Multiscale approach to the morphology,structure, and segmental dynamics of complex degradable aliphatic polyurethanes

A multiscale approach spanning from the segmental (subnanometer) up to micrometer level was applied for detailed study of the self‐assembly of aliphatic block polyurethane (PU) elastomers. To understand the principles of the self‐organization of hard and soft segments in the complex multi‐component systems, several two‐component model PU samples, that is, the products of 1,6‐diisocyanatohexane (HDI) with three diols differing in the length and constitution were also prepared, characterized, and investigated: (i) polycarbonate‐based macrodiol (MD), (ii) biodegradable oligomeric diol (DL‐L; product of butane‐1,4‐diol and D,L‐lactide), and (iii) butane‐1,4‐diol (BD). The study (particularly ¹³C‐¹H PILGRIM NMR spectra) reveals complex internal organization and interesting (application appealing) behavior of multi‐component PUs. Hard segments (HDI+BD products) feature self‐assembled and significantly folded chain conformations with interdomain spacing 15–22 nm (small‐angle X‐ray scattering analysis). The small domains are hierarchically assembled in various structural formations of µm size (spherulites) depending on PU composition, as detected by transmission electron microscopy and atomic force microscopy. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41590.     

Batch and Fed‐Batch Degradation of Enrofloxacin by the Fenton Process

Enrofloxacin is a synthetic second‐generation fluoroquinolone used as an antimicrobial agent exclusively in veterinary medicine. To simulate the treatment of wastewater contaminated by enrofloxacin, four‐day long fed‐batch runs were carried out according to the Fenton process with an enrofloxacin solution as model, to which hydrogen peroxide and ferrous ion were added twice a day. The residual enrofloxacin concentration was practically coincident to that detected at the end of the batch tests. Hydrogen peroxide was almost completely consumed after each feeding period, while the total organic carbon (TOC) concentration decreased gradually within three days, corresponding to a reduction > 58 %. From the third day on, the TOC falling rate was quite low. A yellow sludge settled due to the precipitation of both Fe(OH)₃ and a complex formed by ferric ion with adsorbed enrofloxacin and/or its oxidation products.     

Kinetics of lipid oxidation in the presence of cinnamic acid derivatives

The effects of seven (prenyl‐ and methoxy‐) derivatives of cinnamic acid (0.1 mM) on the kinetics of lipid (sunflower oil triacylglycerols, TGSO) bulk phase oxidation at 80 °C have been compared. Synthesis of prenyl cinnamic acid derivatives: 3‐prenyl‐4‐hydroxy‐cinnamic acid (PHC), 3,5‐diprenyl‐4‐hydroxy‐cinnamic acid (DPHC), 2,2‐di‐methyl‐6‐carboxy‐ethenyl‐2H‐benzopyran (DMCB), 2,2‐dimethyl‐6‐carboxy‐ethenyl‐8‐prenyl‐2H‐benzopyran (DCEPB) present in Brazilian propolis has been performed. The monoprenyl derivative (PHC) has been found to exert a higher antioxidant activity as compared to the diprenyl derivative (DPHC). However, cinnamic acid derivatives DMCB and DCEPB have caused no change in the kinetics of TGSO oxidation. The results obtained have been compared with those on related compounds containing a cinnamic acid moiety as a structural feature, such as 4‐hydroxy‐cinnamic (p‐coumaric), 3‐methoxy‐4‐hydroxy‐cinnamic (ferulic) and 3,5‐dimethoxy‐4‐hydroxy‐cinnamic (sinapic) acids, as well as with data on butylated hydroxytoluene (BHT) and α‐tocopherol (αToc). PHC has shown a stronger antioxidant efficiency than BHT, p‐coumaric and ferulic acid, but a weaker antioxidant efficiency than α‐Toc and sinapic acid. The observed antioxidant effect of DPHC was stronger than that of p‐coumaric and ferulic acids and weaker than that of α‐Toc, BHT and sinapic acid.     

Microwave assisted combustion synthesis in the system Ti–Si–C for the joining of SiC: Experimental and numerical simulation results

Microwaves at 2.45 GHz have been applied to ignite the combustion synthesis of compacted Ti–Si–C powders mixtures, having 1:1:1 atomic ratio, in order to join SiC-based components. A mixture of different refractory phases such as TiC and TiSi₂ were obtained. Depending on the synthesis conditions, no residual silicon in the joint was detected, suggesting the suitability of the here proposed experimental joining approach for nuclear plants and high temperature applications. A simplified model was developed with the aim of obtaining a deeper understanding of the here proposed rapid, almost pressure-less and localized heating joining method. Experimental and numerical simulation results demonstrate that joining of SiC can be rapidly obtained with minimization of heat affected zones in the SiC substrates. Maximum apparent shear strength values of the joints ranged from 9.9 to 45.1 MPa, depending on the process conditions.     

Electrochemical comparison of IrO2 prepared by anodic oxidation of pure iridium and IrO2 prepared by thermal decomposition of H2IrCl6 precursor solution

Surface redox activities, oxygen evolution reaction (OER), oxidation of formic acid (FA), and anodic stability were investigated and compared for IrO₂ electrodes prepared by two techniques: the thermal decomposition of H₂IrCl₆ precursor (TDIROF) and the anodic oxidation of metallic iridium (AIROF). Surface redox activities involved on the AIROF were found to be much faster than those involved on the TDIROF. Concerning the oxygen evolution reaction, both films show a similar mechanism and specific electrocatalytic activities. The situation seems to be different for FA oxidation. In fact, on TDIROF, the oxidation of FA and the OER compete involving the same surface redox couple Ir(VI)/Ir(IV) contrary to FA oxidation on AIROF, where the Ir(V)/Ir(IV) surface redox couple is involved. Finally, electrode stability measurements have shown that contrary to TDIROF, which are very stable under anodic polarization, the AIROF are rapidly corroded under anodic treatment. This corrosion is enhanced even further in the presence of formic acid.     

Effect of sonolysis on waste activated sludge solubilisation and anaerobic biodegradability

Activated sludge processes are key technologies in wastewater treatment. These biological processes produce huge amounts of waste activated sludge (WAS) or otherwise biosolids. Mechanical, thermal, and/or chemical WAS conditioning techniques have been proposed to reduce the sludge burden. Among the WAS treatments, the pre-treatment with ultrasound (US) is one of the most innovative processes. In many anaerobic digestion processes for the treatment of the sludge produced in wastewater treatment plants, the hydrolysis of the organic matter has been identified as the rate limiting step.This study is focused on the effect of US pre-treatment of WAS to the anaerobic digestion. Particle size reduction, Chemical Oxygen Demand (COD) solubilization and biodegradability by anaerobic digestion were monitored in order to find the optimal dose in US pre-treatment.The results show the better sonolysis conditions (US density, sonication time, specific energy) which can significantly improve the COD solubilisation and the anaerobic biodegradability.     

Tailored-Made Polydopamine Nanoparticles to Induce Ferroptosis in Breast Cancer Cells in Combination with Chemotherapy

Ferroptosis is gaining followers as mechanism of selective killing cancer cells in a non-apoptotic manner, and novel nanosystems capable of inducing this iron-dependent death are being increasingly developed. Among them, polydopamine nanoparticles (PDA NPs) are arousing interest, since they have great capability of chelating iron. In this work, PDA NPs were loaded with Fe³⁺ at different pH values to assess the importance that the pH may have in determining their therapeutic activity and selectivity. In addition, doxorubicin was also loaded to the nanoparticles to achieve a synergist effect. The in vitro assays that were performed with the BT474 and HS5 cell lines showed that, when Fe³⁺ was adsorbed in PDA NPs at pH values close to which Fe(OH)₃ begins to be formed, these nanoparticles had greater antitumor activity and selectivity despite having chelated a smaller amount of Fe³⁺. Otherwise, it was demonstrated that Fe³⁺ could be released in the late endo/lysosomes thanks to their acidic pH and their Ca²⁺ content, and that when Fe³⁺ was co-transported with doxorubicin, the therapeutic activity of PDA NPs was enhanced. Thus, reported PDA NPs loaded with both Fe³⁺ and doxorubicin may constitute a good approach to target breast tumors.