The influence of electron beam irradiation,plastic deformation,and re‐irradiation on crystallinity degree,mechanical and sclerometric properties of GUR 1050 used for arthroplasty

The article describes the influence of an electron beam irradiation (I), plastic deformation (D), and re‐irradiation (R) on the properties of ultrahigh molecular weight polyethylene (GUR 1050). It was found that the modification through irradiation entailed a gradual increase in the degree of crystallinity (after irradiation–I). After plastic deformation and re‐irradiation (IDR) the degree of crystallinity decreases which had a direct influence on the mechanical properties. The polymer irradiation only (technique I) resulted in an increase in the maximum stress as compared with the material in the initial state. The application of deformation and re‐irradiation (technique IDR) allowed increasing the deformation resistance by more than 40%. Moreover, the irradiation with an electron beam resulted in the increase in hardness (H) and Young's modulus (E) proportionally to the applied irradiation dose and in the reduction of total indentation work (W_tot) and its components. After deformation and re‐irradiation the polyethylene hardness went down. The application of technique (I) caused an improvement to the material abrasion resistance (reduction of parameter PD–working scratch depth) with the increasing irradiation dose. The introduction of deformation and re‐irradiation did not have a material impact on parameter (PD) increasing at the same time elastic properties of UHMWPE (increase in parameter NPS–elastic recovery). Modification IDR has changed the wear mechanism (β) toward ploughing and has increased the abrasion‐resistance index (W_β) and also significantly reduced the coefficient of friction (μ) of GUR 1050. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43683.     

Artificial Maturation of the Highly Active Heterodimeric [FeFe] Hydrogenase from Desulfovibrio desulfuricans ATCC 7757

Hydrogenases catalyze the reduction of protons and oxidation of molecular hydrogen with high turnover frequencies and low overpotentials under ambient conditions. The heterodimeric [FeFe] hydrogenase from Desulfovibrio desulfuricans has an exceptionally high activity, and can be purified aerobically in an oxygen-stable inactive state. Recently, it was demonstrated that monomeric [FeFe] hydrogenases produced recombinantly in Escherichia coli can be artificially maturated by simply incubating the inactive “apo” enzymes with the synthetic [2Fe] cofactor mimic [Fe₂(adt)(CO)₄(CN)₂]²⁻. Here, we use the same technique to produce the heterodimeric “apo” hydrogenase from D. desulfuricans in E. coli with a high yield and purity, and maturate the “apo” enzyme with [Fe₂(adt)(CO)₄(CN)₂]²⁻ to generate fully active “holo” enzyme. Interestingly, the rate of the artificial maturation process with D. desulfuricans is significantly slower than that for all other hydrogenases tested so far. The artificially maturated enzyme is spectroscopically and electrochemically identical to the native enzyme and shows high rates of hydrogen production (3700 s⁻¹) and hydrogen oxidation (63,000 s⁻¹). We expect that our highly efficient production method will facilitate future studies of this enzyme and other related [FeFe] hydrogenases from Desulfovibrio species.     

Optimization of subtractive-transformative hybrid processes supported by the technological heredity concept

This paper presents the optimization procedure of a hybrid removal-forming type process based on the minimum energy consumption and demanded surface roughness which is supported by the analysis of transformation of the surface and sublayer properties termed as the technological heredity. The experimental investigation covers an alloy steel hardened to 35 HRC and 55 HRC which was initially turned using coated carbide and CBN tools and subsequently burnished to produce surfaces with Ra roughness parameter of about 0.15 μm. The modifications of the initial surface profiles, microstructure and microhardness of the sublayer were determined and relevant technological limits are selected.     

Modeling of the degradation kinetics of biodegradable scaffolds: The effects of the environmental conditions

The rate of hydrolytic degradation of tissue‐engineered scaffolds made from bioresorbable polyesters is dependent on several factors. Some are related to the properties of the degrading polymeric material, but others are related to the geometry of the porous structure and the operating environment. It is well known that the rate of hydrolytic degradation of a given object, porous or nonporous, is lower when it is exposed to dynamic conditions, a flowing medium, than when it operates in static conditions. The most likely reason is the more efficient removal of the acidic degradation products from the vicinity of the polymeric material when it is operating in a flowing medium. In this article, we present a new phenomenological reaction–diffusion model of aliphatic polymer degradation. The model can be used to predict the significance of various factors in in vitro degradation tests, with particular reference to the flow of the degradation medium, and the frequency of medium replacement in the case of static conditions. The developed model was used to simulate the degradation of poly(dl ‐lactide‐co‐glycolide) scaffolds with different porosities subjected to static and dynamic testing conditions. The results confirm that the porosity of the scaffold had a significant influence on the degradation rate. It was shown that the combination of dynamic conditions and high porosity effectively reduced the mass loss and molecular weight loss of the degrading polymer. However, the effect of changes in the velocity of the flowing medium had a negligible effect on the rate of degradation. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40280.     

Clickable poly(ionic liquid)s for modification of glass and silicon surfaces

Covalent attachment of poly(ionic liquid)s (PILs) by click chemistry on glass or silicon (Si) surfaces was performed. Poly[1-(4-vinylbenzyl)-3-butylimidazolium bis(trifluoromethylsulfonyl)imide] (polyVBBI⁺Tf₂N⁻), and copolymers of polyVBBI⁺Tf₂N⁻ with fluorescein O-methacrylate were synthesized by conducting an atom transfer radical polymerization (ATRP) from initiators containing azide or thioacetate groups. The azide- and thiol-terminated PILs were then successfully grafted onto alkyne and alkene modified glass/Si wafers by thermal azide–alkyne cycloaddition and photoinitiated thiol-ene click reactions, respectively. The modified surfaces were characterized by contact angle measurements and ellipsometry. The fluorescent PIL functionalized surfaces showed strong fluorescence under UV irradiation. This procedure of tethering PILs to substrates also provides an easy way to change the surface hydrophilicity by replacing the anions in the grafted PILs. The present approach could be readily applied for surface modifications with other types of PILs or their copolymers to achieve different functionalities on various surfaces.     

On the Effect of pH,Temperature, and Surfactant Structure on Bovine Serum Albumin–Cationic/Anionic/Nonionic Surfactants Interactions in Cacodylate Buffer–Fluorescence Quenching Studies Supported by UV Spectrophotometry and CD Spectroscopy

Due to the fact that surfactant molecules are known to alter the structure (and consequently the function) of a protein, protein–surfactant interactions are very important in the biological, pharmaceutical, and cosmetic industries. Although there are numerous studies on the interactions of albumins with surfactants, the investigations are often performed at fixed environmental conditions and limited to separate surface-active agents and consequently do not present an appropriate comparison between their different types and structures. In the present paper, the interactions between selected cationic, anionic, and nonionic surfactants, namely hexadecylpyridinium chloride (CPC), hexadecyltrimethylammonium bromide (CTAB), sodium dodecyl sulfate (SDS), polyethylene glycol sorbitan monolaurate, monopalmitate, and monooleate (TWEEN 20, TWEEN 40, and TWEEN 80, respectively) with bovine serum albumin (BSA) were studied qualitatively and quantitatively in an aqueous solution (10 mM cacodylate buffer; pH 5.0 and 7.0) by steady-state fluorescence spectroscopy supported by UV spectrophotometry and CD spectroscopy. Since in the case of all studied systems, the fluorescence intensity of BSA decreased regularly and significantly under the action of the surfactants added, the fluorescence quenching mechanism was analyzed thoroughly with the use of the Stern–Volmer equation (and its modification) and attributed to the formation of BSA–surfactant complexes. The binding efficiency and mode of interactions were evaluated among others by the determination, comparison, and discussion of the values of binding (association) constants of the newly formed complexes and the corresponding thermodynamic parameters (ΔG, ΔH, ΔS). Furthermore, the influence of the structure of the chosen surfactants (charge of hydrophilic head and length of hydrophobic chain) as well as different environmental conditions (pH, temperature) on the binding mode and the strength of the interaction has been investigated and elucidated.     

Why Do We Need More Active ATRP Catalysts?

Atom transfer radical polymerization (ATRP) is a staple technique for the preparation of polymers with well-defined architecture. In ATRP, the catalyst governs the equilibrium between propagating radicals and dormant species, thus affecting the polymerization control for a range of monomers and transferable atoms employed in the process. The design and the use of highly active catalysts could diminish the amount of transition metal complexes, extend ATRP to less active monomers and give access to new chain-end functionalities. At the same time, very active catalysts can be involved in formation of organometallic species. Herein, the role of the catalyst on the ATRP equilibrium is carefully elucidated, together with recent observations on the impact of the catalyst nature on formation of organometallic species and relevant side reactions. Based on this knowledge, a perspective on the benefits and challenges that derive from the use of highly active ATRP catalysts is presented.     

Investigating the Potential Use of Chemical Biopsy Devices to Characterize Brain Tumor Lipidomes

The development of a fast and accurate intraoperative method that enables the differentiation and stratification of cancerous lesions is still a challenging problem in laboratory medicine. Therefore, it is important to find and optimize a simple and effective analytical method of enabling the selection of distinctive metabolites. This study aims to assess the usefulness of solid-phase microextraction (SPME) probes as a sampling method for the lipidomic analysis of brain tumors. To this end, SPME was applied to sample brain tumors immediately after excision, followed by lipidomic analysis via liquid chromatography-high resolution mass spectrometry (LC-HRMS). The results showed that long fibers were a good option for extracting analytes from an entire lesion to obtain an average lipidomic profile. Moreover, significant differences between tumors of different histological origin were observed. In-depth investigation of the glioma samples revealed that malignancy grade and isocitrate dehydrogenase (IDH) mutation status impact the lipidomic composition of the tumor, whereas 1p/19q co-deletion did not appear to alter the lipid profile. This first on-site lipidomic analysis of intact tumors proved that chemical biopsy with SPME is a promising tool for the simple and fast extraction of lipid markers in neurooncology.