All-cellulose nanocomposite fibers produced by melt spinning cellulose acetate butyrate and cellulose nanocrystals

Bio-based continuous fibers were prepared by melt spinning cellulose acetate butyrate (CAB), cellulose nanocrystals (CNC) and triethyl citrate. A CNC organo-gel dispersion technique was used and the prepared materials (2 and 10 wt% CNC) were melt spun using a twin-screw micro-compounder and drawn to a ratio of 1.5. The microscopy studies showed that the addition of CNC in CAB resulted in defect-free and smooth fiber surfaces. An addition of 10 wt% CNC enhanced the storage modulus and increased the tensile strength and Young’s modulus. Fiber drawing improved the mechanical properties further. In addition, a micromechanical model of the composite material was used to estimate the stiffness and showed that theoretical values were exceeded for the lower concentration of CNC but not reached for the higher concentration. In conclusion, this dispersion technique combined with melt spinning can be used to produce all-cellulose nanocomposites fibers and that both the increase in CNC volume fraction and the fiber drawing increased the mechanical performance.     

Thermodynamics of cesium complexes formation with 18-crown-6 in ionic liquids

Thermodynamic data for cesium complexes formation with 18-crown-6 (18C6, L) [Cs(18C6)]⁺ in N-butyl-4-methyl-pyridinium tetrafluoroborate ([BMPy][BF₄], I), in 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF₄], II) and in 1-butyl-3-methylimidazolium dicyanamide ([BMIM][N(CN)₂], III) were measured with NMR ¹³³Cs technique at 23–50 °C. The stability of cesium complex in RTILs is estimated to be in the range between water and DMFA. Stability constants for [Cs(18C6)]⁺ are found to decrease as temperature is increasing. The following values for lgK(Cs+L) and ΔH(Cs+L) at 23 °C are determined: 2.6 (0.3), ?47(1) kJ/mol (RTIL I); 2.8(0.3), ?80(3) kJ/mol (RTIL II) and 3.03 (0.08), ?47(2) kJ/mol (RTIL III). It is demonstrated that enthalpy change promotes complex formation while the corresponding change of entropy is negative and provides decomposition of [Cs(18C6)]⁺.     

Secreted fungal sulfhydryl oxidases: sequence analysis and characterisation of a representative flavin-dependent enzyme from <Emphasis Type="Italic">Aspergillus oryzae</Emphasis>

Background  

Sulfhydryl oxidases are flavin-dependent enzymes that catalyse the formation of de novo disulfide bonds from free thiol groups, with the reduction of molecular oxygen to hydrogen peroxide. Sulfhydryl oxidases have been investigated in the food industry to remove the burnt flavour of ultraheat-treated milk and are currently studied as potential crosslinking enzymes, aiming at strengthening wheat dough and improving the overall bread quality.     

Exploring laccase-like multicopper oxidase genes from the ascomycete <Emphasis Type="Italic">Trichoderma reesei</Emphasis>: a functional,phylogenetic and evolutionary study

Background  

The diversity and function of ligninolytic genes in soil-inhabiting ascomycetes has not yet been elucidated, despite their possible role in plant litter decay processes. Among ascomycetes, Trichoderma reesei is a model organism of cellulose and hemicellulose degradation, used for its unique secretion ability especially for cellulase production. T. reesei has only been reported as a cellulolytic and hemicellulolytic organism although genome annotation revealed 6 laccase-like multicopper oxidase (LMCO) genes. The purpose of this work was i) to validate the function of a candidate LMCO gene from T. reesei, and ii) to reconstruct LMCO phylogeny and perform evolutionary analysis testing for positive selection.     

Biocompatible Fibrous Networks of Cellulose Nanofibres and Collagen Crosslinked Using Genipin: Potential as Artificial Ligament/Tendons

Bio‐based fibrous nanocomposites of cellulose nanofibres and non‐crosslinked/crosslinked collagen were prepared by in situ pH‐induced fibrillation of collagen phase and sterilized using gamma rays at 25 KGy. Collagen phase is crosslinked using genipin, a bio‐based crosslinker that introduces flexible crosslinks. Microscopy studies of the prepared materials showed nanostructured fibrous collagen and cellulose dispersed in collagen matrix. Mechanical performance of the sterilized nanocomposites was close to that of natural ligament and tendon, in simulated body conditions. Cytocompatibility studies indicated that these nanocomposites allowed human ligament cell and human endothelial cell adhesion, growth, and differentiation; which is eminently favourable to ligament tissue engineering.

     

Stability and Photoisomerization of Stilbenes Isolated from the Bark of Norway Spruce Roots

Stilbenes or stilbenoids, major polyphenolic compounds of the bark of Norway spruce (Picea abies L. Karst), have potential future applications as drugs, preservatives and other functional ingredients due to their antioxidative, antibacterial and antifungal properties. Stilbenes are photosensitive and UV and fluorescent light induce trans to cis isomerisation via intramolecular cyclization. So far, the characterizations of possible new compounds derived from trans-stilbenes under UV light exposure have been mainly tentative based only on UV or MS spectra without utilizing more detailed structural spectroscopy techniques such as NMR. The objective of this work was to study the stability of biologically interesting and readily available stilbenes such as astringin and isorhapontin and their aglucones piceatannol and isorhapontigenin, which have not been studied previously. The effects of fluorescent and UV light and storage on the stability of trans stilbenes were assessed and the identification and characterisation of new compounds formed during our experiments were carried out by chromatographic (HPLC, GC) and spectroscopic techniques (UV, MS, NMR). The stilbenes undergo a trans to cis isomerisation under extended UV irradiation by intramolecular cyclisation (by the formation of a new C-C bond and the loss of two hydrogens) to phenanthrene structures. The characterised compounds are novel and not described previously.     

Glucomannan composite films with cellulose nanowhiskers

Spruce galactoglucomannans (GGM) and konjac glucomannan (KGM) were mixed with cellulose nanowhiskers (CNW) to form composite films. Remarkable effects of CNW on the appearance of the films were detected when viewed with regular and polarizing optical microscopes and with a scanning electron microscope. Addition of CNW to KGM-based films induced the formation of fiberlike structures with lengths of several millimeters. In GGM-based films, rodlike structures with lengths of several tens of micrometers were formed. The degree of crystallinity of mannan in the plasticized KGM-based films increased slightly when CNW were added, from 25 to 30%. The tensile strength of the KGM-based films not containing glycerol increased with increasing CNW content from 57 to 74 MPa, but that of glycerol-plasticized KGM and GGM films was not affected. Interestingly, the notable differences in the film structure did not appear to be related to the thermal properties of the films.     

Sensor for the detection of local contrast gloss of products

We introduce a sensor for providing information on the local contrast gloss (or luster) of products. The sensor also provides information of the local specular gloss of the object. The signals of this sensor are produced by diffractive optical elements from fields that are scattered in the diffuse and specular directions from the object. We present specular gloss, diffuse-reflectance factor related to the contrast gloss, and visibility maps measured from black prints on paper. High variation can be observed in the relevant gloss parameters obtained from the printed area. In addition, borders of the print can be clearly detected from the diffuse-reflectance-factor maps. The sensor also allows detection of raster points of a print. This sensor opens up entirely new means to study prints and other substances.     

Tracing the allomerization pathways of chlorophylls by (18)O-labeling and mass spectrometry

The Willst?tter allomerization reaction of chlorophylls (Chl) has posed a difficult problem in Chl and photosynthesis research over the past 90 years. Here, we present strong additional evidence, based on (18)O-labeling and mass spectrometry, for the previously published free-radical allomerization (FRA) mechanism (Hynninen, Z. Naturforsch. 1981, 36b, 1010-1016). This mechanism is also complemented now by describing two alternative pathways for the formation of 13(2)(S/R)-hydroxy-Chl a. The results from the (18,18)O(2)-experiments suggest that the predominant route for the formation of the 13(2)(S/R)-hydroxy-Chl a under essentially anhydrous conditions (anhydrous Chl and thoroughly dried methanol) is the homolytic cleavage of the C-13(2)-hydroperoxide intermediate. However, if Chl dihydrate and undried methanol are used in the reaction mixture, the direct route from the Chl C-13(2) radical to 13(2)(S/R)-hydroxy-Chl a can be predicted to become significant. The results from the (18,18)O(2)-allomerization experiments described in this paper also verified that the 13(2)(S/R)-methoxy-lactone derivatives and the 15-glyoxylic acid derivative of Chl a incorporated each a single (18)O-atom, whereas 13(2)(R/S)-methoxy-Chl a remained unlabeled. Consequently, these allomers are formed via the pathways previously suggested in the original FRA mechanism. The possible factors contributing to the control of the allomerization reactions are considered. Finally, the relationship between the allomerization reactions of Chl a and those of Chl b and BChl a is briefly discussed.