Wood Polysaccharides Research Articles

Characterizing the chemistry of artificially degraded Scots pine wood serving as a model of naturally degraded waterlogged wood using1H–13C HSQC NMR

AbstractChemically and biologically degraded Scots pine wood was prepared as a model material for the research on new conservation agents for waterlogged archeological wood. In this study, the model wood was characterized using a 2D1H–13C solution-state NMR technique without derivatization, isolation, or extraction to assess the effect of applied degradation processes on its chemical composition and structure. The results clearly show how the two artificially degraded model wood types are chemically different. Biological decay by the brown-rot fungus Coniophora puteana caused degradation of wood polysaccharides, with heavy depletion in arabinan, mannan, and galactan, along with an increase in the cellulose's reducing ends (i.e., lowering the degree of polymerization) and partial deacetylation of mannan. The fungus cleaved roughly one-fifth of the β-aryl ethers in lignin, leading to a broadening effect on the lignin aromatic unit contours; other lignin sidechains were left untouched. Chemical degradation by NaOH hydrolysis resulted in a depletion in mannan, galactan, and glucan, as well as efficient deacetylation of mannan. It also decreased lignin content, causing changes in its structure; minor β-aryl ether cleavage along with substantial phenylcoumaran cleavage were evident. Detailed knowledge about the chemical composition and structure of artificially degraded model pine wood obtained in this research is necessary to understand the reactivity of these wood types with chemicals used for their conservation. This research will help explain the differences in the stabilization effectiveness observed between these wood types treated during conservation and understand the stabilization mechanisms, thus contributing to developing new, more effective conservation agents for wooden artifacts of Cultural Heritage.

Role of Lignin in Moisture Interactions of Cellulose Microfibril Structures in Wood

Wood is a complex, multi‐component material with a variety of applications. The properties of wood are especially sensitive to its moisture content and comprehending wood–water interactions is thus paramount. Understanding of the moisture interactions of the wood polysaccharide components, cellulose microfibrils and hemicelluloses, is improving. However, the role of lignin remains less clear. In this work, X‐ray scattering measurements were carried out on delignified spruce undergoing a desorption‐adsorption cycle, and the results were compared to previous data from untreated wood. In addition, a molecular model of the cell wall nanostructure, including the main chemical components, was used to support the experimental results. Based on the small‐angle scattering, delignification affects the arrangement of cellulose microfibrils in the cell wall by increasing their packing distance. Wide‐angle scattering shows that delignification has no substantial effect on the cellulose crystal structure and how it changes with moisture. Both the scattering results and simulations suggest that lignin is a passive, rather than an active participant in the moisture response of microfibril bundles in wood cell walls. Small‐angle scattering from fully wet delignified wood reveals a contribution that can be assigned to aligned nanometer scale pores which close during drying.

Chemical changes of polysaccharides in heat-treated European beech wood

This work deals with the influence of different heat treatment temperatures (140, 150, 160, 170, 180, 190, 200, and 210 °C) on changes in sapwood and red heartwood of European beech (Fagus sylvatica L.). According to the results of wet chemistry methods, HPLC (high-performance liquid chromatography), FTIR (Fourier transform infrared spectroscopy), SEC (size exclusion chromatography), the wood constituents in sapwood and red heartwood behaved similarly to heat treatment, but the individual proportions were different. The loss of hemicelluloses and the increase in extractives with increasing temperature were more pronounced in sapwood. The amount of cellulose in sapwood and red heartwood showed similar behaviour with increasing temperature. Thermal treatment causes changes in cellulose crystallinity, and the formation of aromatic structures, mainly in beech sapwood. However, the increase in the lignin content of red heartwood was significantly lower than that of sapwood due to its auto condensation, and formation of pseudo-lignin. Among the carbohydrates, the most significant changes were observed in xylose content, which was almost twice as high in red heartwood as in sapwood. Other carbohydrates (glucose, mannose, galactose, and arabinose) reached similar values in sapwood and red heartwood.

Structural differences of cell walls in earlywood and latewood of Pinus sylvestris and their contribution to biomass recalcitrance.

Scots pine (Pinus sylvestris L.) is an evergreen coniferous tree with wide distribution and good growth performance in a range of habitats. Therefore, wood from P. sylvestris is produced in many managed forests and is frequently used in industry. Despite the importance of pine wood, we still do not fully understand its molecular structure what limits improvements in its processing. One of the basic features leading to variation in wood properties is the presence of earlywood and latewood which form annual growth rings. Here, we characterise biochemical traits that differentiate cell walls of earlywood and latewood in Scots pine. We discover that latewood is less recalcitrant to enzymatic digestion, with galactoglucomannan showing particularly pronounced difference in accessibility. Interestingly, characterisation of lignin reveals a higher proportion of coniferaldehydes in pine latewood and suggests the presence of a different linkage landscape in this wood type. With complementary analysis of wood polysaccharides this enabled us to propose the first detailed molecular model of earlywood and latewood and to conclude that the variation in lignin structure is likely the main determinant of differences in recalcitrance observed between the two wood types in pine. Our discoveries lay the foundation for improvements in industrial processes that use pine wood since we show clear pathways for increasing the efficiency of enzymatic processing of this renewable material. Our work will help guide future breeding of pine trees with desired timber properties and can help link molecular structure of softwood cell walls to function of the different types of xylem in conifers.

Construction and exploration of a dilute acid pretreatment dataset on poplar wood to propose trade-offs of chemicals evolution

This work provides one of the most comprehensive datasets to date on the chemical evolution of poplar wood polysaccharides and their degradation products during dilute acid pretreatment. Based on the literature, an unprecedented set of 38 conditions was generated using a design of experiment approach within the following parameter ranges: 2–60 min, 120–190 °C, 0–4%wt H2SO4. Solid wood residues and pretreatment liquid, recovered separately, were analyzed for no less than 12 compounds: sugars, inhibitors, and lignin. Particular attention was paid to the sampling and method description so that the dataset, fully available, can be easily shared and reused. This unique dataset was explored using models to follow the evolution of each chemical species. A more original and in-depth analysis was carried out by combining the models using desirability functions, which enabled us to propose trade-offs between the evolution of the different compounds according to the targeted production objectives.

Degradation of Chemical Components of Thermally Modified Robinia pseudoacacia L. Wood and Its Effect on the Change in Mechanical Properties

Currently, emphasis is placed on using environmentally friendly materials both from a structural point of view and the application of protective means. For this reason, it is advisable to deal with the thermal modification of wood, which does not require the application of protective substances, to increase its service life. The main reason for the thermal modification of black locust is that although black locust grows abundantly in our country, it has no industrial use. It is mainly used outdoors, where thermal modification could increase its resistance. This article deals with the thermal modification of black locust wood (Robinia pseudoacacia L.) and the impact of this modification on the chemical components of the wood with an overlap in the change in mechanical properties compared to untreated wood. Static (LOP, MOR, and MOE) and dynamic (IBS) bending properties were evaluated as representative mechanical properties. At the same time, the impact of thermal modification on the representation of chemical components of wood (cellulose, lignin, hemicellulose) was also tested. As a result of the heat treatment, the mechanical properties gradually decreased as the temperature increased. The highest decrease in mechanical values found at 210 °C was 43.7% for LOP and 45.1% for MOR. Thermal modification caused a decrease in the content of wood polysaccharides (the decrease in hemicelluloses content was 33.2% and the drop in cellulose was about 29.9% in samples treated at 210 °C), but the relative amount of lignin in the wood subjected to increased temperature was higher due to autocondensation, and mainly because of polysaccharide loss. Based on the correlations between chemical and mechanical changes caused by thermal modification, it is possible to observe the effects of reducing the proportions of chemical components and changes in their characteristic properties (DP, TCI) on the reduction in mechanical properties. The results of this research serve to better understand the behavior of black locust wood during thermal modification, which can primarily be used to increase its application use.

Ultrastructural behavior of cell wall polysaccharides

Studies on the behavior of wood polysaccharides inside and outside the cell wall were carried out under varying conditions using the electron microscope in combination with physico-chemical methods to gain new information on the super- molecular structure of the polysaccharides. Several fractions containing different polyoses were obtained by fractionation of the alkali extract of holocellulose. Isolated polyoses are at least partially able to arrange themselves in fibrillar elements. After delignification, the cellulose is recognizable within the cell wall as microfibrils with an average diameter of about 250 À. However, these fibrillar units seem to be rather unstable as they can easily be split into units 120 À in diameter by chemical treatment. After partial hydrolysis, isolated cellulose shows more subunits about 30 A in diameter at higher magnification. Moreover, the more sensitive portions of the fibrils in the longitudinal direction are attacked by partial hydrolysis, and these portions seem to grow with increasing duration of the hydrolysis. Fractionation of cellulose isolated from thermally treated wood shows that the chain fragments are multiples about 300 À in length, A tentative model of the supermolecular arrangement of the cellulose in relation to the other cell wall components is presented.

Ionic Liquid Efficiency on Wood Dissolution and Polysaccharide Identification

The wood polysaccharide composition, a new analytical method, based on ionic liquid dissolution of low amount of biomass coupled with an ELISA essay of polysaccharides. In the present work, we synthesized and tested several imidazolium and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) based ILs for their ability to solubilize Douglas-fir wood while preserving the wall polymer integrity. The couple times-temperatures have been essayed for wood dissolution. Then their efficiency for wood biomass dissolution was compared to the impact of IL on storing and/or destroy polysaccharides. Thanks to the ELISA technique with a set of mAbs against epitopes of the main hemicellulose, pectin, and protein families of cell wall components. Wood destructuration at 80˚C with the 1-ethyl-3-methylimidazolium bromide represents a good compromise of wood dissolution efficiency and low polysaccharide destruction.

CHANGES IN THE CHEMICAL COMPOSITION OF WOOD PECEA OBOVATA LEDEB. UNDER THE INFLUENCE OF IPS TYPOGRAPHUS L.

The process of forest destruction is very dynamic and covers the entire boreal zone of the Northern hemisphere. Against the background of deterioration of the sanitary condition of plantings, pathogenic organisms become more active. The article presents materials on the study of the chemical composition of wood of individuals of various life conditions of Siberian spruce (Pícea obovata Ledeb.) in the conditions of distribution of bark beetle (Ips typographus L.). Plants of various life States were studied for the content of water-soluble and resin-like extractives, tannins, lignin, and polysaccharides. The obtained data were subjected to statistical processing. Under the influence of the bark beetle-typographer, no significant differences were found between individuals of different life States in the polymer structural components of spruce wood (lignin and polysaccharides). In the course of the study, it was noted that during the colonization of bark beetles in plants, the content of extractive substances increases. With deterioration, the proportion of phenolic compounds begins to increase from 25.8% in plants of good condition to 37.5% in plants of unsatisfactory condition, with a decrease in the proportion of resinous substances. An increase in phenolic compounds is associated with an increase in tannins. The highest content of all groups of metabolites (including tannins) was observed in individuals of a satisfactory life state and is 7.15% of the a.s.s.

Genomic and Transcriptomic Insight of Giant Sclerotium Formation of Wood-Decay Fungi.

Many fungi form persistent and dormant sclerotia with compact hardened mycelia during unfavorable circumstances. While most of these sclerotia are small in size, Wolfiporia cocos, a wood-decay fungus, grows into giant sclerotia, which are mainly composed of polysaccharides of linear (1→3)-β-D-glucans. To explore the underlying mechanism of converting sophisticated wood polysaccharides for biosynthesis of highly homogenized glucans in W. cocos, we sequenced and assembled the genome of a cultivated W. cocos strain (WCLT) in China. The 62-Mb haploid genome contains 44.2% repeat sequences, of which, 48.0% are transposable elements (TEs). Contrary to the genome of W. cocos from North America, WCLT has independently undergone a partial genome duplication (PGD) event. The large-scale TE insertion and PGD occurrence overlapped with an archeological Pleistocene stage of low oxygen and high temperature, and these stresses might have induced the differences in sclerotium due to geographical distribution. The wood decomposition enzymes, as well as sclerotium-regulator kinases, aquaporins, and highly expanded gene families such as NAD-related families, together with actively expressed 1,3-β-glucan synthase for sclerotium polysaccharides, all have contributed to the sclerotium formation and expansion. This study shall inspire further exploration on how fungi convert wood into simple glucans in the sclerotium of W. cocos.

Antiviral Properties of Water Extracts of Mycelium Inonotus rheades (Pers.) P. Karst. (1882) against the Virus of Tick-Borne Encephalitis Virus in vitro

Background. Tick-borne encephalitis virus is dangerous and widespread pathogen that is transmitted to humans through the bites of hard ticks. Wild fungi, such as xylotrophic basidiomycetes, are widely used in traditional medicine to treat the infectious diseases and are promising natural sources of new antiviral agents. It was previously shown that aqueous extracts from the mycelium of the Inonotus rheades (Pers.) P. Karst. (1882) fungus exhibit significant antiviral activity against tick-borne encephalitis virus, however, the mechanisms of this activity remain unclear.Aim. To analyze the relationship between the virucidal properties of I. rheades extract and the substrate on which the cultivation was carried out.Materials and methods. The mycelium was grown either in a standard liquid medium with wort or on wooden disks from birch. Extracts of water-soluble polysaccharides were prepared from both mycelium samples. The concentration of infectious tick-borne encephalitis virus was determined using the method of titration of plaque-forming components (PFU). Approximately 30 000 PFU of tick-borne encephalitis virus was mixed with an equal volume of corresponding I. rheades extract at concentration of 8 mg/mL and incubated for 30 min at 37 °C. Afterwards, the residual infectivity of tick-borne encephalitis virus was determined using the identical virus sample incubated with sterile water as a reference.Results. It was found that treatment of tick-borne encephalitis virus with extracts from I. rheades mycelium resulted in inhibition of the infectivity of the virus in the cell culture. However, the same strain of I. rheades, grown on medium with wort, did not exhibit antiviral properties.Conclusions. Virucidal substances are likely to be not the main metabolites of the mycelium of I. rheades, but are rather metabolized wood polysaccharides. Further research is needed to more accurately identify the active ingredients and assess their antiviral activity.

Co-production of Xylooligosaccharides and Xylose From Poplar Sawdust by Recombinant Endo-1,4-β-Xylanase and β-Xylosidase Mixture Hydrolysis.

As is well-known, endo-1,4-β-xylanase and β-xylosidase are the rate-limiting enzymes in the degradation of xylan (the major hemicellulosic component), main functions of which are cleavaging xylan to release xylooligosaccharides (XOS) and xylose that these two compounds have important application value in fuel, food, and other industries. This study focuses on enzymatic hydrolysis of poplar sawdust xylan for production of XOS and xylose by a GH11 endo-1,4-β-xylanase MxynB-8 and a GH39 β-xylosidase Xln-DT. MxynB-8 showed excellent ability to hydrolyze hemicellulose of broadleaf plants, such as poplar. Under optimized conditions (50°C, pH 6.0, dosage of 500 U/g, substrate concentration of 2 mg/mL), the final XOS yield was 85.5%, and the content of XOS2−3 reached 93.9% after 18 h. The enzymatic efficiency by MxynB-8 based on the poplar sawdust xylan in the raw material was 30.5%. Xln-DT showed excellent xylose/glucose/arabinose tolerance, which is applied as a candidate to apply in degradation of hemicellulose. In addition, the process and enzymatic mode of poplar sawdust xylan with MxynB-8 and Xln-DT were investigated. The results showed that the enzymatic hydrolysis yield of poplar sawdust xylan was improved by adding Xln-DT, and a xylose-rich hydrolysate could be obtained at high purity, with the xylose yield of 89.9%. The enzymatic hydrolysis yield was higher (32.2%) by using MxynB-8 and Xln-DT together. This study provides a deep understanding of double-enzyme synergetic enzymolysis of wood polysaccharides to valuable products.

Manufacture of Platform Chemicals from Pine Wood Polysaccharides in Media Containing Acidic Ionic Liquids.

Pinus pinaster wood samples were subjected to chemical processing for manufacturing furans and organic acids from the polysaccharide fractions (cellulose and hemicellulose). The operation was performed in a single reaction stage at 180 or 190 °C, using a microwave reactor. The reaction media contained wood, water, methyl isobutyl ketone, and an acidic ionic liquid, which acted as a catalyst. In media catalyzed with 1-butyl-3-methylimidazolium hydrogen sulfate, up to 60.5% pentosan conversion into furfural was achieved, but the conversions of cellulose and (galacto) glucomannan in levulinic acid were low. Improved results were achieved when AILs bearing a sulfonated alkyl chain were employed as catalysts. In media containing 1-(3-sulfopropyl)-3-methylimidazolium hydrogen sulfate as a catalyst, near quantitative conversion of pentosans into furfural was achieved at a short reaction time (7.5 min), together with 32.8% conversion of hexosans into levulinic acid. Longer reaction times improved the production of organic acids, but resulted in some furfural consumption. A similar reaction pattern was observed in experiments using 1-(3-sulfobutyl)-3-methylimidazolium hydrogen sulfate as a catalyst.

Hypoxia is regulating enzymatic wood decomposition and intracellular carbohydrate metabolism in filamentous white rot fungus

BackgroundFungal decomposition of wood is considered as a strictly aerobic process. However, recent findings on wood-decaying fungi to produce ethanol from various lignocelluloses under oxygen-depleted conditions lead us to question this. We designed gene expression study of the white rot fungus Phlebia radiata (isolate FBCC0043) by adopting comparative transcriptomics and functional genomics on solid lignocellulose substrates under varying cultivation atmospheric conditions.ResultsSwitch to fermentative conditions was a major regulator for intracellular metabolism and extracellular enzymatic degradation of wood polysaccharides. Changes in the expression profiles of CAZy (carbohydrate-active enzyme) encoding genes upon oxygen depletion, lead into an alternative wood decomposition strategy. Surprisingly, we noticed higher cellulolytic activity under fermentative conditions in comparison to aerobic cultivation. In addition, our results manifest how oxygen depletion affects over 200 genes of fungal primary metabolism including several transcription factors. We present new functions for acetate generating phosphoketolase pathway and its potential regulator, Adr1 transcription factor, in carbon catabolism under oxygen depletion.ConclusionsPhysiologically resilient wood-decomposing Basidiomycota species P. radiata is capable of thriving under respirative and fermentative conditions utilizing only untreated lignocellulose as carbon source. Hypoxia-response mechanism in the fungus is, however, divergent from the regulation described for Ascomycota fermenting yeasts or animal-pathogenic species of Basidiomycota.

Liberation of recalcitrant cell wall sugars from oak barrels into bourbon whiskey during aging

Oak barrels have been used by humans for thousands of years to store and transport valuable materials. Early settlers of the United States in Kentucky began charring the interior of new white oak barrels prior to aging distillate to create the distinctively flavored spirit we know as bourbon whiskey. Despite the unique flavor and cultural significance of “America’s Spirit”, little is known about the wood-distillate interaction that shapes bourbon whiskey. Here, we employed an inverse method to measure the loss of specific wood polysaccharides in the oak cask during aging for up to ten years. We found that the structural cell wall wood biopolymer, cellulose, was partially decrystallized by the charring process. This pyrolytic fracturing and subsequent exposure to the distillate was accompanied by a steady loss of sugars from the cellulose and hemicellulose fractions of the oak cask. Distinct layers of structural degradation and product release from within the barrel stave are formed over time as the distillate expands into and contracts from the barrel staves. This complex, wood-sugar release process is likely associated with the time-dependent generation of the unique palate of bourbon whiskey.

Engineering Non-cellulosic Polysaccharides of Wood for the Biorefinery.

Non-cellulosic polysaccharides constitute approximately one third of usable woody biomass for human exploitation. In contrast to cellulose, these substances are composed of several different types of unit monosaccharides and their backbones are substituted by various groups. Their structural diversity and recent examples of their modification in transgenic plants and mutants suggest they can be targeted for improving wood-processing properties, thereby facilitating conversion of wood in a biorefinery setting. Critical knowledge on their structure-function relationship is slowly emerging, although our understanding of molecular interactions responsible for observed phenomena is still incomplete. This review: (1) provides an overview of structural features of major non-cellulosic polysaccharides of wood, (2) describes the fate of non-cellulosic polysaccharides during biorefinery processing, (3) shows how the non-cellulosic polysaccharides impact lignocellulose processing focused on yields of either sugars or polymers, and (4) discusses outlooks for the improvement of tree species for biorefinery by modifying the structure of non-cellulosic polysaccharides.

Polyporales Brown Rot Species Fomitopsis pinicola: Enzyme Activity Profiles, Oxalic Acid Production, and Fe3+-Reducing Metabolite Secretion.

Basidiomycota fungi in the order Polyporales are specified to decomposition of dead wood and woody debris and thereby are crucial players in the degradation of organic matter and cycling of carbon in the forest ecosystems. Polyporales wood-decaying species comprise both white rot and brown rot fungi, based on their mode of wood decay. While the white rot fungi are able to attack and decompose all the lignocellulose biopolymers, the brown rot species mainly cause the destruction of wood polysaccharides, with minor modification of the lignin units. The biochemical mechanism of brown rot decay of wood is still unclear and has been proposed to include a combination of nonenzymatic oxidation reactions and carbohydrate-active enzymes. Therefore, a linking approach is needed to dissect the fungal brown rot processes. We studied the brown rot Polyporales species Fomitopsis pinicola by following mycelial growth and enzyme activity patterns and generating metabolites together with Fenton-promoting Fe3+-reducing activity for 3 months in submerged cultures supplemented with spruce wood. Enzyme activities to degrade hemicellulose, cellulose, proteins, and chitin were produced by three Finnish isolates of F. pinicola Substantial secretion of oxalic acid and a decrease in pH were notable. Aromatic compounds and metabolites were observed to accumulate in the fungal cultures, with some metabolites having Fe3+-reducing activity. Thus, F. pinicola demonstrates a pattern of strong mycelial growth leading to the active production of carbohydrate- and protein-active enzymes, together with the promotion of Fenton biochemistry. Our findings point to fungal species-level "fine-tuning" and variations in the biochemical reactions leading to the brown rot type of wood decay.IMPORTANCEFomitopsis pinicola is a common fungal species in boreal and temperate forests in the Northern Hemisphere encountered as a wood-colonizing saprotroph and tree pathogen, causing a severe brown rot type of wood degradation. However, its lignocellulose-decomposing mechanisms have remained undiscovered. Our approach was to explore both the enzymatic activities and nonenzymatic Fenton reaction-promoting activities (Fe3+ reduction and metabolite production) by cultivating three isolates of F. pinicola in wood-supplemented cultures. Our findings on the simultaneous production of versatile enzyme activities, including those of endoglucanase, xylanase, β-glucosidase, chitinase, and acid peptidase, together with generation of low pH, accumulation of oxalic acid, and Fe3+-reducing metabolites, increase the variations of fungal brown rot decay mechanisms. Furthermore, these findings will aid us in revealing the wood decay proteomic, transcriptomic, and metabolic activities of this ecologically important forest fungal species.

Novel biorenewable composite of wood polysaccharide and polylactic acid for three dimensional printing

Hemicelluloses, the second most abundant polysaccharide right after cellulose, are in practice still treated as a side-stream in biomass processing industries. In the present study, we report an approach to use a wood-derived and side-stream biopolymer, spruce wood hemicellulose (galactoglucomannan, GGM) to partially replace the synthetic PLA as feedstock material in 3D printing. A solvent blending approach was developed to ensure the even distribution of the formed binary biocomposites. The blends of hemicellulose and PLA with varied ratio up to 25% of hemicellulose were extruded into filaments by hot melt extrusion. 3D scaffold prototypes were successfully printed from the composite filaments by fused deposition modeling 3D printing. Combining with 3D printing technique, the biocompatible and biodegradable feature of spruce wood hemicellulose into the composite scaffolds would potentially boost this new composite material in various biomedical applications such as tissue engineering and drug-eluting scaffolds.

A possible explanation for the structural inhomogeneity of lignin in LCC networks

Lignin has a very complex structure, and this is partly due to the monomers being connected by many different types of covalent bonds. Furthermore, there are multiple covalent bonds between lignin and polysaccharides in wood, and it is known that the structure of lignin covalently bound to the hemicellulose xylan is different to lignin bound to the hemicellulose glucomannan. Here, synthetic lignin (DHP) is synthesized at different pH and it is shown that lignin made at lower pH has a structure more similar to the lignin bound to xylan, i.e., having higher relative content of β-O-4 ethers. It is hypothesized that xylan due to its carboxylic acids forms a locally lower pH and thus “direct” the lignin structure to have more β-O-4 ethers. The biological significance of these results is discussed.

ジメチロールジヒドロキシエチレン尿素(DMDHEU)で木材多糖を架橋した化学改質紙紙筒によるテンサイの育苗栽培が苗と移植後の生育および収量に及ぼす影響

ジメチロールジヒドロキシエチレン尿素(DMDHEU)で木材多糖を架橋した化学改質紙紙筒によるテンサイの育苗栽培が苗と移植後の生育および収量に及ぼす影響