Nonisothermal crystallization behavior of a biodegradable segmented copolymer constituted by glycolide and trimethylene carbonate units

Nonisothermal crystallization of a segmented copolymer constituted by glycolide and trimethylene carbonate units was studied from both the melt and the glass state by optical microscopy, differential scanning calorimetry and time‐resolved X‐ray diffraction techniques. Positive spherulites with a fibrilar appearance were always obtained and corresponded to the crystallization of the polyglycolide hard segments. A single crystallization regime and the kinetic parameters were inferred from optical microscopy data on crystallizations performed at different cooling/heating rates. The parameters were in good agreement with values previously deduced from isothermal experiments. Isoconversional data of melt and glass nonisothermal crystallizations were combined to obtain the Lauritzen and Hoffman parameters from calorimetric data. Results revealed again the existence of a single crystallization regime with a secondary nucleation constant close to that deduced from isothermal DSC experiments. Morphological changes occurring during the hot and cold crystallization were evaluated by time‐resolved SAXS/WAXD experiments employing synchrotron radiation. Measurements showed that significant differences on the lamellar thicknesses exist depending on the crystallization process. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Macroporous silicon for high-capacitance devices using metal electrodes

In this paper, high-capacity energy storage devices based on macroporous silicon are demonstrated. Small footprint devices with large specific capacitances up to 100 nF/mm², and an absolute capacitance above 15 μF, have been successfully fabricated using standard microelectronics and MEMS techniques. The fabricated devices are suitable for high-density system integration. The use of 3-D silicon structures allows achieving a large surface to volume ratio. The macroporous silicon structures are fabricated by electrochemical etching of silicon. This technique allows creating large structures of tubes with either straight or modulated radial profiles in depth. Furthermore, a very large aspect ratio is possible with this fabrication method. Macroporous silicon grown this way permits well-controlled structure definition with excellent repeatability and surface quality. Additionally, structure geometry can be accurately controlled to meet designer specifications. Macroporous silicon is used as one of the electrodes over which a silicon dioxide insulating layer is grown. Several insulator thicknesses have been tested. The second capacitor electrode is a solid nickel filling of the pores prepared by electroplating in a low-temperature industry standard process. The use of high-conductivity materials allows reaching small equivalent series resistance near 1 Ω. Thanks to these improvements, the presented devices are capable of operating up to 10 kHz.

PACS

84.32.Tt; 81.15.Pq; 81.05.Rm     

The interpretation of X-ray photoelectron spectra of pyrolized S-containing carbonaceous materials

Theoretical models and ab initio Hartree-Fock wavefunctions have been used to investigate the S(2p) core level binding energies (BE), of pyrolized S-containing, carbonaceous materials. Comparison between experimental and calculated data for thiophene permits the accuracy of the present approach to be established. A systematic study of different situations demonstrates that, in these materials, non-oxidized S atoms can show peaks at very high BE relative to the C(1s) peak at 285.0 eV. This study confirms that the peak at 164.1 eV corresponds to ‘thiophenic’ S atoms. On the other hand, it shows that the peaks at higher BE could correspond to S atoms replacing C atoms in three-coordinated structures of graphene layers, in agreement with the arguments suggested in the experimental works. The energetic similarity between the two peaks at very high BE makes it difficult to differentiate between them, although the results of the present study seem to suggest that the peak at experimental BE ≈ 166 eV could correspond to S atoms coordinated to two C and one H atoms at the edge of graphene layers, while the peak at ≈ 169 eV would correspond to S atoms replacing C atoms in inner positions of the graphene layers, and it is bonded to three C atoms.     

Effect of pre‐treatments based on UV photocatalysis and photo‐oxidation on toluene biofiltration performance

BACKGROUND: The integration of UV photocatalysis and biofiltration seems to be a promising combination of technologies for the removal of hydrophobic and poorly biodegradable air pollutants. The influence of pre‐treatments based on UV_{254 nm} photocatalysis and photo‐oxidation on the biofiltration of toluene as a target compound was evaluated in a controlled long‐term experimental study using different system configurations: a standalone biofilter, a combined UV photocatalytic reactor‐biofilter, and a combined UV photo‐oxidation reactor (without catalyst)‐biofilter. RESULTS: Under the operational conditions used (residence time of 2.7 s and toluene concentrations 600–1200 mg C m^?3), relatively low removal efficiencies (6–3%) were reached in the photocatalytic reactor and no degradation of toluene was found when the photo‐oxidation reactor was operated without catalyst. A noticeable improvement in the performance of the biofilter combined with a photocatalytic reactor was observed, and the elimination capacity of the biological process increased by more than 12 g C h^?1 m^?3 at the inlet loads studied of 50–100 g C h^?1 m^?3. No positive effect on toluene removal was observed for the combination of UV photoreactor and biofilter. CONCLUSIONS: Biofilter pre‐treatment based on UV_{254 nm} photocatalysis showed promising results for the removal of hydrophobic and recalcitrant air pollutants, providing synergistic improvement in the removal of toluene. Copyright © 2011 Society of Chemical Industry     

Electrospun nanofibers of a degradable poly(ester amide). Scaffolds loaded with antimicrobial agents

Electrospinning conditions were evaluated to prepare micro/nanofibers of a biodegradable poly(ester amide) constituted by L-alanine, 1,12-dodecanediol and sebacic acid. 1,1,1,3,3,3-Hexafluroroisopropanol appeared as the most appropriate solvent to obtain fibers in a wide range of electrospinning conditions that allowed tuning the final diameter size. Fiber diameter increased with the flow, distance between the needle tip and the collector and decreasing voltage, which made it possible to obtain homogeneous fibers in the 1700–320 nm range. Fibers were loaded with antimicrobial agents like silver and chlorohexidine, and the influence of agent concentration in the electrospinning solutions on the fiber diameter size was determined. The polymer was able to crystallize during the electrospinning process, giving rise to a structure slightly different from that obtained by solution crystallization and related to that attained after crystallization from the melt state. Addition of antimicrobial agents had little effect on the degree of crystallinity, although it decreased slightly when chlorhexidine was employed. Scaffolds prepared from the silver and chlorhexidine loaded samples supported cell adhesion and proliferation. Furthermore, a clear and well differentiated antimicrobial effect against both Gram-positive (e.g. M. luteus) and Gram-negative (e.g. E. coli) bacteria was demonstrated.     

Active nano-CuPt3 electrocatalyst supported on graphene for enhancing reactions at the cathode in all-vanadium redox flow batteries

Graphene-supported monometallic (Pt) and bimetallic (CuPt₃) cubic nanocatalysts have been investigated as new positive electrode materials for improving the VO₂⁺/VO²⁺ redox process occurring in the vanadium redox flow batteries (VRB). High-resolution transmission electron microscopy (HRTEM) and scanning electron microscopy (SEM) have been employed to characterize the electrodes. The presence of the CuPt₃ nanocubes on graphene conferred higher electrocatalytic activity due to the much higher electroactive area compared to that obtained with the Pt nanoparticles. The electrochemical surface area of the nano-(CuPt₃)-decorated graphene electrode was 105% higher compared to non-decorated graphene, being then a promising alternative for improving the VRB.     

Multiarm star poly(glycidol)-block-poly(styrene) as modifier of anionically cured diglycidylether of bisphenol A thermosetting coatings

Well-defined multiarm star copolymer poly(glycidol)-b-poly(styrene) (PGOH-b-PS) with an average number of PS arms per molecule of 85 has been prepared. The core first approach has been selected as the methodology using atom transfer radical polymerization (ATRP) of styrene to grow the arms from an activated hyperbranched poly(glycidol) as core. This activated hyperbranched macroinitiator was prepared by esterification of hyperbranched poly(glycidol) (PGOH) with 2-bromoisobutyryl bromide.PGOH-b-PS was used to modify diglycidylether of bisphenol A coatings cured by anionic ring-opening mechanism using 1-methyl imidazole as the initiator. The kinetics of the curing process, studied by dynamic scanning calorimetry (DSC), was not much affected when PGOH-b-PS was added to the formulation. By rheometry the effect of this new polymer topology on the complex viscosity (η^*) of the reactive mixture was analyzed. The phase-separation of the modified coatings was proved by dynamic thermomechanical analysis (DMTA) and electronic microscopy (SEM and TEM) showing nano- or microphase separation as a function of the modifier content. The addition of this star polymer led to increase in the rigidity in terms of Young's modulus and in the microhardness in comparison to neat DGEBA.     

Improved thermal stability of oxide-supported naked gold nanoparticles by ligand-assisted pinning

We report a method to improve the thermal stability, up to 900 °C, of bare-metal (naked) gold nanoparticles supported on top of SiO(2) and SrTiO(3) substrates via ligand-assisted pinning. This approach leads to monodisperse naked gold nanoparticles without significant sintering after thermal annealing in air at 900 °C. The ligand-assisted pinning mechanism is described.     

Interleukin-1β Modulation of the Mechanobiology of Primary Human Pulmonary Fibroblasts: Potential Implications in Lung Repair

Pro-inflammatory cytokines like interleukin-1β (IL-1β) are upregulated during early responses to tissue damage and are expected to transiently compromise the mechanical microenvironment. Fibroblasts are key regulators of tissue mechanics in the lungs and other organs. However, the effects of IL-1β on fibroblast mechanics and functions remain unclear. Here we treated human pulmonary fibroblasts from control donors with IL-1β and used Atomic Force Microscopy to unveil that IL-1β significantly reduces the stiffness of fibroblasts concomitantly with a downregulation of filamentous actin (F-actin) and alpha-smooth muscle (α-SMA). Likewise, COL1A1 mRNA was reduced, whereas that of collagenases MMP1 and MMP2 were upregulated, favoring a reduction of type-I collagen. These mechanobiology changes were functionally associated with reduced proliferation and enhanced migration upon IL-1β stimulation, which could facilitate lung repair by drawing fibroblasts to sites of tissue damage. Our observations reveal that IL-1β may reduce local tissue rigidity by acting both intracellularly and extracellularly through the downregulation of fibroblast contractility and type I collagen deposition, respectively. These IL-1β-dependent mechanical effects may enhance lung repair further by locally increasing pulmonary tissue compliance to preserve normal lung distension and function. Moreover, our results support that IL-1β provides innate anti-fibrotic protection that may be relevant during the early stages of lung repair.     

The catalytic activity of the Pr2Zr2−xFexO7±δ system for the CO oxidation reaction

One of the alternatives to decrease the concentration of CO is its oxidation reaction to CO₂, which can be made more efficient using catalysts. In this work, it is shown that pyrochlore structures are a promising candidate to act as heterogeneous catalysts due to their chemical and physical properties. For use as a catalyst in this reaction, the Pr₂Zr_2−xFe_xO_7±δ (x = 0, 0.05, 0.10, and 0.15) system was synthesized by the solvothermal method, firing the powder obtained at temperatures of 1200 and 1400°C. The diffraction patterns confirmed the pyrochlore structure as the single phase in all the nominal compositions. The Brunauer–Emmett–Teller method and dynamic light-scattering analysis showed an increase in the particle size and a decrease in the specific surface area when increasing the iron concentration and increasing the calcination temperature. The compositions that presented the best catalytic activity were the samples with the highest iron concentration. Moreover, these samples were able to convert all the CO oxidation reactions in a narrower temperature range than a conventional CeO₂ sample. The presence of vacancies and the redox behavior of the elements present are the key factors for the catalysis of this system in the CO oxidation reaction.