Design of magnetic photonic crystal microdroplet for sensitive detection of cationic organic pollutants by the coupled resonance effect.

Photonic crystals (PCs), periodically arranged nanoparticles, have emerged with extraordinary optical properties for light manipulation owing to their photonic band gaps (PBGs). Here, a novel strategy and method was developed for efficient enrichment and sensitive detection of cationic organic pollutants in water. Size-controlled Fe3O4@poly (4-styrenesulfonic acid-co-maleic acid) (Fe3O4@PSSMA) was prepared, and high surface charge were formed with the coating of PSSMA layer on the surface of Fe3O4, which could be used for adsorption and removal of cationic organic pollutants. The Fe3O4@PSSMA after adsorbing cationic organic pollutant were assembled to magnetic photonic crystal microdroplet (MPCM) structure in an external magnetic field, which was used as surface-enhanced Raman scattering (SERS) substrate. By coupling the magnetically tuned PBGs with Raman laser wavelength, the light utilization efficiency can be improved and the coupled resonance effect was greatly enhanced. The enhancement factor (EF) of MB was more than 800 attributing to the dual function of enrichment and coupled resonance effect of MPCM. The developed analytical strategy is the first time to use MPCM as a SERS substrate to realize the sensitive detection of 10 nmol L-1 MB in real water, which greatly improves the application of MPCM in the field of contaminant analysis and detection in water.

Developing a novel strategy for fabricating matrix film to assess the distribution of potassium perfluorooctanic sulfonate by matrix-assisted laser desorption/ionization mass spectrometry imaging.

Matrix deposition plays a critical role in image quality of matrix-assisted laser desorption/ionization mass spectrometry imaging (MALDI-MSI). To improve the ionization efficiency and overcome the limitation of traditional matrix deposition methods in the face of difficult-to-sublimate or difficult-to-dissolve matrix, covalent organic frameworks (COFs) named COF-DhaTab was successfully synthesized and firstly used as matrix film. It was fabricated by imprinting of sieved COF-DhaTab powder on the surface of a double-sided adhesive tape. Outstanding reproducibility and uniformity of COF-DhaTab film were demonstrated by relative standard deviation (RSD) within 8.37% and 7.71% from dot-to-dot and plate-to-plate, respectively. With the introduction of double-sided adhesive tape, water contact angle (WCA) of COF-DhaTab film increased from 55° to 141°, resulting in significant suppression of analyte diffusion. Moreover, the intensity of potassium perfluorooctanic sulfonate (PFOS, C8F17SO3-, m/z 498.93) was 9.3 × 105, more than six hundred times higher than that using DHB matrix. This enhancement was attributed to the rough surface and multiple branches of the synthesized COF-DhaTab. To verify the ability of COF-DhaTab film as substrate, the spatial distribution of PFOS in zebrafish, rat liver and kidney tissues was explored. Superior imaging capability was displayed with high-spatial resolution and reliable location distribution. These results not only demonstrate the outstanding ability of COF-DhaTab as matrix for MALDI-MS and MALDI-MSI, but also provide a facile approach for fabrication of novel matrix films for MALDI-MSI.

Developing a Noncontact Heating Matrix Spraying Apparatus with Controllable Matrix Film Formation for MALDI Mass Spectrometry Imaging.

Matrix deposition plays an important role in obtaining high-quality and reliable molecular spatial location information for matrix-assisted laser desorption/ionization mass spectrometry imaging (MALDI-MSI). To control the matrix film formation, an automatic matrix spraying apparatus was developed with the introduction of a noncontact heating lamp. Compared with the unheated condition, the noncontact heating lamp suppressed the coffee-ring effect and the diffusion phenomenon of the analyte effectively by controllable matrix film formation. Meanwhile, the signal intensity was increased by 2-5 fold. To prove the ability of the matrix deposition apparatus, the apparatus combined with metabolomics analysis was used to show the spatial distribution of the substance in sprouted potato tubers. The potential biomarkers at m/z 868.5049 and m/z 852.5101 were identified as α-solanine and α-chaconine, and the synthesis pathways were further searched. To further demonstrate the quality of MALDI images including localization and spatial resolution, lipid distribution in rat brain tissue was investigated by the developed noncontact heating matrix spraying apparatus. An excellent match with distinguishable compartments of lipids in the rat brain was obtained between the H&E-stained sections and MALDI-MSI images. These results indicate that the developed noncontact heating matrix spraying apparatus is reliable and provides a low-cost, high-quality, rapid approach for MALDI-MSI.

A novel methodology and strategy to detect low molecular aldehydes in beer based on charged microdroplet driving online derivatization and high resolution mass spectrometry.

The concentration of aldehydes is one of the important indicators in the food quality and safety. To efficiently analyze the four aldehydes (methanal, ethanal, propanal and n-butanal) in beer, charged microdroplet driving online derivatization apparatus coupled with high resolution mass spectrometry was firstly developed. Utilizing the high-speed reaction accelerated by microdroplets, the offline derivative of aldehydes with 2,4-dinitrophenylhydrazine in bulk was transferred into online derivatization. The developed method featured acceptable linearities (R2 ≥ 0.95), high sensitivities (LODs at ng mL-1 level) and qualified precisions (RSDs ≤ 8.4 %) for target compounds. Four aldehydes with trace amount were successfully determined in beer. The results indicated that the novel online analytical strategy did not require complex sample preparation and could conduct simple, rapid, sensitive detection of small molecule aldehydes with high throughput in beer or even other food samples.