@article{pereira_hoeger_ferrer_rencoret_rio_kruus_rahikainen_kellock_gutierrez_rojas_2017, title={Lignin Films from Spruce, Eucalyptus, and Wheat Straw Studied with Electroacoustic and Optical Sensors: Effect of Composition and Electrostatic Screening on Enzyme Binding}, volume={18}, ISSN={["1526-4602"]}, DOI={10.1021/acs.biomac.7b00071}, abstractNote={Lignins were isolated from spruce, wheat straw, and eucalyptus by using the milled wood lignin (MWL) method. Functional groups and compositional analyses were assessed via 2D NMR and 31P NMR to realize their effect on enzyme binding. Films of the lignins were fabricated and ellipsometry, atomic force microscopy, and water contact angle measurements were used for their characterization and to reveal the changes upon enzyme adsorption. Moreover, lignin thin films were deposited on quartz crystal microgravimetry (QCM) and surface plasmon (SPR) resonance sensors and used to gain further insights into the lignin-cellulase interactions. For this purpose, a commercial multicomponent enzyme system and a monocomponent Trichoderma reesei exoglucanase (CBH-I) were considered. Strong enzyme adsorption was observed on the various lignins but compared to the multicomponent cellulases, CBH-I displayed lower surface affinity and higher binding reversibility. This resolved prevalent questions related to the affinity of this enzyme with lignin. Remarkably, a strong correlation between enzyme binding and the syringyl/guaiacyl (S/G) ratio was found for the lignins, which presented a similar hydroxyl group content (31P NMR): higher protein affinity was determined on isolated spruce lignin (99% G units), while the lowest adsorption occurred on isolated eucalyptus lignin (70% S units). The effect of electrostatic interactions in enzyme adsorption was investigated by SPR, which clearly indicated that the screening of charges allowed more extensive protein adsorption. Overall, this work furthers our understanding of lignin-cellulase interactions relevant to biomass that has been subjected to no or little pretreatment and highlights the widely contrasting effects of the nature of lignin, which gives guidance to improve lignocellulosic saccharification and related processes.}, number={4}, journal={BIOMACROMOLECULES}, author={Pereira, Antonio and Hoeger, Ingrid C. and Ferrer, Ana and Rencoret, Jorge and Rio, Jose C. and Kruus, Kristiina and Rahikainen, Jenni and Kellock, Miriam and Gutierrez, Ana and Rojas, Orlando J.}, year={2017}, month={Apr}, pages={1322–1332} }
 @article{lenze_peksa_sun_hoeger_salas_hubbe_2016, title={Intact and broken cellulose nanocrystals as model nanoparticles to promote dewatering and fine-particle retention during papermaking}, volume={23}, ISSN={["1572-882X"]}, DOI={10.1007/s10570-016-1077-9}, number={6}, journal={CELLULOSE}, author={Lenze, Connor J. and Peksa, Caryn A. and Sun, Weimin and Hoeger, Ingrid C. and Salas, Carlos and Hubbe, Martin A.}, year={2016}, month={Dec}, pages={3951–3962} }
 @article{ferrer_hoeger_lu_rojas_2016, title={Reinforcement of polypropylene with lignocellulose nanofibrils and compatibilization with biobased polymers}, volume={133}, ISSN={["1097-4628"]}, DOI={10.1002/app.43854}, abstractNote={Freeze-dried and milled lignocellulose nanofibrils (LCNF) were used to reinforce polypropylene (PP) nanocomposites. The LCNF, containing up to 9% lignin, was obtained from residual Empty Palm Fruit Bunch (EPFB) fibers. Soy protein isolate (SPI) and hydroxypropyl cellulose (HPC) were tested as coupling agents as well as maleic anhydride grafted polypropylene (MAPP), which was used as a reference. A good level of dispersion of LCNF in the PP matrix while mechanical testing and thermal analyses indicated an improvement of the thermo-mechanical behavior of the nanocomposites was revealed upon loading of the lignin-containing nanofibrils. The tensile modulus of PP was increased by 15% upon the addition of 1% LCNF with SPI as a compatibilizer. Likewise, the thermal stability of the composites was most markedly enhanced. Overall, LCNF and SPI, two important bioresources, are introduced here for the development of novel and cost-effective PP-based composites. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43854.}, number={34}, journal={JOURNAL OF APPLIED POLYMER SCIENCE}, author={Ferrer, Ana and Hoeger, Ingrid C. and Lu, Xiaomin and Rojas, Orlando J.}, year={2016}, month={Sep} }
 @article{rojo_peresin_sampson_hoeger_vartiainen_laine_rojas_2015, title={Comprehensive elucidation of the effect of residual lignin on the physical, barrier, mechanical and surface properties of nanocellulose films}, volume={17}, ISSN={["1463-9270"]}, DOI={10.1039/c4gc02398f}, abstractNote={We elucidate the effect of residual lignin on the interfacial, physical and mechanical properties of lignocellulose nanofibrils (LCNF) and respective nanopapers. Fibers containing ∼0, 2, 4, and 14 wt% residual lignin were microfluidized into LCNF aqueous suspensions and were processed into dry films (nanopapers). A systematic decrease in fibril diameter with increasing residual lignin was observed upon fibrillation, consistent with the radical scavenging ability of the lignin that results in better cell wall deconstruction. The stiff nature of the lignin-containing fibrils made them less able to conform during filtration and improved extensively dewatering, owing to a more open structure. However, the softening of the lignin during hot-pressing of the nanopapers and its amorphous nature enabled a binding effect, filling the voids between the nanofibers (thus reducing the number of micropores) and making the surface of the nanopapers smoother. The interfacial free energy of interaction changed drastically with the increased lignin content: the corresponding water contact angles were 35° and 78° for the lignin-free and for the (14%) lignin-containing nanopaper, respectively, revealing the increase in hydrophobicity. Together with the significantly less porous structure of LCNF nanopapers, lower water absorbency was observed with increased lignin content. Lignin in the nanopapers reduced the oxygen permeability by up to 200-fold. Water vapor permeability, in turn, did not correlate linearly with lignin content but depended most significantly on material density. The tensile strength, modulus, and strain for the LCNF nanopapers were found to be in the range 116–164 MPa, 10.5–14.3 GPa, and 1.7–3.5%, respectively. To a good degree of approximation, these mechanical properties were rather insensitive to lignin content and comparable to those of nanopapers derived from fully bleached CNF. Whilst it might be expected that lignin interferes in hydrogen bonding between fibrils, this was apparently counteracted by the uniform distribution of lignin seemingly aiding stress-transfer between fibrils and thus preserving mechanical properties. Overall, LCNF is demonstrated to be a suitable precursor of nanopaper, especially when reduced polarity and low hydrophilicity are desirable in related bio-products.}, number={3}, journal={GREEN CHEMISTRY}, author={Rojo, Ester and Peresin, Maria Soledad and Sampson, William W. and Hoeger, Ingrid C. and Vartiainen, Jari and Laine, Janne and Rojas, Orlando J.}, year={2015}, pages={1853–1866} }
 @article{orelma_morales_johansson_hoeger_filpponen_castro_rojas_laine_2014, title={Affibody conjugation onto bacterial cellulose tubes and bioseparation of human serum albumin}, volume={4}, DOI={10.1039/c4ra08882d}, abstractNote={We attached anti-human serum albumin (anti-HSA) affibody ligands on bacterial cellulose (BC) by EDC–NHS-mediated covalent conjugation and physical adsorption and demonstrate their application for tubular biofiltration of blood proteins. The BC fibrils were first modified by carboxymethyl cellulose (CMC) by incorporation of CMC in the BC culture medium, producing in situ a CMC–BC tubular network that was used as biofilter. Alternatively, BC carboxylation was carried out by alkaline TEMPO–NaBr–NaClO oxidation. The BC and modified BC, grown in the form of tubes or flat films, were characterized by using scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and conductometric titration. Anti-HSA affibody conjugation onto carboxylated cellulose thin film was verified from sensogram data obtained by surface plasmon resonance (SPR). The HSA specific binding capacity of the carboxylated cellulose conjugated with anti-HSA via EDC–NHS was approximately eight-fold larger when compared to the carboxylated cellulose surface carrying physically adsorbed anti-HSA (∼81 compared to 10 ng cm−2, respectively). Further proof of protein binding via anti-HSA affibody conjugated on tubules of CMC- and TEMPO-oxidized BC was obtained by fluorescence imaging. Specific binding of tagged HSA resulted in a linear increase of fluorescence intensity as a function of tagged HSA concentration in the contacting solution.}, number={93}, journal={RSC Advances}, author={Orelma, H. and Morales, L. O. and Johansson, L. S. and Hoeger, I. C. and Filpponen, I. and Castro, C. and Rojas, O. J. and Laine, J.}, year={2014}, pages={51440–51450} }
 @article{hoeger_gleisner_negron_rojas_zhu_2014, title={Mountain Pine Beetle-Killed Lodgepole Pine for the Production of Submicron Lignocellulose Fibrils}, volume={60}, ISSN={["1938-3738"]}, DOI={10.5849/forsci.13-012}, abstractNote={The elevated levels of tree mortality attributed to mountain pine beetle (MPB) (Dendroctonus ponderosae Hopkins) in western North American forests create forest management challenges. This investigation introduces the production of submicron or nanometer lignocellulose fibrils for value-added materials from the widely available resource represented by dead pines after an outbreak. Lodgepole pine (Pinus contorta Dougl. ex Loud.), trees from two different times since infestation and a noninfested live tree as a control were used for mechanical fibrillation. Fiber deconstruction down to the micro-/nanoscale from infested wood was performed using mechanical fibrillation, without any chemical (pre)treatment. The effects of fibrillation were monitored as a function of processing time, and the respective products were characterized. The changes in fibril morphology, cellulose crystallinity, water retention value, and cellulase adsorption capacity were determined. Interestingly, no significant differences were found between fibrillated samples from the live and the MPB-killed trees. It can be concluded that MPB-killed lodgepole pine is a suitable feedstock for the production of lignocellulose micro-/nanofibrils.}, number={3}, journal={FOREST SCIENCE}, author={Hoeger, Ingrid and Gleisner, Rolland and Negron, Jose and Rojas, Orlando J. and Zhu, J. Y.}, year={2014}, month={Jun}, pages={502–511} }
 @article{hoeger_nair_ragauskas_deng_rojas_zhu_2013, title={Mechanical deconstruction of lignocellulose cell walls and their enzymatic saccharification}, volume={20}, ISSN={["1572-882X"]}, DOI={10.1007/s10570-013-9867-9}, number={2}, journal={CELLULOSE}, author={Hoeger, Ingrid C. and Nair, Sandeep S. and Ragauskas, Arthur J. and Deng, Yulin and Rojas, Orlando J. and Zhu, J. Y.}, year={2013}, month={Apr}, pages={807–818} }
 @article{hoeger_filpponen_martin-sampedro_johansson_osterberg_laine_kelley_rojas_2012, title={Bicomponent Lignocellulose Thin Films to Study the Role of Surface Lignin in Cellulolytic Reactions}, volume={13}, ISSN={["1526-4602"]}, DOI={10.1021/bm301001q}, abstractNote={Ultrathin bicomponent films of cellulose and lignin derivatives were deposited on silica supports by spin coating, and after conversion into the respective polymer precursor, they were used as a model system to investigate interfacial phenomena relevant to lignocellulose biocatalysis. Film morphology, surface chemical composition, and wettability were determined by atomic force microscopy, X-ray photoelectron spectroscopy, and water contact angle, respectively. Phase separation of cellulose and lignin produced structures that resembled the cell wall of fibers and were used to monitor enzyme binding and cellulolytic reactions via quartz crystal microgravimetry. The rate and extent of hydrolysis was quantified by using kinetic models that indicated the role of the surface lignin domains in enzyme inhibition. Hydrophobic interactions between cellulases and the substrates and their critical role on irreversible adsorption were elucidated by using acetylated lignin films with different degrees of substitution. Overall, it is concluded that sensors based on the proposed ultrathin films of lignocellulose can facilitate a better understanding of the complex events that occur during bioconversion of cellulosic biomass.}, number={10}, journal={BIOMACROMOLECULES}, author={Hoeger, Ingrid C. and Filpponen, Ilari and Martin-Sampedro, Raquel and Johansson, Leena-Sisko and Osterberg, Monika and Laine, Janne and Kelley, Stephen and Rojas, Orlando J.}, year={2012}, month={Oct}, pages={3228–3240} }
 @article{csoka_hoeger_rojas_peszlen_pawlak_peralta_2012, title={Piezoelectric Effect of Cellulose Nanocrystals Thin Films}, volume={1}, ISSN={2161-1653 2161-1653}, url={http://dx.doi.org/10.1021/mz300234a}, DOI={10.1021/mz300234a}, abstractNote={Ultrathin films of aligned cellulose nanocrystals (CNCs) were assembled on mica supports by using electric field-assisted shear. The relationship between polarization gradients and strain mechanics of the obtained films was examined by monitoring their deflection with an atomic force microscope operated in contact mode. The piezoelectric response of the films was ascribed to the collective contribution of the asymmetric crystalline structure of the cellulose crystals. The magnitude of the effective shear piezoelectric constant (d25) of highly ordered CNC films was determined to be 2.1 Å/V, which is comparable to that of a reference film of a piezoelectric metal oxide.}, number={7}, journal={ACS Macro Letters}, publisher={American Chemical Society (ACS)}, author={Csoka, Levente and Hoeger, Ingrid C. and Rojas, Orlando J. and Peszlen, Ilona and Pawlak, Joel J. and Peralta, Perry N.}, year={2012}, month={Jun}, pages={867–870} }
 @article{csoka_hoeger_peralta_peszlen_rojas_2011, title={Dielectrophoresis of cellulose nanocrystals and alignment in ultrathin films by electric field-assisted shear assembly}, volume={363}, ISSN={["1095-7103"]}, DOI={10.1016/j.jcis.2011.07.045}, abstractNote={Ultrathin films of cellulose nanocrystals (CNCs) are obtained by using a convective assembly setup coupled with a low-strength external AC electric field. The orientation and degree of alignment of the rod-like nanoparticles are controlled by the applied field strength and frequency used during film formation. Calculated dipole moments and Clausius-Mossotti factors allowed the determination of the critical frequencies, the peak dielectrophoresis as well as the principal orientation of the CNCs in the ultrathin films. As a result of the combination of shear forces and low electric field highly ultrathin films with controlled, unprecedented CNC alignment are achieved.}, number={1}, journal={JOURNAL OF COLLOID AND INTERFACE SCIENCE}, author={Csoka, Levente and Hoeger, Ingrid C. and Peralta, Perry and Peszlen, Ilona and Rojas, Orlando J.}, year={2011}, month={Nov}, pages={206–212} }
 @article{martin-sampedro_capanema_hoeger_villar_rojas_2011, title={Lignin Changes after Steam Explosion and Laccase-Mediator Treatment of Eucalyptus Wood Chips}, volume={59}, ISSN={["1520-5118"]}, DOI={10.1021/jf201605f}, abstractNote={Eucalyptus globulus chips were steam exploded followed by treatment with a laccase-mediator system (LMS) under different experimental conditions. Removal of hemicelluloses and, to a lesser extent, lignin was observed. Thermogravimetic analyses of whole meal obtained from chips before and after steam explosion indicated an increase in lignin degradation temperature due to lignin condensation. In contrast, application of LMS treatment caused a reduction in lignin and polysaccharide degradation temperatures. Lignins were isolated from wood samples before and after each treatment and analyzed by 2D NMR and (13)C NMR. An increase in carboxyl and phenolic hydroxyl groups and a significant decrease in β-O-4 structures were found in steam-exploded samples. The most relevant changes observed after laccase treatment were increased secondary OH and degree of condensation.}, number={16}, journal={JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY}, author={Martin-Sampedro, Raquel and Capanema, Ewellyn A. and Hoeger, Ingrid and Villar, Juan C. and Rojas, Orlando J.}, year={2011}, month={Aug}, pages={8761–8769} }
 @article{habibi_hoeger_kelley_rojas_2010, title={Development of Langmuir-Schaeffer Cellulose Nanocrystal Monolayers and Their Interfacial Behaviors}, volume={26}, ISSN={["0743-7463"]}, DOI={10.1021/la902444x}, abstractNote={Model cellulose surfaces based on cellulose nanocrystals (CNs) were prepared by the Langmuir-Schaeffer technique. Cellulose nanocrystals were obtained by acid hydrolysis of different natural fibers, producing rodlike nanoparticles with differences in charge density, aspect ratio, and crystallinity. Dioctadecyldimethylammonium bromide (DODA-Br) cationic surfactant was used to create CN-DODA complexes that allowed transfer of the CNs from the air/liquid interface in an aqueous suspension to hydrophobic solid substrates. Langmuir-Schaeffer horizontal deposition at various surface pressures was employed to carry out such particle transfer that resulted in CN monolayers coating the substrate. The morphology and chemical composition of the CN films were characterized by using atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). Also, their swelling behavior and stability after treatment with aqueous and alkaline solutions were studied using quartz crystal microgravimetry (QCM). Overall, it is concluded that the Langmuir-Schaeffer method can be used to produce single coating layers of CNs that were shown to be smooth, stable, and strongly attached to the solid support. The packing density of the films was controlled by selecting the right combination of surface pressure during transfer to the solid substrate and the amount of CNs available relative to the cationic charges at the interface.}, number={2}, journal={LANGMUIR}, author={Habibi, Youssef and Hoeger, Ingrid and Kelley, Stephen S. and Rojas, Orlando J.}, year={2010}, month={Jan}, pages={990–1001} }