Surface and Structural Characterization of PVTMS Films Treated by Elemental Fluorine in Liquid Perfluorodecalin.

Poly(vinyl trimethylsilane) (PVTMS) films were subjected to direct surface fluorination in liquid medium (perfluorodecalin). The samples were investigated using several techniques: SEM-XEDS, XPS, ATR-IR, and contact angle measurement. The methods used allowed us to estimate chemical changes occurring because of the treatment. ATR-IR showed that most of the changes occurred in the Si(CH3)3 group. Monofluorinated Si(CH3)3 groups formed in the near-surface layer (Ge crystal, 0.66 µm penetration) after 30 min of fluorination, and then di- and trifluorinated groups appeared. Oxidation of the film with oxygen was also shown with the use of ZnSe crystal (2 µm penetration). The XPS method allowed an assessment of the ratio of the main elements at the surface of the fluorinated film. Two different exponential models were proposed to fit the experimental data of SEM-XEDS. Based on the model with the intercept, the depth of fluorination was estimated to be ≤1.1 µm, which is consistent with the result from the literature for the gas-phase fluorination. Contact angle measurements showed that oxidation of the PVTMS surface prevailed for the first 45 min of fluorination (surface hydrophilization) with a subsequent fluorine content increase and hydrophobization of the surface upon 60 min of fluorination.

Hydrophobic-Hydrophilic Properties and Characterization of PIM-1 Films Treated by Elemental Fluorine in Liquid Perfluorodecalin.

A direct fluorination technique was applied for the surface treatment of PIM-1 films in a liquid phase (perfluorodecalin). The fluorinated samples were analyzed by various instrumental techniques. ATR-IR spectroscopy showed that the fluorination predominantly takes place in methylene- and methyl-groups. Cyano-groups, aromatic hydrogens and the aromatic structure of the PIM-1 repeat unit were shown to be relatively stable at the fluorination conditions. XPS confirmed that the concentration of fluorine, as well as oxygen, in the near surface layer (~1 nm) increases with fluorination time. C1s and O1s surface spectra of the fluorinated PIM-1 samples indicated an appearance of newly-formed C-F and C-O functional groups. Scanning electron microscopy and X-ray energy-dispersive spectroscopy of the fluorinated PIM-1 samples showed an increase of the fluorine concentration at the surface (~0.1-1 µm) with the treatment duration. Analysis of the slices of the PIM-1 films demonstrated a decline of the fluorine content within several microns of the film depth. The decline increased with the fluorination time. A model of fluorine concentration dependence on the film depth and treatment duration was suggested. A change in the specific free surface energy as a result of PIM-1 fluorination was revealed. The fluorination time was shown to affect the surface energy (γSV), providing its shift from a low value (25 mJ∙m-2), corresponding to tetrafluoroethylene, up to a relatively high value, corresponding to a hydrophilic surface.

Structure-Property Relationship on the Example of Gas Separation Characteristics of Poly(Arylene Ether Ketone)s and Poly(Diphenylene Phtalide).

Three poly(arylene ether ketone)s (PAEKs) with propylidene (C1, C2) and phtalide (C3) fragments, and one phtalide-containing polyarylene (C4), were synthesized. Their chemical structures were confirmed via 1H NMR, 13C NMR and 19F NMR spectroscopy. The polymers have shown a high glass transition temperature (>155 °C), excellent film-forming properties, and a high free volume for this polymer type. The influence of various functional groups in the structure of PAEKs was evaluated. Expectedly, due to higher free volume the introduction of hexafluoropropylidene group to PAEK resulted in higher increase of gas permeability in comparison with propylidene group. The substitution of the fluorine-containing group on a rigid phtalide moiety (C3) significantly increases glass transition temperature of the polymer while gas permeation slightly decreases. Finally, the removal of two ether groups from PAEK structure (C4) leads to a rigid polymer chain that is characterized by highest free volume, gas permeability and diffusion coefficients among the PAEKs under investigation. Methods of modified atomic (MAC) and bond (BC) contributions were applied to estimate gas permeation and diffusion. Both techniques showed reasonable predicted parameters for three polymers while a significant underestimation of gas transport parameters was observed for C4. Gas solubility coefficients for PAEKs were forecasted by "Short polymer chain surface based pre-diction" (SPCSBP) method. Results for all three prediction methods were compared with the ex-perimental data obtained in this work. Predicted parameters were in good agreement with ex-perimental data for phtalide-containing polymers (C3 and C4) while for propylidene-containing poly(arylene ether ketone)s they were overestimated due to a possible influence of propylidene fragment on indices of oligomeric chains. MAC and BC methods demonstrated better prediction power than SPCSBP method.

Features of the Gas-Permeable Crystalline Phase of Poly-2,6-dimethylphenylene Oxide.

Poly-2,6-dimethylphenylene oxide (PPO) film samples with varying degrees of crystallinity (from 0 to 69%) were obtained by means of different techniques. The films were studied by various physicochemical methods (Fourier-transform infrared spectroscopy, positron annihilation lifetime spectroscopy, X-ray diffraction, and 1H nuclear magnetic resonance relaxation). Solubility coefficients of gases in the PPO samples were measured via sorption isotherms of gases by volumetric technique with chromatographic detection. The apparent activation energy of permeation and the activation energy of diffusion of all gases were estimated based on temperature dependences of gas permeability and diffusivity for amorphous and semi-crystalline PPO in the range of 20-50 °C. The peculiarities of free volume, density, and thermal properties of gas transport confirm the nanoporosity of the gas-permeable crystalline phase of PPO. So, the PPO can be included in the group of organic molecular sieves.

Immunogenic compositions assembled from tobacco mosaic virus-generated spherical particle platforms and foreign antigens.

We reported recently that RNA-free spherical particles (SPs) generated by thermal remodelling of tobacco mosaic virus (TMV) are capable of binding GFP to their surface. Here, we show that SPs represent a universal particle platform that can form compositions by binding a diversity of various foreign proteins/epitopes of viral and non-viral origin to their surface. Numerous molecules of a foreign protein linked to the SP surface were revealed by immunogold electron microscopy. Several SP-based compositions were obtained containing one of the following foreign antigens: antigenic determinant A of rubella virus E1 glycoprotein; a recombinant protein containing the M2e epitope of influenza virus A protein M2; a recombinant antigen consisting of three epitopes of influenza virus A haemagglutinin; potato virus X (PVX) coat protein (CP); BSA; and PVX CP fused with the epitope of plum pox virus CP. The 'mixed' compositions could be also assembled by binding two different foreign antigens to each of the SPs. Immunogenicity of foreign antigens adsorbed or linked covalently to SPs in the SP-based compositions was examined. The antigenic specificity of foreign antigens was retained, whereas their immunogenicity increased significantly. It was inferred that SPs exhibit immunopotentiating activity, in particular in the form of compositions comprising SP and foreign antigen linked covalently to their surface by formaldehyde.

Thermal transition of native tobacco mosaic virus and RNA-free viral proteins into spherical nanoparticles.

Spherical nanoparticles (SNPs) were generated by two-step thermal remodelling of native tobacco mosaic virus (TMV) at 94 °C. Particles of irregular shape and varying size were generated by TMV at 90 °C. They could be converted into SNPs by heating at 94 °C and were considered to be intermediate precursors of SNPs. In addition to SNP monomers (53 nm diameter), generated by individual TMV virions, large SNPs (100-800 nm diameter) were assembled. The size of the SNPs depended on the TMV concentration. The SNPs could be generated by distinct forms of RNA-free TMV coat protein (CP) aggregates and individual CP subunits. A one-step SNP assembly appeared to occur in these cases. These results show that SNPs represent a new type of particle nanoplatform for producing compositions of SNPs with foreign protein molecules bound to their surface.

Characterization of Alternanthera mosaic virus and its Coat Protein.

A new isolate of Alternantheramosaic virus (AltMV-MU) was purified from Portulaca grandiflora plants. It has been shown that the AltMV-MU coat protein (CP) can be efficiently reassembled in vitro under different conditions into helical RNA-free virus-like particles (VLPs) antigenically related to native virus. The AltMV-MU and VLPs were examined by atomic force and transmission electron microscopies. The encapsidated AltMV-MU RNA is nontranslatable in vitro. However, it can be translationally activated by CP phosphorylation or by binding to the TGB1protein from the virus-coded movement triple gene block.