Electroactive phases of poly(vinylidene fluoride): Determination,processing and applications

Poly(vinylidene fluoride), PVDF, and its copolymers are the family of polymers with the highest dielectric constant and electroactive response, including piezoelectric, pyroelectric and ferroelectric effects. The electroactive properties are increasingly important in a wide range of applications such as in biomedicine, energy generation and storage, monitoring and control, and include the development of sensors and actuators, separator and filtration membranes and smart scaffolds, among others. For many of these applications the polymer should be in one of its electroactive phases. This review presents the developments and summarizes the main characteristics of the electroactive phases of PVDF and copolymers, indicates the different processing strategies as well as the way in which the phase content is identified and quantified. Additionally, recent advances in the development of electroactive composites allowing novel effects, such as magnetoelectric responses, and opening new applications areas are presented. Finally, some of the more interesting potential applications and processing challenges are discussed.     

Mild Stereoselective Intermolecular Acetoxylation and Azidation of α‐C−H Bonds in Tröger's Bases

Introduction of oxygen and nitrogen into organic molecules is one of the fundamental strategies for their functionalization. Traditional approaches rely on the formation of an activated intermediate, which is then modified in a subsequent step. Here we report a simple direct oxidative α‐acetoxylation and azidation of α‐C−H bonds in Tröger's base analogues promoted by N‐bromosuccinimide (NBS) and palladium(II)acetate [Pd(OAc)₂] under mild conditions. This approach is pivotal on NBS oxidizing the carbon atoms next to the nitrogen atoms in the presence of Pd(OAc)₂ followed by a reaction with oxygen‐ or nitrogen‐centred nucleophiles such as KOAc or NaN₃ to yield either the mono‐ and bisacetoxylated or azidated Tröger's base derivatives in a stereo‐ and chemoselective manner. The obtained products can be efficiently modified to access synthetically meaningful structures.

     

Recent Advances in Food-Packing,Pharmaceutical and Biomedical Applications of Zein and Zein-Based Materials

Zein is a biodegradable and biocompatible material extracted from renewable resources; it comprises almost 80% of the whole protein content in corn. This review highlights and describes some zein and zein-based materials, focusing on biomedical applications. It was demonstrated in this review that the biodegradation and biocompatibility of zein are key parameters for its uses in the food-packing, biomedical and pharmaceutical fields. Furthermore, it was pointed out that the presence of hydrophilic-hydrophobic groups in zein chains is a very important aspect for obtaining material with different hydrophobicities by mixing with other moieties (polymeric or not), but also for obtaining derivatives with different properties. The physical and chemical characteristics and special structure (at the molecular, nano and micro scales) make zein molecules inherently superior to many other polymers from natural sources and synthetic ones. The film-forming property of zein and zein-based materials is important for several applications. The good electrospinnability of zein is important for producing zein and zein-based nanofibers for applications in tissue engineering and drug delivery. The use of zein’s hydrolysate peptides for reducing blood pressure is another important issue related to the application of derivatives of zein in the biomedical field. It is pointed out that the biodegradability and biocompatibility of zein and other inherent properties associated with zein’s structure allow a myriad of applications of such materials with great potential in the near future.     

Impact of a Stereocentre Inversion in Cyclic Lipodepsipeptides from the Viscosin Group: A Comparative Study of the Viscosinamide and Pseudodesmin Conformation and Self‐Assembly

The viscosin group covers a series of cyclic lipodepsipeptides (CLPs) produced by Pseudomonas bacteria, with a range of biological functions and antimicrobial activities. Their oligopeptide moieties are composed of both L ‐ and D ‐amino acids. Remarkably, the Leu5 amino acid—centrally located in the nonapeptide sequence—is the sole residue found to possess either an L or D configuration, depending on the producing strain. The impact of this D /L switch on the solution conformation was investigated by NMR‐restrained molecular modelling of the epimers pseudodesmin A and viscosinamide A. Although the backbone fold remained unaffected, the D /L switch adjusted the segregation between hydrophobic and hydrophilic residues, and thus the amphipathicity. It also influenced the self‐assembly capacity in organic solvents. Additionally, several new minor variants of viscosinamide A from Pseudomonas fluorescens DR54 were identified, and an NMR assay is proposed to assess the presence of either an L ‐ or D ‐Leu5.     

Effect of feeding pattern and storage on the sludge settleability under aerobic conditions

The selection of filamentous bacteria is often assumed to be associated with specific microbial properties such as growth rate, substrate uptake rate, substrate affinity and potential for substrate storage. In this study we aimed to verify some of these factors. Sequencing batch reactor (SBR) systems were used to scale-down aerobic activated sludge systems with an aerobic selector. Adding acetate in different aerobic feeding periods allowed us to simulate a variable relative size of aerobic selector with different bulk liquid substrate concentrations. The experiments showed that as expected, the aerobic fill time ratio (FTR(ox)) and the corresponding feast period, which can be assumed similar to contact time in an aerobic selector, had a strong effect on the sludge settleability. Promoting a strong substrate gradient in the SBR (FTR(ox)<5.4%) resulted in good sludge settleability (SVI<120mLg(-1)). Whenever acetate was added in a limiting rate (FTR(ox)>6.2%), a condition in which the acetate concentration in the reactor was always very low, the sludge settleability decreased (SVI>150mLg(-1)). Sludge settleability could be improved by changing the feeding strategy to a pulse feed. The maximum specific acetate uptake rate and poly beta-hydroxybutyrate (PHB) production rate of bad settling sludge, including bulking sludge, was similar to well-settling sludge, which is not in accordance with the general assumptions that well settling sludge have a higher maximal substrate uptake rate and better storage capacities. An alternative hypothesis for the development of filamentous structures in biological flocs has been formulated. It is hypothesized that bulking sludge originates from the presence of substrate gradients in sludge aggregates. Whereas at low bulk liquid substrate concentration filamentous bacteria give easier access to the substrate at the outside of the flocs and thereby proliferate, at high bulk liquid substrate concentration there is no substrate advantage for filamentous organisms and smooth bacterial structures predominate. In this hypothesis there is no need for an intrinsic difference in kinetic parameters between floc and filamentous bacteria. Where presence of filamentous bacteria is related to process conditions, the presence of a specific filament is likely due to presence of a specific limiting substrate.     

Naproxen removal from water by chlorination and biofilm processes

Naproxen is an anti-inflammatory pharmaceutical that has been detected in natural and engineered aquatic environments. The primary aim of this research was to study chemical transformations of naproxen following chlorine oxidation, which is common in water and wastewater treatment systems. Synthetic waters containing elevated concentrations of naproxen were oxidized by free chlorine at naproxen:chlorine molar ratios of 0.02-3:1 and pH values of 5-9. The formation of naproxen products was dependent on pH, chlorine dosage and contact time. This study demonstrates that naproxen readily reacts with free chlorine and forms disinfection products. The formation of specific reaction products can vary depending on the characteristics of the water or wastewater and treatment operating conditions. More research is needed to identify intermediate and chemical reaction end products and to understand the reaction kinetics of naproxen chlorination for a range of water and wastewater treatment conditions. A secondary aim of this research was to study effects of naproxen and its chlorination products on biofilm processes, which are common in water and wastewater treatment systems and natural aquatic environments. A bioreactor was fed a naproxen solution and then fed a solution at the same naproxen concentration following contact with free chlorine. Results indicate that naproxen was not degraded biologically for the conditions of this study. In contrast, the naproxen solution containing products of chlorination caused an adverse response by discharging biomass from the bioreactor. Results therefore demonstrate that naproxen products of chlorination can adversely affect a biofilm process, which potentially can impact the performance of biofilm processes in natural and engineered aquatic environments. More research is needed to study naproxen chlorination reactions at low concentrations and in complex matrices, and to understand the toxicological relevance of naproxen and its products of chlorination in natural and engineered aquatic environments.     

Effects of urbanization on Neotropical wasp and bee assemblages in a Brazilian metropolis

The rapid growth of cities in many parts of the world has stimulated an increasing number of ecological studies of urban environments. Here, 12 study sites in the city of Belo Horizonte (MG), southeastern Brazil, were compared to analyze the effects of habitat changes related to urbanization on the species richness and abundance of native wasps and bees. Two spatial scales were considered: large portions of the urban landscape (entire sites) and small areas within these sites (public squares). Overall, the abundance of advanced eusocial bees (i.e. stingless bees), which were the dominant species, was directly affected by the loss of vegetation cover and the increase of buildings associated with urbanization. The magnitude of this effect varied according to the nesting habits of each species. The loss of vegetation cover associated with urbanization also had a negative effect on the abundance and species richness of advanced eusocial wasps. Generalist species of bees and wasps, such as Trigona spinipes and Polybia occidentalis, were very abundant and not sensitive to the habitat changes related to urbanization. Advanced eusocial bees also responded to small-scale habitat changes (size and vegetation cover of public squares). No relation was found between the solitary and the primitive eusocial wasps and bees and the habitat changes considered here. Conservation strategies in urban environments need to consider different spatial scales in order to maintain or enhance the local diversity of wasps and bees.     

Antimicrobial multiresistance in bacteria isolated from freshwater Chilean salmon farms

The intensive use of antimicrobial agents, mainly oxytetracycline, to prevent and control bacterial pathologies in Chilean salmon culture is a frequent practice. A total of 103 gram-negative oxytetracycline-resistant bacteria recovered from various sources of 4 Chilean freshwater salmon farms were identified and investigated for their susceptibility patterns to various antibacterial agents, by using an agar disk diffusion method. Antibacterial resistance patterns of isolates were not correlated with bacterial species or strain source. A high number of bacteria resistant to amoxicillin, ampicillin. erythromycin, and furazolidone, as well as an important frequency of bacterial resistance to florfenicol, chloramphenicol, cefotaxime and trimethoprim-sulfamethoxazole was found. On the contrary, the proportion of bacteria resistant to gentamicin, kanamycin, flumequine and enrofloxacin was rather low. Resistant microflora showed a high taxonomic variability and mainly consisted of non-fermenting bacteria (77.7%). These strains mainly belonged to the species Pseudomonas fluorescens (29), Aeromonas hydrophila (10), Stenotrophomonas maltophilia (6), isolated from salmon fingerlings, and Acinetobacter lwoffii (5) isolated from pelletized feed. The occurrence of simultaneous resistance to various antibacterials was frequent. We observe a high frequency of bacteria resistant to 6-10 antibacterials (74 strains), and antibiotic resistance index (ARI) values ranging from 0.38 to 0.48 for the four salmon farms studied. These results suggest that Chilean salmon farms might play a role as reservoirs of antibacterial multiresistant bacteria, thus prompting the necessity for a more restrictive attitude towards the intensive use of antibacterials in salmon farming.     

A New Methodology to Evaluate the Cure of Resin-Impregnated Paper for HPL

This paper presents a study on the curing conditions of several resin-impregnated papers and its impact on the performance of HPL (high-pressure decorative laminate). A new methodology for evaluating the bond strength development between the different layers of a HPL(overlay, decorative, and kraft papers) was developed using ABES (Automated Bonding Evaluation System) equipment. The proposed method can be applied to the study of the curing step of the different impregnated paper and the development of bonds between them (overlay paper on decorative paper, decorative paper on kraft paper, and kraft paper on kraft paper) trying to simulate the hot-pressing of an industrial HPL. This will permit to establish a more adapted temperature gradient in hot-press in order to achieve the same curing rate for all layers and provide a good final overall product quality.