TiN/anatase/rutile phase junction obtained by in-situ thermal transformation for efficient photothermal-assisted photocatalytic hydrogen generation.

Phase junctions exhibit great potential in photocatalytic energy conversion, yet the narrow light response region and inefficient charge transfer limit their photocatalytic performance. Herein, an anatase/rutile phase junction modified by plasmonic TiN and oxygen vacancies (TiN/(A-R-TiO2-Ov)) is prepared through an in-situ thermal transformation from TiN for efficient photothermal-assisted photocatalytic hydrogen production for the first time. The content of TiN, oxygen vacancies, and phase components in TiN/(A-R-TiO2-Ov) hybrids can be well-adjusted by tuning the heating time. The as-prepared photocatalysts display a large specific area and wide light absorption due to the synergistic effect of plasmonic excitation, oxygen vacancies, and bandgap excitations. Meanwhile, the multi-interfaces between TiN, anatase, and rutile provide built-in electric fields for efficient separation of photoinduced carriers and hot electron injection via ohmic contact and type-Ⅱ band arrangement. As a result, the TiN/(A-R-TiO2-Ov) photocatalyst shows an excellent photocatalytic hydrogen generation rate of 15.07 mmol/g/h, which is 20.6 times higher than that of titanium dioxide P25. Moreover, temperature-dependent photocatalytic tests reveal that the excellent photothermal conversion caused by plasmonic heating and crystal lattice vibrations in TiN/(A-R-TiO2-Ov) has about 25 % enhancement in photocatalysis (18.84 mmol/g/h). This work provides new inspiration for developing high-performance photocatalysts by optimizing charge transfer and photothermal conversion.

Soil differentiation and soil comprehensive evaluation of in wild and cultivated Fritillaria pallidiflora Schrenk.

Few studies have focused on the growth, soil quality and sustainability of medicinal plants under different soil conditions. In this study, the spatial heterogeneity of soil physical and chemical properties, the diversity of rhizosphere soil microbial community structure, and the characteristics of growth of the wild and cultivated medicinal plant, Siberian fritillary (Fritillaria pallidiflora Schrek) were analyzed, and the soil quality and ecosystem sustainability were comprehensively evaluated. The results showed that there was significant spatial variability of soil nutrients in the different habitats. Nitrate nitrogen (NO3-N) was strongly variable, while those of the soil organic carbon (SOC) and available phosphorus (AP) were moderately variable. There was little variability among the soil available potassium (AK), electrical conductivity (EC), pH and ammonium nitrogen (NH4-N). Inverse Distance Weighting spatial interpolation showed that SOC, NO3-N, NH4-H and EC were highly distributed in the southeastern part of the wild area, and the soil was more acidic in the original habitat than in the planting habitat. There was little AK and AP in the native habitat, and there was a high content in the planting habitat. Simultaneously, the soil microbial communities of the two soils also differed. The wild-type soil showed a "fungal" type, while the planted soil showed a "bacterial" type. Pathogenic bacteria were among the primary microflora in the planting area. In general, it is difficult to maintain the sustainable development and geo-herbalism of F. pallidiflora in today's cultivation mode because of the significant differences in soil nature, spatial heterogeneity and microbial community structure for the growth of F. pallidiflora. Therefore, future planting should focus on transforming it from intensive to mountain forest planting. This is highly significant for improving the planting efficiency of F. pallidiflora, protecting their geo-herbalism and germplasm resources, and maintaining the stability and sustainable development of the ecosystem.

An ensemble LSTM-based AQI forecasting model with decomposition-reconstruction technique via CEEMDAN and fuzzy entropy.

Air quality affects people's daily life. Air quality index (AQI) is an essential indicator for controlling air pollution and ensuring public health, whose accurate forecasting can provide timely air pollution warnings and remind people to take protective measures against air pollution in advance. To address this issue, this paper developed a new ensemble learning model for AQI forecasting. In this study, (1) the signal decomposition technique complete ensemble empirical mode decomposition with adaptive noise (CEEMDAN) is introduced to decompose the nonlinear and nonstationary AQI history data series into several more regular and more stable subseries firstly. (2) Fuzzy entropy (FE) is selected as the feature indicator to recombine the subseries with similar trends to avoid the problem of over-decomposition and reduce the computing time. (3) An ensemble long short-term memory (LSTM) neural network is established to forecast each reconstructed subseries, whose values are superimposed to predict the AQI value eventually. To validate the predicting performance of the proposed model, daily AQI data of Wuhan, China, dating from January 1, 2019, to February 28, 2022, is used as the experiment case. And comparative analysis is made between the proposed model and other common-used forecasting models. Benchmarking results of the numerical study demonstrate that the proposed model is superior to the other forecasting models with better AQI prediction accuracy.

Great gerbil burrowing-induced microbial diversity shapes the rhizosphere soil microenvironments of Haloxylon ammodendron in temperate deserts.

In the Gurbantunggut Desert of northwest China, the main habitat of Rhombomys opimus (great gerbil) is under the thickets of Haloxylon ammodendron, the main construction species. In the long-term coexistence, continuous gerbil activities (burrowing, defecating, and gnawing) limited the growth of H. ammodendron, affected the root microenvironment under the H. ammodendron forest, and weakened the desert ecosystem. However, there is a lack of general understanding about the response of desert soil microhabitats to such gerbil disturbance. Accordingly, this study examined the effects of different intensities of gerbil disturbance (none, mild, moderate, or severe disturbances) on soil nutrients content and used high-throughput sequencing to explore the change in diversity and structure of microbial communities (bacteria and fungi) in H. ammodendron rhizosphere at different soil depths (0-20, 20-40, and 40-60 cm). In the arid desert ecosystem, compared with the soil fungal community, the alpha diversity of the soil bacterial community was significantly affected by gerbil disturbance. Meanwhile, both soil depth and gerbil disturbance significantly impacted the beta diversity and relative abundance of soil bacterial and fungal communities. In addition, gerbil disturbance significantly altered the soil characteristics affecting the distribution and composition of soil microbial communities in H. ammodendron rhizosphere, especially the soil bacterial community. This survey provides evidence that remold impact of gerbil disturbance on soil microenvironment of H. ammodendron rhizosphere in desert ecosystems in northwest China, which helps to further understand the potential correlations with changes in the microbial community at a regional scale.

Appeal: the protection of ancient tree species around the world, taking qilian juniper (Juniperus przewalskii) as an example.

Juniperus przewalskii (the Qilian juniper) is a dominant species in the northeast region of the Qinghai-Tibet Plateau. As such, it is of great significance for maintaining the balance and long-term stability of the ecosystem in this biodiversity hotspot. In this paper, we review the literature related to J. przewalskii published in the China National Knowledge Infrastructure and Web of Science. Here, we summarize the main research achievements with regard to this species from ten aspects: tree morphology and phenology, population structure and life history, radial growth and climate response, tree-ring chronology-based history reconstruction, soil physical and chemical properties, chemical composition and activity, physiological ecology, biogeography, breeding and propagation techniques, and occurrence and control of diseases and pests. Considering the ecological importance and research value of J. przewalskii, as well as the shrinking population size, we discuss future research prospects and directions for the conservation of J. przewalskii from four aspects: global climate change, human disturbance, tree regeneration, and pest control. This work provides an important reference for conservation studies of alpine tree species in other biodiversity hotspots around the world.

Toroidal dipole-modulated dipole-dipole double-resonance in colloidal gold rod-cup nanocrystals for improved SERS and second-harmonic generation.

Colloidal metal nanocrystals (NCs) show great potential in plasmon-enhanced spectroscopy owing to their attractive and structure-depended plasmonic properties. Herein, unique Au rod-cup NCs, where Au nanocups are embedded on the one or two ends of Au nanorods (NRs), are successfully prepared for the first time via a controllable wet-chemistry strategy. The Au rod-cup NCs possess multiple plasmon modes including transverse and longitudinal electric dipole (TED and LED), magnetic dipole (MD), and toroidal dipole (TD) modulated LED resonances, producing large extinction cross-section and huge near-field enhancements for plasmon-enhanced spectroscopy. Particularly, Au rod-cup NCs with two embedded cups show excellent surface-enhanced Raman spectroscopy (SERS) performance than Au NRs (75.6-fold enhancement excited at 633 nm) on detecting crystal violet owing to the strong electromagnetic hotspots synergistically induced by MD, LED, and TED-based plasmon coupling between Au cup and rod. Moreover, the strong TD-modulated dipole-dipole double-resonance and MD modes in Au rod-cup NCs bring a 37.3-fold enhancement of second-harmonic generation intensity compared with bare Au NRs, because they can efficiently harvest photoenergy at fundamental frequency and generate large near-field enhancements at second-harmonic wavelength. These findings provide a strategy for designing optical nanoantennas for plasmon-enhanced applications based on multiple plasmon modes. Electronic Supplementary Material: Supplementary material (SEM image of Au rod-one-cup NCs; TEM image of Au/PbS hybrids; SEM image of Au rod-two-cup NCs; low-amplification SEM image of Au rod-two-cup NCs; experimental extinction and calculated electric field distributions of Au NR excited at different wavelengths; calculated absorption and scattering spectra of Au rod-one-cup NCs; schematic illustration of the cut plane and the corresponding magnetic field distribution under L3 excitation; Raman spectra of CV (10-6 M) adsorbed on Au rod-cup NCs with different cup sizes; calculated magnetic field distribution of Au rodcup NCs excited at 532 and 633 nm; calculated electric field distributions of Au rod-one-cup NC excited at 600 nm along TE and LE; the models of Au rod-cup NCs used in the simulations) is available in the online version of this article at 10.1007/s12274-022-4562-5.

Nutrient variation induced by rodent disturbance in Haloxylon ammodendron as a target transfer strategy.

Nutrients form a link between herbivores and plant. This study explored the physiological and ecological response mechanism of Haloxylon ammodendron population to rodent disturbance in Gurbantunggut Desert from the perspective of nutrient cycle. Through field investigation, we quantified rodent disturbance intensity (DI) to H. ammodendron and analyzed the ecological response mechanism of H. ammodendron population to rodent disturbance from the perspective of plant and soil nutrient cycling and changes. The results indicated that moderate rodent DI (number of effective burrows = 3-6) was the maximum limit that can be tolerated by H. ammodendron; the threshold for optimal H. ammodendron response to rodent disturbance was mild (number of burrows = 1-3). Meanwhile, the rodent disturbance caused significant nutrient enrichment (e.g., organic carbon, available phosphorus, and available potassium) in the deeper soil (at 20-40 and 40-60 cm depth) and significantly reduced the soil total salt content (p < .05). Furthermore, as the DI increased, the branches of H. ammodendron showed significantly increased soluble total sugar, crude fiber, and total nitrogen contents (p < .05) but significantly decreased crude fat and crude protein contents (p < .05); these results are related to the nutritional target transfer strategy evolved by H. ammodendron for long-term resistance to rodent disturbance. The current study clarified the optimal disturbance model for mutually beneficial H. ammodendron-great gerbil relationship, on the basis of which the ecological response mechanism of H. ammodendron population to rodent disturbance in deserts was illustrated. The current study provides a scientific basis for the protection mechanisms of desert plants to rodent disturbance.

Strong Visible Light Absorption and Abundant Hotspots in Au-Decorated WO3 Nanobricks for Efficient SERS and Photocatalysis.

Metal/semiconductor hybrids show potential application in fields of surface-enhanced Raman spectroscopy (SERS) and photocatalysis due to their excellent light absorption, electric field, and charge-transfer properties. Herein, a WO3-Au metal/semiconductor hybrid, which was a WO3 nanobrick decorated with Au nanoparticles, was prepared via a facile hydrothermal method. The WO3-Au hybrids show excellent visible light absorption, strong plasmon coupling, high-performance SERS, and good photocatalytic activity. In particular, on sensing rhodamine B (RhB) under 532 nm excitation, bare WO3 nanobricks have a Raman enhancement factor of 2.0 × 106 and a limit of detection of 10-8 M due to the charger-transfer property and abundant oxygen vacancies. WO3-Au metal/semiconductor hybrids display a largely improved Raman enhancement factor compared to pure Au and WO3 components owing to the synergistic effect of electromagnetic enhancement and charge transfer. The Raman enhancement factor and limit of detection are further improved, reaching 5.3 × 108 and 10-12 M, respectively, on increasing the content of Au to 2.1 wt %, owing to the strong plasmon coupling between the Au nanoparticles. Additionally, the WO3-Au hybrids also exhibit excellent photocatalytic activity toward degradation of RhB under visible light irradiation. WO3-Au (2.1 wt %) possesses the fastest photocatalytic rate, which is 6.1 and 2.0 times that of pure WO3 nanobricks and commercial P25, respectively. The enhanced photocatalytic activity is attributed to the strong plasmon coupling and the efficient charge transfer between Au and WO3 nanobricks. The as-prepared materials show great potential in detecting and degrading pollutants in environmental treatment.

Dual Plasmon Resonances and Tunable Electric Field in Structure-Adjustable Au Nanoflowers for Improved SERS and Photocatalysis.

Flower-like metallic nanocrystals have shown great potential in the fields of nanophononics and energy conversion owing to their unique optical properties and particular structures. Herein, colloid Au nanoflowers with different numbers of petals were prepared by a steerable template process. The structure-adjustable Au nanoflowers possessed double plasmon resonances, tunable electric fields, and greatly enhanced SERS and photocatalytic activity. In the extinction spectra, Au nanoflowers had a strong electric dipole resonance located around 530 to 550 nm. Meanwhile, a longitudinal plasmon resonance (730~760 nm) was obtained when the number of petals of Au nanoflowers increased to two or more. Numerical simulations verified that the strong electric fields of Au nanoflowers were located at the interface between the Au nanosphere and Au nanopetals, caused by the strong plasmon coupling. They could be further tuned by adding more Au nanopetals. Meanwhile, much stronger electric fields of Au nanoflowers with two or more petals were identified under longitudinal plasmon excitation. With these characteristics, Au nanoflowers showed excellent SERS and photocatalytic performances, which were highly dependent on the number of petals. Four-petal Au nanoflowers possessed the highest SERS activity on detecting Rhodamine B (excited both at 532 and 785 nm) and the strongest photocatalytic activity toward photodegrading methylene blue under visible light irradiation, caused by the strong multi-interfacial plasmon coupling and longitudinal plasmon resonance.

Plasmon-Mediated 2D/2D Phase Junction for Improved Photocatalytic Hydrogen Generation Activity.

A phase junction fabricated by two crystalline phases of the same semiconductor is a promising photocatalyst with efficient charge transfer and separation. However, the weak light absorption and uncontrolled phase junction interface limit the generation and separation of photogenerated carriers. Herein, a two-dimensional (2D)/2D phase junction was prepared by growing orthorhombic WO3 ultrathin nanosheets on hexagonal WO3 nanosheets through a one-step hydrothermal method. The orthorhombic/hexagonal WO3 possesses large-area phase junction interfaces, rich reactive sites, and built-in electric field, which greatly accelerate the photogenerated charge separation and transfer. Thus, the orthorhombic/hexagonal WO3 displayed excellent photocatalytic hydrogen generation activity from water splitting under light irradiation (λ > 420 nm), which is 2.16 and 2.85 times those of orthorhombic and hexagonal WO3 phase components. Furthermore, Au nanoparticles (about 4.5 nm in diameter) were deposited on both orthorhombic and hexagonal WO3 nanosheets to form a plasmon-mediated phase junction. The hybrids exhibit prominent visible-light absorption and efficient charge transfer, leading to a further improved photocatalytic hydrogen generation activity. Further characterization studies demonstrate that superior photoactivity arises from the excellent visible-light-harvesting ability, appropriate band structure, and high-efficiency and multichannel transferring processes of photogenerated carriers.

Succession of endophytic fungi and arbuscular mycorrhizal fungi associated with the growth of plant and their correlation with secondary metabolites in the roots of plants.

BACKGROUND: To decipher the root and microbial interaction, secondary metabolite accumulation in roots and the microbial community's succession model during the plant's growth period demands an in-depth investigation. However, till now, no comprehensive study is available on the succession of endophytic fungi and arbuscular mycorrhizal fungi (AMF) with roots of medicinal licorice plants and the effects of endophytic fungi and AMF on the secondary metabolite accumulation in licorice plant's root. RESULTS: In the current study, interaction between root and microbes in 1-3 years old medicinal licorice plant's root and rhizospheric soil was investigated. Secondary metabolites content in licorice root was determined using high-performance liquid chromatography (HPLC). The composition and diversity of endophytic and AMF in the root and soil were deciphered using high-throughput sequencing technology. During the plant's growth period, as compared to AMF, time and species significantly affected the diversity and richness of endophytic fungi, such as Ascomycota, Basidiomycota, Fusarium, Cladosporium, Sarocladium. The growth period also influenced the AMF diversity, evident by the significant increase in the relative abundance of Glomus and the significant decrease in the relative abundance of Diversispora. It indicated a different succession pattern between the endophytic fungal and AMF communities. Meanwhile, distance-based redundancy analysis and Mantel tests revealed root's water content and secondary metabolites (glycyrrhizic acid, liquiritin, and total flavonoids), which conferred endophytic fungi and AMF diversity. Additionally, plant growth significantly altered soil's physicochemical properties, which influenced the distribution of endophytic fungal and AMF communities. CONCLUSIONS: This study indicated a different succession pattern between the endophytic fungal and AMF communities. During the plant's growth period, the contents of three secondary metabolites in roots increased per year, which contributed to the overall differences in composition and distribution of endophytic fungal and AMF communities. The endophytic fungal communities were more sensitive to secondary metabolites than AMF communities. The current study provides novel insights into the interaction between rhizospheric microbes and root exudates.

Differences in the endophytic fungal community and effective ingredients in root of three Glycyrrhiza species in Xinjiang, China.

BACKGROUND: Endophytic fungi influence the quality and quantity of the medicinal plant's bioactive compounds through specific fungus-host interactions. Nevertheless, due to the paucity of information, the composition of endophytic fungal communities and the mechanism by which effective ingredients regulate endophytic fungal communities in roots remains unclear. METHODS: In this study, we collected root and soil samples (depth range: 0-20, 20-40, and 40-60 cm) of three Glycyrrhiza species (Glycyrrhiza uralensis, Glycyrrhiza inflata, and Glycyrrhiza glabra). Glycyrrhizic acid and liquiritin content were determined using high-performance liquid chromatography (HPLC), and total flavonoid content was determined using ultraviolet spectrophotometry. High-throughput sequencing technology was employed to explore the composition and diversity of the endophytic fungal community in different root segments of three Glycyrrhiza species. Furthermore, soil samples were subjected to physicochemical analyses. RESULTS: We observed that the liquiritin content was not affected by the root depth (0-20 cm, 20-40 cm, and 40-60 cm). Still, it was significantly affected by the Glycyrrhiza species (Glycyrrhiza uralensis, Glycyrrhiza inflata, Glycyrrhiza glabra) (P < 0.05). In Glycyrrhiza root, a total of eight phyla and 140 genera were annotated so far, out of which Ascomycota and Basidiomycota phyla, and the Fusarium, Paraphoma, and Helminthosporium genera were found to be significantly dominant. Spearman correlation analysis revealed that liquiritin content was accountable for the differences in the diversity of the endophytic fungal community. Furthermore, distance-based redundancy analysis (db-RDA) showed that physicochemical properties of the soil (available potassium and ammonium nitrogen) and the root factors (liquiritin and water content) were the main contributing factors for the variations in the overall structure of the endophytic fungal community. Our results showed that the effective ingredients of Glycyrrhiza root and physicochemical properties of the soil regulated the endophytic fungal community composition and medicinal licorice diversity.

Future N deposition and precipitation changes will be beneficial for the growth of Haloxylon ammodendron in Gurbantunggut Desert, northwest China.

Evaluation of precipitation and nitrogen (N) deposition in desert ecosystems helps to elucidate the reaction of desert ecosystems to future environmental changes. An in-situ field experiment was established to examine the influence of a long-term enhanced precipitation and N deposition on the photosynthetic traits and physiological characteristics of Haloxylon ammodendron in the Gurbantunggut Desert, northwest China, throughout the growing season in 2014-2016. Results showed a significant interaction between precipitation and N applications. Increased precipitation and N deposition and their coupling could significantly improve photosynthetic capacity, alter the variability in amplitude of water potential and change the content of substances regulating osmotic pressure in H. ammodendron. According to the comprehensive evaluation of H. ammodendron's adaptability using six different water and N coupling models, a combination of a 30% increase in precipitation and a 30 kg N ha-1 yr-1 addition in nitrogen deposition, or the addition of N at a concentration of 60 kg N ha-1 yr-1 with natural precipitation were beneficial to H. ammodendron growth and development. Hence, changes in the future global environment can be anticipated to be beneficial to H. ammodendron growth.