Microwave hydrothermal synthesis,characterisation, and catalytic performance of Zn1−x Mn x O in cellulose conversion

Wurtzite-type Zn_1?x Mn _x O (x = 0, 0.03, 0.05, 0.07) nanostructures were successfully synthesised using a simple microwave-assisted hydrothermal route and their catalytic properties were investigated in the cellulose conversion. The morphology of the nanocatalysts is dopant-dependent. Pure ZnO presented multi-plate morphology with a flower-like shape of nanometric sizes, while the Zn_0.97Mn_0.03O sample is formed by nanoplates with the presence of spherical nanoparticles; the Zn_0.95Mn_0.05O and Zn_0.93Mn_0.07O samples are mainly formed by nanorods with the presence of a small quantity of spherical nanoparticles. The catalyst without Mn did not show any catalytic activity in the cellulose conversion. The Mn doping promoted an increase in the density of weak acid sites which, according to the catalytic results, favoured promotion of the reaction.     

Tuning Aqueous Supramolecular Polymerization by an Acid-Responsive Conformational Switch

Besides their widespread use in coordination chemistry, 2,2’-bipyridines are known for their ability to undergo cis–trans conformational changes in response to metal ions and acids, which has been primarily investigated at the molecular level. However, the exploitation of such conformational switching in self-assembly has remained unexplored. In this work, the use of 2,2’-bipyridines as acid-responsive conformational switches to tune supramolecular polymerization processes has been demonstrated. To achieve this goal, we have designed a bipyridine-based linear bolaamphiphile, 1 , that forms ordered supramolecular polymers in aqueous media through cooperative aromatic and hydrophobic interactions. Interestingly, addition of acid (TFA) induces the monoprotonation of the 2,2’-bipyridine moiety, leading to a switch in the molecular conformation from a linear (trans) to a V-shaped (cis) state. This increase in molecular distortion along with electrostatic repulsions of the positively charged bipyridine-H⁺ units attenuate the aggregation tendency and induce a transformation from long fibers to shorter thinner fibers. Our findings may contribute to opening up new directions in molecular switches and stimuli-responsive supramolecular materials.     

Impact of Positional Isomerism on Pathway Complexity in Aqueous Media

Pathway complexity has become an important topic in recent years due to its relevance in the optimization of molecular assembly processes, which typically require precise sample preparation protocols. Alternatively, competing aggregation pathways can be controlled by molecular design, which primarily rely on geometrical changes of the building blocks. However, understanding how to control pathway complexity by molecular design remains elusive and new approaches are needed. Herein, we exploit positional isomerism as a new molecular design strategy for pathway control in aqueous self‐assembly. We compare the self‐assembly of two carboxyl‐functionalized amphiphilic BODIPY dyes that solely differ in the relative position of functional groups. Placement of the carboxyl group at the 2‐position enables efficient pairwise H‐bonding interactions into a single thermodynamic species, whereas meso‐substitution induces pathway complexity due to competing hydrophobic and hydrogen bonding interactions. Our results show the importance of positional engineering for pathway control in aqueous self‐assembly.     

Band gaps in the terahertz frequency range in quasiperiodic one-dimensional magnonic crystals

In this work we investigate magnonic band gaps, in the terahertz (THz) frequency range, in periodic and quasiperiodic (Fibonacci sequence) magnonic crystals formed by layers of Cobalt (Co) and Permalloy (Py). Our theoretical model is based on a magnetic Heisenberg Hamiltonian in the exchange regime, together with a transfer-matrix treatment within the random-phase approximation (RPA). For periodic arrangements the bulk band structure is analogous to those found in photonic crystals, while for quasiperiodic multilayers it presents additional pass bands similar to those found in doped electronic materials.     

Phase diagram of the Ising Model on a Cayley tree in the presence of competing interactions and magnetic field

We study the phase diagram for the Ising Model on a Cayley tree with competing nearest-neighbor interactionsJ ₁ and next-nearest-neighbor interactionsJ ₂ andJ ₃ in the presence of an external magnetic field. To perform this study, an iterative scheme similar to that appearing in real space renormalization group frameworks is established; it recovers, as particular cases, previous works by Vannimenus and by Inawashiroet al. At vanishing temperature, the phase diagram is fully determined, for all values and signs ofJ ₂/J ₁ andJ ₃/J ₂; in particular, we verify that values ofJ ₃/J ₂ high enough favor the paramagnetic phase. At finite temperatures, several interesting features (evolution of reentrances, separation of the modulated region into two disconnected pieces, etc.) are exhibited for typical values ofJ ₂/J ₁ andJ ₃/J ₂.Partially supported by the Brazilian Agencies CNPq and FINEP.     

Theoretical and experimental time series analysis of an inductorless Chua’s circuit

In this paper we have analyzed the time series obtained from an experimental realization of an inductorless version of Chua’s circuit. We have also compared the experimental results with the results emerging by analysis of the time series obtained by numerical simulations of the respective model equations. Lyapunov exponent spectra, the Kaplan-Yorke dimension and phase-space diagrams were used to show the similarities between theoretical and experimental results. We were able to identify the effects of the operational amplifier simulated inductor internal resistance on the Chua’s circuit dynamics. Decreasing internal resistance for decreasing current through the circuit was responsible for the observed bifurcation route.     

Metabisulfite interference in biosensing and Folin-Ciocalteu analysis of polyphenols

Sodium metabisulfite is one of the forms of sulphurous compounds which are added as preservative in food and beverage processing industries. Its interference with different methods of analysis of polyphenols was investigated in the present work. Studies involved the reaction of metabisulfite at platinum electrodes either at a constant applied potential of +100 mV vs. Ag/AgCl electrode with amperometric detection, or at linear potential sweep in cyclic voltammetry experiments. In a second stage, its effect on the analysis of polyphenols that are oxidised by enzymes was examined by the inhibition that metabisulfite caused on caffeic acid oxidation in the presence of free and immobilized laccase. It was found that immobilized laccase was less inhibited than free laccase. A confirmation of the influence of metabisulfite on the Folin-Ciocalteu analysis was also done.     

Accurate Design of Finline Tapers for Millimeter Wave Applications

The design of nonuniform bilateral finlines on anisotropic substrates for millimeter wave applications is presented. The taper consists of a planar circuit with smooth variation of the slot width profile along the structure. The spectral domain method and Galerkin procedure are combined with the transmission line theory for studying the behavior of tapered bilateral finlines and evaluation of their design parameters. The influence of the substrate anisotropy on the propagation characteristics of these structures is also examined. This technique is general and can be applied to investigate a broad class of planar transmission line tapers.     

Formation of catalytic silver nanoparticles supported on branched polyethyleneimine derivatives

A new and straightforward method for screening highly catalytically active silver nanoparticle-polymer composites derived from branched polyethyleneimine (PEI) is reported. The one-step systematic derivatization of the PEI scaffold with alkyl (butyl or octyl) and ethanolic groups led to a structural diversity correlated to the stabilization of silver nanoparticles and catalysis. Analysis of PEI derivative libraries identified a silver nanoparticle-polymer composite that was able to efficiently catalyze the p-nitrophenol reduction by NaBH(4) in water with a rate constant normalized to the surface area of the nanoparticles per unit volume (k(1)) of 0.57 s(-1) m(-2) L. Carried out in the presence of excess NaBH(4), the catalytic reaction was observed to follow pseudo-first-order kinetics and the apparent rate constant was linearly dependent on the total surface area of the silver nanoparticles (Ag-NPs), indicating that catalysis takes place on the surface of the nanoparticles. All reaction kinetics presented induction periods, which were dependent on the concentration of substrates, the total surface of the nanoparticles, and the polymer composition. All data indicated that this induction time is related to the resistance to substrate diffusion through the polymer support. Hydrophobic effects are also assumed to play an important role in the catalysis, through an increase in the local substrate concentration.     

Antiproliferative activity, antioxidant capacity and tannin content in plants of semi-arid northeastern Brazil

The objective of this study was to evaluate antiproliferative activity, antioxidant capacity and tannin content in plants from semi-arid northeastern Brazil (Caatinga). For this study, we selected 14 species and we assayed the methanol extracts for antiproliferative activity against the HEp-2 (laryngeal cancer) and NCI-H292 (lung cancer) cell lines using the (3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazole) (MTT) method. In addition, the antioxidant activity was evaluated with the DPPH (2,2-diphenyl-2-picrylhydrazyl) assay, and the tannin content was determined by the radial diffusion method. Plants with better antioxidant activity (expressed in a dose able to decrease the initial DPPH concentration by 50%, or IC50) and with higher levels of tannins were: Poincianella pyramidalis (42.95±1.77 μg/mL IC50 and 8.17±0.64 tannin content), Jatropha mollissima (54.09±4.36μg/mL IC50 and 2.35±0.08 tannin content) and Anadenanthera colubrina (73.24±1.47 μg/mL IC50 and 4.41±0.47 tannin content). Plants with enhanced antiproliferative activity (% living cells) were Annona muricata (24.94±0.74 in NCI-H292), Lantana camara (25.8±0.19 in NCI-H292), Handroanthus impetiginosus (41.8±0.47 in NCI-H292) and Mentzelia aspera (45.61±1.94 in HEp-2). For species with better antioxidant and antiproliferative activities, we suggest future in vitro and in vivo comparative studies with other pharmacological models, and to start a process of purification and identification of the possible molecule(s) responsible for the observed pharmacological activity. We believe that the flora of Brazilian semi-arid areas can be a valuable source of plants rich in tannins, cytotoxic compounds and antioxidant agents.