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.

Bioaccumulation investigation of bisphenol A in HepG2 cells and zebrafishes enabled by cobalt magnetic polystyrene microsphere derived carbon based magnetic solid-phase extraction.

A magnetic solid-phase extraction (MSPE) technique coupled with high performance liquid chromatography (HPLC) was developed and used for bioaccumulation investigation of bisphenol A (BPA) in HepG2 cells and zebrafishes. Cobalt magnetic polystyrene microsphere derived carbon (C-Co@PST) as an adsorbent was prepared by in situ polymerization reaction and further annealing treatment. Scanning electron microscopy, energy-dispersive X-ray spectroscopy, Fourier transform infrared spectrometry, X-ray photoelectron spectroscopy and X-ray diffraction were employed to confirm successful synthesis of C-Co@PST. A series of extraction parameters including the amount of the sorbent, the type of elute, extraction time and elution time were investigated to achieve high extraction efficiency. C-Co@PST based MSPE combined with HPLC was successfully established for bioaccumulation research of BPA in living creatures. It was found that the bioconcentration values of BPA in HepG2 cells underwent an increase, then a decrease, and finally reached an equilibrium level of 11.60 µg kg-1 at 8 h. The concentration of BPA in zebrafishes increased ranging from 6.05 µg kg-1 to 31.84 µg kg-1 over a culture time from 1 h to 12 h. Furthermore, linear and exponential models were employed to analyse the bioconcentration variation of BPA in organisms over the exposure time. Mathematical models have been developed to predict the transfer characteristics of BPA.

Extraction of benzoylurea insecticides from tea leaves based on thermoplastic polyethyleneimine embedded magnetic nanoparticle carbon materials.

A novel mosaic structured core-shell composite, Silica@C/Ni (Sil@C/Ni), has been prepared by embedding Ni nanoparticles on the surface of silica microspheres via coordination and carbonization reduction, and was used as magnetic solid-phase extraction sorbents in combination with high performance liquid chromatography (HPLC) for the extraction and determination of four benzoylurea insecticides (BUs) in tea leaves. Based on the fact that hydrogen bonding and hydrophobic interactions exist between the material and BUs, allowing BUs on the surface of the material can achieve rapid mass transfer and improved sorption performance, satisfactory extraction recoveries have been achieved in practical sample applications. Under the optimized experimental conditions, the linear ranges were 0.5-200 µg L-1 for diflubenzuron and triflumuron, 1.0-200 µg L-1 for teflubenzuron and 0.8-200 µg L-1 for flufenoxuron with the correlation coefficients R2 ≥ 0.9991. The method has limits of detection and limits of quantification of 0.2-0.4 µg L-1 and 0.5-1.0 µg L-1, respectively. The intra-day and inter-day relative standard deviations were less than 5%. The actual sample recoveries were 76.63-95.26%. In addition, Sil@C/Ni was used repeatedly for 15 times and still showed a relatively satisfactory recovery of the four BUs. Therefore, Sil@C/Ni has a high stability and can be used as an ideal magnetic solid phase extraction sorbent for the trace enrichment of BUs in tea-leaf samples.

High efficiency and simple preparation of polyacrylamide coated silica stationary phase for hydrophilic interaction liquid chromatography.

A polyacrylamide (PAM)-coated silica packing as a novel stationary phase for hydrophilic interaction liquid chromatography (HILIC) was produced firstly by thermal immobilization. The coated layer was formed by a simple and facile physical method that dipping silica spheres into a PAM solution and then stirring the mixture until the solution was evaporated absolutely, leaving a certain amount of PAM on the silica particles. Although there are no chemical bonds involved, the bleeding measurement and the background noise are acceptable. Polyacrylamide coated silica (PAM-Sil, mean diameter: 5 µm) demonstrated a good hydrophilic property and excellent separation efficiency, which was observed especially for several high polar analytes such as saccharides. It is much higher than bare silica or amino columns under the same conditions. Moreover the obtained stationary phase demonstrated good stability under our operation conditions. The specific preparing method offers an easy and economical way to manipulate the thickness of PAM coating and can be extended as a universal way to produce various polymer coated stationary phases with dipping-heating/stirring-evaporating procedure.

Determination of inorganic anions in saliva by electroosmotic flow controlled counterflow isotachophoretic stacking under field-amplified sample injection.

Under a strong counter-electroosmotic flow, five salivary inorganic anions, bromide, iodide, nitrite, nitrate and thiocyanate were determined by field-amplified sample injection in combination with isotachophoretic stacking. Separation and concentration conditions were investigated. A terminating electrolyte, 5mM borate, was added in the sample. Under the optimized conditions, Br(-), I(-) and SCN(-) were concentrated online using 150mM HCl-Tris buffer at pH 7.8 in a bare fused capillary, providing more than ten thousand of sensitivity enrichment compared with normal injections. The relative standard deviations (RSDs, n=5) were less than 1% in migration times, 8% in peak areas. Using direct UV detection at 200nm and 226nm, the limits of detection (LODs, S/N=3) were of 0.002-0.01µM. Unfortunately, NO2(-) and NO3(-) could be observed in purified or deionized water. Therefore, a low dilution factor was applied to saliva samples. Due to the matrix effect, samples were injected in a shorter time, and standard addition method was applied to determine all the five inorganic anions in saliva. The RSDs of the migration times and peak areas were in a range of 0.2-0.4% and 3.0-4.0%, respectively. The LODs were 0.2-2.0µM. The salivary levels of the anions obtained were in accord with the reference data. The external standard method can not be adapted to real samples due to biases caused by electrokinetic injection and errors from high dilutions.

Nanoporous array anodic titanium-supported co-polymeric ionic liquids as high performance solid-phase microextraction sorbents for hydrogen bonding compounds.

A nanoporous array anodic titanium-supported co-polymeric ionic liquids (NAAT/PILs) solid-phase microextraction (SPME) fiber was prepared in situ on the titanium wire. NAAT was selected as the substrate, in view of its high surface-to-volume ratio, easy preparation, mechanical stability, and rich titanol groups on its surface which can anchor silica coupling agent containing vinyl and then introduce ionic liquid copolymers as sorbents. In this work, 1-vinyl-3-nonanol imidazolium bromide ([C9OHVIm]Br) and 1,4-di(3-vinylimidazolium) butane dibromide ([(VIM)2C4]2[Br]) were synthesized and used as monomer and crosslinker, respectively. Extraction properties of the NAAT/PILs fiber for polar alcohols and volatile fatty acids (VFAs) in aqueous matrix were examined using gaseous sampling-SPME (GS-SPME) and headspace SPME (HS-SPME) mode, respectively. Combining the superior properties of NAAT substrate and the strong hydrogen bond interaction of PILs to polar compounds, the NAAT/PILs SPME fiber showed much higher adsorption affinity to aliphatic alcohols than bare NAAT and pure PILs fibers. The detection limits (LOD) of established GS-SPME-GC-FID method are in the range of 0.35-17.30ngL(-1) with a linear range from 0.01 to 500ngmL(-1). Also, it showed high extraction performance toward volatile fatty acids (VFAs) compounds from aqueous matrix. Under the optimized SPME conditions, wide linear ranges were obtained with correlation coefficients (R(2)) greater than 0.99 and limits of detection were in the range of 0.85-8.74ngL(-1). Moreover, real-world samples were analyzed and good results were obtained.