B3LYP/aug-cc-pVDZ anharmonic IR spectra. The presence of at least three, and possibly even six or more, cysteine conformers with and without intramolecular hydrogen bonding is confirmed. On the basis of the calculated vibrational circular dichroism spectra, we predict this technique to be more distinctive for conformers than IR absorption is.

Fibronectin adsorption and arrangement on copolymer surfaces and their significance in cell adhesion.

The adsorption of fibronectin (FN) to (styrene/methyl methacrylate) copolymer surfaces, both sulfonated (hydrophilic) and nonsulfonated (hydrophobic), was studied by means of the radioisotope (125I-FN) and ELISA assays; the latter employed monoclonal antibodies. It was found that the radioiodination-derived isotherms did not follow the Langmuir-type adsorption law within the FN concentration range studied; rather, a quasi-linear FN surface density versus bulk concentration dependence was observed. These isotherms, and our recent ELISA measurements with polyclonal antibodies, allowed us to estimate saturative FN surface densities, which were, within the experimental error, similar on both types of surfaces. This suggested the amount of adsorbed FN to be not responsible for observed differences in leukaemia L1210 cell adhesion (FN-coated sulfonated surfaces are far more pro-adhesive than their nonsulfonated analogues). The presumption that these differences are induced by changes in the FN arrangement was confirmed by the use of monoclonal antibodies directed against distinct FN domains, and by the blocking of alpha5beta1 integrin receptor with the synthetic Gly-Arg-Gly-Asp-Ser-Pro (GRGDSP) peptide. The RGD sequence located within the FN cell-binding domain seems to be masked in the structure adopted on nonsulfonated surfaces, which hinders the integrin-ligand interaction.

Adsorption characteristics of human plasma fibronectin in relationship to cell adhesion.

Adsorption of human plasma fibronectin (FN) on nonsulfonated and sulfonated polymer surfaces was studied, by using a polyclonal antiserum to FN and the ELISA method. ELISA signal was recorded as a function of FN concentration in solutions. The concentration dependence of FN binding shows the saturation effect in the range 5-10 microg/mL. ELISA data are discussed in the terms of a self-assembled monolayer and different conformations of the FN molecule. The early adhesion of L1210 cells to polymer surfaces after prior adsorption of FN on these surfaces was studied under static conditions. In the case of FN adsorbed on sulfonated surfaces, the relative number of adhering cells increased with the increase of the interfacial surface tension (i.e., the cell adhesion depends on the surface density of sulfonic groups). However, in the case of FN adsorbed on nonsulfonated surfaces, the relative number of adhering cells was low and independent on the interfacial surface tension. The alpha(5)beta(1)-integrin blocking by a monoclonal antibody resulted in a strong inhibition of the cell adhesion to FN adsorbed on sulfonated polymer surfaces. This indicates that cell adhesion to FN adsorbed on these surfaces is mostly mediated by the alpha(5)beta(1)-integrin. In contrast, in the case of FN adsorbed on nonsulfonated surfaces the cell adhesion was not inhibited by the alpha(5)beta(1)-integrin blocking.