Reactive blending of poly(butylene succinate) and poly(triethylene succinate): characterization of the copolymers obtained

Poly[butylene‐co‐(triethylene succinate)] block copolymers (PBSPTES), prepared by reactive blending of the parent homopolymers (PBS and PTES) in the presence of Ti(OBu)₄, were analysed by nuclear magnetic resonance (NMR), wide angle X‐ray diffraction, thermogravimetric analysis and differential scanning calorimetry techniques, in order to investigate the effects of the transesterification reactions on the molecular structure and thermal properties. ¹H‐NMR analysis evidenced the formation of copolymers whose degree of randomness increased with mixing time. After melt quenching, all the copolymers were found to be semicrystalline with the exception of a random copolymer. The results obtained indicated that the block size has a fundamental role in determining the rate of crystallization and therefore the phase behavior of the block copolymers. Copyright © 2012 Society of Chemical Industry     

Miscibility and specific interactions in blends of poly(vinyl phenyl ketone hydrogenated) with poly(2,6‐dimethyl‐1,4‐phenylene oxide)

The miscibility behavior of poly(vinyl phenyl ketone hydrogenated) (PVPhKH) and poly(2,6‐dimethyl‐1,4‐phenylene oxide) (PPO) are studied by differential scanning calorimetry, thermomechanical analysis, and FTIR spectroscopy. Two miscibility windows between 10 to 40 and 60 to 90 wt % PPO are detected. Only the blend with 50 wt % PPO is immiscible. The best fit of the Gordon–Taylor equation of the experimental glass‐transition temperatures for miscible PVPhKH/PPO blends is shown. A study by FTIR spectroscopy suggests that hydrogen bonding interactions are formed between the hydroxyl groups of PVPhKH and the ether groups of PPO. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1887–1892, 2004     

Poly(ethylene terephthalate), modified with bisphenol S units,with increased glass transition temperature

Novel copolyesters have been prepared by melt mixing poly(ethylene terephthalate) (PET) with an ethoxylated bisphenol S, with the aim to prepare new polyesters with increased T_g, to be used in a wider range of temperatures with respect to neat PET. No side reactions occur during the synthesis of the samples, as proved by NMR analysis. The insertion of the bisphenol S (sulfonyldiphenol) groups does not significantly alter the thermal stability of PET. The thermal analysis showed that T_m and crystallization rate of the copolymers decreased with incasing co‐unit content. The T_g of the copolyesters can be increased by bisphenol S insertion, up to 40°C higher with respect to neat PET, that allows the use of amorphous PET in a wider range of applications. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Gas/Particle Partition Measurements of PAH at Hazelrigg,U.K.

During September and October, 1998, the new Integrated Organic Gas and Particle Sampler (IOGAPS), was operated at Hazelrigg, UK, the field measurement station of the University of Lancaster. Gas/particle partition ratios of twenty-two 2–5 ring PAH were determined using both the IOGAPS (in which the gas phase is collected before the particle phase) and a low flow sampler which utilized the traditional filter-sorbent geometry. For compounds of intermediate volatility, less partitioning to the gas phase was observed when the denuder was used. The denuder (8- channel, 60 cm, 16.7 L min^?1 air sampling rate) trapped small amounts of several non-volatile PAH. This result is consistent with particle diffusion losses of 5 to 10% for particles less than 0.05 μm under the flow conditions in the denuder. The 60-cm denuder was probably longer than necessary for the flow rate used. During the sampling, both glass fiber and Teflon-coated glass fiber filters were used. Without a denuder in front of a glass fiber filter, the fine particulate mass (PM 2.5) measurements showed a major positive bias that has been attributed to adsorption of gases by the filter. Teflon-coated glass fiber filters were not subject to this artifact problem, and equal masses were collected on filters from the denuded and non-denuded air flows.     

Synthesis and characterization of novel poly(butylene succinate)‐based copolyesters designed as potential candidates for soft tissue engineering

Poly(butylene succinate/diglycolate) copolymers by reactive blending were subjected to molecular and solid‐state characterization to study the effects of transesterification reactions. ¹³C‐nuclear magnetic resonance analysis evidenced the formation of block copolymers. Thermal measurements showed that all the samples were semicrystalline, with a soft amorphous phase and a rigid crystal phase. Wide‐angle x‐ray diffraction measurements indicated that the copolymers are characterized by cocrystallization. The mechanical properties were found related to crystallinity degree. The random copolymer, characterized by the lowest crystallinity degree, exhibits the lowest elastic modulus and the highest deformation at break. Therefore, solid‐state properties of poly(butylene succinate/diglycolate) copolymers can be tailored by acting on the molecular architecture. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Effect of the cutting process on the fatigue behaviour of press hardened and high strength dual phase steels

Press hardened 22MnB5 steels are steady broadening their applications in vehicles since they allow to meet the increasing demands for weight reduction and safety standards. Press hardened parts have been typically applied as structural reinforcements where high rigidity and crash resistance are required. However, the need for further weight reductions in vehicles leads to potential applications in chassis areas, where parts must face up to cyclic loads. The fatigue behaviour of the press hardened 22MnB5 steel and the effect that post-forming processes (such as trimming or punching that usually follows press hardening) on the fatigue behaviour is scarcely known. Thus, the aim of this work is to analyse the fatigue behaviour of 22MnB5 press hardened steels cut using different strategies. The fatigue limit has been obtained in tensile samples of 22MnB5 with an Al–Si coating. Samples were cut by laser and shearing with two different clearance values. Results are compared to those obtained with a high drawing quality mild steel and a dual phase steel with a tensile strength of 1000 MPa, DP1000. It is shown that the fatigue behaviour of press hardened 22MnB5 steels and DP1000 is governed by the defects introduced in cut edges, while the behaviour of the mild steel is almost independent of the cut edge quality. This finding indicates that high strength steels are markedly sensitive to pre-existent defects, such as burr, cracks at the cut edge or surface cracks, and they can be considered as low damage tolerant steels. On the contrary, mild steels are highly damage tolerant, i.e. the fatigue life is mainly independent of the initial defect size. In press hardened 22MnB5, even when cut edges have a high surface quality, the fatigue limit is still limited by the presence of cracks in the brittle Al–Si coating. Crack propagation due to the low damage tolerance capacity of the press hardened steel has been successfully rationalized through a fracture mechanics approach. Thus, if coated press hardened 22MnB5 steels are to be applied in vehicle components subjected to cyclic loads, they must be designed following fracture mechanics concepts to state the safe loading conditions for adequate fatigue resistance.     

Influence of Hyperglycemia and Diabetes on Cardioprotection by Humoral Factors Released after Remote Ischemic Preconditioning (RIPC)

Remote ischemic preconditioning (RIPC) protects hearts from ischemia–reperfusion (I/R) injury in experimental studies; however, clinical RIPC trials were unsatisfactory. This discrepancy could be caused by a loss of cardioprotection due to comorbidities in patients, including diabetes mellitus (DM) and hyperglycemia (HG). RIPC is discussed to confer protective properties by release of different humoral factors activating cardioprotective signaling cascades. Therefore, we investigated whether DM type 1 and/or HG (1) inhibit the release of humoral factors after RIPC and/or (2) block the cardioprotective effect directly at the myocardium. Experiments were performed on male Wistar rats. Animals in part 1 of the study were either healthy normoglycemic (NG), type 1 diabetic (DM1), or hyperglycemic (HG). RIPC was implemented by four cycles of 5 min bilateral hind-limb ischemia/reperfusion. Control (Con) animals were not treated. Blood plasma taken in vivo was further investigated in isolated rat hearts in vitro. Plasma from diseased animals (DM1 or HG) was administered onto healthy (NG) hearts for 10 min before 33 min of global ischemia and 60 min of reperfusion. Part 2 of the study was performed vice versa—plasma taken in vivo, with or without RIPC, from healthy rats was transferred to DM1 and HG hearts in vitro. Infarct size was determined by TTC staining. Part 1: RIPC plasma from NG (NG Con: 49 ± 8% vs. NG RIPC 29 ± 6%; p < 0.05) and DM1 animals (DM1 Con: 47 ± 7% vs. DM1 RIPC: 38 ± 7%; p < 0.05) reduced infarct size. Interestingly, transfer of HG plasma showed comparable infarct sizes independent of prior treatment (HG Con: 34 ± 9% vs. HG RIPC 35 ± 9%; ns). Part 2: No infarct size reduction was detectable when transferring RIPC plasma from healthy rats to DM1 (DM1 Con: 54 ± 13% vs. DM1 RIPC 53 ± 10%; ns) or HG hearts (HG Con: 60 ± 16% vs. HG RIPC 53 ± 14%; ns). These results suggest that: (1) RIPC under NG and DM1 induces the release of humoral factors with cardioprotective impact, (2) HG plasma might own cardioprotective properties, and (3) RIPC does not confer cardioprotection in DM1 and HG myocardium.     

Targeting Oxidative Stress with Antioxidant Duotherapy after Experimental Traumatic Brain Injury

We assessed the effect of antioxidant therapy using the Food and Drug Administration-approved respiratory drug N-acetylcysteine (NAC) or sulforaphane (SFN) as monotherapies or duotherapy in vitro in neuron-BV2 microglial co-cultures and validated the results in a lateral fluid-percussion model of TBI in rats. As in vitro measures, we assessed neuronal viability by microtubule-associated-protein 2 immunostaining, neuroinflammation by monitoring tumor necrosis factor (TNF) levels, and neurotoxicity by measuring nitrite levels. In vitro, duotherapy with NAC and SFN reduced nitrite levels to 40% (p < 0.001) and neuroinflammation to –29% (p < 0.001) compared with untreated culture. The treatment also improved neuronal viability up to 72% of that in a positive control (p < 0.001). The effect of NAC was negligible, however, compared with SFN. In vivo, antioxidant duotherapy slightly improved performance in the beam walking test. Interestingly, duotherapy treatment decreased the plasma interleukin-6 and TNF levels in sham-operated controls (p < 0.05). After TBI, no treatment effect on HMGB1 or plasma cytokine levels was detected. Also, no treatment effects on the composite neuroscore or cortical lesion area were detected. The robust favorable effect of duotherapy on neuroprotection, neuroinflammation, and oxidative stress in neuron-BV2 microglial co-cultures translated to modest favorable in vivo effects in a severe TBI model.     

Effect of hydrothermal ageing on the performance of Ce-promoted PdO/ZrO2 for methane combustion

The performance of different Ce-modified PdO/ZrO₂ catalysts for methane oxidation in lean mixtures (5000 ppm of CH₄) in presence of external water has been studied in this work. Deactivation experiments carried out in presence of 20,000 ppm of external water showed that water reversibly inhibits the reaction. However, it was observed that these catalysts can increase their activity in presence of water at low temperature (350 °C).In order to explain this behaviour, different samples of this catalyst were treated with wet air (20,000 ppm of H₂O for 30 h). After this pre-treatment, their activity and stability for methane combustion were studied by recording light-off curves for the fresh catalysts and the catalyst after 50 h on stream for the oxidation of methane at 500 °C. As general trend, the hydro-ageing at the lowest temperature (300 °C) leaded to a very active catalyst (similar activity than the parent one), but it was more markedly deactivated. Hydro-ageing of the catalyst at higher temperatures enhanced its thermal stability.     

Effects of captivity and memory-based experiences on the hippocampus in mountain chickadees.

The complexity of an animal's physical environment is known to affect the hippocampus. Captivity may affect hippocampal anatomy and this may be attributable to the limited opportunities for memory-based experiences. This has tangential support, in that differential demands on memory can mediate changes in the hippocampus. What remains unclear is whether captivity directly affects hippocampal architecture and whether providing memory-based experiences in captivity can maintain hippocampal attributes comparable to wild-caught conspecifics. Using food-caching mountain chickadees (Poecile gambeli), we found that wild-caught individuals had larger hippocampal volumes relative to the rest of the telencephalon than captive birds with or without memory-based food-caching experiences, whereas there were no differences in neuron numbers or telencephalon volume. Also, there were no significant differences in relative hippocampal volume or neuron numbers between the captive birds with or without memory-based experiences. Our results demonstrate that captivity reduces hippocampal volume relative to the remainder of the telencephalon, but not at the expense of neuron numbers. Further, memory-based experiences in captivity may not be sufficient to maintain hippocampal volume comparable to wild-caught counterparts. (PsycINFO Database Record (c) 2010 APA, all rights reserved)