Um processo simples e de baixo custo foi proposto para a preparação de redes de nanossensores para determinação eletroquímica de hidrazina. As redes sensores foram confeccionadas sobre substratos de ouro obtidos de circuitos impressos de 8 a 20 terminais. O processo de obtenção dos substratos não demanda ferramenta especial e pode ser preparado por operador (a) sem experiência prévia em processos de microfabricação.
Os microdiscos de ouro preparados mostraram raio médio de 23,5 µm e espaçamento superior a 350 μm entre as unidades adjacentes. Para a preparação dos sensores, os CI contendo os microdiscos de ouro foram embutidos em plataformas cilíndricas ou planares que podem ser facilmente adaptadas para uso em células em batelada ou em soluções em fluxo. O uso microeletrodos de ouro polidos mostrou potencialidades para quantificação voltamétrica de N2H4 em concentração acima de 100 µmol L-1.
A modificação eletroquímica dos substratos de ouro com uso de uma dispersão de GO 1,0 mg mL e solução de Au (III) 0,30 mmol L-1 possibilitou a formação de um filme aderente de rGO recoberto com nanopartículas de Au com diâmetros que variaram de 37 a 60 nm. Arranjos deste nanossensores foram avaliados com técnicas voltamétricas de pulso na detecção de N2H4 em concentrações que variam de 20 a 140 µmol L-1. Com rede de sete nanossensores, o limite de detecção estimado foi de 93 nmol L-1 e o limite quantificação em 0,31 µmol L-1.
A combinação de um sistema de análise por injeção com detecção amperomérica de N2H4 sobre arranjos de 20 nanossensores de rGO e NPsAu permitiu alcançar limite de detecção de 76 nmol.L-1 e assegurar frequência analítica de 65 determinações/hora com injeção de amostra de 25 µL e vazão de do fluido transportador de 0,70 mL.min-1.
O sistema analítico apresentou excelente desempenho na determinação de baixas concentrações de N2H4 (inferior de 10 µmol L-1)em amostras de águas de abastecimento e de rejeitos líquidos de laboratórios.
REFERÊNCIAS BIBLIOGRÁFICAS
AMIN, H. M.; EL-KADY, M. F.; ATTA, N. F.; GALAL, A. Gold Nanoparticles Decorated Graphene as a High-Performance Sensor for Determination of Trace Hydrazine Levels in Water. Electroanalysis, v. 30, p. 1757-1766, 2018.
ALAM, S.N.; SHARMA, N.; KUMAR, L. Synthesis of Graphene Oxide (GO) by Modified Hummers Method and Its Thermal Reduction to Obtain Reduced Graphene Oxide. Graphene, v. 6, p. 1-18, 2017.
ARRIGAN, D. W. M. Nanoelectrodes, nanoelectrode arrays and their applications. Analyst, v. 129, p. 1157-1165, 2004.
ATHAWALE, A. A.; SHAHRIARY, L. Graphene Oxide Synthesized by using Modified Hummers Approach. International Journal of Renewable Energy and Environmental Engineering, v. 02, n. 01, p. 58-63, 2014.
AZZOUZI, M.E.; AOUNITI, A.; TIGHADOUIN, S.; ELMSELLEM, H.; RADI, S.; HAMMOUTI, B.; ASSYRYM, A.E.; BENTISS, F.; ZARROUK, A. Some hydrazine derivates as corrosion inhibitors for mild steel in 1.0M HCl: Weight loss, electrochemical, SEM and theoretical studies. Journal of Molecular Liquids, v. 221, p. 633-641, 2016.
BERTOTTI, M. Sensores Eletroquímicos: Estudos Fundamentais e Aplicações Analíticas. Texto crítico para Livre Docência, Universidade de São Paulo, 110 páginas, 2000.
BRETT, C. M. A.; BRETT. A. M. O. ELECTROCHEMISTRY – Principles, Methods, and Applications. OXFORD UNIVERSITY PRESS, 1a. Edição, p.129-133, 1993.
CAO, J.; HE, P.; MOHAMMED, M. A.; ZHAO, X.; YOUNG, R. J.; DERBY, B.; KINLOCH, I.A.; DRYFE, R. A. W. Two-Step Electrochemical Intercalation and Oxidation of Graphite for the Mass Production of Graphene Oxide. Journal of American Chemical Society, v. 139, p. 17446-17456, 2017.
CHEN, J.; YAO, B.; LI, C.; SHI, G. An improved Hummers method for eco-friendly synthesis of graphene oxide. Carbon, v. 64, 225-229, 2013.
CHEN, L.; XIE, H.; LI, J. A sensitive hydrazine electrochemical sensor based on electrodeposition of gold nanoparticles on choline film modified glassy carbon electrodes. Sensors and Actuators B: Chemical, v. 153, n. 01, p. 239-245, 2011.
CHEN, L.; TANG, Y.; WANG, K.; LIU, C.; LUO, S. Direct electrodeposition of reduced graphene oxide on glassy carbon electrode and its electrochemical application. Electrochemistry Communications, v. 13, p. 133-137, 2011.
CHEN, Y.; YEH, C. A new approach for the formation of alloy nanoparticles: laser synthesis of gold-silver alloy from gold-silver colloidal mixtures. Chemical Communications, v. 02, p.371-372, 2001.
COMPTON, R. G; O’MAHONY, A.; HUANG, X. Microelectrode arrays for electrochemistry: approaches to Fabrication. Small, v. 05, n. 07, 776-788, 2009.
COMPTON, R. G.; HENSTRIGDE, M. C. Mass Transport to Micro – and Nanoelectrodes and their arrays: a review. The Chemical Record, v. 12, 63-81, 2012.
COLLART, E.; SHULKA, A.; GÉLÉBART, F.; MORAND, M.; MALGRANDE, C.; BARDOU, N.; MADOURI, A.; PELOUARD, J. L. Spherically bent analyzers for resonant inelastic X-ray scattering with intrinsic resolution below 200 meV. Journal of Synchrotron Radiation, v. 12, p. 473–478, 2005.
COLEMAN, J. N. Liquid-Phase Exfoliation of Nanotubes and Graphene. Advanced Functional Materials, v. 19, n. 23, p.3680-3695, 2009.
CORAUX, J.; N’DIAYE, A. T.; BUSSE, C.; MICHELY, T. Structural coherency of graphene on Ir (111). Nano Letters, v. 8, n. 2, p. 565-570, 2008.
CUI, H.; LI, N.; DUAN, C., HE, Y.; LIU, B. Platinum nanoparticle-catalyzed lucigenin- hydrazine chemiluminescence. Journal of Photochemistry and Photobiology A: Chemistry, v. 217, p.62-67, 2011.
DAHMAN, Y.; RADWAN, A.; Nesic, B. ISBISTER, J. Nanossensors, capítulo 4, p. 67-91, 2017. Disponível em: <https://www.oreilly.com/library/view/nanotechnology-and- functional/9780323524667/xhtml/chp004.xhtml>
DING, S.; YOU, E.; TIAN, Z.; MOSKOVITS, M. Electromagnetic theories of surface- enhanced Raman spectroscopy. Chemical Society Reviews, v. 46, p. 4042-4076, 2017. DOYEN, M.; BARTIK, K.; BRUYLANTS, G. UV-Vis and NMR study of the formation of gold nanoparticles by citrate reduction: observation of gold citrates aggregates. Journal of Colloid and Interface Science, v. 399, p. 1-5, 2013.
DUTTA, S.; RAY, C.; MALLICK, S.; SARKAR, S.; ROY, A.; PAL, T. Au@Pd core-shell nanoparticles-decorated reduced graphene oxide: a highly sensitive and selective platform for electrochemical detection of hydrazine. RSC Advances, v. 5, p. 51690-51700, 2015.
FERRARI, A. C. Raman spectroscopy of graphene and grafite: Disorder, electron-phonon coupling, doping and nonadiabatic effects. Solid State Communications, v. 143, n. 1-2, p. 47- 57, 2007.
FOGUEL, M.V. ULIANA, C.V.; TOMAZ, P. R. U.; MARQUES, O. P. R. B.; YAMANAKA, H.; FERREIRA, P. A. A. Avaliação da limpeza de CDtrodo construídos a partir de CD de ouro gravável/fita adesiva de galvanoplastia. Eclética Química, v. 34, n. 02, 2009.
GU, X.; CAMDEN, J. P. Surface-Enhanced Raman Spectroscopy-Based Approach for Ultrasensitive ans Selective Detection of Hydrazine. Analytical Chemistry, v. 87, n. 13, p. 6460-6464, 2015.
HUMMERS, W. S. Jr.; OFFEMAN, R. E. Preparation of Graphitic Oxide. Journal of the American Chemical Society, v. 80, n. 06, p. 1339, 1957.
HAISS, W.; THANH, N. T. K.; AVEYARD, J.; FERNIG, D. G. Determination of size and concentration of gold nanoparticles from UV-Vis Spectra. Analytical Chemistry, v. 79, p. 4215-4221, 2007.
HEIDARI, R.; BABAEI, H.; EGHBAL, M. A. Cytoprotective effects of taurine against toxicity induced by isoniazid and hydrazine in isolated rat hepatocytes. Archives of Industrial Hygiene and Toxicology, v. 64, 201-210, 2013.
HIDAYAH, N. M. S.; LIU, W.; LAI, C.; NORIMAN, N. Z.; KHE, C.; HASHIM, U.; LEE, C. Comparison on graphite, graphene oxide and reduces graphene oxide: synthesis and
characterization. AIP Conference Proceedings, v. 1892, 150002, 2017. Disponível em: <https://aip.scitation.org/doi/pdf/10.1063/1.5005764?class=pdf>
HU, C.; SUN, W.; CAO, J.; GAO, P. WANG, J.; FAN, J.; SONG, F.; SUN, S.; PENG, X. A ratiometric near-infrared fluorescent probe for hydrazine and its in vivo applications. Organic Letters, v. 15, n. 15, p. 4022-4025, 2013.
ISENBERG, S. L.; CARTER, M. D.; CROW, B. S.; GRAHAM, L. A.; JOHNSON, D.; BENINATO, N.; STELLE, K.; THOMAS, J. D.; JOHNSON, R. C. Quantification of hydrazine in human urine by HPLC-MS/MS. Journal of Analytical Toxicology, v. 40, n. 04, p. 248-254, 2016.
JIA, F.; YU, C.; AI, Z.; ZHANG, L. Fabrication of Nanoporous Gold Microelectrodes with Ultrahigh Surface Area and Electrochemical Activity. Chemistry of Materials, v. 19, p. 3648- 3653, 2007.
KANNAN, P. K.; MOSHKALEV, S. A.; ROUT, C.S. Electrochemical sensing of hydrazine using multilayer graphene nanobelts. RSC Advances, v. 06, p. 11329-11334, 2016.
KHAN, I.; KHAN, I.; SAEED, K. Nanoparticles: Properties, applications and toxicities.
Arabian Journal of Chemistry, In Press, 2017. DOI:
<https://doi.org/10.1016/j.arabjc.2017.05.011>. Disponível em: < https://www.sciencedirect.com/science/article/pii/S1878535217300990>.
KING, A. A. K., DAVIES, B.R., NOORBEHEST, N.; NEWMAN, P.; CHURCH, T. L.; HARRIS, A. T.; RAZAL, J. M.; MINETT, A. I. A new Raman metric characterisation of graphene oxide and its derivates. Scientific Reports, n.6, p. 19491-19497, 2016.
KOSYAKOV, D. S.; POKOVSKOI, I. I.; UL’YANOVSKII, N. V.; KOZHENIKOV, A. Y. Direct determination of hydrazine, methylhydrazine, and 1,1-dimethylhydrazine by zwitterionic hydrophilic interaction liquid chromatography with amperometric detection. International Journal of Environmental Analytical Chemistry, v. 97, n. 04, p. 313-319, 2017.
LI, D.; MÜLLER, M. B.; GILJE, S.; KANER, R. B.; WALLACE, G. G. Processable aqueous dispersions of graphene nanosheets. Nature Nanotechnology, v. 03, p. 101, 2008.
LOBO, A. L.; MARTIN, A. A.; ANTUNES, E. F.; TRAVA-AIROLDI, V. J.; CORAT, E. J. Caracterização de materiais carbonosos por espectroscopia Raman. Revista Brasileira de Aplicações de Vácuo. V. 24, n. 2, p. 98-103, 2005.
LIU, Y.; QIU, Z.; WAN, Q.; WANG, Z.; WU, K,; YANG, N. High-performance hydrazine sensor based on graphene nano platelets supports metal nanoparticles. Electroanalysis, v. 28, p. 126-132, 2016.
LU, X.; WANG, P.; WANG, X.; GUO, Y. Electrodeposition of gold nanoparticles on electrochemically reduced graphene oxide for sensitive hydrazine electrochemical determination in agriculture wastewater. International Journal of Electrochemical Science, v. 11, p. 5279-5288, 2016.
MANIKANDAN, V. S.; LIU, Z.; CHEN, A. Simultaneous detection of hydrazine, sulfite and nitrite based on a nanoporous gold microelectrode. Journal of Electroanalytical Chemistry, v. 819, p. 524-534, 2018.
MART ÍNEZ, J. C.; CHEQUER, N. A.; GONZÁLEZ, J. L.; CORDOVA, T. Alternative methodology for gold nanoparticles diameter characterization using PCA technique and UV- VIS spectrophotometry. Nanoscience and nanotechnology, v. 2, n. 06, p. 184-189, 2012. METTERS, J. P. BANKS, C. E. Nanoparticle modified electrodes for trace metal ion analysis. In: HONEYCHURCH, K.C. Nanossensors for Chemical and Biological Applications:
Sensing with Nanotubes, Nanowires and Nanoparticles. Woodhead Publishing, 2014, p. 59- 79. Disponível em: <https://doi.org/10.1533/9780857096722.1.54 >
NG, A. M. H.; KENRY, LIM, C. T.; LOW, H. L.; LOH, K. P. Highly sensitive reduced graphene oxide microelectrode array sensor. Biosensors and bioelectronics, v. 65, p. 265-273, 2015.
NOVOSELOV, K. S.; GEIM, A. K., MOROZOV, S. V.; JIANG, D.; ZHANG, Y.; DUBONOS, S. V., GRIGORIEVA, I. V.; FIRSOV, A. A. Electric fields effect in atomically thin carbon films, Science, v. 306, p. 666-669, 2004.
OLIVEIRA, P. H. R; OLIVEIRA, V. G,; TOLENTINO, N. M. C. Hidrazina (CAS 302-01-2). Revista Virtual de Química, v. 07, n. 4, p.1570-1578, 2015.
PATIL, K. C.; RATTAN, T. M. Inorganic Hydrazine Derivates: Synthesis, Properties and Applications. Editora John Wiley & Sons Ltd, 284 páginas, 2014.
PACHECO, B. D.; VALÉRIO, J.; ANGNES, L.; PEDROTTI, J. J. Fast batch injection analysis of H2O2 using an array of Pt-modified gold microelectrodes obtained from split electronic chips. Analytica Chimica Acta, v. 24, p. 53-58, 2011.
PEDROTTI, J.J.; GUTZ, I. G. R.; ANGNES, L.; AUGELI. M.A.; NASCIMENTO, V. B. Arrays of Gold Microelectrodes Made from Split Integrated Circuit Chips. Electroanalysis , v. 09, n. 04, p. 335-339, 1996.
PRIVETT, B. J.; SHIN, J. H.; SCHOENFISCH, M.H. Electrochemical Sensors. Analytical Chemistry, v. 82, n. 12, 2010.
PUMERA, M. Electrochemistry of graphene, graphene oxide and others graphenoids: Review. Electrochemistry Communications, v. 36, p. 14-18, 2013.
RAJESHWAR, K.; IBANEZ, J. Environmental Electrochemisty: Fundamentals and Applications in Pollution Abatement, Academic Press: San Diego, 790 páginas, 1997.
Disponível em:
<https://www.researchgate.net/publication/284100018_Environmental_Electrochemistry_Fun damentals_and_Applications_in_Pollution_Abatement>
REDDY, K. L.; VENKATESWARULU, M.; SHANKAR, K. R.; GHOSH, S. D.; KRISHNAN, V. D. Up conversion Luminescent Material‐Based Inorganic‐Organic Hybrid Sensing System for the Selective Detection of Hydrazine in Environmental Samples. Chemistry Select v. 03, n. 06, p. 1793-1800, 2018.
ROBERTS, M. W.; CLEMONS, C.B., WILBER, J. P.; YOUNG, G. W.; BULDUM, A.; QUINN, D. D. Continuum Plate Theory and Atomistic Modelling to Find the Flexural Rigidity of a Graphene Sheet Interacting with a Substrate. Journal of Nanotechnology, vol. 2012, p. 1- 8, 2010.
SANTOS, J. F. L; SANTOS, M. J. L.; THESING, A.; TAVARES, F.; GRIEP, J.; RODRIGUES, M. R. F. Ressonância de Plasmon de Superfície localizado e aplicação em biossensores e células. Química Nova, v. 39, n. 09, p. 1098-1111, 2016.
SAWANGPHURUK, M.; LUANWUTHI, S.; SRIMUK, P, KRITTAYAVATHANANON, A. Palladium Nanoparticles Decorated on Reduced Graphene Oxide Rotating Disk Electrodes toward Ultrasensitive Hydrazine Detection: Effects of Particle Size and Hydrodynamic Diffusion. Analytical Chemistry, v. 86, n. 24, p. 12272-12278, 2014.
SINHA, B. K.; MASON, R. P. Biotransformation of hydrazine derivates in the mechanism of toxicity. Journal of drug metabolism and toxicology, v. 05, n. 03, 168, 2014.
SHAO, Y.; WANG, J.; ENGELHARD, M.; WANG, C.; LIN, Y. Facile and controllable electrochemical reduction of graphene oxide and its applications. Journal
SHIN, H.; PARK, J.; OH, J. Sensitive determination of hydrazine in water by gas chromatography-mass spectrometry after derivatization with ortho-phthaldehyde. Analytica Chimica Acta, v. 769, p.79-83, 2013.
SILVA, E. C.; PAOLA, M. V. R. V.; MATOS, J. R. Análise térmica aplicada à cosmetologia. Revista Brasileira de Ciências Farmacêuticas, v. 43, n. 3, p. 347-356, 2007.
STRADIOTTO, N.R.; YAMANAKA, H.; ZANONI, M. V. Electrochemical Sensors: A Powerful Tool in Analytical Chemistry. Journal of Brazilian Chemical Society, v. 14, n. 2, p. 159-173, 2003.
SUN, M.; GUO, J.; YANG, Q.; XIAO, N.; LI, Y. A new and colorimetric sensor for hydrazine and its application in biological systems. Journal of Materials Chemistry B, v. 02, p. 1846- 1851, 2014.
TANG, B.; GOUXIN, H.; GAO, H. Raman Spectroscopic Characterization of Graphene. Applied Spectroscopy Reviews, v. 45, n. 5, p. 369-407, 2010.
TANG, Y.; KAO, C.; CHEN, P. Electrochemical detection of hydrazine using a highly sensitive nanoporous gold electrode. Analytica Chimica Acta, v. 711, p. 32-39, 2012.
TURKEVICH, J.; STEVENSON, P. C.; HILLIER, J. A study of the nucleation and growth processes in the synthesis of colloidal gold. Discussions of the Faraday Society, v. 11, p.55- 75, 1951.
THOMPSON, David. Michael Faraday’s recognition of ruby gold: the birth of modern nanotechology. Gold Bulletin, v. 40, n. 4, p. 267-269, 2007.
VAARI, J. L.; HAUTOJÄRVI, P. The adsorption and decomposition of acetylene on clean and K-covered Co (0001). Catalysis Letters, v. 44, n. 1, p. 43-49, 1997.
VILAR, E. O.; SEGUNDO VIEIRA, J. E. D. Grafeno: Uma revisão sobre propriedades, mecanismos de produção e potenciais aplicações em sistemas energéticos. Revista Eletrônica de Materiais e Processos, v. 11, n. 2, 2016.
WU, X.; QU, N., ZENG, Y. ZHU, D. Modelling of the liquid membrane electrochemical etching of a nano-tip. International Journal of Advanced Manufacturing Technology, v. 69, n. 1-4, p. 723-729, 2013.
YUAN, Min; MITZI, D. B. Solvent properties of hydrazine in the preparation of metal chalcogenide bulk materials and films. Dalton Transactions, v. 31, 6078-6088, 2009.
YANG, C.; DENNO, M. E; VENTON, B.J. Recents trends in carbon nanomaterial-based electrochemical sensors for biomolecules: a review. Analytica Chimica Acta, v. 887, p.017- 37, 2015.
ZELNICK, S. D.; MATTIE, D. R.; STEPANIAK, P. C. Occupational exposure to Hydrazine: Treatment of Acute Central Nervous System Toxicity. Aviation, Space and Environmental Medicine, v. 74, n. 12, p. 1285-1291, 2003.
ZHANG, H.; HUANG, J.; HOU, H.; YOU, T. Electrochemical detection of hydrazine based on electrospun palladium nanoparticles/carbon nanofibers. Electroanalysis, v. 21, n. 16, 1869- 1874, 2009.
ZHANG, J.; NING, L.; LIU, J.; WANG, J.; YU, B.; LIU, X.; YAO, X.; ZHANG, Z.; ZHANG, H. Naked-Eye and Near-Infrared Fluorescence Probe for Hydrazine and Its Application in In Vitro and In Vivo Bioimaging. Analytical Chemistry, v. 87, n. 17, p. 9101-9107, 2015. ZHANG, Y.; XU, S.; QUIAN, Y. YANG, X.; LI, Y. Preparation, electrochemical responses and sensing application of Au disk nanoelectrodes down to 5 nm. RSC Advances, v. 05, p. 77248-77254, 2015.
ZHAO, S.; WANG, L.; WANG, T.; HAN, Q.; XU, S. A high-performance hydrazine electrochemical sensor based on gold nanoparticles/single-wallet carbon nanohorns composite film. Applied Surface Science, v. 369, p. 36-42, 2016.