Developing magnetic functionalized dendritic fibrous mesoporous silica as advanced adsorbent for quaternary ammonium alkaloids.

A novel π-conjugated polymer-modified magnetic dendritic fibrous mesoporous silica adsorbent (MB@KCC-1@π-CP) is reported for the accurate determination of quaternary ammonium alkaloids (QAAs) in complex body fluid matrices. It is demonstrated that the magnetic dendritic fibrous mesoporous silica (MB@KCC-1) is an excellent carrier combining magnetism, high specific surface area, unique hierarchical pore structure, and fast mass transfer rate. The π-conjugated polymer (π-CP) can efficiently retain QAAs (berberine, coptisine, palmatine, jatrorrhizine) by multiple interactions. In addition, the adsorption kinetics and adsorption mechanism were also studied and discussed. Under optimized extraction conditions, MB@KCC-1@π-CP-based magnetic solid-phase extraction (MSPE) and high-performance liquid chromatography (HPLC) method affords a wide linear range (0.5-20000 ng mL-1), low limits of detection (0.2-2 ng mL-1), and satisfactory relative standard deviations (RSD) of inter-day (< 2.4%) and intra-day (< 3.1%) for QAAs. Trace QAAs in complex human blood plasma samples were successfully detected by the established method.

Carbonized π-conjugated polymer-coated porous silica: preparation and evaluating its extraction ability for berberine.

In view of the limitations of existing berberine solid-phase extraction adsorbents, this paper proposes a novel carbonized π-conjugated polymer-coated porous silica (SiO2@C-π-CP) adsorbent with simple process and low cost for efficient extraction of berberine by multiple interactions. Characterization methods, including Brunner-Emmet-Teller measurement, thermogravimetric analysis, X-ray photoelectron spectroscopy, and scanning electron microscopy techniques, were used to verify the successful modification of carbonized π-conjugated polymer on the surface of porous silica. The berberine was selected as target molecule, and the adsorption mechanism and process were investigated through adsorption kinetics, adsorption isotherms, and thermodynamic studies. The fitting results show that the adsorption of berberine by SiO2@C-π-CP well conforms to the pseudo-second-order and Langmuir models. By optimizing the main SPE parameters, the SPE method based on SiO2@C-π-CP was developed. Excellent results were obtained, including low limit of detection (0.75 ng mL-1) and limit of quantification (2 ng mL-1), wide linearity (2-13,000 ng mL-1), and satisfactory relative standard deviations (RSD) of inter-day (1.5%) and intra-day (6.2%). Finally, the SiO2@C-π-CP also has been successfully used to the enrichment of berberine in real urine samples. This research makes clear that SiO2@C-π-CP has outstanding potential for trace enrichment of berberine alkaloids.

Hyperoxia Provokes Time- and Dose-Dependent Gut Injury and Endotoxemia and Alters Gut Microbiome and Transcriptome in Mice.

Background: Oxygen therapy usually exposes patients to hyperoxia, which induces injuries in the lung, the heart, and the brain. The gut and its microbiome play key roles in critical illnesses, but the impact of hyperoxia on the gut and its microbiome remains not very clear. We clarified the time- and dose-dependent effects of hyperoxia on the gut and investigated oxygen-induced gut dysbiosis and explored the underlying mechanism of gut injury by transcriptome analysis. Methods: The C57BL/6 mice were randomly divided into the control group and nine different oxygen groups exposed to hyperoxia with an inspired O2 fraction (FiO2) of 40, 60, and 80% for 24, 72, and 168 h (7 days), respectively. Intestinal histopathological and biochemical analyses were performed to explore the oxygen-induced gut injury and inflammatory response. Another experiment was performed to explore the impact of hyperoxia on the gut microbiome by exposing the mice to hyperoxia (FiO2 80%) for 7 days, with the 16S rRNA sequencing method. We prolonged the exposure (up to 14 days) of the mice to hyperoxia (FiO2 80%), and gut transcriptome analysis and western blotting were carried out to obtain differentially expressed genes (DEGs) and signaling pathways related to innate immunity and cell death. Results: Inhaled oxygen induced time- and dose-dependent gut histopathological impairment characterized by mucosal atrophy (e.g., villus shortening: 80% of FiO2 for 24 h: P = 0.008) and enterocyte death (e.g., apoptosis: 40% of FiO2 for 7 days: P = 0.01). Administered time- and dose-dependent oxygen led to intestinal barrier dysfunction (e.g., endotoxemia: 80% of FiO2 for 72 h: P = 0.002) and potentiated gut inflammation by increasing proinflammatory cytokines [e.g., tumor necrosis factor alpha (TNF-α): 40% of FiO2 for 24 h: P = 0.003)] and reducing anti-inflammatory cytokines [Interleukin 10 (IL-10): 80% of FiO2 for 72 h: P < 0.0001]. Hyperoxia induced gut dysbiosis with an expansion of oxygen-tolerant bacteria (e.g., Enterobacteriaceae). Gut transcriptome analysis identified 1,747 DEGs and 171 signaling pathways and immunoblotting verified TLR-4, NOD-like receptor, and apoptosis signaling pathways were activated in oxygen-induced gut injury. Conclusions: Acute hyperoxia rapidly provokes gut injury in a time- and dose-dependent manner and induces gut dysbiosis, and an innate immune response is involved in an oxygen-induced gut injury.

Performance evaluation of silica microspheres functionalized by different amine-ligands for hydrophilic interaction chromatography.

In this work, for the first time five amine-ligands including mono-amine, di-amine, tri-amine, secondary and tertiary amine, were functionalized on mesoporous micro-silicas and developed as stationary phases for hydrophilic interaction liquid chromatography (HILIC). The investigations about the retention mechanisms, effects of different chromatographic conditions and stability were systematically conducted. Three kinds of polar and hydrophilic compounds (saccharides, sulfonamides, nucleosides and nucleobases) were selected as probe molecules to evaluate their separation performances. Among the five stationary phases, only aminopropyl-bonded silica has already gained wide developments and applications. Whereas, there are no related researches about the other four to be utilized as separation media. By a series of chromatographic evaluations, the results revealed the other four mesoporous micro-silica materials functionalized with di-amine, tri-amine, secondary and tertiary amine, had great potential to be explored as novel stationary phases of HILIC. Particularly, the two stationary phases functionalized with di-amine and tri-amine exhibited outstanding separation and retention abilities. This work offered some insights on the understanding of retention in HILIC mode and provided us possibility to explore other amine-based HILIC stationary phases.

Design of GO-Ag-functionalized Fe3O4@CS composite for magnetic adsorption of rhodamine B.

In this study, a novel magnetic composite (Fe3O4@CS/GO/Ag) modified with chitosan (CS), graphene oxide (GO) and Ag nanoparticles (Ag NPs) was successfully prepared as an efficient adsorbent for detection of rhodamine B (RB) combined with a fluorescence technique. The properties of the magnetic composite were confirmed by field emission scanning electron microscopy, energy dispersive X-ray spectroscopy, and vibrating sample magnetometry. The components of Fe3O4@CS/GO/Ag endowed it with excellent extraction performance and convenient operation. The main parameters affecting extraction and desorption efficiency were all investigated systematically. Under the optimized experimental conditions, the proposed method showed linear ranges (0.2-6.0 µg L-1) with R 2 = 0.9992. The limits of detection (LODs) and quantification (LOQs) were 0.05 and 0.2 µg L-1 (n = 3), respectively. Fe3O4@CS/GO/Ag exhibited outstanding extraction efficiency for RB, compared with CS-coated Fe3O4 nanoparticles (Fe3O4@CS) and GO-modified Fe3O4@CS (Fe3O4@CS/GO). The applicability of the proposed method was investigated by analyzing four real samples (waste water, soft drink, shampoo, and red pencil) and the spiked recoveries ranged between 94% and 97% with RSD ranging from 3% to 6%, which showed that the proposed method had satisfactory practicability and operability.

Octadecylimidazolium ionic liquid-modified magnetic materials: Preparation, adsorption evaluation and their excellent application for honey and cinnamon.

A novel and versatile adsorbent based on 1-octadecylimidazolium ionic liquid modified magnetic nanoparticles (Fe3O4@SiO2@ImC18) possessing of both magnetic property and excellent adsorption ability was successfully synthesized. Twelve compounds from four kinds of substances (alkylbenzenes, PAHs, flavonoids and organic acids) were chosen as probe molecules to evaluate adsorption properties of the new adsorbent. A series of adsorption experiments were conducted and results indicated both synergism and competition effects were existed and multiple interactions took place during adsorption process. After considerable acquaintances with the adsorbent, it was successfully applied for real samples analysis of honey and cinnamon. Three flavonoid compounds of myricetin, quercetin and luteolin from honey and cinnamic acid from cinnamon were all detected and quantified. Meanwhile, it reached 280-fold concentration reduction of interferent during the extraction of cinnamic acid from cinnamon. The recoveries were in the range of 85.4-94.8% with relative standard deviations (n=3) of 2.5-5.6%.The current study not only provided a strategy to evaluate new adsorbent, but also demonstrated the novel Fe3O4@SiO2@ImC18 material was reliable, accurate and suitable for sample pretreatment in pharmaceutical and food chemistry.

A new route for synthesis of N-methylimidazolium-grafted silica stationary phase and reevaluation in hydrophilic interaction liquid chromatography.

In this work, a "solvent-free" and green method for controllable and quantitative preparation of chromatographic stationary phase has been proposed. About the method, the largely excess of functional monomer and strict control of the proportion between silane and silica are the two most important points. Due to the existence of excessive functional monomer, silane can be utilized at the maximum extent, thereby achieving quantitative and reproducible bonding. Meanwhile, the excessive monomer can also be well recycled. By this new method, we controllably synthesized three Sil-MIm columns with various bonding amounts to investigate how the bonding amounts influence separation performances. The experiment results stated in some cases the columns with appropriate bonding amounts rather than maximum, were the best to fulfil some specific tasks. Meanwhile, it also demonstrated how important it was to control the bonding amounts of stationary phase.

Preparation and evaluation of 2-methylimidazolium-functionalized silica as a mixed-mode stationary phase for hydrophilic interaction and anion-exchange chromatography.

In this paper, a novel 2-methylimidazolium-functionalized silica stationary phase was prepared and further used for hydrophilic interaction and anion-exchange mixed-mode chromatography. The stationary phase was characterized by elemental analysis and Fourier transform infrared spectrometry. The chromatographic properties of this stationary phase were investigated by hydrophilic chromatography for the separation of nucleosides, nucleobases, water soluble vitamins, sulfonamides and saccharides, and ion chromatography for the separation of inorganic anions. The effect of acetonitrile content, salt concentration and pH values of the mobile phase on the retention of the stationary phases was also investigated. Compared with 1-methylimidazolium-functionalized silica stationary phase, this new stationary phase demonstrated similar or better separation selectivity. This new column demonstrated good performance and separation selectivity even better than a commercial hydrophilic column. Besides, 2-methylimidazolium-functionalized silica is possible to be modified again and used as a precursor to derivate some new stationary phases from the 3-position nitrogen.

Solid-phase extraction of flavonoids in honey samples using carbamate-embedded triacontyl-modified silica sorbent.

In this study, carbamate-embedded triacontyl-modified silica (Sil-CBM-C30) is successfully prepared and used as an efficient sorbent for solid-phase extraction. The extraction performance of the resultant sorbent is evaluated with five flavonoids including myricetin, quercetin, luteolin, kaempferol and isorhamnetin. Main parameters, which affect extraction efficiencies, are carefully investigated and optimized. Comparative experiments between Sil-CBM-C30 and commercial C18 sorbents indicate that the extraction efficiencies of the former one surpass the latter one. The modification of carbamate-embedded triacontyl group on surface of silica causes analytes extracted by hydrophobic, hydrogen bonding and π-π interactions. Under optimal conditions, good linearities and satisfied LODs and LOQs are achieved. The SPE-HPLC-DAD method is successfully developed and applied for the honey sample analysis.