Identification and variation analysis of the composition and content of essential oil and fragrance compounds in Phoebe zhennan wood at different tree ages.

Wood essential oil and wood products with special fragrances are high value-added forest products. Despite the availability of essential oil and volatile organic compounds (VOCs) from Phoebe zhennan wood, their variation and dependence on tree age have not been examined. After essential oil extraction and wood processing, the yields and compositions of essential oils and VOCs in wood from P. zhennan trees of different ages (10a, 30a, and 80a) were determined. The yield of essential oil from 30a wood was significantly greater than that from 10a and 80a wood. Liquid chromatography-mass spectrometry (LC-MS) and gas chromatography-mass spectrometry (GC-MS) revealed 672 and 41 volatile compounds, respectively, in the essential oil and wood, the majority of which exhibited large fluctuations in relative content and composition depending on tree age. Sesquiterpenoids, fatty acids and conjugates may greatly contribute to the main components of essential oil from wood. Almost all major sesquiterpenoid compounds, such as caryophyllene α-oxide, eudesmo, and cubebene, were identified in the essential oils from the 30a and 80a wood, and their relative contents were much greater than those in the 10a wood. The main components of the wood fragrance were sesquiterpenoids. The types and relative contents of sesquiterpenoids from wood increased with tree age. These results suggest that choosing wood from trees of a suitable age will significantly improve the efficiency of wood utilization.

Two all-biomass cellulose/amino acid spherical nanoadsorbents based on a tri-aldehyde spherical nanocellulose II amino acid premodification platform for the efficient removal of Cr(VI) and Cu(II).

Adsorbents consisting of spherical nanoparticles exhibit superior adsorption performance and hence, have immense potential for various applications. In this study, a tri-aldehyde spherical nanoadsorbent premodification platform (CTNAP), which can be grafted with various amino acids, was synthesized from corn stalk. Subsequently, two all-biomass spherical nanoadsorbents, namely, cellulose/l-lysine (CTNAP-Lys) and cellulose/L-cysteine (CTNAP-Cys), were prepared. The morphologies as well as chemical and crystal structures of the two adsorbents were studied in detail. Notably, the synthesized adsorbents exhibited two important characteristics, namely, a spherical nanoparticle morphology and cellulose II crystal structure, which significantly enhanced their adsorption performance. The mechanism of the adsorption of Cr(VI) onto CTNAP-Lys and that of Cu(II) onto CTNAP-Cys were studied in detail, and the adsorption capacities were determined to be as high as 361.69 (Cr(VI)) and 252.38 mg/g (Cu(II)). Using the proposed strategy, it should be possible to prepare other all-biomass cellulose/amino acid spherical nanomaterials with high functional group density for adsorption, medical, catalytic, analytical chemistry, corrosion, and photochromic applications.

Comparative Metabolomics and Transcriptome Analysis Reveal the Fragrance-Related Metabolite Formation in Phoebe zhennan Wood.

Nanmu (Phoebe zhennan) has a unique fragrance and is a high-quality tree species for forest conservation. The types and contents of volatile compounds in different tissues of nanmu wood are different, and the study of its volatile metabolites can help us to understand the source of its fragrance and functions. In order to explore the metabolites related to the wood fragrance of nanmu and to find out the unique volatile substances in the heartwood, gas chromatography-mass spectrometry (GC-MS) was performed to analyze the non-targeted metabolomics in five radial tissues from the sapwood to the heartwood of nanmu. A total of 53 volatile metabolites belonging to 11 classes were detected in all tissues, including terpenes, aromatic hydrocarbons, organoheterocyclics, phenols, esters, organic acids, alcohols, alkaloids, alkane, indoles derivatives, and others. And most of the volatile metabolites were identified for the first time in nanmu wood. Among them, terpenes and aromatic hydrocarbons were the main volatile components. In addition, 22 differential metabolites were screened from HW and SW, HW, and TZ via metabolomic analysis. Among these DAMs, three volatile metabolites (cadinene, a sesquiterpenoid; p-cymene, a monoterpenoid; 1,3,5-triisopropylbenzene, an aromatic hydrocarbon) contributed heavily to the characteristic fragrance of the heartwood. Additionally, the expression of transcripts showed that the unigenes in the terpenoid biosynthesis pathway were especially up-regulated in the SW. Therefore, we speculated that fragrance-related metabolites were synthesized in SW and then deposited in heartwood during sapwood transformed to heartwood. The expression levels of transcription factors (e.g., WRKY, C2H2, NAC) acted as the major regulatory factors in the synthesis of terpenoid. The results lay the foundations for further studies on the formation mechanism of fragrance components in nanmu wood and also provide a reference for the further development and utilization of nanmu wood.

Nanocellulose-based polyurethane foam adsorbent for pressure-driven dye-contaminated water purification.

Dye-contaminated water has caused a worldwide pollution, which is threatening aquatic organisms and human health. In this work, a pressure-driven foam adsorbent (PFA) was bioinspired from the tapestry turban for purifying the dye-contaminated water. The PFA was prepared using an one-step method from nanocellulose (NC), amino-functionalized ZIF-8 (ZIF-8-NH2), and high resilience polyurethane foam (PUF). It was applied to efficiently remove methyl orange (MO) and crystal violet (CV) dyes from dye-contaminated waste solutions. The maximum adsorption capacity of PFA for MO and CV was 225.9 mg/g (25 °C, pH = 2) and 41.6 mg/g (25 °C, pH = 10), respectively, which were acceptable as compared with the reported works. The dyes could be efficiently removed from various river water samples. After 5 cycles, the removal efficiencies of MO and CV decreased from 92.0% and 85.7% to 84.7% and 76.1%, respectively. Moreover, the PFA relied on pressure-driven force to release the purified water under a low pressure.

Supramolecular structure of microwave treated bamboo for production of lignin-containing nanocellulose by oxalic acid dihydrate.

Supramolecular structure of cellulosic materials from microwave treatment were throughly investigated for production of lignin-containing nanocellulose. The results revealed that both the intermolecular and intramolecular hydrogen bonds were altered by microwave irradiation. Cellulose Iß was the main component in microwave treated bamboo (MTB) with smaller interplanar spacing, and the cellulose molecules were loosely connected resulting in a loose structure. Thereafter, MTB was used to produce lignin-containing nanocellulose by using oxalic acid dihydrate (OAD) to test the feasibility on its efficiency. The chemical consumed for the preparation of lignin-containing nanocellulose (LCN) with a comparable yield (68.08-82.33 %) from MTB was merely 1/10 that from conventional cellulosic materials, indicating the supramolecular structural changes of bamboo cellulose induced by microwave treatment provided suitable conditions for the subsequent hydrolysis of OAD to prepare LCN. The LCN was further added into the polyvinyl alcohol (PVA) matrix endowed excellent UV shielding property and thermal stability for the PVA/LCN films. This study was aimed to provide an environmentally friendly method on the production and application of LCN from bamboo by employing microwave treatment from the perspective of supramolecular level.

Integrated Transcriptomic, Metabolomic, and Physiological Analyses Reveal New Insights into Fragrance Formation in the Heartwood of Phoebe hui.

Phoebe hui is an extremely valuable tree that is the main source of the fragrant golden-thread nanmu wood. Although the fragrance of wood has been investigated in several trees, the potential substances and gene regulation mechanisms that are involved in fragrance formation are poorly understood. Here, three radial tissues, sapwood (SW), heartwood (HW), and the transition zone (TZ) in between them, were compared via integrative physiological, volatile-metabolomic, and transcriptomic analyses to identify the key metabolites and regulatory mechanisms involved in fragrance formation. During heartwood formation, gradual starch grain loss was accompanied by the deposition of lipids and extractives in the cell lumen. Extracts of terpenoids were synthesized and accumulated in the heartwood, including monoterpenoids (limonene and p-cymene) and sesquiterpenes (cubebene and guaiadiene); these were identified as being closely related to the special fragrance of the wood. Additionally, the expression of transcripts showed that the genes related to primary metabolism were specifically upregulated in the SW, whereas genes annotated in terpenoid biosynthesis were specifically upregulated in the HW. Therefore, we speculated that terpenoid biosynthesis occurs in situ in the HW via the HW formation model of Type-III (Santalum) using the precursors that were produced by primary metabolism in the SW. The expression levels of transcription factors (e.g., MYB, WRKY, and C2H2) acted as the major regulatory factors in the synthesis of terpenoids. Our results explain the special fragrance in P. hui and broaden the current knowledge of the regulatory mechanisms of fragrance formation. This work provides a framework for future research that is focused on improving wood quality and value.

Analysis of Components and Properties of Extractives from Alnus cremastogyne Pods from Different Provenances.

Chemical components with anti-oxidant, anti-inflammatory, and anti-cancer properties extracted from Alnus bark and leaves have been extensively studied. However, less attention has been paid to extractives from Alnus pods, which are mostly treated as waste. Here, extractives of Alnus cremastogyne pods from 12 provenances in Sichuan Province were studied for high value-added utilization of Alnus waste. The extractives were analyzed by Gas Chromatography-Mass Spectrometer (GC-MS), Ultraviolet-visible spectroscopy (UV-Vis spectra), and 1,1-diphenyl-2-picrylhydrazyl (DPPH) scavenging activity. A total of 58, 49, and 51 chemical components were found when the organic solvents of ethanol, petroleum ether, and ethyl acetate were used to collect extractives, respectively. These chemical components including Phytol, CIS-5,8,11,14,17-eicosapentaenoic acid, Germacrene D, Lupeol, and ß-sitosterol, etc., have wide applications in the fields of pharmacy and cosmetics. Moreover, it was also found that extractives in ethanol and ethyl acetate had impressive UV resistance, especially for UV-C and UV-B blocking. The results showed that the maximum block ratio towards UV-C and UV-B could reach 99%. In addition, the ethanol extract showed good anti-oxidant activity with a maximum free radical scavenging rate of 96.19%. This comprehensive and systematic study on extractives from Alnus cremastogyne pods promotes the development of high-value utilization of Alnus components.

Integrative Metabolomic and Transcriptomic Analysis Reveals the Mechanism of Specific Color Formation in Phoebe zhennan Heartwood.

Nanmu (Phoebe zhennan) is an extremely valuable tree plant that is the main source of famous "golden-thread nanmu" wood. The potential metabolites and gene regulation mechanisms involved in golden thread formation are poorly understood, even though the color change from sapwood to heartwood has been investigated in several tree plants. Here, five radial tissues from sapwood to heartwood were compared via integrative metabolomic and transcriptomic analysis to reveal the secondary metabolites and molecular mechanisms involved in golden thread formation. During heartwood formation, gradual starch grain loss is accompanied by the cell lumen deposition of lipids and color-related extractives. Extractives of 20 phenylpropanoids accumulated in heartwood, including cinnamic acids and derivatives, coumarin acid derivatives, and flavonoids, which were identified as being closely related to the golden thread. Phenylpropanoids co-occurring with abundant accumulated metabolites of prenol lipids, fatty acyls, steroids, and steroid derivatives may greatly contribute to the characteristics of golden thread formation. Additionally, the expression of nine genes whose products catalyze phenylpropanoid and flavonoids biosynthesis was upregulated in the transition zone, then accumulated and used to color the heartwood. The expression levels of transcription factors (e.g., MYB, bHLH, and WRKY) that act as the major regulatory factors in the synthesis and deposition of phenylpropanoid and flavonoids responsible for golden thread formation were also higher than in sapwood. Our results not only explain golden thread formation in nanmu, but also broaden current knowledge of special wood color formation mechanisms. This work provides a framework for future research focused on improving wood color.

Synthesis of cellulose II-based spherical nanoparticle microcluster adsorbent for removal of toxic hexavalent chromium.

Since natural cellulose is mostly cellulose I and has a fibrous form, most cellulose-based adsorbents are fibrous/rod-shaped and exhibit the cellulose I crystal structure. This study reports a cellulose II-based spherical nanoparticle microcluster adsorbent (SNMA), synthesized from biomass by a bottom-up approach, for removing toxic hexavalent chromium (Cr(VI)). The basic structure of SNMA was investigated. Notably, the prepared adsorbent was a microcluster composed of spherical nanoparticles, while exhibiting cellulose II crystal structure, resulting in higher thermal stability and significantly enhanced adsorption performance. The adsorption process and mechanism of SNMA on Cr(VI) were studied in detail. The SNMA achieved a high adsorption capacity (225.94 mg/g) and receptor site density. The SNMA is expected to be used as a bio-based spherical nanoparticle microcluster adsorbent platform for the adsorption of different toxic substances by changing the surface functional groups of its components, spherical nanoparticles.

Preparation of flexible and UV-blocking films from lignin-containing cellulose incorporated with tea polyphenol/citric acid.

Lignin-containing bamboo cellulose, fractionated from a pilot-scale microwave liquefaction of bamboo was dissolved in tetrabutylammonium acetate/dimethyl sulfoxide (TBAA/DMSO) for the fabrication of highly flexible, transparent and UV-blocking films. Tea polyphenol (TP) or citric acid (CA) was added during the dissolving process in order to modify the film's properties. The results showed that the addition of TP obviously improved the elongation at break (triple that of the control) and UV-blocking ability of the films. Both the addition of TP and CA could increase the water contact angle of the films. The films incorporated with TP and CA were much more thermal stable than previously reported similar films. The proposed film fabrication mechanism revealed that stable hydrogen bonds formed between the lignin-cellulose matrix and TP/CA, resulting in the enhancement on the properties of the films. This present study showed that lignin-containing cellulose with the incorporation of TP/CA had great potential in the preparation of films in place of plastic.

Thermal Degradation Kinetics of Urea-Formaldehyde Resins Modified by Almond Shells.

Almond shell-modified urea-formaldehyde resins (AUF) were prepared in this study. The optimal addition amount of almond shells was selected by formaldehyde emission and wet shear strength. The activation energy (E a) values at different conversion rates and the reaction kinetics were estimated based on the Flynn-Wall-Ozawa method. The results indicated that almond shells can significantly reduce the formaldehyde emission and increase wet shear strength and thermal stability of the urea-formaldehyde resin adhesive. The optimal addition of almond shells is 3 wt %.

Kinetics and Thermodynamic Analysis of Recent and Ancient Buried Phoebe zhennan Wood.

Kinetics and thermogravimetric analysis of recent Phoebe zhennan wood (RZ) and ancient buried P. zhennan wood (ABZ) were investigated under a nitrogen atmosphere at different heating rates of 5, 10, 15, and 20 K/min. The activation energy values were estimated based on the Flynn-Wall-Ozawa model-free method, and then, the Coats-Redfern model-fitting method was used to predict the reaction mechanism. The best model of RZ for regions 1 and 2 was based on the diffusional and reaction order (second-order) mechanism, respectively, while a diffusional (Jander equation) mechanism is the best model for ABZ. The change in enthalpy and activation energy of the RZ was lower than that of the ABZ at different conversion rates. When the conversion rate was less than 0.4, the RZ may require lower thermal decomposition reaction energy, but the overall energy of thermal decomposition reactions and the degree of disorder was not much different.

Characterization of Ethyl Acetate and Trichloromethane Extracts from Phoebe zhennan Wood Residues and Application on the Preparation of UV Shielding Films.

In this work, ethyl acetate (EA) and trichloromethane (TR) extracts were extracted from Phoebe zhennan wood residues and the extracts were then applied to the preparation of UV shielding films (UV-SF). The results revealed that substances including olefins, phenols and alcohols were found in both EA and TR extracts, accounting for about 45% of all the detected substances. The two extracts had similar thermal stability and both had strong UV shielding ability. When the relative percentage of the extract is 1 wt% in solution, the extract solution almost blocked 100% of the UV-B (280-315 nm), and UV-A (315-400 nm). Two kinds of UV-SF were successfully prepared by adding the two extracts into polylactic acid (PLA) matrix. The UV-SF with the addition of 24 wt% of the extractive blocked 100% of the UV-B (280-315 nm) and more than 80% of the UV-A (315-400 nm). Moreover, the UV shielding performance of the UV-SF was still stable even after strong UV irradiation. Though the addition of extracts could somewhat decrease the thermal stability of the film, its effect on the end-use of the film was ignorable. EA extracts had less effect on the tensile properties of the films than TR extracts as the content of the extract reached 18%. The results of this study could provide fundamental information on the potential utilization of the extracts from Phoebe zhennan wood residues on the preparation of biobased UV shielding materials.

Chemical composition, UV/vis absorptivity, and antioxidant activity of essential oils from bark and leaf of phoebe zhennan S. K. Lee & F. N. Wei.

The chemical composition of essential oils (EO) from bark and leaf of P. zhennan was identified by GC-MS. The compounds of α-calacorene, τ-cadinol, ß-eudesmol and d-cadinene were found in the essential oils from both bark and leaf. The UV-Vis spectra results indicated the EO could completely absorbed the UV light at the wavelength range of 200-370 nm, revealing that EO had great potential as additives for manufacturing UV light blocking products. The radical DPPH scavenging activity assay showed that both the bark and leaf EO possessed strong DPPH radical scavenging activity of 90.25% and 82.10% respectively, which provides an important theoretical guiding in exploiting the value of P. zhennan bark and leaf.[Formula: see text].

Bio-based UV protective films prepared with polylactic acid (PLA) and Phoebe zhennan extractives.

In this study, diethyl ether extractives were isolated from Phoebe zhennan wood and then added into PLA matrix for the preparation of UV protective films (UV-PF). The results revealed that the diethyl ether extractives had good compatibility with PLA. The prepared UV-PF with the addition of 24 wt% extractives showed complete absorption of UV-C (200-280 nm) and UV-B (280-315 nm) and more than 90% absorption of UV-A (315-400 nm), indicating the addition of extractives into PLA contributed to the super UV resistant ability of the PLA based films. The UV-PF still exhibited excellent UV absorbability after strong UV light irradiation. The differential Scanning Calorimetry (DSC) analysis of the films showed that the UV-PF had relatively low thermal degradation temperature compared to the neat PLA films (PF), while the UV-PF showed stronger tensile strength with comparison to that of the PF. The results on the chemical composition analysis of the diethyl ether extractives revealed that the UV absorbability of the UV-PF may own to the benzene structure, CO bonds, CC bonds in the constituents of the extractives, which all have strong absorption in the near UV-region (200-400 nm).