ARTIFICIAL NEURAL NETWORKS APPLIED IN QUANTITATIVE CHEMICAL ANALYSIS

Luiza H.S. Nunes Computer Science, FATEC Faculdade de Tecnologia de So Jos dos Campos So Jos dos Campos, So Paulo, 12247-004 Brazil Matheus R.C. Teixeira Computer Science, FATEC Faculdade de Tecnologia de So Jos dos Campos So Jos dos Campos, So Paulo, 12247-004 Brazil Lucia Codognoto Chemistry, UNICASTELO - Universidade Camilo Castelo Branco So Jos dos Campos, So Paulo, 12247-004 Brazil Rogrio Marinke Computer Science, FATEC Faculdade de Tecnologia de So Jos dos Campos So Jos dos Campos, So Paulo, 12247-004 Brazil

ABSTRACT The quantitative analysis of samples, aiming the separation of compounds, can determine, classify and identify a compound and its concentration in a mixture. However these methods are expensive and laborious and one of the main problems in quantitative analysis of samples using instrumental methods is the interelemental effects, like the matrix which interferes in the accurate determination of the analytes and requires a complicated pretreatment of the sample. With technological advances, new methods of analysis have emerged in order to minimize these problems, for example, the appearance of techniques using artificial intelligence. Thereafter, by developing an Artificial Neural Network, the analytical processes become automated and the datas processing generated is intended to be more efficient and sophisticated. Keywords: Quantitative analysis, samples, separation of compounds, new methods of analysis, Artificial Neural Networks. INTRODUCTION The chemical separation of compounds in analytical chemical, aim the data identification, classification and quantification. To perform the characterization and quantification of analytes of interest in this area, one of the most used techniques that can be cited is the chromatographic. However, these methods are expensive and laborious and not always easily accessible to the organs of control. Problems like the matrix effect, which interferes in the accurate determination of the analytes and requires a complex pretreatment of the sample, are common in this kind of techniques. Considering the necessity of organizing the vast amount of information about chemical compounds that arise every year, it becomes necessary to use analytical tools and also the knowledge for the formulation of new techniques of quantitative and qualitative determination of chemical elements contained in samples. The demand for new methods that could help in the optimization of the separation and identification of chemical compounds, requires the development of a new instrumental analytical technique that with the technological advances, brings technical approaches aimed at concepts of Artificial Intelligence such as Artificial Neural Networks (ANNs) [1].

The determination of certain analytes in complex matrices, requires the use of more sophisticated separation techniques, such as chromatographic, which can make the analysis more laborious and increase costs. Thus, the use of techniques of artificial intelligence, specifically artificial neural networks, can be a viable alternative for the analysis of complex samples, reducing the time and cost analysis. ARTIFICIAL NEURAL NETWORKS Among the most important and efficient mathematical methods in forecasting results without chemical interferences and currently existing in the area of drug analysis, are artificial neural networks, which bring innovations in the models already in use and are fundamental in this areas development, besides the analytical procedures becoming automated and the processing of generated data more efficient and sophisticated. The ANN's suppress the problems previously presented by instrumental techniques such as modeling of nonlinear systems, and can be used in conjunction with instrumental analytical techniques in order to become a complementary tool [1],[6]. Conducted studies in the analytical chemistrys area had successful application of artificial neural networks. The Kohonen neural networks were used in the prediction of the chemical elements in the periodic table. The network trained by Backpropagation algorithm was able to map and classify the elements of the periodic table, as was done by Mendeleev in 1869 and this training was conducted using 5000 epochs [3].

EXPECTATIONS AND GOALS The aim of this work is the development of an artificial neural network to assist in analytical separation and quantification of compounds of environmental interest and pharmaceutical in different matrices in order to facilitate the process of sample treatment, making the analysis of these samples more accessible agencies control. To do it, a Multi-layer Perceptron network will be implemented, which uses the Error Backpropagation algorithm to train the network.

The formulation of the correct architecture of a network is crucial for the correct prediction of the data that will be analyzed. The algorithm of Error Backpropagation is widely used in applications of ANNs in the chemistry field for data modeling and pattern recognition [4],[5]. The function used to activate the network will be the sigmoid function, because this function allows the activation function to take negative values, a fact that improves the convergence of the algorithm training and for having the nearest exit of a biological neuron [7],[8],[12],[13]. The results of eletroanalytical determination of nitrosamines compouds (N-nitrosodimethylamine (NDMA), Nnitrosodiethylamine (NDEA), N- nitrosopiperidine (NPIP) and Nnitrosopyrrolidine (NPYR)) will be used in training and validation Artificial Neural Network. N-nitrosamines are Nnitroso compounds which are considered powerful carcinogenic, teratogenic and mutagenic effect in laboratory animals[14]. These compounds can be found in several matrices, like as, foods, soil, waters, air, pesticides, cigarette, rubber products and cosmetics[15],[16],[17],[18],[19],[20],[21]. Electrochemical identification of these compounds in the mixture is not possible without a prior separation, since they present values of peak potential very close (NDMA 1.91 V vs Ag/AgCl, NDEA 1.79 V vs Ag/AgCl, NPIP 1.81 V vs Ag/AgCl and NPYR 1.84 V vs Ag/AgCl in Na2HPO4 0,10 mol L-1, pH 4,0). This results can be observed in figure 1.
Mistura NDMA NDEA NPIR NPIP

REFERENCES [1] Nagata, N., Bueno, M. I. M. S., Peralta-Zamora, P. G., Mtodos Matemticos para Correo de Interferncias Espectrais e Efeitos Interelementos na Anlise Quantitativa por Fluorescncia de Raios-X, Qumica Nova, Vol. 24, N4, 531-539, 2001. [2] Bishop, C. M.; Neural Networks for Pattern Recognition, 1st ed., University Oxford: Oxford,1995. [3] Lemes, M.R., Jnior, A.D. P, A Tabela Peridica dos Elementos Qumicos Prevista por Redes Neurais Aritficiais de Kohonen, Quim. Nova, Vol. 31, No. 5, 1141-1144, 2008. [4] Zuppan, J. and Gasteiger, J., Neural Networks for Chemists, VCH, 1st ed., 1993, New York. [5] Zuppan, J. and Gasteiger, J., Anal. Chim. Acta, 248: 1, 1991. [6] Barthus, R. C., Mazo, L. H., Poppi, R. J., Aplicao de Mtodos de Calibrao Multivariada para a Determinao Simultnea de Riboflavina (VB2), Tiamina (VB1), Piridoxina (VB6) e Nicotinamida (VPP), Qumica Nova, Vol. 30, N7, 1638-1643, 2007. [7] Borsato, D., Moreira, I., Nobrega, M. M., Moreira, M. B., Dias, G.H., Aplicao de Redes Neurais Artificiais na Identificao de Gasolinas Adulteradas Comercializadas na Regio de Londrina Paran, Qumica Nova, Vol. 32, N9, 2328-2332, 2009. [8] Braga, A. P.; Carvalho, A. C. P. L. F.; Ludermir, T. B.; Redes Neurais Artifciais: Teoria e Aplicaes, 1 ed., LTC: Rio de Janeiro, 2000.

80 60 40 20 0

I / A

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1,8

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E / V vs Ag/AgCl

[9] Pereira, A.M., Estudo AB-Initio e DFT das Nitrosaminas, Joo Pessoa Paraba, Maro, 2008. [10] Filho, P.J.S., Zanin, K.D., Caramo, E.B., Garcia, R.C., Rios, A., Valcrcel, M., Pr-Concentrao de Nitrosaminas a partir de Amostras Aquosas por Extrao em Fase Slida e Cromatografia Capilar Eletrocintica Micelar, Qumica Nova vol.26 no. 2 So Paulo, 2003. [11] Britto, A.V., Cncer de Estmago, Cad. Sade Pblica, Rio de Janeiro, 13(Supl. 1): 7-13, 1997. [12] Silva, D.R.C., Redes Neurais Artificiais no Ambiente de Redes Industriais Foundation Fieldbus Usando Blocos Padres, UFRN, Natal, 2005. [13] Cerqueira, E.O., Andrade, J.C., Poppi, R.J., Mello, C., Redes Neurais e suas Aplicaes em Calibrao Multivariada, Qumica Nova, Vol. 24, No. 6, 864-873, 2001. [14] MAFF (Ministry of Agriculture, Fisheries and Food, Great Britain). Nitrate, nitrite and N-nitroso compounds in food: Second Report. Food Surveillance Paper N32, 1992. [15] Douglass, M.L.; Kabacoff, B.L.; Anderson, G.A. and Cheng, M.C.; J. Soc. Cosmet. Chem., v. 29, p. 581, 1978.

Figure 1: Square wave voltammograms for the mixture of Nnitrosamines in the concentration of 11.7 10-5 mol L-1 and obtained individually for each N-nitrosamines (f = 100 s-1, a = 50 mV, Es = 2 mV, Na2HPO4 0.1 mol L-1 , pH 4.0). The variation of intensity peak current with the concentration is different for each studied nitrosamine, which generates a curve with sensitivity and values of limits of detection and quantification different. However, when you have a mixture of these nitrosamines in the same solution, it is not possible to separate the peaks using the voltammetric techniques. Thus, the use of artificial neural networks can be a viable alternative for the analytical separation of these compounds in a mixture.[9],[10],[11]. As output, the data that refers the quantification of the same compounds in a mixture will be presented, in other words, each compound has a different concentration, which must be determined in the mixture. The presentation of the estimated output is justified because it is a supervised learning ANN. The expectation is that the network can be capable to learn from the data related to the compounds separately and can identify and quantify them in the presented mixture. The result of this work will be shown in future articles.

[16] Gray, J.I. and Randall, C.J,. J. Food Protection, v. 42, n. 2, p. 168, 1979. [17] IFT - Institute of Food Technologists. Nitrite Safety Council. A survey of nitrosamines in sausage and dry-cured meat products. Food Technology, 34(7), 45, July 1980. [18] IFT- Institute of Food Technologists Scientific status summary - Nitrate, nitrite, and nitroso compounds in Foods Food Technol., v.41, n.4, p.127-134, 1987. [19] Reyes, F.G.R. and Scanlan, R.A. N-nitrosaminas: Formao e ocorrncia em alimentos. Boletim Soc. Bras. Cinc. Tecnol. Alim. (SBCTA), Campinas, 18(4), 299-309, 1984. [20] Hill, M.J. Nitrosamines, In: Shuker, D.E.G. The chemistry of N-nitrosation, 169p. 1988. [21] Walters, C.L.; Ssmith, P.L. and Reed, P.I. In: O'Neill, I.K.; Von Borstel, R.C.; Miller, C.T.; Long, J. and Bartsch, H., eds. Nnitroso Compounds: Occurrence, Biological Effects and Relevance to Human Cancer (IARC Scientific Publications No.57), Lyon, International Agency for Research on Cancer, pp. 113-119,