Polymerization of aniline in the presence of cellulose nano-fiber (CNF) is carried out. We used dried CNF, CNF suspension, and CNF treated by enzyme and ultra-sonification to obtain polyaniline (PANI)/CNF as a synthetic polymer/natural nano-polymer composite. The polymerization proceeds on the surface of CNF as a nano-reaction field. Resultant composites show extended effective π-conjugation length because CNF as a reaction field in molecular level produced polymer with expanded coil structure with an aid of orientation effect of CNF. Possibility of PANI β-pleats structure in molecular level of PANI on the CNF is also discussed. SEM observation showed that fine structure is easily obtained by combining PANI with CNF. Carbonization of PANI/CNF allows production of nano-fine form with shape preserved carbonization (SPC).
To understand the positional and temporal defense mechanisms of coniferous tree bark at the tissue and cellular levels, the phloem topochemistry and structural properties were examined after artificially induced bark defense reactions. Wounding and fungal inoculation with Endoconidiophora polonica of spruce bark were carried out, and phloem tissues were frequently collected to follow the temporal and spatial progress of chemical and structural responses. The changes in (+)-catechin, (−)-epicatechin, stilbene glucoside, and resin acid distribution, and accumulation patterns within the phloem, were mapped using time-of-flight secondary ion mass spectrometry (cryo-ToF-SIMS), alongside detailed structural (LM, TEM, SEM) and quantitative chemical microanalyses of the tissues. Our results show that axial phloem parenchyma cells of Norway spruce contain (+)-catechins, the amount of which locally increases in response to fungal inoculation. The preformed, constitutive distribution and accumulation patterns of (+)-catechins closely follow those of stilbene glucosides. Phloem phenolics are not translocated but form a layered defense barrier with oleoresin compounds in response to pathogen attack. Our results suggest that axial phloem parenchyma cells are the primary location for (+)-catechin storage and synthesis in Norway spruce phloem. Chemical mapping of bark defensive metabolites by cryo-ToF-SIMS, in addition to structural and chemical microanalyses of the defense reactions, can provide novel information on the local amplitudes and localizations of chemical and structural defense mechanisms and pathogen–host interactions of trees.
Changes in the dimensions of lignocellulose nanofibrils (LCNFs) with different lignin contents from betung bamboo (Dendrocalamus asper) by enzymatic hydrolysis using endoglucanase (EG) were investigated. Lignin contents were adjusted from 3% to 27% by NaClO2/acetic acid treatment, and LCNFs were prepared using a wet disk-mill (WDM). The dimensions of the LCNFs significantly decreased with decreasing lignin content and increasing EG addition. With increasing EG content, the average diameter of the LCNFs significantly decreased, even though they contained parts of hemicellulose and lignin. The crystal structure showed the typical cellulose I structure in all samples, but the intensity of the diffraction peak slightly changed depending on the lignin and EG contents. The crystallinity index (CrI) values of the LCNFs increased a maximum of 23.8% (LCNF-L27) under increasing EG addition, regardless of the lignin content. With the EG addition of three times the LCNF amount, LCNF-L3 showed the highest CrI value (59.1%). By controlling the composition and structure of LCNFs, it is expected that the wide range of properties of these materials can extend the property range available for existing materials.