LIGNOCELLVALUE-ADDED MATERIALS AND FUNCTIONAL STRUCTURES FROM LIGNOCELLULOSICS

Transcription

1 LIGNOCELLVALUE-ADDED MATERIALS AND FUNCTIONAL STRUCTURES FROM LIGNOCELLULOSICS Nanofibrillated cellulose soy protein based templates for gold nanoparticles production Steering group meeting Maria Soledad Peresin Improve mechanical properties of NFC films (i.e. elongation) Improve selective barrier properties Provide functional groups for potential applications 2 1

2 Cellulose nanocrystals Acid hydrolysis Natural cellulosic fiber Microcrystalline fibril bundles Adapted from Paakko, et al. Biomacromolecules (27) 8 p.1934 Nano-Microfibrillated cellulose 3 Study on the effect of the addition of soy proteins in NFC Proteins as additive (Reversed matrix!) Adsorption behavior of proteins on NFC Characterization (chemical, morphological, mechanical, ) Films manufacture and Applications 2

3 OIL INDUSTRY Body Care Products Candles Cleaners Crayons Diesel Additives Fabric Conditioner Flooring Hair Conditioners Hair Styling Aids Hand Cleaners Paint Removers Pens Polish Shampoos Solvents Tables/Furniture Waxes Composite Materials Glycinin (11S) Precipitate De-fated soy flour Supernatant ph adjusted to 6.4 Stored overnight at 4oC Centrifuge 2min 65 rpm Extracted 15 fold water ph 7.5 for 1 h. filtrate through mesh 12 centrifuge 3min, 9 rpm Sodium bisulfite Supernatant NaCl Dilute 2 fold water ph adjusted to 5 Centrifuge 3min 9 rpm Conglycinin (7S) Whey protein Procedure: Nagano et al. (Journal of Agricultural and Food Chemistry 1992, 4 (6) 3

4 Glycinin (11S) and a Conglycinin (7S) Size: 1 x 1 x 7 A Mw: 32, 35, Radius of gyration: 44 A ~ 8-9% of the total amount of proteins in soy beans Globulins Precipitation ph ~ subunits: 6 acidic subunits (4-5%); Mw: 37, 4, 6 basic units (5-6%); Mw: 19,9 2, Random combination of 3 subunits a Mw: 57, 76, a = Mw: 57, 83, = 42, 53, Badley et al. (Biochimica et Biophysica ACTA (BBA) Protein structure 1975, 412 (2) Characteristics and amino acid composition of the globulin soy proteins fractions Garcia et al. (Critical reviews in Food Science and Nutrition 1997, 37 (4) 4

5 + Homogenization by stirring Pre-curing NFC in water Glycinin ph = mm (in Buffer phosphate) Cooling of the suspension till room temperature while stirring Storage in refrigerator Films manufacture (Over pressure) Oven dried Hot press Protein content (% wt/wt) Roughness Rq (nm)

6 1% cellulose (ref) Blank NFC NFC + 7.5% 11S NFC + 5.% 11S NFC + 2.5% 11S Protein loaded samples are similar Elevated N amount Possible surface saturation Blank NFC NFC + 7.5% 11S NFC + 5.% 11S NFC + 2.5% 11S 15 2 Stress-Strain curves - strain curves (DMA) Stress (MPa) Stress (MPa) Blank NFC NFC + 2.5% 11S NFC + 5% 11S NFC + 7.5% 11S Strain (%) Blank NFCDMA force limit = 18 N NFC + 2.5% 11S (not enough to break the sample) Modulus Strain (GPa) (%) NFC + 5% 11S NFC + 7.5% 11S (Values reported in literature for YM for NFC: GPa) * Henriksson, M.et al. 28. Biomacromolecules 9,

7 Young s Modulus (MTS 4) Breaking strain (MTS 4) Young's Modulus (GPa) Breaking strain (%) Protein loading (%) Protein loading (wt %) (Values reported in literature for YM for NFC: GPa) * Henriksson, M.et al. 28. Biomacromolecules 9, Gold Nanoparticles production sodium citrate, (H[AuCl 4 ]), Au (solid NPs) (H[AuCl 4 ]), Soy protein, (glutamic acid) Au (solid NPs) Supported on NFC films (medicine, biology, bio-sensors) RCS Publishing - Ralph Sperling of Philipps-University Marburg, Germany 15 7

8 NFC - 25% Glycinin film 11 o C 14 o C AuCl 3 in water (stirring) Reduction to Ag NP Film composite (NFC - Au NPs) Glutamic acid as reducing agent for Au ions to Au NP T = 11 o C T = 14 o C 3 films superposed NFC-25% Glycinin 8

9 Weight (%) Absorbance Absorbance Weight (%) UV-Vis analysis T = 11 o C T = 14 o C NFC-Glycinin Untreated NFC Untreated NFC NFC-25% Glycinin.2.15 NFC-Glycinin Untreated NFC Untreated NFC NFC-25% Glycinin wavelenght (cm-1) wavelenght (cm-1) Surface Plasmon Resonance Au NP ~ 55 cm -1 Thermal Gravimetric Analysis Untreated NFC NFC-25% Glycinin Blank NFC Pure 11S soy protein fraction NFC film/25% 11S soy protein fraction 2 NFC-25% Glycinin NFC-25% Glycinin + Au NP NFC film/25% 11S soy protein fraction NFC/11S film with Au NPs Temperature ( o C) Temperature ( o C) 18% Au NP on the NFC Film 9

10 Weight (%) Weight (%) Thermal Gravimetric Analysis Control Au +3 Au NPs Untreated NFC NFC-25% Glycinin Blank NFC Pure 11S soy protein fraction NFC film/25% 11S soy protein fraction 2 NFC-25% Glycinin NFC-25% Glycinin + Au NP NFC film/25% 11S soy protein fraction NFC/11S film with Au NPs Temperature ( o C) Temperature ( o C) 18% Au NP on the NFC Film Fast and simple procedure for NFC film production Homogeneous, defect-free films with different loadings of glycinin from soy flour Immobilized functionalities of soy protein used as reducing agent for Au NPs production 1

11 Effect of Glycinin on the oxygen permeability of the NFC films at different relative humidity Bigger films, same technique >> Standard mechanical properties Evaluation of the particle size of the Au nanoparticles (TEM, AFM) Study of different soy protein fractions Carlos Salas, Orlando J. Rojas, Monika Österberg and Janne Lainne VTT (NFC) and Archer Daniel Michael (soy flour) samples Leena-Sisko Johansson, Abdelrahman Abdelgawad (Abdo), Ritva Kivella (Risu) Members of Colloids and Interfaces (NC State) and Forest Products Surface Chemistry (Aalto) Groups LignoCell (Tekes and Academy of Finland) 23 11

12 Thank you for your kind attention Maria Soledad Peresin