2, 2.5 and 0.9% (RSD, n = 6), respectively. The developed sensor was validated with river water, dust, and soil samples, and the achieved spiked recoveries were immensely satisfied from 98.1% to 102.0%. The Fe@SiO2-NH2 possessed excellent reusability. This sensor exhibits that it is simple, sensitive and selective, and will be a vital analytical tool for TNT in many fields.Highly specific capture of phosphopeptides, especially multi-phosphopeptides, from complex biological samples is critical for comprehensive phosphoproteomic analysis, but it still poses great challenges due to the lack of affinity material with ideal enrichment efficiency. Here, two-dimensional (2D) covalent organic framework (COFs) nanosheets was applied for selective separation of phosphopeptides for the first time. Particularly, by incorporating guanidinium units, the 2D guanidinium-based COF nanosheets (denoted as TpTGCl CONs) exhibited controllable and specific enrichment performance towards global/multi-phosphopeptides. TpTGCl CONs was easy to prepare and showed large surface area, low steric hindrance, abundant accessible interaction sites and high chemical stability. Taking these merits together, TpTGCl CONs exhibited excellent efficiency for phosphopeptide enrichment, such as low detection limits (0.05 fmol μL-1 for global phosphopeptides and 0.1 fmol μL-1 for multi-phosphopeptides), high selectivity (15000 of molar ratios of β-casein/BSA for both global and multi-phosphopeptides), high adsorption capacity (100 mg g-1 for global phosphopeptides and 50 mg g-1 for multi-phosphopeptides). Furthermore, TpTGCl CONs could be reused due to the high chemical stability. In addition, TpTGCl CONs were successfully applied to controllable and specific capture of endogenous global/multi-phosphopeptides from human serum and human saliva, indicating its good potential in rapid and sensitive detection of biomarkers from biological fluid. Finally, rat liver protein digest was used to confirm the high specificity of TpTGCl CONs towards multi-phosphopeptides and demonstrated its potential as an ideal enrichment probe for comprehensive phosphoproteomic analysis.In this work, a synergistic imprinting strategy combined with metal coordination based on ligand-free Fe3O4-Cu was proposed to fabricate molecularly imprinted polymers (MIPs) for the recognition and isolation of bovine hemoglobin (BHb) specifically in biological samples. Copper doped magnetic microspheres prepared solvothermally in a one-pot pathway act as both magnetic core and metal affinity substrate. Upon anchoring BHb to Fe3O4-Cu through metal coordination, the imprinted layer was formed via dopamine self-polymerization. Profiting from the synergistic effect, the obtained imprinted microspheres exhibited an enhanced adsorption performance with the adsorption capacity of 400.86 mg g-1, imprinting factor of 11.88, selectivity coefficient above 5.8, superior to most of other reported BHb-MIPs. Furthermore, kinetic adsorption analyses pointed to a chemisorption-limited process as described by the pseudo-second-order model, and the isothermal adsorption analyses implied monolayer adsorption, as described by the Langmuir model. ART26.12 solubility dmso In addition, the resultant magnetic MIPs can be used at least six adsorption-desorption cycles without re-incubation in the metallic salt solution, avoiding secondary environmental pollution. Furthermore, the well-defined materials showed selectivity both in individual protein samples and bovine serum, providing a promising potential in bioseparation.Traditional non-targeted chemometric workflows for gas chromatography-mass spectrometry (GC-MS) data rely on using supervised methods, which requires a priori knowledge of sample class membership. Herein, we propose a simple, unsupervised chemometric workflow known as variance rank initiated-unsupervised sample indexing (VRI-USI). VRI-USI discovers analyte peaks exhibiting high relative variance across all samples, followed by k-means clustering on the individual peaks. Based upon how the samples cluster for a given peak, a sample index assignment is provided. Using a probabilistic argument, if the same sample index assignment appears for several discovered peaks, then this outcome strongly suggests that the samples are properly classified by that particular sample index assignment. Thus, relevant chemical differences between the samples have been discovered in an unsupervised fashion. The VRI-USI workflow is demonstrated on three, increasingly difficult datasets simulations, yeast metabolomics, and human cane underlying nature of their dataset.Titanium dioxide nanoparticles (TiO2 NPs) are widely used in industry as a white pigment (paints, paper industry and toothpastes), photocatalysts (environmental decontamination and photovoltaic cells), inorganic UV filter (sunscreens and personal care products) and as a food additive (E171) and antimicrobial food packaging material. Silver nanoparticles (Ag NPs) are used in photonics, microelectronics, catalysis and medicine due to their catalytic activity, magnetic and optical polarizability, electrical and thermal conductivities and enhanced Raman scattering. They also have antibacterial, antifungal and antiviral activities, as well as anti-inflammatory potential. The huge increase in the use of nano-based products, mainly metallic NPs, implies the presence of nanomaterials in the environment, and hence, the unintentional human ingestion through water or foods (gastrointestinal tract is the main pathway of NPs intake in humans). The presence of TiO2 NPs and Ag NPs in seafood samples was firstly established using an ultrasound assisted enzymatic hydrolysis procedure and sp-ICP-MS analysis. Several clams, cockles, mussels, razor clams, oysters and variegated scallops, which contain TiO2 NPs and Ag NPs, were subjected to an in vitro digestion process simulating human gastrointestinal digestion in the stomach and in the small and large intestine to determine the bioaccessibility of these NPs. Caco-2 cells were selected as model of human intestinal epithelium for transport studies because of the development of membrane transporters that are responsible for the uptake of chemicals. Parameters as transepithelial electrical resistance (TEER) and permeability of Lucifer Yellow were studied for establishing cell monolayer integrity. TiO2 NPs and Ag NPs transport as well as total Ti and Ag concentrations passing through the gastrointestinal epithelial barrier model (0-2 h) were assessed by sp-ICP-MS and ICP-MS in several molluscs.