Natural abundance 13C - 13C coupling constants observed via double quantum coherence. Structural elucidation by the one- and the two-dimensional NMR experiements of velloziolone,a new seco-diterpene.

With the help of Natural Abundance ¹³C - ¹³C Coupling Constants, observed via double quantum coherence, the structural determination of VELLOZIOLONE (1), a new diterpene, has been carried out.     

Simultaneous Differential Pulse Voltammetric Determination of Ascorbic Acid and Caffeine in Pharmaceutical Formulations Using a Boron‐Doped Diamond Electrode

A cathodically pretreated boron‐doped diamond electrode was used for the simultaneous anodic determination of ascorbic acid (AA) and caffeine (CAF) by differential pulse voltammetry. Linear calibration curves (r=0.999) were obtained from 1.9×10^?5 to 2.1×10^?4 mol L^?1 for AA and from 9.7×10^?6 to 1.1×10^?4 mol L^?1 for CAF, with detection limits of 19 μmol L^?1 and 7.0 μmol L^?1, respectively. This method was successfully applied for the determination of AA and CAF in pharmaceutical formulations, with results equal to those obtained using a HPLC reference method.     

Ethylbenzene to chemicals: Catalytic conversion of ethylbenzene into styrene over metal-containing MCM-41

Isomorphously substituted (MeDM) and impregnated metal-containing MCM-41 (MeO_x/IM) catalysts, in which Me = Co, Cu, Cr, Fe or Ni, have been prepared. Structural and textural characterizations of the catalysts were performed by means of X-ray diffraction (XRD), chemical analysis, Raman spectroscopy, electron paramagnetic resonance (EPR), N₂ adsorption isotherms and temperature programmed reduction (TPR). Cu²⁺, Co²⁺, and Cr⁴⁺/Cr³⁺ species were found over the catalysts as cations incorporated in the MCM-41 structure (MeDM) or highly dispersed oxides on the surface (MeO_x/IM). The MeDM catalysts exhibited a good performance in the dehydrogenation of ethylbenzene with CO₂. However, MeO_x/IM catalysts had a low performance in styrene production (activity less than 15 × 10^?3 mmol h^?1 and selectivity for styrene less than 80%) due to the high reducibility of the metals species. However, Ni²⁺ or Fe³⁺ coordinated with the MCM-41 framework, as well as NiO_x and Fe₂O₃ extra-framework species, is continuously oxidized by the CO₂ to maintain the active sites for dehydrogenating ethylbenzene. Deactivation studies on the FeDM sample showed that Fe³⁺ species produced active sp² carbon compounds, which are removed by CO₂; the referred sample is catalytically selective for styrene and stable over 24 h of reaction. In contrast, highly active Ni²⁺ and Ni⁰ species produced a large amount of polyaromatic carbonaceous deposits from styrene, as identified by TPO, TG and Raman spectroscopy. An acid–base mechanism is proposed to operate to adsorb ethylbenzene and abstract the β-hydrogen. CO₂ plays a role in furnishing the lattice oxygen to maintain the Fe³⁺ active sites in the dehydrogenation of ethylbenzene to form styrene.     

Thermal characterization of hydrotalcite used in the transesterification of soybean oil

Hydrotalcite was synthesised by co-precipitation method, calcined and characterized by XRD, BET, IR and TG/DTA/DTG analyses and tested as solid base catalyst in the transesterification of soybean oil with methanol, achieving a methyl ester content of 99.5%. The thermal decomposition of hydrotalcite calcined occurred in four mass loss steps at 28, 105, 203 and 400 °C. The hydrotalcite was recovered and through a simple evaluation by TG/DTA/DTG techniques it was found that at 500 °C is the temperature, where the organic matter should be eliminated from the catalyst. This study shows the importance of thermal analysis in the evaluation of the recovery temperature of hydrotalcite.     

Development of a classical force field for the oxidized Si surface: application to hydrophilic wafer bonding

We have developed a classical two- and three-body interaction potential to simulate the hydroxylated, natively oxidized Si surface in contact with water solutions, based on the combination and extension of the Stillinger-Weber potential and of a potential originally developed to simulate SiO(2) polymorphs. The potential parameters are chosen to reproduce the structure, charge distribution, tensile surface stress, and interactions with single water molecules of a natively oxidized Si surface model previously obtained by means of accurate density functional theory simulations. We have applied the potential to the case of hydrophilic silicon wafer bonding at room temperature, revealing maximum room temperature work of adhesion values for natively oxidized and amorphous silica surfaces of 97 and 90 mJm(2), respectively, at a water adsorption coverage of approximately 1 ML. The difference arises from the stronger interaction of the natively oxidized surface with liquid water, resulting in a higher heat of immersion (203 vs 166 mJm(2)), and may be explained in terms of the more pronounced water structuring close to the surface in alternating layers of larger and smaller densities with respect to the liquid bulk. The computed force-displacement bonding curves may be a useful input for cohesive zone models where both the topographic details of the surfaces and the dependence of the attractive force on the initial surface separation and wetting can be taken into account.     

Characterization of Biocatalysts Prepared with Thermomyces lanuginosus Lipase and Different Silica Precursors,Dried using Aerogel and Xerogel Techniques

The use of lipases in industrial processes can result in products with high levels of purity and at the same time reduce pollutant generation and improve both selectivity and yields. In this work, lipase from Thermomyces lanuginosus was immobilized using two different techniques. The first involves the hydrolysis/polycondensation of a silica precursor (tetramethoxysilane (TMOS)) at neutral pH and ambient temperature, and the second one uses tetraethoxysilane (TEOS) as the silica precursor, involving the hydrolysis and polycondensation of the alkoxide in appropriate solvents. After immobilization, the enzymatic preparations were dried using the aerogel and xerogel techniques and then characterized in terms of their hydrolytic activities using a titrimetric method with olive oil and by the formation of 2-phenylethyl acetate in a transesterification reaction. The morphological properties of the materials were characterized using scanning electron microscopy, measurements of the surface area and pore size and volume, thermogravimetric analysis, and exploratory differential calorimetry. The results of the work indicate that the use of different silica precursors (TEOS or TMOS) and different drying techniques (aerogel or xerogel) can significantly affect the properties of the resulting biocatalyst. Drying with supercritical CO₂ provided higher enzymatic activities and pore sizes and was therefore preferable to drying, using the xerogel technique. Thermogravimetric analysis and differential scanning calorimetry analyses revealed differences in behavior between the two biocatalyst preparations due to the compounds present.     

A volatolomic approach using cerumen as biofluid to diagnose bovine intoxication by Stryphnodendron rotundifolium

An innovative volatolomic approach employs the detection of biomarkers present in cerumen (earwax) to identify cattle intoxication by Stryphnodendron rotundifolium Mart., Fabaceae (popularly known as barbatimão). S. rotundifolium is a poisonous plant with the toxic compound undefined and widely distributed throughout the Brazilian territory. Cerumen samples from cattle of two local Brazilian breeds (‘Curraleiro Pé-Duro’ and ‘Pantaneiro’) were collected during an experimental intoxication protocol and analyzed using headspace (HS)/GC–MS followed by multivariate analysis (genetic algorithm for a partial least squares, cluster analysis, and classification and regression trees). A total of 106 volatile organic metabolites were identified in the cerumen samples of bovines. The intoxication by S. rotundifolium influenced the cerumen volatolomic profile of the bovines throughout the intoxication protocol. In this way, it was possible to detect biomarkers for cattle intoxication. Among the biomarkers, 2-octyldecanol and 9-tetradecen-1-ol were able to discriminate all samples between intoxicated and nonintoxicated bovines. The cattle intoxication diagnosis by S. rotundifolium was accomplished by applying the cerumen analysis using HS/GC–MS, in an easy, accurate, and noninvasive way. Thus, the proposed bioanalytical chromatography protocol is a useful tool in veterinary applications to determine this kind of intoxication.     

Thermal, rheological, and structural behaviors of natural and modified cassava starch granules, with sodium hypochlorite solutions

The use of chemically modified starches is widely accepted in various industries, with several applications. In this research, natural cassava starch granules were treated with standard sodium hypochlorite solution at 0.8, 2.0, and 5.0 g Cl/100 g starch. The native and modified starch samples were investigated by means of the following techniques: simultaneous thermogravimetry–differential thermal analysis, which allowed us to verify the thermal decomposition associated with endothermic or exothermic phenomena; and differential scanning calorimetry that was used to determine gelatinization enthalpy as well as the rapid viscoamylographic analysis that provided the pasting temperature and viscosity. By means of non-contact-atomic force microscopy method and X-ray powder patterns diffractometry, it was possible to observe the surface morphology, topography of starch granules, and alterations in the granules’ crystallinity.     

Heteronuclear Cross‐Relaxation Effects in the NMR Spectroscopy of Hyperpolarized Targets

Dissolution dynamic nuclear polarization (DNP) enables high‐sensitivity solution‐phase NMR experiments on long‐lived nuclear spin species such as ¹⁵N and ¹³C. This report explores certain features arising in solution‐state ¹H NMR upon polarizing low‐γ nuclear species. Following solid‐state hyperpolarization of both ¹³C and ¹H, solution‐phase ¹H NMR experiments on dissolved samples revealed transient effects, whereby peaks arising from protons bonded to the naturally occurring ¹³C nuclei appeared larger than the typically dominant ¹²C‐bonded ¹H resonances. This enhancement of the satellite peaks was examined in detail with respect to a variety of mechanisms that could potentially explain this observation. Both two‐ and three‐spin phenomena active in the solid state could lead to this kind of effect; still, experimental observations revealed that the enhancement originates from ¹³C→¹H polarization‐transfer processes active in the liquid state. Kinetic equations based on modified heteronuclear cross‐relaxation models were examined, and found to well describe the distinct patterns of growth and decay shown by the ¹³C‐bound ¹H NMR satellite resonances. The dynamics of these novel cross‐relaxation phenomena were determined, and their potential usefulness as tools for investigating hyperpolarized ensembles and for obtaining enhanced‐sensitivity ¹H NMR traces was explored.     

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.