Incorporation of Alpha‐Linolenic Acid and Enhancement of n‐3 Fatty Acids in Nile Tilapia: a Factorial Design

A 2² factorial design (two factors at two levels, in triplicate) was performed to investigate the influence of factors A (time of treatment, 15 and 30 days) and B (chia oil content in a supplemented diet, at 2.1 and 4.2 %) in three responses of interest referring to: (a) the incorporation of alpha‐linolenic acid (LNA) in lipids of Nile tilapia fillet; (b) the enhancement of n‐3 fatty acids; and (c) the decrease in the omega‐6/omega3 (n‐6/n‐3) ratio in fish. Factors A and B were significant in the three regression models obtained and the interaction AB was a significant contributor to the LNA and n‐6/n‐3 ratio. Analysis of variance suggested three significant and predictive mathematical models. Response surfaces analyses from designs indicated higher LNA and n‐3 contents and a lower n‐6/n‐3 ratio using both factors A and B in the higher levels (30 days of treatment and 4.2 % of chia oil in the diet for fish) chosen for this study.     

Synthesis of a PPV‐fluorene derivative: Applications in luminescent devices

Synthesis of a polyfluorene/poly(p‐phenylene vinylene) derivative, the Poly [(9,9′‐di‐hexylfluorenediylvinylene‐alt‐1,4‐phenylenevinylene)‐co‐((9,9′‐(3‐t‐butylpropanoate) fluorene‐1,4‐phenylene)] (LaPPS 42) was performed following Wittig and Suzuki routes. Polyfluorenes and derivatives have been used in electroluminescent devices, and the synthesis described here has the advantage in pave the way to get distinct structures having different emission spectra. An extensive study of its electrochemical, thermomechanical, optical, and structural properties was carried out, as well as its application in electroluminescent devices. Polymer light‐emitting diodes (PLEDs) and polymer light‐emitting electrochemical cells (PLECs) were built using LaPPS 42 as active layer, and their electric and optical characterizations confirm they have a potential as active element in electroluminescent devices. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42579.     

Chemo-enzymatic synthesis of amino acid-based surfactants

The application of lipases to the synthesis of amino acid-based surfactants was investigated. Low yields (2–9%) were obtained in the acylation of free amino acids, such as l-serine and l-lysine, as well as their ethyl esters and amides with fatty acids, owing in part to low miscibility of the reactants. When the N-carbobenzyloxy (Cbz)-l-amino acids were used in an effort to improve miscibility of the amino acid derivatives with the acyl donor, a dramatic improvement was observed for N-Cbz-l-serine (92% yield) but not for N _α-Cbz- or N _ζ-Cbz-l-lysine (7 and 2% yield, respectively). As an alternative, and efficient synthesis of N _ζ-acyl-l-lysines was developed, based on the regiospecific chemical acylation of copper(II) lysinate. In pursuit of a general route to amino acid-fatty acid surfactants, the utility of a polyol linker was investigated. Thus, the glycerol ester of N _α′ N _ζ-di-Cbz-l-lysine was prepared and evaluated as a substrate for acylation. As expected, this and other glycer-1-yl esters of N-protected amino acids were excellent substrates for lipase-catalyzed acylation. Their reaction with myristic acid in the presence of Novozyme resulted in the regioselective acylation of the primary hydroxyl group of the glycerol moiety to afford the corresponding 1-O-(N-Cbz-l-aminoacyl)-3-O-myris-toylglycerols with conversions of 50–90%. These were readily deprotected to give a range of 1-O-(aminoacyl)-3-O-myristoyl-glycerols with overall yields of 27–71%.     

Characterization of a water-based paint for corrosion protection

Corrosion of steel rebars in reinforced concrete is one of the major problems in the construction industry. Carbonation reactions of concrete with carbon dioxide and, mainly, the chloride salts action are the main causes responsible for concrete degradation. Protective coatings help to improve the durability of concrete structures by acting as a physical barrier against the corrosion agents. Waterborne paints are usually used for concrete protection rather than solvent-based paints since they are less pollutant. The aim of this work is to investigate the influence of the pore size and porosity on the permeability of the paints films toward sodium chloride. Three characterization methods from membrane science were implemented to characterize paint coatings. The time-lag method was used to determine the permeability toward the sodium chloride and toward helium and argon, these for approximately 100% relative humidity. From the seven waterborne paints formulated, only one was found to be suitable for surface protection of reinforced concrete, since its permeability toward NaCl was smaller than 10⁻¹⁴ m² s⁻¹, the threshold value required by National Laboratory of Civil Engineering (LNEC) in Portugal. For the formulated paints, it was observed that the average pore size correlates well with the permeability toward sodium chloride. This is an important result since obtaining the permeability toward sodium chloride of corrosion protective paints is very time consuming, while the average pore size can be obtained in a much shorter time.     

Developing conductive immiscible polystyrene/polypropylene blends with a percolated conducting polyaniline/polyamide filler by tuning its specific interactions with the styrene-based triblock compatibilizer grafted with maleic anhydride

An approach to induce conductivity in immiscible polystyrene/polypropylene (PS/PP) blends is described using a percolated conducting polyaniline/polyamide (PANI/PA) filler combined with a polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene-graft-maleic anhydride compatibilizer. The approach is based on the ability of the compatibilizer to concomitantly stabilize the cocontinuous morphology and to improve the state of dispersion of the PANI/PA filler. Selective localization of PANI/PA in the PS phase with improved filler dispersion is achieved with the optimal master batch (MB) preparation technique followed by its optimized sequence addition to the blend components. This results in an increase in the dc conductivity by six decades as compared with that of the neat compatibilized blend at an effective 4.8-wt % PANI concentration. An investigation of the effect of functionality and concentration of the filler and the compatibilizer on the filler connectivity in the blend is performed. The prevailing specific interactions are analyzed by Fourier transform infrared spectroscopy and thermogravimetric analysis of the MBs. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48433.     

Hydrothermal syntheses of ETS-10 like vanadosilicates using chiral organic molecules. Part I

Vanadosilicates with the structures of ETS-10 and AM-6 microporous materials have been hydrothermally synthesized using organic directing structures agent (SDAs) derivatives of decahydroquinoline, 3,5-dimethyl-piperidine, 2,6-dimethyl-piperidine and (S)-Sparteine. Derivatives of these chiral amines have not been explored before in the sol gel chemistry of vanadosilicates. Physicochemical characterization of the obtained vanadosilicate materials with these different chiral templates was carried out by X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman and infrared (IR) spectroscopy, solid-state NMR spectroscopy, and differential thermogravimetric analysis (DTA)/thermogravimetric analysis (TGA). The results suggest that the presence of the chiral organic templates have different effects in terms of the final phase of the synthesized materials and their morphology. The products obtained using chiral template derivatives of decahydroquinoline reveal that certain products might be very enriched with chiral polymorph A while others present structures which are similar to other large-porous vanadosilicate such as AM-6 and AM-13. Derivatives of 2,6-dimethyl-piperidine and 3,5-dimethyl-piperidine have not favored any structure that resembles a chiral polymorph A, but only known vanadosilicates such as AM-6, AM-13. Derivatives of (S)-Sparteine, on the other hand, have not only favored the formation of structures enriched with a large amount of chiral polymorph A, but also their use has resulted in other unknown vanadosilicate structures whose physicochemical characterizations are in progress.     

Increased Activity of Cell Surface Peptidases in HeLa Cells Undergoing UV-Induced Apoptosis Is Not Mediated by Caspase 3

We have previously shown that in HeLa cells treated with a variety of agents there is an increase in cell surface peptidase (CSP) activity in those cells undergoing apoptosis. The increase in CSP activity observed in UVB-irradiated cells undergoing apoptosis was unaffected when the cultures were treated with the aminopeptidase inhibitor bestatin, and matrix metalloprotease inhibitor BB3103, but greatly enhanced when treated with the caspase 3 inhibitor-DEVD, and reduced in the presence of the poly(ADP-ribose) polymerase (PARP) inhibitor-3-aminobenzamide (3AB). Neither 3AB nor DEVD had an effect on the gross morphology of the apoptotic cells observed under electron microscopy, nor did they have an effect on phosphatidylserine eversion on the cell membrane, or that of PARP cleavage. All the agents except for DEVD had no effect on the level of caspase 3 activity in the cells. The results suggest that other caspases may cleave PARP in these cells. Both 3AB and DEVD treatment reduced the level of actin cleavage seen in the apoptotic cells. The increase in CSP activity observed in cells undergoing UVB-induced apoptosis appears to involve PARP but not caspase 3.     

Growth and branching of gold nanoparticles through mesoporous silica thin films

Composite materials made of mesoporous oxide thin films containing metallic nanoparticles are of high interest in various fields, including catalysis, biosensing and non-linear optics. We demonstrate in this work the fabrication of such composite materials containing a sub-monolayer of gold nanoparticles (GNPs) of various shapes covered with mesoporous silica thin films. Additionally, the shape of the GNPs (and thus their optical properties) can be modified in situ through seeded growth and branching. Such growth proceeds upon wetting with HAuCl(4) solution, a surfactant (cetyltrimethylammonium bromide, CTAB) and a mild reducing agent (ascorbic acid, AA). The effect of varying several reaction parameters (time and CTAB and AA concentrations) was evaluated, showing that more anisotropic particles are obtained at longer reaction times, lower CTAB concentration and higher AA concentration. The final shape of the GNPs was also found to depend on their initial shape and size, as well as the pore size of the mesoporous film covering them. Because the growth proceeds through the pores of the film, it may lead to shapes that are not easily obtained in solution, such as particles with branches on one side only. Finally, we have confirmed that no damage was induced to the mesoporous silica structure during the growth process and thus the final particles remain well covered by the thin film, which can eventually be used as a filter between the GNPs and the outer medium.     

A Facile and Green Microwave-Assisted Strategy to Induce Surface Properties on Complex-Shape Polymeric 3D Printed Structures

Light- induced polymeric 3D printing is becoming a well-established fabrication method, showing manifold advantages such as control of the local chemistry of the manufactured devices. It can be considered a green technology, since the parts are produced when needed and with minimum amount of materials. In this work 3D printing is combined with another green technology, microwave-assisted reaction, to fabricate objects of complex geometry with controllable surface properties, exploiting the presence of remaining functional groups on the surface of 3D printed specimens. In this context, surface functionalization with different amines is studied, optimizing formulations, reaction times, and avoiding surface deterioration. Then, two different applications are investigated. MW-functionalized filter-type structures have been tested against Staphylococcus aureus bacteria, showing high bactericidal activity on the surface along all areas of the complex-shaped structure. Second, a fluidic chip composed of three separated channels is 3D printed, filled with different amine-reactive dyes (dansyl and eosine derivatives), and made to react simultaneously. Complete and independent functionalization of the surface of the three channels is achieved only after 2 min of irradiation. This study demonstrates that light induced 3D printing and microwave-induced chemistry can be used together effectively, and used to produce functional devices.     

Increased globotriaosylceramide in familial dysautonomia

Familial Dysautonomia (FD) is an autosomal recessive disease of unknown etiology, occurring primarily in Ashkenazi Jews. Patients are neurologically impaired, with deficits primarily in autonomic and sensory functions. The biochemical and genetic defects have remained elusive, precluding carrier detection and prenatal diagnosis. High-performance liquid chromatography data indicated up to a threefold increase in the neutral glycosphingolipid globotriaosylceramide in Dysautonomic fibroblasts and lymphoblasts. Total ganglioside values, measured by colorimetric, fluorometric or specific sodium borohydride incorporation, were decreased. Affected fibroblasts exhibited a range of pleomorphic phenotypes, such that the usual swirl-like confluent growth pattern of normal fibroblasts was distorted to varying degrees, suggesting abnormalities in the FD plasma membrane, possibly affecting cell-cell contacts. The glycosphingolipid increase could not be accounted for on the basis of markedly decreased α-galactosidase activity, as in Fabry's disease, where patients also display decreased autonomic function.