A review of recent progress in the application of Raman spectroscopy and SERS detection of microplastics and derivatives.

The global environmental concern surrounding microplastic (MP) pollution has raised alarms due to its potential health risks to animals, plants, and humans. Because of the complex structure and composition of microplastics (MPs), the detection methods are limited, resulting in restricted detection accuracy. Surface enhancement of Raman spectroscopy (SERS), a spectral technique, offers several advantages, such as high resolution and low detection limit. It has the potential to be extensively employed for sensitive detection and high-resolution imaging of microplastics. We have summarized the research conducted in recent years on the detection of microplastics using Raman and SERS. Here, we have reviewed qualitative and quantitative analyses of microplastics and their derivatives, as well as the latest progress, challenges, and potential applications.

Synthesis of nanoparticles via microfluidic devices and integrated applications.

In recent years, nanomaterials have attracted the research intervention of experts in the fields of catalysis, energy, biomedical testing, and biomedicine with their unrivaled optical, chemical, and biological properties. From basic metal and oxide nanoparticles to complex quantum dots and MOFs, the stable preparation of various nanomaterials has always been a struggle for researchers. Microfluidics, as a paradigm of microscale control, is a remarkable platform for online stable synthesis of nanomaterials with efficient mass and heat transfer in microreactors, flexible blending of reactants, and precise control of reaction conditions. We describe the process of microfluidic preparation of nanoparticles in the last 5 years in terms of microfluidic techniques and the methods of microfluidic manipulation of fluids. Then, the ability of microfluidics to prepare different nanomaterials, such as metals, oxides, quantum dots, and biopolymer nanoparticles, is presented. The effective synthesis of some nanomaterials with complex structures and the cases of nanomaterials prepared by microfluidics under extreme conditions (high temperature and pressure), the compatibility of microfluidics as a superior platform for the preparation of nanoparticles is demonstrated. Microfluidics has a potent integration capability to combine nanoparticle synthesis with real-time monitoring and online detection, which significantly improves the quality and production efficiency of nanoparticles, and also provides a high-quality ultra-clean platform for some bioassays.

General Microwave Route to Single-Crystal Porous Transition Metal Nitrides for Highly Sensitive and Stable Raman Scattering Substrates.

The synthesis of metallic transition metal nitrides (TMNs) has traditionally been performed under harsh conditions, which makes it difficult to prepare TMNs with high surface area and porosity due to the grain sintering. Herein, we report a general and rapid (30 s) microwave synthesis method for preparing TMNs with high specific surface area (122.6-141.7 m2 g-1) and porosity (0.29-0.34 cm3 g-1). Novel single-crystal porous WN, Mo2N, and V2N are first prepared by this method, which exhibits strong surface plasmon resonance, photothermal conversion, and surface-enhanced Raman scattering effects. Different from the conventional low-temperature microwave absorbing media such as water and polymers, as new concept absorbing media, hydrated metal oxides and metallic metal oxides are found to have a remarkable high-temperature microwave heating effect and play key roles in the formation of TMNs. The current research results provide a new-concept microwave method for preparing high lattice energy compounds with high specific surface.

δ-MoN Yolk Microspheres with Ultrathin Nanosheets for a Wide-Spectrum, Sensitive, and Durable Surface-Enhanced Raman Scattering Substrate.

Facing the complex environment of on-site detection, the development of active substrates with wide-spectrum surface-enhanced Raman scattering (SERS) activity is essential. Herein, we report on the low temperature and reproducible synthesis of plasmonic δ-MoN yolk microspheres by in situ-nitriding amorphous MoO2 microspheres at 500 °C and 1 atm. The yolk-structured δ-MoN exhibits strong and wide-spectrum surface plasmon resonance and SERS effects and can perform highly selective detection for probes with different absorption wavelengths under excitation of 532, 633, and 785 nm lasers, with a limitation of 10-11 M and an enhanced factor of 3.6 × 107. Moreover, the plasmonic δ-MoN yolk microspheres have high environmental durability, which can maintain high sensitivity in strong acid and alkaline solutions.

Nitrogen-Doped Titanium Monoxide Flexible Membrane for a Low-Cost, Biocompatible, and Durable Raman Scattering Substrate.

The development of low-cost, biocompatible, and durable high-performance substrates is an urgent issue in the field of surface-enhanced Raman scattering (SERS). Herein, by reducing and exfoliating the TiO2-layered nanoplates in the gas phase, nitrogen-doped titanium monoxide (N-TiO) ultrathin nanosheets composed of 2-3 single layers with a thickness of only ∼1.2 nm are synthesized. Compared with pure TiO, the oxidation resistance of N-TiO is greatly improved, in which the oxidation threshold is significantly increased from 187.5 to 415.6 °C. The N-TiO ultrathin nanosheets are found to have strong surface plasmon resonance in the visible region. These ultrathin N-TiO nanosheets can be easily assembled into a large-scale flexible membrane and exhibit remarkable SERS effects. Moreover, this low-cost flexible SERS substrate combines the high durability of noble-metal substrates and the high biocompatibility of semiconductor substrates.

Controllable Self-Assembly of SERS Hotspots in Liquid Environment.

Controllable synthesis of novel metal nanoparticles and effective capture of hotspots are of great significance for SERS (surface-enhanced Raman spectroscopy) detection. Therefore, in this paper, a green controllable synthesis method of gold nanoparticle was achieved via epigallocatechin gallate reduction. Different morphologies of gold nanoparticles were synthesized just by changing the solution pH values, and the growth kinetics of AuNPs (gold nanoparticles) were systematically studied. The synthetic AuNPs were put in a droplet to study dynamic variations of self-assembly SERS hotspots from the liquid sol state to the solid dry state. The addition of halogen ions in the droplet can controllably regulate the self-assembly three-dimensional hotspot model of gold nanoparticles in the evaporation process of a droplet, during which the most enhancement effect can be easily captured. The dynamically changing images of nanoparticles in the process were graphically described based on the internal interaction forces of a droplet. Two stronger areas in the changes of SERS intensity were achieved with a high concentration of halogen ions, while only one maximum intensity area was obtained with a low concentration of halogen ions added. This method can effectively avoid complex and unpredictable microenvironments of SERS substrates in the liquid drop, further improving the reproducibility of SERS detection as well as broadening it to biological applications.

Dual-wavelength wide area illumination Raman difference spectroscopy for remote detection of chemicals.

Remote Raman instruments have become powerful analytical tools in some special environments. However, ambient daylight is the main limitation in the data acquisition process. To suppress daylight background interference and obtain a high signal-to-background ratio (SBR), we develop a dual-wavelength wide area illumination Raman difference spectroscopy (WAIRDS) system for daytime remote detection. In the WAIRDS system, a wide area illumination scheme and shifted-excitation Raman difference spectroscopy method are used to improve the reliability of collected Raman spectra. Measurements of polystyrene indicate that the WAIRDS system can be operated to obtain background-free Raman spectra under different levels of daylight background interference. The remote results show that the improvement in SBR is about three- to fivefold, and the system can work at distances of up to 9.2 m on a sunny afternoon. Moreover, to be close to the actual detection, the system is used for mineral and explosive raw material detection during daytime measurement. Measurements show that the WAIRDS system will be a useful tool for many remote applications in the future.

Dual-wavelength excitation combined Raman spectroscopy for detection of highly fluorescent samples.

As fluorescence is the major limitation in Raman scattering, near-infrared excitation wavelength (>780nm) is preferred for fluorescence suppression in Raman spectroscopy. To reduce the risk of fluorescence interference, we developed a dual-wavelength excitation combined Raman spectroscopy (DWECRS) system at 785 and 830 nm. By a common optical path, each laser beam was focused on the same region of the sample by a single objective lens, and the dual-wavelength excitation Raman spectra were detected by a single CCD detector; in addition, 785 and 830 nm excitation Raman spectra can be directly constructed as combined Raman spectrum in the DWECRS system. The results of pure peanut oil and glycerol indicate that the combined Raman spectrum cannot only reduce fluorescence interference but also keep a high signal-to-noise ratio in the high-wavenumber region. The results of dye-ethanol solutions with different concentrations show that the handheld DWECRS system can be used as a smart method to dodge strong fluorescence. Furthermore, we developed a peak intensity ratio method with the DWECRS system to distinguish different types of edible oils. The peak intensity ratio distribution chart of edible oils showed each oil normalized center was relatively independent and nonoverlapped, which can be used as the basis of edible oil classification analysis. In the future, the DWECRS system has potential to be used as a tool for more complex applications.

Surface-enhanced shifted excitation Raman difference spectroscopy for trace detection of fentanyl in beverages.

In recognition of the misuse risks of fentanyl, there is an urgent need to develop a useful and rapid analytical method to detect and monitor the opioid drug. The surface-enhanced shifted excitation Raman difference spectroscopy (SE-SERDS) method has been demonstrated to suppress background interference and enhance Raman signals. In this study, the SE-SERDS method was used for trace detection of fentanyl in beverages. To prepare the simulated illegal drug-beverages, fentanyls were dissolved into distilled water or Mizone as a series of test samples. Based on our previous work, the surface-enhanced Raman spectroscopy detection was performed on the beverages containing fentanyl by the prepared AgNPs and the SE-SERDS spectra of test samples were collected by the dual-wavelength rapid excitation Raman difference spectroscopy system. In addition, the quantitative relationship between fentanyl concentrations and the Raman peaks was constructed by the Langmuir equation. The experimental results show that the limits of quantitation for fentanyl in distilled water and Mizone were 10 ng/mL and 200 ng/mL, respectively; the correlation coefficients for the nonlinear regression were as high as 0.9802 and 0.9794, respectively; and the relative standard deviation was less than 15%. Hence, the SE-SERDS method will be a promising method for the trace analyses of food safety and forensics.

A balsam pear-shaped CuO SERS substrate with highly chemical enhancement for pesticide residue detection.

Simple and traditional hydrothermal fabrication of a novel balsam pear-shaped CuO with high SERS enhancement is presented. XRD (X-ray diffraction), SEM (scanning electronic microscopy), TEM (transmission electron microscope), HRTEM (high-resolution transmission electron microscope), UV-Vis, and Raman are adopted to ensure that this balsam pear-shaped CuO with dense nanoparticle protuberance is successfully prepared. The LOD of this CuO SERS substrate is 4.79 µg L-1 with R6G as molecular probe. By using DFT (density functional theory) calculation and FDTD (finite difference time domainmethod) simulation, both EM (electromagnetic enhancement) and CM (chemical enhancement) mechanisms are investigated, and the results show that these two-enhancement mechanisms can coexist in this balsam pear-shaped CuO. Finally, the prepared substrate has been applied for the determination of trace levels of paraquat in solution , and results show that its LOD for paraquat is 275 µg L-1 (optimum Raman band: 1646 cm-1 Raman shift), which is better than the government standard in China. A dexterous and facile way for fabrication of CuO SERS-active substrates with low cost and high performance, quite promising in detection of chemically hazardous substances and pesticide residue is provided. Graphical abstract.

Visual Electrofluorochromic Detection of Cancer Cell Surface Glycoprotein on a Closed Bipolar Electrode Chip.

This work reports an electrofluorochromic strategy on the basis of electric field control of fluorescent signal generation on bipolar electrodes (BPEs) for visualizing cancer cell surface glycoprotein (mucin 1). The device included two separate cells: anodic sensing cell and cathodic reporting cell, which were connected by a screen-printing electrode patterned on poly(ethylene terephthalate) (PET) membrane. In the sensing cell, anti-MUC1 antibody immobilized on a chitosan-multiwalled carbon nanotube (CS-MWCNT)-modified anodic BPE channel was used for capturing mucin-1 (MUC1) or MCF-7 cancer cells. Then ferrocene (Fc)-labeled mucin 1 aptamers were introduced through hybridization. Under an applied voltage, the ferrocene was oxidized and the electroactive molecules of 1,4-benzoquinone (BQ) in the cathodic reporting cell were reduced according to electroneutrality. This produced a strongly basic 1,4-benzoquinone anion radical (BQ•-), which turned on the fluorescence of pH-responsive fluorescent molecules of (2-(2-(4-hydroxystyryl)-6-methyl-4 H-pyran-4-ylidene)malononitrile) (SPM) coexisting in the cathode reporting cell for both spectrophotometric detection and imaging. This strategy allowed sensitive detection of MUC1 at a concentration down to 10 fM and was capable of detecting a minimum of three MCF-7 cells. Furthermore, the amount of MUC1 on MCF-7 cells was calculated to be 6.02 × 104 molecules/cell. Our strategy also had the advantages of high temporal and spatial resolution, short response time, and high luminous contrast and is of great significance for human health and the promotion of life science development.

Rapid and direct mass spectrometric analysis of antibiotics in seawater samples.

A method based on droplet spray ionization (DSI) mass spectrometry was described for rapid, direct analysis of seawater samples. By spontaneous desalting (SD) of droplet seawater on a cover slip corner, the target analytes could be separated from the salts. The separated targets are then dissolved in a spray solvent for mass spectrometric analysis. The desorption/ionization of salts is impeded due to their microsolubility or even insolubility in the spray solvent, thus greatly reducing the suppression of ionization of the analyte. It has been demonstrated that the desalting process is spontaneous and highly effective, which simplifies the operation. The dependence of signal intensity on the operation parameters was investigated as well. With this method, a wide range of antibiotics including sulfonamides, macrolides, amphenicols, quinolones, rifamycins, and mixtures in seawater have been successfully detected in either positive or negative ion modes. Limits of detection (S/N ≥ 3) were determined to be 0.52 and 0.20 pg for trimethoprim and clarithromycin, respectively. Moreover, satisfactory accuracy and precision were obtained according to the analysis of real seawater samples. Our results show that the combination of DSI and spontaneous desalting is a simple, sensitive, and rapid method for direct detection of analytes in seawater.

[Morphology and Spectral Properties Study of LaCeF3:Tb Microcrystalline].

LaCeF3:Tb microcrystalline was synthesized by microemulsion method, oleic acid-assisted solvothermal method, ultrasonic-assisted solvothermal method separately. LaCeF3:Tb microcrystalline synthesized by ultrasonic-assisted solvothermal method is rarely reported. Using X-ray diffraction (XRD), scanning electron microscope (SEM), fluorescence spectroscopy (PL) method such as the crystal phase, morphology and luminescence properties of the samples have been characterized. XRD results show that the crystallization product is good, microcrystalline and standard card PDF# 38-0452 (the six-party LaCeF3) is corresponding, SEM images showing the product has uniform size and morphology, under 250 nm excitation nanoparticlesshows strong green light, the main emission peaks respectively belonged to 5D4-->7F6 (489 nm), 5D4-->7F5 (545 nm), 5D4-->7F4 (585 nm) and 5D4-->7F3 (621 nm) transition of Tb³âº. Through LaCeF3 and LaCeF3:Tb spectral studies prove the existence of the Ce-Tb energy transfer. Calculated the critical doping concentration of Tb in LaCeF3microcrystalline synthesized by different methods.

[The Synthesis, Luminescence and Energy Transmission of NaLa(MoO4) 2 : Eu3+/Tb3+/Tm3+ Materials].

A series of Eu3+ /Tb3+ /Tm3+ single/co-doped NaLa(MoO4)2 (NLM) phosphors have been synthesized by microemulsion-hydrothermal method. Phosphor crystal structure, morphology and luminescent properties were tested and studied by X-ray diffraction (XRD), scanning electron microscopy (SEM) and fluorescence spectroscopy. The results show that the prepared samples are all tetragonal single crystals. By way of substitution, the sites of La3+ are replaced by Eu3+, Tb3+ and Tm3+. Morphology of the samples are tetragonal sheet structure and the size of particles is 1 - 1.5 µm. When the doping concentration of Eu3+ is 9%, NLM : 9%Eu3+ phosphor emission peak is the strongest at 616 nm, the critical transfer distance (R(c)) between Eu3+ in the NLM matrix is about 15.20 Å at this time. At the emission spectrum of NLM : 9%Eu3+, the peak at 591 nm is the magnetic dipole transition of 5D0 to 7F1 of Eu3+. The peak at 616 nm is the electric dipole transition of 5D0 to 7 F2 of Eu3+. Electric dipole transition emission intensity is about 10 times of the strength of the magnetic dipole transition. This indicates that Eu3+ is located at noninversion symmetry site. By Fixing Eu3+ (Tb3+) concentration and varying the concentration of Tb3+ (Eu3+), the energy transfer mechanism between Eu3+ and Tb3+ was studied. By adjusting the Eu3+, Tb3+ and Tm3+ doping concentrations, tunable luminescence of visible light region is implemented under the single matrix. The luminescence of NLM x%Eu3+, y%Tb3+, z%Tm3+ phosphors are translated from blue (0.205, 0.135) to pseudo-white (0.305, 0.266) under 360 nm irradiation.

[The Different Phase, Morphology Controllable Synthesis and Luminescent Properties Investigation of NaYF4: Yb, Er].

Using sodium fluoride and rare earth nitrate as raw materials and sodium citrate as surfactant, micron grade NaYF4 upconversion luminescent materials were prepared by hydrothermal method. By X-ray diffraction(XRD), scanning electron microscope(SEM) and fluorescence spectrometer, the crystal phase, morphology and luminescent characteristics of the prepared samples were investigated. The results showed that the phase of the samples could generate a transition from cubic phase to hexagonal phase by adjusting the proportion (5, 6, 7, 8, 9, 11) of NaF/RE , and the X ray diffraction peaks for the cubic and hexagonal phase of samples exactly matched with those of the standard card of PDF# 77-2042 and PDF# 16-0334, respectively. The SEM photographs showed that the crystallinity of samples was high and the dispersibility was favourable, the morphology were translated from microrods to hexagonal microplates. The samples upconversion luminescent spectra showed the intensity enhancement of red and green light emission peaks with increasement of the ratio of NaF/RE3+. The green emission peaks of samples at 520 and 539 nm corresponded to the ²H¹¹/²-4-->I15/2 and 4S3/2-->4I15/2 level transition of Er³âº ion, and the red light emission peaks of samples at 653 nm corresponded to the 4F9/2-->4I15/2 levelt ransition of Er+ ion. The chromaticity coordinate diagram exhibited that the change of the luminescent color of samples could be achieved by adjusting the ratio of NaF/RE³âº. With the increasing of NaF/RE³âº ratio, for the whole light-emitting colors of samples, the shift from yellow region to near red region could be realized. It can be concluded that through the relatively simple experimental procedure and lower cost materials, the change of phase and morphology, the moving of light-emitting color for sample NaYF4:Yb³âº, Er³âº could be well controlled only by changing the single component (NaF) molar ratio in the raw materials. The effect of phase and morphology of fluorescent materials on their upconversion luminescence has great potential applications in photonic devices and bioanalysis research.

[Study of fast pretreatment method in detection of melamine in liquid milk using liquid chromatography and Raman spectroscopy].

The present paper proposed for the first time the flocculation-filtration method for separation of interfering substances in milk, such as fat. In this method only two steps were carried out. Firstly, aluminum chloride (PAC, Al2 (OH)nCl6-n,) is used to flocculate the milk; Secondly, water filter was used to filter the mixture. Then the clear filtrate could be used for the detection of melamine. The whole preprocessing would not take more than one minute. The pretreatment process was optimized. Experiments show that the adding proportion of PAC should be about 2%-3% for best filtration efficiency, and that it would have the best flocculation effect when the mixture was mildly alkaline. High performance liquid chromatography experiments show that the melamine recovery of this method is more than 90%. Samples pretreated by the flocculation--filtration method were clearer and the baselines of spectral curve obtained by sensitizing Raman method were more smooth which means better purification compared to those samples pretreated by centrifugal pretreatment method. The pretreatment method proposed can be used in HPLC and Raman spectroscopy methods for rapid detecting melamine in liquid milk. This method shows better separation effect, simpler operation, and lower time and money cost than those pretreatment processes in the existing standard melamine detection method for milk. By use of this pretreatment method, the melamine rapid detection efficiency would be greatly improved.

Detection of carbofuran in fruits and vegetables by Raman spectroscopy combined with immunochromatography.

It has long been desired to develop rapid methods for the rapid identification and quantification of pesticides and their metabolites. Carbofuran, a representative pesticide of the carbamate group, is highly systemic and is used on vegetables, fruits and grains, which has led many countries to test for residues in food and the environment. In this study, gold and silver composite core-shell (Au@Ag) nanoparticles were used to label the carbofuran antibody and Raman molecule 5,5-dithiobis-2-nitrobenzoic acid (DTNB) to synthesize Raman immune probes. The signal value of DTNB was read using a Raman spectrometer, and the quantitative detection technology of carbofuran was established based on lateral flow immunochromatographic assay (ICA) combined with surface-enhanced Raman spectroscopy (SERS). SERS-ICA is a rapid, quantitative and ultrasensitive test for the determination of carbofuran in fruits and vegetables with a sensitivity of 0.1 pg mL-1. Consequently, the results demonstrate that the SERS-based lateral flow immunosensor developed in this study has the advantages of excellent assay sensitivity and remarkable multiplexing capability, and thus it will have great application potential in food safety monitoring.

A highly sensitive europium nanoparticle-based lateral flow immunoassay for detection of chloramphenicol residue.

A europium nanoparticle-based lateral flow immunoassay for highly sensitive detection of chloramphenicol residue was developed. The detection result could be either qualitatively resolved with naked eye or quantitatively analyzed with the assistance of a digital camera. In the qualitative mode, the limit of detection (LOD) was found to be 0.25 ng/mL. In the quantitative mode, the half-maximal inhibition concentration (IC50) was determined to be 0.45 ng/mL and the LOD can reach an ultralow level of 0.03 ng/mL, which is ~100 times lower than that of the conventional colloidal gold-based lateral flow immunoassay. Potential application of the established method was demonstrated by analyzing representative cow milk samples.

[Research progress in Raman spectra and its test sample pretreatment].

It is generally accepted that Raman spectroscopy is an advanced method with simple operation, small amount of specimens needed as well as rapid on-line screening, detection and identification. However, in the technology of determination, sample preparation is also an significant factor during analysis process. It would affect the accuracy and precision of the results, and normally involved complicated procedure. Developing a rapid and effective sample preparation method coupled with Raman detective technology is a method worth study. In the present paper, the simply basic principle, the origin and development of generating Raman spectra were introduced, some Raman technology, such as the surface-enhanced Raman spectroscopy, tip-enhanced Raman spectroscopy, shell-isolated nanoparticle enhanced Raman spectroscopy and the sample preparation were discussed.

[Influence of Bi3+ doping on properties of CaMoO4 : Eu3+ phosphors].

Europium doped CaMoO4 and bismuth co-doped CaMoO4 : Eu3+ phosphors were prepared via microemulsion-hydrothermal method. The structure, morphology and luminescence properties of samples were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and fluorescence spectroscopy, respectively. The XRD patterns of as-prepared samples were in agreement with the PDF # 29-0351 of CaMoO4, which indicated that the phosphor possessed tetragonal crystal structure. SEM images showed that the samples were basically flake in shape and their average size was 1.5-2.5 microm. The critical molar concentration of activator (Eu3+) in CaMoO4 : Eu3+ was 5%, and the predominant peak of CaMoO4 : Eu3+ located at 616 nm, corresponding to the 5D0 -->7 F2 electronic dipole transition of Eu3+. The photoluminescence color can be tuned from orange-yellow (0.514, 0.537) to white (0.339, 0.333) by adjusting the doping concentrations of Eu3+ ions. To enhance the red emission intensity of Eu3+, Bi3+ was used to co-dope CaMoO4 : Eu3+ as sensitizers. When the concentration of Bi3+ is 3%, luminescence intensity was maximum. The chromaticity coordinates (CIE) varied from orange (0.497, 0.347) to red (0.585, 0.349) with increasing the content of Bi3+.