The mechanism of enhanced lignin regulating foliar Cd absorption and yield in rice (Oryza sativa L.).

The impact of atmospheric deposition of cadmium (Cd) in cereal crops has become a global concern. Enhanced lignin content was expected to benefit the plant performance against Cd exposure. To date, however, the underlying mechanisms of lignin regulating foliar Cd absorption in rice (Oryza sativa L.) and its effect on grain yield remains unclear. In present study, the effect and mechanism of rice in response to leaf Cd exposure were investigated using 113Cd stable isotope and a lignin-increased rice mutant. The highest Cd uptake efficiency and uptake amount was observed in wild type (WT) plant grown in the maturity period, which were 3-fold higher than in mutant plant. Compared to WT, the mutant exhibited 14.75% and 25.43% higher contents in G- and S-unit of lignin monomers. Lignin biosynthesis and polymerization related genes (OsPAL/OsCOMT/Os4CL3/OsLAC5/OsLAC15) were significantly up-regulated in mutants. In addition, the enzyme activities involved in the above process were also significantly increased by 1.24-1.49-fold. The increased Cd retention in cell wall and decreased gene expression levels of OsNRAMP5, OsHMA3 and OsIRT1 in mutant indicated that lignin effectively inhibited Cd transportion in plant tissues. Moreover, the antioxidant capacity and photosynthesis efficiency in mutant plant were obviously improved, leading to higher Cd tolerance and increased grain yield. Our results revealed the molecular and physiological mechanisms of enhanced lignin regulating foliar Cd absorption and yield in rice, and provided the valuable rice genotype to ensure food safety.

Host responses and metabolic profiles of wood components in Dutch elm hybrids with a contrasting tolerance to Dutch elm disease.

BACKGROUND AND AIMS: Changes occurring in the macromolecular traits of cell wall components in elm wood following attack by Ophiostoma novo-ulmi, the causative agent of Dutch elm disease (DED), are poorly understood. The purpose of this study was to compare host responses and the metabolic profiles of wood components for two Dutch elm (Ulmus) hybrids, 'Groeneveld' (a susceptible clone) and 'Dodoens' (a tolerant clone), that have contrasting survival strategies upon infection with the current prevalent strain of DED. METHODS: Ten-year-old plants of the hybrid elms were inoculated with O. novo-ulmi ssp. americana × novo-ulmi. Measurements were made of the content of main cell wall components and extractives, lignin monomer composition, macromolecular traits of cellulose and neutral saccharide composition. KEY RESULTS: Upon infection, medium molecular weight macromolecules of cellulose were degraded in both the susceptible and tolerant elm hybrids, resulting in the occurrence of secondary cell wall ruptures and cracks in the vessels, but rarely in the fibres. The (13)C nuclear magnetic resonance spectra revealed that loss of crystalline and non-crystalline cellulose regions occurred in parallel. The rate of cellulose degradation was influenced by the syringyl:guaiacyl ratio in lignin. Both hybrids commonly responded to the medium molecular weight cellulose degradation with the biosynthesis of high molecular weight macromolecules of cellulose, resulting in a significant increase in values for the degree of polymerization and polydispersity. Other responses of the hybrids included an increase in lignin content, a decrease in relative proportions of d-glucose, and an increase in proportions of d-xylose. Differential responses between the hybrids were found in the syringyl:guaiacyl ratio in lignin. CONCLUSIONS: In susceptible 'Groeneveld' plants, syringyl-rich lignin provided a far greater degree of protection from cellulose degradation than in 'Dodoens', but only guaiacyl-rich lignin in 'Dodoens' plants was involved in successful defence against the fungus. This finding was confirmed by the associations of vanillin and vanillic acid with the DED-tolerant 'Dodoens' plants in a multivariate analysis of wood traits.

Discoloration and Surface Changes in Spruce Wood after Accelerated Aging.

Spruce wood is widely used in outdoor applications, but its susceptibility to degradation under exposure to sunlight and moisture is a major concern. This study investigates the impact of accelerated aging on spruce wood's surface chemistry, microstructure, geometry, and discoloration. The study was performed in two outdoor aging modes: dry and wet. The accelerated aging effects were evident in the changes in spruce wood structure, as well as in the other studied properties. During aging, it developed significant discoloration. Under simulated rainless outdoor conditions (dry mode), spruce wood gradually became dark brown. Under conditions involving rain (wet mode), the discoloration was qualitatively different from the dry mode. FTIR spectroscopy showed that during the accelerated aging of wood, lignin was mainly degraded, especially in the early stages of the process. A linear correlation was found between the changes in lignin and the color changes in the wood. There was an increase in carbonyl groups in the dry mode, which contributed to the color change and was also influenced by changes in extractives. The wet mode caused the leaching out of carbonyl groups. The observed decrease in cellulose crystallinity, together with the degradation of hydrophobic lignin, may result in the increased hydrophilicity of photodegraded wood. For both modes, there were different changes in the wood micro- and macrostructure, reflected in the surface morphology. The roughness increased during the aging process in both modes. The slightest changes in the roughness parameters were identified in the grain direction in the dry mode; the most evident was that the roughness parameters increased perpendicular to the grain in the wet mode. The demonstrated mechanism backing up the aging-related changes to the spruce wood structure and the relations unveiled between these changes and the changes in the spruce wood surface properties can provide an issue point for seeking ways how to mitigate the negative effects of the environmental factors the wood is exposed to.

Evaluating the Effectiveness of Cellulose-Based Surfactants in Expandable Graphite Wood Coatings.

This study deals with the design of modern environmentally friendly and non-toxic flame retardants based on expandable graphite 25 K + 180 (EG) modified by cellulose ethers (Lovose TS 20, Tylose MH 300, Klucel H) and nanocellulose (CNC) that are biocompatible with wood and, therefore, are a prerequisite for an effective surfactant for connecting EG to wood. The effectiveness of the formulations and surfactants was verified using a radiant heat source test. The cohesion of the coating to the wood surface and the cohesion of the expanded graphite layer were also assessed. The fire efficiency of the surfactants varied greatly. Still, in combination with EG, they were all able to provide sufficient protection-the total relative mass loss was, in all cases, in the range of 7.38-7.83% (for untreated wood it was 88.67 ± 1.33%), and the maximum relative burning rate decreased tenfold compared to untreated wood, i.e., to 0.04-0.05%·s-1. Good results were achieved using Klucel H + EG and CNC + EG formulations. Compared to Klucel H, CNC provides significantly better cohesion of the expanded layer, but its high price increases the cost of the fireproof coating.

Evaluation of Selected Cellulose Macromolecular Properties after Its Chemical Treatment Using Size Exclusion Chromatography.

This work evaluates the effect of using selected inorganic chemicals as the main components of waterborne wood preservative systems on the degradation of the cellulose constituent in wood from model samples. The polymeric properties of cellulose and the homogeneity of the degradation process primarily reflect very well the degree of cellulose deterioration. Whatman papers, as pure cellulose model samples, were impregnated with 10 different 5 wt% solutions of inorganic salts and distilled water and consequently subjected to wet-thermal accelerated aging (T = 85 °C, RH = 65%, for 30 days). The samples were then derivatized to cellulose tricarbanilates (CTCs) through two different procedures (by precipitation in a methanol-water mixture/by evaporation of pyridine from the reaction mixture) and finally analyzed using size exclusion chromatography (SEC). Chemically treated and aged cellulose samples showed different changes in the degree of polymerization (DP) and polydispersity (PD) in terms of untreated non-aged standard caused by different ongoing degradation reactions, such as dehydration, hydrolysis, oxidation, and crosslinking. In general, the lowest degradation rate after treatment by chemicals and after accelerated aging was observed in samples treated by borates, NaCl, and ZnSO4·7H2O. The greatest depolymerization after treatment and after accelerated aging was caused by sulphates containing NH4+, Cu2+, and Fe3+ cations, with aging by NH4Cl and (NH4)2HPO4-treated samples also leading to significant depolymerization. The higher DP values are linked to the precipitated method of CTC preparation, though not for chlorides and phosphates. PD is also generally higher in precipitated and aged samples and is heavily influenced by the presence of low molecular weight products. This paper brings new insights regarding the complex evaluation of the polymeric properties of degraded cellulose by considering all important factors affecting the sample and the analysis itself through the use of statistics. From the statistical point of view, the influences of all factors (solution, aging, method) and their interactions (except aging*method) on DP are statistically significant. The influence of the sample processing method used for analysis of the desired results becomes important mainly in practice. This work recommends the evaporation method for more accurate description of more degraded cellulose.

Chromophores' Contribution to Color Changes of Thermally Modified Tropical Wood Species.

This work examines the effect of thermal modification temperature (180, 200, and 220 °C) in comparison with reference (untreated) samples on selected optical properties of six tropical wood species-Sp. cedar (Cedrala odorata), iroko (Chlorophora excelsa), merbau (Intsia spp.), meranti (Shorea spp.), padouk (Pterocarpus soyauxii), and teak (Tectona grandis). The main goal is to expand the existing knowledge in the field of wood thermal modification by understanding the related degradation mechanisms associated with the formation of chromophoric structures and, above all, to focus on the change in the content of extractive substances. For solid wood, the CIELAB color space parameters (L*, a*, b*, and ΔE*), yellowness (Y), ISO brightness, and UV-Vis diffuse reflectance spectra were obtained. Subsequently, these wood samples were extracted into three individual solvents (acetone, ethanol, and ethanol-toluene). The yields of the extracted compounds, their absorption spectra, and again L*, a*, b*, ΔE*, and Yi parameters were determined. With increasing temperatures, the samples lose brightness and darken, while their total color difference grows (except merbau). The highest yield of extractives (mainly phenolic compounds, glycosides, and dyes) from thermally modified samples was usually obtained using ethanol. New types of extractives (e.g., 2-furaldehyde, lactones, formic acid, some monomer derivatives of phenols, etc.) are already created around a temperature of 180 °C and may undergo condensation reactions at higher temperatures. For padouk, merbau, teak, and partially iroko modified at temperatures of 200 and 220 °C, there was a detected similarity in the intensities of their UV-Vis DR spectra at the wavelength regions corresponding to phenolic aldehydes, unsaturated ketones, quinones, stilbenes, and other conjugated carbonyl structures. Overall, a statistical assessment using PCA sorted the samples into five clusters. Cluster 3 consists of almost all samples modified at 200 and 220 °C, and in the other four, the reference and thermally modified samples at 180 °C were distributed. The yellowness of wood (Y) has a very high dependence (r = 0.972) on its brightness (L*) and the yellowness index of the extractives in acetone Yi(Ac), whose relationship was described by the equation Y = -0.0951 × Y(Ac) + 23.3485.

Antioxidant Protection of Paper Heritage Objects with 4-Amino-2,2,6,6-Tetramethylpiperidine.

In protecting cultural heritage, deacidification is used to stabilize acidic papers, ensuring the neutralization of acids present in the paper. But in the process of aging, several mechanisms of degradation occur simultaneously. Therefore, substances used to stabilize the paper should contain an antioxidant component in addition to the deacidifying component. The effect of the antioxidant (hindered amine light stabilizers-HALS type) on the stabilization of lignin-containing acid papers during accelerated aging was studied in this work. The effective deacidification component was magnesium; the solvent was hexamethyldisiloxane (HMDSO). The 4-amino-2,2,6,6-tetramethylpiperidine series of hindered amine light stabilizers (HALS) was selected as appropriate for creating a modifying system based on HMDSO. The modification system was tested on samples of a model test acid lignin-containing paper (NOVO) and naturally aged acidic paper from the real book. The addition of substances to the proposed deacidification system has a favorable effect on stabilizing the pH during aging and provides the inhibition of the oxidative degradation products and stabilization of the cellulose degree of polymerization. It was confirmed that the application of the system containing deacidification and an antioxidant component may increase the effectiveness of the protection of acid groundwood paper heritage objects. Adding a tested antioxidant to the proposed deacidification system has a favorable effect on stabilizing the pH value for a long time in accelerated aging.

Chitosan-induced biotic stress tolerance and crosstalk with phytohormones, antioxidants, and other signalling molecules.

Several polysaccharides augment plant growth and productivity and galvanise defence against pathogens. Such elicitors have ecological superiority over traditional growth regulators, considering their amplified biocompatibility, biodegradability, bioactivity, non-toxicity, ubiquity, and inexpensiveness. Chitosan is a chitin-derived polysaccharide that has recently been spotlighted among plant scientists. Chitosan supports plant growth and development and protects against microbial entities such as fungi, bacteria, viruses, nematodes, and insects. In this review, we discuss the current knowledge of chitosan's antimicrobial and insecticidal potential with recent updates. These effects are further explored with the possibilities of chitosan's active correspondence with phytohormones such as jasmonic acid (JA), salicylic acid (SA), indole acetic acid (IAA), abscisic acid (ABA), and gibberellic acid (GA). The stress-induced redox shift in cellular organelles could be substantiated by the intricate participation of chitosan with reactive oxygen species (ROS) and antioxidant metabolism, including hydrogen peroxide (H2O2), superoxide dismutase (SOD), catalase (CAT), and peroxidase (POD). Furthermore, we propose how chitosan could be intertwined with cellular signalling through Ca2+, ROS, nitric oxide (NO), transcription factors (TFs), and defensive gene activation.

Release of terpenes from fir wood during its long-term use and in thermal treatment.

Building structures made from fir wood are often attacked by wood-destroying insects for which the terpenes it contains serve as attractants. One of the possibilities for extending the lifetime of structures is to use older wood with a lower content of terpenes and/or thermally modified wood. The study evaluated the levels of terpenes in naturally aged fir wood (108, 146, 279, 287 and 390 years) and their decrease by thermal treatment (the temperature of 60 °C and 120 °C, treatment duration of 10 h). Terpenes were extracted from wood samples by hexane and analyzed by gas-chromatography mass-spectrometry (GC-MS). The results indicate that recent fir wood contained approximately 60 times more terpenes than the oldest wood (186:3.1 mg/kg). The thermal wood treatment speeded up the release of terpenes. The temperature of 60 °C caused a loss in terpenes in the recent fir wood by 62%, the temperature of 120 °C even by >99%. After the treatment at the temperature of 60 °C the recent fir wood had approximately the same quantity of terpenes as non-thermally treated 108 year old wood, i.e., approximately 60-70 mg/kg. After the thermal treatment at the temperature of 120 °C the quantity of terpenes dropped in the recent as well as the old fir wood to minimum quantities (0.7-1.1 mg/kg). The thermal treatment can thus be used as a suitable method for the protection of fir wood from wood-destroying insects.

Changes in Chemical Structure of Thermally Modified Spruce Wood Due to Decaying Fungi.

Fungi play a critical role in the decomposition of wood and wood-based products in use. The ability of decaying fungi to cause degradation of polysaccharides and lignin in the thermally modified Norway spruce (Picea abies L. Karst.) wood was examined with pure culture decomposition tests in laboratory conditions using the brown-rot fungus Serpula lacrymans (Schumacher ex Fries) S.F. Gray and white-rot fungus Trametes versicolor (Linnaeus ex Fries) Pilat. Spruce wood samples were primary thermally treated under atmospheric pressure at the temperatures of 100, 150, 200, 220, 240 and 260 °C during 1, 3 and 5 h, whereby larger losses in their mass, holocellulose, mannose and xylose were achieved at harder thermal regimes. Meanwhile, the holocellulose percent content reduced considerably, and the percent content of lignin increased sharply. Spruce wood thermally modified at and above 200 °C better resisted to brown-rot fungus S. lacrymans than the white-rot fungus T. versicolor. Due to the decay processes, the mass fractions of holocellulose, cellulose and hemicelluloses were lower in those spruce wood samples in which thermal degradation was more intensive, with achieving the highest mass loss values after thermal treatments, after which the decay attacks were poorer or even none with the minimal mass loss values due to action by the brown-rot fungus S. lacrymans and the white-rot fungus T. versicolor. The mannose and glucose percent content in thermally-fungally attacked spruce wood was intensive reduced, e.g., by 17% to 98% in wood after thermal treatments at temperature equal and above 200 °C.

Changes of Meranti, Padauk, and Merbau Wood Lignin during the ThermoWood Process.

Thermal modification is an environmentally friendly process in which technological properties of wood are modified using thermal energy without adding chemicals, the result of which is a value-added product. Wood samples of three tropical wood species (meranti, padauk, and merbau) were thermally treated according to the ThermoWood process at various temperatures (160, 180, 210 °C) and changes in isolated lignin were evaluated by nitrobenzene oxidation (NBO), Fourier-transform infrared spectroscopy (FTIR), and size exclusion chromatography (SEC). New data on the lignins of the investigated wood species were obtained, e.g., syringyl to guaiacyl ratio values (S/G) were 1.21, 1.70, and 3.09, and molecular weights were approx. 8600, 4300, and 8300 g·mol-1 for meranti, padauk, and merbau, respectively. Higher temperatures cause a decrease of methoxyls and an increase in C=O groups. Simultaneous degradation and condensation reactions in lignin occur during thermal treatment, the latter prevailing at higher temperatures.

The Influence of Nanoparticles on Fire Retardancy of Pedunculate Oak Wood.

Traditional flame retardants often contain halogens and produce toxic gases when burned. Hence, in this study, low-cost, environmentally friendly compounds that act as fire retardants are investigated. These materials often contain nanoparticles, from which TiO2 and SiO2 are the most promising. In this work, pedunculate oak wood specimens were modified with sodium silicate (Na2SiO3, i.e., water glass) and TiO2, SiO2, and ZnO nanoparticles using the vacuum-pressure technique. Changes in the samples and fire characteristics of modified wood were studied via thermal analysis (TA), infrared spectroscopy (FTIR), and scanning electron microscopy, coupled with energy-dispersive X-ray spectroscopy (SEM-EDX). The results of TA showed the most significant wood decomposition at a temperature of 350 °C, with a non-significant influence of the nanoparticles. A dominant effect of sodium silicate was observed in the main weight-loss step, resulting in a drop in decomposition temperature within the temperature range of 36-44 °C. More intensive decomposition of wood treated with water glass and nanoparticles led to a faster release of non-combustible gases, which slowed down the combustion process. The results demonstrated that wood modifications using sodium silicate and nanoparticle systems have potentially enhanced flame retardant properties.

Flammability Characteristics of Thermally Modified Meranti Wood Treated with Natural and Synthetic Fire Retardants.

This paper deals with the effect of synthetic and natural flame retardants on flammability characteristics and chemical changes in thermally treated meranti wood (Shorea spp.). The basic chemical composition (extractives, lignin, holocellulose, cellulose, and hemicelluloses) was evaluated to clarify the relationships of temperature modifications (160 °C, 180 °C, and 210 °C) and incineration for 600 s. Weight loss, burning speed, the maximum burning rate, and the time to reach the maximum burning rate were evaluated. Relationships between flammable properties and chemical changes in thermally modified wood were evaluated with the Spearman correlation. The thermal modification did not confirm a positive contribution to the flammability and combustion properties of meranti wood. The effect of the synthetic retardant on all combustion properties was significantly higher compared to that of the natural retardant.

Structural Changes of Oak Wood Main Components Caused by Thermal Modification.

Thermal modification of wood causes chemical changes that significantly affect the physical, mechanical and biological properties of wood; thus, it is essential to investigate these changes for better utilization of products. Fourier transform infrared spectroscopy and size exclusion chromatography were used for evaluation of chemical changes at thermal treatment of oak wood. Thermal modification was applied according to Thermowood process at the temperatures of 160, 180 and 210 °C, respectively. The results showed that hemicelluloses are less thermally stable than cellulose. Chains of polysaccharides split to shorter ones leading to a decrease of the degree of polymerization and an increase of polydispersity. At the highest temperature of the treatment (210 °C), also crosslinking reactions take place. At lower temperatures degradation reactions of lignin predominate, higher temperatures cause mainly condensation reactions and a molecular weight increase. Chemical changes in main components of thermally modified wood mainly affect its mechanical properties, which should be considered into account especially when designing various timber constructions.

Chemical alterations of pine wood saccharides during heat sterilisation.

Alterations in saccharides during heat sterilisation of pine wood (Pinus sylvestris L.) were investigated. The mass loss, extractives, lignin, cellulose, holocellulose and hemicelluloses were determined. Changes in saccharides were evaluated by the determination of monosaccharides in wood, size exclusion chromatography (SEC) as well as Fourier transform infrared (FTIR) spectroscopy. During heat sterilisation of pine wood the slight mass loss, an increase in extractives and a decrease in lignin and polysaccharides were observed. Hemicelluloses are degraded approximately twice as fast as cellulose. The degree of polymerisation of cellulose decreases approximately by 10% and it increases in holocellulose (by approx. 8%) as a result of a faster degradation of shorter hemicellulose chains. FTIR spectroscopy shows that sterilisation results in the deacetylation of cellulose and the formation of new carbonyl groups, an increase in the total crystallinity index (TCI) and a decrease in the lateral order index (LOI) and the hydrogen-bond intensity (HBI).

Properties Characterization of Chemically Modified Hemp Hurds.

The effect of chemical treatment of hemp hurds slices in three solutions (EDTA (Ethylenediaminetetraacetic acid), NaOH and Ca(OH)2) on the properties of natural material was discussed in this paper. Changes in the morphology, chemical composition and structure as well as thermal stability of hemp hurds before and after their modification were investigated by using FTIR (Fourier transform infrared spectroscopy), XRD (X-ray powder diffraction analysis) and TG (thermogravimetry)/DSC (differential scanning calorimetry). Size exclusion chromatography (SEC) measurements were used for determination of degree of cellulose polymerization of hemp hurd samples. Chemical modification is related to the partial removal of non-cellulosic components of lignin, hemicellulose and pectin as well as waxes from the surface of hemp hurd slices. Another effect of the chemical treatment applied is connected with increasing the crystallinity index of cellulose determined by FTIR and XRD methods. Decrease in degree of cellulose polymerization and polydispersity index in chemically modified hemp hurds compared to the original sample was observed. Increase in thermal stability of treated hemp hurd was found. The most significant changes were observed in alkaline treated hemp hurds by NaOH.

Effects of thermal treatment on chemical, mechanical and colour traits in Norway spruce wood.

In several different branches of the wood industry heat treatment is a growing application as it changes the chemical, mechanical, physical and biological properties of wood. Investigations using wet chemical analyses, Fourier transform infrared spectroscopy, size exclusion chromatography, and CIELab colour system have been conducted to study the changes in Norway spruce wood subjected to temperature up to 270°C over a 30 min time period. The results showed that mass loss (ML), total crystallinity index (TCI) of cellulose, total colour difference (ΔE*), and the content of lignin and extractives increased with the temperature, whereas degree of polymerization (DP) of cellulose, modulus of rupture (MOR), modulus of elasticity (MOE), lightness difference (ΔL*), and the content of holocellulose, cellulose and hemicelluloses all decreased with the thermal treatment. Relationships between temperature and the examined wood traits were all fitted by exponential curves. Power law relationships were found to fit the trends for DP of cellulose with ΔE*, ΔL*, and TCI of cellulose. Also found were power law regressions for the content of hemicelluloses with MOE, MOR, ΔL*, and ML. Temperatures ranging from 20 to 187°C formed a compact cluster, clearly separated from the higher examined temperatures in the multivariate wood trait space.