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.     

Hydrogenation of vegetable oil using highly dispersed Pt/γ-Al2O3 catalyst: Effects of key operating parameters and deactivation study

In the present work, Pt/γ-Al₂O₃ catalysts with high metal dispersion were prepared and characterized using chloroplatinic acid and platinum acetylacetonate as metal precursors. The activity and selectivity of the catalysts were evaluated in the hydrogenation of sunflower oil. A comprehensive analysis of the effects of key operational parameters on catalytic performance was carried out. The experimental variables were hydrogen pressure (275.8–551.6 kPa), temperature (160–200°C), and catalyst loading (0.005–0.015 kg Pt_exp/m³_oil). Platinum catalysts were active, with a double bond conversion of 28% at 2 h. The metal precursor affected catalyst selectivity. The catalyst prepared with chloroplatinic acid exhibited a lower formation of trans-isomers compared with Pt acetylacetonate. The γ-Al₂O₃ supported platinum catalyst with a metal loading of 0.51 wt.% and a metal dispersion of 98% maintained its initial catalyst activity and selectivity after 10 consecutive uses (1200 min accumulate operation time), without changes in its catalytic properties. The obtained results suggested that Pt catalysts are an attractive alternative to conventional nickel catalysts for the hydrogenation of vegetable oil.     

Mathematical modeling of the partial hydrogenation of vegetable oil in a monolithic stirrer reactor

Experimental and theoretical studies on the partial hydrogenation of vegetable oil in a monolithic stirrer reactor are reported. A complete mathematical model of the reactor was developed, including hydrogenation and isomerization kinetics, catalyst deactivation, external gas–liquid and liquid–solid as well as internal mass transfer. The experimental studies were carried out in a Pd/Al₂O₃/Al monolithic stirrer reactor, at a wide range of temperatures (353–373 K), pressures (414–552 kPa), and catalyst loadings (0.00084–0.00527 kg_Pd,exp m^?3). Based on this model, simulated data can be used to evaluate the catalyst (Pd/Al₂O₃/Al) and the hydrogenation process in consecutive catalytic tests under different operating conditions. © 2014 American Institute of Chemical Engineers AIChE J, 60: 3524–3533, 2014     

Study of thermodegradation and thermostabilization of poly(lactide acid) using subsequent extrusion cycles

The thermomechanical degradation and thermostabilization of poly(lactic acid) (PLA) have been studied using subsequent extrusion cycles under different temperature profiles. Primary and secondary antioxidants were used to avoid degradation process during extrusion. Melt flow index (MFI), size exclusion chromatography (SEC), and infrared spectroscopy (FTIR) analysis were used to evaluate the degradation and stabilization of PLA. The MFI and SEC analysis show that the main thermodegradation mechanism of PLA is governed by scission reactions. FTIR analysis confirmed the SEC results and showed that the synergetic effect between primary and secondary antioxidant is a suitable way to thermostabilize the PLA. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 40023.     

Effects of benzoyl peroxide on some properties of composites based on hemp and natural rubber

The obtaining and characterization of polymer composites based on natural rubber and hemp, in which the elastomer crosslinking has been achieved with benzoyl peroxide, are presented. The mechanical characteristics, gel fraction, crosslink density, water uptake swelling parameters and FTIR of the composites based on natural rubber and hemp fiber vulcanized by dibenzoyl peroxide have been investigated as a function of the hemp content. The hardness, modulus at 100 % elongation, tearing strength, tensile strength and elongation at break have been improving with the increasing of fiber content in composites materials due to the better interaction of fiber in natural rubber composites. These results indicate that hemp has a reinforcing effect on natural rubber. Gel fraction value is over 95 % for all blends and varies irregularly depending on the amount of hemp in the composites. The crosslinking density (ν) of samples increases as the amount of hemp in blends increases, because hemp act as a filler in natural rubber blends and leads to reinforcement of the blends. The water uptake and swelling parameters also increases with the increasing of the amount of fiber content, because of the hemp hydrophilic characteristics.     

Study of thermal behavior of polyimides containing pendent-substituted azobenzene units

Thermal stability and degradation kinetic of the polyimides containing pendent-substituted azobenzene units were investigated by thermogravimetric analysis in nitrogen at different heating rates. Freeman–Carroll, Coats–Redfern and Flynn–Wall–Ozawa methods were utilized to obtain the kinetic parameters (activation energy E _a, pre-exponential factor A and order of reaction n) or variation of activation energy with conversion degree from thermogravimetric and derivative thermogravimetric curves. The thermogravimetric analysis revealed that the decomposition of azopolyimides proceeds in three or four stages, regardless of heating rate.     

Overexpression of microRNAs miR-25-3p,miR-185-5p and miR-132-3p in Late Onset Fetal Growth Restriction,Validation of Results and Study of the Biochemical Pathways Involved

In a prospective study, 48 fetuses were evaluated with Doppler ultrasound after 34 weeks and classified, according to the cerebroplacental ratio (CPR) and estimated fetal weight (EFW), into fetuses with normal growth and fetuses with late-onset fetal growth restriction (LO-FGR). Overexpression of miRNAs from neonatal cord blood belonging to LO-FGR fetuses, was validated by real-time PCR. In addition, functional characterization of overexpressed miRNAs was performed by analyzing overrepresented pathways, gene ontologies, and prioritization of synergistically working miRNAs. Three miRNAs: miR-25-3p, miR-185-5p and miR-132-3p, were significantly overexpressed in cord blood of LO-FGR fetuses. Pathway and gene ontology analysis revealed over-representation of certain molecular pathways associated with cardiac development and neuron death. In addition, prioritization of synergistically working miRNAs highlighted the importance of miR-185-5p and miR-25-3p in cholesterol efflux and starvation responses associated with LO-FGR phenotypes. Evaluation of miR-25-3p; miR-132-3p and miR-185-5p might serve as molecular biomarkers for the diagnosis and management of LO-FGR; improving the understanding of its influence on adult disease.     

Synthesis of Mammalian Gonadoliberin Analogs with the N-terminal glutamine or glutamine or glutamic acid

Synthesis of two mammalian gonadoliberin analogs, [Gln¹]GnRH and [Glu¹]GnRH, in solution by the peptide segment coupling of the [(2 + 4) + 4] type has been described.     

Charge Transport Calculation along Two-Dimensional Metal/Semiconductor/Metal Systems

Two-dimensional transistors are promising candidates for the next generation of nanoscale devices. Like the other alternatives, they also encounter problems such as instability under standard condition (STP), low channel mobility, small band gaps, and difficulty to integrate metal contacts. The latter poses a great challenge since metal/semiconductor interface significantly affects the transistor‘s performance. Some of these obstacles can be solved by using two-dimensional transition metal di-chalcogenides (TMDC) materials. In this study, we performed charge transport calculation based on density functional theory (DFT) followed by wave dynamics to evaluate the performance of six two-dimensional TMDC metal/semiconductor/metal systems. Each semiconductor monolayer was laterally connected, at both ends to metal contacts consisting of VS₂ or FeS₂ monolayers. We found that charge transport was more efficient in systems containing a CrS₂ semiconductor monolayer compared to systems with MoS₂ or WS₂ as the semiconductor monolayer. The electronic characterization of the monolayer TMDC materials by DFT estimates well the trend in charge transport efficiency calculated using wave packet dynamics.