A spherical covalent-organic framework for enhancing laser desorption/ionization mass spectrometry for small molecule detection.

A spherical vinyl-functionalized covalent-organic framework (COF-V) was prepared at room temperature by a facile method and applied as a novel substrate for surface-enhanced laser desorption/ionization mass spectrometry (SELDI-MS). Compared with conventional organic matrices, the spherical COF-V with high crystallinity and good monodispersity exhibited high sensitivity, no matrix background interference, wide-range applicability, high salt tolerance and reproducibility in the characterization of small molecules. Considering these advantages, the applicability of the spherical COF-V-based SELDI-MS method was successfully demonstrated by determining trace amounts of glucose in diabetic urine, which would be a promising candidate for clinical diagnosis of diabetes. In addition, the morphological effect and the desorption/ionization mechanism of the COF-V were investigated in detail and the results indicated that the spherical COF-V substrate could greatly enhance the LDI process compared with the bulk COF-V. This work not only extends the application of COFs in MS, but also offers a promising alternative for small molecule identification and clinical diagnosis of diabetes.

Surface-enhanced laser desorption/ionization mass spectrometry for rapid analysis of organic environmental pollutants by using polydopamine nanospheres as a substrate.

Polydopamine nanospheres (PDA) were designed to serve as a new substrate for surface-enhanced desorption/ionization mass spectrometry (SELDI-MS). Compared with conventional organic matrices, the PDA substrate showed superior LDI performance for analyzing a wide variety of environmental pollutants, including polycyclic aromatic hydrocarbons, bisphenols, benzophenones, sulfonamides, perfluorinated compounds and estrogens. Benzoapyrene was used to evaluate the ability of quantitative analysis and its corresponding limit of detection (LOD) of as low as 0.1 ng was achieved. High sensitivity and good reproducibility of PDA-based SELDI-MS allowed us to determine ultratrace PAHs in airborne particulate matters (PM2.5), and the corresponding concentration of BaP in different PM2.5 were 5.32, 8.97 and 9.79 ng m-3. Significantly, PDA exhibits the characteristics of simple synthesis, low cost, non-toxicity and less matrix interference, which provides the possibility for the sensitive analysis of organic small molecule pollutants at low concentrations in complex environmental samples.

High-throughput screening of bisphenols using magnetic covalent organic frameworks as a SELDI-TOF-MS probe.

Core-shell structured magnetic covalent organic framework (Fe3O4@COF) nanospheres were rapidly synthesized at room temperature using the monodisperse Fe3O4 nanoparticles (NPs) as magnetic core and benzene-1,3,5-tricarbaldehyde (BTA) and 3,3'-dihydroxybenzidine (DHBD) as two building blocks (denoted as Fe3O4@BTA-DHBD), respectively. They can serve as a mass spectrometry probe for rapid and high-throughput screening of bisphenols (BPs) from pharmaceuticals and personal care products (PPCPs) by surface-enhanced laser desorption/ionization time-of-flight mass spectrometry (SELDI-TOF-MS). The Fe3O4@BTA-DHBD nanospheres showed some superior features involving average pore size distribution (2.82 nm), high magnetization values (42.5 emu g-1), high specific surface area (82.96 m2 g-1), and good chemical/thermal stability. It was used as both ideal adsorbent for enrichment of BPs and new substrate to assist ionization in SELDI-TOF-MS. The method exhibited good linearity in the range 0.05-4000 ng mL-1 with correlation coefficients (r) higher than 0.9920. Low limits of detection (LODs) (500 pg mL-1 for bisphenol A (BPA), 2 pg mL-1 for bisphenol B (BPB), 28 pg mL-1 for bisphenol C (BPC), 60 pg mL-1 for bisphenol F (BPF), 33 pg mL-1 for bisphenol AF (BPAF), 200 pg mL-1 for bisphenol BP (BPBP), 10 pg mL-1 for bisphenol S (BPS), 90 pg mL-1 for tetrabromobisphenol A (BPA(Br)4), and 380 pg mL-1 for tetrabromobisphenol S (BPS(Br)4)) and good recoveries (80.6-115%) of BPs in PPCPs were achieved. The relative standard deviations (RSDs) of spot-to-spot (n = 10) and sample-to-sample (n = 5) were in the ranges 5-11% and 5-12%, respectively. The dual-function platform was successfully applied to the quantitative determination of BPs in PPCPs. It not only expanded the scope of the application of COFs but also provided an alternative strategy for the determination of hazardous compounds in PPCPs. Graphical abstract Schematic representation of the synthesis of core-shell structured magnetic covalent organic framework nanospheres (Fe3O4@COFs) and its application in the analysis of bisphenols by using Fe3O4@BTA-DHBD nanospheres as a MS probe based on surface-enhanced laser desorption/ionization time-of-flight mass spectrometry.

Poly-l-lysine-based tissue embedding compatible with matrix-assisted laser desorption ionization-mass spectrometry imaging analysis of dry and fragile aristolochia plants.

The integrity of tissue is crucial for a high-quality analysis of matrix-assisted laser desorption ionization-mass spectrometry image (MALDI-MSI). Various embedding media utilized in traditional tissue-sectioning techniques are generally not recommended for MALDI-MSI of dry and fragile plant tissues because of the ion suppression effect in MALDI ionization in the low-mass region as well as the undesirable structural deformation during the sample preparation. In this work, a novel poly-L-lysine (PLL)-based tissue embedding method was developed for MALDI-MSI analysis of dry and fragile aristolochia plant (AP) tissues. The practical application in fixation, embedding, cryosectioning, and mounting of the dry and fragile AP tissues demonstrated that the PLL-based embedding technique could provide good rigidity to the plant tissues analysis compared to that without embedding and gelatin embedding. With the assistance of the PLL embedding medium, high spatial resolution molecular ion maps of main compounds, including aristolochic acids I (AAI) and aristolochic acids II (AAII) in AP root tissue, could be achieved by MALDI-MSI with enhanced signal intensities and no obvious background interference. This work provides an alternative approach for embedding the dry and fragile plant tissues comparable with MALDI-MSI analysis.