Simple, mild, and highly efficient synthesis of 2-substituted benzimidazoles and bis-benzimidazoles

A new convenient method for preparation of 2-substituted benzimidazoles and bis-benzimidazoles is presented. In this method, o-phenylenediamines were condensed with bisulfite adducts of various aldehydes and di-aldehydes under neat conditions by microwave heating. The results were also compared with results of synthesis by conventional heating under reflux. Structures of the products were confirmed by infrared, ¹H- and 13C-NMR spectroscopy. Short reaction times, good yields, easy purification of products, and mild reaction conditions are the main advantages of this method.

CARACTERIZAÇÃO E ATIVIDADE CATALÍTICA DE K2CO3/AL2O3 NA TRANSESTERIFICAÇÃO DO ÓLEO DE GIRASSOL COM AQUECIMENTO CONVENCIONAL E MICRO-ONDAS

Commercial and synthetic mesoporous aluminas impregnated with potassium carbonate were characterized by X-ray diffraction (XRD), nitrogen physisorption, infrared spectroscopy and 27Al MAS NMR. The activities in the transesterification reaction of sunflower oil with methanol for biodiesel production were evaluated. 27Al MAS NMR spectra evidenced the presence of AlIV and AlVI in the samples, and also of AlV sites in the mesoporous synthesized alumina, which disappeared after impregnation with potassium salt followed by calcination. All aluminas containing potassium were active for biodiesel production from sunflower seed oil, with high conversions by both conventional heating and microwave irradiation.

REAÇÃO DE CONDENSAÇÃO DO GLICEROL COM COMPOSTOS CARBONÍLICOS. SÍNTESE, CARACTERIZAÇÃO E APLICAÇÃO EM CRISTAIS LÍQUIDOS

Condensation reactions of glycerol with aldehydes and ketones were performed under thermal heating and microwave irradiation regimes. Homogeneous and heterogeneous catalysts were tested in both conditions. A silica sulfated (SiO2-SO3H) heterogeneous catalyst demonstrated the best performance relative to a selectivity of >95% in favor of 5-membered ketals. For acetals, preference in favor of 5-membered or 6-membered functional groups depends on the nature of the catalyst. Homogenous catalysts favor the more stable 6-membered acetals, whereas heterogeneous catalysts favor the less stable 5-membered acetals. However, the isomer ratios in the acetalization reaction are too low, and hence the reaction cannot be used in a synthetic plan for functional materials. Ketalization processes mediated by SiO2-SO3H show a high selectivity in favor of a 5-membered ring (1,3-dioxolane). The scope of condensation was tested with different ketones. A mechanism for heterogeneous catalysis related to the selectivity in the cyclization process is presented herein. Solketal, a commercial product, was also obtained by a condensation reaction of glycerol and propanone, and showed a high selectivity in favor of 1,3-dioxolane. It was transformed to potential allylic and chiral intermediates. A mesogenic core was connected to the organic framework of glycerol to produce a monomer liquid crystal material with a stable smectic-C mesophase.

Microwave Processes in Ferrite-ferroelectric Layered Structure

This work is devoted to investigation of wave processes in new hybrid ferrite/ferroelectric structures. Spin wave devices based on ferrite films have disadvanteges. And their applications are limited. Investigated structures allow to overcome disadvantages. This investigation helps to create new class of devices. Electromagnetic analysis of hybrid spin-electromagnetic waves in ferrite/ferroelectric structures were done. As a result dispersion relation was found. Numerical solution of this dispersion relation gave us follow results. These structures can be effectively tuned by external electric and magnetic field. Methods to increase tuning range were suggested. It was found that such structures have one basic disadvantage which is connected with presence of thick ferroelectric layer. To solve this problem is to use thin ferroelectric films. But this decreases tuning range. It was confirmed by experiment that this structures can be effectively tuned by electric and magnetic fields. Resonance characteristics of ferrite/ferroelectric resonator were succesfully tuned by magnetic and electric field.

Simultaneous determination of Cd and Pb in antibiotics used in sugar-cane fermentation process by GFAAS

A method has been developed for the simultaneous determination of Cd and Pb in antibiotics used in sugar-cane fermentation by GFAAS. The integrated platform of transversely heated graphite atomizer was treated with tungsten to form a coating of tungsten carbide. Six samples of commercial solid antibiotics were analyzed by injecting 20 µL of digested samples into the pretreated graphite platform with co-injection of 5 µL of 1000 mg L-1 Pd as chemical modifier. Samples were mineralized in a closed-vessel microwave-assisted acid-digestion system using nitric acid plus hydrogen peroxide. The pyrolysis and atomization temperatures of the heating program of the atomizer were selected as 600°C and 2200°C, respectively. The calculated characteristic mass for Cd and Pb was 1.6 pg and 42 pg, respectively. Limits of detection (LOD) based on integrated absorbance were 0.02 µg L-1 Cd and 0.7 µg L-1 Pb and the relative standard deviations (n = 10) for Cd and Pb were 5.7% and 8.0%, respectively. The recoveries of Cd and Pb added to the digested samples varied from 91% to 125% (Cd) and 80% to 112% (Pb).

Heating control of an electrical motor

Electrical motors on a ship attackable to different factors which decrease these lifetimes. One of the main external factors on a ship which usually is a reason of the motor failure is a moisture condensation which decreases the motor winding insulation and increase a probability of the short circuit. Therefore, the protection against moisture is necessary for ship electrical motors. The motor should be protected against moisture all time when it does not operate. The necessity of such protection requires a lot of energy consumption. This master’s thesis is focused on the creation of the electrical motor thermal model and on the different methods of the motor protection against moisture analysis with energy consumption point of view.

Network Structures and Modularity among Biofuel Heating System Manufacturers

The aim of this thesis was to study network structures and modularity among biofuel heating system manufacturers in the Finnish bioenergy sector by utilizing the perspectives of numerous Finnish bioenergy specialists. The study is qualitative due to the fact that the research material was gathered with semi-structured theme interviews during May and June 2010. The research methodology used in the thesis combines conceptual and action-oriented approach. Networks, value nets, and modularity were studied from different perspectives. Three network and platform strategies were discovered and a general network structure was formed. Moreover, benefits and disadvantages of networks and modularity among biofuel heating system manufacturers were illustrated. The analysis provides a comprehensive perception of the industry. The results of the research were constructed by implementing existing theories into practice. Also future recommendations for the biofuel heating system manufacturers were given. The results can be considered to be beneficial because the number of previous studies about the subject is relatively small. The reliability of the study is eminent because the number of the interviews was inclusive.

Utilization of Automatic Meter Reading in the Improvement of a District Heating System

A district heating system comprises production facilities, a distribution network, and heat consumers. The utilization of new energy metering and reading system (AMR) is increasing constantly in district heating systems. This heuristic study shows how the AMR system can be exploited in finding optimization opportunities in district heating system. In this study, the district heating system is mainly considered from the viewpoint of operational optimization. The focus is on the core processes, heat production and distribution. Three objectives were set to this study. The first one was to examine general optimization opportunities in district heating systems. Second, to figure out the benefits of AMR for general optimization opportunities. Finally, to define a methodology for process improvement endeavors. This study shows, through a case study, the usefulness of AMR in specifying current deficiencies in a district heating system. Based on a literature review, the methodology for the improvement of business processes is presented. Additionally, some issues related to future competitiveness of district heating are concerned. As a conclusion, some optimization objectives are considered more desirable than others. Study shows that AMR is useful in the specification of optimization targets in the district heating system. Further steps in optimization process were not examined in detail. That would seem to be interesting topic for further studies.

Modeling and simulation of forced-air cooling of strawberries using variable convective coefficient

In the forced-air cooling process of fruits occurs, besides the convective heat transfer, the mass transfer by evaporation. The energy need in the evaporation is taken from fruit that has its temperature lowered. In this study it has been proposed the use of empirical correlations for calculating the convective heat transfer coefficient as a function of surface temperature of the strawberry during the cooling process. The aim of this variation of the convective coefficient is to compensate the effect of evaporation in the heat transfer process. Linear and exponential correlations are tested, both with two adjustable parameters. The simulations are performed using experimental conditions reported in the literature for the cooling of strawberries. The results confirm the suitability of the proposed methodology.

Effective diffusivity and convective mass transfer coefficient during the drying of bananas

In this article, a methodology is used for the simultaneous determination of the effective diffusivity and the convective mass transfer coefficient in porous solids, which can be considered as an infinite cylinder during drying. Two models are used for optimization and drying simulation: model 1 (constant volume and diffusivity, with equilibrium boundary condition), and model 2 (constant volume and diffusivity with convective boundary condition). Optimization algorithms based on the inverse method were coupled to the analytical solutions, and these solutions can be adjusted to experimental data of the drying kinetics. An application of optimization methodology was made to describe the drying kinetics of whole bananas, using experimental data available in the literature. The statistical indicators enable to affirm that the solution of diffusion equation with convective boundary condition generates results superior than those with the equilibrium boundary condition.

Spatial variability of air dry bulb temperature and black globe humidity index in a broiler house during the heating phase

The air dry-bulb temperature (t db),as well as the black globe humidity index (BGHI), exert great influence on the development of broiler chickens during their heating phase. Therefore, the aim of this study was to analyze the structure and the magnitude of the t db and BGHI spatial variability, using geostatistics tools such as semivariogram analysis and also producing kriging maps. The experiment was conducted in the west mesoregion of the states of Minas Gerais in 2010, in a commercial broiler house with heating system consisting of two furnaces that heat the air indirectly, in the firsts 14 days of the birds' life. The data were registered at intervals of five minutes in the period from 8 a.m. to 10 a.m. The variables were evaluated by variograms fitted by residual maximum likelihood (REML) testing the Spherical and Exponential models. Kriging maps were generated based on the best model used to fit the variogram. It was possible to characterize the variability of the t db and BGHI, which allowed observing the spatial dependence by using geostatistics techniques. In addition, the use of geostatistics and distribution maps made possible to identify problems in the heating system in regions inside the broiler house that may harm the development of chicks.

Evaluation of the heating of broilers in shed by means of gas hoods and underfloor heating

This study was conducted to evaluate and compare the behavior of the heating inside poultry shed through gas hood and underfloor heating. The experiment was conducted in poultry shed belonging to the Federal Institute of Education, Science and Technology of Triângulo Mineiro Region, Uberlândia city – state of Minas Gerais (MG), Brazil. The dimensions of the shed are 24 meters long and 9.6 meters wide and with a ceiling height of 3.2 meters. The temperature was measured with an optical thermometer of Minipa brand, MT 350 model. It was used, to the analysis of temperature behavior, the public domain software FEMM 4.2, which uses finite elements techniques, with data collected from two lots. Underfloor heating is made using hot water flowing through a serpentine type system, which is installed below the bed; this hot water is from solar heaters. An energetic and economic assessment of the warming shed for raising chickens was realized. From the results obtained with the simulations, it may observe that the heating through the floor provides a more homogeneous distribution of temperature when compared with the hood heating. The flow of heat is upwards supplying, thus, the greatest need of heating of the bird, which is the pectoral part.

Solar energy use for water pre-heating in boilers of agro-industries

Energy consumption in the world has been growing every year. The industrial sector represents 27.32% of the world energy demand. Heating systems that use solar energy may contribute with a percentage of the total energy required by industries. This work aimed to study the use of vacuum solar collectors for water pre-heating in boilers. We used four collectors installed according to NBR 15,569; water flow through the tubes was 0.058 L/s, and temperature in the inlet and outlet pipes was measured. Results showed that instantaneous radiation, and inlet fluid and room temperatures are variables that influence the process, reaching water maximum temperature in the solar collector outlet of 97.9 °C, and efficiency of approximately 65% for most experiments. For the financial viability evaluation, the payback study was applied, which resulted in 4; 7 and 5 years, for the respective sources: firewood, LPG (liquefied petroleum gas), and electricity. Regarding the calculation of the annual contribution to the reduction of greenhouse gases, it was, respectively, 2.162 and 356 kg of CO2 per m² of collector tubes, in comparison with firewood and LPG.

Microwave-assisted solvent extraction and analysis of shikimic acid from plant tissues

A better method for determination of shikimate in plant tissues is needed to monitor exposure of plants to the herbicide glyphosate [N-(phosphonomethyl)glycine] and to screen the plant kingdom for high levels of this valuable phytochemical precursor to the pharmaceutical oseltamivir. A simple, rapid, and efficient method using microwave-assisted extraction (MWAE) with water as the extraction solvent was developed for the determination of shikimic acid in plant tissues. High performance liquid chromatography was used for the separation of shikimic acid, and chromatographic data were acquired using photodiode array detection. This MWAE technique was successful in recovering shikimic acid from a series of fortified plant tissues at more than 90% efficiency with an interference-free chromatogram. This allowed the use of lower amounts of reagents and organic solvents, reducing the use of toxic and/or hazardous chemicals, as compared to currently used methodologies. The method was used to determine the level of endogenous shikimic acid in several species of Brachiaria and sugarcane (Saccharum officinarum) and on B. decumbens and soybean (Glycine max) after treatment with glyphosate. The method was sensitive, rapid and reliable in all cases.

Ionic liquid mediated biomass deconstruction: from analysis challenges to fermentable sugars

Ionic liquids, ILs, have recently been studied with accelerating interest to be used for a deconstruction/fractionation, dissolution or pretreatment processing method of lignocellulosic biomass. ILs are usually utilized combined with heat. Regarding lignocellulosic recalcitrance toward fractionation and IL utilization, most of the studies concern IL utilization in the biomass fermentation process prior to the enzymatic hydrolysis step. It has been demonstrated that IL-pretreatment gives more efficient hydrolysis of the biomass polysaccharides than enzymatic hydrolysis alone. Both cellulose (especially cellulose) and lignin are very resistant towards fractionation and even dissolution methods. As an example, it can be mentioned that softwood, hardwood and grass-type plant species have different types of lignin structures leading to the fact that softwood lignin (guaiacyl lignin dominates) is the most difficult to solubilize or chemically disrupt. In addition to the known conventional biomass processing methods, several ILs have also been found to efficiently dissolve either cellulose and/or wood samples – different ILs are suitable for different purposes. An IL treatment of wood usually results in non-fibrous pulp, where lignin is not efficiently separated and wood components are selectively precipitated, as cellulose is not soluble or degradable in ionic liquids under mild conditions. Nevertheless, new ILs capable of rather good fractionation performance have recently emerged. The capability of the IL to dissolve or deconstruct wood or cellulose depends on several factors, (e.g. sample origin, the particle size of the biomass, mechanical treatments as pulverization, initial biomassto-IL ratio, water content of the biomass, possible impurities of IL, reaction conditions, temperature etc). The aim of this study was to obtain (fermentable) saccharides and other valuable chemicals from wood by a combined heat and IL-treatment. Thermal treatments alone contribute to the degradation of polysaccharides (e.g. 150 °C alone is said to cause the degradation of polysaccharides), thus temperatures below that should be used, if the research interest lies on the IL effectiveness. On the other hand, the efficiency of the IL-treatment can also be enhanced to combine other treatment methods, (e.g. microwave heating). The samples of spruce, pine and birch sawdust were treated with either 1-Ethyl-3-methylimidazolium chloride, Emim Cl, or 1-Ethyl-3-methylimidazolium acetate, Emim Ac, (or with ionized water for comparison) at various temperatures (where focus was between 80 and 120 °C). The samples were withdrawn at fixed time intervals (the main interest treatment time area lied between 0 and 100 hours). Double experiments were executed. The selected mono- and disaccharides, as well as their known degradation products, 5-hydroxymethylfurfural, 5-HMF, and furfural were analyzed with capillary electrophoresis, CE, and high-performance liquid chromatography, HPLC. Initially, even GC and GC-MS were utilized. Galactose, glucose, mannose and xylose were the main monosaccharides that were present in the wood samples exposed to ILs at elevated temperatures; in addition, furfural and 5-HMF were detected; moreover, the quantitative amount of the two latter ones were naturally increasing in line with the heating time or the IL:wood ratio.