COST FP1205 March , Stockholm Glycidyl methacrylate modified nanocellulose from cotton waste and bacterial nanocellulose

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1 COST FP1205 March , Stockholm Glycidyl methacrylate modified nanocellulose from cotton waste and bacterial nanocellulose Bongio C., Bernardi A., Zarattini M., Cosentino C., Vismara E.

2 OUTLINE COST FP1205 March , Stockholm Scientific background Preparation of nanocelluloses COST FP1205 March , Stockholm Functionalization of nanocelluloses Potential applications Conclusions and further perspectives

3 SCIENTIFIC BACKGROUND From CELLULOSIC TEXTILES to NANOCELLULOSE

4 SCIENTIFIC BACKGROUND From cellulosic textiles Engineered glycidyl methacrylate (GMA) cotton fibers as adsorbents for the removal of aromatic pollutants from wastewaters GMA C-GMA Glycidyl form COST FP1205 March , Stockholm Epoxide hydrolysis Different affinities, in agreement with the polarity of cellulosic branches and tested aromatics C-GMAOH Glycerol form Vismara, E. Journal of Hazardous Materials, 170, , 2009.

5 SCIENTIFIC BACKGROUND From cellulosic textiles Engineered glycidyl methacrylate (GMA) cotton fibers as drug delivery systems. COST FP1205 March , Stockholm C-GMA promotes reversible adsorption of antibacterial drugs (AMX and VC). The adsorption capability is enhanced by the chemical trasformation into C-GMAOH Graziani, G.; Montanelli, A.; Melone,L.; Vismara, E.; Torri, G. EP B1 (2015)

6 SCIENTIFIC BACKGROUND From cellulosic textiles Engineered glycidyl methacrylate (GMA) cotton for developing drug delivery systems. Microbiological inhibition tests on S. Aureus by 1) cellulose, 2) C-GMA and 3) C-GMAOH impregnated with VC (Kirby Bauer method) Graziani, G.; Montanelli, A.; Melone, L.; Vismara, E.; Torri, G. EP B1 (2015)

7 SCIENTIFIC BACKGROUND From cellulosic textiles Engineered glycidyl methacrylate (GMA) cotton for developing drug delivery systems. The adsorption can be correlated to: favorable polar interaction molar substitution ratio (MS) of cellulosic materials molecular structure of tested antibiotics Effect of the MS on the adsorption of VC and AM onto C-GMAOH Graziani, G.; Montanelli, A.; Melone, L.; Vismara, E.; Torri, G. EP B1 (2015)

8 SCIENTIFIC BACKGROUND to nanocelluloses WHY NANOCELLULOSE? Modification or improvement of some properties preserving the overall nature of the original cellulose Very large surface-to-volume ratio Mechanical properties Chemical and morphological controllability Biocompatibility Biodegradability Toxicity ENVIRONMENTAL APPLICATIONS BIOMEDICAL APPLICATIONS Lin, N. European Polymer Journal, 59, , 2014 Jin, S.F. Advanced Materials Research, 662, , 2013

9 PREPARATION OF NANOCELLULOSES WHICH TYPE OF NANOCELLULOSES? DIFFERENT TYPES OF NANOCELLULOSE IN VIEW OF THEIR APPLICATION Hydrolyzed nanocellulose (HNC) From cotton waste Oxidized nanocellulose (ONC) Bacterial nanocellulose (BNC) From glucose units

10 PREPARATION OF NANOCELLULOSES HNC & ONC STARTING MATERIAL: industrial cotton waste from an Italian company (CFT) Cellulose CFT SEM images of CFT 13 C CP-MAS solid state NMR spectra

11 PREPARATION OF NANOCELLULOSES Hydrolyzed nanocellulose (HNC) Cr.I % CFT = 59% CFT H2SO4 64% 45 C, 6h HNC Integration gives the crystallinity index: Cr.I (%)= 68% SEM images of HNC 13 C CP-MAS solid state NMR of HNC FT-IR of HNC Siqueira, G.; Bras, J.; Dufresne, A. Biomacromolecules 10, , TEM images of HNC

12 PREPARATION OF NANOCELLULOSES Oxydized nanocellulose (ONC) CFT TEMPO, NaBr NaClO 10%, ph=10, T amb ONC CO signal SEM images of ONC CO signal 13 C CP-MAS FT-IR solid state of ONC NMR of ONC Okita, Y. Biomacromolecules 11, , 2010 TEM image of ONC

13 PREPARATION OF NANOCELLULOSES Bacterial nanocellulose (BNC) Gluconacetobacter Xylinus BNC TEM image of BNC FT-IR of BNC 13 C CP-MAS solid state NMR of BNC El-Saied, H. Bioresources, 3, , 2008

14 FUNCTIONALIZATION OF NANOCELLULOSES GMA GRAFTING HNC ONC BNC HNC-GMA ONC-GMA BNC-GMA 1. NANOCELLULOSE ACTIVATION: Fenton-type reaction (H 2 O 2 /Fe 2+ ) Very stable C-C bond 2. GMA GRAFTING Very stable glycidyl ester Epoxide group useful for further modifications 3. WASHING (removal of not-grafted GMA homopolymer)

15 FUNCTIONALIZATION OF NANOCELLULOSES CHARACTERIZATION OF GMA-CELLULOSES 13 C CP-MAS solid state NMR New detectable signals: methyl group, epoxide ring carbonyl ( 178 ppm). No presence of signals related to olefinic carbons ( ppm) Cellulose C-GMA absence of unreacted GMA.

16 FUNCTIONALIZATION OF NANOCELLULOSES CHARACTERIZATION OF GMA-CELLULOSES FT-IR analysis Cellulose C-GMA MS = molar substitution degree average number of GMA residue for glucose unit

17 FUNCTIONALIZATION OF NANOCELLULOSES HNC-GMA 13 C CP-MAS NMR of HNC-GMA SEM image of HNC-GMA MS = 1,9 VERY HIGH FT-IR of HNC-GMA

18 FUNCTIONALIZATION OF NANOCELLULOSES ONC-GMA 13 C CP-MAS NMR of ONC-GMA MS = 2,4 VERY HIGH FT-IR of ONC-GMA

19 FUNCTIONALIZATION OF NANOCELLULOSES BNC-GMA MS = 0,12 MS = 0,7 13 C CP-MAS NMR of BNC-GMA SEM image of BNC-GMA MS = 0,24

20 POTENTIAL APPLICATIONS Removal of aromatic pollutants Hydrolyzed nanocelluloses (HNCs) MS = 1,9 2-Naphtol (2N) Q (mg/g) HNC HNC-GMA time (h) Plot of Q vs. time for the adsorption of 2N on HNC and HNC-GMA Good capacity to adsorb 2N Q = milligrams of adsorbed molecules on grams of nanocellulose The presence of GMA strongly enhances this property

21 POTENTIAL APPLICATIONS Removal of aromatic pollutants Oxydized nanocelluloses (ONCs) 2-Naphtol (2N) Q (mg/g) 0,2 0,15 0,1 0,05 0 ONC ONC-GMA MS = 2, time (h) Plot of Q vs. time for the adsorption of 2N on ONC and ONC-GMA Both ONCs show an insignificant capacity to absorb 2N, although the presence of GMA slightly increase the adsorbed amount.

22 POTENTIAL APPLICATIONS Removal of aromatic pollutants BNCs were not testes for this purpose because considered sophisticated 2-Naphtol (2N) materials more suitable for biomedical applications (properties and costs)

23 POTENTIAL APPLICATIONS Drug delivery 600 Both 400ONCs show an extremely significant Q (mg/g) 200 HNCs time (h) MS = 1,9 HCN HCN GMA capacity to absorb AMX, with no differences onto the process kinetics. Amoxicillin (AMX) Q (mg/g) MS = 2,4 time (h) ONCs Blank HNC shows moderate properties of AMX adsorbtion. GMA-functionalization ONC ONC-GMA quadruplicate this tendency. roughly Plot of Qt vs. time for the adsorption of AMX on HNC and HNC-GMA Plot of Qt vs. time for the adsorption of AMX on ONC and ONC-GMA

24 POTENTIAL APPLICATIONS Drug delivery BNCs Amoxicillin (AMX) Q (mg/g) BNC BNC-GMA 0.7 < MS < time (h) Blank BNC do not adsorb AMX in effective way. GMA functionalization induces a significant effect on AMX adsorption capacity Plot of Qt vs. time for the adsorption of AMX on BNC and BNC-GMA

25 POTENTIAL APPLICATIONS Drug delivery Q(mg/g) < MS <1 BNCs BNC BNC-GMA Vancomycin (V) time (h) Plot of Qt vs. time for the adsorption of V on BNC and BNC-GMA Both BNCs show a significant capacity to adsorb Vancomycin GMA functionalization induces a slight increment in adsorption of the antibiotic

26 CONCLUSIONS GMA was grafted successfully to all the nanocellulosic materials GMA functionalization promotes an effective decrease of the amount of active molecules (pollutants and antibiotics) in solution, in comparison with the native materials

27 FURTHER PERSPECTIVES Evaluate the parameters (polarity, MS ) that are responsible for different adsorption profiles Open the epoxide ring of GMA-nanocelluloses (the reaction has already be performed) and investigate the adsorption capacities of the new obtained materials Modulate the GMA grafting (decrease of MS)

28 ACKNOWLEDGMENTS THANKS TO: My supervisor, Prof. Elena Vismara My colleagues Non Profit Foundation Istituto G. Ronzoni staff (Milano, Italy) CFT Pietro Masserini Spa (Bergamo, Italy) ALL OF YOU FOR YOUR KIND ATTENTION AND OPPORTUNITY!