Preparation of magnetic molecularly imprinted polymers based on a deep eutectic solvent as the functional monomer for specific recognition of lysozyme.

A magnetized molecularly imprinted polymer (MIP) was prepared via a surface-imprinting technique. An allyl-based deep eutectic solvent was chosen as the functional monomer to obtain the polymer for specific recognition of lysozyme. It was deposited on silica-coated magnetite nanoparticles. The structure of the polymer was confirmed by X-ray diffraction, Fourier transform infrared spectrometry, transmission electron microscopy, thermogravimetric analysis and vibrating sample magnetometry. The maximum binding capacity of the imprinted polymer is found to be 108 mg·g-1, which is higher than that of non-imprinted polymer. Compared to reference proteins such as cytochrome C, bovine hemoglobin and bovine serum albumin, the MIP shows favorable selectivity for lysozyme. Besides, the imprinted polymer can be further used to specifically recognize lysozyme from the protein mixture and chicken egg white. Reusability studies demonstrate that the polymer can be recycled four times without significant loss of adsorption capacity. The LOD of the method is 12.8 µg·mL-1. The relative standard deviations (for n = 3) are 1.38% for precision and 2.76% for repeatability. Its facile synthesis, high adsorption performance and excellent selectivity to capture lysozyme make this polymer an attractive candidate to be applied in biomacromolecular purification. Graphical abstract Magnetic molecularly imprinted polymer (MIP) based on deep eutectic solvent as functional monomer was fabricated and applied for the specific recognition of lysozyme. The MIP exhibits high adsorption capacity and excellent selectivity for lysozyme.

Aqueous biphasic systems formed by hydrophilic and hydrophobic deep eutectic solvents for the partitioning of dyes.

Two kinds of hydrophobic deep eutectic solvents (DESs), including hexafluoroisopropanol (HFIP)-based DESs and polypropylene glycol 400 (PPG400)-based DESs, were synthesized to construct aqueous biphasic systems (ABSs) with choline chloride (ChCl)-based hydrophilic DESs for the first time, respectively. Three kinds of dyes with different hydrophobicity, including tartrazine, methylene blue and sudan Ⅲ, were chosen as the target analytes to evaluate the partitioning behaviors of the DES/DES ABSs. The effect of the types of hydrophilic DESs on dyes extraction were investigated and ChCl-glycol (ChCl-G) was selected as the phase-forming component. Then the partitioning of dyes in diverse DES/DES ABSs with different hydrophobicity was addressed by altering the carbon chain length of hydrogen bond accepter (HBA) in hydrophobic DES and changing the molar ratio of HBA: hydrogen bond donor (HBD) in hydrophilic DES. The results proved that in the ABSs of HFIP-based DES/DES, the sudan Ⅲ tended to migrate to the hydrophobic DES-rich phase with the increased carbon chain length of hydrophobic DES and was inclined to transfer to the hydrophilic DES-rich phase with the increasing proportion of G in ChCl-G. Afterwards, the methylene blue was chosen to explore the influence factors of the extraction process. And the results showed that the adjusting of pH value could achieve a complete opposite distribution of methylene blue in PPG400-based DES/DES ABSs. Besides, extraction of dyes in real samples were evaluated and recoveries of 92.3%-106.1% were achieved. Moreover, the analysis of mixed samples demonstrated that 88.64% of tartrazine and 92.63% of methylene blue were enriched into the hydrophilic phase, while nearly all of the sudan Ⅲ was moved into the hydrophobic phase. In addition, the phase-forming components could be reused according to the regeneration studies. Method validation proved the good precision, repeatability and stability of the established method. At last, the extraction mechanism was further investigated by dynamic light scattering (DLS) and transmission electron microscope (TEM). It turned out the formation of DES-dye aggregates might be responsible for the separation process. Above all, the results highlighted the possibility of the DES/DES ABSs as tunable systems for the partitioning of dyes with different hydrophobicity.

Ionic liquid modified molybdenum disulfide and reduced graphene oxide magnetic nanocomposite for the magnetic separation of dye from aqueous solution.

A novel ionic liquid (IL) modified magnetic nanocomposite (mag-MoS2-RGO), which was composed of molybdenum disulfide (MoS2) and reduced graphene oxide (RGO), was firstly synthesized and characterized (mag-MoS2-RGO-IL). Compared with mag-MoS2-RGO, the mag-MoS2-RGO-IL exhibited the higher adsorption capacity of 143.9 mg/g for methylene blue (MB) under optimum conditions. Experimental results were imitated by adsorption isotherms and kinetic models, revealing a monolayer adsorption on the homogeneous surface governed by chemisorption. The removal rate was maintained 78% after 5 cycles of regeneration, indicating its good reutilization. Methodological study suggested that the method possessed excellent repeatability, precision and stability. The recoveries from the real samples were in the range of 87.0-98.8% with relative standard deviation of ≤5.2%. Benefiting from composite structure and magnetic Fe3O4, the stable magnetic adsorbent can be quickly separated from aqueous solution. All of above proves that the prepared mag-MoS2-RGO-IL has great application potential in dye separation.

Poly(deep eutectic solvent)-functionalized magnetic metal-organic framework composites coupled with solid-phase extraction for the selective separation of cationic dyes.

Novel polymeric deep eutectic solvents (PDES) based on 3-acrylamidopropyl trimethylammonium chloride/D-sorbitol functionalized amino-magnetic (Fe3O4NH2) metal-organic framework (HKUST-1-MOF) composites (Fe3O4NH2@HKUST-1@PDES) were synthesized and characterized by field emission transmission electron microscope (FE-SEM), transmission electron microscope (TEM), X-ray diffraction (XRD), fourier transform infrared spectrometry (FT-IR), thermal gravimetric analysis (TGA), vibrating sample magnetometer (VSM) and zeta potentials. Then the composites were firstly utilized to selectively separate malachite green (MG) and crystal violet (CV) coupled with magnetic solid-phase extraction (MSPE). A response surface methodology (RSM) based on Latin hypercube sampling (LHS) was selected to analytically optimize the extraction parameters including initial concentration of dyes, extraction time, pH value and extraction temperature. The maximum extraction amount and optimal extraction conditions predicted by the RSM model matched well with the actual experimental results, and the extraction amount was 966.93 mg g-1 for MG and 788.90 mg g-1 for CV,respectively. The results indicated that the model possessed higher calculation accuracy through analyzing fewer sample points, thereby achieving theoretical prediction of extraction amount and conditions and being a prefect supplementary to actual experiments. The electrostatic interaction between the composites and cationic dyes played the main roll in the extraction process. The proposed extraction method exhibited lower limit of detection (98.19 ng mL-1 for MG and 23.97 ng mL-1 for CV) and preeminent precision (RSD ˂ 0.4%). Spiked recoveries of fish samples at three spiking levers ranged from 89.43% to 100.65% for MG and 95.29%-98.03% for CV. All results highlighted the excellent potential of Fe3O4NH2@HKUST-1@PDES-MSPE strategy in selective separation of cationic dyes in complex medium.

Fabrication of magnetic polymers based on deep eutectic solvent for separation of bovine hemoglobin via molecular imprinting technology.

In this work, molecularly imprinted polymers (MIPs) were prepared with vinyl-coated magnetic particles (Fe3O4@VTEO) as the support material, deep eutectic solvent (DES) based on vinyl as the functional monomer, respectively. N,N-methylenebisacrylamide (MBAAm) was used as the crosslinker on account of its abundant carbon-carbon double bonds. The MIPs were prepared with the addition of bovine hemoglobin (BHb) acted as the template. The MIPs particles can be collected quickly by a magnetic field. The composition and morphology of the MIPs particles were characterized by transmission electron microscopy (TEM), dynamic light scattering (DLS), fourier transform infrared spectrometry (FT-IR) and thermo-gravimetric analysis (TGA). X-ray diffraction (XRD) was used to illustrate the cubic inverse spinel structure of Fe3O4. Meanwhile, vibrating sample magnetometer (VSM) was applied to characterize the magnetism of the MIPs. Adsorption experiments were performed to attain the optimum adsorption conditions. Under the optimized conditions, the obtained maximum adsorption capacity (Q, mg·g-1) of the MIPs particles is found to be 164.20 mg g-1, and the imprinting factor (IF) is 4.93. Four reference molecules were used to test the selectivity of the MIPs particles, which indicates that the recognition sites can adsorb template molecules with selectivity. Furthermore, the prepared magnetic MIPs particles were applied to capture BHb from the real samples (calf blood) effectively.

Development of deep eutectic solvent-based aqueous biphasic system for the extraction of lysozyme.

Aqueous Biphasic Systems (ABSs) based on deep eutectic solvents (DESs) were determined and applied in the extraction of lysozyme from chicken egg white. Tetrabutylammonium bromide (TBAB) and benzyltributylammonium bromide were utilized as hydrogen-bond acceptors to synthesize six kinds of DESs with different carboxylic acids (such as glycolic acid, Gly). The phase-formation ability of these DESs was evaluated by combining several salts. The results revealed that the content of hydrophilic group and the alkyl side chain length of the carboxylic acids played a crucial role in phase separation process, and the introduce of the benzyl group for quaternary ammonium salt had an aptitude to promote two-phase splitting. Then the system comprising [TBAB][Gly] and Na2SO4 was used to appraise the effect of different experimental parameters on the extraction efficiency, including the amount of DES and salt, the temperature, the values of pH and the ionic strength. More than 98% of lysozyme was transferred into the DES-rich phase at the optimum condition. The activity of lysozyme after the process of extraction still retained 91.73% of initial activity, demonstrating high biocompatibility of the studied system. What's more, the proposed method was successfully utilized for the real sample analysis. Finally, UV-vis, FT-IR, circular dichroism spectra, dynamic light scattering and transmission electron microscopy were employed to investigate the extraction mechanism. All of these results verify the excellent feasibility of the proposed system in the analysis of biological samples.

Preparation of ionic liquid modified magnetic metal-organic frameworks composites for the solid-phase extraction of α-chymotrypsin.

A novel magnetic solid-phase extraction (MSPE) method based on 1-hexyl-3-methyl imidazolium chloride ionic liquid (IL) modified magnetic Fe3O4 nanoparticles, hydroxylated multiwall carbon nanotubes (MWCNTs-OH) and zeolitic imidazolate frameworks (ZIFs) nanocomposites (Fe3O4-MWCNTs-OH@ZIF-67@IL) were proposed and applied to extract α-chymotrypsin. The magnetic materials were synthesized successfully and characterized by X-ray diffraction (XRD), transmission electron microscope (TEM), thermal gravimetric analysis (TGA), fourier transform infrared spectrometry (FT-IR), vibrating sample magnetometer (VSM) and zeta potentials. Subsequently, the UV-vis spectrophotometer at about 280 nm was utilized to quantitatively analyze the α-chymotrypsin concentration in the supernatant. Furthermore, single factor experiments revealed that the extraction capacity was influenced by initial α-chymotrypsin concentration, ionic strength, extraction time, extraction temperature and pH value. The extraction capacity could reach up to about 635 mg g-1 under the optimized conditions, absolutely higher than that of extraction for Ovalbumin (OVA), Bovine serum albumin (BSA) and Bovine hemoglobin (BHb). In addition, the regeneration studies showed Fe3O4-MWCNTs-OH@ZIF-67@IL particles could be reused several times and kept a high extraction capacity. Besides, the study of enzymatic activity also indicated that the activity of the extracted α-chymotrypsin was well maintained 93% of initial activity. What's more, the proposed method was successfully applied to extract α-chymotrypsin in porcine pancreas crude extract with satisfactory results. All of above conclusions highlight the great potential of the proposed Fe3O4-MWCNTs-OH@ZIF-67@IL-MSPE method in the analysis of biomolecules.

Aqueous biphasic systems formed by deep eutectic solvent and new-type salts for the high-performance extraction of pigments.

Deep eutectic solvent (DES) composed of polypropylene glycol 400 (PPG 400) and tetrabutylammonium bromide (TBAB) was combined with a series of new-type salts such as quaternary ammonium salts, amino acid and polyols to form Aqueous Biphasic Systems (ABSs). Phase-forming ability of the salts was investigated firstly. The results showed that polyols had a relatively weak power to produce phases within studied scopes. And the shorter of carbon chain length of salts, the easier to obtain phase-splitting. Then partitioning of three pigments in PPG 400/betaine-based ABSs was addressed to investigate the effect of pigments' hydrophobicity on extraction efficiency. It was found that an increase in hydrophobicity contributed to the migration of pigments in the DES-rich phase. On the other hand, with a decline in phase-forming ability of salts, the extraction efficiency of the whole systems started to go down gradually. Based on the results, selective separation experiment was conducted successfully in the PPG 400/betaine-based systems, including more than 93.00% Sudan Ⅲ in the top phase and about 80.00% sunset yellow FCF/amaranth in the bottom phase. Additionally, ABSs constructed by DES/betaine for partitioning amaranth were further utilized to explore the performances of influence factors and back extraction. It can be concluded that after the optimization above 98.00% amaranth was transferred into the top phase. And 67.98% amaranth can be transferred into the bottom phase in back-extraction experiment. At last, dynamic light scattering (DLS) and transmission electron microscope (TEM) were applied to probe into extraction mechanism. The results demonstrated that hydrophobicity played an important role in the separation process of pigments. Through combining with new-type DES, this work was devoted to introducing plentiful salts as novel compositions of ABSs and providing an eco-friendly extraction way for partitioning pigments, which boosted development of ABSs in the monitoring food safety field.

Magnetic solid-phase extraction for the removal of mercury from water with ternary hydrosulphonyl-based deep eutectic solvent modified magnetic graphene oxide.

A novel ternary hydrosulphonyl-based deep eutectic solvent (THS-DES) comprised of choline chloride/itaconic acid/3-mercaptopropionic acid (molar ratio 2:1:1) was firstly synthesized. The composition, property and microscopic structure of the new magnetic adsorbent (THS-DES@M-GO) based on the THS-DES modified the magnetic graphene oxide (M-GO) was characterized by the system. Magnetic solid-phase extraction (MSPE) based THS-DES@M-GO was firstly researched for the removal of mercury (Hg2+) from water. Various influencing factors such as the mass of adsorbent, solution pH, initial Hg2+ concentration, the removal time and temperature had been systematically tested. Under optimized conditions the removal efficiency (R%) could achieved 99.91%. The precision, repeatability and stability experiments were investigated in detail to evaluate the presented method. The relative standard deviations (RSD) of the removal efficiency were 0.053%, 1.49% and 1.55%, respectively. The maximum adsorption capacity (Qmax) was 215.1 mg g-1 and the data of the experiment fitted well with Langmuir model. Elution experimental studies shown that 94.94% of Hg2+ could be eluted by ethylenediaminetetraacetic acid (EDTA). After seven cycles of adsorption-desorption processes, the THS-DES@M-GO still retained a high removal efficiency of 90.23%. Compared with other adsorbents prepared in this work, THS-DES@M-GO displayed higher removal efficiency for Hg2+. Interference study proved the composites was tolerated and stabled under the complex matrix. What's more, the analysis of mercury contaminated water (from Guizhou, P.R., China) proved that the proposed method could be used to remove Hg2+ in practical application.

A novel aqueous biphasic system formed by deep eutectic solvent and ionic liquid for DNA partitioning.

In this work, aqueous biphasic systems (ABSs) composed of ionic liquids (ILs) and deep eutectic solvents (DESs) were developed and utilized to efficiently extract DNA for the first time. Four kinds of ILs/DESs were mainly constituted by betaine/carboxylic acid and betaine/carbohydrates respectively. While another DES ([TBAB][PPG400]) was formed by polypropylene glycol 400 (PPG 400) and tetrabutylammonium bromide (TBAB). The phase-formation ability of the studied ABSs was evaluated by using [TBAB][PPG400]/(ILs/DESs) and [TBAB][PPG400]/inorganic salts. The results revealed that the phase forming ability of ABSs involved with the size of anion alky chain of ILs, the viscosity, the density and the hydrophilicity of DESs, ionic radius and ionic valence of inorganic salts. Then the system comprising [TBAB][PPG400]/IL was selected to ascertain the optimum extraction conditions for the extraction of DNA by the influence factor experiments. Meanwhile the maximum extraction efficiency could be attained 99.60%. Mixed sample experiments were implemented to separate DNA/cytochrome C (Cyt-c) and DNA/bovine hemoglobin (BHb), where the DNA mainly partitioned to IL-rich bottom phase. It turned out that the relationship between the isoelectric point of analytes and the pH of the system played an important role in the separation process. The result also showed that the studied system can be applied to selectively separate mixtures of nucleic acids and proteins in a single-step. Moreover, the developed system was successfully applied to the extraction of DNA from bovine whole blood with satisfactory result. Finally, the extraction mechanisms associated with the separation process were explored by FT-IR spectra, circular dichroism spectra (CD), dynamic light scattering (DLS), transmission electron microscopy (TEM). Overall, the novel systems have been proven to be a remarkable performance in the separation of DNA, which is expected to be widely used and provide further possibilities in separation fields.

Creating magnetic ionic liquid-molecularly imprinted polymers for selective extraction of lysozyme.

A novel magnetic (Fe3O4) surface molecularly imprinted polymer (MIP) based on ionic liquid (IL) (Fe3O4@VTEO@IL-MIPs) was prepared for the selective extraction of lysozyme (Lys). As the functional monomer of the MIPs, an imidazolium-based IL with vinyl groups was prepared. It can provide multiple interactions with template molecules. The amount of IL was optimized (200 mg). Fourier transform infrared spectrometry (FT-IR), transmission electron microscopy (TEM), dynamic light scattering (DLS), thermogravimetric analysis (TGA) and a vibrating sample magnetometer (VSM) were used to characterize the MIP. The results indicate the successful formation of an imprinting polymer layer. The concentration of Lys in the supernatant was determined by UV-vis spectrophotometry at a wavelength of 280 nm. The maximum adsorption capability of the MIP is 213.7 mg g-1 and the imprinting factor (IF) is 2.02. It took 2.5 h for the MIP to attain adsorption equilibrium. The structure of the protein was evaluated using circular dichroism (CD) spectra and UV-visible spectra. The adsorption performance was further investigated in detail by selective adsorption experiments, competitive rebinding tests, and reusability and stability experiments. Furthermore, it was utilized to separate the template protein from a mixture of proteins and real samples successfully because of the high adsorption capacity for Lys.

A novel dianionic amino acid ionic liquid-coated PEG 4000 modified Fe3O4 nanocomposite for the magnetic solid-phase extraction of trypsin.

A novel magnetic extractant, PEG 4000 modified Fe3O4nanomaterial that coated with dianionic amino acid ionic liquid (Fe3O4@PEG@DAAAIL), was successfully synthesized and characterized. X-ray diffraction (XRD), transmission electron microscope (TEM), vibrating sample magnetometer (VSM), fourier transform infrared spectrometry (FT-IR), thermal gravimetric analysis (TGA) and zeta potentials were used to confirm that the novel nanocomposite was successfully synthesized. Subsequently, the prepared Fe3O4@PEG@DAAAIL nanocomposite was used as the extractant for trypsin coupled with magnetic solid-phase extraction (MSPE). The concentrations of trypsin in the supernatant were detected by UV-vis spectrophotometer at 278nm. The extraction ability turned out to be better than the other four kinds of extractants prepared in this work. Furthermore, the influence of a series of factors, such as extraction time and temperature, initial trypsin concentration, the value of pH and ionic strength, was systematically investigated. Under the optimal extraction condition, the extraction capacity for trypsin could reach up to 718.73mg/g, absolutely higher than that of other adsorbents reported. This satisfactory extraction capacity could be maintained unchangeable after at least eight days, and kept over 90% of initial extraction capacity after eight recycles. What's more, the activity of trypsin after extraction retained 92.29% of initial activity, verifying the biocompatibility of the prepared extractant. Finally, the developed Fe3O4@PEG@DAAAIL-MSPE method was successfully applied to the real sample analysis with satisfactory results. All of above proves the potential value of Fe3O4@PEG@DAAAIL-MSPE in the analysis of biomass.