Photoreduction of Shewanella oneidensis Extracellular Cytochromes by Organic Chromophores and Dye‐Sensitized TiO2

The transfer of photoenergized electrons from extracellular photosensitizers across a bacterial cell envelope to drive intracellular chemical transformations represents an attractive way to harness nature's catalytic machinery for solar‐assisted chemical synthesis. In Shewanella oneidensis MR‐1 (MR‐1), trans‐outer‐membrane electron transfer is performed by the extracellular cytochromes MtrC and OmcA acting together with the outer‐membrane‐spanning porin ? cytochrome complex (MtrAB). Here we demonstrate photoreduction of solutions of MtrC, OmcA, and the MtrCAB complex by soluble photosensitizers: namely, eosin Y, fluorescein, proflavine, flavin, and adenine dinucleotide, as well as by riboflavin and flavin mononucleotide, two compounds secreted by MR‐1. We show photoreduction of MtrC and OmcA adsorbed on Ru^II‐dye‐sensitized TiO₂ nanoparticles and that these protein‐coated particles perform photocatalytic reduction of solutions of MtrC, OmcA, and MtrCAB. These findings provide a framework for informed development of strategies for using the outer‐membrane‐associated cytochromes of MR‐1 for solar‐driven microbial synthesis in natural and engineered bacteria.     

Use of Repetitive Sequences for Molecular and Cytogenetic Characterization of Avena Species from Portugal

Genomic diversity of Portuguese accessions of Avena species—diploid A. strigosa and hexaploids A. sativa and A. sterilis—was evaluated through molecular and cytological analysis of 45S rDNA, and other repetitive sequences previously studied in cereal species—rye subtelomeric sequence (pSc200) and cereal centromeric sequence (CCS1). Additionally, retrotransposons and microsatellites targeting methodologies—IRAP (inter-retrotransposon amplified polymorphism) and REMAP (retrotransposon-microsatellite amplified polymorphism)—were performed. A very high homology was detected for ribosomal internal transcribed sequences (ITS1 and ITS2) between the species analyzed, although nucleolar organizing regions (NOR) fluorescent in situ hybridization (FISH) analysis revealed distinct number of Nor loci between diploid and hexaploid species. Moreover, morphological diversity, evidenced by FISH signals with different sizes, was observed between distinct accessions within each species. pSc200 sequences were for the first time isolated from Avena species but proven to be highly similar in all genotypes analyzed. The use of primers designed for CCS1 unraveled a sequence homologous to the Ty3/gypsy retrotransposon Cereba, that was mapped to centromeric regions of diploid and hexaploid species, being however restricted to the more related A and D haplomes. Retrotransposon-based methodologies disclosed species- and accessions-specific bands essential for the accurate discrimination of all genotypes studied. Centromeric, IRAP and REMAP profiles therefore allowed accurate assessment of inter and intraspecific variability, demonstrating the potential of these molecular markers on future oat breeding programs.     

Laser surface nanostructuring for reliable Si3N4/Si3N4 and Si3N4/Invar joined components

IR pulsed laser radiation in air was applied to Si₃N₄ and Invar to obtain reliable Si₃N₄/Si₃N₄ and Si₃N₄/Invar adhesive bonded components. The laser pre-treatment produced a homogeneous nanostructured oxide layer on the surfaces, which effectively increased the adhesion at the adhesive/adherends interface and led to cohesive failure in the joining material. The mechanical strength of Si₃N₄/ Si₃N₄ and Si₃N₄/Invar joined components was measured, with and without laser nanostructuring, before and after thermal cycling from room temperature to 50?K, and it resulted that the exposure to extremely low temperatures did not affect the mechanical integrity of the joints. It was also demonstrated that this laser pre-treatment did not alter the mechanical properties of the ceramic substrate.     

An octaethylene glycol monododecyl ether-based mixed micellar assay for determining the lipid acyl hydrolase activity of patatin

Patatin was extracted from potato tubers (Solanum tuberosum L. cv. Spunta) and purified to homogeneity by ammonium sulfate salt fractionation and one sole chromatographic step. A spectrophotometric mixed micellar assay for patatin lipid acyl hydrolase (LAH) activity was designed with the detergent octaethylene glycol monododecyl ether (C₁₂E₈). Patatin LAH used p-nitrophenyl butyrate (PNP-butyrate) as substrate when solubilized in (C₁₂E₈) micelles. In the mixed micellar system, patatin LAH responds to the PNP-butyrate surface concentration expressed as mol% (=[PNP-butyrate]·100/([detergent]-critical micellar concentration)) and not to the molarity of PNP-butyrate. The kinetic parameters were determinined; V _max was independent of the mixed micelle concentration, as was K _m, when expressed as mol%. However, K _m was dependent on C₁₂E₈ concentration when expressed in molar concentration. C₁₂E₈/PNP-butyrate proved to be a reliable system for assaying patatin LAH activity and is superior to the commonly used Triton X-100 and SDS methods. It permits investigation of the substrate requirements of patatin LAH activity because the concentration-independent K _m can be determined both in mol% and as the absolute number of substrate molecules per micelle. In addition, the detergent did not affect the enzyme activity.     

Benzodioxoles as alternative coinitiators for radical polymerization in a model‐dental adhesive resin

This study evaluated the effectiveness of benzodioxole derivatives as coinitiators of radical polymerization in a model‐dental adhesive resin. To compose the adhesive resin, a monomer mixture based on 50 wt % of Bis‐GMA, 25 wt % of TEGDMA, and 25 wt % of HEMA was used. Camphorquinone (CQ) 1 mol % was used as a photoinitiator to initiate polymerization. 1,3‐Benzodioxole (BDO) and piperonyl alcohol (PA) were used as coinitiators at 0.25, 0.5, 1, 2, 4, 8, and 16 mol % level. In addition, tertiary amine, ethyl 4‐dimethylamino benzoate (EDAB) was used as coinitiator in the control group. Some physical, chemical, and mechanical properties of the polymer formed in the experimental adhesives were evaluated using the kinetics of polymerization, sorption and solubility, flexural strength, and elastic modulus tests. The results indicated that BDO and PA were effective coinitiators in the photoinitiator system based on CQ. Comparisons between the benzodioxoles derivative coinitiators and EDAB showed similar performance in the kinetics of polymerization and flexural strength. For water sorption and solubility evaluation, BDO and PA demonstrated significantly more sorption of water and less solubility than the EDAB control group. The findings suggest that BDO and PA were feasible alternatives to conventional amine as coinitiator. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Anti-fog chitosan/sodium lauryl ether sulfate films

The aim of this study was the preparation and characterization of hydrophobic–hydrophilic chitosan films obtained through interaction between the cationic biopolymer, chitosan (CH), with sodium lauryl ether sulfate (SLES), an anionic surfactant, which has also nonionic surfactant properties. The chitosan flat films were obtained at different concentrations of SLES, in the range of 0.02–0.1 M, where spherical capsules were also obtained. The wettability, quantified by the values of contact angle, indicated the hydrophobic character of the films. The significant values of swelling capacity in water, and in 1 % acetic acid solution confirmed the hydrophilic character of the obtained films. Weight loss of CH/SLES films after 24 h, in water and 1 % acetic acid solution was less than 3 % for the all samples. The structure of CH/SLES complex was determined by FTIR spectroscopy method. The morphology of CH/SLES film surfaces determined by atomic force microscopy showed a film surface with nanoroughness structure, determined by the SLES self-assembled nanostructures. The obtained CH/SLES films are transparent and have anti-fogging properties, compared with CH/sodium lauryl sulfate film, which is also transparent but, it gets fogged when coming in contact with warm air.     

Hybrid MCM-41 grafted by a general microwave-assisted procedure: a characterization study

Hybrid materials obtained through a Microwave-assisted grafting of organic functional groups on mesoporous silica (MCM-41 type) have been characterized by X-ray powder diffraction, TG-DSC, N₂ adsorption, solid state ¹³C- and ²⁹Si-NMR, TEM and SEM. The studied grafting procedure is effective in the preparation of hybrid organosilicas under solvent-free conditions. Microwaves allows an ultra-fast and clean functionalization of the mesoporous materials and the method has been applied to produce a wide series of functional materials. The hybrid materials maintain the original mesoporous structure when the loading of linked organic groups does not exceed 10 %. In this cases, the slight pore volume reduction is linearly correlated to the organic amount in the product. If functional groups able to interact among them through hydrogen bond are used, hybrid materials exhibit high Organic/SiO₂ ratios and low pore volumes due to the formation of a network occluding the pores, where functional groups of free organosilane molecules interacts with the functional groups of molecules linked to the matrix. NMR data confirm that the network is composed by organosilane molecules linked or not to the framework. Acid washing is able to labilize hydrogen bond and open the network. In the case of bulky but chemically inert functionalising agents the network is not produced.     

Impact of tire debris on in vitro and in vivo systems

Background  

It is estimated that over 80% of respirable particulate matter (PM₁₀) in cities comes from road transport and that tire and brake wear are responsible for the 3–7% emission of it. Data on the indicators of environmental impact of tire debris (TD), originated from the tire abrasion on roads, are extremely scarce, even though TD contains chemicals (zinc and organic compounds) which can be released in the environment.     

The Effect of Age and Intrinsic Aerobic Exercise Capacity on the Expression of Inflammation and Remodeling Markers in Rat Achilles Tendons

Old age, adiposity, and metabolic disorders are known as risk factors for chronic tendinopathy, which is a common problem in both athletes and the general population. However, the importance of these influencing factors has not yet been well understood. This study investigated alterations in gene expression and histology of Achilles tendons of young (10 weeks) and old (100 weeks) rats bred for low (low capacity runners, LCR) and high (high capacity runners, HCR) intrinsic aerobic exercise capacity. In this rat model, LCR displayed a phenotype of reduced exercise capacity, higher body weight, and metabolic dysfunctions compared to HCR. We hypothesized that the risk factors for tendinopathy in old LCR could lead to more pronounced impairments in Achilles tendon tissue. In quantitative real-time PCR (qPCR), age-related downregulation of tenocyte markers e.g., tenomodulin, genes related to matrix modeling and remodeling (e.g., collagens, elastin, biglycan, fibronectin, tenascin C) as well as transforming growth factor beta 3 (Tgfb3) have been detected. Inflammation marker cyclooxygenase 2 (Cox2) was downregulated in old rats, while microsomal prostaglandin E synthase 2 (Ptges2) was upregulated in old HCR and old LCR. In all groups, interleukin 6 (Il6), interleukin 1 beta (Il1b), and tumor necrosis factor alpha (Tnfa) showed no significant alteration. In histological evaluation, tendons of old rats had fewer and more elongated tenocyte nuclei than young rats. Even though a higher content of glycosaminoglycans, a sign of degeneration, was found in old HCR and LCR, no further signs of tendinopathy were detectable in tendons of old rats by histological evaluation. Low intrinsic aerobic exercise capacity and the associated phenotype did not show significant effects on gene expression and tendon histology. These findings indicate that aging seems to play a prominent role in molecular and structural alterations of Achilles tendon tissue and suggests that other risk factors associated with intrinsic aerobic exercise capacity are less influential in this rat model.