Modeling the effect of a superabsorbent polymer material as desiccant in maize drying using CFD

Maize is an important foodstuff in many countries, and one of most susceptible crops to mold and aflatoxin contamination, which results in considerable postharvest losses and is a burden to consumers’ health, especially in developing countries. The timely drying of harvested maize is essential to halt mold development, ensuring safe storage. The effect of the incorporation of a superabsorbent polymer (SAP) as desiccant in a maize dryer was studied using computational fluid dynamics simulations which accounted for heat and mass transfer between maize, SAP and air. The adsorption capacity and adsorption rate of a commercial SAP material were experimentally determined at different temperature and relative humidity levels, which served as basis for the adsorption model required in the simulations. A maize bulk with SAP packages distributed in it was modeled. Results showed that the SAP material increases the drying rate substantially, particularly in the upper bulk zone where the air reaching it is dehumidified the most. The maize closer to the upper bulk surface starts drying from the beginning of the process instead of lagging for hours or days before the drying front reaches it. An inconvenience of the SAP material is the tendency of granules to swell and stick together as moisture reaches a threshold, which may reduce its performance. Thus, provided this issue is resolved or minimized, SAP materials could successfully assist the rapid drying of maize and other crops. They may also be used during storage to avoid rewetting of the crops during periods of high relative humidity.     

Gold Stabilized with Iridium on Ceria–Niobia Catalyst: Activity and Stability for CO Oxidation

Topics in Catalysis - Monometallic gold and iridium, and bimetallic gold–iridium on ceria–niobia (Nb2O5–CeO2) catalysts were synthesized by deposition–precipitation with...     

Microscopic study of electrical properties of CrSi<Subscript>2</Subscript> nanocrystals in silicon

Semiconducting CrSi₂ nanocrystallites (NCs) were grown by reactive deposition epitaxy of Cr onto n -type silicon and covered with a 50-nm epitaxial silicon cap. Two types of samples were investigated: in one of them, the NCs were localized near the deposition depth, and in the other they migrated near the surface. The electrical characteristics were investigated in Schottky junctions by current-voltage and capacitance-voltage measurements. Atomic force microscopy (AFM), conductive AFM and scanning probe capacitance microscopy (SCM) were applied to reveal morphology and local electrical properties. The scanning probe methods yielded specific information, and tapping-mode AFM has shown up to 13-nm-high large-area protrusions not seen in the contact-mode AFM. The electrical interaction of the vibrating scanning tip results in virtual deformation of the surface. SCM has revealed NCs deep below the surface not seen by AFM. The electrically active probe yielded significantly better spatial resolution than AFM. The conductive AFM measurements have shown that the Cr-related point defects near the surface are responsible for the leakage of the macroscopic Schottky junctions, and also that NCs near the surface are sensitive to the mechanical and electrical stress induced by the scanning probe.     

Contribution of Compositional Parameters to the Oxidative Stability of Olive and Walnut Oil Blends

Oil blending was conducted to study the effects of changes in fatty acid composition (FAC), tocopherols and total phenol content (TPC) on oxidative stability of virgin olive oil (VOO):walnut oil (WO) blends. The measurement of the antioxidant activity of bioactive components present in the parent oils and blends was achieved by their ability to scavenge the free stable 2,2-diphenyl-1-picrylhydrazyl radical (DPPH·). The highest percentage of DPPH· inhibition was found for pure VOO, and the lowest one for pure WO. EC₅₀ values obtained from the DPPH assay correlated significantly and inversely with TPC. The generation of volatile flavor components in VOO indicated the predominance of C₆ compounds produced through biochemical (enzymatic) pathways, whereas WO showed increased concentrations of medium chain (C₇–C₁₁) aldehydes produced through chemical (oxidative) pathways. The results obtained confirm the importance of VOO phenolics in providing protection against oxidation in VOO and VOO/WO blends. However, considering the impact of FAC and the content of endogenous antioxidant substances mentioned previously on the oxidative stability of the oils analyzed, the effect of an elevated unsaturation level (WO) prevails over a high amount of such bioactive components (VOO).     

Behavior of phenols and phenoxyacids on a bisphenol-a imprinted polymer. Application for selective solid-phase extraction from water and urine samples

A molecularly imprinted polymer (MIP), obtained by precipitation polymerisation with 4-vinylpyridine as the functional monomer, ethylene glycol dimethacrylate as cross-linker, and bisphenol-A (BPA) as template, was prepared. The binding site configuration of the BPA-MIP was examined using Scatchard analysis. Moreover, the behaviour of the BPA-MIP for the extraction of several phenolic compounds (bisphenol-A, bisphenol-F, 4-nitrophenol, 3-methyl-4-nitrophenol) and phenoxyacid herbicides such as 2,4-D, 2,4,5-T and 2,4,5-TP has been studied in organic and aqueous media in the presence of other pesticides in common use. It was possible to carry out the selective preconcentration of the target analytes from the organic medium with recoveries of higher than 70%. In an aqueous medium, hydrophobic interactions were found to exert a remarkably non-specific contribution to the overall binding process. Several parameters affecting the extraction efficiency of the BPA-MIP were evaluated to achieve the selective preconcentration of phenols and phenoxyacids from aqueous samples. The possibility of using the BPA-MIP as a selective sorbent to preconcentrate these compounds from other samples such as urine and river water was also explored.     

From stochastic single atomic switch to nanoscale resistive memory device

We study the switching characteristics of nanoscale junctions created between a tungsten tip and a silver film covered by a thin ionic conductor layer. Atomic-sized junctions show spectacular current induced switching characteristics, but both the magnitude of the switching voltage and the direction of the switching vary randomly for different junctions. In contrast, somewhat larger junctions with diameters of a few nanometres display a well defined, reproducible switching behavior attributed to the formation and destruction of nanoscale channels in the ionic conductor surface layer. Our results define a lower size limit of 3 nm for reliable ionic nano-switches, which is well below the resolution of recent lithographic techniques.     

Comparison of a pair of synthetic tea-catechin-derived epimers: synthesis, antifolate activity, and tyrosinase-mediated activation in melanoma

Despite bioavailability issues, tea catechins have emerged as promising chemopreventive agents because of their efficacy in various animal models. We synthesized two catechin-derived compounds, 3-O-(3,4,5-trimethoxybenzoyl)-(-)-catechin (TMCG) and 3-O-(3,4,5-trimethoxybenzoyl)-(-)-epicatechin (TMECG), in an attempt to improve the stability and cellular absorption of tea polyphenols. The antiproliferative and pro-apoptotic activities of both compounds were analyzed with various cancer cell systems, and TMCG, which was easily synthesized in excellent yield, was more active than TMECG in both melanoma and non-melanoma cell lines. TMCG was also a better inhibitor of dihydrofolate reductase and was more efficiently oxidized by tyrosinase, potentially explaining the difference in activity between these epimers.     

Self-standing nanoparticle membranes and capsules

We perform coarse-grained molecular dynamics simulations of self-standing nanoparticle membranes observed in recent experiments (K. E. Mueggenburg et al., Nat. Mater., 2007, 6, 656). In order to make our simulations feasible, we model 2-3 times smaller gold nanoparticles (core radius of r(core) ≈ 0.8 nm) covered with alkanethiol ligands (length of l(ligand) ≈ 0.5-2.6 nm). We study the structure, stability, and mechanical properties of these membranes and show that these characteristics are controlled by the ratio of R(LC) = l(ligand)/r(core). For R(LC) ≈ 0.6, the ligated nanoparticles form well ordered monolayers with hexagonal packing, in agreement with the experiments (R(LC) ≈ 0.44). For R(LC) ≈ 1.6, the nanoparticles form less organized multilayers, which are more stable and flexible. We show that these membranes could potentially form stable capsules for molecular storage and delivery.     

Photochemistry of group 6 Fischer carbene complexes: beyond the photocarbonylation reaction

The seminal report by Hegedus in 1982, showing that alkoxychromium(0) carbenes reacted with imines under bright Colorado sunlight to yield β-lactams, marked the beginning of a key reaction in organometallic chemistry. Very little was known about the mechanism of this reaction. In fact, Hegedus proposed the reversible generation of a chromium-coordinated ketene, which would react with nucleophiles. This coordinated species would show all the advantages of ketenes without their shortcomings, namely, dimerization, formation of undesired adducts, and so forth. The quest for the detection of these species and the pursuit of the mechanism of the photocarbonylation (a reaction exclusive to Cr(0) and Mo(0) carbene complexes, not W(0) carbene complexes) remained unabated over the next 15 years. In fact, all attempts to experimentally determine the mechanism of this useful reaction have been fruitless. At the same time, the photocarbonylation of Cr(0) carbenes matured into a valuable synthetic reaction, allowing access to several families of organic compounds. Unfortunately, reactions other than photocarbonylation remained elusive. We used a combination of experimental and computational methodologies to study the photocarbonylation of Cr(0) carbene complexes and the subsequent reaction of the photogenerated ketenes with nucleophiles. In parallel, we discovered new photochemical processes and succeeded in making photoreactive the so-called "unreactive" W(0) carbene complexes. In this Account, we discuss the disentangling of the mechanisms of these transformations, thereby shedding some light onto the photochemistry of group 6 metal (Fischer) carbene complexes. The original designation of the electronic transitions of group 6 carbene complexes was reassigned, and the photocarbonylation step was analyzed again, resulting in the sequence S(0)-T(1)-S(0), which is far removed from conventional organic photochemistry. The T(1) species is a chromacyclopropanone; its unpaired electrons are primarily localized in the metal fragment and in the former carbene carbon atom. The T(1)-S(0) intersystem crossing occurs with the participation of the solvent through an unusual loose-bolt radiationless mechanism. The photogenerated S(0) species reacts with imines to form the final β-lactams in a mechanism that resembles the organic Staudinger reaction, but here the metal is present during the entire reaction coordinate. The selectivity of these reactions is defined by the nucleophilic attack on the O-bonded metallaketene instead of the subsequent conrotatory ring closure, a distinct departure from the organic reaction. Appropriate modification of the substituents of the carbene ligand or in the coordination sphere of the complex results in new photoprocesses; these include 1,2-metalladyotropic rearrangements as well as α-fragmentations in which W(0) carbene complexes become photoreactive. Moreover, the inclusion of additional metal centers usually results in new reactions, such as the formation of fulvenes by η(5)→ η(3) photoslippage, or in the complete inhibition of the photoreactivity. The photochemistry of group 6 metal-carbene complexes thus offers unexplored territory for pursuing new reactions and reaction mechanisms.