Microwave hydrothermal synthesis, characterisation, and catalytic performance of Zn1-xMnxO in cellulose conversion

Wurtzite-type Zn1-xMnxO (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 Zn0.97Mn0.03O sample is formed by nanoplates with the presence of spherical nanoparticles; the Zn0.95Mn0.05O and Zn0.93Mn0.07O 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. © 2013 Institute of Chemistry, Slovak Academy of Sciences.

Rapid preparation of alpha-FeOOH and alpha-Fe2O3 nanostructures by microwave heating and their application in electrochemical sensors

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Effect of pressure-assisted heat treatment on photoluminescence emission of α-Bi2O3 needles

Materials with high photoluminescence (PL) intensity can potentially be used in optical and electronic devices. Although the PL properties of bismuth(III) oxide with a monoclinic crystal structure (α-Bi2O3) have been explored in the past few years, methods of increasing PL emission intensity and information relating PL emission to structural defects are scarce. This research evaluated the effect of a pressure-assisted heat treatment (PAHT) on the PL properties of α-Bi2O3 with a needlelike morphology, which was synthesized via a microwave-assisted hydrothermal (MAH) method. PAHT caused an angular increase between the [BiO6]-[BiO6] clusters of α-Bi2O3, resulting in a significant increase in the PL emission intensity. The Raman and XPS spectra also showed that the α-Bi2O3 PL emissions in the low-energy region (below ∼2.1 eV) are attributed to oxygen vacancies that form defect donor states. The experimental results are in good agreement with first-principles total-energy calculations that were carried out within periodic density functional theory (DFT).

Uma nova abordagem analítica sobre teores de 'Zn' por HR-CSAAS em plantas medicinais voltadas ao emagrecimento

The following research project deals with the development of new analytical procedures aimed at the identification and quantification of the element zinc in different fractions of vegetable drugs used for weight loss, using the high-resolution continuum source atomic absorption spectrometry in flame. The determination of the levels of zinc was made in an AnalytikJena ContrAA 300 spectrometer in the principal line of Zn at 213.857 nm and wavelength integrated absorbance equal to 3 pixels. Calibration curves were obtained with linear dynamic range from 0.10 to 1.00 mg L-1, correlation coefficient equal to 0.9991 and limit of detection equal to 0.020 mg L-1. The total Zn content in the samples obtained after microwave-assisted acid digestion system were: 28.06 mg kg-1 (Artichoke), 31.49 mg kg-1 (Chamomile), 77.16 mg kg-1 (Gorse), 105.38 mg kg-1 (Horsetail), 32.37 mg kg-1 (Fennel) and 5.00 mg kg-1 (Senna). The extraction in aqueous environment assisted by microwave radiation produced extracts containing: 5.40 mg kg-1 (Artichoke), 10.65 mg kg-1 (Chamomile), 14.83 mg kg-1 (Gorse), 18.90 mg kg-1 (Horsetail), 7.80 mg kg-1 (Fennel), 3.24 mg kg-1 (Senna), corresponding to 19%, 34%, 19%, 18%, 24% and 64% of their total content of Zn, respectively. The amounts of Zn in the extracted samples from some plants indicate that this metal was strongly bounded to the plant's matrix. The sequential extraction using solvents and mixtures with different polarities (n-hexane, ethyl acetate, propanol, methanol, ethanol-water 1:1 (v/v), water) aimed the separation of different Zn containing species and water was considered the most efficient extractor. The Zn contents extracted were: 14.82 mg kg-1 (Artichoke), 16.82 mg kg-1 (Chamomile), 34.09 mg kg-1 (Gorse), 4.75 mg kg-1 (Senna), corresponding to 53% in the first two samples, 44% and 95% for the last two, respectively. It was observed that Zn is found complexed under

Quantum Mechanics Insight into the Microwave Nucleation of SrTiO3 Nanospheres

An extensive investigation of strontium titanate, SrTiO3 (STO), nanospheres synthesized via a microwave-assisted hydrothermal (MAH) method has been conducted to gain a better insight into thermodynamic, kinetic, and reaction phenomena involved in STO nucleation and crystal growth processes. To this end, quantum chemical modeling based on the density functional theory and periodic super cell models were done. Several experimental techniques were employed to get a deep characterization of structural and optical features of STO nanospheres. A possible formation mechanism was proposed, based on dehydration of titanium and strontium clusters followed by mesoscale transformation and a self-assembly process along an oriented attachment mechanism resulting in spherical like shape. Raman and XANES analysis renders a noncentrosymmetric environment for the octahedral titanium, while infrared and first order Raman modes reveal OH groups which are unsystematically incorporated into uncoordinated superficial sites. These results seem to indicate that the key component is the presence of distorted TiO6 clusters to engender a luminescence property. Analysis of band structure, density Of states, and charge map shows that there is a close relationship among local broken symmetry, polarization, and energy split of the 3d orbitals of titanium. The interplay among these electronic and structural features provides necessary conditions to evaluate its luminescent properties under two energy excitation.

Microwave-Mediated Hetero Diels-Alder reaction: Synthesis of biologically active compounds

Heterocyclic compounds represent almost two-thirds of all the known organic compounds: they are widely distributed in nature and play a key role in a huge number of biologically important molecules including some of the most significant for human beings. A powerful tool for the synthesis of such compounds is the hetero Diels-Alder reaction (HDA), that involve a [4+2] cycloaddition reaction between heterodienes and suitable dienophiles. Among heterodienes to be used in such six-membered heterocyclic construction strategy, 3-trialkylsilyloxy-2-aza-1,3-dienes (Fig 1) has been demonstrated particularly attractive. In this thesis work, HDA reactions between 2-azadienes and carbonylic and/or olefinic dienophiles, are described. Moreover, substitution of conventional heating by the corresponding dielectric heating as been explored in the frame of Microwave-Assisted-Organic-Synthesis (MAOS) which constitutes an up-to-grade research field of great interest both from an academic and industrial point of view. Reaction of the azadiene 1 (Fig 1) will be described using as dienophiles carbonyl compounds as aldehyde and ketones. The six-membered adducts thus obtained (Scheme 1) have been elaborated to biologically active compounds like 1,3-aminols which constitutes the scaffold for a wide range of drugs (Prozac®, Duloxetine, Venlafaxine) with large applications in the treatment of severe diseases of nervous central system (NCS). Scheme 1 The reaction provides the formation of three new stereogenic centres (C-2; C-5; C-6). The diastereoselective outcome of these reactions has been deeply investigated by the use of various combination of achiral and chiral azadienes and aliphatic, aromatic or heteroaromatic aldehydes. The same approach, basically, has been used in the synthesis of piperidin-2-one scaffold substituting the carbonyl dienophile with an electron poor olefin. Scheme 2 As a matter of fact, this scaffold is present in a very large number of natural substances and, more interesting, is a required scaffold for an huge variety of biologically active compounds. Activated olefins bearing one or two sulfone groups, were choose as dienophiles both for the intrinsic characteristic flexibility of the “sulfone group” which may be easily removed or elaborated to more complex decorations of the heterocyclic ring, and for the electron poor property of this dienophiles which makes the resulting HDA reaction of the type “normal electron demand”. Synthesis of natural compounds like racemic (±)-Anabasine (alkaloid of Tobacco’s leaves) and (R)- and (S)-Conhydrine (alkaloid of Conium Maculatum’s seeds and leaves) and its congeners, are described (Fig 2).

Heat transfer in microwave heating

Heat transfer is considered as one of the most critical issues for design and implement of large-scale microwave heating systems, in which improvement of the microwave absorption of materials and suppression of uneven temperature distribution are the two main objectives. The present work focuses on the analysis of heat transfer in microwave heating for achieving highly efficient microwave assisted steelmaking through the investigations on the following aspects: (1) characterization of microwave dissipation using the derived equations, (2) quantification of magnetic loss, (3) determination of microwave absorption properties of materials, (4) modeling of microwave propagation, (5) simulation of heat transfer, and (6) improvement of microwave absorption and heating uniformity. Microwave heating is attributed to the heat generation in materials, which depends on the microwave dissipation. To theoretically characterize microwave heating, simplified equations for determining the transverse electromagnetic mode (TEM) power penetration depth, microwave field attenuation length, and half-power depth of microwaves in materials having both magnetic and dielectric responses were derived. It was followed by developing a simplified equation for quantifying magnetic loss in materials under microwave irradiation to demonstrate the importance of magnetic loss in microwave heating. The permittivity and permeability measurements of various materials, namely, hematite, magnetite concentrate, wüstite, and coal were performed. Microwave loss calculations for these materials were carried out. It is suggested that magnetic loss can play a major role in the heating of magnetic dielectrics. Microwave propagation in various media was predicted using the finite-difference time-domain method. For lossy magnetic dielectrics, the dissipation of microwaves in the medium is ascribed to the decay of both electric and magnetic fields. The heat transfer process in microwave heating of magnetite, which is a typical magnetic dielectric, was simulated by using an explicit finite-difference approach. It is demonstrated that the heat generation due to microwave irradiation dominates the initial temperature rise in the heating and the heat radiation heavily affects the temperature distribution, giving rise to a hot spot in the predicted temperature profile. Microwave heating at 915 MHz exhibits better heating homogeneity than that at 2450 MHz due to larger microwave penetration depth. To minimize/avoid temperature nonuniformity during microwave heating the optimization of object dimension should be considered. The calculated reflection loss over the temperature range of heating is found to be useful for obtaining a rapid optimization of absorber dimension, which increases microwave absorption and achieves relatively uniform heating. To further improve the heating effectiveness, a function for evaluating absorber impedance matching in microwave heating was proposed. It is found that the maximum absorption is associated with perfect impedance matching, which can be achieved by either selecting a reasonable sample dimension or modifying the microwave parameters of the sample.

Chemical reactions of double bonds in activated carbon:microwave and bromination methods

The reaction of localised C=C bonds on the surface of activated carbons has been shown to be an effective method of chemical modification especially using microwave-assisted reactions.

Desenvolvimento de método para determinação de espécies de mercúrio empregando MSPD e GC-MS

Neste trabalho é proposto pela primeira vez, o desenvolvimento e validação de um método analítico baseado no emprego da dispersão da matriz em fase sólida (MSPD) modificada, para extração das espécies CH3Hg+ e Hg2+ em amostras de peixe e determinação por cromatografia em fase gasosa acoplada à espectrometria de massas (GC-MS). O método de extração utilizando a MSPD combina o rompimento da estrutura física da amostra, através da maceração e do uso de SiO2 como suporte sólido, com o método da extração ácida, utilizando uma solução de HCl 4,2 mol L-1 e NaCl 0,5 mol L-1. Para otimização da MSPD, foram avaliados parâmetros como massa de amostra, massa de suporte sólido, concentração de HCl, concentração de NaCl, tipo de suporte sólido e o tempo de agitação, com auxílio da metodologia de superfície de resposta. Além disso, a etapa de derivatização e a separação cromatográfica também foram otimizadas na determinação de CH3Hg+ e Hg2+ por GC-MS. O método mostrouse adequado para extração e determinação de espécies de mercúrio através da aplicação em materiais de referência certificados de fígado de peixe (DOLT-3) e músculo de peixe (DORM-2), apresentando boas concordâncias com os valores certificados e desvio padrão relativo inferior a 9,5%. Os limites de detecção foram de 0,06 e 0,12 µg g-1 para CH3Hg+ e Hg2+, respectivamente. Além disso, foi observado um significativo efeito de matriz e, por isso, a calibração foi feita com curvas preparadas com o extrato da MSPD. O método mostrou boa concordância na comparação entre a soma da concentração das espécies e a concentração de mercúrio total determinada por espectrometria de massas com plasma indutivamente acoplado com geração de vapor frio (CVG-ICP-MS), após digestão assistida por micro-ondas (MAD) em peixes do tipo atum (Thunnus thynnus), cação anjo (Squatina squatina) e cação viola (Rhinobatos blochii.).

Extraction and detection of mycotoxins in medicinal and aromatic plants: a case study with Aloysia citrodora P.

Plants frequently suffer contaminations by toxigenic fungi, and their mycotoxins can be produced throughout growth, harvest, drying and storage periods. The objective of this work was to validate a method for detection of toxins in medicinal and aromatic plants, through a fast and highly sensitive method, optimizing the joint co-extraction of aflatoxins (AF: AFB1, AFB2, AFG1 and AFG2) and ochratoxin A (OTA) by using Aloysia citrodora P. (lemon verbena) as a case study. For optimization purposes, samples were spiked (n=3) with standard solutions of a mix of the four AFs and OTA at 10 ng/g for AFB1, AFG1 and OTA, and at 6 ng/g of AFB2 and AFG2. Several extraction procedures were tested: i) ultrasound-assisted extraction in sodium chloride and methanol/water (80:20, v/v) [(OTA+AFs)1]; ii) maceration in methanol/1% NaHCO3 (70:30, v/v) [(OTA+AFs)2]; iii) maceration in methanol/1% NaHCO3 (70:30, v/v) (OTA1); and iv) maceration in sodium chloride and methanol/water (80:20, v/v) (AF1). AF and OTA were purified using the mycotoxin-specific immunoaffinity columns AflaTest WB and OchraTest WB (VICAM), respectively. Separation was performed with a Merck Chromolith Performance C18 column (100 x 4.6 mm) by reverse-phase HPLC coupled to a fluorescence detector (FLD) and a photochemical derivatization system (for AF). The recoveries obtained from the spiked samples showed that the single-extraction methods (OTA1 and AF1) performed better than co-extraction methods. For in-house validation of the selected methods OTA1 and AF1, recovery and precision were determined (n=6). The recovery of OTA for method OTA1 was 81%, and intermediate precision (RSDint) was 1.1%. The recoveries of AFB1, AFB2, AFG1 and AFG2 ranged from 64% to 110% for method AF1, with RSDint lower than 5%. Methods OTA1 and AF1 showed precision and recoveries within the legislated values and were found to be suitable for the extraction of OTA and AF for the matrix under study.

Quantification of free auxins in semi-hardwood plant cuttings and microshoots by dispersive liquid–liquid microextraction/microwave derivatization and GC/MS analysis

Several studies have suggested that differences in the natural rooting ability of plant cuttings could be attributed to differences in endogenous auxin levels. Hence, during rooting experiments, it is important to be able to routinely monitor the evolution of endogenous levels of plant hormones. This work reports the development of a new method for the quantification of free auxins in auxin-treated Olea europaea (L.) explants, using dispersive liquid–liquid microextraction (DLLME) and microwave assisted derivatization (MAD) followed by gas chromatography/mass spectrometry (GC/MS) analysis. Linear ranges of 0.5–500 ng mL 1 and 1–500 mg mL 1 were used for the quantification of indole-3-acetic acid (IAA) and indole-3-butyric acid (IBA), respectively. Determined by serial dilutions, the limits of detection (LOD) and quantification (LOQ) were 0.05 ng mL 1 and 0.25 ng mL 1, respectively for both compounds. When using the calibration curve for determination, the LOQ corresponded to 0.5 ng mL 1 (IAA) and 0.5 mg mL 1 (IBA). The proposed method proved to be substantially faster than other alternatives, and allowed free auxin quantification in real samples of semi-hardwood cuttings and microshoots of two olive cultivars. The concentrations found in the analyzed samples are in the range of 0.131–0.342 mg g 1 (IAA) and 20–264 mg g 1 (IBA).

A greener and highly sensitive flow-based procedure for carbaryl determination exploiting long pathlength spectrophotometry and photochemical waste degradation

An environmentally friendly analytical procedure with high sensitivity for determination of carbaryl pesticide in natural waters was developed. The flow system was designed with solenoid micro-pumps in order to improve mixing conditions and minimize reagent consumption as well as waste generation. A long pathlength (100 cm) flow cell based on a liquid core waveguide (LCW) was employed to increase the sensitivity in detection of the indophenol formed from the reaction between carbaryl and p-aminophenol (PAP). A clean-up step based on cloud-point extraction was explored to remove the interfering organic matter, avoiding the use of toxic organic solvents. A linear response was observed within the range 5-200 mu g L(-1) and the detection limit, coefficient of variation and sampling rate were estimated as 1.7 mu g L(-1) (99.7% confidence level), 0.7% (n=20) and 55 determinations per hour, respectively. The reagents consumption was 1.9 mu g of PAP and 5.7 mu g of potassium metaperiodate, with volume of 2.6 mL of effluent per determination. The proposed procedure was selective for the determination of carbaryl, without interference from other carbamate pesticides. Recoveries within 84% and 104% were estimated for carbaryl spiked to water samples and the results obtained were also in agreement with those found by a batch spectrophotometric procedure at the 95% confidence level. The waste of the analytical procedure was treated with potassium persulphate and ultraviolet irradiation, yielding a colorless residue and a decrease of 94% of total organic carbon. In addition, the residue after treatment was not toxic for Vibrio fischeri bacteria. (c) 2010 Elsevier B.V. All rights reserved.

Preliminary studies of laser-induced breakdown spectrometry for the determination of Ba, Cd, Cr and Pb in toys

The performance of laser-induced breakdown spectrometry (LIBS) for the determination of Ba, Cd, Cr and Pb in toys has been evaluated by using a Nd:YAG laser operating at 1064 nm and an Echelle spectrometer with intensified charge-coupled device detector. Samples were purchased in different cities of Sao Paulo State market and analyzed directly without sample preparation. Laser-induced breakdown spectrometry experimental conditions (number of pulses, delay time. integration time gate and pulse energy) were optimized by using a Doehlert design. Laser-induced breakdown spectrometry signals correlated reasonably well with inductively coupled plasma optical emission spectrometry (ICP OES) concentrations after microwave-assisted acid digestion of selected samples. Thermal analysis was used for polymer identification and scanning electron microscopy to Visualize differences in crater geometry of different polymers employed for toy fabrication. Results indicate that laser-induced breakdown spectrometry can be proposed as a rapid screening method for investigation of potentially toxic elements in toys. The unique application of laser-induced breakdown spectrometry for identification of contaminants in successive layers of ink and polymer is also demonstrated. (C) 2009 Elsevier B.V. All rights reserved.

Method development and optimization for the determination of selenium in bean and soil samples using hydride generation electrothermal atomic absorption spectrometry

The present investigation is the first part of an initiative to prepare a regional map of the natural abundance of selenium in various areas of Brazil, based on the analysis of bean and soil samples. Continuous-flow hydride generation electrothermal atomic absorption spectrometry (HG-ET AAS) with in situ trapping on an iridium-coated graphite tube has been chosen because of the high sensitivity and relative simplicity. The microwave-assisted acid digestion for bean and soil samples was tested for complete recovery of inorganic and organic selenium compounds (selenomethionine). The reduction of Se(VI) to Se(IV) was optimized in order to guarantee that there is no back-oxidation, which is of importance when digested samples are not analyzed immediately after the reduction step. The limits of detection and quantification of the method were 30 ng L(-1) Se and 101 ng L(-1) Se, respectively, corresponding to about 3 ng g(-1) and 10 ng g(-1), respectively, in the solid samples, considering a typical dilution factor of 100 for the digestion process. The results obtained for two certified food reference materials (CRM), soybean and rice, and for a soil and sediment CRM confirmed the validity of the investigated method. The selenium content found in a number of selected bean samples varied between 5.5 +/- 0.4 ng g(-1) and 1726 +/- 55 ng g(-1), and that in soil samples varied between 113 +/- 6.5 ng g(-1) and 1692 +/- 21 ng g(-1). (C) 2011 Elsevier B.V. All rights reserved.

Ultrasound Irradiation Promoted Large-Scale Preparation in Aqueous Media and Antioxidant Activity of Azoles

The scaled-up preparation of 1H-pyrazole, 1-phenylpyrazole and isoxazole via sonocatalysis is reported. The products were isolated in good yields in short time reaction. These compounds had been assayed for antioxidant activity by ORAC and DPPH methodologies. The results showed that only 1-phenylpyrazole presented good antioxidant activity compared with Trolox(R).