Chain flexibility versus molecular entanglement response to rubbing deformation in designing poly(oxadiazole-naphthylimide)s as liquid crystal orientation layers

Four poly(oxadiazole-imide)s containing naphthalene rings, with different flexibility and molecular weight, are investigated with respect to their rheological properties to establish the optimal processing conditions from solution phase to film state for liquid crystal orientation purposes. The film uniformity and strength are determined by monitoring the flow behavior and chain entanglements. The solution rheological data are in agreement with film tensile testing, revealing that higher molecular weight favors chain entanglements and implicitly the film mechanical resistance. In order to analyze the suitability of these films as alignment layers their surface is patterned by rubbing with two types of velvet. Liquid crystal alignment of 4′-pentyl-4-biphenylcarbonitrile nematic is tested by polarized light microscopy. The resulting behavior is correlated with the polyimide malleability and characteristics of the textile fibers, namely their polarity, size, and mechanical features. The competitive effects between chain flexibility and entanglements, together with the interactions occurring between the polymer and velvet are analyzed in order to explain the surface regularity, which influences the uniformity of the liquid crystal alignment. The contrast between dark and bright states recorded on the liquid crystal cell indicates that some of these polynaphthalimides are promising candidates for liquid crystal display devices.     

Ethanol reforming and partial oxidation with Cu/Nb2O5 catalyst

Ethanol reforming and partial oxidation were studied on Cu/Nb₂O₅ and Ni/Al₂O₃ catalysts. Compared to the Ni/Al₂O₃ catalyst, the Cu/Nb₂O₅ catalyst presents conversion as high as Ni/Al₂O₃ catalyst, however, for the same level of formation of hydrogen it occurs at much lower temperature on the Cu/Nb₂O₅ catalyst, 200 °C lower than for the Ni/Al₂O₃ catalyst, with remarkable little formation of CO, which can be attributed to the strong interaction between copper and niobia. Temperature-programmed desorption (TPD-ethanol) and surface reactions (TPSR) of partial oxidation of ethanol showed formation of ethylene, acetaldehyde, ethane and mainly H₂ and CO₂ besides little methane. DRIFTS results are in accordance with TPD analysis and the formation of acetate species at room temperature suggests reactivity of the surface and its oxidative dehydrogenation capacity. The adsorption of ethanol gives rise to ethoxide species, which form acetate and acetaldehyde that can be oxidized to CO₂ via carbonate. A comparison with reported results for Cu/Al₂O₃ this catalyst is promising, yielding high level of H₂ with little CO production during reforming and partial oxidation reaction. The maximum H₂ formation for the partial oxidation of ethanol was 41% at ratio (O₂/Et) 0.8, increasing to 50% at ratio 1.5. The H₂/CO is around 10 for the partial oxidation and 7 for steam reforming, which is excellent, compared to the Ni/Al₂O₃ catalyst with a factor 4–8 lower.     

Biocompatibility and cutaneous reactivity of cellulosic polysaccharide film in induced skin wounds in rats

The development of a skin substitute suitable for immediately performing the function of the lost dermis and epidermis could result in a positive impact on the treatment of patients with extensive skin lesions. A biopolymer film was applied to skin wounds to investigate the biocompatibility and cutaneous reaction and to test its activity as a mechanical barrier and conductor in the healing process. Forty Wistar rats of both sexes were used in the present study. Two excisions were performed in the dorsal part of the skin flaps. The polysaccharide film was applied over one of the incisions and other incision was washed with saline. The time spent for complete healing of both lesions was virtually the same in both groups, during 21 days of observation. The film remained attached to the bed of the exposed wound for an average period of 6 days. There were no statistically significant differences with regard to lesion measurement area at assessment times of 2nd, 7th and 14th postoperative days. At day 21, the scar area showed a significant difference (0.0229). After 40 days, all wounds were completely healed. No statistically significant differences were found between the histological parameters assessed in the experimental and control groups. The cellulosic polysaccharide film integrated well with the tissue showing high biocompatibility and low skin reactivity.     

Removal of heavy metals from wastewater using magnetic nanocomposites: Analysis of the experimental conditions

This contribution provides insight on the elimination of heavy metals from water resources using magnetic separation. Nanocomposites based on magnetite and chitosan were prepared. An exhaustive characterization of the magnetic adsorbents was developed. Adsorption assays were performed in batch using Cu, Zn, Cd, and Cr as model heavy metals. The efficiency of magnetic adsorbents followed the order: Cu > Cd > Zn > Cr, with maximum values of 188, 159, 72, and 46 mg of Me/g of nanocomposite, respectively. Kinetics and mechanistic issues were studied. The magnetic materials were efficient for five to eight cycles using Cu(II),Cd(II), and Cr(VI).     

Structure–property relationship of sodium deoxycholate based poly(ester ether)urethane ionomers for biomedical applications

New sodium deoxycholate based poly(ester ether)urethane ionomers were prepared for the development of biomedical materials. A structure–property relationship in the tested biomaterials was established by cross‐examination of the dynamic mechanical and dielectric properties, attenuated total reflection–Fourier transform infrared investigation, thermogravimetric analysis, and surface morphology characterization. A stronger ionic interaction and solvation capacity of the ions and a higher ionic conductivity were manifested in the case of poly(ethylene oxide)‐rich segments than for poly(propylene oxide)‐rich segments in these polyurethane ionomers. The molecular and ionic interactions of the bile‐salt moiety with different polyether cosoft segments influenced chain packing and conformation, supramolecular organization, and the resulting surface morphological microstructures of the polyurethane biomembranes. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42921.     

Structural Analysis of the Black-Legged Tick Saliva Protein Salp15

Salp15 is one of the proteins in the saliva of the tick Ixodes scapularis. Together with other biomolecules injected into the mammalian host at the biting site, it helps the tick to sustain its blood meal for days. Salp15 interferes with the cellular immune response of the mammalian host by inhibiting the activation of CD4⁺ T-lymphocytes. This function is co-opted by pathogens that use the tick as a vector and invade the host when the tick bites, such as Borrelia burgdorferi, the causative agent of Lyme borreliosis. Because of the immunity-suppressing role of Salp15, it has been proposed as a candidate for therapeutic applications in disorders of the immune system. The protein is produced as a 135-residue long polypeptide and secreted without its N-terminal signal 1–21 sequence. Detailed structural studies on Salp15 are lacking because of the difficulty in producing large amounts of the folded protein. We report the production of Salp15 and its structural analysis by NMR. The protein is monomeric and contains a flexible N-terminal region followed by a folded domain with mixed α + β secondary structures. Our results are consistent with a three-dimensional structural model derived from AlphaFold, which predicts the formation of three disulfide bridges and a free C-terminal cysteine.     

Biological Implications of a Stroke Therapy Based in Neuroglobin Hyaluronate Nanoparticles. Neuroprotective Role and Molecular Bases

Exogenous neuroprotective protein neuroglobin (Ngb) cannot cross the blood–brain barrier. To overcome this difficulty, we synthesized hyaluronate nanoparticles (NPs), able to deliver Ngb into the brain in an animal model of stroke (MCAO). These NPs effectively reached neurons, and were microscopically identified after 24 h of reperfusion. Compared to MCAO non-treated animals, those treated with Ngb-NPs showed survival rates up to 50% higher, and better neurological scores. Tissue damage improved with the treatment, but no changes in the infarct volume or in the oxidative/nitrosative values were detected. A proteomics approach (p-value < 0.02; fold change = 0.05) in the infarcted areas showed a total of 219 proteins that significantly changed their expression after stroke and treatment with Ngb-NPs. Of special interest, are proteins such as FBXO7 and NTRK2, which were downexpressed in stroke, but overexpressed after treatment with Ngb-NPs; and ATX2L, which was overexpressed only under the effect of Ngb. Interestingly, the proteins affected by the treatment with Ngb were involved in mitochondrial function and cell death, endocytosis, protein metabolism, cytoskeletal remodeling, or synaptic function, and in regenerative processes, such as dendritogenesis, neuritogenesis, or sinaptogenesis. Consequently, our pharmaceutical preparation may open new therapeutic scopes for stroke and possibly for other neurodegenerative pathologies.     

SI-ATRP Decoration of Magnetic Nanoparticles with PHEMA and Post-Polymerization Modification with Folic Acid for Tumor Cells’ Specific Targeting

Targeted nanocarriers could reach new levels of drug delivery, bringing new tools for personalized medicine. It is known that cancer cells overexpress folate receptors on the cell surface compared to healthy cells, which could be used to create new nanocarriers with specific targeting moiety. In addition, magnetic nanoparticles can be guided under the influence of an external magnetic field in different areas of the body, allowing their precise localization. The main purpose of this paper was to decorate the surface of magnetic nanoparticles with poly(2-hydroxyethyl methacrylate) (PHEMA) by surface-initiated atomic transfer radical polymerization (SI-ATRP) followed by covalent bonding of folic acid to side groups of the polymer to create a high specificity magnetic nanocarrier with increased internalization capacity in tumor cells. The biocompatibility of the nanocarriers was demonstrated by testing them on the NHDF cell line and folate-dependent internalization capacity was tested on three tumor cell lines: MCF-7, HeLa and HepG2. It has also been shown that a higher concentration of folic acid covalently bound to the polymer leads to a higher internalization in tumor cells compared to healthy cells. Last but not least, magnetic resonance imaging was used to highlight the magnetic properties of the functionalized nanoparticles obtained.