biomateriais + nanotecnologia perspectivas e desafios para
TRANSCRIPT
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Biomateriais + Nanotecnologia – perspectivas e desafios para
aplicações práticas Caue Ribeiro
Senior Researcher
Coordinator – Research Network in Nanotechnology applied to
Agribusiness – Agronano Network
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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
https://www.embrapa.br/nano
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WoS report of publications (nanotechnology and related terms) in Embrapa
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Technical Workshops
* Joint organization - FAO – Embrapa
49 resumos
extendidos
87 resumos
extendidos 206
resumos*
166 resumos
extendidos 192 resumos
extendidos
156 resumos
extendidos
https://www.embrapa.br/nano
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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
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Filmes biodegradáveis por laminação
Aplicação em Tecnologia de Alimentos
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Peachs (Prunus persica L.)
Losses occurs during
processing of most fruits
Carriots (Daucus carota L.)
(Losses of 40%)
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NEW APPROACH FOR BIOPOLYMERS PROCESSING
Dr. Tara McHugh, leading scientist in fruit puree edible films for
food packaging (WRRC-ARS/USDA).
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Summary of Mechanical Properties of polysaccharide films made by continuous casting*
Polymer 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.
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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
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cristalite
Cellulose nanowhiskers from coconut fiber
SEM / TEM
nanowhiskers
coir - T2 (120 min)
nanowhiskers
coir - T1 (90 min)
nanowhiskers
cotton - T1 (90 min)
nanowhiskers from coconut
• different shape
• lengh: 100 – 500 nm
• diameter: 4 – 6 nm
• aspect ratio ~ 28
bleached coconut fiber
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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.
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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).
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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 film-forming 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).
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Reinforcement and novel properties: Nanoparticles of biopolymers (chitosan, pectin, starch, nanocellulose)
Applications: packaging, antimicrobial, strength reinforcement, controlled release
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Chitosan-NP synthesis
TPP Solution
QS Solution
Stirring
CSNP
Ionotropic gelation
Chitosan
tripolyphosphate
Chitosan Chitosan
NH3+
NH3+
NH3+
NH3+
NH3+
NH3+
+H3
N
+H3
N
+H3
N
+H3
N
+H3
N +H3
N
CSNP
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HPMC film
Tensile Strength = ± 29 MPa
0 5 10 15 20
25
30
35
40
45
50
55
60
65
70
CS-NP/ 60 nm CS-NP/ 80 nm
only CS solution
only HPMC
Te
ns
ile
Str
en
gth
(M
Pa
)
% of chitosan in HPMC
CS-NP/ 110 nm
Chitosan-PMAA NP/HPMC films
Moura et al. Journal of Colloid and Interface Science, v. 321, p. 477-483, 2008
Moura et al. Journal of Food Engineering, v. 92, p. 448-453, 2009
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Inhibition zones. Typical inhibition zones created around (A) HP, (B) HPP, (C) HPP7, (D) HPP12, and (E) HPP16 films against Salmonella enterica.
Pectin/papaya puree/cinnamaldehyde
nanoemulsion edible films
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.
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Biomateriais para liberação lenta / controlada
Aplicação em Insumos (fertilizantes /defensivos/ veterinária)
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Conceitos
Liberação comum Liberação lenta
Liberação controlada
tempo
Qu
anti
dad
e lib
era
da
Faixa de interesse
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Coberturas poliméricas biodegradáveis: PU a partir de óleos vegetais
Bortoletto-Santos, Ribeiro e Polito, J. Appl. Polym. Sci., 2016
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Shape matters: Sustainable release of progesterone nanofibers (electrospinning / solution blow spinning)
Journal of Applied Polymer Science, v. 127, p. 4463-4469, 2013 Journal of Nanoscience and Nanotechnology, v. 10, p. 5144-5152, 2010
Biodegradable matrix
input
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a) 100PEC:40G, b) 100TPS:40G, c) 50TPS:50PEC:40G e d) 25TPS:75PEC:40G
Blendas TPS/PEC com HA para Liberação controlada de fosfato em meio aquoso
0 20 40 60 80 100 120 140 160 180 200 220 240
0
2
4
6
8
10
12
14
16
18
20
22
24
So
lub
ilid
ad
e (
pp
m)
Tempo (h)
0h
48h
96h
Patente requerida Embrapa / UFSCar (2014)
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Nanocompósitos Amido / MMt / Ametrina
45
significativamente para 17%, 19% e 29%, respectivamente. A diferença
observada entre os perfis de liberação da ametrina pode ser explicada pelas
características estruturais dos nanomateriais.
0 50 100 150 200 250 300 350
0
20
40
60
80
100
St/Amet 1:1
1:2Amet
1:4 Amet
Ametrina
1:1 Amet
% L
ibera
da
Tempo/min 0 20 40 60 80 100 120 140 160
0
10
20
30
40
50
60
70
80
90
100
110
St/Amet 1:1
2a fase
% L
ibe
rad
a
Tempo/horas
1:2 Amet 1:4 Amet
Ametrina
1:1 Amet
1a fase
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.
Para o St/Amet 1:1 pode-se verificar um comportamento mais
próximo ao da ametrina pura: em apenas 20 minutos os grânulos de amido
absorvem água o suficiente para começar a liberação da ametrina, mostrando
que o uso apenas de amido como encapsulante não retarda a liberação do
herbicida.
Nota-se que a cinética de liberação para os nanocompósitos (1:1,
1:2 e 1:4 Amet) pode ser dividida em duas etapas. A primeira etapa é regida pela
difusão de água através dos grânulos de amido, onde estes tendem a inchar e a
relaxar os poros onde estariam presentes as moléculas de ametrina. Neste estágio
a concentração de amido é responsável pelo comportamento cinético da
liberação. Como pode ser observado na FIGURA 4.16a, os materiais que
apresentavam os maiores teores de amido foram os responsáveis pela menor
porcentagem de liberação. Com grânulos de amido já inchados, deu-se inicio a
(a) (b)
Journal of Applied Polymer Science, v. 131, p. 41188-1-9, 2014
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Nanocompósitos Amido / MMt / Ametrina
Reactive & Functional Polymers, v. 93, p. 156-162, 2015
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Nanocompósito para solubilização de fosfatos minerais
Giroto, Fidelis and Ribeiro. RSC Advances, v. 5, p. 104179-104186, 2015
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Further Reading….
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Acknowledgments
Dr. Luiz Mattoso (CNPDIA)
Dr. Jose Marconcini (CNPDIA)
Dra. Elaine Paris (CNPDIA)
Dr. Daniel Correa (CNPDIA)
Dr. Henriette Azeredo (CNPAT)
Dr. Alberto Bernardi (CPPSE)
Dr. Humberto Brandao (CNPGL)
Dra. Juliana Gern (CNPGL)
Prof. Dr. Wagner Polito (USP)
Prof. Dr. Ed Hoffmann (USP)
Dr. Tara McHugh (ARS/USDA)
Dr. Roberto Avena-Bustillos (ARS/USDA)
Prof. Dr. Marcia de Moura (UNESP)
Prof. Dr. Fauze Aouada (UNESP)
Prof. Dr. Francys Moreira (UFSCar)
Prof. Dr. Juliano Oliveira (UFLA)
Prof. Dr. Nilda Soares (UFV)
Prof. Dr. Geanny Camilloto (UEFS)
Dr. Gelton Guimaraes (PD)
Dra. Adriana de Campos (PD)
Amanda Giroto (DR)
Ricardo Bortoletto-Santos (DR)
Caio Gomide (DR)
Marcos Lorevice (DR)
Camila Sciena (DR)
Laís de Camargo (MS)
Renato Cruz (IC)
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Rede Agronano – Workshop 2014, Embrapa Gado de Leite
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Embrapa Instrumentação http://www.embrapa.br/instrumentacao
Rua XV de Novembro, 1452 São Carlos, SP - Brasil - CEP 13560-970
Fone: (16) 2107 2800 Fax: (16) 2107 2902
Rede Agronano
http://www.embrapa.br/nano [email protected]