Ethylene Dimethacrylate Research Articles

Organic Boronate Affinity Sorbent for Capture of cis-Diol Containing Compounds Eman Alzahrani

Boronate affinity chromatography (BAC) is argued to be a critical tool in specific capture and separation of cis-diol containing compounds. In present study, organic boronate affinity monolith poly(3-acrylamido phenylboronic acid-co-ethylene dimethacrylate) (AAPBA-co-EDMA) is prepared through one-step in situ polymerization procedure within a micropipette through the application of a pre-polymerization mixture which contains functional monomer (3-acrylamido phenylboronic acid), cross-linker (ethylene dimethacrylate), porogenic solvent (methanol with poly ethylene glycol) and initiator (2,2-dimethoxy-2-phenyl-acetophenone). Following the optimization of time exposure to UV lamp with 365 nm, the macroporous organic boronate monolith was selected. Several approaches including SEM and BET analysis, FT-IR spectroscopy and measuring contact angle were applied in the characterization of the morphology of the monolith. Several cis-diol compounds that include catechol and galactose are applied in the assessment of the boronate affinity of the organic monolithic material. Additionally, the capture of glucose from urine sample is also conducted. The basic principle of the approach is that boronic acid forms covalent bond with cis-diols in basic solutions whereas the ester bonds are dissociated under acidic media. By using the study results, monolith demonstrate good selectivity towards cis-diol containing compounds. Due to the hydrophilic property of monolith, the affinity chromatography monolith can be performed for several cis-diol compounds including glycoproteins and nucleosides. Also, fabrication of the organic boronate monolithic in microfluidic equipment is essential in facilitating the extraction of boronate affinity using small-volume samples.

One-pot preparation of zwitterionic sulfoalkylbetaine monolith for rapid and efficient separation of lysozyme from egg white

A porous zwitterionic monolithic column was prepared to rapidly and efficiently separate lysozyme from egg white. The monolith was synthesized in a stainless steel HPLC column (5 cm × 4.6 mm i.d.) by in-situ thermal initiated co-polymerization of N,N-dimethyl-N-methacryloxyethyl-N-(3-sulfopropyl) ammonium betaine (MSA) and ethylene dimethacrylate (EDMA). Due to the combination of quaternary ammonium and sulfonic groups on the monolithic matrix in one-pot process, the hydrophobic carbon chain and hydrophilic radical were obtained, which provided multiple driving forces for neutral, basic and acidic analytes, thus mix-mode chromatography mechanism contributed to the retention of different charged proteins. Properties such as composition, morphology and stability of the MSA-co-EDMA monolithic column were characterized by various analytical methods and the results showed that the monolith has large through-pores, good hydrophilicity and permeability. The effects of mobile phase pH and ionic strength on proteins were investigated, drawing the conclusion that the main adsorption and elution mechanism of lysozyme on MSA-co-EDMA monolith was electrostatic interaction, while those of other proteins included hydrophobic, hydrophilic and electrostatic interactions. Therefore, efficient separation of lysozyme and other proteins could be successfully achieved by switching the pH of mobile phase. Lysozyme can be adsorbed using 20 mmol/L phosphate buffer (pH 7.0) and eluted with 20 mmol/L phosphate buffer (pH 2.0). To prove the practicality of the monolithic column, it was also applied in the separation of lysozyme in egg white, which means the work has the potential for further development in proteome analysis of real biological samples.

Preparation of a hydroxypropyl-β-cyclodextrin functionalized monolithic column by one-pot sequential reaction and its application for capillary electrochromatographic enantiomer separation

In this study, a hydroxypropyl-β-cyclodextrin (HP-β-CD) functionalized monolithic capillary column was prepared by one-pot sequential reaction for the first time. The preparation of the HP-β-CD functionalized monolithic column involves two sequential reactions in one pot: (1) the ring opening reaction between HP-β-CD and glycidyl methacrylate (GMA) catalyzed by 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU); (2) the copolymerization of GMA-HP-β-CD, ethylene dimethacrylate (EDMA) and 2-acrylamido-2-methyl propane sulfonic acid (AMPS). A series of monolithic columns were successfully prepared by varying the temperature of the ring opening reaction or several copolymerization parameters (the type and composition of porogenic solvents, ratio of GMA-HP-β-CD to EDMA and polymerization temperature). Then, the morphologies and structures of the resulting monolithic stationary phases were characterized by optical microscopy, scanning electron microscopy (SEM) and nitrogen adsorption analysis. Raman spectroscopy clearly indicated the successful bonding of HP-β-CD onto the monolith. When the prepared chiral stationary phase (CSP) was applied for the separation of a set of racemic compounds by capillary electrochromatography (CEC), including racemic anticholinergic drugs, β-adrenergic drugs, meptazinol and its intermediates, satisfactory separation selectivities were obtained. Additionally, the column also showed excellent separation abilities towards four flavanone glycosides epimers. Furthermore, the prepared monolithic columns exhibited satisfactory stability and reproducibilities of retention time, resolution and column efficiency. These results demonstrated the potential and usefulness of the developed one-pot sequential strategy in the preparation of other derivatized CD functionalized monolithic columns.

NMR spectroscopy for assessing cocaine-functional monomer interactions when preparing molecularly imprinted polymers

Synthesis of molecularly imprinted polymers (MIPs) implies a previous pre-polymerization stage in which the template (the molecule for which the MIP offers the specific recognition cavities) interacts with the adequate functional monomer, just before the addition of the cross-linker and the initiator for performing the polymerization synthesis. The recognition properties, as well as the physical properties of the prepared MIP beads, are dependent on the successful template-monomer interaction during the pre-polymerization stage. Investigations by proton nuclear magnetic resonance (1H NMR) and nuclear overhauser effect (NOE) were performed to study the interactions between the template (cocaine) and the monomers (methacrylic acid and ethylene dimethacrylate). Experimental results were additionally compared to those obtained by in silico studies.

Enhanced solid phase extraction of DNA using hydrophilic monodisperse poly(methacrylic acid-co-ethylene dimethacrylate) microparticles.

The efficiency of solid phase extraction (SPE) of DNA on polymer particles is limited by the features of the applied solid support, such as size, hydrophilicity, and functionality and their application in SPE also requires additional steps and compounds to finally obtain sufficient amount of high-quality DNA. The present study describes a preparation of sub-micrometer monodisperse poly(methacrylic acid-co-ethylene dimethacrylate) (PME) particles by precipitation polymerization. The effect of the ethylene dimethacrylate (EDMA) crosslinker concentration on morphology and particle size, which varied from 730 to 900nm, was investigated. The particles with 5 and 15wt% EDMA were selected for a study of SPE of plasmid DNA under various adsorption and elution conditions, followed by the enzymatic restriction of isolated DNA to verify a quality the nucleic acid. The particles with 15wt% EDMA were suitable for the SPE because they retained better colloidal stability during the adsorption without additional induction of DNA conformational change. The quality of isolated DNA was finally verified by enzymatic restriction by restriction endonuclease EcoRI. Moreover, the developed method using PME particles was successfully utilized for DNA isolation from Escherichia coli lysate.

Preparation of citrinin-selective molecularly imprinted polymer and its use for on-line solid-phase extraction coupled to liquid chromatography.

A new selective molecularly imprinted polymer has been prepared and used for extraction in on-line SPE-HPLC to achieve the selective determination of citrinin. Four different imprinted polymers varying in combinations of components were prepared by bulk polymerization and evaluated in terms of binding capacity and selectivity. Imprinted polymer prepared from a mixture comprising 1-hydoxy-2-naphtoic acid as the template molecule, acrylamide as the structural monomer, ethylene dimethacrylate as the cross-linker (in a molar ratio of 1:4:16), and acetonitrile as the porogenic solvent exhibited the best properties. The selectivity of this sorbent was confirmed by comparison with the non-imprinted counterpart prepared using the same polymerization carried out in the absence of template. Imprinted polymer was packed in a 20 × 3mm i.d. steel cartridge and coupled to the on-line SPE-HPLC system through a six-port switching valve. The method for determination of citrinin including the on-line extraction step was then developed and validated. The sample in the form of methanolic extract was loaded, cleaned, and preconcentrated in the imprinted SPE cartridge. Subsequent separation of citrinin from residual interferences was achieved using the analytical column Kinetex Biphenyl 100 × 4.6mm i.d., 5μm particle size, and fluorescence detection (Ex 335, Em 500nm). The total analysis time was only 9.50min. Our fully validated method was also applied to analysis of food supplements based on red yeast rice extracts, the control of which is implemented in European legislation. Only minor yet acceptable contamination was found in tested samples.

Preparation of macroscopic carbon nanohorn-based monoliths in polypropylene tips by medium internal phase emulsion for the determination of parabens in urine samples

A porous monolithic solid based on single-walled carbon nanohorns dahlia-like structure, produced from a medium internal phase emulsion (MIPE), was prepared in a polypropylene tip using UV energy. Thus, single-walled carbon nanohorns (SWNHs) were added to the organic phase where they polymerized in the presence of a radical initiator. A cross-linker (ethylene dimethacrylate, EDMA) was also used in order to obtain a more robust structure. On the other hand, aqueous phase was the responsible for generating the pores in the final solid being inside the droplets generated by the surfactant (Pluronic L121) used to stabilize the polymerization emulsion. Variables related to the formation of the monolithic phase including the stability and composition of emulsion mixture, size of pores, solvent flow resistance and robustness, were studied in detail. In addition, the potential of the SWNH-monolith as extractant phase was evaluated using parabens as target analytes. The LODs ranged from 1 to 7 μg L−1, while the linear range was extended up to 5000 μg L−1. The reproducibility of the extraction procedure with different batches of emulsions was acceptable with RSD values < 16% and one prepared SWNH-tip can be used for more than 100 times without apparent extraction losses. The microextraction unit yielded an enrichment factor of 20 for all analytes (extraction efficiency of 100%), with recovery values between 80% and 116% in human urine samples.

Allylthiourea functionalized magnetic adsorbent for the extraction of cadmium, copper and lead ions prior to their determination by atomic absorption spectrometry.

A quick and sensitive method was developed for the trace determination of Cd(II), Pb(II) and Cu(II) ions in water and bean samples. It is based on a combination of magnetic solid phase extraction (MSPE) and graphite furnace atomic absorption spectrometry (GFAAS). Allylthiourea (which contains abundant sulfur and nitrogen atoms) was copolymerized with ethylene dimethacrylate on the surface of magnetite (Fe3O4) nanoparticles to prepare a new adsorbent for use in MSPE. Various technologies were used to characterize the morphology, spectroscopic and magnetic properties of the adsorbent, and several parameters that affect the extraction performance were optimized. The adsorbent can enrich Cd(II), Pb(II) and Cu(II) ions via chelation interaction. Following elution with 0.1mol·L-1 HNO3, the ions were quantified by GFAAS. Under the most favorable conditions, the limits of detection are from 3.3-7.2 ng·L-1 for water samples,and 1.1-1.5μg·kg-1for beans. The method displays wide linear analytical ranges and good precision. It was successfully applied to the determination of the metal ions in water and bean samples. The recoveries from spiked samples ranged between 80.5 and 114% in water, andfrom 82.2 to 118% in bean samples. The relative standard deviations of reproducibility were < 10%. Graphical abstract Schematic presentation of the magetic solid phase extraction (MSPE) for the analysis of Cd(II), Pb(II) and Cu(II). MNP: magnetic nanoparticles; ATED: allylthiourea ethylene dimethacrylate copolymer.

Synthesis of zirconia, organic and hybrid nanofibers for reinforcement of polymethyl methacrylate denture base: evaluation of flexural strength and modulus, fracture toughness and impact strength

Objective The objective of this study was to synthesize and characterize inorganic zirconium oxide (ZrO2), organic [bisphenol A diglycidyl ether dimethacrylate (Bis-GMA)+triethylene glycol dimethacrylate (TEGDMA)+polyethylene glycol dimethacrylate (PEGDMA)] and hybrid (ZrO2+ Bis-GMA + TEGDMA) nanofibers and the use of these nanofibers for improving flexural strength (FS) and flexural modulus (FM), fracture toughness (FT) and impact strength (IS) of polymethyl methacrylate (PMMA) resin. Materials and methods Inorganic, organic and hybrid nanofibers were synthesized by wet electrospinning technique. The study was divided into four groups according to the type of added nanofibers (6%) to the heat-curing PMMA denture base resin; control group: PMMA without nanofibers, inorganic group: PMMA with silanized ZrO2 nanofibers, organic group: PMMA with Bis-GMA/TEGDMA/PEGDMA nanofibers and hybrid group: PMMA with ZrO2/Bis-GMA/TEGDMA nanofibers. According to ISO FDIS 20795-1:2013, three-point bending test was used to measure FS, FM and FT for each group (n = 10). According to ISO 197-A1: 2005, impact tester was used to measure IS for each group (n = 10). One-way analysis of variance was used for statistical significance between groups and post-hoc (Tukey's test) was used for multiple comparisons. P value less than or equal to 0.01 was considered significantly different. Results The synthesized pure forms of three types of nanofibers were characterized by scanning electron microscope and Fourier transform infrared spectroscopy. Nanofibers-reinforced groups (ZrO2, hybrid and organic, respectively) recorded high means % than that of the control group as follows: 205, 184 and 170% for FS (MPa), 184, 149 and 120% for FM (GPa), 210, 189 and 177% for FT (MPa m1/2) and 151, 180 and 176% for IS (KJ/m2). In each of the four tested mechanical properties, one-way analysis of variance revealed a significant differences between the studied groups (P = 0.000) and post-hoc (Tukey's test) revealed that nanofibers-reinforced groups were markedly significantly higher than control group (P = 0.000). Conclusion ZrO2, Bis-GMA/TEGDMA/PTEGDMA and ZrO2/Bis-GM/TEGDMA hybrid nanofibers synthesized by electrospinning technique improved significantly FS, FM, FT and IS of PMMA resin (P = 000).

Melamine detection in liquid milk based on selective porous polymer monolith mediated with gold nanospheres by using surface enhanced Raman scattering.

A rapid and fast detection of trace amounts of melamine in milk is reported by using Gold Nano Spheres embedded monolith conjugates. Monolith was synthesized by the polymerization of Glycidyl Methacrylate (GMA) and Ethylene Dimethacrylate(EDMA) (cross linker and functional monomer), Cyclohexanol (Porogen formation) and 2, 2-Dimethoxy-2-phenyl-acetophenone (photo-initiator) on gold coated silicon wafer. In order to gauge the influence of monolith on SERS signal activity, three shapes of gold nanoparticles namely Gold Nano Spheres (GNSs), Gold Nanorods (GNRs) and Triangular Gold Nanoprisms (GNPrs) were immobilized on monolithic surface and analyzed by the signal molecule Rhodamine (R6G). The Raman Enhancement efficiency of the above three shapes incorporated with monolith was monitored by calculating their maximum enhancement factors. Among three morphologies, Gold Nano Spheres integrated in GMA-EDMA Monolith Sensor (GNS@GEMS) was found more effective for detection of R6G than two others and was therefore projected in analysis of melamine sensing in commercial milk. A linear relationship of regression model (R2 = 0.99) was observed between melamine SERS intensity (at 710 cm-1) and varied concentrations (6.5 < mg/L < 0.125). The lower limit of detection (LOD) and limit of quantification (LOQ) for melamine was determined 0.11 mg/L and 0.38 mg/L respectively. The time window for detection of melamine was 10 min and hence our method is compatible with the FDA's tolerance limit in USA and China (1 mg/L).

In situ synthesis of a monolithic material with multi-sized pores and its chromatographic properties for the separation of intact proteins from human plasma

The fabrication of a monolithic allyl phenoxyacetate-based material was proposed via the in situ radical polymerization using ethylene dimethacrylate as the crosslinker and 2,2′-azobisisobutyronitrile as the initiator within a stainless steel column (50 mm × 4.6 mm i.d.). The effects of the porogen composition, the crosslinker amount and the monomer type on the resulting monoliths were investigated. The morphology of the monoliths was characterized using scanning electron microscopy and a nitrogen adsorption-desorption instrument, and the pore structure was characterized using mercury intrusion porosimetry. The results indicate that the optimized monolith has a micro-, meso- and macro- multi-sized pore structure with a high specific surface area of 260.66 m2 g−1. The resulting monoliths were used as stationary phases for the separation of proteins from bio-samples, including a mixture of six standard proteins, chicken egg whites, snailase and human plasma, using high-performance liquid chromatography. Compared to optimized glycidyl methacrylate-based and styrene-based monolithic columns, the allyl phenoxyacetate-based monolithic column exhibited improved selectivity in the separation of proteins. Furthermore, the present method avoids the masking of highly abundant proteins, such as human serum albumin, immunoglobulin G and human fibrinogen, in the detection of middle- or low-abundance proteins in human plasma. The protein identification results obtained from liquid chromatography/mass spectrometry indicate that the present method is an outstanding method for efficient fractionation of human plasma, which will be especially useful in future plasma proteomics research.

Monolithic thin-layer chromatography plates with covalently bonded matrix for hyphenation with matrix-assisted laser desorption/ionization.

Monolithic layers prepared by the copolymerization of ethylene dimethacrylate and glycidyl methacrylate and deposited onto the surface of glass and silicon plates were investigated as thin-layer chromatography separation media in hyphenated thin-layer chromatography with matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) analysis. Varying composition of the polymerization mixture and polymerization conditions layers of different porosities and MALDI-MS compatibility were synthesized. Compatibility with MALDI-MS was tested using polyethylene glycol and it was demonstrated that layers prepared without glycidyl methacrylate are not compatible with MALDI-MS and do not allow obtaining any mass spectra. Best results were achieved with layers containing 19 to 29% glycidyl methacrylate. These layers allow the measurement of mass spectra without additional depositing matrix compounds supplying mass spectra almost "clean" in low molar mass range.

Monolithic column with polymeric deep eutectic solvent as stationary phase for capillary electrochromatography

A novel monolithic column based on the copolymerization of ethylene dimethacrylate and a deep eutectic solvent (DES), which composed of chlorocholine chloride and itaconic acid, was developed for capillary electrochromatography (CEC). The structure and morphology of the obtained monolithic column was characterized by Fourier transform infrared spectra and scanning electron microscopy, which showed a porous monolithic structure with good permeability. The influence of pH value and acetonitrile content on electroosmotic flow (EOF) of DES-based monolithic column was investigated. The DES-based monolithic column was used as the separation column of CEC and exhibited excellent performance for the separation of neutral compounds, phenols, toluidines, nucleosides, nucleotide bases and alkaloids. The retention mechanism might be attributed to synergistic effect of hydrophobic interaction, hydrogen bond interaction and electronic interaction. The DES-based monolithic column showed good repeatability with relative standard deviations of migration time less than 0.80%, 2.15%, 4.26% and 3.08% for intra-day, inter-day, column-to-column and batch-to-batch, respectively. Thus, organic polymer monolithic columns with DESs as functional monomers are a promising option in chromatographic separation.

Biological and Mechanical Evaluation of Novel Prototype Dental Composites

The breakdown of the polymeric component of contemporary composite dental restorative materials compromises their longevity, while leachable compounds from these materials have cellular consequences. Thus, a new generation of composite materials needed to be designed to have a longer service life and ensure that any leachable compounds are not harmful to appropriate cell lines. To accomplish this, we have developed concurrent thiol-ene-based polymerization and allyl sulfide–based addition-fragmentation chain transfer chemistries to afford cross-linked polymeric resins that demonstrate low shrinkage and low shrinkage stress. In the past, the filler used in dental composites mainly consisted of glass, which is biologically inert. In several of our prototype composites, we introduced fluorapatite (FA) crystals, which resemble enamel crystals and are bioactive. These novel prototype composites were benchmarked against similarly filled methacrylate-based bisphenol A diglycidyl ether dimethacrylate / triethylene glycol dimethacrylate (bisGMA/TEGDMA) composite for their cytotoxicity, mechanical properties, biofilm formation, and fluoride release. The leachables at pH 7 from all the composites were nontoxic to dental pulp stem cells. There was a trend toward an increase in total toughness of the glass-only-filled prototype composites as compared with the similarly filled bisGMA/TEGDMA composite. Other mechanical properties of the glass-only-filled prototype composites were comparable to the similarly filled bisGMA/TEGDMA composite. Incorporation of the FA reduced the mechanical properties of the prototype and bisGMA/TEGDMA composite. Biofilm mass and colony-forming units per milliliter were reduced on the glass-only-filled prototype composites as compared with the glass-only-filled bisGMA/TEGDMA composite and were significantly reduced by the addition of FA to all composites. Fluoride release at pH 7 was greatest after 24 h for the bisGMA/TEGDMA glass + FA composite as compared with the similarly filled prototypes, but overall the F- release was marginal and not at a concentration to affect bacterial metabolism.

Molecular dynamics simulations on self-healing behavior of photo-polymerization network

Recently, a variety of reversible chemical bonds are incorporated into thermoset polymers to design stimuli-responsive materials. Light-triggered dynamic network is advantageous since it is simple, inexpensive and easy controlled. In this paper, the dynamic photo-responsive network structure with labile bonds and free ethylene dimethacrylate (EGDMA) molecules was constructed. Under the stimulus of UV light, the labile bonds homolytically cleaved and the network was separated into small sections. Then the EGDMA monomers linked these small sections together to form a new network with higher crosslink density. Such depolymerization and polymerization processes would result in the self-healing of materials. Therefore, molecular dynamics method was applied to simulate the interface self-healing process of this polyurethane material under light stimulation condition. The mechanical properties of the healed networks under uniaxial tension were examined. The results showed that self-healing occurs at the interface of materials due to the polymerization, and the mechanical properties of the healed materials are strengthened when compared to that of the fresh samples. Moreover, the effect of crosslinking agent on the self-healing was investigated. The best mechanical properties of healed sample are obtained when the crosslinking agent reacts exactly with the polyurethane network.

Enhancement of Electrical Conductivity and Tensile Properties of Conductive Poly(vinyl Chloride)/Poly(ethylene Oxide)/Polyaniline Conductive Composite Films: Effect of Polyaniline Loading and Ethylene Dimethacrylate

Enhancement of Electrical Conductivity and Tensile Properties of Conductive Poly(vinyl Chloride)/Poly(ethylene Oxide)/Polyaniline Conductive Composite Films: Effect of Polyaniline Loading and Ethylene Dimethacrylate

"Single-pot" approach towards the preparation of alkyl and polyfluoroalkyl organo-silica monolithic capillaries for reversed-phase liquid chromatography.

Organo-silica monolithic capillary columns were prepared using thermally initiated polymerization of mixtures containing 3-(methacryloyloxy)propyltrimethoxysilane as the silicon-containing monomer, an aqueous acid catalyst, ethylene dimethacrylate as the cross-linker, a functional monomer selected from the group comprising octadecyl methacrylate, trifluoroethyl methacrylate, pentafluoropropyl methacrylate, and heptadecafluorodecyl methacrylate, toluene as the porogen, and 2,2'-azobisisobutyronitrile as the initiator. The permeability of the monoliths was controlled by varying the composition of the polymerization mixture. Chromatographic properties of resulting monolithic 100μm i.d. capillaries were evaluated utilizing four sets of probe compounds under isocratic elution conditions in the reversed-phase mode. Baseline separation of alkylbenzenes and the best steric selectivity were achieved using the octadecyl methacrylate monolithic column verifying that its surface was the most hydrophobic. In contrast, separation of a mixture containing polar compounds was observed using columns prepared in the absence of the functional monomer due to the presence of residual surface silanols at the pore surface. Polyfluoroalkyl stationary phases, especially those with a high number of fluorine atoms, exhibited the highest selectivity towards fluorine-containing analytes.

Chiral separation and determination of amino acid enantiomers in fruit juice by open-tubular nano liquid chromatography.

A novel chiral porous-layer stationary phase was developed for use in open-tubular nano liquid chromatography. The stationary phase was prepared by an in-situ polymerization of 3-chloro-2-hydroxypropylmethacrylate (HPMA-Cl) and ethylene dimethacrylate (EDMA). The reactive chloro groups at the surface of the porous stationary phase were reacted with β-Cyclodextrin (β-CD). The resulting morphology was characterized by using scanning electron microscopy (SEM) and Fourier-transform infrared spectroscopy (FT-IR). The chromatographic performance of the column was evaluated by hydrophilic interaction chromatography (HILIC). Amino acids were used as test solutes. The running buffer conditions for the enantioseparation were found to be 85% acetonitrile (ACN):10%MeOH: 5% H2 O at 0.1% v/v trifluoro acetic acid (TFA) (flow rate: 800nL/min). The enantioseparation provided high theoretical plate numbers up to 26000 platesm-1 . A good retention capacity within satisfactory retention times was also achieved. Real sample applicability of this column to the separation of amino acid enantiomers in fruit juice sample was demonstrated.

Poly[(2-(acryloyloxy) ethyl]trimethylammonium chloride-co-ethylene dimethacrylate monolith on-line solid-phase extraction coupled with liquid chromatography and tandem mass spectrometry for the fast determination of salicylic acid in foodstuffs.

We report the fabrication of an anion-exchange monolithic column in a stainless-steel chromatographic column (10mm×2.1mm i.d.) using [2-(acryloyloxy) ethyl]trimethylammonium chloride as the monomer and ethylene dimethacrylate as the crosslinker. The prepared monolith was developed as the adsorbent for the on-line solid-phase extraction of salicylic acid in various animal-origin foodstuffs combined with liquid chromatography and tandem mass spectrometry. The monolith was characterized by using Fourier transform infrared spectroscopy, scanning electron microscopy, nitrogen adsorption analysis, and elemental analysis. Potential factors affecting the on-line solid-phase extraction and liquid chromatography with tandem mass spectrometry analysis were studied in detail. Under the optimized conditions, the total analysis time including cleanup and liquid chromatography with tandem mass spectrometry separation was 17min. The developed method gave the linear range of 15-750μg/kg, detection limits (S/N=3) of 5μg/kg, and quantification limits (S/N=10) of 15μg/kg. The recoveries obtained by spiking 10, 20, and 100μg/kg of salicylic acid in the animal-origin food samples were in the range of 85.2-98.4%. In addition, the monolith was stable enough for 550 extraction cycles with the precision of peak area ≤11.6%.

Controlled grafting of molecularly imprinted films on gold microelectrodes using a self-assembled thiol iniferter

Herein, a straightforward approach for the controlled coating of gold microelectrodes with molecularly imprinted polymer (MIP) thin films is presented. To this end, a new iniferter has been synthesised, 3-mercaptopropyl diethylcarbamodithioate, which contains terminal thiol groups capable of forming self-assembled monolayers (SAM) on gold substrates. The iniferter SAM was activated under UV radiation after the immersion of the microelectrode in the polymerisation solution, containing 4-ethylphenol (4EP) as template and 4-vinylpyridine and ethylene dimethacrylate as functional monomer and cross-linker respectively. The voltammetric behaviour of the resulting MIP-coated microsensor was assessed next, finding that electrochemical response was linear to the concentration of the target analyte (4EP) in a range comprised between 10−6 and 10−3 mol L−1, showing a sensitivity of 1.02 ± 0.02 (nA L μmol−1) (R2: 0.9983). Measurement repeatability was also evaluated performing a series of measurements with the same sensor at two concentrations levels of 4EP, 5 × 10−6 mol L−1 and 10−4 mol L−1, obtaining relative standard deviations (RSD) of 3.41% and 1.92% respectively. Similarly, sensor-to-sensor repeatability was also determined obtaining RSD values of 10.02% and 16.97% respectively. Sensor selectivity was finally studied comparing the peak current intensity of 4EP with current intensities registered with structural analogues. It was found that sensor was capable of discriminating the target compound from structural analogues presenting remarkable selectivity, even for almost identical compounds such as 4-vinylphenol.