A DNA machine-based magnetic resonance imaging nanoprobe for in vivo microRNA detection.

In situ monitoring microRNA (miRNA) expression in vivo holds immense potential for directly visualizing the occurrence and progression of tumors. However, the significant barrier to developing a probe that can overcome the low abundance of miRNAs while providing an output signal with unlimited tissue penetration depth remains formidable. In this study, we developed a DNA machine-based magnetic resonance imaging nanoprobe (MRINP) for amplified detection of miR-21 in vivo. The MRINP was constructed with superparamagnetic Fe3O4 nanoparticles (NPs), paramagnetic Gd-DOTA complexes, and miR-21-activated DNA machines; the DNA machine was composed of hairpin DNAzyme (HD) strands serving as the DNAzyme walker and hairpin substrate (HS) strands serving as the track. Once uptake into tumor cells, the intracellular miR-21 specifically recognized and hybridized with the HD strand, restoring the activity of DNAzyme. Subsequently, the DNAzyme walker autonomously traveled on the surface of MRINP, and each step movement of the DNAzyme walker resulted in the cleavage of its substrate strands and the ensued release of the Gd-DOTA complex-labeled oligonucleotides, turning on the T1 signal of Gd-DOTA complexes for in situ imaging of miR-21 in tumor-bearing mice. This strategy would offer a promising approach for mapping tumor-specific biomarkers in vivo with unlimited penetration depth.

Yeast Extract Peptides Alleviate Depression in Chronic Restraint Stress Rats by Alleviating Hippocampal Neuronal Apoptosis and Dysbiosis of the Gut Microbiota.

SCOPE: Depression as a global neurological disorder, and hippocampal neuronal apoptosis and disorders of the gut microbiota are closely related to it. This study aims to expose the ameliorative effect of enzyme peptides (AP) from brewer's yeast on depressive behavior caused by chronic restraint stress (CRS) in rats. METHODS AND RESULTS: After 4 weeks of AP intervention, a significant alleviation of depressive behavior in the sucrose preference test (SPT), forced swim test (FST), and light-dark test (LDT) is observed in depressed rats. AP ameliorates neuronal damage with increased the expression of the key CREB/BDNF/TrkB/Akt signaling pathway, which increases the levels of the monoamine neurotransmitters 5-hydroxytryptamine (5-HT) and norepinephrine (NE) in the hippocampus, buffering hyperactivity of the hypothalamo-pituitary-adrenal axis (HPA), and decreasing the serum cortisol (CORT) and adrenocorticotropic hormone (ACTH) levels in rats. In addition, AP modulates the disruption of the rat gut microbiota by chronic restraint stress (CRS), and the changes in the abundance of Lactobacillus animalis and Lactobacillus johnsonii are probably the key for AP performing antidepressant benefits. A strong correlation is found between gut microbiota and biochemical markers of depression. CONCLUSION: AP, as a natural and safe active substance, has a positive effect in the treatment of depression.

Versatile, reusable and highly sensitive SERS-based point-of-care testing microplatform for reliable ATP detection.

The advancement in miniaturized Raman spectrometers, coupled with the single-molecule-level sensitivity and unique fingerprint identification capability of surface-enhanced Raman scattering (SERS), offers great potential for point-of-care testing (POCT). Despite this, accurately quantifying analyte molecules, particularly in complex samples with limited sample volumes, remains difficult. Herein, we present a versatile and reusable SERS microplatform for highly sensitive and reliable quantitative detection of adenosine triphosphate (ATP) in biological fluids. The platform utilizes gold-Prussian blue core-shell nanoparticles modified with polyethyleneimine (Au@PB@PEI NPs), embedded within gold nanoparticle-immobilized capillary-based silica monolithic materials. PB acts as an internal standard, while PEI enhances molecular capture. The periodic, bimodal porous structure of the silica monolithic materials provides uniform and abundant sites for nanoparticle attachment, facilitating rapid liquid permeation, intense SERS enhancement, and efficient enrichment. The platform regulates ATP capture and release through magnesium ions in the liquid phase, eliminating matrix interferences and enabling platform reuse. Integrating efficient molecular enrichment, separation, an interference-free internal standard, a liquid flow channel, and a detection chamber, our platform offers simplicity in operation, exceptional sensitivity and accuracy, and rapid analysis (∼10 min). Employing PB as an internal calibration standard, ratiometric Raman signals (I732/I2123) facilitate precise ATP quantification, achieving a remarkable limit of detection down to 0.62 pM. Furthermore, this platform has been proven to be highly reproducible and validated for ATP quantification in both mouse cerebrospinal fluid and human serum, underscoring its immense potential for POCT applications.

Multivariate surface self-assembly strategy to fabricate ionic covalent organic framework surface grafting monolithic sorbent for enrichment of aristolochic acids prior to high performance liquid chromatography analysis.

Herein, an ionic covalent organic framework (iCOF) surface grafting monolithic sorbent was prepared by the multivariate surface self-assembly strategy for in-tube solid-phase microextraction (SPME) of trace aristolochic acids (AAs) in serum, traditional Chinese medicines (TCMs) and Chinese patent drug. Via adjusting the proportion of ionic COF building block during the self-assembly, the density of quaternary ammonium ions in the iCOF was modulated for the enhanced adsorption of AAs. The successful preparation of iCOF surface grafting monolithic sorbent was confirmed by different means. A multiple mode mechanism involving π-π stacking, hydrophobic, electrostatic and hydrogen-bonding interactions was primarily attributed to the adsorption. Several in-tube SPME operating conditions, such as the dosage of ionic COF building block, ACN percentage and TFA percentage in the sampling solution, ACN percentage and TFA percentage in eluent and the collection time span, were optimized to develop the online in-tube SPME-HPLC method for analysis of AAs. Under the optimized conditions, a good linearity was obtained in the concentration range of 20-1000 ng/mL for target AAs in serum samples, the limits of detection (LODs) were less than 10 ng/mL, while the recoveries ranged from 90.3 % to 98.7 % with RSDs (n = 5) below 7.9 %. This study developed a feasible approach to iCOF functionalized monolithic sorbent for SPME and further exhibited the vast potential for the application of COF based monolithic sorbent in sample preparation.

Online highly selective recognition of domoic acid by an aptamer@MOFs affinity monolithic column coupled with HPLC for shellfish safety monitoring.

Enabling cost-effective safety monitoring of shellfish is an important measure for the healthy development of the coastal marine economy. Herein, a new aptamer@metal-organic framework (MOF)-functionalized affinity monolithic column was proposed and applied in selective in-tube solid-phase microextraction (IT-SPME) coupled with HPLC for the accurate recognition of domoic acid (DA) in shellfish. Using a surface engineering strategy, ZIF-8 MOF was grown in situ inside the poly(epoxy-MA-co-POSS-MA) hybrid monolith. A high BET surface area and abundant metal reactive sites of the MOF framework were obtained for anchoring massive aptamers with terminal-modified phosphate groups. Various characterizations, such as SEM, elemental mapping, XRD, and BET, were performed, and the affinity performance was also studied. The presence of a massive amount of aptamers with a super coverage density of 3140 µmol L-1 bound on ZIF-8 MOF activated a high-performance bionic-affinity interface, and perfect specificity was exhibited with little interference of tissue matrixes, thus assuring the highly selective capture of DA from the complex matrixes. Under the optimal conditions, DA toxins in shellfish were detected with the limit of detection (LOD) of 7.0 ng mL-1 (equivalent to 14.0 µg kg-1), representing a 5-28 fold enhancement in detection sensitivity over traditional SPE or MIP adsorbents reported previously. The recoveries of fortified mussel and clam samples were achieved as 91.8 ± 1.2%-94.1 ± 1.9% (n = 3) and 91.2 ± 1.1%-94.5 ± 3.6% (n = 3), respectively. This work sheds light on a cost-effective method for online selective IT-SPME and the accurate monitoring of DA toxins using an aptamer@MOF-mediated affinity monolith system coupled with the inexpensive HPLC-UV technique.

Dual-Responsive Turn-On T1 Imaging-Guided Mild Photothermia for Precise Apoptotic Cancer Therapy.

Apoptosis has gained increasing attention in cancer therapy as an intrinsic signaling pathway, which leads to minimal leakage of waste products from a dying cell to neighboring normal cells. Among various stimuli to trigger apoptosis, mild hyperthermia is attractive but confronts limitations of non-specific heating and acquired resistance from elevated expression of heat shock proteins. Here, a dual-stimulation activated turn-on T1 imaging-based nanoparticulate system (DAS) is developed for mild photothermia (≈43 °C)-mediated precise apoptotic cancer therapy. In the DAS, a superparamagnetic quencher (ferroferric oxide nanoparticles, Fe3 O4 NPs) and a paramagnetic enhancer (Gd-DOTA complexes) are connected via the N6-methyladenine (m6 A)-caged, Zn2+ -dependent DNAzyme molecular device. The substrate strand of the DNAzyme contains one segment of Gd-DOTA complex-labeled sequence and another one of HSP70 antisense oligonucleotide. When the DAS is taken up by cancer cells, overexpressed fat mass and obesity-associated protein (FTO) specifically demethylates the m6 A group, thereby activating DNAzymes to cleave the substrate strand and simultaneously releasing Gd-DOTA complex-labeled oligonucleotides. The restored T1 signal from the liberated Gd-DOTA complexes lights up the tumor to guide the location and time of deploying 808 nm laser irradiation. Afterward, locally generated mild photothermia works in concert with HSP70 antisense oligonucleotides to promote apoptosis of tumor cells. This highly integrated design provides an alternative strategy for mild hyperthermia-mediated precise apoptotic cancer therapy.

Bioinspired polydopamine-mediated metal-organic framework click-grafting aptamers functionalized fabric for highly-specific recognition of microcystin-leucine arginine.

Fabricating functional electrospun nanofiber coating for highly selective extraction of microcystin-LR (MC-LR) was of significant importance for water-safety monitoring. Herein, a novel MOF@aptamer functionalized nanofabric was presented via a facile and reliable strategy integrating polydopamine (PDA) mediation and thiol-ene chemistry and applied for specific recognition of the MC-LR model analyte. Using polydopamine (PDA) as the mediating layer, vinyl-UiO-66 MOF was grown in situ, followed by post-synthetic modification (PSM) of Zr4+ with vinyl phosphate and rapid UV-initiated click reaction of aptamers. Uniform deposition of Zr-based MOF (vinyl-UiO-66) on the nanofibers was directly produced, and the tedious co-electrospinning process was abandoned to prevent the aggregation and encapsulation of MOF. Via an efficient "thiol-ene" chemistry, massive thiol-terminated aptamers were grafted on MOF within one step under friendly conditions, rather than the time-consuming nanoparticle adsorption or unfriendly covalent chemical reactions. As a result, the robust MOF@aptamer-coated nano-fabrics were obtained, and a highly selective performance towards MC-LR was illustrated with a limit of detection (LOD) at 0.002 ng/mL, good precision (CV<8.3%), good repeatability (2.2∼6.0%) when coupled with LC-MS. Almost 1∼2 orders of magnitude higher detection sensitivity was exhibited than that of the common non-specific SPE/SPME fiber reported so far. Applied to water samples, the good matrix-resistance ability, and acceptable recovery yields were achieved with high specificity. This strategy might provide a rapid and friendly protocol to efficiently fabricate MOF@aptamer functionalized nano-fabrics through electrospinning and interfacial "thiol-ene" chemistry for highly-selective microextraction.

Facile one-step synthesis of graphene oxide/polyhedral oligomeric silsesquioxane composite-coated fiber for high-efficiency solid-phase microextraction of polycyclic musks.

Efficient fabrication of excellent fiber coatings for high-performance solid-phase microextraction (SPME) is interesting. Here, a high-efficiency synthesis strategy on graphene oxide/polyhedral oligomeric silsesquioxane (GO/POSS) composite-coated fiber was exploited via an ultra-fast UV polymerization in one step, and applied to excellent SPME of polycyclic musks (PCMs). Using methacryloxy siloxane-grafted GO and POSS-methacryl substituted (POSS-MA) as functional monomers, a facile and direct UV polymerization of multiple reactions including alkenyl radical reaction and thiol-ene click chemistry was fulfilled on thiol-pretreated fiber in only 5 min without tedious process. Characteristics such as morphology, FT-IR, XPS, BET and TG of fiber coating were studied in detail, as well as the SPME performance. Attributing to the rigid stereo conformation of POSS and large conjugate plane of GO-based nanosheet, the significant surface area, high hydrophobicity and intrinsic π-π interactions were adopted in fiber coating. In comparison of commercial SPME fibers, POSS-based or GO-based SPME fibers, a superior extraction performance towards PCMs was achieved with GO/POSS-coated fiber. High-efficiency extraction of PCMs was gained with prominent enrichment factors and the sensitive detection limits of PCMs were of 0.04-0.12 ng/L. In particular, the extraction efficiency was robust and still maintained a high level above 93% for PCMs even after 150 cycle's applications. Good recoveries of PCMs reached 86.6%-102.1% and 86.7%-101.3% in river water and cosmetic samples, respectively. It lights an attractive approach to efficiently fabricating robust GO/POSS-coated fiber for high-performance SPME of PCMs.

Efficient and selective solid-phase microextraction of polychlorinated biphenyls by using a three-dimensional covalent organic framework as functional coating.

Developing functional fiber coating for selective solid phase microextraction (SPME) of trace pollutants is critical in environmental analysis. Herein, the novel covalent organic frameworks (COFs) with three-dimensional (3D) frameworks and multiple interactions were designed and presented for the selective SPME of polychlorinated biphenyls (PCBs). Using tetra (p-aminophenyl) methane (TAM) and 1,3,5-triformylphloroglucinol (Tp) as the monomers, the 3D TpTAM-COF was synthesized and possessed a large specific surface area, high thermal stability, and spatial selectivity toward PCBs. Characterizations such as morphology, XPS, XRD, thermal stability, and enhancement factors (EFs) were studied. Multiple interactions including π-π conjugation, hydrophobic interaction, and selectivity toward non-planar structure were adopted, which resulted in a superior adsorption affinity toward PCBs on TpTAM-COF. Under the optimal conditions, the spatial selectivity toward PCBs, organic analogs (o-dichlorobenzene, biphenyl) and polycyclic aromatic hydrocarbons (naphthalene, pyrene, and anthracene)) was achieved. Efficient and selective adsorption of fifteen PCBs was fulfilled with the highest EF up to 10305. Using the HS-SPME-GC-MS method, the recoveries of PCBs in the river water and soil samples were determined to be 84.8 ± 7.8% ∼ 117.2 ± 8.5% (n = 3) and 84.4 ± 8.6% ∼ 114.7 ± 7.6% (n = 3), respectively. Compared with most commercial SPME fibers and other COFs-based fibers, the resultant TpTAM-COF-coated fibers possessed higher selectivity and EFs of PCBs. It proposed a promising approach for selective SPME of trace PCBs by multiple interactions in the steric structure of 3D COFs.

Sensitive detection of the okadaic acid marine toxin in shellfish by Au@Pt NPs/horseradish peroxidase dual catalysis immunoassay.

Based on the catalysis enhancement strategy of Au@Pt nanoparticles (Au@Pt NPs) and horseradish peroxidase (HRP) related to the TMB-H2O2 indicator, a sensitive colorimetric immunoassay was established for trace okadaic acid (OA) detection. The anti-OA monoclonal antibody (McAb) with a high Kaff constant was prepared and modified on Au@Pt NPs. Through grafting the HRP conjugated goat anti-mouse IgG antibody (IgG) on Au@Pt/McAb, bifunctional composites with Au@Pt-Ab and HRP were prepared and adopted. Characteristics including morphology, specificity and catalytic performance were evaluated. Under the optimal conditions, the sensitivity of the resultant enzyme immunoassay was significantly improved, and a low limit of detection (LOD) of OA was achieved at 0.04 ng mL-1 (equivalent to 0.6 µg kg-1 in mussel tissue), which was better than that of most HRP or Au/HRP enzyme-linked immunosorbent assays. When applied to fortified shellfish samples (e.g. oysters, mussels and clams), the recoveries ranging from 98.3 ± 2.3% to 106.0 ± 9.0% were acceptable and comparable with those of the LC-MS method. Acceptable precision was achieved with a variation coefficient (CV) of 2.3-8.4%. The method provides a promising alternative for the highly sensitive detection of the OA marine toxin at trace levels.

Aptamer-functionalized metal-organic framework-coated nanofibers with multi-affinity sites for highly sensitive, selective recognition of ultra-trace microcystin-LR.

A novel aptamer-functionalized metal-organic framework nanofibrous composite (viz. PAN/UiO@UiO2-N3-aptamer) with a high aptamer coverage density was proposed based on the electrospinning and seeded growth method, and used for specific affinity recognition of trace Microcystin-LR (MC-LR). Heterobifunctional ligand was used to modify the metal-organic framework nanoparticles (MOF NPs) surface, which could passivate the MOF surface with respect to unmodified DNA, followed by coupling massive aptamers on MOF of the solid-phase microextraction (SPME) fiber using click chemistry. Characterizations including morphology, spectra analysis, mechanical stability, binding capacity and specificity were fulfilled. Applied to the analysis of MC-LR, the good selective and sensitive recognition were obtained with the detection limit as low as 0.003 ng/mL, which was better than most non-specific SPME or solid-phase extraction (SPE) protocols. The stability and reproducibility were acceptable, and the intra-day, inter-day and column-to-column relative standard deviations (RSDs) for the recovery of MC-LR were gained in the range from 2.5% to 14.3%, respectively. Satisfactory recoveries of MC-LR in environmental water samples were measured as 96.3 ± 4.7% - 98.9 ± 2.7% (n = 3) in tap water, 94.4 ± 2.5% - 96.1 ± 3.5% (n = 3) in pond water, and 97.0 ± 2.1% - 97.9 ± 3.1% (n = 3) in river water, respectively. This work demonstrated that the electrospun nanofibrous composite with massive aptamers would be a better alternative for ultra-trace MC-LR detection with good selectivity, matrix-resistance ability and high resolution.

Facile DNA adsorption enabling ammonium-based hydrophilic affinity monolithic column for high-performance online selective microextraction of ochratoxin A.

Herein, a facile protocol of simple DNA adsorption on UV-initiated polymerization supports was proposed for effectively fabricating aptamer-based affinity monolithic column. Hydrophilic cationic monolith with an excellent mechanical stability was achieved within 7 min and then massive aptamers were directly bound by DNA charge-dependent adsorption. Strong cationic quaternary ammonium-based monomer was employed to provide effective and stable positive charge surface for aptamer immobilization in a wide range of pH. An ultra-high aptamer coverage density of 6813 pmol/µL was achieved to gain a highly specific online recognition performance. Limitations such as low aptamer capacity, tedious modification and time-consuming reactions in the traditional biological or covalent modification strategies were avoided. By using ochratoxin A (OTA) as the given analyte, the selective recognition and high recoveries were successfully achieved, and little cross-reactivity towards OTB analogue was only 0.5% even if the content of OTB got up to 125 folds of OTA. Applied to sample analysis, the satisfactory discriminations of trace OTA were obtained at 93.9 ± 1.9% - 96.5 ± 1.7%（n = 3）in beer, wheat and chicken liver samples. It might light a cost-effective access to efficiently preparing high-performance affinity monoliths towards the selective in-tube microextraction of OTA.

In situ photo-initiated polymerized oligonucleotide-functionalized hydrophilic capillary affinity monolith for highly selective in-tube microextraction of ochratoxin A mycotoxin.

A photo-initiated polymerized oligonucleotide-grafted hydrophilic affinity monolithic column was synthesized in situ, and exploited for selective in-tube solid phase micro-extraction (IT-SPME) protocol towards the sensitive detection of ochratoxin A (OTA). Only 7 min was required for the rapid polymerization of aptamer-based affinity monolith, which was much less than the reaction time of most thermal polymerization (12-16 h) and sol-gel chemistry methods (up to 52 h). Characterizations such as polymerization recipes, structure morphology, FTIR spectrum, elemental mapping, mechanical stability, and specific recognition performance were evaluated. A significantly hydrophilic nature with a low contact angle of 15° was observed, and a mixed-mode mechanism including aptamer affinity recognition and hydrophilic interaction (HI) was employed. By coupling with HPLC-fluorescence detection, the highly specific online recognition performance was achieved with an extremely low nonspecific adsorption of the analogues. The calibration curve of OTA was obtained in the concentration range 0.05-50.00 ng·mL-1 with a limit of detection (LOD, S/N = 3) of 0.012 ng·mL-1. Applied to sample analysis, acceptable recovery yields of 95.1 ± 1.4% - 99.5 ± 2.2% (n = 3) were obtained in beer and red wine. The proposed method lighted a promising way to efficiently preparing a hydrophilic aptamer-affinity monolith for highly specific recognition of trace mycotoxin by IT-SPME coupled with HPLC. A hydrophilic oligonucleotide-based affinity capillary monolith was explored via in situ photopolymerization for overcoming low preparation efficiency and achieving high-performance online IT-SPME of OTA mycotoxin.

A facile aptamer immobilization strategy to fabricate a robust affinity monolith for highly specific in-tube solid-phase microextraction.

Developing a functional affinity monolithic column towards in-tube solid-phase microextraction (IT-SPME) for selective sample pretreatment is critical. Herein, a high-performance capillary affinity monolithic column with an ultra-high aptamer coverage density was rapidly fabricated via a simple adsorption strategy, in which aptamers with natural sequences were directly immobilized on an ammonium-based strongly cationic matrix. Limitations of the traditional biological or covalent methods such as time-consuming modification reactions, special requirement of active groups (e.g. -NH2 and -SH) on the aptamer, and low aptamer coverage density levels were avoided. An ultra-high coverage density of 8616 pmol µL-1 was achieved with excellent stability, and the highest aptamer-modification level among all the current methods was reached. Selective recognition and high recovery yields of the model mycotoxin ochratoxin A (OTA) were achieved in 95.9 ± 0.98%-97.9 ± 0.28% (n = 3). In particular, there was little cross-reactivity towards the OTB analogue of only 0.5% even in the case of 250 fold of the analogue OTB, which was not reported in previous affinity monoliths. Upon sample analysis, satisfactory discriminations of trace OTA were obtained at 93.7 ± 1.4%-95.5 ± 2.5% (n = 3) in beer and wheat. A facile and direct method for efficiently fabricating an aptamer-based affinity monolith towards online selective IT-SPME was proposed.

Aptamer-functionalized metal-organic framework-based electrospun nanofibrous composite coating fiber for specific recognition of ultratrace microcystin in water.

A novel aptamer@AuNPs@UiO-66-NH2 electrospun nanofibrous coating fiber for specific recognition of microcystin-LR (MC-LR) was proposed by using electrospinning, metal-organic frameworks (MOF) seed growth and AuNPs bridging aptamer strategies. Characterization of morphology, structure and stability of the obtained affinity nanofibrous coating fiber were investigated. High loading of MOFs and aptamers on the nanofibrous fiber were achieved and successfully applied for accurate identification of MC-LR by solid-phase microextraction (SPME) coupled with LC-MS. Highly specific recognition of MC-LR with little interference of analogs was achieved with extremely low LOD (0.004 ng/mL), good precision (CV% < 11.0%) and low relative error (RE% = -1.5% to -10.0%), which was rather better than that of the traditional SPME or SPE protocols. Satisfactory recoveries of MC-LR were obtained in the range of 92.0-96.8% (n = 3) in fortified tap water, raw pond water and river water samples. This work revealed an attractive alternative access to specific recognition and super-sensitive analysis of MC-LR in water.

Towards highly specific aptamer-affinity monolithic column by efficient UV light-initiated polymerization in "one-pot".

Time-consuming or tedious operation in multiple-step process might is the obstacle for efficiently preparing aptamer-affinity monolithic column. Here, a new and facile strategy to prepare aptamer-based hybrid affinity monolith in "one-pot" at room temperature was exploited, in which UV light-initiated free-radical polymerization and "thiol-ene" click reaction were implemented simultaneously. Only 7 min was cost for finishing the polymerization reaction, which was only 1/100 of that for the traditional thermal polymerization. Using ochratoxin A (OTA) as the model analyte, the recipe for photo-initiated polymerization was optimized, and SEM morphology, FTIR, EDS, pore size distribution and specific recognition performance were also studied. Compared with traditional thermal polymerization, the resultant monolith was achieved more facilely and displayed better results such as more homogeneous skeleton structure, higher reaction efficiency of aptamer (>88.2%) and better specific selectivity to OTA. Besides, an extremely low nonspecific adsorption of analogues was obtained and showed a level at only 1/25 of that in the similar aptamer-affinity monolith prepared by thermal polymerization. Applied to beer and red wine samples, good recovery yields about 99.7 ± 4.0% -101.2 ± 2.3% (n = 3)was achieved with the acceptable RSDs. It would open up a rapid and promising access to efficiently preparing high-performance aptamer-based affinity monolithic columns for online specific recognition.

Heteroporous 3D covalent organic framework-based magnetic nanospheres for sensitive detection of bisphenol A.

Covalent organic frameworks (COFs) showed great promise in effective adsorption of target molecule via size selectivity. Although various magnetic 2D COFs composites have been studied and exhibited the intensive applications, the incorporation of 3D COFs and magnetic nanoparticles to form a new class of magnetic adsorbents with enhanced function still has no reports. Herein, a novel Fe3O4@3D COF with heteroporous structure matching to the sizes of bisphenol A (BPA) was firstly synthesized for better adsorption of BPA than common magnetic 2D-COFs. Three Fe3O4@3D COFs nanospheres were synthesized under the solvothermal conditions in autoclave, and the optimum Fe3O4@3D-COF denoted as Fe3O4@COF-TpTAM (Tp, 1,3,5-triformylphloroglucinol; TAM, tetra(p-aminophenyl)-methane) was selected and employed. Detailed characteristics of Fe3O4@COF-TpTAM were evaluated via various techniques including TEM, FTIR, TGA, XRD and BET. Excellent chemical and thermal stability, high surface area (294.6 m2 g-1) and pore volume (0.2 m3 g-1) with multiple pore sizes comparable with the simulated three-dimensional sizes of BPA were exhibited. A high adsorption capacity of BPA up to 209.9 mg/g that was better than common 2D-COFs was achieved, and the sensitive MSPE-LC-MS method with wide linear range (10-5000 pg/mL), low detection limit (4 pg/mL, S/N = 3) was built. Satisfactory recoveries of BPA as 93.8 ± 1.4%-101.4 ± 5.1% (n = 3) and 100.4 ± 1.9% ~ 107.3 ± 1.2% (n = 3) were obtained in milk and river water samples, respectively. This work demonstrates the promising application of Fe3O4@3D COF as efficient adsorbents of trace BPA, and opens up a new access for the efficient MSPE in sample pretreatment for food or environmental safety analysis.

Online specific recognition of mycotoxins using aptamer-grafted ionic affinity monolith with mixed-mode mechanism.

Herein, a facile and practical aptamer-grafted ionic affinity monolith with mixed-mode mechanism was explored as a versatile platform for online specific recognition of polar and non-polar mycotoxins. The mixed-mode mechanism including molecular affinity adsorption (between aptamers and targets), hydrophilic interaction and ionic interaction (between stationary phase and targets) were adopted and provided a better flexibility in adjusting separation selectivity to reduce nonspecific adsorption with respect to the single mode. Preparation and characterization of aptamer-based affinity monoliths were investigated, The characterization of pore size distribution, Brunauer-Emmett-Teller (BET) surface area and the specificity and cross-reaction were also evaluated. As a result, the hydrophilic nature and negative charge on affinity monolith were obtained. Multiple interactions including aptamer affinity binding, hydrophilic interaction (HI) and ion exchange (IE) could be adopted for online selective extraction. Specific recognitions of polar ochratoxin A (OTA), non-polar zearalenone (ZEN) and aflatoxin B1 (AFB1) was fulfilled with LODs as 0.03, 0.05 and 0.05 µg/L, respectively. Applied to real cereals, good recoveries of the fortified OTA, AFB1 and ZEN were achieved as 92.6 ± 1.3% ~ 95.6 ± 1.3% (n=3), 93.9 ± 2.3% ~ 98.2 ± 3.4% (n=3) and 92.7 ± 2.0% ~ 96.9 ± 3.5% (n=3) in corn, wheat and rice, respectively. The results displayed that Apt-MCs with hydrophilic and ionic interaction mixed-mode mechanism were efficient enough and competent for the online recognition of mycotoxins in cereals.

Online high-efficient specific detection of zearalenone in rice by using high-loading aptamer affinity hydrophilic monolithic column coupled with HPLC.

Via the facile photopolymerization and thiol-ene click chemistry, a hydrophilic polyhedral oligomeric silsesquioxane (POSS)-containing affinity monolithic column with a high load of aptamers and fast preparation was presented, and successfully applied to the efficient specific recognition and sensitive detection of zearalenone (ZEN) by coupling with HPLC. Optimization of polymerization reaction and polymer recipe were studied, and characteristics such as structural morphology, affinity performance and specificity to ZEN were evaluated. A highly hydrophilic POSS-based aptamer affinity monolith was rapidly prepared in 1.1 h, and a high capacity of aptamer reached 2772.61 pmol/µL that was much higher than that of the current POSS-based aptamer affinity monoliths. By this way, the hydrophilic nature and aptamer coverage indensity in POSS monoliths were well improved. The mixed-mode mechanism including aptamer affinity recognition and hydrophilic interaction were employed for the specific analysis of ZEN. Applied to the monitoring of ZEN, a good selective recognition and sensitive detection were obtained with the detection limit (LOD) of 0.02 ng/mL. The stability and reproducibility were acceptable and the intra-day, inter-day and column-to-column relative standard deviations (RSDs) of the ZEN recovery were gained in the range from 2.28% to 5.32%, respectively. Satisfactory recoveries of ZEN in rice samples were realized ad 98.6 ± 2.8%-100.8 ± 2.0%. It might provide a preferable access to online specific analysis of ZEN via the hydrophilic POSS-based affinity monolith with a large capacity of aptamers and a high preparation efficiency.

Towards online specific recognition and sensitive analysis of bisphenol A by using AuNPs@aptamer hybrid-silica affinity monolithic column with LC-MS.

Highly specific sample pretreatment for the sensitive detection of trace bisphenol A (BPA) in compliacted samples is critical. Herein, a new protocol towards online specific recognition and sensitive detection of BPA was proposed by using Aptamer@AuNPs-modified affinity monolith coupled with LC-MS. Optimization of polymerization conditions and characterization such as the morphology, energy spectrum, mechanical stability, aptamer coverage density and specific performance of the affinity monolith were studied. Nano-gold particles (AuNPs) densely distributed on the rigid hybrid-silica substrates, and an unusually high aptamer coverage density reached 3388 pmol/µL, which was favorable to fulfill the effective identification of BPA with high selectivity and inhibit the interference of analogs including BPB and BPC. A highly sensitive recognition of BPA was obtained with the limit of detection (LOD) as low as 0.02 ng/mL. Applied to dairy milk products and serum samples, trace BPA could be sensitive detected by this strategy, while the poor response was achieved by using traditional non-specific SPE column for sample pretreatment. Satisfactory recoveries of fortified BPA were measured as 97.45 ± 2.24%-98.03 ± 4.36% (n = 3) in powdered infant formulas, 96.64 ± 3.37% ~ 99.42 ± 3.22% (n = 3) in bottled milk, 94.69 ± 2.15% ~ 100.96 ± 1.94% (n = 3) in boxed milk, and 93.71 ± 1.53% ~ 96.73 ± 2.56% (n = 3) in children serum samples, respectively. This protocol lights a new access to online specific identification of trace BPA from complex matrix with good detection sensitivity by using aptamer-affinity monolithic column.