Biodegradable poly(L‐lactic acid)/TiO2 nanocomposites: Thermal properties and degradation

Poly(L ‐lactic acid)‐titanium dioxide nanocomposites (with various loadings of TiO₂: 0.5, 1, 2, 5, and 10 wt %) were produced by solution casting method. The influence of TiO₂ on thermal properties and crystallinity of PLA was investigated by DSC and FTIR spectroscopy. The TiO₂ nano filler has no significant influence on the characteristic temperatures (T_g, T_c, and T_m), but has high impact on the crystallinity of these systems. The degree of crystallinity X_c significantly increases for PLA nanocomposites loaded with up to 5 wt % of TiO₂, while for 10 wt % load of TiO₂ it drops below X_c of the pure resin. The degradation of the prepared composites was evaluated hydrolytically in 1N NaOH, enzymatically in α‐amylase solutions, and under UV irradiation. The catalytic effect of TiO₂ nano particles on the degradation processes under UV light exposure (λ = 365 nm) and hydrolytic degradation was confirmed with the increase of the filler content. The opposite effect was identified in enzymatic degradation experiments. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Modeling of kinetics of pertechnetate removal by amino-functionalized glycidyl methacrylate copolymer

Technetium-99 comprises a significant health risk, since edible plants can bioaccumulate and convert it to more lipophilic species that cannot be excreted through urine. Batch kinetics of pertechnetate removal from aqueous solutions by two samples of crosslinked poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate) functionalized with diethylene triamine (PGME-deta) was investigated at the optimum pH value of 3.0, and the initial solution activity of 325 MBq dm⁻³. PGME-deta was characterized by elemental analysis, mercury intrusion porosimetry, and scanning electron microscopy. Five kinetic models (pseudo-first, pseudo-second order, Elovich, Bangham, and intraparticle diffusion) were used to determine the best-fit equation for pertechnetate sorption. After 24 h, PGME-deta samples sorbed more than 98% of pertechnetate present, with maximum sorption capacity of 25.5 MBq g⁻¹, showing good potential for remediation of slightly contaminated groundwater.     

A microporous and high surface area active carbon obtained by the heat-treatment of chitosan

A method is described for converting chitosan into a high surface area and porous active carbon using a Na₂CO₃ solution impregnated into a partly depolymerized, protonated and water soaked chitosan. The wet chitosan paste is heat treated and transformed into a nonporous solid i.e. a carbon-rich matrix with uniformly suspended Na₂CO₃ nanocrystallites. Subsequent HCl etching opens cavities in the matrix due to the removal of the Na₂CO₃. The active carbon is high surface area (above 400 m²/g), microporous (below 1 nm) and nitrogen-rich (above 6% atomic).     

Metallocenyl 7-ACA Conjugates: Antibacterial Activity Studies and Atomic-Resolution X-ray Crystal Structure with CTX-M β-Lactamase

The conjugation of organometallic groups to current β-lactam antibiotics is a field of increasing study due to the ability of certain organometallic groups to enhance the antibiotic potency of these drugs. Herein, we report the antibacterial properties of two metallocenyl (ferrocenyl and ruthenocenyl) 7-aminocephalosporanic acid (7-ACA) antibiotic conjugates. Continuing a trend we found in our previous studies, the ruthenocenyl conjugate showed greater antibacterial activity than its ferrocenyl counterpart. Compared with the previously published 7-aminodesacetoxycephalosporanic acid (7-ADCA) conjugates, the 3-acetyloxymethyl group significantly improved the compounds’ activity. Furthermore, the Rc-7-ACA compound was more active against clinical Staphylococcus aureus isolates than the ampicillin reference. Noticeably, neither of the two new compounds showed an undesirable toxic effect in HeLa and L929 cells at the concentrations at which they displayed strong antibacterial effects. The antibacterial activity of the two metallocenyl 7-ACA derivatives was further confirmed by scanning electron microscopy (SEM). SEM micrographs showed that bacteria treated with metallocenyl 7-ACA derivatives feature cell wall damage and morphology changes. Using a CTX-M-14 β-lactamase competition assay based on nitrocefin hydrolysis, we showed that the Rc-7-ACA bound more favorably to CTX-M-14 than its ferrocenyl counterpart, again confirming the superiority of the ruthenocenyl moiety over the ferrocenyl one in interacting with proteins. We also report a 1.47 Å resolution crystal structure of Rc-7-ACA in complex with the CTX-M-14 E166A mutant, an enzyme sharing a similar active site configuration with penicillin-binding proteins, the molecular target of β-lactam antibiotics. These results strengthen the case for the antibacterial utility of the Rc and Fc groups.     

Biological Characteristics and Osteogenic Differentiation of Ovine Bone Marrow Derived Mesenchymal Stem Cells Stimulated with FGF-2 and BMP-2

Cell-based therapies using mesenchymal stem cells (MSCs) are a promising tool in bone tissue engineering. Bone regeneration with MSCs involves a series of molecular processes leading to the activation of the osteoinductive cascade supported by bioactive factors, including fibroblast growth factor-2 (FGF-2) and bone morphogenetic protein-2 (BMP-2). In this study, we examined the biological characteristics and osteogenic differentiation potential of sheep bone marrow MSCs (BM-MSCs) treated with 20 ng/mL of FGF-2 and 100 ng/mL BMP-2 in vitro. The biological properties of osteogenic-induced BM-MSCs were investigated by assessing their morphology, proliferation, phenotype, and cytokine secretory profile. The osteogenic differentiation was characterized by Alizarin Red S staining, immunofluorescent staining of osteocalcin and collagen type I, and expression levels of genetic markers of osteogenesis. The results demonstrated that BM-MSCs treated with FGF-2 and BMP-2 maintained their primary MSC properties and improved their osteogenic differentiation capacity, as confirmed by increased expression of osteocalcin and collagen type I and upregulation of osteogenic-related gene markers BMP-2, Runx2, osterix, collagen type I, osteocalcin, and osteopontin. Furthermore, sheep BM-MSCs produced a variety of bioactive factors involved in osteogenesis, and supplementation of the culture medium with FGF-2 and BMP-2 affected the secretome profile of the cells. The results suggest that sheep osteogenic-induced BM-MSCs may be used as a cellular therapy to study bone repair in the preclinical large animal model.     

Detailed Insight into the Interaction of Bicyclic Somatostatin Analogue with Cu(II) Ions

Somatostatin analogues are useful pharmaceuticals in peptide receptor radionuclide therapy. In previous studies, we analyzed a new bicyclic somatostatin analogue (BCS) in connection with Cu(II) ions. Two characteristic sites were present in the peptide chain: the receptor- and the metal-binding site. We have already shown that this ligand can form very stable imidazole complexes with the metal ion. In this work, our aim was to characterize the intramolecular interaction that occurs in the peptide molecule. Therefore, we analyzed the coordination abilities of two cyclic ligands, i.e., P1 only with the metal binding site and P2 with both sites, but without the disulfide bond. Furthermore, we used magnetic circular dichroism (MCD) spectroscopy to better understand the coordination process. We applied this method to analyze spectra of P1, P2, and BCS, which we have described previously. Additionally, we analyzed the MCD spectra of P3 ligand, which has only the receptor binding site in its structure. We have unequivocally shown that the presence of the Phe-Trp-Lys-Thr motif and the disulfide bond significantly increases the metal binding efficiency.     

The Pathophysiological Role of CoA

The importance of coenzyme A (CoA) as a carrier of acyl residues in cell metabolism is well understood. Coenzyme A participates in more than 100 different catabolic and anabolic reactions, including those involved in the metabolism of lipids, carbohydrates, proteins, ethanol, bile acids, and xenobiotics. However, much less is known about the importance of the concentration of this cofactor in various cell compartments and the role of altered CoA concentration in various pathologies. Despite continuous research on these issues, the molecular mechanisms in the regulation of the intracellular level of CoA under pathological conditions are still not well understood. This review summarizes the current knowledge of (a) CoA subcellular concentrations; (b) the roles of CoA synthesis and degradation processes; and (c) protein modification by reversible CoA binding to proteins (CoAlation). Particular attention is paid to (a) the roles of changes in the level of CoA under pathological conditions, such as in neurodegenerative diseases, cancer, myopathies, and infectious diseases; and (b) the beneficial effect of CoA and pantethine (which like CoA is finally converted to Pan and cysteamine), used at pharmacological doses for the treatment of hyperlipidemia.     

Impact of particle morphology on structure,crystallization kinetics,and properties of PCL composites with TiO<Subscript>2</Subscript>-based particles

Crystallization kinetics of polycaprolactone (PCL) filled with TiO₂-based particles (TiX) was shown to depend on the TiX particle type and concentration, which were associated with a slight polymer matrix degradation. The partially degraded, shorter, and more mobile polymer chains increased the overall crystallization rate at the initial stage of crystallization, while at the later stages, the non-nucleating TiX particles acted as a sterical hindrance, slowing down the crystallization process. The PCL/TiX composites were prepared by melt-mixing and contained 2.5 and 5 wt% of the filler. The investigated TiX particles included isometric anatase microparticles (mTiO₂) and titanate nanotubes with high-aspect ratio (TiNT). Light and electron microscopy showed very homogeneous dispersion of the mTiO₂ particles in the PCL matrix, while the TiNT formed large agglomerates. In situ polarized light microscopy displayed faster isothermal crystallization of all PCL/TiX composites, but the micrographs indicated that the TiX particles did not act as nucleation centres. Isothermal DSC experiments, evaluated in terms of Avrami theory, confirmed the PLM results and showed that the overall rate of isothermal crystallization increased in the following order: PCL <PCL/TiNT <PCL/mTiO₂. Non-isothermal DSC and rheological measurements revealed the correlation between the crystallization rate and the polymer matrix degradation—the well-dispersed mTiO₂ particles with high specific surface caused the highest PCL degradation and, consequently, the earliest start of non-isothermal crystallization as well as the fastest isothermal crystallization. Microindentation hardness measurements confirmed that the partial degradation of the polymer matrix did not have a significant impact on the mechanical performance of PCL/mTiO₂ composites.     

The impact of drying and steaming processes on surface color changes of tension and normal beech wood

Abstract

Beech wood has a high frequency of defects such as red heartwood, reaction wood (tension wood). For the experimental measurements four logs without visible defects like red heartwood, which can noticeably affects the measurements' results were qualified. The drying medium temperature in the first phase of the process before the moisture content of the specimens fell below the FSP was maintained at 45?°C. Then, the temperature was gradually increased to the maximum value 65?°C. The results showed that different initial wood moisture content does not affect to final value of tension and normal wood. The colorimetric parameter L* was much higher for tension wood. After steaming, there were greater differences in the colorimetric parameters, respectively, a* and b*. After drying the difference of all colorimetric parameters between tension and normal wood was significantly less. The color changes were only noticed in the surface layers of specimens. Differences were small, and thus, the impact of the tension wood on the color changes was not confirmed. However, since the lightness of tension wood plays a key role for its visual detection, it may be adequate to only measure the lightness parameter (L*).