Methacrylate-ethylene Glycol Dimethacrylate Research Articles

Metal-Organic Framework (MOF-199) Coated by Molecularly Imprinted Poly MMA-EGDMA for Solid Phase Extraction of Carbofuran from Fruit Samples

A selective adsorbent was synthesized based on the coating of a molecularly imprinted poly (methyl methacrylate-ethylene glycol dimethacrylate) (poly (MMA-EGDMA)) on the surface of metal-organic frameworks (MOFs) to obtain MMA-EGDMA@MOF-199 and used for the separation and preconcentration of carbofuran. Subsequently, carbofuran was determined by high-performance liquid chromatography with a diode array detector (HPLC-DAD). X-ray diffraction, field-emission scanning electron microscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis were used to characterize the synthesized adsorbent. Both pH and extraction time were optimized as crucial extraction parameters. The adsorption capacity of the adsorbent was 20 mg g−1. The selectivity of the synthesized adsorbent for similar compounds was also investigated. Under the optimal conditions, the calibration curve was linear from 1.0 to 400 μg L−1. A high extraction efficiency (94%) was obtained for carbofuran with a limit of detection (LOD) of 0.4 µg L−1. The adsorbent was successfully applied to the SPE of carbofuran from fruit samples after its extraction, followed by high-performance liquid chromatography analysis.

Magnetic field-induced self-assembly of urchin-like polymeric particles: mechanism, dispersity, and application in wastewater treatment

Pollutant treatment is critical in modern society and existing purification methods often cannot address this problem quickly and economically. Recently, hierarchically organized particles have attracted much academic attention in wastewater treatment because of their unusual geometry associated with the favorable properties of nanoscale units and three-dimensional assemblies synchronously. Here, we synthesized hierarchically organized Fe3O4/poly(glycidyl methacrylate-ethylene glycol dimethacrylate) (poly(GMA-EDMA)) meso-particles (UPPs) by a magnetic field-induced self-assembly strategy. Under the orientation of the external magnetic field, poly(GMA-EDMA) nanoparticles polymerized by GMA and EDMA organically self-assembled around Fe3O4 nanoparticles into mesoscale UPPs. The obtained UPPs showed high dispersity in both aqueous and organic solutions due to that the spikes on the surface of UPPs weaken attractive van der Waals forces between particles. The high dispersity in solutions guarantees the high mass transfer efficiency between UPPs and solutions. Moreover, the incorporation of Fe3O4 nanoparticles endows UPPs with a fast reversible macroscopic assembly & disassembly ability by controlling the external magnetic field, which is beneficial to the collection and regeneration of UPPs. Taking advantage of the features, we grafted iminodiacetic acid (IDA) on the surface of UPPs to obtain a heavy metal ion adsorbent. The IDA-modified UPPs showed high adsorption capacities, fast adsorption rates, and good recyclability for Cu2+ and Pb2+. Besides, the IDA-modified UPPs can allow to be loaded by β-FeOOH nanocatalyst, showing a good photocatalytic performance toward methylene blue, promising a great potential in wastewater treatment.

Molecularly Imprinted Polymers Based Surface Plasmon Resonance Sensor for Sulfamethoxazole Detection

Sulfamethoxazole (SMX) is a sulfonamide antibiotic primarily used to treat urinary tract infections and used in veterinary and industrialized husbandry to treat diseases and food additives. Like other antibiotics, SMX is considered as a pollutant in water and food that threaten local life. This study developed a surface plasmon resonance (SPR) sensor chip that is fast, highly selective, and reusable, and requires no pretreatment for detecting SMX. As a receptor, SMX imprinted methacrylic acid-2-hydroxyethyl methacrylate-ethylene glycol dimethacrylate polymer [poly(MAA-HEMA-EGDMA)] was used. The surface of the gold SPR chips was coated with a drop-casting method. The nanofilm coated chips were characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM), ellipsometer, contact angle measurement, and Fourier-transform infrared spectrometry (FTIR). Imprinting factor (IF) was calculated as: ΔR[MIP(molecularly imprinted polymers)]/ΔR[NIP(non-imprinted)]=12/3.5=3.4. Limit of detection (LOD) and limit of quantification (LOQ) values were calculated with 3 s/m and 10 s/m methods, and the results were found to be 0.001 1 µg/L for LOD 0.003 4 µg/L for LOQ. Adsorption studies on both standard SMX solution and commercial milk samples were applied. Also, we investigated the developed chip’s reusability, storability, and selectivity with amoxicillin and cefalexin.

Schiff base network-1 incorporated monolithic column for in-tube solid phase microextraction of antiepileptic drugs in human plasma

A novel monolithic column incorporated with Schiff base network-1 (SNW-1) was prepared for in-tube solid phase microextraction (SPME) of antiepileptic drugs. The SNW-1 nanoparticles was synthesized by a solvent thermal method and embedded in the poly(glycidyl methacrylate-ethylene glycol dimethacrylate) (GMA-EGDMA) monolithic column by in situ polymerization. The amount of SNW-1 in polymerization solution for preparation of monolithic column was optimized. Fourier transform infrared spectrometry and scanning electron microscope were used to characterize the obtained monolithic column. The SNW-1-monolithic column was connected to the high-performance liquid chromatography (HPLC) system and applied for online extraction and analysis of antiepileptic drugs. The extraction conditions including sample solution flow rate, desorption time, acetonitrile content, pH of sample solution and sample volume were investigated. Under optimal conditions, the proposed SPME-HPLC method showed high extraction efficiency, good linearity, low limits of detection (0.2 ng/mL) and good repeatability (relative standard deviations < 2.41%). This method was also applied to the analysis of antiepileptic drugs in human plasma samples and the recoveries were in the range of 88.6–106.1% with RSDs less than 3.51%.

Glycidyl Methacrylate-ethylene Glycol Dimethacrylate Copolymers with Varied Pore Structures Prepared with Different Reaction Parameters

Abstract Copolymers based on glycidyl methacrylate (GMA) are considered attractive as sorbents because the epoxy groups can be easily converted into other groups. Studies involving the influence of the synthesis parameters on the morphological characteristics of these copolymers are scarce. This work investigates the synthesis of copolymers of poly(GMA-co-EGDMA) with different porosity degrees obtained by varying the synthesis parameters. GMA-EGDMA copolymers were synthesized by suspension polymerization employing varied conditions and characterized by measuring apparent density, surface area and pore volume distribution, optical and scanning electron microcopies, FT-IR, thermogravimetry and titration of epoxide rings. The copolymer with highest surface area and pore volume (260.4 m2/g and 0.5 cm3/g) was prepared employing cyclohexane as diluent, 80% EGDMA in monomeric composition and 100% of dilution degree. There was a relation between the epoxide content of the copolymers determined by titration and the residue content formed in the first decomposition stage.

Preparation of Black Poly(Methyl Methacrylate-Ethyleneglycol Dimethacrylate) Microspheres Using Metallic Complex Dyes

In this study, we synthesized polymethyl methacrylate cross-linked microspheres and functionalized the surface of the microspheres with amine groups, and discussed the effect of functionalization and the change of the surface morphology of the microspheres. This research uses 1:2 metal composite acid dye to dye self-synthesized microspheres with uniform particle size, and successfully prepares black polymethyl methacrylate cross-linked microspheres, which are applied to spacer microspheres.

Polymer microspheres for replacement of biological carriers in test systems operating on the principle of latex agglutination reaction

The results of the study of various modification methods of polymer microspheres for their use in immunochemical reactions as bioligand carriers are reported. Ion etching and electron microscopy were used to show that the copolymer microspheres have a porous structure non-uniform in density. The Maillard reaction was used for the first time in the modification of copolymer microspheres by dextrans of different molecular weight as a simplest way of covalent immobilization of saccharides on their surface. The physicochemical properties of polystyrene-divinylbenzene and polyglycidyl methacrylate-ethylene glycol dimethacrylate microspheres modified with diamines and dextrans were determined for the first time. The conditions under which the bioligand (diphtheria toxoid) immobilized on their surface retained the native conformation and the diagnostics obtained on their basis have high sensitivity were revealed.

Preparation of Monodisperse Enrofloxacin Molecularly Imprinted Polymer Microspheres and Their Recognition Characteristics.

This study presents a new strategy for the detection of enrofloxacin (ENR) in food samples by the use of monodisperse ENR molecularly imprinted polymers (MIPs). Using enrofloxacin as template molecule, methacrylic acid as functional monomer, and ethylene diglycidyl ether as cross-linker, surface molecularly imprinted polymers (MIPs) were prepared on the surface of polymeric glycidyl methacrylate-ethylene glycol dimethacrylate (PGMA-EDMA) microspheres. The surface morphology and imprinting behavior of PGMA-EDMA@MIPs were investigated and optimized. Synthesized PGMA-EDMA@MIPs showed good physical and chemical stability and specific recognition toward fluoroquinolones. The introduction of PGMA-EDMA microspheres greatly increased the adsorption area of PGMA-EDMA@MIPs and increased the adsorption capacity of target molecules. The core shell structure increased the adsorption rate, and adsorption equilibrium was achieved within 6 min, much higher than that of MIPs synthesized by traditional methods. Enrofloxacin in milk samples was detected by molecular imprinting solid phase extraction (MISPE) combined with high performance liquid chromatography (HPLC). Implementing this method resulted in a recovery rate of 94.6~109.6% with a relative standard deviation (RSD) of less than 3.2%. The limit of detection (LOD) of this method was identified as three times the signal-to-noise ratio (10 μg/L). In summary, this work proposed a sensitive, rapid, and convenient method for the determination of trace ENR in food samples.

Cobalt Phthalocyanine Tetracarboxylic Acid Functionalized Polymer Monolith for Selective Enrichment of Glycopeptides and Glycans.

In this study, poly(glycidyl methacrylate-ethyleneglycol dimethacrylate) monolith functionalized with cobalt phthalocyanine tetracarboxylic acid is prepared. The polymer monolithic material is used for glycopeptides enrichment coupled with MALDI-TOF MS. By taking advantage of cobalt phthalocyanine including hydrogen bonds between isoindole subunits of phthalocyanine and glycans, coordination interaction between cobalt and glycopeptides, the monolithic material is successfully applied to the enrichment of glycopeptides efficiently and selectively. With IgG and horse radish peroxidase as the model glycoproteins, 28 and 17 glycopeptides could be identified respectively after enrichment with the monolith, only four and three glycopeptides could be obtained for direct analysis. The monolith is also employed to the digests mixture of BSA and IgG (50:1, m/m), indicating the high enrichment selectivity of glycopeptides even in the presence of a large interference ratio. The detection limit is determined to be 6.7fmol, implying that the present method had great potential for trace sample analysis. In addition, the monolith was successfully applied to the enrichment of N-linked glycans in human serum samples, demonstrating its great potential for the analysis of glycoproteins.

Preparation of copper tetra(N-carbonylacrylic) aminephthalocyanine functionalized zwitterionic-polymer monolith for highly specific capture of glycopeptides.

In this work, poly(glycidyl methacrylate-ethyleneglycol dimethacrylate) monolith functionalized with copper tetra(N-carbonylacrylic) aminephthalocyanine and iminodiacetic acid was successfully synthesized. Owing to hydrogen bonding and hydrophilic interactions, the monolith exhibited good performance for glycopeptide enrichment. When the tryptic digests of horseradish peroxidase were enriched by the developed monolith, a total of 20 glycopeptides could be captured and identified by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry analysis with a detection limit as low as 0.5fmolμL-1. With the mixture of bovine serum albumin and horseradish peroxidase digests (200:1, m/m) as the sample, 14 glycopeptides were identified after enrichment, showing the high selectivity of the monolith. Moreover, the functionalized monolith exhibited good stability and reproducibility. It was successfully applied to enrich glycopeptides from human serum, demonstrating its potential applications in selective and efficient capture of glycopeptides in complex biological samples. Graphical abstract ᅟ.

An environmentally benign methodology to elaborating polymer nanocomposites with tunable properties using core-shell nanoparticles and cellulose nanocrystals

An environmentally benign concept based on waterborne systems is developed for preparation of novel nanocomposite materials with tunable properties. The designed nanocomposites are based on combination of core-shell latex nanoparticles, cellulose nanocrystals (CNC) and polyethylene glycol (PEG). First, core-shell latex nanoparticles from copolymer (methyl methacrylate-ethylene glycol dimethacrylate)-core and copolymer (methyl methacrylate-butyl acrylate)-shell (CS15) are prepared by starved emulsion polymerization. Likewise, incorporation of CNC aqueous suspension into the core-shell latex without any further chemical modification of the nanofiller while assuring good compatibility between both entities is achieved. PEG is effectively added to the suspension to assure multiple functions in the final material. After mixing of the ternary systems, the nanocomposites are prepared by three approaches, i.e. solution casting, solution casting followed by compression molding, and freeze drying followed by compression molding. SEM analysis shows that compression molding processes lead to the highest degree of coalescence of CS15 nanoparticles. This effect is however reduced in presence of PEG or PEG/CNC. It is further observed that the presence of PEG helps protecting CNC from thermal degradation. Thermal and thermo-mechanical analyses prove a high plasticizing performance of PEG and its good confinement between the nanoparticles and at interstitial spaces. Furthermore, it is revealed that the level of material reinforcement by CNC depends strongly on the ratio between CNC and PEG due to the establishment of strong interactions via hydrogen bonding between both components, which can affect the formation of CNC percolating network. These findings allow tuning the microstructure and related properties of the nanocomposites.

Preparation of cobalt phthalocyanine functionalized polymer monolith and application to enrichment of transferrin glycopeptides

Poly(glycidyl methacrylate-ethyleneglycol dimethacrylate) (Poly(GMA-EDMA)) monolith functionalized with cobalt phthalocyanine tetracarboxylic acid (CoPcTc) was prepared. The monolith was used for transferrin (Tf) glycopeptide enrichment. By taking advantage of hydrogen bonds between isoindole subunits of phthalocyanine and glycans and coordination interaction between cobalt and glycopeptides, the monolithic material was efficient and selective. After enrichment of transferrin through the functionalized monolith, 17 glycopeptides were identified by electrospray ionization quadrupole time-of-flight mass spectrometry. When the concentration of transferrin was reduced to 8.8×10-10mol/L, three glycopeptides could still be obtained. The present method has great potential for trace sample analysis.

Preparation of monolithic fibers with deep eutectic solvent for solid phase microextraction of polycyclic aromatic hydrocarbons in lake water

A monolithic fiber of poly(butyl methacrylate-ethylene glycol dimethacrylate)[poly(BMA-EDMA)] was prepared using deep eutectic solvent (DES) of choline chloride-ethanediol as a porogen. The prepared fibers were applied to direct extraction of three polycyclic aromatic hydrocarbons (PAHs) in lake water samples by solid phase microextraction (SPME). The extracts were determined by ultra performance liquid chromatography (UPLC). The fiber without DES was prepared at the same time. Both fibers (with and without DES) were compared with a commercial polydimethylsiloxane (PDMS) fiber. The highest extraction efficiency was clearly obtained with poly(BMA-EDMA) fiber. The extraction time, extraction solvent, desorption time, desorption solvent, and ionic strength were optimized. Under the optimum conditions, the linear ranges for the three PAHs (naphthalene, biphenyl, and phenanthrene) were 0.1-6.0 mg/L (r ≥ 0.9903). The limits of detection (LODs) of the three PAHs were in the range of 2.1-4.9 μg/L. The recoveries of the three PAHs spiked in lake water samples were 86.4%-111.3% with relative standard deviations (RSDs, n=6) of 11.2%-15.1%. This method is simple, stable, and inexpensive, and can be used for the determination of the PAHs in lake water samples.

One-pot synthesis of zeolitic imidazolate framework-8/poly (methyl methacrylate-ethyleneglycol dimethacrylate) monolith coating for stir bar sorptive extraction of phytohormones from fruit samples followed by high performance liquid chromatography-ultraviolet detection

In this work, zeolitic imidazolate framework-8 (ZIF-8)/poly (methyl methacrylate-ethyleneglycol dimethacrylate) (MMA-EGDMA) composite monolith was in situ synthesized on stir bar by one-pot polymerization. Compared with the neat monolith, ZIF-8/poly(MMA-EGDMA) composite monolith has larger surface area and pore volume. It also exhibits higher extraction efficiency for target phytohormones than poly(MMA-EGDMA) monolith and commercial polyethylene glycol (PEG) coated stir bar. Based on it, a method of ZIF-8/poly(MMA-EGDMA) monolith coated stir bar sorptive extraction (SBSE)-high performance liquid chromatography-ultraviolet detection (HPLC-UV) was established for the analysis of five phytohormones in apple and pear samples. The developed method exhibited low limits of detection (0.11–0.51μg/L), wide linear range (0.5–500μg/L) and good recoveries (82.7–111%), which demonstrated good application potential of the ZIF-8/monolith coated stir bar in trace analysis of organic compounds.

Polyethylenimine and tris(2-aminoethyl)amine modified p(GA–EGMA) microbeads for sorption of uranium ions: equilibrium, kinetic and thermodynamic studies

Poly(glycidyl methacrylate-ethyleneglycol dimethacrylate), p(GA–EGMA), microbeads were prepared through suspension polymerization. It was decorated with polyethylene imine (PEIM) and tris(2-aminoethyl)amine (TAEA) ligands to decorate with polyamine groups. These microbeads were used for sorption of uranium ions from aqueous solution. The maximum sorption of uranium ions on the PEIM and TAEA modified microbeads was observed at pH 6.0. The maximum sorption capacity of acid hydrolyzed p(GA–EGMA)–OH, p(GA–EGMA)–PEIM and p(GA–EGMA)–TAEA microbeads was found to be 7.21, 87.8 and 64.3 mg g−1. The sorption process conforms to the pseudo-second order kinetic model and the Langmuir and Temkin isotherm models well.

Radiochemical “degelation” of polymethyl methacrylate networks

Methyl methacrylate-ethylene glycol dimethacrylate networks were synthetized and submitted to radiochemical degradation, with ageing monitored by means of sol-gel analysis. The networks were shown to undergo chain scission predominantly, which leads to their degelation, i.e., the recovery of a thermoplastic-like behavior with loss of all elastically active chains. The degelation dose was shown to increase with crosslink density and the corresponding critical conversion ratio was discussed regarding a recent and general statistical theory that covers radiochemical as well as chemical chain scissions.

Preparation and characterization of macroporous monoliths imprinted with erythromycin.

The synthesis of macroporous molecularly imprinted monoliths was performed using the monomers system 2-hydroxyethyl methacrylate-ethylene glycol dimethacrylate and erythromycin as a template. The copolymerization was carried out in situ inside 50 mm × 4.6 mm i.d. stainless-steel tubing. The morphology of the monoliths was examined with scanning electron microscopy. The porous characteristics were determined both from the data of hydrodynamic permeability of monoliths and by means of mercury intrusion porosimetry. The retention parameters of target substance (erythromycin), values of calculated imprinting factors and apparent dynamic dissociation constants were obtained for monoliths prepared with the application of different amount of template (4, 8 and 12 mol%). The separations of the mixtures azithromycin/erythromycin and ciprofloxacin/erythromycin were demonstrated. Additionally, the possibility of erythromycin quantification in human blood plasma was shown.

On-line SPE of Three Steroids with a Novel Polymeric Monolith

In this report, a novel poly (N-isopropyl acrylamide-glycidyl methacrylate-ethylene glycol dimethacrylate) monolithic column was introduced for solid phase extraction. The monolith was prepared using N-isopropyl acrylamide and glycidyl methacrylate as the functional monomers, ethylene glycol dimethacrylate as the cross linker. In order to evaluate the mechanical stability and permeability of the material, the pressure drop across the column was measured in different flow-rates. Moreover, the monolith was used as on-line solid phase extraction material and coupled to high performance liquid chromatography to determine dexamethasone acetate, norgestrel and halcinonide in urine samples.

Supermacroporous polymer monolith prepared with polymeric porogens via viscoelastic phase separation for capillary electrochromatography

Supermacroporous poly(methacrylic acid-butyl methacrylate-ethylene glycol dimethacrylate) monoliths with the pore size up to 5–10μm were successfully prepared in a ternary polymeric porogens utilizing viscoelastic effect. High concentration (over 20mg/mL) of polystyrene (PS) in porogen was used to achieve the desirable characteristics of the monolithic capillary. Modification of the co-porogen composition, i.e., the content of dimethyl sulfoxide and isooctane, enabled tailoring of the supermacropore structure with a wide range of pore size. The effects of the amount of polymer porogen and molecular weights of PS on the formation of supermacropore were also studied. In preliminary applications, the separations of alkyl phenones and alkylbenzenes were achieved on the supermacropore columns using a mode of capillary electrochromatography. The study demonstrated successfully the ability of polymer porogen to form supermacropore monolith via viscoelastic phase separation

Trypsin Immobilized on Magnetic Beads via Click Chemistry: Fast Proteolysis of Proteins in a Microbioreactor for MALDI-ToF-MS Peptide Analysis

In the present work, magnetic poly(2-hydroxyethyl methacrylate–ethyleneglycol dimethacrylate) (mp(HEMA-EGDMA)) beads were prepared by suspension polymerization. The beads were grafted with poly(hydroxylpropyl methacrylate) (pHPMA) and used for immobilization of trypsin via click chemistry. The p(HPMA) units in the brushes made the fibrous polymer hydrophilic. Synthesized beads were characterized by swelling studies, Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM). The bromo groups of the grafted polymer were modified into azide groups, and the enzyme was alkyne-functionalized for conjugation with azide-modified magnetic beads via click reaction. The kinetic constants (Km and Vmax) were determined by measuring initial reaction rates using the artificial chromogenic substrate N-benzoyl-dl-arginine 4-nitroanilide hydrochloride (BApNA). The optimal pH value for the immobilized enzyme was slightly higher compared to free enzyme. The immobilized trypsin possessed much high...