Notes

Single-shot time-reversed eye focusing straight into and through spreading mass media.
Untargeted LC-MS based metabolomics is a useful approach in many research areas such as medicine, systems biology, environmental sciences or even ecology. In such an approach, annotation of metabolomes of non-model organisms remains a significant challenge. In this study, an analytical workflow combining a classical phytochemical approach, using the isolation and the full characterization of the chemical structure of natural products, together with the use of MS/MS-based molecular networking with various levels of restrictiveness was developed. This protocol was applied to the marine brown seaweed Taonia atomaria, a cosmopolitan algal species, and allowed to annotate more than 200 metabolites. First, the algal organic crude extracts were fractionated by flash-chromatography and the chemical structure of eight of the main chemical constituents of this alga were fully characterized by means of spectroscopic methods (1D and 2D NMR, HRMS). These compounds were further used as chemical standards. In a second step, the main fractions of the algal extracts were analyzed by UHPLC-MS/MS and the resulting data were uploaded to the Global Natural Products Social Molecular Networking platform (GNPS) to create several molecular networks (MNs). A first MN (MN-1) was built with restrictive parameters and allowed the creation of clusters composed by nodes with highly similar MS/MS spectra. Then, using database hits and chemical standards as "seed" nodes and/or similarity between MS/MS fragmentation pattern, the main clusters were easily annotated as common glycerolipids and phospholipids, much rare lipids -such as acylglycerylhydroxymethyl-N,N,N-trimethyl-ß-alanines or fulvellic acid derivatives- but also new glycerolipids bearing a terpene moiety. Lastly, the use of less and less constrained MNs allowed to further increase the number of annotated metabolites.We report a novel three-dimensional microfluidic paper-based analytical device (3D-μPAD) with colorimetric detection, using Mn-ZnS quantum dot embedded molecularly imprinted polymer (Mn-ZnS QD-MIP), for selective glyphosate determination in whole grain samples. Detection is based on the catalytic activity of Mn-ZnS QD-MIP in the H2O2 oxidation of ABTS. Glyphosate imprinted polymer is successfully synthesized on the Mn-ZnS QD surface using a poly (N-isopropylacrylamide) (NIPAM) and N, N'-Methylenebisacrylamide (MBA) as the functional monomers. The catalytic activity depends on binding or non-binding of glyphosate molecules on the synthetic recognition sites of the Mn-ZnS QD-MIP. Glyphosate selectively binds to the cavities embedded on the Mn-ZnS QD surface, and subsequently turns-off or inhibits the ABTS oxidation and color change to light green. The change of reaction color from dark green to light green depends on the concentration of glyphosate. We report, for the first time, using the relatively new penguard enamel colour to create a hydrophobic barrier. The foldable 3D-μPAD comprises three layers (top/center/bottom), named as the detection zone, immobilized Mn-ZnS QD-MIP disc, and sample loading. Assay on the 3D-μPAD can determine glyphosate by ImageJ detection, over an operating range of 0.005-50 μg mL-1 and with a detection limit of 0.002 μg mL-1. Our 3D-μPAD exhibits high accuracy, with a 0.4% (intra-day) and 0.7% (inter-day) relative difference from the certified CRM value. Moreover, the fabricated 3D-μPAD provides good reproducibility (1.7% RSD for ten devices). The developed 3D-μPAD was successfully applied to determine the glyphosate concentration in whole grain samples and shows great promise as an alternative highly selective and sensitive colorimetric method. The 3D-μPAD is well suited to food-quality control and onsite environmental-monitoring applications, without sophisticated instrumentation.1,4-Dihydropyridines are a class of drugs with a wide range of biological activities and pharmacological effects. However, there are few reports on its optical activity, especially its application on fluorescent CN- probe. In this experiment, we designed and synthesized a fluorescent probe based on 1,4-dihydropyridines to detect CN-. Interestingly, the probe exhibited outstanding properties such as 100% water soluble, near infrared, ratiometric, fast response, high selectivity and anti-interference ability for other ions. The color change indicated that the probe can be used for naked eye identification. In particular, the probe showed a super large fluorescent emission peak shift (260 nm). In addition, the reaction mechanism of the probe has been studied by 1H NMR titration, high resolution mass spectrometry and theoretical calculations.Tumor-derived exosomes that inherit molecular information on parental cells hold great promise for cancer diagnostics. Currently, two main technical challenges, time-consuming and labor-intensive isolation of exosome and nucleic acid extraction with limited recovery that have restricted the detection of ultralow abundance exosomal nucleic acids. Here, we proposed a simple, efficient and "lab in a tube" system for the detection of exosomal nucleic acids, which fully integrated exosomes enrichment using immunomagnetic beads (IMB) (10 min), fast exosomes lysis based on NP-40 lysate (5 min) and sensitive loop-mediated isothermal amplification (LAMP) in a tube. This method was demonstrated by detecting two exosomal long noncoding RNA biomarkers of gastric cancer (HOTTIP and lncRNA-GC1) with a dynamic detection ranging from 300 ng/μL to 10 ng/μL, and the detection limit of LAMP was 10 ng/μL. Additionally, this platform exhibited good performance in the analysis of exosomal HOTTIP RNA directly in human serum samples, which has the potential for detection of low-abundance exosomal nucleic acid biomarkers from cancers.Hypersensitive detection of organic pollutions with high toxicity in drinking water always keeps its challenge in electroanalysis due to their low concentration and electrochemical redox inert. In this work, a novel nanomaterial modified electrode for the sensitive detection of nitrobenzene (NB) is presented, based on environmental friendly and cost-effective Ni/Fe layered double hydroxides functionalized with sodium dodecyl sulfate (Ni/Fe(SDS)-LDH). Such 2D layered composites were prepared and used to improve the sensitivity for NB detection, due to its good catalytic activity for NB reduction. Besides, the proposed electrode shows a remarkably promoted sensitivity to NB compared to Ni/Fe-LDHs modified one. It is because that the surface modifier SDS can provide more adsorption sites to significantly improve the adsorption of NB, which has been confirmed by the adsorption experiment and the characterization of Fourier transform infrared spectroscopy (FTIR). As a result, an impressive sensing behaviour is achieved at the proposed Ni/Fe(SDS)-LDHs modified electrode with a sensitivity of 15.79 μA μM-1 cm-2. This work provides a promising way to build more advanced nanomaterials to electrochemical detection of organic pollution based on energetically synergizing of adsorption by surface functionalization engineering.A novel magnetic C3N5 framework material (Fe3O4/C3N5) was developed as a high selectivity extractant for La(III) determination in food samples. The Fe3O4/C3N5 material was synthesized by thermal deammoniation method and has larger surface area (100.3 m2 g-1) and more effective adsorption sites compared with that of individual C3N5 material (19.4 m2 g-1). click here It was proved that Fe3O4/C3N5 material displayed excellent selectivity and adsorption capacity for La(III). In addition, adsorption isotherm and kinetic data indicated that La(III) adsorption based on Fe3O4/C3N5 material is a monolayer adsorption which is compatible with Langmuir model and follows a pseudo-second-order kinetic equation. By using Fe3O4/C3N5 material as extractant, an analytical method was established with low limits of detection (3σ, n = 6) of 10.4 μg L-1, reasonable recoveries ranged from 86% to 106% and good precision with the RSD less than 10.7%. The analytical method was further applied to the determination of trace La(III) in food sample. It evinced that the concentration of La(III) in sea fish is 13.2 μg kg-1 and the content of 138La is 0.138 μg kg-1, which is 1.03% of total La(III).In this paper, a cysteine-functionalized zwitterionic stationary phase (Cys-silica) was prepared based on the "thiol-ene" click chemistry between cysteine and vinyl-functionalized silica, and was further modified with bromoethane, 1-bromooctane and 1-bromooctadecane, respectively, to obtain a series of quaternary ammoniation-functionalized stationary phases (Cys-silica-Cn, n = 2, 8 and 18). These zwitterionic stationary phases were regarded as reversed-phase/ion-exchange (RP/IEC) mixed-mode chromatography (MMC) stationary phases for protein separation. The retention behaviors of proteins on these zwitterionic stationary phases were carefully investigated. The results indicated that the retentions of acidic and basic proteins on these zwitterinonic stationary phases were significantly influenced by the acetonitrile and salt concentrations, pH of mobile phase as well as the hydrophobicity of the ligand. The separation selectivity of proteins on these zwitterionic stationary phases strongly depended on the pH value of mobile phase. The baseline separation of 6 kinds of basic proteins can be achieved at pH 8.0 using Cys-silica-C2 or Cys-silica-C8 column, and 5 kinds of acidic proteins can also be separated completely at pH 4.0 with Cys-silica-C2 column. Moreover, owing to the quaternary ammoniation-functionalization on Cys-silica by using appropriately hydrophobic bromoalkanes, the selectivity and separation efficiency of proteins can be enhanced greatly. As a result, the acidic and basic proteins can be separated completely step by step from the complex sample by adjusting pH of mobile phase using a single Cys-silica-C2 column, which illustrates that the cysteine-functionalized zwitterionic stationary phase has a great potential for protein separation.Bioaccessibility of trace elements (Li, Be, Ti, Ga, Cu, Ag, Hg, Cd, Cs, Pt, Tl, Pb, As, Cr, Co, Ni, V, Se, Sn and Sb) and major elements (Rb, Ba, Al, Fe, Zn, Si, Ca, Mg, Mn, Mo, Sr, P and K) in tea infusions has been assessed using an in vitro dialyzability protocol. Gastric simulation (using pepsin solution) and intestinal simulation (using pancreatin and bile salts) were used to perform the in vitro digestion. ICP-MS, ICP-OES and FAES were used for elements determination in digested tea leaves, their infusions and the dialyzate fractions from tea infusions. Microwaves assisted acid digestion was used for the total element determination in tea leaves, while tea infusions were prepared by brewing tea leaves for 5 min in boiling water. The LODs for elements determined in tea leaves were in the range of 0.11-656 ng g-1 and 0.02-145.6 μg g-1 for trace and major elements, respectively. For elements' determination in tea infusions, the LODs were ranged between 0.23 and 399.9 ng L-1 for trace elements and 0.2-1248 μg L-1 for major elements. The LODs for the elements in the dialyzable fraction varied from 0.018 to 142 μg L-1. The accuracy of the total element determination was evaluated using certified reference materials (Tea Leaves INCT-TL-1 and Rye Grass). The analytical recoveries were also assessed for analyzed elements in digested tea leaves (95-114%) and their infusions (92-115%), showing good recoveries. Among the studied elements, K was the most abundant element in tea leaves and tea infusions in almost all samples, followed by Ca, Mg, and P. Zn, Cs, and K showed the highest dialyzability percentages up to 84%, 76%, and 54%, respectively, followed by Si and Ca and K that show moderate to high dialyzability percentages. The accuracy of the dialysis process was evaluated using a mass-balance study.
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