Glucosinolates of Sisymbrium officinale and S. orientale

Glucosinolates (GSLs) from Sysimbrium officinale and S. orientale were analyzed qualitatively and quantitatively by their desulfo-counterparts using UHPLC-DAD-MS/MS. Eight GSLs were identified in S. officinale, including Val-derived (glucoputranjivin) and Trp-derived (4-hydroxyglucobrassicin, glucobrassicin, 4-methoxyglucobrassicin, and neoglucobrassicin) as the major ones followed by Leu-derived (Isobutyl GSL), Ile-derived (glucocochlearin) and Phe/Tyr-derived (glucosinalbin). Different S. orientale plant parts contained six GSLs, with Met-derived (progoitrin, epiprogoitrin, and gluconapin) and homoPhe-derived (gluconasturtiin) as the major ones, followed by glucosinalbin and neoglucobrassicin. GSL breakdown products obtained by hydrodistillation (HD) and microwave-assisted distillation from S. officinale, as well as isopropyl isothiocyanate, as the major volatile in both isolates, were tested for their cytotoxic activity using a 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay. Generally, all volatile isolates showed similar activity toward the three cancer cell lines. The best activity was shown by isopropyl isothiocyanate at a concentration of 100 µg/mL after 72 h of incubation, with 53.18% for MDA-MB-231, 56.61% for A549, and 60.02% for the T24 cell line.     

A DFT Study of the Reaction of Acrylamide with L-Cysteine and L-Glutathione

Thermal processing of certain foods implies the formation of acrylamide, which has been proven to provoke adverse effects on human health. Thus, several strategies to mitigate it have been developed. One of them could be the application of organosulfur compounds obtained from natural sources to react with the acrylamide, forming non-toxic adducts. A DFT study of the acrylamide reaction with the organosulfur model compounds L-cysteine and L-glutathione by Michael addition and a free radical pathway complemented by a kinetic study of these model molecules has been applied. The kinetic evaluation results demonstrate that the L-glutathione reaction exhibited a higher rate constant than the other studied compound.     

Amino-Acid-Conjugated Natural Compounds: Aims,Designs and Results

Protein is one of the essential macronutrients required by all living things. The breakdown of protein produces monomers known as amino acids. The concept of conjugating natural compounds with amino acids for therapeutic applications emerged from the fact that amino acids are important building blocks of life and are abundantly available; thus, a greater shift can result in structural modification, since amino acids contain a variety of sidechains. This review discusses the data available on amino acid–natural compound conjugates that were reported with respect to their backgrounds, the synthetic approach and their bioactivity. Several amino acid–natural compound conjugates have shown enhanced pharmacokinetic characteristics, including absorption and distribution properties, reduced toxicity and increased physiological effects. This approach could offer a potentially effective system of drug discovery that can enable the development of pharmacologically active and pharmacokinetically acceptable molecules.     

Unveiling a New Selenocyanate as a Multitarget Candidate with Anticancer,Antileishmanial and Antibacterial Potential

Currently, cancer, leishmaniasis and bacterial infections represent a serious public health burden worldwide. Six cinnamyl and benzodioxyl derivatives incorporating selenium (Se) as selenocyanate, diselenide, or selenide were designed and synthesized through a nucleophilic substitution and/or a reduction using hydrides. Ferrocene was also incorporated by a Friedel–Crafts acylation. All the compounds were screened in vitro for their antiproliferative, antileishmanial, and antibacterial properties. Their capacity to scavenge free radicals was also assessed as a first approach to test their antioxidant activity. Benzodioxyl derivatives 2a–b showed cytotoxicity against colon (HT-29) and lung (H1299) cancer cell lines, with IC₅₀ values below 12 µM, and were also fairly selective when tested in nonmalignant cells. Selenocyanate compounds 1–2a displayed potent antileishmanial activity in L. major and L. infantum, with IC₅₀ values below 5 µM. They also exhibited antibacterial activity in six bacterial strains, notably in S. epidermidis with MIC and MBC values of 12.5 µg/mL. Ferrocene-containing selenide 2c was also identified as a potent antileishmanial agent with radical scavenging activity. Remarkably, derivative 2a with a selenocyanate moiety was found to act as a multitarget compound with antiproliferative, leishmanicidal, and antibacterial activities. Thus, the current work showed that 2a could be an appealing scaffold to design potential therapeutic drugs for multiple pathologies.     

Evaluation of proton conductivity of sulfonated polyimide/dihydroxy naphthalene charge‐transfer complex hybrid membranes

Sulfonated polyimide (SPI)/dihydroxynaphthalene (DHN) charge‐transfer (CT) complex hybrid films were investigated as possible alternative for polymer electrolyte membranes in polymer electrolyte fuel cells. SPI/DHN CT complex hybrid films include CT complexes, which might work as electronic conductors, and sulfonic acid units, which could work as proton conductors. Therefore, the origin of the conductivity of SPI/DHN complex hybrid films was evaluated by four‐probe impedance measurements in the through‐plane direction of the films. The obtained conductivity of the CT complex hybrid films increased with the increase of ion exchange capacity of the CT films and the decrease of CT complex concentration in the films. These results indicated that proton transfer dominantly occurred in the CT complex hybrid films. Proton conductivity of the CT complex hybrid films consisting of 2,6‐ or 1,5‐DHN showed the similar values, although the molecular geometries of the CT complex were different. The activation energy values for proton conductivity in the CT films were approximately the same as that of Nafion 212. Water uptake (WU) results were also conducted and suggest that CT complex formation could control the degree of WU of the films and prevent dissolution of SPI. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2991–2997     

Development of an immunosensor for the detection of Francisella tularensis antibodies

Tularemia, also known as rabbit fever, is a highly infectious zoonotic disease caused by a non-motile and non-spore-forming Gram-negative coccoid rod bacterium, Francisella tularensis. It occurs naturally in lagomorphs (rabbits and hares), but many animals have been reported to be susceptible. Transmission to humans is mostly caused by inhalation of aerosolised bacteria, handling of infected animals, arthropod stings, and ingestion of contaminated foods and water. At present, pathogenic isolation, molecular detection, and serology are the most commonly used methods to confirm the diagnosis of tularemia. In this work, an electrochemical immunosensor for the detection of anti-F. tularensis antibodies was developed, consisting of gold-based self-assembled monolayers of a carboxylic-group-terminated bipodal alkanethiol that is covalently linked to a lipopolysaccharide (LPS) that can be found in the outer membrane of the bacteria F. tularensis. The presence of anti-F. tularensis antibodies was measured using horseradish peroxidase-labelled protein A (HRP-protein A) from Staphylococcus aureus, and the developed immunosensor gave a stable quantitative response to different anti-F. tularensis FB11 antibody concentrations after 30 min with a limit of detection of 15 ng/mL, RSD of 9 %, n?=?3. The developed immunosensor was tested with serum from animals infected with tularemia and was compared to the results obtained using ELISA showing an excellent degree of correlation.     

Hybrid films of polyetherimide containing in situ grown Ag,Pd, and AgPd alloy nanoparticles: Synthesis route,morphology, and gas transport properties

In this study, bimetallic/polymer films are synthesized from polyetherimide (PEI), palladium acetate and silver nitrate for a wide range of total metal amount (from 0 to 30 wt %) and different Ag to Pd molar ratios. Hybrid precursor films are first prepared from polymer/metal complex solutions and the metal nanoparticles are then generated within the PEI matrix by annealing the precursor film under specific conditions. Reference neat PEI films and monometallic films are prepared in the same conditions. Interestingly, formation of AgPd alloys directly within the polymer films is for the first time obtained from a very simple and environmentally friendly route. Based on X‐ray diffraction and transmission electron microscopy analyses, a nanostructuration mechanism is proposed. The interactions of hydrogen towards the nanocomposites are investigated and discussed as a function of the nanoparticle composition. The impact of the nanostructuration is also studied on H₂, CO₂, and He permeation properties. Significant improvement of barrier properties is achieved. The pertinent parameters of the gas transport are identified and modelled for each gas/composite system. Finally, from both morphological and gas transport analyses, it is concluded that in situ generation AgPd alloys with Pd to Ag ratio above 1 leads to very interesting and promising materials. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1211–1220     

Polymer‐Derived Silicoboron Carbonitride Foams for CO2 Capture: From Design to Application as Scaffolds for the in Situ Growth of Metal–Organic Frameworks

A template‐assisted polymer‐derived ceramic route is investigated for preparing a series of silicoboron carbonitride (Si/B/C/N) foams with a hierarchical pore size distribution and tailorable interconnected porosity. A boron‐modified polycarbosilazane was selected to impregnate monolithic silica and carbonaceous templates and form after pyrolysis and template removal Si/B/C/N foams. By changing the hard template nature and controlling the quantity of polymer to be impregnated, controlled micropore/macropore distributions with mesoscopic cell windows are generated. Specific surface areas from 29 to 239 m² g^?1 and porosities from 51 to 77 % are achieved. These foams combine a low density with a thermal insulation and a relatively good thermostructural stability. Their particular structure allowed the in situ growth of metal–organic frameworks (MOFs) directly within the open‐cell structure. MOFs offered a microporosity feature to the resulting Si/B/C/N@MOF composite foams that allowed increasing the specific surface area to provide CO₂ uptake of 2.2 %.