Area-Selective Depolymerization of Hydroxycinnamates Visualized by Raman Imaging in Miscanthus sinensis cv. Cell Wall.

Lignin-carbohydrate complexes (LCCs) are regarded as a barrier for lignocellulosic biomass refinery. Here, confocal Raman microspectroscopy has been used to visualize the dissolution of hydroxycinnamates (HCMs) incorporated into LCCs by ether and ester bonds for energy crops Miscanthus sinensis cv. during successive NaOH (2.5% w/w) treatment. Raman spectral analysis indicated that mild NaOH treatment resulted in a higher proportion of HCM depolymerization in highly lignified middle lamella areas (>66.0%) than carbohydrate-abundant secondary walls. Furthermore, Raman imaging revealed preferential depolymerization of lignin from the sclerenchyma fiber (Sf) and parenchyma (Par) secondary wall with an increment of treatment time from 0 to 25 min, while middle lamella areas of Sf and Par were less affected where the depolymerization of HCMs was closely related with that of lignin (coefficient factors > 0.96). A better understanding of the depolymerization behavior for HCMs accompanied by lignin depolymerization was important to break LCC bonds in herbaceous biomass efficiently.

Screening of potential chemical marker with interspecific differences in Pterocarpus wood and a spatially-resolved approach to visualize the distribution of the characteristic markers.

Profiling the spatial distributions and tissue changes of characteristic compounds with interspecific differences is critical to elucidate the complex species identification during tree species traceability, wood anti-counterfeiting verification and timber trade control. In this research, in order to visualize the spatial position of characteristic compounds in two species with similar morphology (Pterocarpus santalinus and Pterocarpus tinctorius), a high coverage MALDI-TOF-MS imaging method was used to found the mass spectra fingerprints of different wood species. 2-Mercaptobenzothiazole matrix was used to spray wood tissue section to enhance the detection effect of metabolic molecules, and the mass spectrometry imaging data were obtained. Based on this technology, the spatial location of fifteen potential chemical markers with remarkable interspecific differences in 2 Pterocarpus timber species were successfully obtained. Distinct chemical signatures obtained from this method can promote rapid identification at the wood species level. Thus, matrix-assisted laser desorption/time-of-flight/ionization mass spectrometry imaging (MALDI-TOF-MSI) provides a spatial-resolved way for traditional wood morphological classification and breaking through the limitations of traditional wood identification technology.

Rapid Identification for the Pterocarpus Bracelet by Three-Step Infrared Spectrum Method.

In order to explore a rapid identification method for the anti-counterfeit of commercial high value collections, a three-step infrared spectrum method was used for the pterocarpus collection identification to confirm whether a commercial pterocarpus bracelet (PB) was made from the precious species of Pterocarpus santalinus (P. santalinus). In the first step, undertaken by Fourier transform infrared spectroscopy (FTIR) spectrum, the absorption peaks intensity of PB was slightly higher than that of P. santalinus only at 1594 cm-1, 1205 cm-1, 1155 cm-1 and 836 cm-1. In the next step of second derivative IR spectra (SDIR), the FTIR features of the tested samples were further amplified, and the peaks at 1600 cm-1, 1171 cm-1 and 1152 cm-1 become clearly defined in PB. Finally, by means of two-dimensional correlation infrared (2DIR) spectrum, it revealed that the response of holocellulose to thermal perturbation was stronger in P. santalinus than that in PB mainly at 977 cm-1, 1008 cm-1, 1100 cm-1, 1057 cm-1, 1190 cm-1 and 1214 cm-1, while the aromatic functional groups of PB were much more sensitive to the thermal perturbation than those of P. santalinus mainly at 1456 cm-1, 1467 cm-1, 1518 cm-1, 1558 cm-1, 1576 cm-1 and 1605 cm-1. In addition, fluorescence microscopy was used to verify the effectiveness of the above method for wood identification and the results showed good consistency. This study demonstrated that the three-step IR method could provide a rapid and effective way for the anti-counterfeit of pterocarpus collections.

Synthesis of Microporosity Dominant Wood-Based Activated Carbon Fiber for Removal of Copper Ions.

Steam activation treatments were introduced in the preparation of activated carbon fiber from liquefied wood (LWACF), to enlarge its specific surface area and develop the pore size distribution. With increasing activation time, the average fiber diameter of LWACF decreased from 27.2 µm to 13.2 µm, while the specific surface area increased from 1025 to 2478 m2/g. Steam activation predominantly enhanced the development of microporosity, without significant pore widening. Prolonging the steam activation time exponentially increased the removal efficiency of Cu2+ at a constant adsorbent dose, as a result of an increase in the number of micropores and acidic-oxygenated groups. Moreover, for LWACF activated for 220 min at 800 °C, the removal efficiency of Cu2+ increased from 55.2% to 99.4%, when the porous carbon fiber dose went from 0.1 to 0.5 g/L. The synthesized LWACF was proven to be a highly efficient adsorbent for the treatment of Cu2+ ion-contaminated wastewater.

Lignin Distribution on Cell Wall Micro-Morphological Regions of Fibre in Developmental Phyllostachys pubescens Culms.

Bamboo is a natural fibre reinforced composite with excellent performance which is, to a certain extent, an alternative to the shortage of wood resources. The heterogeneous distribution and molecular structure of lignin is one of the factors that determines its performance, and it is the key and most difficult component in the basic research into the chemistry of bamboo and in bamboo processing and utilization. In this study, the distribution of lignin components and lignin content in micro-morphological regions were measured in semi-quantitative level by age and radial location by means of visible-light microspectrophotometry (VLMS) coupled with the Wiesner and Maule reaction. There as guaiacyl lignin and syringyl lignin in the cell wall of the fibre. Lignin content of the secondary cell wall and cell corner increased at about 10 days, reached a maximum at 1 year, and then decreased gradually. From 17 days to 4 years, the lignin content of the secondary cell wall in the outer part of bamboo is higher than that in the middle part (which is, in turn, higher than that in the inner part of the bamboo). VLSM results of the micro-morphological regions showed that bamboo lignification developed by aging. Guaiacyl and syringl lignin units can be found in the cell wall of the fibre, parenchyma, and vessel. There was a difference in lignin content among different ages, different radial location, and different micro-morphological regions of the cell wall. The fibre walls were rich in guaiacyl lignin in the early stage of lignification and rich in syringyl units in the later stage of lignification. The guaiacyl and syringyl lignin deposition of bamboo green was earlier than that of the middle part of bamboo culm, and that of the middle part of bamboo culm was earlier than that of bamboo yellow. The single molecule lignin content of the thin layer is higher than that of thick layers, while the primary wall is higher than the secondary cell wall, showing that lignin deposition is consistent with the rules of cell wall formation. The obtained cytological information is helpful to understand the origin of the anisotropic, physical, mechanical, chemical, and machining properties of bamboo.

Enhancement of Removal of VOCs and Odors from Wood by Microwave-Activated Persulfate.

Since traditional methods for removing volatile organic compounds (VOCs) from wood consume large amounts of energy and generate environmental pollution, it is desired to develop a convenient and green treatment method. Oxidation by microwave-activated persulfate (MW-PS) is a promising alternative method that has been used to eliminate VOCs from wood. The penetration of microwave energy can destroy the wood pit membranes and increase VOC emissions. The VOCs are further degraded by ·OH and SO4 •-, which are generated via the activation of microwaves. This phenomenon can be detected by the electron paramagnetic resonance spectrometry. The 35 types of main VOCs of natural wood were determined, including alkanes/terpenes, alcohols/ethers, esters, aldehydes/ketones, and others. In the MW-PS system, 23 compounds were removed with an efficiency of 100%. Specifically, as one of the major compounds, the content of alkanes/terpenes was sharply decreased, and no alcohols/ethers and esters were detected. It was found that the optimal conditions of the MW-PS system for the minimum release of VOCs from wood were the microwave power of 462 W, irradiation time of 30 min, and PS dosage of 0.5 mmol/L.