Arto almidoian oinarritutako nanokonposite film eta hidrogelen garapena polisakarido eta grafenotik eratorritako nanoegiturak erabiliz

239 p.Doktorego tesi honen helburua almidoian oinarritutako materialen lorpena eta karakterizazioa izan da. Aplikazio desberdinetan erabiltzeko bi material mota garatu dira.: plastifikatutako almidoi film eta nanokonposite filmak paketatze aplikazioetan erabilitako ohiko polimero sintetikoen ordezkari bezala eta saretutako almidoi nanokonposite hidrogelal biomedikuntza aplikazioetarako. Horrela, plastifikatzaileak materialen amaierako propietateetan eta erretrogradazioan duen eragina aztertu da. Bestalde, nanokonposite filmak nanokristal polisakaridoak gehituta prestatu dira, almidoi eta zelulosa nanokristalak erabiliz hain zuzen. Horrez gain, estrusio/konpresio bidez almidoi termoplastiko filmak lortzeko bideragarritasuna ebaluatu da Bestalde, plastifikatutako almidoi nanokonposite filmak karbono nanopartikulak gehituta lortu dira. Grafeno eta grafeno oxido eduki desberdinak plastifikatutako almidoi matrizean gehitzeak duen eragina aztertu da. Nanokonposite hidrogelen sintesiari dagokionez, alde batetik, saretutako hidrogelak furano taldeaz eraldatutako almidoia eta tetramaleimida baten arteko Diels-Alder erreakzioaren bitartez lortu dira zelulosa nanokristalak gehituz. Zelulosa nanokristal edukiak hidrogelen propietate erreologiko, puzte gaitasuna, morfologia, botika askapen zinetika eta zelula itsaspen gaitasunean duen eragina aztertu da. Gainera, nanokonposite hidrogel antibakterial eta eroaleak lortu dira, grafenoa eta Salvia estraktuak egonkortzaile bezala erabiliz.GMT Materials + Technologies Research Grou

Arto almidoian oinarritutako nanokonposite film eta hidrogelen garapena polisakarido eta grafenotik eratorritako nanoegiturak erabiliz

239 p.Doktorego tesi honen helburua almidoian oinarritutako materialen lorpena eta karakterizazioa izan da. Aplikazio desberdinetan erabiltzeko bi material mota garatu dira.: plastifikatutako almidoi film eta nanokonposite filmak paketatze aplikazioetan erabilitako ohiko polimero sintetikoen ordezkari bezala eta saretutako almidoi nanokonposite hidrogelal biomedikuntza aplikazioetarako. Horrela, plastifikatzaileak materialen amaierako propietateetan eta erretrogradazioan duen eragina aztertu da. Bestalde, nanokonposite filmak nanokristal polisakaridoak gehituta prestatu dira, almidoi eta zelulosa nanokristalak erabiliz hain zuzen. Horrez gain, estrusio/konpresio bidez almidoi termoplastiko filmak lortzeko bideragarritasuna ebaluatu da Bestalde, plastifikatutako almidoi nanokonposite filmak karbono nanopartikulak gehituta lortu dira. Grafeno eta grafeno oxido eduki desberdinak plastifikatutako almidoi matrizean gehitzeak duen eragina aztertu da. Nanokonposite hidrogelen sintesiari dagokionez, alde batetik, saretutako hidrogelak furano taldeaz eraldatutako almidoia eta tetramaleimida baten arteko Diels-Alder erreakzioaren bitartez lortu dira zelulosa nanokristalak gehituz. Zelulosa nanokristal edukiak hidrogelen propietate erreologiko, puzte gaitasuna, morfologia, botika askapen zinetika eta zelula itsaspen gaitasunean duen eragina aztertu da. Gainera, nanokonposite hidrogel antibakterial eta eroaleak lortu dira, grafenoa eta Salvia estraktuak egonkortzaile bezala erabiliz.GMT Materials + Technologies Research Grou

3D printing of customized all-starch tablets with combined release kinetics

[EN] Starch-based tablets with tailored releases were prepared by 3D printing using a hydrophobic drug. The importance of the origin of the excipient in the inks and tablets was analyzed. Besides, the effect of the geometry of the tablet on the drug release profile was also evaluated. The rheological properties of the inks was influenced by the botanic origin of the starch. Consequently, tablets presented different microporous structure and particular compression and swelling behaviors. Normal maize starch showed a non-well-defined porous morphology, not being able to form a stable structure whereas, waxy maize and potato starches exhibited a well-defined porous structure and were both able to maintain their integrity after long time immersion. Finally, tablets combining different starches and geometries were printed tailoring the drug release from 10 min to 6 h and designing two-steps profiles. The applicability of the developed 3D printed drug release systems in personalized therapies was demonstrated.Financial support from the University of the Basque Country (UPV/EHU) (GIU18/216 Research Group), from the Basque Government in the frame of Elkartek KK-2020/00053 and PIBA2020-1-0041 and from Spanish Ministry of Science and Innovation and Spanish State Research Agency (MCIN/AEI/10.13039/501100011033) in the frame of PID2019-105090RB-I00 project, are gratefully acknowledged. Moreover, we are grateful to the Macrobehavior-Mesostructure-Nanotechnology SGIker unit of the UPV/EHU. K. González thanks the University of the Basque Country for the grant “Contratación de doctores recientes hasta su integración en programas de formación postdoctoral en la UPV/EHU «DOKBERRI» 2020-I” (DOCREC20/07)

Integral Valorization of Grape Pomace for Antioxidant Pickering Emulsions

Full harnessing of grape pomace (GP) agricultural waste for the preparation of antioxidant Pickering emulsions is presented herein. Bacterial cellulose (BC) and polyphenolic extract (GPPE) were both prepared from GP. Rod-like BC nanocrystals up to 1.5 µm in length and 5–30 nm in width were obtained through enzymatic hydrolysis (EH). The GPPE obtained through ultrasound-assisted hydroalcoholic solvent extraction presented excellent antioxidant properties assessed using DPPH, ABTS and TPC assays. The BCNC-GPPE complex formation improved the colloidal stability of BCNC aqueous dispersions by decreasing the Z potential value up to −35 mV and prolonged the antioxidant half-life of GPPE up to 2.5 times. The antioxidant activity of the complex was demonstrated by the decrease in conjugate diene (CD) formation in olive oil-in-water emulsions, whereas the measured emulsification ratio (ER) and droplet mean size of hexadecane-in-water emulsions confirmed the physical stability improvement in all cases. The synergistic effect between nanocellulose and GPPE resulted in promising novel emulsions with prolonged physical and oxidative stability.Financial support from the Basque Government as part of the Grupos Consolidados (IT1690-22) and PIBA2020-1-0041 and from the Spanish Ministry of Science and Innovation and Spanish State Research Agency (MCIN/AEI/10.13039/501100011033) as part of the PID2019-105090RB-I00 project is gratefully acknowledged. Moreover, the authors also thank the technical support and personnel from the Macrobehavior-Mesostructure-Nanotechnology unit, Servicio de Lipidómica y Metabolomica and the Central Analysis Service of Bizkaia of SGIker (UPV/EHU, MICINN, GV/E.G., ESF). J. Díaz-Ramírez wishes to acknowledge the Department of Agriculture, Fisheries and Food policy of the Basque Government for his PhD grant (00020-PIT2019-22)

Cationically photocured epoxy/polycaprolactone materials processed by solution electrospinning, melt electrowriting and 3D printing: Morphology and shape memory properties

Epoxy/polycaprolactone (PCL) blends containing cationic photo-initiator were prepared by both solution and melt blending. These materials were processed by solvent casting, solution electrospinning (SE), melt electrowriting (MEW), and Fused Deposition Modeling (FDM) 3D printing. The final materials were obtained after UV curing at room temperature. FTIR, and gel content measurements showed that all the materials were crosslinked and that the PCL was part of the network. The shape memory abilities (measured by DMA experiments) depended on the processing technique. Thus, the fixity and recovery ratios were optimal for electrospun fibers, while the 3D printed sample was not able to recover any shape, probably because of the poor adhesion between the printed layers. According to AFM images, samples obtained by MEW and 3D printing produced materials with spherulitic morphology, while solution electrospinning rendered fibers with Shish-Kebab-type crystalline morphology. The latter was highly anisotropic, and many chains were oriented along the nanofiber axis interdispersed with amorphous regions where the epoxy resin formed covalent links with the PCL chains. This morphology conferred extraordinary solvent resistance and shape memory properties to the electrospun mats. The latter manifested a very high affinity towards chloroform, and accordingly, they displayed potential applications as chloroform sensors.AJM acknowledges funding by the Basque Government through grant IT1503-22. LI acknowledges funding by the Basque Government through grant IT1667-22