Espectroscopia de Ressonância Magnética Nuclear de 13C no estudo de rotas biossintéticas de produtos naturais

During the last five decades, as a result of an interaction between natural product chemistry, synthetic organic chemistry, molecular biology and spectroscopy, scientists reached an extraordinary level of comprehension about the natural processes by which living organisms build up complex molecules. In this context, 13C nuclear magnetic resonance spectroscopy, allied with isotopic labeling, played a determinant role. Nowadays, the widespread use of modern NMR techniques allows an even more detailed picture of the biochemical steps by accurate manipulation of the atomic nuclei. This article focuses on the development of such techniques and their impact on biosynthetic studies.

Teores de corantes artificiais em alimentos determinados por cromatografia líquida de alta eficiência

Synthetic dyes are much used in processed foods. HPLC was applied to different types of snacks, such as colored cereals, chocolate confetti, chewing gums and candies for the determination of those additives. In the case of artificially colored breakfast cereals, 71% of the samples exceeded the allowed limits. Regarding the portions recommended for consumption by the makers of two of the samples, the amounts exceeded those allowed by the Brazilian legislation. In the case of chocolate confetti and candies none of the samples showed higher amounts than those allowed. However 37% of the chewing gum samples presented larger contents than the authorized ones, and one sample contained five times more synthetic dyes than allowed.

Determinação de açúcar total em café cru por espectroscopia no infravermelho próximo e regressão por mínimos quadrados parciais

In this work a fast method for the determination of the total sugar levels in samples of raw coffee was developed using the near infrared spectroscopy technique and multivariate regression. The sugar levels were initially obtained using gravimety as the reference method. Later on, the regression models were built from the near infrared spectra of the coffee samples. The original spectra were pre-treated according to the Kubelka-Munk transformation and multiplicative signal correction. The proposed analytical method made possible the direct determination of the total sugar levels in the samples with an error lower by 8% with respect to the conventional methodology.

Construção de um calorímetro isotérmico diferencial de alta sensibilidade e baixo custo

The high cost of sensitivity commercial calorimeters may represent an obstacle for many calorimetric research groups. This work describes the construction and calibration of a batch differential heat conduction calorimeter with sample cells volumes of about 400 μL. The calorimeter was built using two small high sensibility square Peltier thermoelectric sensors and the total cost was estimated to be about US$ 500. The calorimeter was used to study the excess enthalpy of solution of binary mixtures of liquids, as a function of composition, for the following binary systems of solvents: water + 1,4-dioxane or + dimethylsulfoxide at 298,2 ± 0,5 K.

Estudo por espectroscopia micro-Raman dos mecanismos de separação de fase em vidros fosfatos de metais de transição

Glass-ceramics are prepared by controlled separation of crystal phases in glasses, leading to uniform and dense grain structures. On the other hand, chemical leaching of soluble crystal phases yields porous glass-ceramics with important applications. Here, glass/ceramic interfaces of niobo-, vanado- and titano-phosphate glasses were studied by micro-Raman spectroscopy, whose spatial resolution revealed the multiphase structures. Phase-separation mechanisms were also determined by this technique, revealing that interface composition remained unchanged as the crystallization front advanced for niobo- and vanadophosphate glasses (interface-controlled crystallization). For titanophosphate glasses, phase composition changed continuously with time up to the equilibrium composition, indicating a spinodal-type phase separation.

Validação e estimativa da incerteza de método para análise de licopeno e β-caroteno em polpa de tomate por cromatografia líquida de alta eficiência

A method to quantify lycopene and β-carotene in freeze dried tomato pulp by high performance liquid chromatography (HLPC) was validated according to the criteria of selectivity, sensitivity, precision and accuracy, and uncertainty estimation of measurement was determined with data obtained in the validation. The validated method presented is selective in terms of analysis, and it had a good precision and accuracy. Detection limit for lycopene and β-carotene was 4.2 and 0.23 mg 100 g-1, respectively. The estimation of expanded uncertainty (K = 2) for lycopene was 104 ± 21 mg 100 g-1 and for β-carotene was 6.4 ± 1.5 mg 100 g-1.

Aplicações de cromatografia líquida de alta eficiência para o estudo de poluentes orgânicos emergentes

Emerging organic pollutants (EOP) include many environmental contaminants based on commercial products such as pharmaceuticals, personal care products, detergents, gasoline, polymers, etc. EOP may be candidates for future regulation as they offer potential risk to environmental and human health due to their continual entrance into the environment and to the fact that even the most modern wastewater treatment plants are not able to totally transform / remove these compounds. High performance liquid chromatography is recommended to separate emerging organic pollutants with characteristics of high polarity and low volatility, especially pharmaceuticals, from environmental matrices.

Experimento didático de quimiometria para análise exploratória de óleos vegetais comestíveis por espectroscopia no infravermelho médio e análise de componentes principais: um tutorial, parte I

This manuscript aims to show the basic concepts and practical application of Principal Component Analysis (PCA) as a tutorial, using Matlab or Octave computing environment for beginners, undergraduate and graduate students. As a practical example it is shown the exploratory analysis of edible vegetable oils by mid infrared spectroscopy.

Desenvolvimento de um algoritmo para identificação e correção de spikes em espectroscopia Raman de imagem

Raman imaging spectroscopy is a highly useful analytical tool that provides spatial and spectral information on a sample. However, CCD detectors used in dispersive instruments present the drawback of being sensitive to cosmic rays, giving rise to spikes in Raman spectra. Spikes influence variance structures and must be removed prior to the use of multivariate techniques. A new algorithm for correction of spikes in Raman imaging was developed using an approach based on comparison of nearest neighbor pixels. The algorithm showed characteristics including simplicity, rapidity, selectivity and high quality in spike removal from hyperspectral images.

Resolução do ibuprofeno: um projeto para disciplina de química orgânica experimental

A practical and didactic sequence of experiments was proposed to illustrate the stereochemistry concept, optically active compounds, resolution of racemates, and use of the NMR technique, including 2D-COSY for identification of organic compounds, on a laboratory course for undergraduate students. The sequence was: extractions of racemic ibuprofen and chiral naproxen from commercial tablets; syntheses of diastereoisomeric amides reacting chiral (S)-(-)-α-methylbenzylamine with (±)-ibuprofen; separation and determination of absolute configuration of amides by ¹H NMR spectroscopy and GC analysis, and hydrolysis of amides to obtain (+)- and (-)-ibuprofen.

Avaliação de perdas invisíveis na colheita mecanizada em dois fluxos de massa de cana-de-açúcar

In this work the performance of a sugar cane chopped harvester was analysed when fed with two sugar cane mass flows, measuring the invisible losses, which are impossible to measure in the field, harvester sugar cane cleaning efficiency and air velocity on extractors exit. The trial was done under controlled conditions at Copersucar Technology Center in January 2000. The results showed that the flow of sugar cane through the harvester doesn't influence the magnitudes of total invisible losses and raw material cleaning efficiency. The mean air velocity on the primary extractors exit was 12.0 m s-1, and 9.2 m s-1 on the secondary extractor, with a coefficient of variation of 21%, indicating that the poor cleaning performance of the harvester could be related to air velocity difference inside the extractor. Analyzing the data collected in the trials, it was possible to conclude that invisible losses in sugar cane harvester were 10% and the cleaning efficiency was 87%.

Transferência de massa e secagem em leitos vibrofluidizados: uma revisão

Development of processing technology and equipments requires new methods and better quality of the processed product. In the continuous drying process, utilization of equipments that promotes an increment in the transfer coefficients becomes of the major interest. The use of vibrational energy has been recommended to the dispersed materials. Such method is based on the use of vibrational energy applied to disperse media. Thus, a literature review on the mass transfer and drying in vibro-fluidized beds was carried out, showing experimental results and mathematical modeling.

Avaliação de linhas de beneficiamento e impactos de queda na qualidade de caqui Rama Forte

Excessive and inadequate handling of fruits and vegetables provides high incidences of physical damage, consequently, post harvest losses. The main goal of this work was to evaluate the impact magnitude in persimmon packing lines, Rama Forte, and to determine, at the laboratory, its impact limits. For evaluating the critical points it was used an instrumented sphere of 76 mm of diameter (Technmark, Inc, Lansing, USA), which registered the impact magnitude in seven distinctive impact lines located in four packing houses. For determining physical damages, tests were carried out at the laboratory, where fruit drop was related to impact magnitude, physical damage incidence and fruit post harvest losses. At the packing lines, the values found varied from 21 to 87 G on the transfer points and the majority of registered impacts (over 94%) were down 50G. Drops from 20 cm caused an increase in weight losses after six days of storage at room temperature. Drops from 20 and 30 cm caused skin darkness (low L values), associated to a decrease in color intensity (chroma). Impact drop did not affect pulp fruit chemical features.

Fundações de construções submetidas a esforços de tração em solo de alta porosidade da região de Campinas - SP

This paper presents the behavior of three bored piles conducted in diabasic soil submitted to uplift forces. The piles were built at the site for Experimental Studies in Soil Mechanics and Foundations of UNICAMP, located in the city of Campinas, Brazil. Field tests have already been conducted at the site (SPT, CPT, DMT and PMT), as well as laboratory tests by using sample soils taken from a well up to 17 m deep. The water table is not checked until a depth of 17 m. In order to check the behavior of the piles when submitted to uplift forces, slow static load tests were carried out as the recommendations of NBR 12131. The carrying capacity of these piles was also provided by means of theoretical methods, appropriate for uplift forces, and through semi-empirical methods appropriate for compression forces, considering only the portion of lateral resistance. The values estimated by using the considered methods were compared to those obtained by means of load tests. One of the tested piles was extracted from the soil to be the subject of a study on its geometry.

COMPARAÇÃO DAS PROPRIEDADES REOLÓGICAS DA MASSA DE CACAU TORRADA CONVENCIONALMENTE E POR MICROONDAS

Two kinds of roasting cocoa system: conventional batch method in electrical oven, and by microwaves, in a continuous microwave rotary applicator (2450MHz), were compared with respect to viscosity. Cocoa was roasted in whole beans and in nibs. The variable used in the microwave treatment was the power density applied to the whole beans (254,45 to 290,80 Wh/kg) and to the nibs (227,27 to 262,23 Wh/kg), with a constant holding time of 10 minutes. The variable used in the conventional roasting process was the roasting time of the beans (40 to 44 min) and the nibs (34 to 38 min), with constant temperature in the jacket of electric oven (150°C). Viscosity was measured in a Brookfield rheometer (mod RV-DVIII) at 40°C. In general, the plastic viscosity of the microwaved samples was lower than that of the conventional roasted samples. Also the nibs showed lower viscosities than the whole beans when roasted in the electric oven. The viscosity of the samples roasted in the microwave oven was lower in the whole beans than in the nibs. The product was sensorially evaluated by three experts in cocoa flavour, and it was shown that the flavour of the microwave roasted products was similar to that of the conventionally roasted products, with the advantage of a reduction in process time.