Iron oxide magnetic nanoparticles used as probing agents to study the nanostructure of mixed self-assembled monolayers

Self-assembled monolayers (SAMs) of organic molecules are of exceptional technological importance since they represent a convenient, flexible, and simple system for tuning the chemical and physical properties of surfaces. The fine control of surface properties is directly dependent on the structure of mixed SAMs which is difficult to characterize at the nanoscale with usual techniques such as scanning probe microscopies. In this study, we report on a general method to investigate at the nanoscale the structure of molecular patterns which consist in SAMs of two components. Iron oxide nanoparticles (NPs) have been used as probing agents to study indirectly the structure of mixed SAMs. Mixed SAMs were prepared by the replacement of mercaptododecane (MDD) adsorbed by mercaptoundecanoic acid (MUA) molecules on gold substrates. Therefore, the SAM surface displays both chelating carboxylic terminal groups and non-chelating methylene terminal groups. As NPs have been previously demonstrated to specifically interact with carboxylic acid groups, the increasing density in NPs was correlated with the evolution of the COOH/CH(3) terminal groups ratio. Therefore the structure of mixed SAMs was studied indirectly as well as the kinetic of the replacement reaction and its mechanism. With this aim, we took advantage of the SPR properties of the gold substrate and of the high refractive index of iron oxide nanoparticles to follow their assembling on mixed SAMs as a time resolved study. The high sensitivity and tuning of the SPR signal over a wide range of wavelengths are correlated with the NP density. Furthermore, SEM combined with image analysis has allowed studying the replacement rate of MDD by MUA in SAMs. We took also advantages of the magnetic properties of NPs to evaluate qualitatively the replacement of thiol molecules.     

Low Concentrations of Salicylic Acid Stimulate Insect Elicitor Responses in <Emphasis Type="Italic">Zea mays</Emphasis> Seedlings

Salicylic acid (SA) generally is thought to suppress jasmonic acid (JA) related signaling events. However, when we treated the roots of corn seedlings overnight with low physiological concentrations of SA (50 μM), we found a priming effect of this pretreatment on typical insect elicitor (IE)-induced responses in the leaves of these plants. IE-induced JA was more than 2-fold up regulated in SA-pretreated plants. Consequently, IE-induced volatile organic compounds (VOC) release also was significantly increased. In contrast, when corn seedlings were treated with SA overnight and then mechanically damaged, we found no significant differences in JA accumulation. We also found that the application of even lower concentrations of SA (5 μM) had no significant effect on IE-induced responses, while higher concentrations (500 μM) inhibited IE-induced JA accumulation. Likewise, shorter exposure to SA did not affect subsequent JA accumulation induced by IE or mechanical wounding. These results provide evidence for the existence of non-compatible defense priming by signaling molecules that usually are involved in a conflictive defense signaling pathway and suggests common elements in the regulation of priming plant defense responses.     

Microkinetic model for the pyrolysis of methyl esters: From model compound to industrial biodiesel

A tool for the generation of decomposition schemes of large molecules has been developed. These decomposition schemes contain radicals which can be eliminated from the model equations if both the μ‐hypothesis and the pseudosteady‐state approximation are valid. The reaction rate coefficients and thermodynamic parameters have been calculated by incorporating a comprehensive group additive framework. A microkinetic model for the pyrolysis of methyl esters with a carbon number of up to 19 has been generated using this tool. It is validated by comparing calculated and experimental yields of the pyrolysis of methyl decanoate and novel rapeseed methyl ester pyrolysis data in the temperature range from 800 to 1100 K and methyl ester partial pressure range from 1 × 10^?3 to 1 × 10^?2 MPa. This modeling frame work allows to not only assess the use of methyl ester mixtures as potential feedstock for olefin production but also their effect as blend‐in or trace impurity. © 2015 American Institute of Chemical Engineers AIChE J, 61: 4309–4322, 2015     

Mechanisms of Enzyme-Catalyzed Reduction of Two Carcinogenic Nitro-Aromatics, 3-Nitrobenzanthrone and Aristolochic Acid I: Experimental and Theoretical Approaches

This review summarizes the results found in studies investigating the enzymatic activation of two genotoxic nitro-aromatics, an environmental pollutant and carcinogen 3-nitrobenzanthrone (3-NBA) and a natural plant nephrotoxin and carcinogen aristolochic acid I (AAI), to reactive species forming covalent DNA adducts. Experimental and theoretical approaches determined the reasons why human NAD(P)H:quinone oxidoreductase (NQO1) and cytochromes P450 (CYP) 1A1 and 1A2 have the potential to reductively activate both nitro-aromatics. The results also contributed to the elucidation of the molecular mechanisms of these reactions. The contribution of conjugation enzymes such as N,O-acetyltransferases (NATs) and sulfotransferases (SULTs) to the activation of 3-NBA and AAI was also examined. The results indicated differences in the abilities of 3-NBA and AAI metabolites to be further activated by these conjugation enzymes. The formation of DNA adducts generated by both carcinogens during their reductive activation by the NOQ1 and CYP1A1/2 enzymes was investigated with pure enzymes, enzymes present in subcellular cytosolic and microsomal fractions, selective inhibitors, and animal models (including knock-out and humanized animals). For the theoretical approaches, flexible in silico docking methods as well as ab initio calculations were employed. The results summarized in this review demonstrate that a combination of experimental and theoretical approaches is a useful tool to study the enzyme-mediated reaction mechanisms of 3-NBA and AAI reduction.     

Synthetic and Biological Studies of Sesquiterpene Polygodial: Activity of 9‐Epipolygodial against Drug‐Resistant Cancer Cells

Polygodial, a terpenoid dialdehyde isolated from Polygonum hydropiper L., is a known agonist of the transient receptor potential vanilloid 1 (TRPV1). In this investigation a series of polygodial analogues were prepared and investigated for TRPV1‐agonist and anticancer activities. These experiments led to the identification of 9‐epipolygodial, which has antiproliferative potency significantly exceeding that of polygodial. 9‐Epipolygodial was found to maintain potency against apoptosis‐resistant cancer cells as well as those displaying the multidrug‐resistant (MDR) phenotype. In addition, the chemical feasibility for the previously proposed mechanism of action of polygodial, involving the formation of a Paal–Knorr pyrrole with a lysine residue on the target protein, was demonstrated by the synthesis of a stable polygodial pyrrole derivative. These studies reveal rich chemical and biological properties associated with polygodial and its direct derivatives. These compounds should inspire further work in this area aimed at the development of new pharmacological agents, or the exploration of novel mechanisms of covalent modification of biological molecules with natural products.     

Preparation and Reinforcement of Dual‐Porous Biocompatible Cellulose Scaffolds for Tissue Engineering

Biocompatible cellulose‐based aerogels composed of nanoporous struts, which embed interconnected voids of controlled micron‐size, have been prepared employing temporary templates of fused porogens, reinforcement by interpenetrating PMMA networks and supercritical carbon dioxide drying. Different combinations of cellulose solvent (Ca(SCN)₂/H₂O/LiCl or [EMIm][OAc]/DMSO) and anti‐solvent (EtOH), porogen type (paraffin wax or PMMA spheres) and porogen size (various fractions in the range of 100–500 μm) as well as intensity of PMMA reinforcement have been investigated to tailor the materials for cell scaffolding applications. All aerogels exhibited an open and dual porosity (micronporosity >100 μm and nanoporosity extending to the low micrometer range). Mechanical properties of the dual‐porous aerogels under compressive stress were considerably improved by introduction of interpenetrating PMMA networks. The effect of the reinforcing polymer on attachment, spreading, and proliferation of NIH 3T3 fibroblast cells, cultivated on selected dual‐porous aerogels to pre‐evaluate their biocompatibility was similarly positive.     

Strain‐induced deformation mechanisms of polylactide plasticized with acrylated poly(ethylene glycol) obtained by reactive extrusion

This work aimed at identifying the tensile deformation mechanisms of an original grade of plasticized polylactide (pPLA) obtained by reactive extrusion. This material had a glass transition temperature of 32.6 °C and consisted of a polylactide (PLA) matrix grafted with poly(acryl‐poly(ethylene glycol)) (poly(Acryl‐PEG)) inclusions. pPLA behaved like a rubber‐toughened amorphous polymer at 20 °C, and its tensile behavior evolved toward a rubbery semicrystalline polymer with increasing temperature. The drawing of pPLA involved orientation of amorphous and crystalline chains, crystallization, and destruction of crystals. It was found that crystal formation and crystal destruction were in competition below 50 °C, resulting in a constant or slightly decreasing crystallinity with strain. Increasing temperature enhanced crystal formation and limited crystal destruction, resulting in an increased crystallinity with the strain level. Drawing yielded a transformation of the initial spherical poly(Acryl‐PEG) inclusions into ellipsoids oriented in the tensile direction. This mechanism may engender the formation of nanovoids within the inclusions due to a decreased density, assumed to be responsible for the whitening of the specimen. © 2015 Society of Chemical Industry