Uma nova abordagem para resolver deficiência de posto, desalinhamento de pico e interferências na análise de aminas biogênicas em peixes usando HPLC-DAD

Biogenic amines (BAs) are used as food spoilage marker and can cause damage to the body at high concentrations levels. BAs are produced by the action of microorganisms through the enzymatic decarboxylation of natural amino acids. There are several BAs, however only histamine is monitored by a monitoring agency as ESFA (European Food Safety Authority) and FAO/WHO (Food and Agriculture Organization of the United Nations/World Health Organization). Some drawbacks are present in the BAs analyzes. The high electron transition energy requires a derivatization step prior to the HPLC-DAD (high-performance liquid chromatography – diode array detector) analysis. The most common derivation is the one using dansyl chloride. However, this is a non-selective reaction that occurs with any primary or secondary amine, leading to interferers with highly correlated profiles, and resulting in rank deficiency. In addition to rank deficiency, the data present trilinearity break due to time misalignment frequently present in chromatographic data. The most common way of solving rank deficiency is by using a more selective detector, however, this approach increases the cost of analysis and the complexity of data processing, besides not always this selective detector exists. The proposed methodology uses of a four minutes’ isocratic elution, which raises the analytical frequency and is in agreement with the principles of the green analytical chemistry by reducing the solvent consumption. Quantification limits were between 0.08 and 0.15 mg kg-1 for synthetic samples and between 0.04 and 0.17 mg kg-1 for fish samples were obtained with the developed approach, which are way below the maximum limit of 50 mg kg-1 established by FAO/WHO and by the EFSA for histamine in fish. Accuracy results was obtained in the prediction of the sixteen synthetic samples with REP (root error of prediction) varying between 4.0 and 8.0%. BAs were initially identified is fresh fish samples at low concentration levels, however the increase of this concentration can be observed when a kinetic study of degradation of the four samples conditioned at 4 ° C for thirteen days was performed. In this work, the efficiency of the peak alignment with the coshift on restoring the trilinearity of the HPLC-DAD data was shown. So, it was then possible to achieve the secondorder advantage using the MCR-ALS (Multivariate curve resolution - alternating least squares) augmented in the spectral mode. So far there was no proposal to achieve the second-order advantage in data with these characteristics without the previously separation of the constituents that cause rank deficiency or the use of another more selective detector.Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPqAs aminas biogênicas (ABs) são usadas como indicadores de degradação em alimentos e em elevadas concentrações podem causar danos ao organismo. As ABs são produzidas pela ação de microrganismos através da descarboxilação enzimática de aminoácidos naturais. Existem diversas ABs, no entanto, apenas a histamina é controlada por órgãos regulamentadores como ESFA (European Food Safety Authority) e FAO/WHO (Food and Agriculture Organization of the United Nations/World Health Organization). Alguns inconvenientes estão presentes nas análises de ABs. A elevada energia de transição eletrônica requer uma etapa de derivatização previamente à análise usando HPLC-DAD (high-performance liquid chromatography – diode array detector). A derivatização mais comum é a que utiliza o cloreto de dansil. No entanto, esta é uma reação não seletiva que ocorre com qualquer amina primária ou secundária o que leva a interferentes coeluidos com perfis muito correlacionados, resultando em deficiência de posto. Além da deficiência de posto, os dados apresentam quebra da trilinearidade devido ao deslocamento da retenção frequentemente presente em dados de cromatografia. A forma mais comum de resolver deficiência de posto é o uso de um detector mais seletivo, no entanto, essa abordagem eleva o custo da análise e a complexidade no tratamento de dados, além de nem sempre esse detector mais seletivo existir para a análise em questão. A metodologia proposta neste trabalho faz uso de uma eluição isocrática de apenas quatro minutos, o que eleva a frequência analítica e está de acordo com os princípios da química analítica verde por reduzir o volume de solvente gasto. Com esta abordagem desenvolvida foi possível obter limites de quantificação entre 0,08 e 0,15 mg kg-1 em amostras sintéticas e entre 0,04 e 0,17 mg kg-1 em amostras de peixe, que estão bem abaixo do limite máximo de 50 mg kg-1 estabelecido pela FAO/WHO e pela ESFA para histamina. Foram alcançados resultados exatos na predição das dezesseis amostras sintéticas com REP (root error of prediction) variando entre 4,0 e 8,0 %. Foi possível identificar as ABs nas amostras de peixe recém-pescado em baixas concentrações, no entanto o aumento desta concentração pode ser observado ao realizar um estudo cinético de degradação das quatro amostras acondicionadas a 4 °C por treze dias. Neste trabalho, mostrou-se a eficiência do alinhamento de pico com o coshift em restaurar a trilinearidade dos dados HPLC-DAD. Desse modo, foi possível alcançar a vantagem de segunda ordem usando o MCR-ALS (Multivariate curve resolution - alternating least squares) aumentado no modo espectral. Até o momento não havia proposta para alcançar a vantagem de segunda ordem em dados com essas características sem recorrer à separação dos constituintes que causam deficiência de posto ou ao uso de outro detector sincronizado que seja mais seletivo

Uma metodologia analítica rápida para quantificação simultânea de estrógenos em águas usando HPLC-DAD e calibração de segunda ordem

With the increasing use of manufactured products such as pharmaceuticals, cosmetics and toiletries, a new category of water bodies pollutants, called emerging contaminants, is gaining prominence in the environmental issues and preservation scenario of the planet's fresh water. Among these are endocrine disruptors, such as estrogens that has concerned the scientific community that has been warning for need to establish maximum concentration levels of these types of substances in the drinking water. Parallel to the legislation s rises to control these pollutants is necessary the development of rapid analytical methodologies, robust and with low waste generation. Almost all the analytical methods for quantification of estrogens in water samples make use of liquid or gas chromatography coupled to mass spectra associated to long chromatographic runs. In this work a fast method is presented for simultaneous quantification of four estrogens (E1, E2, E3 and EE2) in surface water samples using HPLC-DAD and multiway calibration with the purpose to exploit the potentialities of the second order advantage to circumvent the problems of sample complexities. Second order calibration models based on PARAFAC, MCR-ALS, N and U-PLS/RBL methods were constructed using individual pattern of analytes (pure standard) solutions. These models were then validated using a set of synthetic mixtures of these analytes with two potential interferences (daizein and biochanin A) to simulate the organic load and to demonstrate second order advantage. Satisfying statistical validation parameters were obtained, especially for U and N-PLS/RBL models. Finally river and sewage samples fortified with four estrogens were subjected to a pre-concentration and sample clean up using SPE-C18 cartridge followed by chromatographic analysis. The application of the calibration model to the fortified waters' samples led to, most cases, a recovery between 70 and 120%, reflecting the good accuracy of the proposed methodCoordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPESCom o uso cada vez maior de produtos industrializados, como os farmacêuticos, os cosméticos e os de higiene pessoal, uma nova categoria de poluentes dos corpos aquáticos, chamados de contaminantes emergentes, vem ganhando destaque no cenário das questões ambientais e preservação da água potável do planeta. Entre estes estão os alteradores endócrinos, como é o caso dos estrógenos que têm preocupado a comunidade científica que já vem alertando para necessidade de se estabelecer limite máximo de concentração dessas substâncias nas águas de abastecimento. Paralelamente ao surgimento de legislação para controle desses poluentes é necessário que ocorra o desenvolvimento de metodologias analíticas rápidas, robustas e com baixa geração de resíduos. Em quase sua totalidade os métodos analíticos para quantificação de estrógenos em amostras de águas fazem de uso da cromatografia líquida ou gasosas acopladas a espectros de massa, associada a longas corridas cromatográficas. Neste trabalho é proposta uma metodologia rápida para quantificação simultânea de quatro estrógenos (E1, E2, EE2 e E3) em amostras de águas superficiais empregando HPLC-DAD e calibração multivias com propósito de explorar as potencialidades da vantagem de segunda ordem para contornar os problemas da complexidade da matriz. Modelos de calibração de segunda ordem baseados nos métodos PARAFAC, MCR-ALS, N e U-PLS/RBL foram construídos usando soluções padrão individual dos analitos (padrões puros). Estes modelos foram depois validados empregando-se um conjunto de misturas sintéticas destes analitos com mais dois potenciais interferentes (a daizeina e biochanina A) para simular a carga orgânica e demonstrar a vantagem de segunda ordem. Estas misturas sintéticas foram construídas usando planejamento Taguchi. Parâmetros estatísticos de validação satisfatórios foram obtidos, em especial para os modelos U e N-PLS/RBL. Por fim amostras de rio e esgoto fortificadas com os quatro estrógenos foram submetidas a uma pré-concentração e limpeza da amostra usando cartuchos SPE-C18, seguido da análise cromatográfica. A aplicação dos modelos de calibração as amostras de águas fortificadas levou para a maioria dos casos a uma recuperação entre 70 e 120%, refletindo a boa exatidão do método propost

A simplified and versatile multivariate calibration procedure for multiproduct quantification of pharmaceutical drugs in the presence of interferences using first order data and chemometrics

In the present work, a methodology for multiproduct quantification of paracetamol, caffeine and sodium diclofenac using ultraviolet (UV) detection (first order data) associated with multivariate curve resolution with alternating least squares (MCR-ALS) and Partial Least Squares (PLS), was developed. Generally, for first order data modelling, a high number of samples are required to include all the constituents present in future samples. However, it is possible that interferences impair the use of the calibration model when it comes to multiproduct analyses. We propose a methodology based on the use of individually built calibration curves, one for each analyte, similarly to a univariate calibration, and use chemometrics approaches to accurately quantify the analytes in the presence of interferences. Two strategies were evaluated: 1) the individual curves were grouped in a calibration matrix and 2) only the curve of the analyte of interest was used for calibration. These strategies were applied to two sample sets: 1) a test set prepared with a mixture of the analytes, according to a Central Composite Design and 2) 15 commercial drug products with very different compositions and dosage forms. Partial Least Squares (PLS) and Multivariate Curve Resolution with Alternating Least Squares (MCR-ALS) were compared and are discussed regarding first and second order advantages in the two approaches. PLS presented adequate performance using strategy 1 and the test set mixture, indicating that there was no need to prepare mixtures of the analytes for calibration. MCR-ALS achieved accurate results for both strategies and both sample sets, fulfilling the requirements to achieve first and second order advantages, which are related to the capability of providing the analyst with information about the presence of unmodelled compounds in unknown samples, on the one hand, and achieving an accurate quantification in the presence of these unknown compounds, on the other hand. Building a calibration set with standards of pure compounds not only will reduce the number of samples required for calibration, but makes it easier to update the model by simply including new calibration samples for the quantification of new compounds. This is an interesting strategy for pharmaceutical analysis, since the composition of samples is known by the manufacturer146202209CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO - CNPQCOORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIOR - CAPESFUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULO - FAPESP465389/2014-7; 150482/2018-3não tem2016/05636-9; 14/50867-319th Brazilian meeting on analytical chemistry / 7th Iberoamerican congress on analytical chemistry2018Caldas Novas, GOCentro de Convenções diRom

A fast chromatographic method for determination of daidzein and genistein in spiked water river samples using multivariate curve resolution

This work reports the development of a fast chromatography methodology for quantitation of two phytoestrogens: daidzein (DAI) and genistein (GEN), in river water samples. The proposed method is based on High performance liquid chromatography-diode array detection (HPLC-DAD) data, and multivariate curve resolution-alternative least square (MCR-ALS) second-order calibration. Initially, the method was evaluated analysing a synthetic validation set, prepared based on a Taguchi design. Subsequently, the method was applied to predict the concentration of the phytoestrogens in river water samples, previously pre-processed by solid phase extraction (SPE). By implementation of the present methodology, a 50 % of reduction in operation time was achieved (from 7.00 to 3.25 min) when compared with previous work in literature. Precision were achieved even in the presence non modelled constituents and strong background. Thus, it has shown that the proposed method to be abecome in a rapid and robust alternative for the quantitation of studied phytoestrogens.Fil: Moreira, Edilene D.T.. Universidade Federal da Paraíba. Departamento de Química. Laboratorio de Automacao e instrumentacao em quimica analitica e quimiometria; BrasilFil: Pinto, Licarion. Universidade Federal da Paraíba. Departamento de Química. Laboratorio de Automacao e instrumentacao em quimica analitica e quimiometria; BrasilFil: Gomes, Adriano A.. Universidade Federal da Paraíba. Departamento de Química. Laboratorio de Automacao e instrumentacao em quimica analitica e quimiometria; BrasilFil: Goicoechea, Hector Casimiro. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas; ArgentinaFil: Araujo, Mario C.U.. Universidade Federal da Paraíba. Departamento de Química. Laboratorio de Automacao e instrumentacao em quimica analitica e quimiometria; Brasi

Handling time misalignment and rank deficiency in liquid chromatography by multivariate curve resolution: Quantitation of five biogenic amines in fish

Biogenic amines (BAs) are used for identifying spoilage in food. The most common are tryptamine (TRY), 2-phenylethylamine (PHE), putrescine (PUT), cadaverine (CAD) and histamine (HIS). Due to lack of chromophores, chemical derivatization with dansyl was employed to analyze these BAs using high performance liquid chromatography with a diode array detector (HPLC-DAD). However, the derivatization reaction occurs with any primary or secondary amine, leading to co-elution of analytes and interferents with identical spectral profiles, and thus causing rank deficiency. When the spectral profile is the same and peak misalignment is present on the chromatographic runs, it is not possible to handle the data only with Multivariate Curve Resolution and Alternative Least Square (MCR-ALS), by augmenting the time, or the spectral mode. A way to circumvent this drawback is to receive information from another detector that leads to a selective profile for the analyte. To overcome both problems, (tri-linearity break in time, and spectral mode), this paper proposes a new analytical methodology for fast quantitation of these BAs in fish with HPLC-DAD by using the icoshift algorithm for temporal misalignment correction before MCR-ALS spectral mode augmented treatment. Limits of detection, relative errors of prediction (REP) and average recoveries, ranging from 0.14 to 0.50 μg mL-1, 3.5-8.8% and 88.08%-99.68%, respectively. These are outstanding results obtained, reaching quantification limits for the five BAs much lower than those established by the Food and Agriculture Organization of the United Nations and World Health Organization (FAO/WHO), and the European Food Safety Authority (EFSA), all without any pre-concentration steps. The concentrations of BAs in fish samples ranged from 7.82 to 29.41 μg g-1, 8.68-25.95 μg g-1, 4.76-28.54 μg g-1, 5.18-39.95 μg g-1 and 1.45-52.62 μg g-1 for TRY, PHE, PUT, CAD, and HIS, respectively. In addition, the proposed method spends less than 4 min in an isocratic run, consuming less solvent in accordance with the principles of green analytical chemistry.Fil: Pinto, Licarion. Universidade Estadual da Paraiba; BrasilFil: Díaz Nieto, César Horacio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; ArgentinaFil: Zon, María Alicia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; ArgentinaFil: Fernandez, Hector. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; ArgentinaFil: de Araujo, Mario Cesar Ugulino. Universidade Estadual da Paraiba; Brasi

Multivariate curve resolution-alternating least-squares and second-order advantage in first-order calibration. A systematic characterisation for three-component analytical systems

Background: Recent interest has been focused on the application of multivariate curve resolution-alternatingleast-squares (MCR-ALS) to systems involving the measurement of first-order and non-bilinear second-orderdata. The latter pose important challenges to bilinear decomposition models, due to the phenomenon of rotationalambiguity in the solutions, even under the application of the full set of chemical constraints that is usuallyemployed in MCR-ALS calibration.Results: After the analysis of several simulated and experimental datasets, important conclusions regarding therole of the selectivity patterns in the constituent spectra have been drawn concerning the achievement of the second-order advantage. Theoretical considerations based on the calculation of the areas of feasible solutionshelped to support the observations regarding the predictive ability of MCR- ALS in the various datasets.Significance: The understanding of the impact of rotational ambiguity in obtaining the second-order advantagewith both first-order and non-bilinear second-order data is of paramount importance in the future developmentof analytical protocols of complex samples.Fil: Chiappini, Fabricio Alejandro. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Laboratorio de Desarrollo Analítico y Quimiometría; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; ArgentinaFil: Pinto, Licarion. Universidade do Estado de Rio do Janeiro; BrasilFil: Alcaraz, Mirta Raquel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentina. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Laboratorio de Desarrollo Analítico y Quimiometría; ArgentinaFil: Omidikia, Nematollah. Netherland Institute For Sea Research; Países BajosFil: Goicoechea, Hector Casimiro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentina. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Laboratorio de Desarrollo Analítico y Quimiometría; ArgentinaFil: Olivieri, Alejandro Cesar. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentin

Highly sensitive quantitation of pesticides in fruit juice samples by modeling four-way data gathered with high-performance liquid chromatography with fluorescence excitation-emission detection

A study regarding the acquisition and analytical utilization of four-way data acquired by monitoring excitation-emission fluorescence matrices at different elution time points in a fast HPLC procedure is presented. The data were modeled with three well-known algorithms: PARAFAC, U-PLS/RTL and MCR-ALS, the latter conveniently adapted to model third-order data. The second-order advantage was exploited when analyzing samples containing uncalibrated components. The best results were furnished with the algorithm U-PLS/RTL. This fact is indicative of both no peak time shifts occurrence among samples and high colinearity among spectra. Besides, this latent-variable structured algorithm is capable of better handle the need of achieving high sensitivity for the analysis of one of the analytes. In addition, a significant enhancement in both predictions and analytical figures of merit was observed for carbendazim, thiabendazole, fuberidazole, carbofuran, carbaryl and 1-naphtol, when going from second- to third-order data. LODs obtained were ranged between 0.02 and 2.4 μg L-1.Fil: Montemurro, Milagros. Universidad Nacional del Litoral; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; ArgentinaFil: Pinto, Licarion. Universidade Federal da Paraíba; BrasilFil: Véras, Germano. Universidade Estadual da Paraíba; BrasilFil: de Araújo Gomes, Adriano. Universidade Federal da Paraíba; BrasilFil: Culzoni, Maria Julia. Universidad Nacional del Litoral; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; ArgentinaFil: Ugulino de Araújo, Mario Cesar. Universidade Federal Da Paraíba; BrasilFil: Goicoechea, Hector Casimiro. Universidad Nacional del Litoral; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentin

Quantification of palm oil bioactive compounds by ultra-high-performance supercritical fluid chromatography and chemometrics

International audienceLycopene, beta-carotene, coenzyme Q10, and lutein are minor constituents of palm oil that are removed during biodiesel production to produce light-colored oils. With the aim to investigate the recovery of these valuable compounds, a separation method was developed to quantify carotenoids and coenzyme Q10 in palm oil by ultra-highperformance supercritical fluid chromatography. Due to the presence of interferents

Biologically Active Volatile Organic Compounds (VOCs) Produced by Rhizospheric Actinobacteria Strains Inhibit the Growth of the Phytopathogen Colletotrichum musae

The antifungal potential of volatile organic compounds (VOCs) produced by actinobacterial strains Streptomyces sp. (ACTB-77) and Amycolatopsis sp. (ACTB-290) from the rhizosphere of Caatinga plants against Colletotrichum musae was investigated. VOCs produced by these microorganisms (axenic and co-culture) were investigated using headspace-solid phase micro-extraction (HS-SPME) and gas chromatography-mass spectrometry (GC-MS). Although no exclusive VOC peaks were observed in the co-culture with ACTB-77, the same experiment involving ACTB-290 yielded five new peaks, including two identified alcohols, suggested as bioreductive products of the corresponding ketones by the fungus. Statistical analysis revealed that co-culture ACTB-77/C. musae has a closer similarity to the fungus than to the actinobacteria, while the co culture ACTB-290/C. musae showed closer similarity to the actinobacteria. These confirmed the more pronounced antifungal activity of the ACTB-290 strain, as observed in the fungus growth inhibition experiments. The antifungal activity of ACTB-290 was associated to its sulfur-containing metabolites, while linalool was suggested as responsible for the ACTB-77 activity.</div