Biomateriais + Nanotecnologia perspectivas e desafios para aplicações práticas

Biomateriais + Nanotecnologia perspectivas e desafios para aplicações práticas Caue Ribeiro Senior Researcher Coordinator Research Network in Nanotechnology applied to Agribusiness Agronano Network

https://www.embrapa.br/nano Coordination: Embrapa Instrumentação + 150 researchers/ 50 institutions Research: Sensors and biosensors Edible films and smart packaging Bionanocomposites Novel applications for synthetic materials in agri s Impact assessment in nano s + agri s Technology transference in nano s + agri s

WoS report of publications (nanotechnology and related terms) in Embrapa

Technical Workshops 49 resumos extendidos 87 resumos extendidos 206 resumos* 166 resumos extendidos 192 resumos extendidos 156 resumos extendidos * Joint organization - FAO Embrapa https://www.embrapa.br/nano

Perspectivas e desafios Uso/valoração de resíduos Novos usos para biomateriais estabelecidos Ciclo de vida (descarte amigável)? Performance em comparação a materiais convencionais? Capacidade de produção em grande escala

Filmes biodegradáveis por laminação Aplicação em Tecnologia de Alimentos

Carriots (Daucus carota L.) (Losses of 40%) Peachs (Prunus persica L.) Losses occurs during processing of most fruits

NEW APPROACH FOR BIOPOLYMERS PROCESSING Dr. Tara McHugh, leading scientist in fruit puree edible films for food packaging (WRRC-ARS/USDA).

Polymer Summary of Mechanical Properties of polysaccharide films made by continuous casting* Elastic Modulus (MPa) Tensile Strength (MPa) Elongation at Break (%) Pectin 3000-4000 20-100 2-4 Chitosan 1900-3000 20-50 2-18 HPMC 1500-2000 30 40 4-10 CMC 1000-1200 6 17 6-20 Starch 1000-1200 15-20 2-5 LLDPE** 130-520 9 20 100-1200 LHDPE** 60-290 10-60 N.D. Data were collected following the ASTM D 882 protocol, cross-head speed of 10 mm min - 1 *, load cell of 10 Kgf. A. Prasad, Polymer Data Handbook, J. E. Mark, Ed. Oxford University Press, Oxford, 1999, 524.

Wood Fibers Nanocrystal Modulus of elasticity 10 GPa 40-70 GPa 130-250 GPa Tensile strength 100 MPa 130-250 MPa 800-10.000 MPa Wang, Forestry, Wildlife & Fisheries University of Tennessee, FWF Seminar September 24, 2007

Cellulose nanowhiskers from coconut fiber SEM / TEM cristalite nanowhiskers coir - T1 (90 min) bleached coconut fiber nanowhiskers from coconut different shape lengh: 100 500 nm diameter: 4 6 nm aspect ratio ~ 28 nanowhiskers cotton - T1 (90 min) nanowhiskers coir - T2 (120 min)

Nanocomposite Edible Films from Mango Puree Reinforced with Cellulose Nanofibers AZEREDO, H. M. C.; MATTOSO, L.H.C. ; WOOD, D. ; WILLIAMS, T.G. ; AVENA-BUSTILLOS, R.J. ; McHUGH, T.H. Journal of Food Science, v. 74, p. N31-N35, 2009.

HPMC films incorporated with cellulose fiber using microfluidizer technique: (a) Zero passes; (b) after seven passes; (c) after 10 passes; and (d) after 20 passes through the microfluidizer. * M. R. de Moura, R. J. Avena-Bustillos, T. H. McHugh, D. F. Wood, C. G. Otoni, L. H. C. Mattoso. Journal of Food Engineering, 104, 154 (2011).

Effect of cellulose fibers (CF1) reduced in sizes after successive passes in a Microfluidizer on thickness, elastic modulus, and elongation of HPMC films. Particle size of hydroxylpropyl methylcellulose/cellulose fiber filmforming solutions affected by increasing number of passes in a Microfluidizer. * M. R. de Moura, R. J. Avena-Bustillos, T. H. McHugh, D. F. Wood, C. G. Otoni, L. H. C. Mattoso. Journal of Food Engineering, 104, 154 (2011).

Reinforcement and novel properties: Nanoparticles of biopolymers (chitosan, pectin, starch, nanocellulose) Applications: packaging, antimicrobial, strength reinforcement, controlled release

Chitosan-NP synthesis Ionotropic gelation Chitosan TPP Solution + H 3 N + H 3 N NH 3 + NH 3 + NH 3 tripolyphosphate + CSNP Stirring + H 3 N NH 3 + QS Solution CSNP + H 3 Chitosan N + H 3 N + H 3 N NH 3 + NH 3 + Chitosan

Tensile Strength (MPa) Chitosan-PMAA NP/HPMC films 70 CS-NP/ 110 nm 65 60 CS-NP/ 80 nm CS-NP/ 60 nm 55 50 45 40 35 30 25 only HPMC only CS solution 0 5 10 15 20 % of chitosan in HPMC Moura et al. Journal of Food Engineering, v. 92, p. 448-453, 2009 Moura et al. Journal of Colloid and Interface Science, v. 321, p. 477-483, 2008 HPMC film Tensile Strength = ± 29 MPa

Pectin/papaya puree/cinnamaldehyde nanoemulsion edible films Inhibition zones. Typical inhibition zones created around (A) HP, (B) HPP, (C) HPP7, (D) HPP12, and (E) HPP16 films against Salmonella enterica. OTONI, C.G.; MOURA, M.R. ; AOUADA, F.A. ; CAMILLOTO, G.P. ; CRUZ, R.S. ; LOREVICE, M. V. ; SOARES, N.F.F. ; MATTOSO, L.H.C. Food Hydrocolloids, v. 41, p. 188-194, 2014.

Biomateriais para liberação lenta / controlada Aplicação em Insumos (fertilizantes /defensivos/ veterinária)

Quantidade liberada Conceitos Liberação comum Liberação lenta Faixa de interesse Liberação controlada tempo

Coberturas poliméricas biodegradáveis: PU a partir de óleos vegetais Bortoletto-Santos, Ribeiro e Polito, J. Appl. Polym. Sci., 2016

Shape matters: Sustainable release of progesterone nanofibers (electrospinning / solution blow spinning) input Biodegradable matrix Journal of Applied Polymer Science, v. 127, p. 4463-4469, 2013 Journal of Nanoscience and Nanotechnology, v. 10, p. 5144-5152, 2010

Blendas TPS/PEC com HA para Liberação controlada de fosfato em meio aquoso Solubilidade (ppm) 24 22 20 18 16 14 12 10 8 6 4 2 0 0h 48h 96h 0 20 40 60 80 100 120 140 160 180 200 220 240 Tempo (h) a) 100PEC:40G, b) 100TPS:40G, c) 50TPS:50PEC:40G e d) 25TPS:75PEC:40G Patente requerida Embrapa / UFSCar (2014)

observada entre os perfis de liberação da ametrina pode ser explicada pelas Nanocompósitos Amido / MMt / Ametrina características estruturais dos nanomateriais. 100 80 (a) Ametrina St/Amet 1:1 110 100 90 80 (b) 1 a fase 2 a fase St/Amet 1:1 Ametrina 1:1 Amet % Liberada 60 40 20 0 1:4 Amet 1:2Amet 1:1 Amet % Liberada 70 60 50 40 30 20 10 0 1:4 Amet 1:2 Amet 0 50 100 150 200 250 300 350 Tempo/min 0 20 40 60 80 100 120 140 160 Tempo/horas FIGURA 4.16 - Taxa de liberação de ametrina em função do tempo para ametrina puro e cada um dos compósitos em ph 7 e à temperatura ambiente: (a) ampliação da primeira fase e (b) curva completa de liberação. Journal of Applied Polymer Science, v. 131, p. 41188-1-9, 2014 Para o St/Amet 1:1 pode-se verificar um comportamento mais

Nanocompósitos Amido / MMt / Ametrina Reactive & Functional Polymers, v. 93, p. 156-162, 2015

Nanocompósito para solubilização de fosfatos minerais Giroto, Fidelis and Ribeiro. RSC Advances, v. 5, p. 104179-104186, 2015