Química combinatória de materiais com análise por microdifração de raios X. Primeira parte: fundamentos

Combinatorial chemistry refers to techniques to rapidly fabricate tens, hundreds or even thousands of different micro samples. The analysis of the large number of samples generated by combinatorial methods requires highly efficient analytical methods. In this case, the challenges are due not only to the large number of samples to be analyzed, but also to the small amount of sample available for analysis. This paper describes the fundamentals of combinatorial chemical methods applied to discover of materials and the development in x-ray diffraction to analyze micro samples.

Elucidando os estados de oxidação do nitrogênio através da espectroscopia de absorção de raios-X na borda K do nitrogênio

The potentialities of X-ray Absorption Near Edge Spectroscopy (XANES) of the N K edge (N K) obtained with the spherical grating monochromator beam line at the Brazilian National Synchrotron Light Laboratory are explored in the investigation of poly(aniline), nanocomposites and dyes. Through the analysis of N K XANES spectra of conducting polymers and many other dye compounds that are dominated by 1s®p* transitions, it was possible to correlate the band energy value with the nitrogen oxidation states. An extensive N K XANES spectral database was obtained, thus permitting the elucidation of the nature of different nitrogens present in the intercalated conducting polymers.

Análise arqueométrica de cerâmica Tupiguarani da região central do Estado do Rio Grande do Sul, Brasil, usando fluorescência de raios X por dispersão de energia (EDXRF)

Energy dispersive X-ray fluorescence methodology (EDXRF) was used to determine Al, Ba, Ca, Cr, Fe, K, Mn, Pb, Rb, S, Si, Sr, Ti, V, Zn in pottery sherds from seven archaeological sites in the central region of Rio Grande do Sul State, Brazil. The potteries' chemical fingerprints from Ijuí River, Ibicuí Mirim River, Vacacaí Mirim River and Jacuí River were identified. Interactions between sites from the Jacuí River, Vacacaí Mirim River and Ibicui Mirim River could have occurred because some samples from these sites are overlapping in a principal component analysis (PCA) graphic. The pottery provenance could be the same.

Raios-x: fascinação, medo e ciência

This work presents the discovery and the use of x-rays at the end of the XIXth and the beginning of the XXth century. X-rays greatly impacted science and everyday life. Their existence broke the idea that knowledge had reached a limiting step. In general, people regarded x-rays as a marvel of science, but reactions against their use were also found. Several applications were proposed, especially in medicine. However, little or no attention was paid to security measures, leading to health damages and even death. The development of the radiological protection took into account the accidents with the x-rays.

Emprego da fluorescência de raios X por dispersão de energia para o mapeamento de troncos de árvores em Campinas, São Paulo

Dendrochemistry is based on the determination of elements retained in tree rings, which can be useful to characterize environmental occurrences. This work shows elemental mappings obtained by EDXRF of the cross section of a tree stem. The tree is originated from a polluted area in Campinas, São Paulo. Some profiles, as the sulfur one, show variations that can be attributed to external contributions, whereas the silicon one can be inferred to a protection defense natural mechanism. Besides being simultaneous and multielementar, the main advantages here are its performance through a non-destructive sample treatment and the ease of operation of XRF equipments.

Caracterização dos níveis de elementos químicos em solo, submetido a diferentes sistemas de uso e manejo, utilizando espectrometria de fluorescência de raios-x por energia dispersiva (EDXRF)

This study aimed to evaluate the chemical elements levels in soil, submitted to different management systems and use by the Energy Dispersive X-Ray Fluorescence Spectrometry - EDXRF. The systems were T1 - agro forestry (SAF), T2 - Native Field (CN), T3 - Native Forest (NM), T4 - Tillage Forest (PF); T5 - conventional tillage system (SPC) and T6 - System tillage (NT). Samples were collected at 0-10 and 10-20 cm, dried and ground for analysis in EDX-720. The soil showed no difference in the average concentrations of chemical elements analyzed in the profiles, but the systems presented different concentrations of metal elements, and T3 had the highest K, Ca and Zn at 0-10 cm and higher contents of K, Ca, Cu, Zn and Mn in the layer of 10-20 cm.

Sistema para realização de medidas de luminescência com excitação por Raios X

In this work is presented a versatile system for X-ray excited optical luminescence (XEOL) measurements. The apparatus was assembled from a sample holder connected to an optical fiber responsibly for the acquisition of the scintillation signal. The spectrum is registered with a CCD coupled in a spectrograph provided with diffraction gratings. The system performance was analyzed by exciting GdAlO3:Eu3+ 3.0 at.% with X-rays from a diffractometer and measuring the emission spectra. The system can be used to obtain precise and reliable spectroscopic properties of samples with various conformations without the loss of the required safety when dealing with ionizing radiations.

Quantificação de antimônio em garrafas de politereftalato de etileno (PET) brasileiras por fluorescência de raios-X e avaliação quimiométrica para verificar a presença de pet reciclado através do teor de ferro

Antimony is a common catalyst in the synthesis of polyethylene terephthalate used for food-grade bottles manufacturing. However, antimony residues in final products are transferred to juices, soft drinks or water. The literature reports mentions of toxicity associated to antimony. In this work, a green, fast and direct method to quantify antimony, sulfur, iron and copper, in PET bottles by X-ray fluorescence spectrometry is presented. 2.4 to 11 mg Sb kg-1 were found in 20 samples analyzed. The coupling of the multielemental technique to chemometric treatment provided also the possibility to classify PET samples between bottle-grade PET/recycled PET blends by Fe content.

Determinação de Mn e Zn em arroz empregando espectrometria de fluorescência de raios x de energia dispersiva

A simple, fast and inexpensive method was developed to determine essential elements in pellets of rice samples using energy dispersive X-ray fluorescence spectrometry (EDXRF). The accuracy and precision were evaluated using Standard Reference Material (rice flour NIST 1568a), and yielding relative standard deviation below 5%. The paired t-test showed good agreement within 95% confidence values. The detection limits (3σ) of Mn and Zn were 5.1 and 2.2 mg kg-1, respectively. The proposed method proved to be effective when used to determine Mn and Zn in commercial samples of rice without go by stage of decomposition.

Análise exploratória rápida e não destrutiva (screening) da presença de elementos químicos tóxicos em material escolar por fluorescência de raios x

Compulsory in Brazil, toy certification aims to prevent possible risks in toy use. The Brazilian National Institute of Metrology (INMETRO) establishes the maximum concentration of toxic elements (TE) that may be present in toys. This study evaluates the presence of TE in different crayons, gouache and modeling clays using X-ray fluorescence. This technique is fast, has low operating cost and minimum sample pretreatment, resulting in a clean procedure without reagent consumption and waste generation. Bromine (in gouache) and Barium (in crayons) were the only potentially TE identified in the samples studied.

Acoplamento de cloreto de 4-nitrofenildiazônio com nucleófilos alifáticos: experimento integrado de síntese orgânica e cristalografia de raios X

This article describes an undergraduate experiment for the synthesis of p-nitrophenyldiazonium chloride and its coupling with acetylacetone and two enaminones, 4-phenylamino-pent-3-en-2-one and 4-amino-pent-3-en-2-one, in an adaptation of a previously reported synthetic protocol. The azo dyes 4-(E)-phenylamino-3-[(E)-2-(4-nitrophenylazo)]-3-penten-2-one and 4-(E)-amino-3-[(E)-2-(4-nitrophenylazo)]-3-penten-2-one were obtained, and the solid state structure of this latter azo compound was characterized by single crystal X-ray diffraction studies. This two-week integrated laboratory approach involves simple synthetic experiments and microwave chemistry in the organic laboratory plus crystallography analysis, suitable for novice students on undergraduate experimental chemistry courses.

Aplicação da espectroscopia no infravermelho e difração de raio-X na determinação de sacarina em adoçantes líquidos artificiais pelo método volumétrico com Ag+

O uso de adoçantes líquidos com sacarina sódica é uma questão de saúde pública pela relação com obesidade e fonte de sódio. Os níveis de sacarina foram avaliados em quatro marcas de diferentes fabricantes em amostras adquiridas no comércio de Vitória/ES, entre os anos de 2006 e 2008. Foram encontrados níveis com valores entre 260 e 505 vezes acima da Resolução-RDC N0 8, 25/03/2008 (ANVISA), que é de 0,015 g/100 mL para sacarina e seus sais derivados. O perfil das amostras cristalizadas dos adoçantes foram avaliados por espectroscopia na região do infravermelho e por difração de raio-X de pó. A seletividade do método clássico de precipitação com AgNO3 também foi verificada por essas técnicas aplicadas nos precipitados de sacarinato de prata.

DENSITOMETRIA DE RAIOS X NA MADEIRA E CARVÃO DE CLONE DEEucalyptus grandis W. Hill ex Maiden X Eucalyptus urophylla S. T. Blake1

RESUMO O objetivo deste trabalho foi determinar a densidade relativa aparente por meio da técnica de raios X da madeira e do carvão de um clone de Eucalyptus grandis x Eucalyptus urophylla com 6 anos. A amostragem consistiu na retirada de baguetas de 2 cm de diâmetro no DAP, com trado motorizado, em 50 árvores distribuídas em três classes de diâmetro. Após a determinação da densidade relativa aparente das baguetas, pela técnica de densitometria por raios X, as amostras foram carbonizadas em um forno elétrico (mufla) e suas densidades, determinadas pela mesma técnica. Os valores mais altos de densidade aparente da madeira utilizando a técnica de raios X foram encontrados nas classes diamétricas de 14,1 e 11,4 cm. Os valores de densidade relativa aparente nas amostras de carvão tenderam a aumentar no sentido medula-casca em todas as classes diamétricas.

Utilização do teste de raios-X na avaliação da qualidade de sementes de canafístula (Peltophorum dubium (Sprengel) Taubert

Sementes de leguminosas florestais, como canafístula, muitas vezes são alvos de injúrias durante sua extração e processamento, além de apresentarem problemas de má-formação do embrião. Estes danos não são comumente detectados, devido à presença de tegumento espesso e duro que impede a visualização das estruturas internas das sementes. O objetivo deste trabalho foi definir a metodologia e verificar a possibilidade de utilização do teste de raios-X, na avaliação dos danos internos em sementes de canafístula, bem como, verificar o efeito desses danos na germinação das sementes. Sementes de três lotes de canafístula foram expostas a radiação em aparelho de raios-X Faxitron HP modelo 43855A por vários tempos e intensidades. Posteriormente, foram divididas em três categorias, de acordo com a anatomia interna visualizada nas radiografias, em sementes cheias, sementes com pequenos danos e sementes com danos severos. Após tratamento para a quebra da dormência, as sementes das diferentes categorias foram submetidas ao teste de germinação. A morfologia interna de sementes de canafístula pode ser visualizadas, com exposição a raios-X por 60 segundos na intensidade de 25 KVp. Os danos na morfologia interna visualizados em radiografias, classificados como severos (mais de 50% da área do embrião danificada) afetam drasticamente a germinação das sementes, justificando sua remoção para promover a melhoria da qualidade física e fisiológica de lotes de sementes de canafístula.