ALBERT

Description:    A synthetic route is described here for novel peptide-cellulose conjugates containing O -phospho- l -serine. First, Boc-Ser(PO 3 Ph 2 ) and the related dipeptides, Boc-Ser(PO 3 Ph 2 )-Asp(OBzl) and Boc-Asp(OBzl)-Ser(PO 3 Ph 2 ), were synthesized by adopting the phosphoryl-protection strategy. The condensation reaction between the α -carboxyl group of the protected Boc-Ser(PO 3 Ph 2 ) and the β -amino groups of β -Ala-Cellulose using isobutyl chloroformate and N -methylmorpholine yielded the product conjugate, N β -[Boc-Ser(PO 3 Ph 2 )]- β -Ala-Cellulose. The degree of substitution of Boc-Ser(PO 3 Ph 2 ) towards the β -amino groups of β -Ala-Cellulose was estimated as DS N  = 0.75 (maximum, 1.0). Similar reactions between β -Ala-Cellulose and two kinds of protected dipeptides, Boc-Asp(OBzl)-Ser(PO 3 Ph 2 ) and Boc-Ser(PO 3 Ph 2 )-Asp(OBzl), gave the corresponding conjugates, and the DS N was estimated to be 0.95 and 0.69, respectively. The phenyl, benzyl, and Boc groups were removed in one-pot using the Pt 2 O catalyst in 50 % trifluoroacetic acid/acetic acid. The 31 P-NMR and UV–Visible spectra indicated the complete deprotection without any observable elimination of the phosphorylated peptides. Content Type Journal Article Category Original Paper Pages 1-14 DOI 10.1007/s10570-012-9822-1 Authors Kesavan Devarayan, Faculty of Textile Science and Technology, Institute of High Polymer Research, Shinshu University, Tokida 3-15-1, Ueda, 386-8567 Japan Masakazu Hachisu, Research Institute of Genome-based Biofactory, National Institute of Advanced Industrial Science and Technology (AIST), 2-17-2-1, Tsukisamu-higashi, Toyohira-ku, Sapporo, 062-8517 Japan Jun Araki, Division of Chemistry and Materials, Faculty of Textile Science and Technology, Shinshu University, Tokida 3-15-1, Ueda, 386-8567 Japan Kousaku Ohkawa, Faculty of Textile Science and Technology, Institute of High Polymer Research, Shinshu University, Tokida 3-15-1, Ueda, 386-8567 Japan Journal Cellulose Online ISSN 1572-882X Print ISSN 0969-0239

Description:    Well soluble dextran-, cellulose-, starch-, and pullulan aryl carbonates were synthesized applying p -NO 2 -phenyl chloroformate, phenyl chloroformate, and phenyl fluoroformate. Aminolysis of the products obtained, using aliphatic amines or benzyl amines, yield novel soluble polysaccharide carbamates. The influence of the reaction conditions on the reaction efficiency depending on polysaccharide, reagent, and reaction parameters including temperature was studied. Thus a synthesis strategy was developed for the easy and efficient design of structures of polysaccharide-based materials. The products were characterized by means of NMR-, UV-Vis- and FTIR spectroscopy, elemental analysis, and size exclusion chromatography. Content Type Journal Article Category Original Paper Pages 1-15 DOI 10.1007/s10570-012-9819-9 Authors Thomas Elschner, Center of Excellence for Polysaccharide Research, Institute of Organic Chemistry and Macromolecular Chemistry, Friedrich Schiller University of Jena, Humboldtstraße 10, 07743 Jena, Germany Kristin Ganske, Center of Excellence for Polysaccharide Research, Institute of Organic Chemistry and Macromolecular Chemistry, Friedrich Schiller University of Jena, Humboldtstraße 10, 07743 Jena, Germany Thomas Heinze, Center of Excellence for Polysaccharide Research, Institute of Organic Chemistry and Macromolecular Chemistry, Friedrich Schiller University of Jena, Humboldtstraße 10, 07743 Jena, Germany Journal Cellulose Online ISSN 1572-882X Print ISSN 0969-0239

Description:    Flexible composite films were produced by impregnating aqueous phenol formaldehyde (PF) resin into water-swollen cellulose nanofibril (CNF) films. CNF films were prepared using a pressurized filtration method in combination with freeze drying. The freeze-dried films were swollen with water then impregnated with PF resin by soaking in aqueous resin solutions of varying concentrations. Small amounts of PF slightly enhanced the tensile properties of CNF films. The formulation with the best mechanical properties was CNF/PF films with 8 wt % resin exhibiting tensile stress and toughness of 248 MPa and 26 MJ/m 3 , respectively. Resin concentrations higher than about 8 % resulted in composites with decreased tensile properties as compared to neat CNF films. The wet strength of the composite films was significantly higher than that of the neat CNF films. The resulting composites showed greater resistance to moisture absorption accompanied by reduced thickness swelling when soaked in water as compared to neat CNF films. The composites also showed decreased oxygen permeability at low humidity compared to neat films, but the composites did not show improved barrier properties at high humidity. Content Type Journal Article Category Original Paper Pages 1-11 DOI 10.1007/s10570-012-9815-0 Authors Yan Qing, School of Materials Science and Engineering, Central South University of Forestry and Technology, 498 Shaoshan South Road, Changsha, 410004 China Ronald Sabo, Forest Products Laboratory, United States Department of Agriculture, 1 Gifford Pinchot Drive, Madison, 53726-2398 WI, USA Zhiyong Cai, Forest Products Laboratory, United States Department of Agriculture, 1 Gifford Pinchot Drive, Madison, 53726-2398 WI, USA Yiqiang Wu, School of Materials Science and Engineering, Central South University of Forestry and Technology, 498 Shaoshan South Road, Changsha, 410004 China Journal Cellulose Online ISSN 1572-882X Print ISSN 0969-0239

Description:    Hydrorepellency was conferred to cotton fabrics by an hybrid organic–inorganic finishing via sol–gel. The nanosol was prepared by co-hydrolysis and condensation of tetraethoxysilane (TEOS) and 1H,1H,2H,2H–fluorooctyltriethoxysilane (FOS), or hexadecyltrimethoxysilane (C 16 ), as precursors in weakly acid medium. The application on cotton was carried out by padding with various impregnation times, followed by drying and thermal treatment, varying the FOS add-on from 5 till 30 % on fabric weight or C 16 add-on from 5 to 10 %. Treated samples were tested in terms of contact angles, drop absorption times, washing fastness and characterized by SEM, XPS and FTIR-ATR analyses. In the case of FOS modified nanosol applied with an impregnation time of 24 h or C 16 modified nanosol, water contact angles values very close or even higher than 150° were measured, typical of a superhydrophobic surface. The application of the proposed sol–gel process yielded also a satisfactory treatment fastness to domestic washing, in particular for FOS modified nanosol. Content Type Journal Article Category Original Paper Pages 1-10 DOI 10.1007/s10570-012-9821-2 Authors Monica Periolatto, Dipartimento di Scienza Applicata e Tecnologia, Politecnico di Torino, C.so Duca degli Abruzzi 24, 10129 Turin, Italy Franco Ferrero, Dipartimento di Scienza Applicata e Tecnologia, Politecnico di Torino, C.so Duca degli Abruzzi 24, 10129 Turin, Italy Alessio Montarsolo, CNR ISMAC, Istituto per lo Studio delle Macromolecole, C.so Pella 16, 13900 Biella, Italy Raffaella Mossotti, CNR ISMAC, Istituto per lo Studio delle Macromolecole, C.so Pella 16, 13900 Biella, Italy Journal Cellulose Online ISSN 1572-882X Print ISSN 0969-0239

Description:    Transparent and water repellent gas barrier cellulose films were fabricated by surface modification of alkali/urea regenerated cellulose (AUC) films by soaking in cationic alkylketene dimer (AKD) dispersion, drying, and heating. Highly water repellent and excellent gas barrier properties were obtained for AKD-treated and heated AUC films due to covering of the film surfaces by hydrophobic AKD components. The maximum AKD content of the films was 0.2 %. Oxygen transmission rates for AKD-treated AUC films at 0 % relative humidity (RH) were less than 0.0005 mL m −2 day −1 kPa −1 , the lowest detection limit of the instrument. Water contact angles on the AUC film increased from 50 to 110° after AKD treatment, and water uptake (immersion in water for 6 days) decreased from 92 to 20 %. Moreover, oxygen permeability decreased from 0.56 and 5.8 to 0.13 and 2.1 mL μm m −2 day −1 kPa −1 at 50 and 75 % RH, respectively, when the AKD content of the film was increased from 0 to 0.2 %. The present AKD-treated AUC film also had high light transparency (88 % at 600 nm), tensile strength (168 MPa), elongation at break (29 %), and work of fracture (37 MJ m −3 ). FT–IR analysis showed that AKD components were still present as major species on the AKD-treated film surfaces without hydrolysis at 2 months after conditioning the films at 23 °C and 50 % RH, indicating that such AKD molecules contributed to the hydrophobic nature of the AKD-treated AUC films. Content Type Journal Article Category Original Paper Pages 1-9 DOI 10.1007/s10570-012-9790-5 Authors Quanling Yang, Graduate School of Agricultural and Life Sciences, The University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo, 113-8657 Japan Tsuguyuki Saito, Graduate School of Agricultural and Life Sciences, The University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo, 113-8657 Japan Akira Isogai, Graduate School of Agricultural and Life Sciences, The University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo, 113-8657 Japan Journal Cellulose Online ISSN 1572-882X Print ISSN 0969-0239

Description:    Unbleached (UN), oxygen-delignified and fully-bleached (FB) birch fibers with a residual lignin content of ca. 3, 2 and 〈1 %, respectively, were used to produce nanofibrillated cellulose (NFC) and nanopaper by using an overpressure device. The tensile index, elongation and elastic modulus of nanopaper were compared and the effect of residual cell wall components accessed. Under similar manufacturing conditions, UN NFC produced nanopaper with a density of 0.99 g/cm 3 , higher than that from FB NFC (0.7 g/cm 3 ). This translated in much lower air permeability in the case of UN nanopaper (1 and 11 mL/min for UN and FB samples, respectively). Fundamentally, these observations are ascribed to the finer fibrils produced during microfluidization of UN fibers compared to those from lower yield counterparts (AFM roughness of 8 and 17 nm and surface areas of 124 and 98 m 2 /g for NFC from UN and FB fibers, respectively). As a result, values of stress at break and energy absorption of nanopaper from high yield fibers are distinctively higher than those from fully bleached NFC. Interactions of water with the surface and bulk material were affected by the chemical composition and structure of the nanofibrils. While UN nanopaper presented higher water contact angles their sorption capacity (and rate of water absorption) was much higher than those measured for nanopaper from FB NFC. These and other observations provided in this contribution are proposed to be related to the mechanoradical scavenging capacity of lignin in high shear microfluidization and the presence of residual heteropolysaccharides. Content Type Journal Article Category Original Paper Pages 1-15 DOI 10.1007/s10570-012-9788-z Authors Ana Ferrer, Department of Chemical Engineering, University of Cordoba, Cordoba, Spain Elisabet Quintana, Textile and Paper Engineering Department, Universitat Politècnica de Catalunya, 08222 Terrassa, Spain Ilari Filpponen, School of Chemical Technology, Department of Forest Products Technology, Aalto University, 00076 Aalto, Finland Iina Solala, School of Chemical Technology, Department of Forest Products Technology, Aalto University, 00076 Aalto, Finland Teresa Vidal, Textile and Paper Engineering Department, Universitat Politècnica de Catalunya, 08222 Terrassa, Spain Alejandro Rodríguez, Department of Chemical Engineering, University of Cordoba, Cordoba, Spain Janne Laine, School of Chemical Technology, Department of Forest Products Technology, Aalto University, 00076 Aalto, Finland Orlando J. Rojas, School of Chemical Technology, Department of Forest Products Technology, Aalto University, 00076 Aalto, Finland Journal Cellulose Online ISSN 1572-882X Print ISSN 0969-0239

Description:    Bacterial cellulose (BC) membranes were modified with oxygen (O 2 ), nitrogen (N 2 ), and tetrafluoromethane (CF 4 ) plasmas in order to enhance cell affinity. The surface properties of the pristine and plasma-treated BCs were analyzed through water contact angles, electron spectroscopy for chemical analysis (ESCA), and scanning electron microscopy. O 2 and N 2 plasmas changed the surface of BCs to more hydrophilic while CF 4 plasma altered BCs to be very hydrophobic. ESCA analyses indicated that O 2 , N 2 , and CF 4 plasmas incorporated the functionalities of carbon–oxygen, amides and amino, and carbon-fluoride on BCs, respectively. The effects of the plasma treatments on the adhesion of L-929 fibroblast and Chinese hamster ovary cell lines showed that the cell adhesion and proliferation of both cells was significantly improved on BC-CF 4 , in contrast with that on the pristine BC, BC-O 2 , and BC-N 2 , revealing a functionality-specific effect resulted from different plasmas. Moreover, protein adsorption tests indicated that a higher quantity of proteins in cell culture medium was adsorbed on the CF 4 plasma-treated BCs which presumably played the role of enhancing the subsequent cell growth. This work highlights the great potential of plasma treatments on the improvement of biocompatibility and surface property of BCs for biomedical applications. Content Type Journal Article Category Original Paper Pages 1-14 DOI 10.1007/s10570-012-9785-2 Authors Hengky Kurniawan, Department of Chemical Engineering, National Taiwan University of Science and Technology, 43, Keelung Rd., Sec. 4, Taipei, 106 Taiwan Jinn-Tsyy Lai, The Food Industry Research and Development Institute (FIRDI), 331 Shih-Pin Road, Hsinchu, 300 Taiwan Meng-Jiy Wang, Department of Chemical Engineering, National Taiwan University of Science and Technology, 43, Keelung Rd., Sec. 4, Taipei, 106 Taiwan Journal Cellulose Online ISSN 1572-882X Print ISSN 0969-0239

Description:    Fe 3 O 4 /chitosan/poly(acrylic acid) (Fe 3 O 4 /CS/PAA) composite particles, which are reusable, biodegradable and of high adsorption capacity, have been prepared through polymerizing acrylic acid in chitosan and Fe 3 O 4 nanoparticles aqueous solution. By varying in-feed mole ratio of carboxyl to amino group (n c /n a ) and reactant concentration, the average diameter of Fe 3 O 4 /CS/PAA composite particles can be controlled to vary from 100 to 300 nm. FT-IR, XRD and TEM were used to characterize Fe 3 O 4 /CS/PAA composite particles. Results showed that Fe 3 O 4 was indeed incorporated into CS/PAA particles. The composite particles showed high efficient to remove copper ions (II) in aqueous solution. Adsorption kinetic studies showed that the adsorption process followed a pseudo-second-order kinetic model and the equilibrium data agreed well with the Langmuir model. The saturated adsorption capacity obtained from the experimental was 193 mg/g in close to proximity to the data 200 mg/g calculated from Langmuir model. The saturated adsorption capacity still retained 100 mg/g after three cycles of adsorption–desorption of copper ions (II). Content Type Journal Article Category Original Paper Pages 1-11 DOI 10.1007/s10570-012-9783-4 Authors Sai Zhang, Anhui Province Key Laboratory of Environment-friendly Polymer Materials, College of Chemistry and Chemical Engineering, Anhui University, Hefei, 230039 People’s Republic of China YiFeng Zhou, Anhui Province Key Laboratory of Environment-friendly Polymer Materials, College of Chemistry and Chemical Engineering, Anhui University, Hefei, 230039 People’s Republic of China WangYan Nie, Anhui Province Key Laboratory of Environment-friendly Polymer Materials, College of Chemistry and Chemical Engineering, Anhui University, Hefei, 230039 People’s Republic of China LinYong Song, Anhui Province Key Laboratory of Environment-friendly Polymer Materials, College of Chemistry and Chemical Engineering, Anhui University, Hefei, 230039 People’s Republic of China Journal Cellulose Online ISSN 1572-882X Print ISSN 0969-0239

Description:    Seven varieties of flax ( Linum usitatissimum ) fibres were analyzed in order to gain a deeper insight into the morphological features of the crystalline assembly. Different spectroscopic techniques and a chemical bleaching process were used to provide an accurate description of the lateral arrangement of the polysaccharide chains within the fibre cell wall. The flax fibres were analyzed in their natural state and after an extraction treatment of the non-crystalline components such as hemicelluloses, pectins and phenolics. The chemical bleaching process consisted of a Soxhlet extraction in toluene, a sodium chlorite treatment and an alkaline extraction of the residual hemicelluloses. Solid-state 13 C nuclear magnetic resonance (NMR) confirmed the sequential removal of the non-cellulosic components from the flax cell wall. Both wide-angle X-ray diffraction (WAXD) and solid-state 13 C NMR provided measures of the crystallite thicknesses and overall crystallinities before and after treatment. The existence of non-cellulosic highly ordered paracrystalline domains was also evidenced by proton spin relaxation time calculation. Whereas the overall crystallinity determined by WAXD decreased after treatment, the cellulose crystallinity calculated with the help of the solid-state 13 C NMR slightly increased. This is explained by the difference in chemical selectivity between these two techniques and by the paracrystalline state of both hemicelluloses and pectins. Strong adhesion between cellulose crystallites, hemicelluloses and pectins in the fibres was evidenced by low spin–spin relaxation times and by an increase in crystallite thickness after bleaching. A simple model is proposed that describes the rearrangement of the macromolecules during the bleaching process. Content Type Journal Article Category Original Paper Pages 1-18 DOI 10.1007/s10570-012-9786-1 Authors Benoît Duchemin, LOMC, UMR 6294, CNRS-Université du Havre, 53 rue Prony, 76058 Le Havre, France Anthony Thuault, LOMC, UMR 6294, CNRS-Université du Havre, 53 rue Prony, 76058 Le Havre, France Aurélie Vicente, Laboratoire Catalyse et Spectrochimie (LCS), ENSICAEN, Université de Caen, CNRS, 14050 Caen, France Baptiste Rigaud, Laboratoire Catalyse et Spectrochimie (LCS), ENSICAEN, Université de Caen, CNRS, 14050 Caen, France Christian Fernandez, Laboratoire Catalyse et Spectrochimie (LCS), ENSICAEN, Université de Caen, CNRS, 14050 Caen, France Sophie Eve, Laboratoire de Cristallographie et de Sciences des Matériaux, ENSICAEN, Université de Caen, CNRS, 14050 Caen, France Journal Cellulose Online ISSN 1572-882X Print ISSN 0969-0239

Description:    Chemical surface modification of nanofibrillated cellulose (NFC) was performed using a long aliphatic isocyanate chain. Different molar ratios of the coupling agents were tested, i.e., 1, 10, 30 equivalents with respect to hydroxyl groups of the NFC surface. FE-SEM analyses revealed that there were no changes in their morphology thus keeping nanofibril-like structure with about 30 nm of diameter. All these samples were characterized by different techniques (e.g., FTIR) to check the efficiency of the grafting. Hydrophobic NFC were achieved whatever the grafting agent ratio. The Degree of Substitution was determined by Elemental Analyses and the Degree of Substitution of the Surface was calculated thanks to X-ray Photoelectron Spectroscopy data. Combining these two techniques, the Internal Degree of Substitution was proposed for the first time. It indicates if the modification occurs also within NFC internal layers. Surface (contact angle), rheological (water suspension viscosity) and thermal properties (ThermoGravimetric Analysis) of grafted NFC do not follow the expected linear evolution of properties with the increase of molar ratio. X-Ray Diffraction analyses showed that the grafted aliphatic chains display crystalline waxy domains at some ratios. A model for aliphatic chain organization at the surface is proposed and clearly explained for the first time why a compromise in molar ratio is necessary to achieve best properties. Content Type Journal Article Category Original Paper Pages 1-17 DOI 10.1007/s10570-012-9780-7 Authors Karim Missoum, Laboratory of Pulp and Paper Science (LGP2), 461, rue de la papeterie, BP65, 38402 St-Martin-d’Hères Cedex, France Julien Bras, Laboratory of Pulp and Paper Science (LGP2), 461, rue de la papeterie, BP65, 38402 St-Martin-d’Hères Cedex, France Mohamed Naceur Belgacem, Laboratory of Pulp and Paper Science (LGP2), 461, rue de la papeterie, BP65, 38402 St-Martin-d’Hères Cedex, France Journal Cellulose Online ISSN 1572-882X Print ISSN 0969-0239