Mid-infrared tunable absorber based on an Ag/SiO2/VO2/Ag/VO2 multilayer structure and its molecular sensing capability.

We present a design of middle-infrared modulation absorbers based on vanadium dioxide (VO2). By using the electron beam evaporation technique, the Ag/SiO2/VO2/Ag/VO2 multilayer structure can achieve double band strong absorption in the mid-infrared, and dynamically adjust the absorption performance through VO2. The simulation results demonstrate a remarkable absorption rate of 91.8% and 98.9% at 9.09 µm and 10.25 µm, respectively. The high absorption is elucidated by analyzing the field strength distribution in each layer. Meanwhile, based on the phase change characteristics of VO2, the absorber has exceptional thermal regulation, with a remarkable 78% heat regulation range in the mid-infrared band. The size altering of the absorbing layer is effective in enhancing and optimizing the structure's absorption performance. The structure is used to characterize probe molecules of CV and R6 G by mid-infrared spectroscopy, which illustrates an impressive limit of detection (LOD) of 10-7 M for both substances. These results provide valuable insights for designing future high-performance tunable optical devices.

Mechanistic insights into the removal of As(III) and As(V) by iron modified carbon based materials with the aid of machine learning.

The machine learning (ML) technique was used to examine the effects of different microscopic material features on the ability of iron modified carbon-based materials (Fe-CBMs) to remove As(V) and As(III). The findings showed that specific CBMs and Fe-CBMs features (such as surface functionality) from sophisticated microscopic and spectroscopic techniques led to models that were more accurate than those constructed using more basic information, such as bulk elemental composition and surface area (the root-mean-square error fell by 44.7% for As(V) and 56.9% for As(III), respectively). The high non-polar carbon (NPC) content of CBMs and Fe-CBMs had a detrimental influence on As(V) and As(III) removal capability, whereas surface oxygen-containing functional groups (SOFGs) contents on CBMs and Fe-CBMs played an essential role in arsenic removal based on ML approaches. The relative importance of CO was greater by 77.8% and 40.6% than that of C-O on the elimination of As(V) and As(III), respectively. The accurate ML models are helpful for the future design of Fe-CBMs and the relative importance and partial dependence plot analysis can direct the use of Fe-CBMs for arsenic removal in a sensible manner under different application situations.

Highly sensitive AuNSs@AgNR SERS substrates for rapid determination of aromatic amines.

The leakage of aromatic amines will pose a great threat to human health and the ecological environment. Therefore, there is an urgent need to achieve rapid and high-sensitivity detection of such substances. In this study, a simple surface-enhanced Raman scattering (SERS) method based on gold nanostars-modified silver nanorods (AuNSs@AgNRs) was established for the detection of benzidine and 4-aminobiphenyl (4-ABP). The enhancement factors of the substrate towards rhodamine 6G (R6G) and crystal violet (CV) were 4.67 × 108 and 1.11 × 108, respectively. Combined with density functional theory (DFT), the AuNSs@AgNR substrate achieved the rapid detection of benzidine and 4-ABP and obtained low detection limits (LODbenzidine = 7.09 × 10-9 M; LOD4-ABP = 1.20 × 10-9 M). Furthermore, the AuNSs@AgNR substrate can realize the high-sensitivity detection of benzidine and 4-ABP in the spiked river water samples within 3 min, which means that the AuNSs@AgNR-based SERS method can be used as a portable platform to realize the on-site rapid detection of environmental pollutants.

Nutrient dynamics and microbial community response in macrophyte-dominated lakes: Implications for improved restoration strategies.

Although lakes dominated by macrophytes are conducive to ecological balance, this balance is easily disrupted by excessive nutrients flowing into the lake. However, knowledge of whether excessive nutrients lead to different microbial environmental vulnerabilities in the lake sediment between macrophyte-dominated areas and macrophyte-free areas is a prerequisite for the implementation of targeted protection measures. In this study, we investigated bacterial communities in sediments using high-throughput sequencing of 16S rRNA genes. Our results showed that the sources of total nitrogen (TN) and organic matter (OM) were related to the macrophytes. The structure, drivers, and interspecific associations of bacterial community, which were more susceptible to increased changes in TN and OM, differed significantly between macrophyte-dominated areas and macrophyte-free areas. More precisely, the lake edge, where was occupied by macrophytes, had a higher proportion of deterministic phylogenetic turnover (88.89%) than other sites, as well as a wider ecological niche and a tighter network structure. Further, as the difference in TN increased, the main assembly processes in surface sediments changed from stochastic to deterministic. However, the majority of phyla from the lake edge showed a greater correlation with excessive nutrients, and the selection of the community by excessive nutrients was more obvious at the edge of the lake. In addition, our results demonstrated that the stability of the bacterial community in macrophyte-free areas is greater than in macrophyte-dominated areas, while an excessively high deterministic process ratio and nutrient (TN and OM) concentration significantly reduced bacterial community stability at macrophyte-dominated areas. Taken together, these results provide a better understanding of the effects of excessive nutrients derived from macrophytes on bacterial community patterns, and highlight the importance of avoiding the accumulation of TN and OM in macrophyte-dominated areas to enhance the sustainability of the ecosystem after restoration of lakes with macrophytes.

Visible transparent mid-infrared broadband absorbers based on gradient refractive indexes and multi-size cavity resonances.

We proposed a multi-layered nanorod structure with the same tilt angle and different diameters, which has high visible transmittance and strong 3-5 µm absorption based on the principles of the gradient of the refractive index and the multi-size cavity resonances. The indium tin oxide (ITO) was selected as the target material to fabricate the structure by using a glancing angle deposition method. The experimental results show that when the deposition angle θ is 80°, swing deposition is successively done with the rotation angle φ of ±8°, ± 5°, ± 3°, and 0° on the surface of the substrate, and the quartz crystal microbalance thicknesses of ITO nanorods are 220 nm for each deposition, the average transmittance is 80.5% in the range of 400-800 nm and the integrated absorption is 86% in the 3-5 µm band. Such a simple, low-cost, and easy-to-fabricate device has potential applications in window stealth materials and other related fields.

3-5 µm mid-infrared broadband absorbers composed of layered ITO nanorod arrays with high visible light transmittance.

A mid-infrared broadband absorber with high visible light transmittance is proposed in this paper. The absorber is composed of layered ITO nanorod arrays with increasing angles fabricated by oblique angle deposition technique. The experimental results show that the average transmittance of the absorber reaches 80% in the 400-800 nm band and the integrated absorption reaches 82.9% in the 3-5 µm band, when the QCM thickness of the first layer of film is 100 nm and the deposition angle θ is 10°, the QCM heights of the second to fifth layers of nanorods are all 330 nm, and their deposition angles are 55°, 68°, 80°, and 87°, respectively. The high transmittance in the visible band is attributed to the gradient of the refractive index. The broadband absorption in the mid-infrared band results from different resonances in the empty cavities with different sizes. Such a simple and large-area absorber has potential applications in window materials and infrared cloaking.

ITO/Si/ITO semi-cone-shell chiral complexes on silicon nanocones with broadband circular dichroism in the mid-infrared wavelength.

This paper proposed ITO/Si/ITO semi-cone-shell chiral complexes on silicon nanocones with broadband CD in the mid-infrared band. The experimental results show that when the deposition angle θ = 45°, the first ITO deposition of ta = 100 nm, the second Si deposition of tb = 200 nm with the azimuth angle unchanged, and the third ITO deposition of tc = 200 nm after rotating the azimuth angle of 60°, the prepared chiral structure has a broadband CD response in the mid-infrared band of 2.5-4 µm. The broadband CD effect is produced by the internal resonance of the three-dimensional open cavity. The cone structure can be regarded as a plurality of planar open resonant rings with different diameters, and these rings resonate at different wavelengths. The experimental results also show that the proposed chiral ITO structure exhibits a better broadband CD response than that of the structure composed of traditional metal Ag. Such a chiral structure provides a new method for the design of CD devices in the mid-infrared band.

Novel Fluorescent Probe Based on Rare-Earth Doped Upconversion Nanomaterials and Its Applications in Early Cancer Detection.

In this paper, a novel rare-earth-doped upconverted nanomaterial NaYF4:Yb,Tm fluorescent probe is reported, which can detect cancer-related specific miRNAs in low abundance. The detection is based on an upconversion of nanomaterials NaYF4:Yb,Tm, with emissions at 345, 362, 450, 477, 646, and 802 nm, upon excitation at 980 nm. The optimal Yb3+:Tm3+ doping ratio is 40:1, in which the NaYF4:Yb,Tm nanomaterials have the strongest fluorescence. The NaYF4:Yb, Tm nanoparticles were coated with carboxylation or carboxylated protein, in order to improve their water solubility and biocompatibility. The two commonly expressed proteins, miRNA-155 and miRNA-150, were detected by the designed fluorescent probe. The results showed that the probes can distinguish miRNA-155 well from partial and complete base mismatch miRNA-155, and can effectively distinguish miRNA-155 and miRNA-150. The preliminary results indicate that these upconverted nanomaterials have good potential for protein detection in disease diagnosis, including early cancer detection.

Rhizosphere microbial community composition and survival strategies in oligotrophic and metal(loid) contaminated iron tailings areas.

In this study, the metal(loid) fractions in two alkaline iron tailings areas with similar physico-chemical properties and the enrichment ability of dominant plants in these areas were investigated. Additionally, high-throughput sequencing and metagenome analysis were used to examine the rhizosphere microbial community structures and their strategies and potential for carbon fixation, nitrogen metabolism, and metal(loid) resistance in mining areas. Results showed that Salsola collina, Setaria viridis, and Xanthium sibiricum have strong enrichment capacity for As, and the maximum transport factor for Mn can reach 4.01. The richness and diversity of bacteria were the highest in rhizosphere tailings, and the dominant phyla were Proteobacteria, Actinobacteria, Ascomycota, and Thaumarchaeota. The key taxa present in rhizosphere tailings were generally metal(loid) resistant, especially Sphingomonas, Pseudomonas, Nocardioides, and Microbacterium. The reductive citrate cycle was the main carbon fixation pathway of microorganisms in tailings. Rhizosphere microorganisms have evolved a series of survival strategies and can adapt to oligotrophic and metal(loid) polluted mining environments. The results of this study provide a basis for the potential application of plant-microbial in situ remediation of alkaline tailings.

The exploration of quantum dot-molecular beacon based MoS2 fluorescence probing for myeloma-related Mirnas detection.

Highly sensitive and reliable detection of multiple myeloma remains a major challenge in liquid biopsy. Herein, for the first time, quantum dot-molecular beacon (QD-MB) functionalized MoS2 (QD-MB @MoS2) fluorescent probes were designed for the dual detection of multiple myeloma (MM)-related miRNA-155 and miRNA-150. The results indicate that the two probes can effectively detect miRNA-155 and miRNA-150 simultaneously with satisfactory recovery rates, and the limit of detections (LODs) of miRNA-155 and miRNA-150 in human serum are low to 7.19 fM and 5.84 fM, respectively. These results indicate that our method is the most sensitive detection so far reported and that the designed fluorescent probes with signal amplification strategies can achieve highly sensitive detection of MM-related miRNAs for MM diagnosis.

Super-resolution scanning imaging based on metal-dielectric composite metamaterials.

We propose super-resolution scanning imaging by using a metamaterial composed of a silver-silicon dioxide composite covered by a layer of chromium containing one slit and a silicon dioxide substrate. By simulating a distribution of energy flow in the metamaterial for an H-polarized wave, we find that the output beam exhibits focusing accompanied with good directional radiation, which is able to be designed as a super-resolution scanning probe. We also demonstrate numerically super-resolution imaging by scanning our designed metamaterial over a sub-wavelength object.

Graphene-embedded oblique V-shaped silver nanoarrays for hydrophobic pollutants pre-concentration and high-sensitivity SERS detection.

A surface enhanced Raman scattering (SERS) substrate of silver nanorod modified with graphene and silver nanorod (AgNR@Graphene@AgNR) has been fabricated to improve the sensitivity of SERS detection of hydrophobic pollutants, in which, graphene is an interlayer and AgNR is arranged on both sides of the graphene. The embedded graphene could help the oblique V-shaped AgNR structure to improve the sensitivity of SERS detection with a significant electric field enhancement effect. The annealing treatment of the substrate, shortening the nanometer gap between the graphene and AgNR, is benefit for producing a large number of "hot spots" at the fold, which has been verified by the finite difference time domain (FDTD) simulation. The enhancement factor (EF) of AgNR@Graphene@AgNR could reach up to 1.6 × 108 with a good reproducibility. The substrate could achieve high-sensitivity detection of 4-chlorobiphenyl (PCB-3) and 3, 3', 4, 4'-tetrachlorobiphenyl (PCB-77) with the limit of detections (LODs) of 1.72 × 10-10 M and 2.11 × 10-8 M, and the effective identification of PCBs mixture has been realized through principal component analysis (PCA), which means that the AgNR@Graphene@AgNR substrate has a potential significance for the detection and analysis of hydrophobic pollutant mixtures in the environment.

Transcriptomics and Metabolomics Revealed the Biological Response of Chlorella pyrenoidesa to Single and Repeated Exposures of AgNPs at Different Concentrations.

Increased release of engineered nanoparticles (ENPs) from widely used commercial products has threatened environmental health and safety, particularly the repeated exposures to ENPs with relatively low concentration. Herein, we studied the response of Chlorella pyrenoidesa (C. pyrenoidesa) to single and repeated exposures to silver nanoparticles (AgNPs). Repeated exposures to AgNPs promoted chlorophyll a and carotenoid production, and increased silver accumulation, thus enhancing the risk of AgNPs entering the food chain. Notably, the extracellular polymeric substances (EPS) content of the 1-AgNPs and 3-AgNPs groups were dramatically increased by 119.1% and 151.5%, respectively. We found that C. pyrenoidesa cells exposed to AgNPs had several significant alterations in metabolic process and cellular transcription. Most of the genes and metabolites are altered in a dose-dependent manner. Compared with the control group, single exposure had more differential genes and metabolites than repeated exposures. 562, 1341, 4014, 227, 483, and 2409 unigenes were differentially expressed by 1-0.5-AgNPs, 1-5-AgNPs, 1-10-AgNPs, 3-0.5-AgNPs, 3-5-AgNPs, and 3-10-AgNPs treatment groups compared with the control. Metabolomic analyses revealed that AgNPs altered the levels of sugars and amino acids, suggesting that AgNPs reprogrammed carbon/nitrogen metabolism. The changes of genes related to carbohydrate and amino acid metabolism, such as citrate synthase (CS), isocitrate dehydrogenase (IDH1), and malate dehydrogenase (MDH), further supported these results. These findings elucidated the mechanism of biological responses to repeated exposures to AgNPs, providing a new perspective on the risk assessment of nanomaterials.

Large-area mid-infrared broadband absorbers based on spiral ITO resulting from the combination of two different broadening absorption methods.

A large-area mid-infrared broadband absorber is proposed in this paper. The absorber is a spiral ITO structure grown on a hexagonal lattice arrangement of silicon nanopillars by using a glancing angle deposition method. The experimental results show that when the heights of the silicon nanopillars are 1.7 µm and the number of rotation depositions is n = 5, that is, the rotation angle is 150 degrees, the absorber absorbs more than 81% of electromagnetic waves in the 2.5-6 µm spectral range. In the atmospheric window of 3-5 µm, the integral absorption reaches 96%. The experimental results also show that the absorbing ability of the ITO structure in the mid-infrared atmospheric window is significantly stronger than that of the structure composed of silver under the same preparation conditions. The main reasons for the broadband absorption are that the spiral ITO structure has resonant absorption of electromagnetic waves with different wavelengths in the empty cavity regions with different sizes, and ITO has longer penetration depths than noble metals in the mid-infrared band, which brings about stronger broadband absorption. The combination of the two leads to a broadening of the total absorption spectrum. The higher heights of the silicon nanopillars enhance absorption further. Additionally, the loose spiral ITO distributions indicate lower mean plasma concentration and then increase penetration depths further, resulting in stronger light absorption. Such a large-area mid-infrared absorption structure with a simple preparation method has potential applications in mid-infrared cloaking and sensing.

Potentially Toxic Element Contaminations and Lead Isotopic Fingerprinting in Soils and Sediments from a Historical Gold Mining Site.

Lead (Pb) isotopes have been widely used to identify and quantify Pb contamination in the environment. Here, the Pb isotopes, as well as the current contamination levels of Cu, Pb, Zn, Cr, Ni, Cd, As, and Hg, were investigated in soil and sediment from the historical gold mining area upstream of Miyun Reservoir, Beijing, China. The sediment had higher 206Pb/207Pb ratios (1.137 ± 0.0111) than unpolluted soil did (1.167 ± 0.0029), while the soil samples inside the mining area were much more variable (1.121 ± 0.0175). The mean concentrations (soil/sediment in mg·kg-1) of Pb (2470/42.5), Zn (181/113), Cu (199/36.7), Cr (117/68.8), Ni (40.4/28.9), Cd (0.791/0.336), As (8.52/5.10), and Hg (0.168/0.000343) characterized the soil/sediment of the studied area with mean Igeo values of the potentially toxic element (PTE) ranging from -4.71 to 9.59 for soil and from -3.39 to 2.43 for sediment. Meanwhile, principal component analysis (PCA) and hierarchical cluster analysis (HCA) coupled with Pearson's correlation coefficient among PTEs indicated that the major source of the Cu, Zn, Pb, and Cd contamination was likely the mining activities. Evidence from Pb isotopic fingerprinting and a binary mixing model further confirmed that Pb contamination in soil and sediment came from mixed sources that are dominated by mining activity. These results highlight the persistence of PTE contamination in the historical mining site and the usefulness of Pb isotopes combined with multivariate statistical analysis to quantify contamination from mining activities.

Preparation of a silver nano-tripod structure by a tilting angle deposition technique and its SERS application.

A silver nano-tripod (AgNT) structure with a high-density "hot spots" distribution was fabricated by a tilting angle deposition technique. The electric field simulation distribution showed that the electric field enhancement of the AgNT structures is optimal when the tilting angle is 72°. Such AgNT substrates were successfully obtained experimentally when the included angle between the silver vapor and the normal of the sample platform was set to 86°. R6G and CV were used as probe molecules to investigate the SERS activity of AgNT, which revealed that the detection limits of AgNT for R6G and CV were 2.24×10-8 M and 4.01×10-8 M, the relative standard deviations (RSDs) were 4.26% and 4.44%, and the enhancement factors (EFs) were 9.58×106 and 1.16×107, respectively. The AgNT substrates with simple preparation and high distribution density of "hot spots" illustrate a good application prospect in environmental monitoring.

Bacterial response to soil property changes caused by wood ash from wildfire in forest soils around mining areas: Relevance of bacterial community composition, carbon and nitrogen cycling.

The different physical-chemical properties of the black ash (200-500 °C) and white ash (>510 °C) generated by wildfire may result in varied impacts on soil biological and abiotic indicators. Many studies have highlighted the environmental impacts of wood ash application due to its complex mixture of beneficial and detrimental compounds. However, few studies have compared the effect of black ash and white ash on soil, especially for the heavy metal polluted soil. In this study, we used the comparative analysis of parallel microcosm experiments to study the impacts of white ash and black ash on bioavailable heavy metals and metabolic potentials of microbial community. The results indicated that both white ash and black ash increased the concentration of soil bioavailable As and Cr, while the increasing trend of bioavailable As could be limited by Ca in the treatment of white ash. The addition of black ash could enhance the abundance of genes related to the Calvin cycle (CBB). Different kinds of wood ash inputs into soils could cause the differences in the microbial taxa for carbon fixation, as indicated by the dominance of different taxa for carbon fixation in white ash versus black ash treatments. Additionally, both white ash and black ash impaired dissimilatory nitrate reduction to ammonium (DNRA), nitrate assimilation and nitrification, while white ash enhanced denitrification.

Deciphering the toxic effects of metals in gold mining area: Microbial community tolerance mechanism and change of antibiotic resistance genes.

Mine tailing dumps represent significant threats to ecological environments due to the presence of toxic substances. The present work investigated the relationship among microbial activity, the community, antibiotic resistance genes (ARGs) and trace metals in soil surrounding gold mine tailings. Using microbial metabolic activity and high-throughput sequencing analysis, we found the trace metals Cd and Hg could be main factors influencing the microbial community. According to bacterial co-occurrence pattern analysis, the effects of total cadmium and total mercury on bacterial diversity are potentially mediated by influencing bacteria community in the keystone module II. Additionally, most of metal-resistant bacteria belong to Actinobacteria and Proteobacteria, and the metal tolerance suggested to be linked with various functions including replication, recombination and repair, as well as inorganic ion transport and metabolism based on PICRUSt2 analysis. We also found that metals generated by mining activity may trigger the co-selection of antibiotic resistance in the phyla Actinobacteria and Proteobacteria due to co-resistance or cross resistance. Additionally, PLS-PM analysis revealed that metals could indirectly affect ARGs by influencing bacterial diversity in gold mining areas.

Label-free discrimination of glioma brain tumors in different stages by surface enhanced Raman scattering.

According to the WHO classification criteria, the most common intracranial tumor gliomas can be divided into four grades based on their symptoms. Among them, Grade Ⅰ and Grade II are low-grade gliomas, and Grade III and Grade IV are high-grade gliomas. Because gliomas have a high lethal rate, they have received widespread attention in the medical field. Based on these circumstances, a rapid and facile surface enhanced Raman scattering (SERS) method using silver nano particle-decorated silver nanorod (AgNPs@AgNR) as substrates were developed for the discrimination of gliomas. Compared with SERS-active silver nanoparticles and silver nanorod substrates, the prepared AgNPs@AgNR substrates showed an outstanding SERS performance with an enhancement factor up to 1.37 × 109. Combined AgNPs@AgNR substrate with principal component analysis (PCA), we achieved rapid discrimination of healthy brain tissue and gliomas at different grades. The spectra obtained from the tissue illustrate prominently spectral differences which can be applied to identify whether it came from a healthy region or from a glioma. The most prominently difference between the SERS spectrum of healthy brain tissue and that of gliomas at different grades is the reduction in quotient of two characteristic peaks at 653 and 724 cm-1. Furthermore, healthy brain tissue and Grade II gliomas as low grade gliomas as well as Grade III and Grade IV as high-grade gliomas can be clearly distinguished by three-dimensional PCA. Preliminary results indicate that the SERS spectra based on AgNPs@AgNR substrates can be applied for a rapid identification owing to its simple preparation of specimen and high-speed spectral acquirement.

Leaching behavior of metals from iron tailings under varying pH and low-molecular-weight organic acids.

The migration of metals (e.g., Fe, Cd, Co, Cr, Cu, Mn, Ni, and Zn) in both of iron tailings under different pH leachates was studied by laboratory static leaching experiments. The results indicated that Fe showed the highest leaching concentration at an initial pH of 2, reaching 16.19 and 51.72 mg L-1 in the Qian'anling (Q0) and Majuanzi (M0) iron tailings, respectively. Metal ions manifested a strong pH dependence. In addition, the leaching behavior of Cd, Cr, Fe, and Cu for the two tailings was also evaluated under leaching by three low-molecular-weight organic acids (LMWOAs). The results indicated the leaching of Cd and Fe followed the order of citric acid > malic acid > oxalic acid and that the leaching order for Cr and Cu was citric acid > oxalic acid > malic acid. The concentration of Fe was low in 5 mM oxalic acid leaching for 20 days because of the hydrolysis precipitation of iron ions and the complexation with organic ligand. The crystal lattice on the tailings was significantly damaged after leaching. The CO32- peak appeared in M0 with different treatments, and the proportion of COO- fitting peak areas increased markedly after leaching with LMWOAs.