Glycol Dimethacrylate Cross-linker Research Articles

Temperature-Dependent Gas Transport Behavior in Cross-Linked Liquid Crystalline Polyacrylate Membranes

Stable, cross-linked, liquid crystalline polymer (LCP) films for membrane separation applications have been fabricated from the mesogenic monomer 11-(4-cyanobiphenyl-4′-yloxy) undecyl methacrylate (CNBPh), non-mesogenic monomer 2-ethylhexyl acrylate (2-EHA), and cross-linker ethylene glycol dimethacrylate (EGDMA) using an in-situ free radical polymerization technique with UV initiation. The phase behavior of the LCP membranes was characterized using differential scanning calorimetry (DSC) and X-ray scattering, and indicated the formation of a nematic liquid crystalline (LC) phase above the glass transition temperature. The single gas transport behavior of CO2, CH4, propane, and propylene in the cross-linked LCP membranes was investigated for a range of temperatures in the LC mesophase and the isotropic phase. Solubility of the gases was dependent not only on the condensability in the LC mesophase, but also on favorable molecular interactions of penetrant gas molecules exhibiting a charge separation, such as CO2 and propylene, with the ordered polar mesogenic side chains of the LCP. Selectivities for various gas pairs generally decreased with increasing temperature and were discontinuous across the nematic–sotropic transition. Sorption behavior of CO2 and propylene exhibited a significant change due to a decrease in favorable intermolecular interactions in the disordered isotropic phase. Higher cross-link densities in the membrane generally led to decreased selectivity at low temperatures when the main chain motion was limited by the lack of mesogen mobility in the ordered nematic phase. However, at higher temperatures, increasing the cross-link density increased selectivity as the cross-links acted to limit chain mobility. Mixed gas permeation measurements for propylene and propane showed close agreement with the results of the single gas permeation experiments.

Preparation of polyurethane-acrylate and silica nanoparticle hybrid composites by a free radical network formation method

In this study, hybrid composites of polyurethane-acrylate (PUA) and silica nanoparticle were prepared by a radical method. For this aim, silica nanoparticles were chemically functionalized with 3-methacryloxypropyltrimethoxysilane. Polyurethane was synthesized and then modified with 2-hydroxyethyl methacrylate to yield PUA. Then, different amounts of modified-silica were used to prepare PUA composites by the addition of an ethylene glycol dimethacrylate crosslinker. Fourier-transform infrared spectroscopy confirmed the successful functionalization of silica nanoparticles and the preparation of PUA. Structural investigation of the functionalized-nanoparticles and also nanocomposites was carried out using X-ray diffraction and electron microscopy. According to the thermal gravimetric analysis results, char residue of \(\hbox {HSiO}_{2}\) is 86.6%, which decreases to 81.3% in the case of \(\hbox {MSiO}_{2}\) as a result of its modifier degradation content of 5.3%. PUAS5 shows main decomposition temperatures of 396.5 and \(454.9{^{\circ }}\hbox {C}\) and also char content of 5.7% at \(700{^{\circ }}\hbox {C}\). The high amount of \(\hbox {MSiO}_{2}\) can also be resulted in higher degree of crosslinking and therefore higher thermal stabilities and char residue.

Impacts of cross-linker chain length on the physical properties of polyampholyte hydrogels.

Polymeric tissue engineering scaffolds have shown promise to aid in regeneration and repair of damaged tissue. In particular, nonfouling polymers have been proposed for eliminating biomaterial-induced concerns such as infection, scarring, and rejection by the immune system. Polyampholyte polymers are one class of nonfouling polymers that are composed of an equimolar mixture of positively and negatively charged monomer subunits. They possess nonfouling properties, bioactive molecule conjugation capabilities, and tunable mechanical properties. In this study, the influence of the cross-linker species on the degradation behavior, mechanical strength, and nonfouling properties of polyampholytes composed of a 1:1 molar ratio of [2-(acryloyloxy)ethyl] trimethylammonium chloride (positively charged) and 2-carboxyethyl acrylate (negatively charged) monomers was investigated. Specifically, the impact of ethylene glycol repeat units on the overall material performance was evaluated by synthesizing and characterizing hydrogels containing di-, tri-, and tetra-ethylene glycol dimethacrylate cross-linker species. The degradation studies were conducted for over 100 days in Sorenson's buffer with pH values of 4.5, 7.4, and 9.0 by tracking the swelling behavior and weight change over time. The mechanical properties were assessed using compression and tensile testing to failure. The retention of the nonfouling and protein conjugation capabilities was demonstrated using fluorescently labeled bovine serum albumin. The results demonstrate the tunability of both degradation behavior and mechanical properties through the cross-linker selection, without impacting the underlying nonfouling and biomolecule delivery capabilities. Therefore, it is concluded that polyampholyte hydrogels represent a promising platform for tissue engineering.

A Cross-Linker-Based Poly(Ionic Liquid) for Sensitive Electrochemical Detection of 4-Nonylphenol.

In this study, we report a cross-linker-based poly(ionic liquid) (PIL) for the sensitive detection of 4-nonylphenol (4-NP). PIL was poly(1,4-butanediyl-3,3′-bis-l-vinylimidazolium dibromide) (poly([V2C4(mim)2]Br2)). Poly([V2C4(mim)2]Br2) was prepared via one-step free-radical polymerization. The poly([V2C4(mim)2]Br2) was characterized by infrared spectroscopy, Raman spectroscopy, thermal gravimetric analyzer and scanning electron microscope. The poly([V2C4(mim)2]Br2) was then drop-cast onto a glassy carbon electrode (GCE) to obtain poly([V2C4(mim)2]Br2)/GCE. In comparison with a bare GCE, poly([V2C4(mim)2]Br2)/GCE exhibited higher peak current responses for [Fe(CN)6]3−/4−, lower charge transfer resistance, and larger effective surface area. While comparing the peak current responses, we found the peak current response for 4-NP using poly([V2C4(mim)2]Br2)/GCE to be 3.6 times higher than a traditional cross-linker ethylene glycol dimethacrylate (EGDMA) based poly(EGDMA) modified GCE. The peak current of poly([V2C4(mim)2]Br2) sensor was linear to 4-NP concentration from 0.05 to 5 μM. The detection limit of 4-NP was obtained as 0.01 μM (S/N = 3). The new PIL based electrochemical sensor also exhibited excellent selectivity, stability, and reusability. Furthermore, the poly([V2C4(mim)2]Br2)/GCE demonstrated good 4-NP detection in environmental water samples.

Novel nanocomposite derived from ZnO/CdS QDs embedded crosslinked chitosan: An efficient photocatalyst and effective antibacterial agent.

A novel nanocomposite (cl-Ch-pMAc@ZnO/CdSQDs) has been developed under microwave irradiation via fabrication of ZnO/CdS quantum dots on anionically functionalized chitosan [i.e. poly (methacrylic acid) crosslinked chitosan (cl-Ch-pMAc) in the presence of diethylene glycol dimethacrylate (DEGDMA) crosslinker]. The structural, morphological and chemical/physical properties of crosslinked chitosan and the nanocomposites have been investigated using 13C nuclear magnetic resonance spectroscopy (13C NMR spectroscopy), high resolution-transmission electron microscopy (HR-TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) analyses. The nanocomposite demonstrates outstanding efficacy towards the photocatalytic degradation of cationic dyes [malachite green (MG), and safranin (SF)] and toxic organic molecule 2,4-dichloro phenol (2,4-DCP) under the exposure of sunlight. Liquid chromatography mass spectroscopy (LC-MS) studies predict that small molecules are produced by degradation. Moreover, the composite exhibits excellent antibacterial activity towards E-coli and B. subtilis. Finally, the nanocomposite can be regenerated effectively with changing the solution pH and also shows 5 times reusability without significant reduction on its efficiency.

Dummy molecularly imprinted solid phase extraction of climbazole from environmental water samples

Dummy molecularly imprinted polymer (DMIP) for climbazole (CBZ) was synthesized for the first time employing miconazole (MNZ) as the dummy template together with methacrylic acid (MAA) monomer, ethylene glycol dimethacrylate (EGDMA) cross-linker and acetonitrile (ACN) porogen. The selectivity and capacity of the prepared MNZ-DMIP was estimated for CBZ by high-performance liquid chromatography (HPLC) and equilibrium binding experiments. Imprinting factor (IF) with a value of 7.0 was achieved, much higher than the CBZ templated MIP (IF = 3.5). Heterogeneous binding sites were found in the MNZ-DMIP, the corresponding saturation capacity and dissociation constant for the high and low affinity binding sites were 6.761 μmol g–1 and 0.3027 mmol L–1, 43.60 μmol g–1 and 4.055 mmol L–1, respectively. High efficient method based on dummy molecularly imprinted solid phase extraction (DMISPE) coupled with HPLC was established for the selective enrichment of CBZ in river and tap water using MNZ-DMIP as sorbent. DMISPE conditions including sample loading pH/volume, selective washing and elution solvents were carefully optimized. The developed method showed good recoveries (82.3–96.2%) and repeatability (RSDs 0.6–4.9%, n = 5) for samples spiked at three different concentration levels (0.2, 1.0 and 5.0 μg L–1). The detection limit was determined as 0.012 μg L–1. The results demonstrated good potential of this method for sample pretreatment of CBZ in environmental water samples.

A computational and experimental approach to develop minocycline-imprinted hydrogels and determination of their drug delivery performances

In this study, minocycline-imprinted hydrogels are developed for controlled drug delivery in ocular disease treatments. An integrated computational and experimental study are conducted for investigating the relationship between design parameters and the drug loading/release performance of hydrogels. First, suitable functional monomers are determined for successful drug-imprinting by studying pre-polymerization conditions with full-atom molecular dynamics (MD) simulations. MD simulations suggest that acrylic acid and itaconic acid are suitable monomers for imprinting minocycline. Then, minocycline-imprinted hydrogels are synthesized with acrylic acid, commonly used in hydrogels, and three different amounts of cross-linker ethylene glycol dimethacrylate, 1, 2 and 3 mol%. All hydrogels are characterized and their drug loading and release performances are determined. Our computational and experimental calculations indicate an optimum cross-linker amount of 2 mol% for controlled minocycline release from imprinted hydrogels with an imprinting factor of almost 3. Finally, the drug release kinetics are determined by Korsmeyer-Peppas model.

Thin Melamine Imprinted Sol Gel Coating on Silica Beads: Experimental and Statistical Physics Study

In this work, a surface molecular imprinted polymer was developed at the silica surface by the action of ethylene glycol dimethacrylate crosslinking agent with methacrylamide surface grafts. The produced adsorbents were tested for the adsorption of melamine. The adsorption mechanism of melamine was checked by means of adsorption kinetic measurements and inspection of the models governing the adsorption isotherm. The adsorption kinetics followed a pseudo-second order kinetic reaching a maximum adsorption of 2.16 mg g−1. Beside the known binding isotherm models of Langmuir and Freundlich, the adsorption isotherms were also inspected using a statistical physics model based on the energies of binding sites. It appeared that the experimental results were better described by this last approach. The variation in adsorption capacities recorded between low and high concentration ranges was related to the entropy value.

Preparation of Molecularly Imprinted Microspheres as Biomimetic Recognition Material for In Situ Adsorption and Selective Chemiluminescence Determination of Bisphenol A.

Bisphenol A (BPA) is an endocrine disrupter in environments which can induce abnormal differentiation of reproductive organs by interfering with the action of endogenous gonadal steroid hormones. In this work, the bisphenol A (BPA) molecularly-imprinted microspheres (MIMS) were prepared and used as biomimetic recognition material for in situ adsorption and selective chemiluminescence (CL) determination of BPA. Through non-covalent interaction, the BPA-MIMS was successfully prepared by Pickering emulsion polymerization using a BPA template, 4-vinylpyridine (4-VP) monomer, ethylene glycol dimethacrylate (EGDMA) cross-linker, and a SiO2 dispersion agent. The characterization of scanning electron microscopy (SEM) and energy-disperse spectroscopy (EDS) showed that the obtained MIMS possessed a regular spherical shape and narrow diameter distribution (25–30 μm). The binding experiment indicated BPA could be adsorbed in situ on the MIMS-packing cell with an apparent maximum amount Qmax of 677.3 μg g−1. Then BPA could be selectively detected by its sensitive inhibition effect on the CL reaction between luminol and periodate (KIO4), and the inhibition mechanism was discussed to reveal the CL reaction process. The CL intensity was linear to BPA concentrations in two ranges, respectively from 0.5 to 1.5 μg mL−1 with a detection limit of 8.0 ng mL−1 (3σ), and from 1.5 to 15 μg mL−1 with a limit of detection (LOD) of 80 ng mL−1 (3σ). The BPA-MIPMS showed excellent selectivity for BPA adsorption and the proposed CL method has been successfully applied to BPA determination in environmental water samples.

Phosphate barrier on pore-filled cation-exchange membrane for blocking complexing ions in presence of non-complexing ions

In present work, an approach has been used to form a phosphate groups bearing surface barrier on a cation-exchange membrane (CEM). Using optimized conditions, the phosphate bearing monomer bis[2-(methacryloyloxy)ethyl] phosphate has been grafted on the surface of the host poly(ethersulfone) membranes using UV light induced polymerization. The detailed characterizations have shown that less than a micron layer of phosphate barrier is formed without disturbing the original microporous structure of the host membrane. The pores of thus formed membrane have been blocked by cationic-gel formed by in situ UV-initiator induced polymerization of 2-acrylamido-2-methyl-1-propane sulphonic acid along with crosslinker ethylene glycol dimethacrylate in the pores of the membrane. UV-initiator is required for pore-filling as UV light would not penetrate the interior matrix of the membrane. The phosphate functionalized barrier membrane has been examined for permselectivity using a mixture of representative complexing Am3+ ions and non-complexing Cs+ ions. This experiment has demonstrated that complex forming Am3+ ions are blocked by phosphate barrier layer while non-complexing Cs+ ions are allowed to pass through the channels formed by the crosslinked cationic gel.

Biopolymeric nanogel derived from functionalized glycogen towards targeted delivery of 5-fluorouracil

We report the synthesis, characterization and application of a novel biocompatible nanogel (n-Gly/pHEMA) synthesized from glycogen and 2-hydroxyethyl methacrylate using ethylene glycol dimethacrylate crosslinker. Here mesoporous silica has been used as template. The structure of the nanogel has been investigated with the help of FTIR, 1H NMR and 13C NMR spectroscopy. The FESEM, HR-TEM and DLS analyses exhibit that the size of the nanogel is in the range of 10–50 nm. Thermal degradation kinetics suggests the higher stability of the n-Gly/pHEMA nanogel after crosslinking. The gel strength has been assessed by measurement of rheological parameters. The native nanogel shows a good compatibility with MG-63 cell lines. The n-Gly/pHEMA nanogel can effectively load 5-fluorouracil (5-FU) with encapsulation efficiency of ∼60% after 48 h. The intercellular release experiment demonstrates that 5-FU loaded nanogel can efficiently kill the MG-63 cancer cells. In vitro release profile demonstrates controlled release behaviour with higher 5-FU release rate at pH 5.5 compared to pH 7.4.

Silicon nanoparticles coated with an epitope-imprinted polymer for fluorometric determination of cytochrome c.

The authors describe a composite consisting of silicon nanoparticles that were first coated with SiO2 and then with a molecularly imprinted polymer (SiNP@SiO2@MIP). The MIP was generated by dual epitope imprinting such that it can recognize cytochrome c (Cyt c). The MIP on the NPs was prepared from the functional monomer zinc(II) acrylate (ZnA), the crosslinker ethylene glycol dimethacrylate and the initiator 2,2'-azoisobutyronitrile. Dual epitope templates for Cyt c included (a) a C-terminal nonapeptide (AYLKKATNE), and (b) an N-terminal nonapeptide (GDVEKGKKI). The chelation between Zn(II) of ZnA and the amino groups or hydroxy groups of the template nonapeptides warrants good recognition and capture of Cyt c. The fluorescence originating from SiNPs has excitation/emission peaks at 360/480nm and is quenched by Cyt c in the 0.50-40.0μM concentration range. The correlation coefficient for the calibration plot of the imprinted NPs is 0.9937. The detection limit is 0.32 ± 0.01μM, the precisions of six replicate detections at levels of 0.5, 20 and 40μM Cyt c are 3.2, 2.7 and 2.8%, respectively, and the imprinting factor is 2.43. Compared to single epitope template imprinting, dual epitope imprinting results in improved selectivity. The imprinted nanoparticles can discriminate Cyt c even if one amino acid is mismatched. The method was applied to the determination of Cyt c in spiked diluted human serum and gave recoveries between 94.0 and 107.5%. Graphical Abstract A fluorescent material of the architecture silicon nanoparticle@SiO2@molecularly imprinted polymer (SiNP@SiO2@MIP) was fabricated by dual epitope imprinting and a metal-chelating method. The chelation between Zn(II) of the functional monomer zinc(II) acrylate and the amino groups or hydroxy groups of template warrants that the material recognizes and captures cytochrome c well, and this results in fluorescence quenching.

Development and Characterisation of the Imiquimod Poly(2-(2-methoxyethoxy)ethyl Methacrylate) Hydrogel Dressing for Keloid Therapy.

The imiquimod-poly(2-(2-methoxyethoxy)ethyl methacrylate) hydrogel (poly(MEO2MA) hydrogel) dressing was developed for the keloid therapy application. Four groups of the hydrogels, including the imiquimod-poly(MEO2MA) hydrogel, crosslinked with 0.2 mol %, 0.4 mol %, 0.6 mol %, and 0.8 mol % of di(ethylene glycol) dimethacrylate cross-linker (DEGDMA), were synthesised and characterised for fabricating the imiquimod-poly(MEO2MA) hydrogel pad. The lower critical solution temperature (LCST) of the poly(MEO2MA) hydrogel was measured at approximately 28 °C and was used as a trigger to control the imiquimod loading and release. The loaded amounts of the imiquimod in the poly(MEO2MA) hydrogel, crosslinked with 0.2 mol % and 0.8 mol % of DEGDMA, were about 27.4 μg and 14.1 μg per 1 mm3 of the hydrogel, respectively. The imiquimod-release profiles of two samples were characterised in a phosphate buffered saline (PBS) solution at 37 °C and the released imiquimod amount were about 45% and 46% of the total loaded imiquimod. The Cell Counting Kit-8 (CCK-8) assay was utilised to analyse the cell viability of keloid fibroblasts cultured on the samples of imiquimod-poly(MEO2MA) hydrogel, crosslinked with 0.2 mol % and 0.8 mol % of DEGDMA. There was around a 34% decrease of the cell viabilities after 2 days, compared with the pure-poly(MEO2MA) hydrogel samples. Therefore, the developed imiquimod-poly(MEO2MA) hydrogel dressing can affect the proliferation of keloid fibroblasts. It should be possible to utilise the hydrogel dressing for the keloid therapy application.

Investigation of the thermal properties of glycidyl methacrylate\u2013ethylene glycol dimethacrylate copolymeric microspheres modified by Diels\u2013Alder reaction

The study describes the thermal properties of functional microspheres composed of glycidyl methacrylate (GMA) and crosslinking agent ethylene glycol dimethacrylate (EGDMA). Copolymeric poly(GMA-co-EGDMA) microspheres were prepared via suspension–emulsion polymerization in the presence of toluene and decan-1-ol as porogens. In order to introduce functional groups, the porous methacrylate network was modified by epoxy ring opening with the use of sodium cyclopentadienide and then the Diels–Alder addition with maleic anhydride. The thermal properties of poly(GMA-co-EGDMA) materials were evaluated by thermogravimetry and differential scanning calorimetry. By TG/FTIR, it was observed that new functional materials exhibited multi-staged decomposition patterns, different from parent poly(GMA-co-EGDMA) microspheres. The synthesized poly(GMA-co-EGDMA) microspheres exhibited rather high thermal stability in inert atmosphere. Their initial decomposition temperature determined at the temperature of 2% of mass loss was about 210 °C; however, after the chemical modification it was slightly lower. The thermal degradation of parent poly(GMA-co-EGDMA) copolymer runs mainly according to the depolymerization mechanism, while functionalized by cyclopentadienyl group and maleic anhydride microspheres decompose through the chain scission mechanism.

In Situ Silver Nanowire Deposited Cross-Linked Carboxymethyl Cellulose: A Potential Transdermal Anticancer Drug Carrier.

Recently, a novel biopolymeric nanocomposite hydrogel comprised of in situ formed silver nanowires (AgNWs) deposited chemically cross-linked carboxymethyl cellulose (CMC) has been developed, which demonstrates superior efficacy as anticancer drug-curcumin carrier. The cross-linked polymer has been prepared by grafting poly [2-(methacryloyloxy) ethyl trimethylammonium chloride] on CMC using diethylene glycol dimethacrylate cross-linker. The nanocomposite hydrogel has the capability to encapsulate both hydrophobic/hydrophilic transdermal drugs. With variation in reaction conditions/parameters, several composite materials have been synthesized and depending on lower swelling/higher cross-linking and greater gel strength, an optimized grade of nanocomposite hydrogel has been selected. The developed nanocomposite hydrogel is characterized with FTIR/NMR spectra, FESEM/XRD/TGA/AFM/XPS analyses, and UV-visible spectroscopy. Rheological study has been performed to enlighten the gel strength of the composite material. The synthesized nanocomposite hydrogel is biodegradable and nontoxic to mesenchymal stem cells (hMSCs). In vitro release of curcumin suggests that in situ incorporation of AgNWs on cross-linked CMC enhanced the penetration power of nanocomposite hydrogel and released the drug in sustained way (∼62% for curcumin released in 4 days). Ex vivo rat skin permeation study confirms that the drug from both the cross-linked and nanocomposite hydrogel was permeable through the rat skin in controlled fashion. Additionally the curcumin loaded composite hydrogel can efficiently kill the MG 63 cancer cells, which has been confirmed by apoptosis study and therefore, probably be a suitable carrier for curcumin delivery toward cancer cells.

Synthesis, characterization and toxicological evaluation of pH-sensitive polyelectrolyte Nanogels

Nanogels are polymeric nanoparticles that have similar characteristic to hydrogels, but have the size in nano range. The pH-sensitive nanogel have gained much interest in the field of pharmaceutical nanotechnology as they have potential to be used as nanocarriers in drug delivery system. The aim of the present study was to synthesize pH-sensitive polyelectrolyte MMA/IA nanogels using free radical polymerization containing methyl methacrylate (MMA), itaconic acid (IA), and a crosslinker ethylene glycol dimethacrylate (EGDMA). In the synthesis of nanogels four parameters i.e. ethanol/water ratios (v/v), dilution volume using ethanol/water (v/v), crosslinker EGDMA concentration, and monomers MMA/IA ratios were optimized. Their effect on particle size, PdI, zeta potential and swelling ratio were evaluated. The swelling behaviour of the nanogels was studied by measuring swelling ratio using gravimetric method. The optimized nanogels were characterized by proton nuclear magnetic resonance (1H NMR), Fourier transform infrared spectroscopy (FTIR), liquid chromatography/time-of-flight/mass spectrometry (LC-TOF-MS), X-ray powder diffraction (X-RD) and transmission electron microscopy (TEM). Polyelectrolyte characteristic was confirmed by measuring isoelectric point using aqueous electrophoresis. The in-vitro and in-vivo toxicity studies were performed by MTT assays using Caco-2 cells and Limit test using female Sprague Dawly rats, respectively. The nanogels were amorphous in nature, exhibited pH-responsive property and polyelectrolyte characteristics, which showed an isoelectric point at pH 2.78. They had an average particle size <250 nm, narrow size distribution (PdI < 0.3), and negative zeta potential. The in-vitro MTT assays indicated that the nanogels had no sign of cytotoxicity. The in vivo Limit test showed that the LD50 was greater than 2000 mg/kg body weight. The necrospy, histopathology and hematological studies also revealed no sign of toxicity. These findings suggested that the MMA/IA nanogels are pH-sensitive, non-toxic and have potential to form a polyelectrolyte complex with oppositely charged of macromolecular drugs.

Selective separation and determination of glucocorticoids in cosmetics using dual-template magnetic molecularly imprinted polymers and HPLC

Molecularly imprinting polymers (MIPs) are typically prepared using a single template molecule, which allows selective separation and enrichment of only one target analyte. It is not suitable for determination of complex real samples containing multiple analytes. In order to expand the practical application of imprinted polymers, novel dual-template magnetic molecularly imprinted polymers (MMIPs) were synthesized by surface polymerization using hydrocortisone and dexamethasone as the dual-template molecules in this study. The dual-template MMIPs were prepared by copolymerization on the surface of Fe3O4@ SiO2-NH2, the template molecules, the functional monomer acrylamide (AM), the cross-linking agent ethylene glycol dimethacrylate (EGDMA), and the initiator 2,2-azobisisobutyronitrile. The morphology, magnetic properties and adsorption characteristics of the obtained dual-template MMIPs were studied by field emission scanning electron microscopy, dynamic light scattering, Fourier transform infrared spectroscopy, thermal gravimetric analysis, and vibrating sample magnetometry, and re-binding experiments. The results indicated that dual-template MMIPs had uniform particle size, strong magnetic properties, high thermal stability, and good mass transfer rate. To investigate the selectivity of dual-template MMIPs, the template molecules were mixed along with their structural analogs. The dual-template MMIPs revealed a significantly higher adsorption amount for the template molecule than its structure analog. The dual-template MMIPs can be used for the enrichment and determination of hydrocortisone and dexamethasone in cosmetic products with the recoveries of spiked cosmetic samples ranging from 86.8–107.5% and 91.2–104.3%, respectively. The relative standard deviation (RSD) for hydrocortisone was <2.89%, and RSD for dexamethasone was <2.62%.

Preparation of Magnetic Surface-Imprinted Polymer Microspheres with Hydrophilic External Layers for Selective Extraction of Fluoroquinolones from Eggs

A novel method of one-pot covalently grafting a hydrophilic organic polymer imprinted layer on the surface of magnetic microspheres was developed for the preparation of restricted access materials–molecularly imprinted magnetic microspheres (RAM-MIMMs) with water compatibility and ability to exclude biomacromolecules and selectively enrich analytes. The magnetic nanoparticles were coated with silica gel, modified with vinyl groups, polymerized with the template (enrofloxacin), functional monomer (glycidyl methacrylate, methacrylic acid), and cross-linking agent (ethylene glycol dimethacrylate) in chloroform, and then the hydrophilic surface was formed by a ring-opening reaction. The RAM-MIMMs were characterized by transmission electron microscopy, FT-IR spectroscopy, and adsorption experiments and demonstrated average diameters around 400 nm and a coating thickness in the range of 50 nm. They exhibited high selectivity of the imprinted cavities and hydrophilicity of the external surface with water compatibility and exclusion of biomacromolecules. The RAM-MIMMs were used for the magnetic dispersion microextraction of fluoroquinolones from egg samples with satisfactory results.

Synthesis and Study of Guest-Rebinding of MIP Based on MAA Prepared using Theophylline Template

A molecularly imprinted polymer (MIP) based on methacrylic acid (MAA) monomer and theophylline template has been synthesized using a modified bulk polymerization method. Theophylline was employed as a template and it formed a complex with MAA through hydrogen bonding. Self-assembly of template-monomer was followed by cross-linking process using ethylene glycol dimethacrylate (EGDMA) cross-linker. The polymerization process was initiated by thermal decomposition of benzoyl peroxide (BPO) as the initiator at 60oC after cooling treatment at -5oC. After 7 hours, a rigid polymer was obtained and followed by grinding the polymer and removing the template. As a reference, a nonimprinted polymer (NIP) has also been synthesized using similar procedure by excluding the template. FTIR study was carried out to investigate the presence of theophylline in the as- prepared polymer, MIP, and NIP. The spectra indicated that theophylline was successfully incorporated in the as-prepared polymer. This result was also confirmed by EDS analysis showing that N atoms of the as-prepared polymer were derived from amino group of theophylline. Furthermore, the polymer particles of MIP were irregular in shape and size as shown by its SEM image. The capability of guest-rebinding of the MIP was analyzed through Batchwise guest-binding experiment. The results showed that for initial concentration of theophylline in methanol/chloroform (1/1, v/v) of 0.333 mM, the binding capacity of the MIP was 23.22 /mol/g. Compared to the MIP, the adsorption capacity of the NIP was only 3.73 /mol/g. This result shows that MIP has higher affinity than NIP.

하이드록시기를 포함한 아크릴레이트계 모노머들의 하이드로젤 친수성 렌즈 소재로의 응용 및 특성

The hydrophilic ophthalmic lens with addition of 2-hydroxyethyl acrylate (HEA), 2-hydroxyethyl methacrylate (HEMA), hydroxypropyl methacrylate (HPMA) and Ag nanoparticles were manufactured. And also, the cross-linker ethylene glycol dimethacrylate (EGDMA) and the initiator azobisisobutyronitrile (AIBN) were used for polymerization. The polymerization of the hydrogel lens material was conducted through thermal polymerization in 100 C for 1h. The optical and physical characteristics of hydrogel lens were evaluated by measuring water content, refractive index and optical transmittance. The water content of sample containing HEA, HEMA and HPMA was in the average of 82.12%, 37.06% and 21.57%, respectively. And also, refractive index of the sample containing HEA, HEMA and HPMA was in the average of 1.3540, 1.4330 and 1.4649, respectively. In case of the optical properties of the sample, the results showed that the near-UV transmittance was 82.67%, 80.32% and 79.83%, and the visible transmittance was 89.72%, 88.24% and 86.89%, respectively. And also, optical transmittance of the sample containing Ag nanoparticles showed that the near-UV transmittance of 10.59% and visible transmittance of 43.74% were obtained. From the results, the molecular length influenced on the water content and refractive index of the polymerized material.