Ju y 15-17, 2015
Polytechnic Institute of Bragan~a 1 PCT-TMAD Brigantia EcoPark
Bragan~a
· Portugal
WORKSHOP
PROCEEDINGS
Eds.- M. F. Barreiro, 0. Ferreira, A.l. Pereira
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Title
6th Workshop- Green Chemistry and Nanotechnologies in Polymer Chemistry
Edited by
M.F. Barreiro, 0. Ferreira, A. I. Pereira
Graphic Design
Soraia Maduro- CIPweb IPB
First edition 07/2015
ISBN 978-972-745-188-3
Edition
Institute Politecnico de Braganca
0
c_th
Green Chemistry and Nanotechnologies
in Polymer Chemistry
Committees
Scientific Committee
Aleksander Prociak, Cracow University of Technology, Poland
Alessandro Gandini, IQSC University of Sao Paulo, Brazil
Alfonso Jimenez, University of Alicante, Spain
Allrio Rodrigues, University of Porta, Portugal
Ana Vera Machado, University of Minho, Portugal
Andrea Lazzeri, University of Pisa, Italy
Arantxa Eceiza, University of the Basque Country, Spain
Armando Silvestre, University of Aveiro, Portugal
Bela Pukansky, Budapest University, Hungary
Fernao Magalhaes, University of Porta, Portugal
Filomena Barreiro, Polytechnic Institute of Bragan~a. Portugal
Helena Gil, University of Coimbra, Portugal
Janusz Datta, Gdansk University of Technology, Poland
Joanna Ryszkowska, Warsaw University of Technology, Poland
Joao Mano, University of Minho, Portugal
Jose Vega Baudrit, Centra Nacional de Alta Tecnologra (CeNAT), Costa Rica
Juan Francisco Rodriguez, University of Castilla La Mancha, Spain
Luisa Carvalho, Polytechnic Institute of Viseu, Portugal
Mario Rui P.F.N. da Costa, University of Porta, Portugal
Mirta Aranguren, CONICET University of Mar de Plata, Argentina
Naceur Belgacem, Grenoble INP-Pagora, France
Tom as Vlcek, TOSEDA S.R.O.Research & Development Center, Czech Republic
Tomasz Sterzynski, Poznan University of Technology, Poland
Ugis Cabulis, Institute of Wood Chemistry, Latvia
Organizing Committee
Ana lsabel Pereira, Polytechnic Institute of Bragan~a. Portugal
Filomena Barreiro, Polytechnic Institute of Bragan~a. Portugal
Helder Games, Polytechnic Institute of Braganca, Portugal
lsabel Ferreira, Polytechnic Institute of Bragan~a. Portugal
Joana Amaral, Polytechnic Institute of Braganca. Portugal
Jose Santos, Polytechnic Institute of Braganca, Portugal
Olga Ferreira, Polytechnic Institute of Bragan~a. Portugal
Paulo Piloto, Brigantia Ecopark, Portugal
6th Workshop on Green Chemistry and Nanotechnologies in Polymer Chemistry
Table of Contents
INVITED LECTURES .....................................................................................................................1
IL I. THE CHEMIC AL MODIFICATION OF N ATUR AL POL YMERS BY THE DIELS-ALDER REACTION .......... 2
A. Gandini
IL II. NANOSTRUCTURED MULTILAYERS OBTAINED FROM NATURAL-BASED POLYMERS:
BIOMEDICAL APPLIC ATIONS .......................................................................................................................................... 2
J.F. Mano
IL III. GREEN SYNTHESIS OF POL YMERS USING SUPERCRITICAL CO2 ........................................................... 3
J.F. Rodriguez, C. Gutierrez
IL IV. APPLIC ATIONS OF NATURAL POL YMERS IN INDUSTRY AND MEDICINE .............................................. 3
M.H. Gil, P. Alves, P. Coimbra, P. Ferreira
ORAL PRES ENTATIONS ..............................................................................................................4
O01. INFLUENCE ON ISOCYANATE INDEX ON SELECTED PROPERTIES OF FLEXIBLE
POLYURETHANE FOAMS MODIFIED WITH VARIOUS BIO-COMPONENTS ....................................................... 5
A. Prociak, E. Malewska, S. Bąk
O02. OXYPROPYLATION OF GREY ALDER BARK AND ITS FRACTIONS TO OBTAIN POLYOLS USABLE
FOR PRODUCTION OF RIGID POLYURETH ANE FOAMS ........................................................................................ 7
L. Vevere, A. Arshanitsa, G. Telysheva
O03. SYNTHESIS, STRUCTURE AND PROPERTIES OF NOVEL POLYHYDROXYURETHANES OBTAINED
BY NON-ISOCYAN ATE ROUTE ....................................................................................................................................... 9
M. Włoch, J. Datta
O04. RIGID POLYURETHANE FOAMS AS THERMAL INSULATION MATERIAL BASED ON RECYCLED
PET AND RAPESEED OIL ............................................................................................................................................... 10
A. Paberza, A. Fridrihsone-Girone, A. Abolins, U. Cabulis
O05. BALANCE BETWEEN RENEWABLE AND RECYCLABLE FEEDSTOCK FOR RIGID POLYURETHANE
FOAMS ................................................................................................................................................................................ 12
U. Cabulis, M. Kirpluks, A. Paberza, A. Fridrihsone-Girone, I. Vitkauskiene
O06. WATERBORNE POL YURETHANE-CELLULOSE NANOCRYSTALS N ANOCOMPOSITES .................... 14
A. Santamaría-Echart, A. Saralegi, L. Martin, M.A. Corcuera, A. Eceiza
O07. BIO-BASED POL YURETHANE EL ASTOMERS - SYNTHESIS AND CHARACTERIZATION ................... 16
J. Datta
O08. POLYURETHANE FOAMS OBTAINED FROM RECOVERED POLYOL THROUGH CHEMICAL
RECYCLING ....................................................................................................................................................................... 17
P. Kopczyńska, J. Datta
O09. INFLUENCE OF PROCESS VARIABLES IN ESTOLIDE SYNTHESIS AND THEIR ESTER
DERIVATIVES FROM OLEIC ACID................................................................................................................................ 18
J.C. de Haro, M.P. Garrido, A. Pérez, M. Carmona, J.F. Rodríguez
O10. GREEN POLYMERS FROM BIOBASED-MONOMERS: KINETICS OF FREE-RADICAL
POLYMERIZATION OF ITACONIC ACID...................................................................................................................... 20
A. Wesołowska, S. Bednarz, D. Bogdał
O11. THE INFLUENCE OF VARIOUS CATALYSTS OF EPOXIDATION OF SOYBEAN OIL ON THE COURSE
OF EPOXY FUSION PROCESS AND THE FUNCTION ALITY OF PRODUCTS OBTAINED .............................. 22
A. Sienkiewicz, P. Czub
O12. PREPARATION OF NANO-HYDROXYAPATITE/CHITOSAN SPONGE-LIKE SCAFFOLDS FOR TISSUE
ENGINEERING................................................................................................................................................................... 24
G. Ruphuy, M.M. Dias, J.C. Lopes, M. F. Barreiro
O13. MAGNETIC AND pH RESPONSIVE MICROC APSULES WITH PROTEIN IMMOBILIZATION ................. 26
N. Dencheva, J. Braz, Z. Denchev
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6th Workshop on Green Chemistry and Nanotechnologies in Polymer Chemistry
P37. MICROENCAPSULATION OF Rosmarinus officinalis L. (ROSEMARY) AQUEOUS EXTRACT FOR
APPLIC ATION IN FUNCTION AL FOODS ...................................................................................................................133
A. Ribeiro, C. Caleja, L. Barros, C. Santos -Buelga, I.C.F.R. Ferreira, M.F. Barreiro
P38. MICROENCAPSULATION OF FENNEL AND CHAMOMILE AQUEOUS EXTRACTS FOR APPLICATION
IN COTTAGE CHEESE...................................................................................................................................................135
C. Caleja, A. Ribeiro, I.C.F.R. Ferreira, M.F. Barreiro
P39. FUNCTIONAL SYNTHETIC TURF SYSTEM WITH IMPROVED COMFORT .............................................137
B. Moura, S. Silva, N. Durães, D. Coelho, L. Rodrigues, F. Monteiro, R. Silva, A. Moreira
P40. CERAMIC MATERIALS WITH IMPROVED THERMAL COMFORT ..............................................................139
A. Sampaio, J. Sousa, J. Branquinho, D. Coelho
P41. MEL AMINE-FOR MALDEHYDE RESINS MODIFIED WITH GLYCEROL .....................................................141
A. Henriques, J. Ferra, J.M. Martins, F. Magalhães, L. Carvalho
P42. MODIFYING RIGID POLYURETHANE FOAM MECHANICAL PROPERTIES BY HIGH RENEWABLE
CARBON CONTENT POL YOL MIXTURES ................................................................................................................143
L. Ugarte, T. Calvo-Correas, A. Santamaría-Echart, S. Gómez-Fernández, M.A. Corcuera, A. Eceiza
P43. THE USE OF BIO-BASED ADDITIVES (LIGNIN, STARCH AND CELLULOSE) IN THERMOPLASTIC
POLYURETHANE FORMULATIONS TO ENHANCE THE BIODEGRADABILITY OF FOOTWEAR
COMPONENTS ................................................................................................................................................................145
I.P. Fernandes, M. Barbosa, J.S. Amaral, V. Pinto, M.J. Ferreira, M.F. Barreiro
P44. SYNTHESIS OF H YDROXYAPATITE WITH N ANOPARTICLES INCLUSIONS.........................................147
D. Malina, A. Sobczak-Kupiec, K. Pluta, K. Bialik-Wąs, B. Tyliszczak
P45. DRYING KINETICS AS TOOL FOR DYN AMIC POROSITY OF C ATAL YST-SUPPORT MATERIALS ..149
J.F. Mata-Segreda
P46. PREPARATION OF POLY(URETHANE-UREA) MICROCAPSULES BY INTERFACIAL
POLYMERIZATION: EFFECT OF PEG MOLECULAR WEIGHT ............................................................................151
M. Silva, I.M.D. Martins, M.F. Barreiro, M.M.Q. Dias, A.E. Rodrigues
P47. BIODEGRADATION PRETREATMENT OF WOOD OF E. grandis, E. dunni, AND E. b entami TO WORK
IN BIORREFINERY PROCESSES................................................................................................................................153
M. Lopretti, S. Baldyga, M. Gonzalez, L. Olazabal, M. Torres
P48. MICROENCAPSULATION OF Ceratonia siliqua L. EXTRACT FOR FOOD PURPOSES: EFFECT OF
EXTR ACT/ALGINATE R ATIO........................................................................................................................................155
I. Rached, I.P. Fernandes, L. Barros, A.E. Rodrigues, A. Ferchichi, I.C.F.R. Ferreira, M.F. Barreiro
P49. NATURAL ADDITIVES FOR REDUCING FORMALDEHYDE EMISSIONS IN UREA-FORMALDEHYDE
RESINS..............................................................................................................................................................................157
F. Pereira, N. Paiva, J. Ferra, J.M. Martins, F. Magalhães, L. Carvalho
P50. PREPARATION AND CHARACTERIZATION OF POLYSACCHARIDES/PVA BLEND NANOFIBROUS
MEMBR ANES PREPARED BY ELECTROSPINNING ..............................................................................................160
A. Sampaio, C. Silva, D. Coelho, A. Zille
P51. VALORISATION OF ALMOND AGRO-INDUSTRIAL RESIDUES: PRODUCTION OF BIOPOLYOLS
FROM ALMOND SHELL .................................................................................................................................................162
J.A. Pinto, I.P. Fernandes, M.F. Barreiro
P52. MICROENCAPSULATION OF PLANT EXTRACTS RICH IN APIGENIN TO BE USED AS
CHEMOPREVENTIVE AGENTS IN FUNCTION AL FOODS ....................................................................................164
F.S. Oliveira, R.C. Calhelha, I.P. Fernandes , B.D. Junior, I.C.F.R. Ferreira, M.F. Barreiro
P53. POLYUREAURETH ANES WITH RAP ESEED POL YOL FOR TECHNICAL APPLIC ATIONS ..................166
M. Auguścik, J. Ryszkowska, M. Zieleniewska, M. Kurańska, A. Prociak, W. Karalus, K. Pietrzak
P54. INVESTIGATION OF TUNISIAN AGRICULTURAL RESIDUES TO PRODUCE CELLULOSE
NANOCRYSTALS AND NANOFIBRILLAR CELLULOSE: APPLICATION TO NANOCOMPOSITE MATERIALS
.............................................................................................................................................................................................168
F. Bettaieb, R. Khiari, F. Mhenni, N. Belgacem, A. Dufresne, S. Boufi
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6th Workshop on Green Chemistry and Nanotechnologies in Polymer Chemistry
P52. MICROENCAPSULATION OF PLANT EXTRACTS RICH IN
APIGENIN TO BE USED AS CHEMOPREVENTIVE AGENTS IN
FUNCTIONAL FOODS
F.S. Oliveira1,2, R.C. Calhelha2, I.P. Fernandes1, B.D. Junior3, I.C.F.R. Ferreira2,*,
M.F. Barreiro1,*
1
Laboratory of Separation and Reaction Engineering (LSRE), Associate Laboratory LSRE -LCM/IPB,
Campus de Santa Apolónia, 1134, 5301-857 Bragança, Portugal.
2 Mountain Research Centre (CIMO), ESA, IPB, Campus de Santa Apolónia, 1172, 5301-855
Bragança, Portugal.
3 Federal University of Technology – Parana (UTFPR), Campus Campo Mourão Via Rosalina Maria
dos Santos,1233,+55 44 3528-1400 Campo Mourão, Paraná, Brazil.
*[email protected], [email protected]
Introduction
Angiogenesis is the process by which new blood vessels are formed from pre-existing vasculature, being
a key process that leads to tumor development. Excessive angiogenesis occurs when diseased cells
produce abnormally large amounts of angiogenesis factors (e.g. vascular endothelial growth factor
(VEGF)) [1]. Some studies recognize phenolic compounds as chemopreventive agents; flavonoids seem
to suppress the growth of tumor cells modifying the cell cycle and inducing apoptosis in several tumor
cell lines [2]. Among them, apigenin derivatives have been recognized as having antiangiogenic effects
on tumor cells being this related to a decrease in VEGF expression or to a VEGFR inhibition [3].
According to Ferreira et al. previous research, Arenaria montana L. is rich in apigenin derivatives [4].
Therefore, this plant source is ideal to prepare apigenin rich extracts to be used as chemoprevent i ve
agents in functional foods. However, bioactive compounds are generally recognized as presenting
problems of instability, which can weaken their bioavailability and potential benefits. Therefore, the use
of microencapsulation is studied here as a way to confer protection and increasing the efficacy of
functional foods incorporating these extracts [5].
In this work, a hydroethanolic extract prepared from A. montana was evaluated for its in vitro
antiangiogenic effects, being further microencapsulated to be used as chemopreventive agent in
functional yogurts.
Experimental
The bioactive ingredient was obtained from Arenaria montana L. through an extraction with ethanol:
water 80:20 (v/v). The obtained extract was evaluated in terms of inhibitory activity of the tyrosine kinase
intracellular domain of the Vascular Endothelium Growth Factor Receptor-2 (VEGFR-2) through an
enzymatic assay. The microspheres were prepared by using an atomization/coagulation technique
where a solution of sodium alginate containing the extract (10 mL, extract/sodium alginate ratio of 50/400
(mg/mg)) was atomized through a nozzle (0.35 mm diameter) and coagulated in a calcium chloride
solution (250 mL, 4% (v/v)). The forming microspheres were characterized by optical microscopy (OM)
during the microencapsulation process to monitor morphology evolution. The encapsulation efficienc y
(EE) was evaluated by HPLC-DAD based on apigenin (the major extract’s aglycone). Additionally, free
and microencapsulated extracts were incorporated into yogurt samples that were thereafter evaluat ed
in terms of in vitro antiangiogenic activity and nutritional composition at two different storage times (0
and 3 days).
Results and discussion
The A. montana extract showed capacity to inhibit the phosphorylation of VEGFR-2 (IC50=63.13 µg/ml),
according to the performed enzymatic fluorescence resonance energy transfer (FRET)-based assay.
This extract was microencapsulated and the obtained microspheres were observed by OM immediately
after the atomization and after 4 hours in contact with the coagulation solution (Fig 1). This analysis
confirmed that the process was conducted successfully. The observed microspheres had a spherical
morphology and no agglomeration was detected (they were presented as individualized structures). The
determined EE pointed out a value reaching 100% since no apigenin (the major extract’s aglycone) was
detected, both in the coagulation and washing solutions.
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6th Workshop on Green Chemistry and Nanotechnologies in Polymer Chemistry
Fig. 1. Optical microscopy of the microcapsules along the microencapsulation process: A - Microspheres
after being sprayed (initial time of the coagulation process); B - Microspheres after coagulation; CMicrospheres after lyophilization (storage form).
The amount of the incorporated extract in the yogurt samples (free or microencapsulated) was twice the
IC50 value which is in accordance with the apigenin daily recommended dose and its relative
concentration in the extract (48%, w/w). For the yogurt added with the free form, and comparatively with
the microencapsulated form, an initially higher antiangiogenic activity was observed. Nevertheless, a
decrease was observed for t3 (3 days), which can be associated with the extract degradation. On the
contrary, in the case of using the microencapsulated form, an increase of antiangiogenic activity was
observed from t0 (initial time) to t3. This could be correlated with an effective protection provided by the
used microencapsulation process, together with a sustained release of the extract with time.
Conclusions
The atomization/coagulation technique allowed the production of viable microspheres enriched with the
plant extract. This final ingredient was effectively incorporated into yogurts, protecting the extract and
envisaging the development of novel functional foods with chemopreventive effects. The evaluation of
the nutritional composition is under progress.
Acknowledgements
FCT for financial support to CIMO (Project PEst-OE/AGR/UI0690/2014). FCT/MEC and FEDER under
Program PT2020 for financial support to LSRE (Project UID/EQU/50020/2013). QREN, ON2 and
FEDER (NORTE-07-0124-FE DER-000014) and PRODER (Project nº 46577- PlantLact). The authors
also thank Ana Maria Carvalho for providing Arenaria montana L. samples.
References
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165