Near-Infrared Light-Excited Reactive Oxygen Species Generation by Thulium Oxide Nanoparticles.

Exploring materials that can absorb near-infrared (NIR) light to produce reactive oxygen species (ROS) is necessary for many fields. Herein we show that thulium oxide nanoparticles are viable for NIR-stimulated ROS generation. This property may be related to the unique energy levels, large absorption cross section, low fluorescence emission, and ∼10-3 s lifetime of the 3H4 state of Tm ions. We further demonstrate the impact of these nanoparticles on photodynamic therapy (PDT), in which impressive tumor inhibition was recorded after exposure to either a broadband halogen lamp or an 808 nm laser. Our results may provide insight into the areas of photocatalysis, pollution treatment, and fine chemical synthesis.

Effects of Ganfule capsule on microbial and metabolic profiles in anti-hepatocellular carcinoma.

AIMS: Based on the gut microbiota and plasma metabolites, the underlying mechanism was analysed for the anti-hepatocellular carcinoma (HCC) effects of Ganfule capsule (GFL) in the study. METHODS AND RESULTS: The UPLC-Q-TOF/MS results showed that 13 key compounds were identified in GFL and the major active ingredients included amygdalin, saikosaponin A, astragaloside I, etc. The nude mice received HepG2 injection, and GFL showed lower volume and weight of the tumour. In addition, the apoptosis proteins (Bax and Bcl2) were altered in response to GFL treatment, and apoptosis cells were increased, indicating an anti-HCC effect. Interestingly, 16S rDNA results showed that GFL treatment improved gut microbiota diversity and compositions, especially for the beneficial bacteria, such as Bacilli, Lactobacillales, Lactobacillus, Lactobacillaceae, Firmicutes, Lactobacillus_reuteri and Lactobacillus_gasseri. Metabonomics further identified 426 metabolites and 343 metabolites variation in the positive and negative ion modes after GFL treatment, which might be associated with amino acid, lipid metabolism and carbohydrate metabolism pathways, indicating these metabolites might involve in the protective role of GFL in HCC. Correlation analysis showed a significant relationship between gut microbiota and plasma metabolites. CONCLUSION: In conclusion, GFL exerted an anti-HCC effect in the nude murine model, which might be associated with microbial and metabolic improvements. SIGNIFICANCE AND IMPACT OF THE STUDY: This study is the first to report the anti-HCC effect of GFL associated with gut microbiota and plasma metabolites. GFL may improve the gut microbiota structure, such as increasing probiotics - Lactobacillus. It also provides a new strategy for the scientific demonstration of the modernization of traditional Chinese medicine.

[Determination of eight neonicotinoid pesticides in wastewater by solid phase extraction combined with liquid chromatography-tandem mass spectrometry].

Neonicotinoid pesticides are a relatively new class of pesticides that have garnered significant attention owing to their potential ecological risks to nontarget organisms. A method combining solid phase extraction with liquid chromatography-tandem mass spectrometry (SPE-LC-MS/MS) was developed for the rapid and accurate detection of eight neonicotinoid pesticides (dinotefuran, E-nitenpyram, thiamethoxam, clothianidin, imidacloprid, imidaclothiz, acetamiprid, and thiacloprid) in wastewater. The chromatographic mobile phase and MS parameters were selected, and a single-factor method was used to determine the optimal column type, extraction volume, sample loading speed, and pH for SPE. The optimal parameters were as follows: column type, HLB column (500 mg/6 mL); sample extraction volume, 500 mL; sample loading speed, 10 mL/min; and sample pH, 6-8. The matrix effects of the wastewater samples were reduced by optimizing the chromatographic gradient-elution program, examining the dilution factor of the samples, and using the isotope internal standard calibration method. Prior to analysis, the wastewater samples were diluted 5-fold with ultrapure water for pretreatment. Subsequently, 2 mmol/L ammonium acetate aqueous solution containing 0.1% (v/v) formic acid and methanol was used as mobile phases for gradient elution on a ZORBAX Eclipse Plus C18 column (100 mm×2.1 mm, 1.8 µm). The samples were quantified using positive-ion multiple reaction monitoring (MRM) mode for 10 min. Imidacloprid-d4 was used as the isotope internal standard. The SPE process was further optimized by applying response surface methodology to select the type and mass of rinsing and elution solvents. The optimal pretreatment of the SPE column included rinsing with 10% methanol aqueous solution and elution with methanol-acetonitrile (1∶1, v/v) mixture (7 mL). The eight neonicotinoid pesticides showed satisfactory linearity within the relevant range, with linear correlation coefficients (r) all greater than 0.9990. The method detection limits (MDLs) ranged from 0.2 to 1.2 ng/L, and the method quantification limits (MQLs) ranged from 0.8 to 4.8 ng/L. The average recoveries of the eight neonicotinoid pesticides were in the range of 82.6%-94.2% at three spiked levels, with relative standard deviations (RSDs) ranging from 3.9% to 9.4%. Finally, the optimized method was successfully applied to analyze wastewater samples collected from four sewage treatment plants. The results indicated that the eight neonicotinoid pesticides could be generally detected at concentrations ranging from not detected (ND) to 256 ng/L. The developed method has a low MDL and high accuracy, rendering it a suitable choice for the trace detection of the eight neonicotinoid pesticides in wastewater when compared with other similar methods. The proposed method can be utilized to monitor the environmental impact and assess the potential risks of neonicotinoid pesticides in wastewater, thus promoting the protection of nontarget organisms and the sustainable use of these pesticides in agriculture.

Recent progress on phytoremediation of urban air pollution.

The rapid growth of population and economy has led to an increase in urban air pollutants, greenhouse gases, energy shortages, environmental degradation, and species extinction, all of which affect ecosystems, biodiversity, and human health. Atmospheric pollution sources are divided into direct and indirect pollutants. Through analysis of the sources of pollutants, the self-functioning of different plants can be utilized to purify the air quality more effectively. Here, we explore the absorption of greenhouse gases and particulate matter in cities as well as the reduction of urban temperatures by plants based on international scientific literature on plant air pollution mitigation, according to the adsorption, dust retention, and transpiration functions of plants. At the same time, it can also reduce the occurrence of extreme weather. It is necessary to select suitable tree species for planting according to different plant functions and environmental needs. In the context of tight urban land use, the combination of vertical greening and urban architecture, through the rational use of plants, has comprehensively addressed urban air pollution. In the future, in urban construction, attention should be paid to the use of heavy plants and the protection and development of green spaces. Our review provides necessary references for future urban planning and research.

Phytoremediation as a potential technique for vehicle hazardous pollutants around highways.

With the synchronous development of highway construction and the urban economy, automobiles have entered thousands of households as essential means of transportation. This paper reviews the latest research progress in using phytoremediation technology to remediate the environmental pollution caused by automobile exhaust in recent years, including the prospects for stereoscopic forestry. Currently, most automobiles on the global market are internal combustion vehicles using fossil energy sources as the primary fuel, such as gasoline, diesel, and liquid or compressed natural gas. The composition of vehicle exhaust is relatively complex. When it enters the atmosphere, it is prone to a series of chemical reactions to generate various secondary pollutants, which are very harmful to human beings, plants, animals, and the eco-environment. Despite improving the automobile fuel quality and installing exhaust gas purification devices, helping to reduce air pollution, the treatment costs of these approaches are expensive and cannot achieve zero emissions of automobile exhaust pollutants. The purification of vehicle exhaust by plants is a crucial way to remediate the environmental pollution caused by automobile exhaust and improve the environment along the highway by utilizing the ecosystem's self-regulating ability. Therefore, it has become a global trend to use phytoremediation technology to restore the automobile exhaust pollution. Now, there is no scientific report or systematic review about how plants absorb vehicle pollutants. The screening and configuration of suitable plant species is the most crucial aspect of successful phytoremediation. The mechanisms of plant adsorption, metabolism, and detoxification are reviewed in this paper to address the problem of automobile exhaust pollution.

Progress in phytoremediation of chromium from the environment.

As chromium (Cr) in ecosystems affects human health through food chain exposure, phytoremediation is an environmentally friendly and efficient way to reduce chromium pollution in the environment. Here, we review the mechanism of absorption, translocation, storage, detoxification, and regulation of Cr in plants. The Cr(VI) form is more soluble, mobile, and toxic than Cr(III), reflecting how various valence states of Cr affect environmental risk characteristics, physicochemical properties, toxicity, and plant uptake. Plant root's response to Cr exposure leads to reactive oxygen species (ROS) generation and apoptosis. Cell wall immobilization, vacuole compartmentation, interaction of defense proteins and organic ligand with Cr, and removal of reactive oxygen species by antioxidants continue plant life. In addition, the combined application of microorganisms, genetic engineering, and the addition of organic acids, nanoparticles, fertilization, soil amendments, and other metals could accelerate the phytoremediation process. This review provides efficient methods to investigate and understand the complex changes of Cr metabolism in plants. Preferably, fast-growing, abundantly available biomass species should be modified to mitigate Cr pollution in the environment as these green and efficient remediation technologies are necessary for the protection of soil and water ecology.

Synthesis and Characterization of an Environmentally Friendly Phenol-Formaldehyde Resin Modified with Waste Plant Protein.

To develop a lower-cost, excellent-performance, and environmentally friendly phenol-formaldehyde (PF) resin, soybean meal was used to modify PF resin, and soybean meal-phenol-formaldehyde (SMPF) resins were prepared. This reveals the effect of soybean meal on the structural, bonding, and curing properties of PF resin, which are very important for its applications in the wood industry. The resins' physicochemical properties and curing performance were investigated, showing that SMPF resins have higher curing temperatures than PF resin. The Fourier transform infrared spectroscopy results indicated that a cross-linking reaction occurred between the amino groups of soybean protein and the hydroxymethyl phenol. Moreover, with the addition of soybean meal, the viscosity of SMPF increased while the gel time decreased. It is worth mentioning that SMPF-2 resin has favorable viscosity, short gel time, low curing temperature (135.78 °C), and high water resistance and bonding strength (1.01 MPa). Finally, all the plywoods bonded with SMPF resins have good water resistance and bonding strength, which could meet the standard (GB/T 17657-2013, type I) for plywood. The optimized SMPF resins showed the potential for application to partially replace PF resin in the wood industry.

Preparation and Characterization of Soybean Protein Adhesives Modified with an Environmental-Friendly Tannin-Based Resin.

Soybean protein-based adhesives are limited in their application due to their poor wet bonding strength and poor water resistance. Herein, we prepared a novel, environmentally friendly soybean protein-based adhesive by adding tannin-based resin (TR) to improve the performance of water resistance and wet bonding strength. The active sites of TR reacted with the soybean protein and its functional groups and formed strong cross-linked network structures, which improved the cross-link density of the adhesives and then improved the water resistance. The residual rate increased to 81.06% when 20 wt%TR was added, and the water resistance bonding strength reached 1.07 MPa, which fully met the Chinese national requirements for plywood (Class II, ≥0.7 MPa). SEM observations were performed on the fracture surfaces of all modified SPI adhesives after curing. The modified adhesive has a denser and smooth cross-section. Based on the TG and DTG plots, the thermal stability performance of the TR-modified SPI adhesive was improved when TR was added. The total weight loss of the adhesive decreased from 65.13% to 58.87%. This study provides a method for preparing low-cost and high-performance, environmentally friendly adhesives.

Essential Design Strength and Unified Strength Condition of ETFE Membrane Material.

This study proposes essential design strength and unified strength condition for ETFE membrane materials based on the structural state-of-stress theory and formula of strength. Firstly, the tested strain data of the uniaxial rectangle-shaped specimen are modeled to obtain its state-of-stress characteristic parameter. Then, the characteristic points in the evolution curve of the characteristic parameter are detected by the cluster analysis (CA) criterion. The characteristic points are the embodiment of the natural law from quantitative change to qualitative change of a system, which define the essential strength and the essential design strength of ETFE membrane materials. Further, the essential principal stresses are derived at the characteristic points in the evolution curves of the characteristic parameters obtained by the state-of-stress analysis of the strain data from the tests of air bubbling models and cruciform specimens. Both essential principal stresses and essential strength lead to the unified formula of strength for ETFE membrane materials. Additionally, the unified strength condition is derived for the design of ETFE membrane material structures. Finally, the essential strength, essential design strength, and the unified strength conditions are compared with the existing conditions, providing a rationality to update the existing analysis and design methods for determining the strength of ETFE membrane materials.

Nano Ag/Co3O4 Catalyzed Rapid Decomposition of Robinia pseudoacacia Bark for Production Biofuels and Biochemicals.

Biomass energy has attracted widespread attention due to its renewable, storage, huge production and clean and pollution-free advantages. Using Robinia pseudoacacia bark (RPB) as raw material, biogas and bio-oil produced by pyrolysis of RPB were detected and analyzed by TG-DTG, TG-FTIR and PY-GC-MS under the action of nanocatalysis. TG results showed that CH4 and CO flammable gases were produced by pyrolysis. PY-GC-MS results showed that RPB was rapidly pyrolyzed to obtain alcohols, ketones, aldehydes and acids bio-oil. The content of phenolic substances was the highest, accounting for 32.18% of all substances.Nanocatalysis has a certain effect on RPB, accelerating the precipitation of pyrolysis products and improving the over-oxidation of bio-oil. In addition, the extracts of RPB were identified and analyzed by FTIR, NMR, GC-MS and LC-Q-TOF-MS, and more than 100 active ingredients, such as Betaine, Epicathin and ß-sitosterol, were detected. Their applications as additive energy in other fields were explored. Therefore, Robinia pseudoacacia bark constitutes a fine biofeedstock for biofuels and biochemicals.

Unveiling the Migration and Transformation Mechanism of Lignin in Eucalyptus During Deep Eutectic Solvent Pretreatment.

Deep eutectic solvents (DESs) have unique advantages in biomass conversion. However, the migration and transformation mechanism of lignin in the cell wall during the DES pretreatment is still elusive. In this work, Eucalyptus blocks were pretreated in choline chloride/lactic acid DES to reveal the lignin migration. Meanwhile, the remaining lignin in the pretreated residue, the regenerated DES lignin, and the solubilized degraded lignin in the recovered DES were investigated to decipher the lignin transformation. Results showed that the DES pretreatment resulted in the penetration of DES from the cell lumen to the cell wall, and lignin in the secondary wall was more easily dissolved than that in the cell corner middle lamella. The syringyl unit of lignin was better stabilized in the DES than the guaiacyl unit of lignin. The condensed lignin fraction mainly remained in the pretreated residue, while the solubilized degraded lignin fraction was monomeric aromatic ketone compounds. This study elucidates the fate of lignin during the DES pretreatment, which could also promote the development of a modern lignocellulosic pretreatment technique.

Incorporation of Nanocatalysts for the Production of Bio-Oil from Staphylea holocarpa Wood.

Biomass has been recognized as the most common source of renewable energy. In recent years, researchers have paved the way for a search for suitable biomass resources to replace traditional fossil fuel energy and provide high energy output. Although there are plenty of studies of biomass as good biomaterials, there is little detailed information about Staphylea holocarpa wood (S. holocarpa) as a potential bio-oil material. The purpose of this study is to explore the potential of S. holocarpa wood as a bio-oil. Nanocatalyst cobalt (II) oxide (Co3O4) and Nickel (II) oxide (NiO) were used to improve the production of bio-oil from S. holocarpa wood. The preparation of biofuels and the extraction of bioactive drugs were performed by the rapid gasification of nanocatalysts. The result indicated that the abundant chemical components detected in the S. holocarpa wood extract could be used in biomedicine, cosmetics, and biofuels, and have a broad industrial application prospect. In addition, nanocatalyst cobalt tetraoxide (Co3O4) could improve the catalytic cracking of S. holocarpa wood and generate more bioactive molecules at high temperature, which is conducive to the utilization and development of S. holocarpa wood as biomass. This is the first time that S. holocarpa wood was used in combination with nanocatalysts. In the future, nanocatalysts can be used to solve the problem of sustainable development of biological resources.

Ultrastructural elucidation of lignin macromolecule from different growth stages of Chinese pine.

Understanding of the morphological changes at different growth stages and lignin accumulation pattern for pine biomass plays the key role in facilitating the further development of value-added utilization and downstream conversion processes. This work systematically revealed the morphological change and lignin accumulation pattern in Chinese pine branches cell walls via confocal Raman microscopy (CRM) technology. Meanwhile, the structural characteristics of isolated lignin samples from different growth stages were synthetically characterized by nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC) techniques. The results indicated that the content of pith in adult pine new branch was bigger than juvenile trees. With the increase of physiological age, the branches in adult pine could accumulate more lignin both in overall content and the concentration of cell corner middle layer. Moreover, the significantly increases of molecular weights and the ß-O-4, ß-ß linkages content revealed that the lignin macromolecule of pine would polymerize faster in the adult stage (14, 35 years). The panorama generated from the structural and chemical features of pine native lignin not only benefited to understand the biosynthetic pathways and lignin macromolecules structural variation in plant cell walls from different growth stages but also contributed to the valorization and deconstruction of biomass.

Effect of integrated treatment on improving the enzymatic digestibility of poplar and the structural features of isolated hemicelluloses.

Herein, a two-step hydrothermal pretreatment combined with alkali extraction method was applied to deconstruct the poplar cell walls for enzymatic hydrolysis. Results revealed that 88.1 % of hemicelluloses and 77.6 % of lignin were removed during the integrated treatment performed at 180 °C and a maximum enzymatic hydrolysis efficiency of 96.1 % was achieved. Confocal Raman microscopy suggested that the removal of hemicelluloses from cell walls was inhomogeneous, and most hemicelluloses were released from the secondary wall. In addition, 35.2-56.8 % of hemicelluloses were isolated from the integrated treatment. Detailed structural analysis revealed that the water-soluble hemicelluloses possessed more branched structure than the alkali-soluble hemicelluloses and the hemicelluloses isolated from the poplar were mainly composed of a linear backbone of (1→4)-ß-d-Xylp with 4-O-Me-α-d-GlcpA attached as side chains. This work provides an efficient pathway to transform poplar into fermentable sugars and hemicelluloses with considerable yield.

Novel recyclable deep eutectic solvent boost biomass pretreatment for enzymatic hydrolysis.

Deep eutectic solvent (DES) with protonic acid shows the great potential for biomass valorization. However, the acid corrosion and recycling are still severe challenges in biorefinery. Herein, a novel DES by coordinating FeCl3 in choline chloride/glycerol DES was designed for effective and recyclable pretreatment. As compared to DESs with FeCl2, ZnCl2, AlCl3 and CuCl2, DES with FeCl3 approvingly retained most of cellulose in pretreated Hybrid Pennisetum (95.2%). Meanwhile, the cellulose saccharification significantly increased to 99.5%, which was six-fold higher than that of raw biomass. The excellent pretreatment performance was mainly attributed to the high removal of lignin (78.88 wt%) and hemicelluloses (93.63 wt%) under the synergistic effect of Lewis acid and proper hydrogen-bond interaction of DES with FeCl3. Furthermore, almost all cellulose still can be converted into glucose after five recycling process. Overall, the process demonstrated designed pretreatment was great potential for the low-cost biorefinery and boost the biofuel development.

Amination of biorefinery technical lignins using Mannich reaction synergy with subcritical ethanol depolymerization.

The alcoholic depolymerization and Mannich reaction were conducted to improve the chemical activity of biorefinery technical lignins and introduce amino groups into lignins, respectively. To understand the chemical structural transformations and examine the reaction mechanism, GPC and solution-state NMR techniques were performed. Element analysis was also used to quantify the amount of amine groups. The NMR characterization the depolymerized lignins indicated of the depolymerization, demethoxylation, and bond cleavage of linkages occurred during the depolymerization process. Results showed that the depolymerization temperature instead of the addition of capping reagents was the main factor for improving the reactivity of lignin under the given conditions. The Mannich reaction was very selective, primarily occurred at H3,5 and G5 positions, and the H units present a higher chemical reactivity. It is believed that the understanding of the fundamental chemistry of lignin during depolymerization and Mannich reaction process will contribute to the extension of high value-added applications of biorefinery lignin.

Revealing the structure and distribution changes of Eucalyptus lignin during the hydrothermal and alkaline pretreatments.

An integrated pretreatment process based on hydrothermal pretreatment (HTP) followed by alkaline pretreatment has been applied to treat Eucalyptus. The chemical composition and structure changes of lignin during the pretreatment were comprehensively characterized. The surface morphology of the cell walls and lignin distribution of the pretreated Eucalyptus were detected by scanning electron and confocal Raman microscopies. It was found that the chemical bonds between lignin and hemicelluloses were cleaved during the pretreatment. The results also indicated that the contents of ß-O-4', ß-ß', and ß-5' linkages were decreased with the increase of hydrothermal pretreatment temperature and the cleavage of ß-O-4' linkages in lignin was accompanied with repolymerization reactions. 31P NMR analysis showed that the content of aliphatic OH was reduced as the temperature increased and the total phenolic OH was elevated and then declined with the increase of temperature. Raman spectra analysis revealed that the dissolution rate of lignin in the secondary wall regions was faster than that in cell corner middle lamella regions during the pretreatment. These results will enhance the understanding of the cell wall deconstruction during the pretreatment and the mechanism of the integrated pretreatment process acting on Eucalyptus.

Effect of compression combined with steam treatment on the porosity, chemical compositon and cellulose crystalline structure of wood cell walls.

The changes of porosity, chemical composition and cellulose crystalline structure of Spruce (Picea abies Karst.) wood cell walls due to compression combined with steam treatment (CS-treatment) were investigated by nitrogen adsorption, confocal Raman microscopy (CRM) and X-ray diffraction (XRD), respectively. A number of slit-shaped mesopores with a diameter of 3.7nm was formed for the CS-treated wood, and more mesopores were found in the steam-treated wood. CRM results revealed cellulose structure was affected by treatment and ß-aryl-ether links associated to guaiacyl units of lignin was depolymerized followed by re-condensation reactions. The crystallinity index (CrI) and crystallite thickness (D200) of cellulose for CS-treated wood were largely increased due to crystallization in the semicrystalline region. Higher degree of increase in both CrI and D200 was observed in both the earlywood and latewood of steam-treated wood, ascribing to the greater amount of mesopores in steam-treated wood than CS-treated wood.

Seasonal development of cambial activity in relation to xylem formation in Chinese fir.

The vascular cambium is a lateral meristem which can differentiate into secondary phloem and xylem. The secondary growth of woody plants resulting from vascular cambium activity has been a focus of considerable attention, but the quantitative relationships between cambial activity and secondary xylem formation have been little studied. Our analysis of cytological changes in the cambium of Chinese fir (Cunninghamia lanceolata), revealed a significant positive correlation between vascular cambium cell numbers and cambium zone width through the seasonal cycle. Cambium cell numbers and the cambium cell radial diameter were closely related to xylem formation. Immuno-labeling showed that de-esterified homogalacturonan and (1-4)-ß-d-galactan epitopes were highly abundant in cell walls of dormant-stage cambium, whereas high methylesterified homogalacturonan was strongly labeled in the active stage. Raman spectroscopy detected significant changes in the chemical composition of cell walls during the active-dormant stage transition. More pectin and less monolignols occurred in radial cell walls than in tangential walls during the dormant stage, but no significant changes were found in other stages, indicating that pectin accumulation facilitates cell wall expansion, with cambium activity transition. Our quantitative analysis of the relationship between cambial activity and xylem formation, as well as the cell wall modification during the active stage provides useful information about cambial characteristics and xylogenesis.

Effect of hydrothermal pretreatment on the structural changes of alkaline ethanol lignin from wheat straw.

Due to the enormous abundance of lignin and its unique aromatic nature, lignin has great potential for the production of industrially useful fuels, chemicals, and materials. However, the rigid and compact structure of the plant cell walls significantly blocks the separation of lignin. In this study, wheat straw was hydrothermally pretreated at different temperatures (120-200 °C) followed by post-treatment with 70% ethanol containing 1% NaOH to improve the isolation of lignin. Results demonstrated that the content of associated carbohydrates of the lignin fractions was gradually reduced with the increment of the hydrothermal severity. The structure of the lignins changed regularly with the increase of the pretreatment temperature from 120 to 200 °C. In particular, the contents of ß-O-4', ß-ß', ß-5' linkages and aliphatic OH in the lignins showed a tendency of decrease, while the content of phenolic OH and thermal stability of the lignin fractions increased steadily as the increment of the pretreatment temperature.