O papel dos programas interlaboratoriais para a qualidade dos resultados analíticos

Interlaboratorial programs are conducted for a number of purposes: to identify problems related to the calibration of instruments, to assess the degree of equivalence of analytical results among several laboratories, to attribute quantity values and its uncertainties in the development of a certified reference material and to verify the performance of laboratories as in proficiency testing, a key quality assurance technique, which is sometimes used in conjunction with accreditation. Several statistics tools are employed to assess the analytical results of laboratories participating in an intercomparison program. Among them are the z-score technique, the elypse of confidence and the Grubbs and Cochran test. This work presents the experience in coordinating an intercomparison exercise in order to determine Ca, Al, Fe, Ti and Mn, as impurities in samples of silicon metal of chemical grade prepared as a candidate for reference material.

Diagramas de Ellingham e de Van't Hoff: algumas considerações

The main subject of this article is to show the parallelism betwen the Ellingham and Van't Hoff diagrams. The first one is a graphic representation of the changes in the standard Gibbs free energy (deltarGtheta) as a function of T and was introduced by Ellingham in 1944, in order to study metallurgic processes involving oxides and sulphides. On the other hand, the Van't Hoff diagram is a representation of the function ln K versus (1/T). The equivalence between both diagrams is easily demonstrated, making simple mathematical manipulations. In order to show the parallelism between both diagrams, they are presented briefly and two examples are discussed. The comparison of the both diagrams surely will be helpful to students and teachers in their learning and teaching activities, and will certainly enrich important aspects of chemical thermodynamics.

Titulações espectrofotométricas de sistemas ácido-base utilizando extrato de flores contendo antocianinas

Considering the attraction of the students' attention by the changes in the colors of vegetable crude extracts caused by the variation of the pH of the medium, the use of these different colors in order to demonstrate principles of spectrophotometric acid-base titrations using the crude extracts as indicators is proposed. The experimental setup consisted of a simple spectrophotometer, a homemade flow cell and a pump to propel the fluids along the system. Students should be stimulated to choose the best wavelength to monitor the changes in color during the titration. Since the pH of the equivalence point depends on the system titrated, the wavelength must be properly chosen to follow these changes, demonstrating the importance of the correct choice of the indicator. When compared with the potentiometric results, errors as low as 2% could be found using Rhododendron simsii (azalea) or Tibouchina granulosa (Glory tree, quaresmeira) as sources of the crude extracts.

Aromaticidade: evolução histórica do conceito e critérios quantitativos

In this paper the evolution of the concept of aromaticity is discussed. It considers not only historical aspects of the aromaticity concept but also the different criteria (theoretical and experimental) that have appeared to explain the properties of the aromatic compounds. The topics range from the isolation of benzene by Faraday (1825) until the modern criteria based on geometries, magnetic properties, resonance energy (RE), aromatic stabilization energy (ASE), topological analyses, and others. A chronological separation of issues concerning aromaticity was made, splitting the definitions before and after the appearance of the quantum chemistry. This work reviews the concept of aromaticity.

Estudos de QSAR 2D baseados em descritores topológicos e fragmentos moleculares para uma série de derivados azólicos ativos contra Candida albicans

Azole derivatives are the main therapeutical resource against Candida albicans infection in immunocompromised patients. Nevertheless, the widespread use of azoles has led to reduced effectiveness and selection of resistant strains. In order to guide the development of novel antifungal drugs, 2D-QSAR models based on topological descriptors or molecular fragments were developed for a dataset of 74 molecules. The optimal fragment-based model (r² = 0.88, q² = 0.73 and r²pred = 0.62 with 6PCs) and descriptor-based model (r² = 0.82, q² = 0.79 and r²pred = 0.70 with 2 PCs), when analysed synergically, suggested that the triazolone ring and lipophilic properties are both important to antifungal activity.

Development and validation of a dissolution test for primaquine/polyethylene oxide matrix tablets

A simple, precise, specific, repeatable and discriminating dissolution test for primaquine (PQ) matrix tablets was developed and validated according to ICH and FDA guidelines. Two UV assaying methods were validated for determination of PQ released in 0.1 M hydrochloric acid and water media. Both methods were linear (R²>0.999), precise (R.S.D.<1.87%) and accurate (97.65-99.97%). Dissolution efficiency (69-88%) and equivalence of formulations (f2) was assessed in different media and apparatuses (basket/100 rpm and paddle/50 rpm) tested. Discriminating condition was 900 mL aqueous medium, basket at 100 rpm and sampling times at 1, 4 and 8 h. Repeatability (R.S.D.<2.71%) and intermediate precision (R.S.D.<2.06%) of dissolution method were satisfactory.

Desenvolvimento e validação de um método analítico por espectrofotometria UV para quantificação de carvedilol

This paper reports the development and validation of a new analytical method using UV spectrophotometry to quantify carvedilol (CRV) in hydrophilic matrices and raw material. This method was shown to be linear, accurate, precise, robust and to have adequate limits of quantification and detection (LQ and LD, respectively), allowing its use in the dissolution test of hydrophilic matrices. The content of CRV determined through this method was compared with two previously validated methods based on the reference techniques of High Performance Liquid Chromatography (HPLC) and Potentiometric Titrations (PT). ANOVA confirmed the equivalence of these methods, showing no significant differences.

A FORMAÇÃO DE LIGAÇÕES DE HIDROGÊNIO π‧‧‧H, F‧‧‧H E C‧‧‧H NOS COMPLEXOS C2H2‧‧‧(HF), C2H2‧‧‧2(HF) E C2H2‧‧‧3(HF)

In this work, a theoretical study on the basis of structural, vibrational, electronic and topological parameters of the C2H2‧‧‧(HF), C2H2‧‧‧2(HF) and C2H2‧‧‧3(HF) complexes concerning the formation of π‧‧‧H, F‧‧‧H and C‧‧‧H hydrogen bonds is presented. The main difference among these complexes is not properly the interaction strength, but the hydrogen bond type whose benchmark is ruled justly by the structure. Meanwhile, the occurrence of π‧‧‧H hydrogen bonds was unveiled in both C2H2‧‧‧(HF) dimer and C2H2‧‧‧3(HF) tetramer, although in latter, this interaction is stronger than C‧‧‧H of the C2H2‧‧‧2(HF) trimer. However, the F‧‧‧H hydrogen bonds within the subunits of hydrofluoric acid are the strongest ones, reaching a partial covalent limit, and thereby contribute decisively to the stabilization of the tetramer structure. In line with this, the largest red-shifts were observed on the hydrofluoric acid trimer of the C2H2‧‧‧3(HF) complex.

Computational modeling for irrigated agriculture planning. Part II: risk analysis

Techniques of evaluation of risks coming from inherent uncertainties to the agricultural activity should accompany planning studies. The risk analysis should be carried out by risk simulation using techniques as the Monte Carlo method. This study was carried out to develop a computer program so-called P-RISCO for the application of risky simulations on linear programming models, to apply to a case study, as well to test the results comparatively to the @RISK program. In the risk analysis it was observed that the average of the output variable total net present value, U, was considerably lower than the maximum U value obtained from the linear programming model. It was also verified that the enterprise will be front to expressive risk of shortage of water in the month of April, what doesn't happen for the cropping pattern obtained by the minimization of the irrigation requirement in the months of April in the four years. The scenario analysis indicated that the sale price of the passion fruit crop exercises expressive influence on the financial performance of the enterprise. In the comparative analysis it was verified the equivalence of P-RISCO and @RISK programs in the execution of the risk simulation for the considered scenario.

Translation and Cross-Cultural Adaptation of the Lymphoedema Functioning, Disability and Health Questionnaire for Lower Limb Lymphoedema into Portuguese Language

Objective The objective of the study is to describe the process of translation and cross-cultural adaptation of the Lymphoedema Functioning, Disability, and Health Questionnaire for Lower Limb Lymphoedema (Lymph-ICF-LL) into (Brazilian) Portuguese. Methods The process was comprised of five steps - translation, back translation, revision by an expert panel, pretest, and final translation. The first translation was performed by two professionals of the healthcare area, and the back translation was performed by two translators. An expert panel assessed the questions for semantics and idiomatic, cultural, and conceptual equivalence. The pretest was conducted on 10 patients with lymphedema. Results Small differences were identified between the translated and back-translated versions, which were revised by the expert panel. The patients included in the pretest found 10 questions difficult to understand; these questions were reassessed by the same expert panel. Conclusion The results of the translation and cross-cultural adaptation of the Lymph- ICF-LL resulted in a Brazilian Portuguese version, which still requires validation with various samples of the local population.

Growth and development of honey weed based on days or thermal units

This work was carried out with the objective of evaluating the growth and development of honey weed (Leonurus sibiricus) based on days or thermal units (growing degree days). Thus, two independent trials were developed to quantify the phenological development and total dry mass accumulation in increasing or decreasing photoperiod conditions. Considering only one growing season, honey weed phenological development was perfectly fit to day scale or growing degree days, but with no equivalence between seasons, with the plants developing faster at increasing photoperiods, and flowering 100 days after seeding. Even day-time scale or thermal units were not able to estimate general honey weed phenology during the different seasons of the year. In any growing condition, honey weed plants were able to accumulate a total dry mass of over 50 g per plant. Dry mass accumulation was adequately fit to the growing degree days, with highlights to a base temperature of 10 ºC. Therefore, a higher environmental influence on species phenology and a lower environmental influence on growth (dry mass) were observed, showing thereby that other variables, such as the photoperiod, may potentially complement the mathematical models.

Concanavalin A-reactive nuclear matrix glycoprotein

The binding capacity of concanavalin A (Con A) to condensed euchromatin and heterochromatin was investigated in chicken erythrocyte nuclei (CEN), mouse liver cells, Zea mays mays meristematic cells and Drosophila melanogaster polytene chromosomes after 4 N HCl hydrolysis to determine whether binding was preferentially occurring in bands and heterochromatin. Dry mass (DM) variation was investigated in CEN by interference microscopy. Feulgen and Con A reactions were employed for all materials to correlate the loci of the two reactions. Quantifications and topological verifications were carried out by video image analysis (high performance cytometry). It was observed that 4 N HCl hydrolysis caused an important DM loss in CEN leaving a level corresponding to the average DNA DM content. In this material, Con A binding was restricted to the nuclear envelope, which reinforces the idea of the absence of a nuclear matrix in these cells. The other cell types exhibited a correspondence of Feulgen-positive and Con A-reactive areas. The Con A reaction was highly positive in the condensed chromatin areas and heterochromatin. This fact led us to speculate that Con A-positive proteins may play a role in the chromatin condensation mechanism, endowing this structure with physico-chemical stability towards acid hydrolysis and contributing to its rheological properties.

Precipitated immune complexes of IgM induce the generation of reactive oxygen species by rabbit polymorphonuclear leucocytes

We report that immune complexes of IgM (ICIgM) antibodies and ovalbumin in the form of a precipitate from the equivalence zone induce the generation of reactive oxygen species by rabbit blood polymorphonuclear leucocytes (PMN), as measured by the chemiluminescence (CL) production in the presence of luminol. The kinetics of CL generation induced by ICIgM is quite different from that induced by precipitated immune complexes of IgG (ICIgG): the maximum rate of CL production for ICIgM occurs around 14 min, whereas for ICIgG it occurs about 5 min after incubation with the cells. Also the triggering of the process requires a higher concentration of ICIgM than of ICIgG. Evidence is presented that these effects are not mediated by interaction of the antigen (ovalbumin) with the cell, since immune precipitates of ovalbumin and the F(ab')2 fragment had no effect. Our observations that precipitated ICIgM can also be an effective stimulus for CL generation and thus for O2- production reveal a new functional capability of PMN. These results may have implications for the understanding of the participation of ICIgM (as well as of ICIgG) in inflammatory reactions mediated by PMN in immune complex diseases, and in the mechanisms of defense against microbes and other non-self agents.

Mental rotation of anthropoid hands: a chronometric study

It has been shown that mental rotation of objects and human body parts is processed differently in the human brain. But what about body parts belonging to other primates? Does our brain process this information like any other object or does it instead maximize the structural similarities with our homologous body parts? We tried to answer this question by measuring the manual reaction time (MRT) of human participants discriminating the handedness of drawings representing the hands of four anthropoid primates (orangutan, chimpanzee, gorilla, and human). Twenty-four right-handed volunteers (13 males and 11 females) were instructed to judge the handedness of a hand drawing in palm view by pressing a left/right key. The orientation of hand drawings varied from 0º (fingers upwards) to 90º lateral (fingers pointing away from the midline), 180º (fingers downwards) and 90º medial (finger towards the midline). The results showed an effect of rotation angle (F(3, 69) = 19.57, P < 0.001), but not of hand identity, on MRTs. Moreover, for all hand drawings, a medial rotation elicited shorter MRTs than a lateral rotation (960 and 1169 ms, respectively, P < 0.05). This result has been previously observed for drawings of the human hand and related to biomechanical constraints of movement performance. Our findings indicate that anthropoid hands are essentially equivalent stimuli for handedness recognition. Since the task involves mentally simulating the posture and rotation of the hands, we wondered if "mirror neurons" could be involved in establishing the motor equivalence between the stimuli and the participants' own hands.

Transduction motif analysis of gastric cancer based on a human signaling network

To investigate signal regulation models of gastric cancer, databases and literature were used to construct the signaling network in humans. Topological characteristics of the network were analyzed by CytoScape. After marking gastric cancer-related genes extracted from the CancerResource, GeneRIF, and COSMIC databases, the FANMOD software was used for the mining of gastric cancer-related motifs in a network with three vertices. The significant motif difference method was adopted to identify significantly different motifs in the normal and cancer states. Finally, we conducted a series of analyses of the significantly different motifs, including gene ontology, function annotation of genes, and model classification. A human signaling network was constructed, with 1643 nodes and 5089 regulating interactions. The network was configured to have the characteristics of other biological networks. There were 57,942 motifs marked with gastric cancer-related genes out of a total of 69,492 motifs, and 264 motifs were selected as significantly different motifs by calculating the significant motif difference (SMD) scores. Genes in significantly different motifs were mainly enriched in functions associated with cancer genesis, such as regulation of cell death, amino acid phosphorylation of proteins, and intracellular signaling cascades. The top five significantly different motifs were mainly cascade and positive feedback types. Almost all genes in the five motifs were cancer related, including EPOR,MAPK14, BCL2L1, KRT18,PTPN6, CASP3, TGFBR2,AR, and CASP7. The development of cancer might be curbed by inhibiting signal transductions upstream and downstream of the selected motifs.