A preliminary study of the temperature-responsive selective extraction performance of hydrogel derived from sulfobetaine methacrylate.

BACKGROUND: The limited extraction selectivity caused by the single extraction selection mechanism of solid phase extraction (SPE) technology is one of the bottlenecks restricting its development. The development of environmentally sensitive materials provides a new opportunity to solve this problem. Based on this, we developed the sulfobetaine methacrylate hydrogel with abundant pore structure, a large number of adsorption sites and especially temperature responsiveness, and used as adsorbent for the extraction of pesticide residues in lychees. RESULTS: The new hydrogel adsorbent was prepared by free radical copolymerization with sulfobetaine methacrylate as monomer, and used for the extraction of benzoylurea insecticides from lychees. Interestingly, the hydrogel showed an almost opposite temperature-selective extraction trend for different benzoylurea insecticides with similar structure and polarity, and opposite hydrophilicity, which may be caused by the temperature-sensitive and the special action site of the hydrogel, and the change of the diffusion of aqueous solution. In addition, the analysis method of three hydrophilic benzoylurea insecticides by sulfobetaine methacrylate hydrogel-SPE-HPLC was established. Under optimal conditions, the low limits of detection (0.030 µg L-1) and quantification (0.10 µg L-1), and the wide linear ranges (0.10-50.0 µg L-1) were achieved. Its application in lychee samples were also tested, and the satisfactory results were obtained, with the spiked recoveries from 80.79 % to 108.31 %. SIGNIFICANCE: This was a great breakthrough in the selective extraction of similar targets. These properties, combined with low-cost, biodegradable raw materials and convenient, green synthesis method make the sulfobetaine methacrylate hydrogel a very promising solid phase adsorbent. Temperature-responsive selective mode can greatly enrich the selective extraction mechanism and promote its development and application in complex actual samples.

Alien species water hyacinth realizes waste into treasure: The preparation of biomass sorbent to determine benzoylurea insecticides in tea products.

A fast and effective analytical method with biomass solid-phase microextraction sorbent combined with a high-performance liquid chromatography-ultraviolet detector was proposed for the determination of benzoylurea (BU) insecticides in tea products. The novel sorbent was prepared by activating and then carbonizing water hyacinth with a fast growth rate and low application value as raw material and showed a high specific surface area and multiple interactions with analytes, such as electrostatic action, hydrogen bonding, and π-π conjugation. After optimizing the three most important extraction parameters (pH [X1], sample loading rate [X2], and solution volume [X3]) by Box-Behnken design, the as-established analytical method showed good extraction performance: excellent recovery (80.13%-106.66%) and wide linear range (1-400 µg/L) with a determination coefficient of 0.9992-0.9999, a low limit of detection of 0.02-0.1 µg/L and the satisfactory practical application results in tea products. All these indicate that the water hyacinth-derived material has the potential as a solid-phase extraction sorbent for the detection and removal of BU insecticides from tea products, and at the same time, it can also achieve the effect of rational use of biological resources, maintaining ecological balance, turning waste into treasure, and achieving industrial production.

Preparation of hydrogel nanocomposite functionalized silica microspheres and its application in mixed-mode liquid chromatography.

Hydrogel is a kind of three-dimensional network structure polymer that can absorb water and swell in water. It has been widely used in many fields due to its flexible functionality. We proposed the design strategy of dual-network hydrogel assisted by a metal-organic-framework (MOF) and modified them on the surface of silica (with average particle diameter of 5 µm and average pore diameter of 76 Å). On the basis of effectively avoiding shortcomings such as osmotic pressure caused by swelling, abundant mesh types of composite material also improves the separation selectivity of the stationary phase. A variety of analytes such as nucleosides/bases, antibiotics, organic acids, carbohydrates, alkylbenzenes, polycyclic aromatic hydrocarbons, pesticides and anions can be selectively separated. The research on the retention behavior and the interaction mechanism proves that the column can be used in mixed mode liquid chromatography. By comparing with the optimized chromatographic conditions of commercial HILIC column and C18 column, this new type of stationary phase also has some significant advantages in the selective separation of mixed analytes. This new stationary phase also has excellent acid/base stability. The intraday relative standard deviation of their retention time under acidic conditions is 0.05%-0.26% (n = 10), and the intraday relative standard deviation under basic conditions is 0.11-0.14% (n = 10). After optimizing the chromatographic conditions, the efficiency of this new type of chromatographic column can reach 90,300 plates/m (sucrose). In short, a new strategy for applying hydrogel to liquid chromatography with high selectivity and chromatographic separation performance is proposed.

Mesoporous nanomaterial-assisted hydrogel double network composite for mixed-mode liquid chromatography.

By introducing functional groups such as quaternary amine groups, sulfonic acid groups, triazine groups, and other mespore nanomaterials into the hydrogel, better separation effect of some organic framework materials has been obtained. Due to a reasonable design and preparation strategy, the hydrogel composite-modified silica can be used in the selective separation of various analytes such as pesticides, alkylbenzenes, polycyclic aromatic hydrocarbons, nucleosides/bases, benzoic acids, antibiotics, and carbohydrates. Through the exploration of chromatographic retention behavior, it is proved that the column can be used in mixed-mode liquid chromatography. The intra-day relative standard deviation for retention time of this new stationary phase is 0.12-0.16% (n = 10), and the inter-day relative standard deviation is less than 0.39% (n = 5). This new stationary phase can also be used for separation in complex samples. The limit of detection (LOD) for chlorotoluron in farm irrigation water is 0.21 µg/L and the linear range is 2-250 µg/L. After optimizing the chromatographic conditions, the highest efficiency of the hydrogel column in RPLC and HILIC modes has reached 32,400 plates/m (chlorobenzuron) and 41,300 plates/m (galactose). This new type of hydrogel composite is a porous network material with flexible functional design and simple preparation method and its application has been expanded in liquid chromatography separation successfully. The hydrogel composed of triallyl cyanate cross-linking agent and 3-(2-(methacryloyloxy) ethyl) dimethylamine) propane-1-sulfonate (SBMA) monomer which were co-modified on the surface of mesoporous silica with MOF-919 for separation in mixed-mode liquid chromatography.

Hydrogel Coating with Temperature Response Retention Behavior and Its Application in Selective Separation of Liquid Chromatography.

We reporte the double-layer hydrogel-coated mesoporous silica material as a new stationary phase for liquid chromatography. The method of combining physical coating and chemical coating was to apply hydrogel coating on the surface of silica, and finally, a new type of liquid chromatography stationary phase with in situ coating of the functional hydrogel on silica was obtained. This hydrogel-functionalized liquid chromatography stationary phase also exhibits a certain temperature responsiveness. Experimental results show that this temperature response is mainly due to changes in the hydrogen bonding between the stationary phase and the analyte at different temperatures in the column oven, which leads to changes in retention behavior. The hydrogel-coated mesoporous silica microspheres showed excellent selectivity for many polar analytes. An excellent column efficiency was obtained (139 000 plates/m for terephthalic acid) after optimization of chromatographic conditions. In addition to rapid separation of some analytes, this new hydrogel stationary phase also has certain superiority in chromatographic performance compared with other new excellent liquid chromatography stationary phases functioned by three-dimensional cross-linking systems. The important thing is that this strategy is relatively easy to prepare a new stationary phase with different properties.

Synthesis and application of smart gel material modified silica microspheres for pH-responsive hydrophilicity in liquid chromatography.

Inspired by porous smart gel materials, we designed pH-responsive polymer-modified silica microspheres as liquid chromatography stationary phase materials by a one-step strategy. The free radicals generated by the oxidation of dopamine are used to initiate the cross-linking polymerization of functional monomers. At the same time, the good adhesion of dopamine enables the polymer to be modified on silica. The hydrophilicity of this new stationary phase can change in response to the pH of the mobile phase and the stationary phase has weaker hydrophilicity under acidic (pH = 3.78) mobile phase conditions and stronger hydrophilicity under neutral mobile phase conditions. The hydrophilicity difference of the stationary phase leads to the selectivity difference in separation. To evaluate the chromatographic performance of this new stationary phase, 10 oligosaccharides and 9 nucleosides/bases were separated on this stationary phase. This paper will provide good guidance for us to achieve more pH-responsive hydrophilic/hydrophobic stationary phases in the future.

Non-conjugated flexible network for the functional design of silica-based stationary phase for mixed-mode liquid chromatography.

The functionalized non-conjugated organic network modified silica microspheres are proposed as the stationary phase of liquid chromatography, which can effectively avoid some defects of organic framework materials in liquid chromatography. Due to the co-existing of pyridine ring, carbonyl group, amide group and triazine ring in the non-conjugated flexible organic network on the silica surface, the developed mixed-mode stationary phase exhibits multiple interactions between the stationary phase and the analytes during the separation process. A variety of nucleoside bases, organic acids, antibiotics, pesticides, alkylbenzenes, polycyclic aromatic hydrocarbons and sulfonamides achieved ideal resolution and flexible selectivity in separation. Compared with the commercial chromatographic columns under their optimized chromatographic conditions, it shows better performance for the separation of complex analytes. The influence of chromatographic conditions on retention behavior indicates that the column's multiple retention mechanisms make it suitable for mixed-mode liquid chromatography. The stationary phase prepared by the new design strategy also has excellent chromatographic reproducibility, repeatability and stability with the intraday RSD of 0.09%-0.12% (n = 10) and the interday RSD of 0.37%-1.64% (n = 5) for the retention time. The separation results of actual samples also prove its potential in the analysis of complex samples. In short, we designed and prepared the non-conjugated flexible network modified silica stationary phase material for liquid chromatography that is different from organic framework materials. Its excellent separation ability shows that we have successfully reported a new kind of liquid chromatography packing with functional design and facile preparation method.

A facile process for the preparation of organic gel-assisted silica microsphere material for multi-mode liquid chromatography.

Organic gel (OG) has excellent characteristics, including a large surface area, adjustable pore/channel size, and good chemical stability, and has attracted great attention in the field of materials. However, the OG packed column is difficult to pack due to the weak mechanical strength and poor monodispersity. Herein, 1-allyl-3-methyl imidazolium hexafluorophosphate-co-1-dodecanethiol ([AMIm]PF6-co-TDDM) was prepared on the silica microsphere for chromatographic packing available in multimode liquid chromatography (LC) mode with the good mechanical properties of silica microspheres through a simple OG synthesis method. [AMIm]PF6-co-TDDM@SiO2 hybrid microspheres with uniform particles and narrow particle size distribution are used as stationary phases of LC. These microspheres are used in anion-exchange (IEC), reversed-phase (RP), and hydrophilic interaction (HILIC) mode for the separation of different analytes. Such microspheres can also be used for the preliminary qualitative analysis of active ingredients in actual samples in addition to organic acids, alkylbenzenes, and nucleoside bases. The [AMIm]PF6-co-TDDM@SiO2 chromatography packing also has good reproducibility and stability. The adhesive properties of organogels and the adsorption properties of silica gel simplify the synthesis of stationary phase materials. This simple and effective strategy for preparing [AMIm]PF6-co-TDDM@SiO2 composite microspheres by one-pot method can expand the application of OG as a functional additive on silica microspheres in LC.

A novel process for the preparation of Cys-Si-NIPAM as a stationary phase of hydrophilic interaction liquid chromatography (HILIC).

l-Cysteine (L-Cys) and N-Isopropyl acrylamide (NIPAM)-modified silica spheres as a novel stationary phase for hydrophilic interaction liquid chromatography (HILIC) was produced firstly by cross-linking polymerization. Some characterizations in this article confirmed that the synthesis of Cys-Si-NIPAM is successful. Some polymer layers can be observed through transmission electron microscopy (TEM). In addition, through nitrogen adsorption porosity method, scanning electron microscopy (SEM), thermal gravimetric analysis (TGA) and other characterization methods, we can find the significant changes after modify. It has good hydrophilic property and higher column effect than bare silica column, Si-Cys column and Si-NIPAM column under the same conditions. It has good separation effect for some hydrophilic analytes such as 5 nucleosides and nucleoside bases, 5 amino acids, 4 sulfonamide drugs and 10 saccharides. The effects including column temperature, pH and organic solvent content on chromatographic performance were studied, which proved that hydrophilic interactions can be simultaneously existed between the stationary phase and the analytes. In addition, reproducibility and efficiency of the Cys-Si-NIPAM column was also investigated, the results illustrated that the stationary phase have passable stability (the intraday RSDs 0.08-0.44%, n = 3 and the interday RSD 0.46-3.50%, n = 3) and ideal efficiency (plates per meter, ~45700 plates/m). In conclusion, the preparation process of this hydrophilic liquid chromatography stationary phase is not only simple, but also can meet the basic requirements for the separation of hydrophilic analytes.