Nomenclatura na língua portuguesa em cromatografia multidimensional abrangente

Comprehensive Multidimensional Chromatography is a relatively new analytic technique, which is receiving growing attention in many parts of the world, including recently in Brazil. This work presents terms in Portuguese which are commonly used in Comprehensive Multidimensional Chromatography in order to help standardize the vocabulary employed in this area in the scientific literature. It also includes some symbols, their nominations, and explanation of some terms, whenever necessary. This proposal does not intend to be comprehensive or definitive; on the contrary, it intends to be a first step in the process of establishing a standardized nomenclature, serving as a base for a further sound discussion in the scientific community realm.

Application of comprehensive gas chromatography (GCxGC) to measurements of volatile organic species in ambient air

The focus of this thesis was the in-situ application of the new analytical technique "GCxGC" in both the marine and continental boundary layer, as well as in the free troposphere. Biogenic and anthropogenic VOCs were analysed and used to characterise local chemistry at the individual measurement sites. The first part of the thesis work was the characterisation of a new set of columns that was to be used later in the field. To simplify the identification, a time-of-flight mass spectrometer (TOF-MS) detector was coupled to the GCxGC. In the field the TOF-MS was substituted by a more robust and tractable flame ionisation detector (FID), which is more suitable for quantitative measurements. During the process, a variety of volatile organic compounds could be assigned to different environmental sources, e.g. plankton sources, eucalyptus forest or urban centers. In-situ measurements of biogenic and anthropogenic VOCs were conducted at the Meteorological Observatory Hohenpeissenberg (MOHP), Germany, applying a thermodesorption-GCxGC-FID system. The measured VOCs were compared to GC-MS measurements routinely conducted at the MOHP as well as to PTR-MS measurements. Furthermore, a compressed ambient air standard was measured from three different gas chromatographic instruments and the results were compared. With few exceptions, the in-situ, as well as the standard measurements, revealed good agreement between the individual instruments. Diurnal cycles were observed, with differing patterns for the biogenic and the anthropogenic compounds. The variability-lifetime relationship of compounds with atmospheric lifetimes from a few hours to a few days in presence of O3 and OH was examined. It revealed a weak but significant influence of chemistry on these short-lived VOCs at the site. The relationship was also used to estimate the average OH radical concentration during the campaign, which was compared to in-situ OH measurements (1.7 x 10^6 molecules/cm^3, 0.071 ppt) for the first time. The OH concentration ranging from 3.5 to 6.5 x 10^5 molecules/cm^3 (0.015 to 0.027 ppt) obtained with this method represents an approximation of the average OH concentration influencing the discussed VOCs from emission to measurement. Based on these findings, the average concentration of the nighttime NO3 radicals was estimated using the same approach and found to range from 2.2 to 5.0 x 10^8 molecules/cm^3 (9.2 to 21.0 ppt). During the MINATROC field campaign, in-situ ambient air measurements with the GCxGC-FID were conducted at Tenerife, Spain. Although the station is mainly situated in the free troposphere, local influences of anthropogenic and biogenic VOCs were observed. Due to a strong dust event originating from Western Africa it was possible to compare the mixing ratios during normal and elevated dust loading in the atmosphere. The mixing ratios during the dust event were found to be lower. However, this could not be attributed to heterogeneous reactions as there was a change in the wind direction from northwesterly to southeasterly during the dust event.

Capital Intelectual: sua divulgação no setor bancário em Portugal

The importance of intangible resources has increased dramatically in recent years comparing to tangible ones. The economy in which we live is the result of competitive pressures that have imposed the implementation of business at an international level as well as a requirement in the application of sophisticated technologies that allow us to follow this fast evolution. In this age of information and innovation organizations will only survive if they are inserted in a global network of strategic relations, generically called as the network economy by Lev (2003). The service sector has stood out against the more traditional sectors of the economy. The intensive use of knowledge and a strong customer orientation created a new reality in today’s organizations: a growing importance attached to innovation, to the quality of products and services offered, to the information and communication technologies adopted, and to the creativity and particular abilities of human resources. The concept of intangible assets is more common in an accounting language and intellectual capital is most often applied in the context of management, being associated with a more comprehensive, multidimensional approach, representing all the knowledge that the institution owns and that it applies in the form of expertise, the creativity and organizational competencies that lead to innovation and to the sustained attainment of future economic benefits. An analysis of the scope of intellectual capital is fundamental to take more appropriate management decisions so that a more appropriate accounting treatment could be given by the accounting standardization organizations. This study intends to analyse the practices of information disclosure of the intellectual capital in the banking sector in Portugal, complementing the analysis of the disclosure of intangible assets in the context of accounting standards with the disclosure of intellectual capital in the context of organizational management. In particular, our main aims are to identify the extent of disclosure of intellectual capital made by banks in Portugal and also to identify the factors that determine such a disclosure. The disclosure in the context of accounting standards will be studied by checking the disclosure of intangible assets through the items listed in the International Accounting Standard 38 developed by the International Accounting Standards Board. The context of management was analysed by means of creating a voluntary disclosure index based on assumptions of the model Intellectus, developed by the Centro de Investigación sobre la Sociedad del Conocimiento – Instituto de Administración de Empresas (CIC-IADE) of the Universidad Autónoma of Madrid, and of the model Intellectual Capital Statement (made in Europe) (InCaS), both promoted by the European Commission and that we have adapted to the banking sector. When analysing the disclosure of intangible assets based on the context of accounting standards and the voluntary disclosure of intellectual capital, this study has tried to raise awareness about the importance of issuing reports on the intellectual capital as an alternative tool to take management decisions in the existing organizations and reflects the transparency and legitimacy that these institutions seek through a more extensive and more detailed information disclosure of their intellectual capital. Based on a complimentarily of economic theories, together with social and political theories, we tried to check the extent, evolution and tendencies of the compulsory disclosure of intangible assets and of the voluntary disclosure of the intellectual capital analysed in the period 2001-2011. Banks characteristics were also analysed in order to deduce those factors that determine or promote a larger disclosure in this sector. Based on these objectives, we adopted a longitudinal approach to explore the extent and the development of the disclosure of intangible assets as well as the factors that have determined it. Furthermore, we sought to assess the impact of the adoption of IAS 38 in the financial statements of the organizations in this sector. The disclosure index created on the basis of the disclosure requirements stated in IAS 38 from IASB was applied to the consolidated financial statements of the seventeen banks that rendered their statements in Portugal from 2001 to 2009. Since the information disclosed in the context of accounting standards may not have an important role as a management tool once it was not able to reflect what really contributes to the competitiveness and organizational growth, the voluntary disclosure of the intellectual capital was analysed according to the information obtained from the 2010 annual individual reports of the banks operating in Portugal in that year and from their respective websites in 2011. We tried to analyse the extent of the voluntary disclosure of the intellectual capital and of each of its components, human capital, structural capital and relational capital. The comparative analysis of their annual reports and their web pages allowed us to assess the incidence of the disclosure and discover what channel the banking sector focuses on when disclosing their intellectual capital. Also in this analysis the study of the disclosure determinants has allowed us to conclude about the influence of particular characteristics in the voluntary disclosure of the intellectual capital. The results of the analysis to the extent of the disclosure of intangible assets in the consolidated financial statements of the banking groups in Portugal in the period 2001-2009 have shown an average information disclosure of 0.24. This information disclosure evolved from an average value of 0.1940 in 2001 to 0.2778 in 2009. The average value is 0.8286 if it is only considered the disclosure of the intangible assets that the banks possessed. The evolution of this index means an increase in the average disclosure from 0.7852 in 2001 to 0.8788 in 2009. From the first results that are related to the extent of the disclosure of intangible assets in the financial statements, we can verify that the banking groups present a low disclosure level of these resources. However, when considering the disclosure of only the intangible assets that each institution owns, the disclosure level appears to be in compliance with the disclosure requirements for this sector. An evolution in the disclosure of intangible assets for the period considered was confirmed, showing an increase in the information disclosure of intangible assets in 2005, the year in which the accounting rules for intangible assets changed. The analysis that focused on the disclosure in the context of management tried to understand the extent, the incidence and the determinants of the voluntary information disclosure of intellectual capital in the annual reports of 2010 and on their web pages in 2011, studying the 32 banks operating in Portugal in this period. The average voluntary disclosure of the intellectual capital in the 2010 annual reports is 0.4342 while that in web pages is 0.2907. A review of the components of the intellectual capital allowed us to assess the importance that the banks confer to each of these components. The data obtained show that the relational capital, and more specifically the business capital, is the most disclosed component by banks in Portugal both in the annual reports and in their institutional web pages, followed by the structural capital and, finally, by the human capital. The disclosure of the human capital and the structural capital is higher in the annual reports than that in the websites, while the relational capital is more disclosed in the websites than in the annual reports. The results have also shown that the banks make a complementary use of both sources when disclosing information about their structural capital and relational capital but they do not show any information about their human capital in their websites. We tried to prove the influence of factors that could determine the accounting disclosure and the voluntary disclosure of the intellectual capital in this sector. The change in the IASB accounting rules as from January 1st 2005 gave a greater disclosure of accounting information of intangible assets in the financial statements of banks. The bank size and corporate governance measures have statistically proved to have an influence on the extent of the accounting disclosure of intangible assets and on the voluntary disclosure of the intellectual capital. Economic and financial variables such as profitability, operating efficiency or solvency were not determinants of information disclosure. The instability that the banking sector has experienced in economic and financial indicators in recent years as a result of the global financial markets imbalance has worsen indicators such as profitability, efficiency and solvency and caused major discrepancies in the economic situation between banks in Portugal. This empirical analysis has contributed to confront the disclosure required by accounting rules performed in the financial statements of organizations with that performed in the main disclosure media which is available for entities and which is increasingly requested in the process of taking management decisions. It also allowed us to verify whether there is homogeneity between institutions in the fulfilment of the requirements for information disclosure of intangible assets. However, as for voluntary disclosure of intellectual capital, there are large disparities in the disclosure extent between organizations. Regardless of this sector specific characteristics, the voluntary disclosure of intellectual capital made by banks in Portugal follows the trends in other sectors and the practices adopted in other countries, namely regarding the amount of information disclosed, the incidence of the disclosure on the indicators of relational capital and the importance of variables such as size as determinants of disclosure of intellectual capital. For a further knowledge in this field, we created a specific index for the banking sector, considering appropriate indicators for an incisive, comprehensive analysis in order to consider the most relevant indicators of intellectual capital components. Besides, confronting the analysis of disclosure in the context of accounting standards with the study of voluntary disclosure brought a new analysis approach to the research on intellectual capital disclosure. With this study, we have also intended to raise greater awareness of the need for harmonization in the intellectual capital disclosure on the part of the regulatory banking authority by means of a demanding, consistent and transparent report of intellectual capital with simple, clear, objective indicators so that those interested in disclosing intellectual capital information in the organizations in this sector may obtain more harmonized and comparable information. A research on the disclosure quality of intellectual capital, together with the application of other analysis methodologies in this sector, might be a promising approach for future research. Applying the voluntary disclosure index to the same sector in other countries may also contribute to the knowledge of disclosure practices in different geographical environments. We highlight the relevance of further studies contributing to the harmonization and consistency in the presentation of an intellectual capital report so as to enable organizations to disclose the resources that contribute most to their competitiveness and growth.

Development of a comprehensive on-line multidimensional high performance column liquid chromatography system for protein and peptide mapping with integrated size selective sample fractionation

Aufbau einer kontinuierlichen, mehrdimensionalen Hochleistungs-flüssigchromatographie-Anlage für die Trennung von Proteinen und Peptiden mit integrierter größenselektiver ProbenfraktionierungEs wurde eine mehrdimensionale HPLC-Trennmethode für Proteine und Peptide mit einem Molekulargewicht von <15 kDa entwickelt.Im ersten Schritt werden die Zielanalyte von höhermolekularen sowie nicht ionischen Bestandteilen mit Hilfe von 'Restricted Access Materialien' (RAM) mit Ionenaustauscher-Funktionalität getrennt. Anschließend werden die Proteine auf einer analytischen Ionenaustauscher-Säule sowie auf Reversed-Phase-Säulen getrennt. Zur Vermeidung von Probenverlusten wurde ein kontinuierlich arbeitendes, voll automatisiertes System auf Basis unterschiedlicher Trenngeschwindigkeiten und vier parallelen RP-Säulen aufgebaut.Es werden jeweils zwei RP-Säulen gleichzeitig, jedoch mit zeitlich versetztem Beginn eluiert, um durch flache Gradienten ausreichende Trennleistungen zu erhalten. Während die dritte Säule regeneriert wird, erfolgt das Beladen der vierte Säule durch Anreicherung der Proteine und Peptide am Säulenkopf. Während der Gesamtanalysenzeit von 96 Minuten werden in Intervallen von 4 Minuten Fraktionen aus der 1. Dimension auf die RP-Säulen überführt und innerhalb von 8 Minuten getrennt, wobei 24 RP-Chromatogramme resultieren.Als Testsubstanzen wurden u.a. Standardproteine, Proteine und Peptide aus humanem Hämofiltrat sowie aus Lungenfibroblast-Zellkulturüberständen eingesetzt. Weiterhin wurden Fraktionen gesammelt und mittels MALDI-TOF Massenspektrometrie untersucht. Bei einer Injektion wurden in den 24 RP-Chromatogrammen mehr als 1000 Peaks aufgelöst. Der theoretische Wert der Peakkapazität liegt bei ungefähr 3000.

In Vivo Determination Of The Volatile Metabolites Of Saprotroph Fungi By Comprehensive Two-dimensional Gas Chromatography.

In this work, we discuss the use of multi-way principal component analysis combined with comprehensive two-dimensional gas chromatography to study the volatile metabolites of the saprophytic fungus Memnoniella sp. isolated in vivo by headspace solid-phase microextraction. This fungus has been identified as having the ability to induce plant resistance against pathogens, possibly through its volatile metabolites. Adequate culture media was inoculated, and its headspace was then sampled with a solid-phase microextraction fiber and chromatographed every 24 h over seven days. The raw chromatogram processing using multi-way principal component analysis allowed the determination of the inoculation period, during which the concentration of volatile metabolites was maximized, as well as the discrimination of the appropriate peaks from the complex culture media background. Several volatile metabolites not previously described in the literature on biocontrol fungi were observed, as well as sesquiterpenes and aliphatic alcohols. These results stress that, due to the complexity of multidimensional chromatographic data, multivariate tools might be mandatory even for apparently trivial tasks, such as the determination of the temporal profile of metabolite production and extinction. However, when compared with conventional gas chromatography, the complex data processing yields a considerable improvement in the information obtained from the samples. This article is protected by copyright. All rights reserved.

Assessment Of Robustness On Analysis Using Headspace Solid-phase Microextraction And Comprehensive Two-dimensional Gas Chromatography Through Experimental Designs.

Plackett-Burman experimental design was applied for the robustness assessment of GC×GC-qMS (Comprehensive Two-Dimensional Gas Chromatography with Fast Quadrupolar Mass Spectrometric Detection) in quantitative and qualitative analysis of volatiles compounds from chocolate samples isolated by headspace solid-phase microextraction (HS-SPME). The influence of small changes around the nominal level of six factors deemed as important on peak areas (carrier gas flow rate, modulation period, temperature of ionic source, MS photomultiplier power, injector temperature and interface temperature) and of four factors considered as potentially influential on spectral quality (minimum and maximum limits of the scanned mass ranges, ions source temperature and photomultiplier power). The analytes selected for the study were 2,3,5-trimethylpyrazine, 2-octanone, octanal, 2-pentyl-furan, 2,3,5,6-tetramethylpyrazine, and 2-nonanone e nonanal. The factors pointed out as important on the robustness of the system were photomultiplier power for quantitative analysis and lower limit of mass scanning range for qualitative analysis.

Characterization of Pinus spp. needles by gas chromatography and mass spectrometry: Application to plant-insect interactions

Dissertação apresentada para obtenção do Grau de Doutor em Ciências do Ambiente pela Universidade Nova de Lisboa, Faculdade de Ciências e Tecn

Specificity and selectivity improvement in doping analysis using comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry

Comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry was used for the identification of forty doping agents. The improvement in the specificity was remarkable, allowing the resolution of analytes that could not be done by one-dimensional chromatographic systems. The sensitivity observed for different classes of prohibited substances was clearly below the value required by the World Anti-Doping Agency. In addition time-of-flight mass spectrometry gives full spectrum for all analytes without any interference from the matrix, resulting in selectivity improvements. These results could support the implementation of an exhaustive monitoring approach for hundreds of doping agents in a single injection.

Comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry combined with solid phase microextraction as a powerful tool for quantification of ethyl carbamate in fortified wines. The case study of Madeira wine

An analytical methodology based on headspace solid phase microextraction (HS-SPME) combined with comprehensive two-dimensional gas chromatography—time-of-flight mass spectrometry (GC × GC–ToFMS) was developed for the identification and quantification of the toxic contaminant ethyl carbamate (EC) directly in fortified wines. The method performance was assessed for dry/medium dry and sweet/medium sweet model wines, and for quantification purposes, calibration plots were performed for both matrices using the ion extraction chromatography (IEC) mode (m/z 62). Good linearity was obtained with a regression coefficient (r2) higher than 0.981. A good precision was attained (R.S.D. <20%) and low detection limits (LOD) were achieved for dry (4.31 μg/L) and sweet (2.75 μg/L) model wines. The quantification limits (LOQ) and recovery for dry wines were 14.38 μg/L and 88.6%, whereas for sweet wines were 9.16 μg/L and 99.4%, respectively. The higher performance was attainted with sweet model wine, as increasing of glucose content improves the volatile compound in headspace, and a better linearity, recovery and precision were achieved. The analytical methodology was applied to analyse 20 fortified Madeira wines including different types of wine (dry, medium dry, sweet, and medium sweet) obtained from several harvests in Madeira Island (Portugal). The EC levels ranged from 54.1 μg/L (medium dry) to 162.5 μg/L (medium sweet).

In-depth search focused on furans, lactones, volatile phenols, and acetals as potential age markers of Madeira wines by comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry combined with solid phase microextraction

The establishment of potential age markers of Madeira wine is of paramount significance as it may contribute to detect frauds and to ensure the authenticity of wine. Considering the chemical groups of furans, lactones, volatile phenols, and acetals, 103 volatile compounds were tentatively identified; among these, 71 have been reported for the first time in Madeira wines. The chemical groups that could be used as potential age markers were predominantly acetals, namely, diethoxymethane, 1,1-diethoxyethane, 1,1-diethoxy-2-methyl-propane, 1-(1-ethoxyethoxy)-pentane, trans-dioxane and 2-propyl-1,3-dioxolane, and from the other chemical groups, 5-methylfurfural and cis-oak-lactone, independently of the variety and the type of wine. GC × GC-ToFMS system offers a more useful approach to identify these compounds compared to previous studies using GC−qMS, due to the orthogonal systems, that reduce coelution, increase peak capacity and mass selectivity, contributing to the establishment of new potential Madeira wine age markers. Remarkable results were also obtained in terms of compound identification based on the organized structure of the peaks of structurally related compounds in the GC × GC peak apex plots. This information represents a valuable approach for future studies, as the ordered-structure principle can considerably help the establishment of the composition of samples. This new approach provides data that can be extended to determine age markers of other types of wines.

Allergic asthma exhaled breath metabolome: a challenge for comprehensive two-dimensional gas chromatography

Allergic asthma represents an important public health issue, most common in the paediatric population, characterized by airway inflammation that may lead to changes in volatiles secreted via the lungs. Thus, exhaled breath has potential to be a matrix with relevant metabolomic information to characterize this disease. Progress in biochemistry, health sciences and related areas depends on instrumental advances, and a high throughput and sensitive equipment such as comprehensive two-dimensional gas chromatography–time of flight mass spectrometry (GC × GC–ToFMS) was considered. GC × GC–ToFMS application in the analysis of the exhaled breath of 32 children with allergic asthma, from which 10 had also allergic rhinitis, and 27 control children allowed the identification of several hundreds of compounds belonging to different chemical families. Multivariate analysis, using Partial Least Squares-Discriminant Analysis in tandem with Monte Carlo Cross Validation was performed to assess the predictive power and to help the interpretation of recovered compounds possibly linked to oxidative stress, inflammation processes or other cellular processes that may characterize asthma. The results suggest that the model is robust, considering the high classification rate, sensitivity, and specificity. A pattern of six compounds belonging to the alkanes characterized the asthmatic population: nonane, 2,2,4,6,6-pentamethylheptane, decane, 3,6-dimethyldecane, dodecane, and tetradecane. To explore future clinical applications, and considering the future role of molecular-based methodologies, a compound set was established to rapid access of information from exhaled breath, reducing the time of data processing, and thus, becoming more expedite method for the clinical purposes.

Determination of disease biomarkers in Eucalyptus by comprehensive two-dimensional gas chromatography and multivariate data analysis

In this paper is reported the use of the chromatographic profiles of volatiles to determine disease markers in plants - in this case, leaves of Eucalyptus globulus contaminated by the necrotroph fungus Teratosphaeria nubilosa. The volatile fraction was isolated by headspace solid phase microextraction (HS-SPME) and analyzed by comprehensive two-dimensional gas chromatography-fast quadrupole mass spectrometry (GC. ×. GC-qMS). For the correlation between the metabolic profile described by the chromatograms and the presence of the infection, unfolded-partial least squares discriminant analysis (U-PLS-DA) with orthogonal signal correction (OSC) were employed. The proposed method was checked to be independent of factors such as the age of the harvested plants. The manipulation of the mathematical model obtained also resulted in graphic representations similar to real chromatograms, which allowed the tentative identification of more than 40 compounds potentially useful as disease biomarkers for this plant/pathogen pair. The proposed methodology can be considered as highly reliable, since the diagnosis is based on the whole chromatographic profile rather than in the detection of a single analyte. © 2013 Elsevier B.V..

Continuous vs. segmented second-dimension system gradients for comprehensive two-dimensional liquid chromatography of sugarcane (Saccharum spp.)

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Comprehensive two-dimensional gas chromatography combined to multivariate data analysis for detection of disease-resistant clones of Eucalyptus

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Development of a comprehensive method for analyzing clerodane-type diterpenes and phenolic compounds from Casearia sylvestris Swartz (Salicaceae) based on ultra high performance liquid chromatography combined with chemometric tools

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)