Magnetic MOF Substrates for the Rapid and Sensitive Surface-Enhanced Raman Scattering Detection of Uranyl.

With the widespread use of uranium in the nuclear industry, achieving rapid and sensitive detection of uranium contaminants is critical for reducing environmental pollution. Surface-enhanced Raman scattering (SERS), with its high sensitivity and unique fingerprint properties, has been used for the analysis of uranyl. However, the weak affinity of Au for uranyl remains a challenge in the development of spherical Au-based SERS substrates. The metal-organic framework (MOF) material ZIF-8 exhibits excellent adsorption capacity for uranyl and could overcome this limitation. In this study, ZIF-8 porous structures were modified on a magnetic SERS substrate, Fe3O4@SiO2@Au (FA), for the rapid and sensitive detection and analysis of the uranyl species. Uranyl was adsorbed by ZIF-8, allowing ready access to the hot spots in the interstices of Au nanoparticles (AuNPs). Symmetrically stretched vibrating bonds of O═U═O were detected at 829 cm-1 as the characteristic peak of uranyl by surface plasmon resonance between the AuNPs. The ZIF-8 coating had minimal influence on target detection as the detection limit for 4-MPY was only half an order of magnitude lower than before modification. The enhancement factor for uranyl reached 106. The substrate showed excellent sensing performance in a neutral or alkaline environment. It was used to detect uranyl in tap water and river water; rapid separation of the species from the water samples was achieved using an external magnet to extract radioactive waste. The proposed substrate offers a route for monitoring and detecting uranyl contamination and an approach for achieving rapid on-site detection, providing a promising application for environmental contaminant detection.

Raman spectroscopy for profiling physical and chemical properties of atmospheric aerosol particles: A review.

Atmosphere aerosols have significant impact on human health and the environment. Aerosol particles have a number of characteristics that influence their health and environmental effects, including their size, shape, and chemical composition. A great deal of difficulty is associated with quantifying and identifying atmospheric aerosols because these parameters are highly variable on a spatial and temporal scale. An important component of understanding aerosol fate is Raman Spectroscopy (RS), which is capable of resolving chemical compositions of individual particles. This review presented strategic techniques, especially RS methods for characterizing atmospheric aerosols. The nature and properties of atmospheric aerosols and their influence on environment and human health were briefly described. Analytical methodologies that offer insight into the chemistry and multidimensional properties of aerosols were discussed. In addition, perspectives for practical applications of atmospheric aerosols using RS are featured.

Adhesive surface-enhanced Raman scattering Cu-Au nanoassembly for the sensitive analysis of particulate matter.

Surface-enhanced Raman scattering (SERS) has been used in atmospheric aerosol detection as it enables the high-resolution analysis of particulate matter. However, its use in the detection of historical samples without damaging the sampling membrane while achieving effective transfer and the high-sensitivity analysis of particulate matter from sample films remains challenging. In this study, a new type of SERS tape was developed, consisting of Au nanoparticles (NPs) on an adhesive double-sided Cu film (DCu). The enhanced electromagnetic field generated by the coupled resonance of the local surface plasmon resonances of AuNPs and DCu led to an enhanced SERS signal with an experimental enhancement factor of 107. The AuNPs were semi-embedded and distributed on the substrate, and the viscous DCu layer was exposed, enabling particle transfer. The substrates exhibited good uniformity and favorable reproducibility with relative standard deviations of 13.53% and 9.74% respectively, and the substrates could be stored for 180 days with no signs of signal weakening. The application of the substrates was demonstrated by the extraction and detection of malachite green and ammonium salt particulate matter. The results demonstrated that SERS substrates based on AuNPs and DCu are highly promising in real-world environmental particle monitoring and detection.

Green-emitting carbon quantum dots as a dual-mode fluorescent and colorimetric sensor for hypochlorite.

In this work, green-emitting carbon quantum dots were successfully prepared through a facile one-step solid-state reaction method. The obtained green-emitting carbon dots (G-CDs) showed good fluorescence stability in NaCl aqueous solution and different pH values. Moreover, the G-CDs showed high sensitivity and selectivity for detecting hypochlorite by both fluorometry and colorimetry. Under the optimized condition, a highly sensitive detection of hypochlorite was established in the range of 0.2-100 µM and 10-150 µM for fluorescent and colorimetric methods, respectively. The corresponding limits of detection (LOD) were 0.0781 µM and 1.82 µM, respectively. Therefore, the G-CDs were successfully applied to determinate hypochlorite in actual water samples. In addition, a paper-based sensor loading with the G-CDs was also developed for rapid visual detection of hypochlorite. The results suggested that the G-CDs could be a promising candidate to detect hypochlorite.

On-site detection of As(III) based on silver nanoparticles aggregation mediated by phosphates using surface-enhanced Raman scattering (SERS).

A portable and simple method was developed for on-site selective determination of As(III) based on the SERS signal of As(III)-O vibration. The method relies on the synergistic effect of nanoparticles aggregation and analyte adsorption. Experimental results demonstrated that phosphate replaced the ligands of HH@Ag NPs, which in turn facilitated the adsorption of As(III) on the surface of HH@Ag NPs. The phosphate was introduced as an agglomerating agent to improve the detection ability of the method for As(III). The method shows good selectivity and linear relationship between 5 × 10-8 and 0.8 × 10-6 M, with the detection limit of 1.8 × 10-9 M. The method was applied to actual water samples and successfully detected As(III), indicating that the method could have application potential in actual detection scenarios.

Constructing a Raman and surface-enhanced Raman scattering spectral reference library for fine-particle analysis.

Fine particles associated with haze pollution threaten the health of over 400 million people in China. Owing to excellent non-destructive fingerprint recognition characteristics, Raman and surface-enhanced Raman scattering (SERS) are often used to analyze the composition of fine particles to determine their physical and chemical properties as well as reaction mechanisms. However, there is no comprehensive Raman spectral library of fine particles. Furthermore, various studies that used SERS for fine-particle composition analysis showed that the uniqueness of the SERS substrates and different excitation wavelengths can produce a different spectrum for the same fine-particle component. To overcome this limitation, we conducted SERS experiments with a portable Raman spectrometer using two common SERS substrates (silver (Ag) foil and gold nanoparticles (Au NPs)) and a 785 nm laser. Herein, we introduced three main particle component types (sulfate-nitrate-ammonium (SNA), organic material, and soot) with a total of 39 chemical substances. We scanned the solid Raman, liquid Raman, and SERS spectra of these substances and constructed a fine-particle reference library containing 105 spectra. Spectral results indicated that for soot and SNA, the differences in characteristic peaks mainly originated from the solid-liquid phase transition; Ag foil had little effect on this difference, while the Au NPs caused a significant red shift in the peak positions of polycyclic aromatic hydrocarbons. Moreover, with various characteristic peak positions in the three types of spectra, we could quickly and correctly distinguish substances. We hope that this spectral library will aid in the future identification of fine particles.

Surface-enhanced Raman scattering for mixing state characterization of individual fine particles during a haze episode in Beijing, China.

The nondestructive characterization of the mixing state of individual fine particles using the traditional single particle analysis technique remains a challenge. In this study, fine particles were collected during haze events under different pollution levels from September 5 to 11 2017 in Beijing, China. A nondestructive surface-enhanced Raman scattering (SERS) technique was employed to investigate the morphology, chemical composition, and mixing state of the multiple components in the individual fine particles. Optical image and SERS spectral analysis results show that soot existing in the form of opaque material was predominant during clear periods (PM2.5 ≤ 75 µg/m3). During polluted periods (PM2.5 > 75 µg/m3), opaque particles mixed with transparent particles (nitrates and sulfates) were generally observed. Direct classical least squares analysis further identified the relative abundances of the three major components of the single particles: soot (69.18%), nitrates (28.71%), and sulfates (2.11%). A negative correlation was observed between the abundance of soot and the mass concentration of PM2.5. Furthermore, mapping analysis revealed that on hazy days, PM2.5 existed as a core-shell structure with soot surrounded by nitrates and sulfates. This mixing state analysis method for individual PM2.5 particles provides information regarding chemical composition and haze formation mechanisms, and has the potential to facilitate the formulation of haze prevention and control policies.

Hairpin-Structured Magnetic SERS Sensor for Tetracycline Resistance Gene tetA Detection.

Antibiotic resistance genes (ARGs) have become emerging environmental contaminants, and the effective on-site detection of ARGs is urgently needed. Herein, we constructed a hairpin-structured magnetic sensor for the analysis of a widespread ARG, tetA, using surface-enhanced Raman scattering (SERS). The SERS sensor was assembled by immobilizing core-satellite structured Fe3O4@SiO2-Au with single-stranded DNA in a folded hairpin structure. The SERS sensor exhibited good sensitivity and specificity for the detection of laboratory-synthesized tetA ssDNA fragments. In addition, this SERS strategy is the first of its kind to be employed for monitoring environmental samples in the field, with a limit of detection reaching as low as 25 copies µL-1. Univariate and multivariate linear regression equations verify the practicability of the SERS sensor for quantitative tetA determination, showing the prospect for an amplification-free alternative platform for sensitive and reliable on-site detection of ARGs in the environment.

Calcium Ions Turn on the Fluorescence of Oxytetracycline for Sensitive and Selective Detection.

Herein, we report an interesting finding about the new application of oxytetracycline (OTC), as a fluorescent probe for the detection of calcium ion (Ca2+), which proved that it can offer an expeditious, highly sensitive, and selective detection method for Ca2+. Upon the addition of Ca2+, the fluorescence of OTC could be significantly enhanced with rapid response and high sensitivity, and achieved a good limit of detection as low as 125 nM in aqueous solution. The complex formed via Ca2+ coordinating to the hydroxyl group of OTC contributes to the fluorescence enhancement, which has been proved by several characterization methods including UV-vis analysis, binding constant determination, and fluorescence titration. The method avoided complexity for EDTA measurement of Ca2+ in running water as proposed previously. Taking advantage of good availability, stability and operability, the OTC was further successfully applied to the detection of Ca2+ in a real environment. Graphical Abstract.

Bombyx mori bidensovirus infection alters the intestinal microflora of fifth instar silkworm (Bombyx mori) larvae.

Bacterial diseases can occur as a result of disruption of the intestinal microbial population in the silkworm, Bombyx mori, and are often induced by bidensovirus (BmBDV) infection. We investigated the effects of BmBDV infection on intestinal microbes and immune gene responses in fifth instar silkworm larvae. Midgut contents were collected from BmBDV-infected and uninfected silkworms at 48, 96, and 144 h post-infection (hpi) and the intestinal flora were analyzed using 16S rRNA gene Illumina MiSeq sequencing technology. The abundance of intestinal bacteria differed between BmBDV-infected and uninfected silkworms. There were no significant differences in bacterial diversity at 48 and 96 hpi, but bacterial diversity in infected larvae was lower at 144 hpi compared with that of uninfected larvae. At the phylum level, the ratio of Proteobacteria was higher in infected larvae than in uninfected larvae at 48 and 96 hpi, but was lower after 144 hpi, while the ratio of Firmicutes had increased relative to uninfected silkworms. At the genus level, the ratio of Enterococcus increased gradually in infected silkworms, however, proportion of bacteria genera Incertae sedis were increased at 96 hpi, and the proportion of Lactococcus had decreased at 96 hpi. Principal component analysis showed that the proportion of Enterococcus species present was negatively correlated with most dominant genera. Increases in the abundances of the genera Anderseniella, Simplicispira, Enterococcus and, genera Incertae sedis, were associated with BmBDV infection. Quantitative reverse transcription-polymerase chain reaction indicated that expression levels of genes associated with immune deficiency (IMD), Toll, and JAK/STAT pathways were higher at 144 hpi with BmBDV infection. Enterococcus abundance was higher and was positively correlated with the expression level of spatzle-1, peptidoglycan recognition protein LE, and peptidoglycan recognition protein LB genes, suggesting that an increase in the abundance of Enterococcus leads to activation of the Toll and IMD immune pathways.

Physicochemical analysis of individual atmospheric fine particles based on effective surface-enhanced Raman spectroscopy.

Fine particles associated with haze pollution threaten the health of more than 400 million people in China. It is therefore of great importance to thoroughly investigate and understand their composition. To determine the physicochemical properties in atmospheric fine particles at the micrometer level, we described a sensitive and feasible surface-enhanced Raman scattering (SERS) method using Ag foil as a substrate. This novel method enhanced the Raman signal intensities up to 10,000 a.u. for ν(NO3-) in fine particles. The SERS effect of Ag foil was further studied experimentally and theoretically and found to have an enhancement factor of the order of ~104. Size-fractionated real particle samples with aerodynamic diameters of 0.4-2.5 µm were successfully collected on a heavy haze day, allowing ready observation of morphology and identification of chemical components, such as soot, nitrates, and sulfates. These results suggest that the Ag-foil-based SERS technique can be effectively used to determine the microscopic characteristics of individual fine particles, which will help to understand haze formation mechanisms and formulate governance policies.

Recent progress in detection of mercury using surface enhanced Raman spectroscopy--A review.

Concerns over exposure to mercury have motivated the exploration of cost-effective, rapid, and reliable method for monitoring Hg(2+) in the environment. Recently, surface-enhanced Raman scattering (SERS) has become a promising alternative method for Hg(2+) analysis. SERS is a spectroscopic technique which combines modern laser spectroscopy with the optical properties of nano-sized noble metal structures, resulting in substantially increased Raman signals. When Hg(2+) is in a close contact with metallic nanostructures, the SERS effect provides unique structural information together with ultrasensitive detection limits. This review introduces the principles and contemporary approaches of SERS-based Hg(2+) detection. In addition, the perspective and challenges are briefly discussed.

Crystal violet-modified Fe3O4@Au SERS probes: a novel highly sensitive method for H2 detection.

A novel breakthrough has been achieved in gas detection through the innovative application of surface-enhanced Raman scattering (SERS) to hydrogen (H2) detection for the first time. This study capitalizes on the unique SERS effects of gold nanoparticles coupled with the redox interaction between hydrogen and crystal violet, allowing for the development of a magnetic SERS probe that demonstrated enhanced sensitivity and specificity. This new probe can detect hydrogen concentrations as low as 1% by volume in gaseous environments, offering a substantial improvement over the detection limits of traditional hydrogen alarms. Further, this report comprehensively detailed the synthesis of the FA-CV materials, instrumental analysis, and an in-depth evaluation of the SERS performance of the FA-CV substrate, underlining the outstanding sensitivity, stability, and recyclability of the probe. The introduction of SERS in this novel capacity not only contributes a valuable approach to gas sensing technologies, but also suggests promising avenues for the application of SERS in environmental monitoring and energy security. This illustrates the adaptability and potential impact of this powerful technique.

Au-NP-Decorated Cotton Swabs as a Facile SERS Substrate for Food-Safety-Related Molecule Detection.

Recently, food safety has received considerable attention, and various analytical techniques have been employed to monitor food quality. One of the promising techniques in this domain is the surface-enhanced Raman scattering (SERS) technique. This study developed a facile, cost-effective SERS method by supporting a wipe-type substrate with a small-head cotton swab. We fabricated Au-nanoparticle (NP)-decorated cotton swabs (CS-Au NP) via the dropwise addition of gold colloid on the cotton fibers. These swabs exhibit reduced gold colloid consumption and a compact fiber structure, allowing for the uniform distribution of Au NPs and easy capture of molecular signals. Experiments were conducted to obtain a CS-Au NP wiper performance optimized for cotton swab selection, NaCl concentration, and Au NP layers. The Raman reporter molecule 4-mercaptopyridine was detected at a concentration of 1 × 10-8 M and a relative standard deviation of ≤10%. The proposed SERS platform enables the facile and reliable detection of food-safety-related molecules such as malachite green on the surface of fruits and vegetables. This paper describes the development of an easy, cost-effective, and environment-friendly method of detecting food-safety-related molecules on various food surfaces through SERS.

Sulfate-nitrate-ammonium as double salts in PM2.5: Direct observations and implications for haze events.

Obtaining detailed information on sulfate-nitrate-ammonium (SNA) is fundamentally important to explain the formation of haze in China, since it is a dominant component of fine particulate matter (PM2.5) and plays a critical role in the deterioration of air quality. Several single-particle analysis methods have been applied to study and explain SNA formation; however, determining its mixture state remains a challenge. This study describes a direct observation of the SNA components in atmospheric particles on a single-particle scale, and details the first use of a non-destructive surface-enhanced Raman scattering (SERS) technique for SNA analysis. We studied PM2.5 collected at a site on the premises of Tsinghua University in Beijing, China, during a winter haze episode (12.15.2016-12.23.2016). The on-line data show that the SNA component accounted for 9.4% to 68.2% of the total mass of PM2.5, becoming dominant on heavy haze days, and the sulfate concentration increased with the nitrate concentration (R2 = 0.72). Furthermore, the off-line SERS and scanning electron microscopy-energy dispersive X ray analysis (SEM-EDS) results for the single particles collected also indicated that SNA increase with increasing haze pollution. The existing state of the SNA component on each haze day was observed directly in a non-destructive manner mainly in the form of double salts such as 3(NH4NO3)·(NH4)2SO4 and 2(NH4NO3)·(NH4)2SO4. A Raman mapping experiment further confirmed that the SNA was internally mixed. Our data also show that SNA can evaporate under high-vacuum scanning electron microscopy conditions, suggesting that SERS is an effective method to directly observe SNA without sample loss and may represent a promising single-particle technique to supplement traditional electron microscopy methods. This work will provide evidence for the SNA formation, particularly during haze events.

Improvement of a combination of TMPA (or IMERG) and ground-based precipitation and application to a typical region of the East China Plain.

Hydrological model and water resource assessment performance are highly dependent on the quality of the precipitation input, which can be improved by means of the optimal interpolation method for the merged precipitation. However, the traditional first-guess field of satellite precipitation often increases the merging error on account of its inherent bias. Some authors have suggested the need of generating a more accurate first-guess field for the merged precipitation, but the research in this improvement is rarely reported. Therefore, an improved merging method is proposed in this paper in which the precipitation from rain gauges is added to the first-guess field when combining the precipitation estimates of Tropical Rainfall Measuring Mission (TRMM) Multi-Satellite Precipitation Analysis (TMPA) 3B42 with rain gauges in a typical region of the East China Plain, China. Furthermore, the influence of the gauge station densities on the merged accuracy of the precipitation is investigated based on the traditional and improved methods. The results show that the improved merging method has effectively reduced the influence of the uncertainty caused by the error of the first-guess field owing to the consideration of the spatial distribution of TMPA precipitation and the precision of the gauge precipitation. Compared with results of traditional interpolation methods using only gauge data, the precipitation-merging method in this study can obtain better performance results only when the observation density is lower than 6.0 × 103 km2 per gauge under average conditions of many years. The higher the observation density, the more notably the accuracy increases. In addition, the greater the precipitation, the more homogeneous the spatial and temporal distribution of the precipitation and the better the improved effect of the merging method. The Integrated Multi-satellitE Retrievals for the Global Precipitation Measurement (GPM) mission (IMERG) data is also used to validate the conclusions here.

Characteristics of the secondary water-soluble ions in a typical autumn haze in Beijing.

Four haze episodes (EPs) were observed in October 2014 in Beijing, China. For better understanding of the characteristics and the formation mechanisms of PM2.5 (particulate matter with an aerodynamic diameter ≤ 2.5 µm), especially secondary water-soluble inorganic species in these haze events, hourly concentrations of PM2.5, sulfate, nitrate, and ammonium (SNA) were measured in this study. Concentrations of gaseous pollutants and meteorological parameters were also measured. The average concentration of PM2.5 was 106.6 ± 83.5 µg m-3, which accounted for around 53% of PM10 (particulate matter with an aerodynamic diameter ≤ 10 µm) mass. Nitrogen dioxide (NO2) concentration was much higher than that of sulfur dioxide (SO2) since October is a non-heating month. SNA is the most abundant secondary water-soluble inorganic species and contributed to 33% of PM2.5 mass concentration. Sulfur oxidation ratio (SOR) was much higher than nitrogen oxidation ratio (NOR). NOR and SOR increased with elevated PM2.5 levels and heterogeneous processes seemed to be the most plausible explanation of this increase. Relative humidity (RH), which is of great influence on aerosol liquid water content (ALWC), played a considerable role in the formation of secondary inorganic aerosols, accelerated the secondary transformation of gaseous precursors, and further aggravated haze pollution. The positive feedback loop associated with high aerosol levels and low planetary boundary layer (PBL) height led to the evolution and exacerbation of heavy haze pollution. Fire maps and 48-h air mass backward trajectories supported the significant impact of biomass burning activities and regional transport on haze formation over Beijing in October 2014.

Effects of transient high temperature treatment on the intestinal flora of the silkworm Bombyx mori.

The silkworm Bombyx mori is a poikilotherm and is therefore sensitive to various climatic conditions. The influence of temperature on the intestinal flora and the relationship between the intestinal flora and gene expression in the silkworm remain unknown. In the present study, changes of the intestinal flora at 48, 96 and 144 h following transient high temperature treatment (THTT) of 37 °C for 8 h were investigated. According to principal component analysis, the abundances of Enterococcus and Staphylococcus showed a negative correlation with other dominant genera. After THTT, the gene expression levels of spatzle-1 and dicer-2 were increased and decreased, respectively, which suggested that the Toll and RNAi pathways were activated and suppressed, respectively. The species-gene expression matrix confirmed that the spatzle-1 and dicer-2 gene expression levels were negatively and positively correlated, respectively, with the abundance of Enterococcus and Staphylococcus in the control. The abundance of Variovorax post-THTT was positively correlated with the spatzle-1 gene expression level, whereas the community richness of Enterococcus was negatively correlated with the spatzle-1 gene expression level and positively correlated with the dicer-2. The results of the present investigation provide new evidence for understanding the relationships among THTT, intestinal flora and host gene expression.

Typical winter haze pollution in Zibo, an industrial city in China: Characteristics, secondary formation, and regional contribution.

Heavy haze pollution occurs frequently in northern China, most critically in the Beijing-Tianjin-Hebei area (BTH). Zibo, an industrial city located in Shandong province, is often listed as one of the top ten most polluted cities in China, particularly in winter. However, no studies of haze in Zibo have been conducted, which limits the understanding of the source and formation of haze pollution in this area, as well as mutual effects with the BTH area. We carried out online and continuous integrated field observation of particulate matter in winter, from 11 to 25 January 2015. SO42-, NO3-, and NH4+ (SIA) and organics were the main constituents of PM2.5, contributing 59.4% and 33.6%, respectively. With the increasing severity of pollution, the contribution of SIA increased while that of organics decreased. Meteorological conditions play an important role in haze formation; high relative humidity (RH) and low wind speed increased both the accumulation of pollutants and the secondary transition from gas precursors (gas-particle phase partitioning). Since RH and the presence of O3 can indicate heterogeneous and photochemistry processes, respectively, we carried out correlation analysis and linear regression to identify their relative importance to the three main secondary species (sulfate, nitrate, and secondary organic carbon (SOC)). We found that the impact of RH is in the order of SO42- > NO3- > SOC, while the impact of O3 is reversed, in the order of SOC > NO3- > SO42-, indicating different effect of these factors on the secondary formation of main species in winter. Cluster analysis of backward trajectories showed that, during the observation period, six directional sources of air masses were identified, and more than 90% came from highly industrialized areas, indicating that regional transport from industrialized areas aggravates the haze pollution in Zibo. Inter-regional joint prevention and control is necessary to prevent further deterioration of the air quality.

Au nanoparticles grafted on Fe3O4 as effective SERS substrates for label-free detection of the 16 EPA priority polycyclic aromatic hydrocarbons.

Several methods and materials have been explored for the sensitive and practicable detection of polycyclic aromatic hydrocarbons (PAHs). However, it is still a challenge to develop simple and cost-effective sensing techniques for PAHs. Herein we report the synthesis and construction of Fe3O4@Au SERS substrate. This magnetic substrate was composed by Fe3O4 microspheres and Au NPs. The size, morphology, and surface composition of Fe3O4@Au were characterized by multiple complimentary techniques including scanning electron microscopy, X-ray photoelectron spectroscopy, and X-ray powder diffraction. The spatial distributions of electro-magnetic field enhancement around Fe3O4@Au was calculated using finite difference time domain (FDTD) simulations. As a result of its remarkable sensitivity, the Fe3O4@Au-based SERS assay has been applied to detect the 16 EPA priority PAHs. The LODs achieved by our method (100-5 nM, 16.6-1.01 µg L(-1)) make it promising for the rapid screening of highly contaminated cases. As a proof-of-concept study, the substrate was applied in SERS sensing of PAHs in river matrix. The 16 PAHs could be differentiated based upon their characteristic SERS peaks. Most importantly, the detection was successfully conducted using a portable Raman spectrometer, which could be used for on-site monitoring of PAHs.