Trimethylolpropane Trimethacrylate Research Articles

Porous Copolymers of 3-(Trimethoxysilyl)propyl Methacrylate with Trimethylpropane Trimethacrylate Preparation: Structural Characterization and Thermal Degradation

Porous polymeric microspheres are among the most effective adsorbents. They can be synthesized from numerous monomers using different kinds of polymerization techniques with a broad selection of synthesis factors. The main goal of this study was to prepare copolymeric microspheres and establish the relationship between copolymerization parameters and the porosity and thermal stability of the newly synthesized materials. Porous microspheres were obtained via heterogenous radical copolymerization using 3-(trimethoxysilyl)propyl methacrylate (TMPSM) as functional monomers and trimethylolpropane trimethacrylate (TRIM) as the crosslinker. In the course of the copolymerization, toluene or chlorobenzene was used as the pore-forming diluent. Consequently, highly porous microspheres were produced. Their specific surface area was established by a nitrogen adsorption/desorption method and it was in the range of 382 m2/g to 457 m2/g for toluene and 357–500 m2/g in the case of chlorobenzene. The thermal degradation process was monitored by thermogravimetry and differential scanning calorimetry methods in inert and oxidative conditions. The copolymers were stable up to 269–283 °C in a helium atmosphere, whereas in synthetic air the range was 266–298 °C, as determined by the temperature of 5% mass loss. Thermal stability of the investigated copolymers increased along with an increasing TMPSM amount in the copolymerization mixture. In addition, the poly(TMSPM-co-TRIM) copolymers were effectively used as the stationary phase in GC analyses.

Removal of polyphenols from anthocyanin-rich extracts using 4-vinylpyridine crosslinked copolymers

In this work, new sorbents for the purification of anthocyanin-rich extracts were evaluated. Copolymers of 4-vinylpyridine crosslinked with trimethylolpropane trimethacrylate (poly(4VP-co-TRIM)) or 1,4-dimethacryloyloxybenzene (poly(4VP-co-14DMB)) were tested for their potential to capture polyphenols. Copolymers were obtained by seed swelling polymerization in the form of microspheres with permanent porous structure – attractive features of sorbents used for sample purification by dispersive solid phase extraction. The microspheres were characterized by AFM, elemental analysis, SEM, and nitrogen adsorption-desorption method. Their capacity to remove polyphenols was evaluated using spectrophotometry, HPLC-DAD, and LC-MS/MS. For proof-of-concept, the aqueous extracts of berries classified into three different groups regarding their anthocyanin composition (strawberries, raspberries, blackcurrants) were selected. It was found that studied microspheres adsorbed flavonoids more effectively compared to primary secondary amine and graphitized carbon black. Copolymers of 4-vinylpyridine also capture anthocyanins and might be used for the purification of extracts of fruits before LC-MS/MS analysis to reduce the matrix effect.

4-Vinylpyridine copolymers for improved LC–MS tryptophan and kynurenine determination in human serum

Tryptophan (an essential amino acid) and its clinically important metabolite—kynurenine contribute to several fundamental biological processes and methods that allow their determination in biological samples are in demand. The novelty of the work was a demonstration of the utility of two polymers: 4-vinylpyridine crosslinked with trimethylolpropane trimethacrylate (poly(4VP-co-TRIM)) or 1,4-dimethacryloyloxybenzene (poly(4VP-co-14DMB))—in terms of human serum clean-up for simultaneous LC–MS determination of tryptophan and kynurenine. The goal was to achieve a reduction of the matrix effect, which is responsible for signal suppression, with minimal capture of analytes. The adsorption properties of the polymeric beads were studied by evaluating the adsorption kinetics and isotherms in model matrices. Therefore, the adsorption capacities of both molecules were not efficient, the tested 4-vinylpyridine-based copolymers have shown great promise (especially poly(4VP-co-TRIM)) as sorbents for serum clean-up. In the model human serum matrix, poly(4VP-co-TRIM) provided good recoveries of tryptophan and kynurenine (76% and 87%, respectively) and allowed for the reduction of the matrix effect. Performances of both copolymers were compared to those of commercially available sorbents (octadecylsilane, activated charcoal, and primary secondary amine).

Chromoionophoric molecular probe infused bimodal porous polymer rostrum as solid-state ocular sensor for the selective and expeditious optical sensing of ultra-trace toxic mercury ions

This study presents a distinctive solid-state naked-eye colorimetric sensing approach by encapsulating a chromoionophoric probe onto a hybrid macro-/meso-pore polymer scaffold for fast and selective sensing of ultra-trace Hg(II). The customized structural/surface properties of the poly(VPy-co-TM) monolith are attained by specific proportions of 2-vinylpyridine (VPy), trimethylolpropane trimethacrylate (TM), and pore-tuning solvents. The interconnected porous network of poly(VPy-co-TM), inherent superior surface area and porosity, is captivating for the homogeneous/voluminous incorporation of probe molecules, i.e., 7-((4-methoxyphenyl)diazenyl)quinoline-8-ol (MPDQ), for the target-specific colorimetric detection. The structural morphology, surface topography, and phase characteristics of the bare poly(VPy-co-TM) monolith and MPDQ@poly(VPy-co-TM) sensor are examined using HR-TEM-SAED (High-Resolution Transmission Electron Microscopy - Selected Area Electron Diffraction), FE-SEM-EDAX (Field Emission Scanning Electron Microscopy - Energy Dispersive X-ray Spectroscopy), XPS (X-ray Photoelectron Spectroscopy), p-XRD (Powder X-Ray Diffraction), FT-IR (Fourier Transform Infrared Spectroscopy), UV-Vis-DRS (Ultraviolet-Visible Diffuse Reflectance Spectroscopy), and BET/BJH (Brunauer-Emmett-Teller / Barrett-Joyner-Halenda) analysis. The distinctive properties of the sensor reveal a constrained geometrical orientation of the MPDQ probe onto the long-range continuous monolithic network of meso-/-macropore template, enabling selective interaction with Hg(II) with peculiar color transfiguration from pale yellow to deep brown. The sensor demonstrates a linear spectral-color alliance in the 0–200 ppb concentration range for Hg(II), with quantification and detection limits of 0.63 and 0.19 ppb. The sensor efficacy is verified using certified contaminated water and tobacco samples, with excellent reusability, reliability, and reproducibility of ≥ 99.23 % (RSD ≤1.89 %) and ≥ 99.19 % (RSD ≤1.94 %) of Hg(II), respectively.

Implementing magnetic molecularly imprinted solid phase extraction to analytical method for determination of 2-phenethylamine in cocoa powder and chocolate by LC-MS/MS system

The main aim of this study was to design, develop, and apply magnetic molecularly imprinted polymer (MMIP) during sample pretreatment before liquid chromatography tandem mass spectrometry (LC-MS/MS) 2-phenylethylamine determination in cocoa powder and chocolate samples. The morphology and structure of MMIP, obtained from methacrylic acid (monomer) and trimethylolpropane trimethacrylate (cross-linker) were characterized using scanning electron microscopy, nitrogen sorption analyses, infra-red spectroscopy, X-ray diffraction measurements, vibrating-sample magnetometry, and thermogravimetry analyses. The analyte adsorption mechanism on MMIP was studied using computational simulation. The magnetic solid phase extraction procedure on MMIP was optimized, resulting in a relative matrix effect of 6.2 % for cocoa powder and 2.8 % for chocolate. The LC-MS/MS quantified the 2-phenethylamine in eighteen cocoa powder and chocolate samples, showing a concentration range between 2.4 and 8.7 μg g−1.

Sensitive and specific detection of Listeria monocytogenes in food samples using imprinted upconversion fluorescence probe prepared by emulsion polymerization method

Listeria monocytogenes (L. monocytogenes) is a foodborne pathogen with high morbidity and mortality rates, necessitating rapid detection methods. Current techniques, while reliable, are labor-intensive and not amenable to on-site testing. We report the design and synthesis of a novel imprinted upconversion fluorescence probe through Pickering emulsion polymerization for the specific detection of L. monocytogenes. The probe employs trimethylolpropane trimethacrylate and divinylbenzene as cross-linkers, acryloyl-modified chitosan as a functional monomer, and the bacterium itself as the template. The developed probe demonstrated high specificity and sensitivity in detecting L. monocytogenes, with a limit of detection of 72 CFU/mL. It effectively identified the pathogen in contaminated salmon and chicken samples, with minimal background interference. The integration of molecular imprinting and upconversion fluorescence materials presents a potent and reliable approach for the rapid and specific detection of L. monocytogenes, offering considerable potential for on-site food safety testing.

Sulfur as an effective sensitizer for natural rubber vulcanized via electron beam irradiation

AbstractA sensitizer or crosslinking promoter must be utilized to improve electron beam irradiation (EBI) vulcanization and achieve optimal results. This work investigated the effect of sensitizers, that is, sulfur and trimethylolpropane trimethacrylate (TMPT), on the properties of EBI‐vulcanized natural rubber (NR). The experiments focused on analyzing the effect of different amounts of sensitizers, that is, 2 and 3 phr, on the swelling, crosslink density, entanglement, and mechanical properties of NR latex. A sample without sensitizers was taken as a reference. Results revealed that the crosslink density of the samples with sensitizers had improved compared with that of the sample without a sensitizer. The sample with sulfur exhibited higher crosslink density than the NR with TMPT. The sulfur‐containing NR exhibited superior mechanical properties, i.e., modulus, tensile strength, and tear strength, as its crosslink density increased. In addition, increasing the sulfur content reduced the crosslink density of the NR latex, resulting in inferior mechanical properties. Furthermore, the different forms, that is, latex and film, of NR were compared. The latex form revealed higher crosslink density than the film form, thus presenting high mechanical properties because it contained water, which could induce the formation of free radical species and enhance crosslinking.

Synthesis and characterization of magnetic molecularly imprinted polymers for the rapid and selective determination of clofazimine in blood plasma samples

Clofazimine (CLF) is a riminophenazine derivative and a new therapeutic option with high efficacy for patients with rifampicin-resistant tuberculosis (TB). The blood levels of CLF are low and suboptimal, so therapeutic drug monitoring is required. Prior to this study, there were no molecular imprinting–based solid phase extraction (SPE) sorbents that could be used to determine the blood CLF levels. Hence, we prepared a magnetic molecularly imprinted polymer (MMIPs) to capture CLF. We employed computational selection of a functional monomer and crosslinker and confirmed these selections based on the association constant (Ka) and a Job plot. We synthesised MMIPs with two surface modifiers and characterized the polymers. Our computational analysis based on the bond energy revealed that methyl methacrylate (MMA) was the most suitable functional monomer at a CLF-to-MMA molar ratio of 1:4. Based on the bond energy, the most suitable crosslinker was trimethylolpropane trimethacrylate (TRIM) at a CLF-to-TRIM molar ratio of 1:1. We determined the Ka of MMA and TRIM in different solvents. Isopropanol produced the highest Ka. The Job plot showed that a template-to-MMA-to-TRIM molar ratio of 1:4:20 was optimal to synthesize imprinted polymer in isopropanol. We prepared MMIPs using two different modifiers, namely aminopropyltrimethoxysilane (APTES) and oleic acid (OA), using the ratio determined from the Job plot. Physical characteristic tests carried out using FT-IR, SEM-EDS, PSA, BET and VSM, showed that the synthesis was success with a spherical and uniform agglomeration of particles, also a flat surface with many holes with a particle size of MMIP-APTES and MMIP-OA respectively 0.14 μm and 0.28 μm, showed a surface area for MMIP-APTES is 2874.51 m2/g and MMIP-OA 2913.07 m2/g, exhibiting superparamagnetic properties with a saturation magnetization value of MMIP-APTES 21.1 emu/g−1 and MMIP-OA 49.9 emu/g−1. Adsorption capacity result showed that MMIP-OA fits well with the Langmuir model, while MMIP-APTES fits better with the Freundlich. Application of MMIP-SPE (Magnetic Molecular Imprinted Polymer-Solid Phase Extraction) APTES resulted 92.3 ± 6.1 % and MMIP-SPE-OA 51.5 ± 8.1 % for recovering CLF in blood. The result of selectivity test also showed that MMIP-SPE-APTES is better than MMIP-SPE-OA and selectively recover CLF from human blood plasma existed together with other TB-Drugs. The study result shows that MMIPs with APTES modification can be used for CLF determination in human blood plasma.

Influence of the Polymerization Parameters on the Porosity and Thermal Stability of Polymeric Monoliths.

Rigid porous polymeric monoliths are robust, highly efficient, versatile stationary phases. They offer simple preparation and convenient modification provided by a whole range of synthesis factors, e.g., starting monomers, cross-linkers, initiators, porogens, polymerization techniques, and temperature. The main aim of this study was to synthesize polymeric monoliths and determine the correlation between polymerization parameters and the porosity and thermal stability of the obtained materials. Polymeric monoliths were synthesized directly in HPLC columns using N-vinyl-2-pyrrolidone (NVP) and 4-vinylpiridine (4VP) as functional monomers, with trimethylolpropane trimethacrylate (TRIM) serving as the cross-linking monomer. During copolymerization a mixture of cyclohexanol/decane-1-ol was used as the pore-forming diluent. Polymerization was carried out at two different temperatures: 55 and 75 °C. As a result, monoliths with highly developed internal structure were synthesized. The value of their specific surface area was in the range of 92 m2/g to 598 m2/g, depending on the monomer composition and polymerization temperature. Thermal properties of the obtained materials were investigated by means of thermogravimetry (TG). Significant differences in thermal behavior were noticed between monoliths synthesized at 55 and 75 °C. Additionally, the poly(NVP-co-TRIM) monolith was successfully applied in GC analyses.

Thermal Characterization of Crosslinked Polymeric Microspheres Bearing Thiol Groups Studied by TG/FTIR/DSC under Non-Oxidative Conditions.

This paper presents the thermal behavior of polymer microspheres based on glycidyl methacrylate (GMA) and crosslinking agents benzene-1,4-diylbis(2-methylprop-2-enoate) (1,4DMB) and trimethylolpropane trimethacrylate (TRIM) before and after functionalization with thioglycolic acid (TGA). The thermal stability of the polymers was determined using thermogravimetric analysis and differential scanning calorimetry under non-oxidizing conditions. The evolved gases were detected by FTIR and NMR spectroscopy, and the chemical structure of solid residues after preheating was assessed by FTIR/ATR spectroscopy. The post-functionalized microspheres showed higher thermal stability (within 270-290 °C) than the initial copolymers (within 240-250 °C). In this paper, examples of decomposition patterns of polymer microspheres before and after functionalization are presented. The decomposition of the initial microspheres starts with the emission of GMA monomers, acrolein, carbon dioxide, and the formation of unsaturated bonds in the solid residue. In the case of functionalized microspheres, degradation involves the transesterification of ester groups with the -SH groups, resulting in the emission of carbonyl sulfide, acrolein and carbon dioxide. Furthermore, lactone groups are created in the solid residue. The degradation of the functionalized copolymers is a complex process due to their crosslinked structure, rendering the identification of all the degradation products unattainable.

Imprinting-based smart syringe: A fast, efficient, and selective approach for extraction of methyl gallate from Caesalpinia pulcherrima extract

A simple, facile, quick, highly selective, and efficient extraction protocol for a medicinal compound methyl gallate (MG) is developed for the first time using molecularly imprinted-based solid phase extraction (MISPE). Density functional theory (DFT) was employed to calculate the binding energies of the complex of MG with the functional monomer in the gas and in the implicit solvent to evaluate the best combination of the functional monomer, crosslinker, and porogen for MG. Decisively, the synthesis of a molecularly imprinted polymer (MIP) and its respective non-imprinted polymer (NIP) was conducted using methacrylamide (MAAm) as a functional monomer, trimethylolpropane trimethacrylate (TRIM) as a crosslinker, and methanol as a porogen. The polymers were characterized by SEM, FT-IR, BET, and TGA, while the adsorption properties of MG-MIP/NIP were evaluated by batch rebinding experiments. Theoretical modeling was done by Langmuir, Freundlich, Scatchard analysis, LF-isotherm, and kinetic models. The MG-MIP appeared to have a higher binding capacity towards MG compared to the corresponding NIP: 57.6 mg/g compared to only 17.6 mg/g rendering an imprinting factor 3.3. Moreover, in competitive recognition studies, the synthesized MG-MIP showed good selectivity towards MG compared to its structural analogs, confirming the presence of MG-specific imprinting sites. In competitive recognition tests and real-sample analysis, HPLC was used to determine the concentration of MG and the analogous compounds. Furthermore, the volume and elution times of the washing solvent (DI water) and elution solvent (acetonitrile) were optimized. Finally, MG-MISPE frits were successfully designed for selective enrichment of MG from Caesalpinia pulcherrima methanolic extract using a syringe, PTFE membrane, and MG-MIPs. Hence, MG-MISPE is a promising alternative of traditional extraction methods for selective extraction and enrichment of MG from complex plant matrices. The approach has potential to be applied to any compound of interest.

Non-chromatographic speciation analysis of antimony in water samples assisted by vinylimidazole-based polymeric sorbent

A functional polymeric material was synthesized via precipitation copolymerization of vinylimidazole and trimethylolpropane trimethacrylate and used as а sorbent for selective separation and determination of Sb(V) and Sb(III). The extraction efficiency of the newly synthesized material toward Sb(III) and Sb(V) was studied in batch mode. In weakly acidic aqueous solutions, at pH 5 – 6, Sb(V) was entirely retained on the polymeric sorbent, while Sb(III) remained in the supernatant. Quantitative elution of Sb(V) was accomplished with 1 mM diammonium hydrogen citrate for 30 min. An analytical procedure for non-chromatographic speciation and determination of inorganic antimony was developed. Concentrations of the target Sb(V) and the non-extractable Sb(III) were measured by ICP-OES with limits of quantitation of 4.2 μg/l and 3.4 μg/l, respectively. The method showed good accuracy, high precision, and applicability to low-mineralized waters, enabling up to 25-fold preconcentration of Sb(V).

A pragmatic approach to analyze the ability of ethylene‐octene copolymer in the long chain branching of polypropylene in molten and solid state

AbstractThe investigation of chain branching in polypropylene (PP) holds significant importance for comprehending the impact of structural modifications on the properties of PP. The utilization of ethylene‐octene copolymer (EOC) presents a valuable opportunity to examine the influence of branching density on the ability of electron beam irradiation or a chemical agent in a PP blend. The introducing long chain branches (LCB) into PP can enhance its mechanical properties, particularly impact strength. This characteristic is of particular significance in applications where the material is subjected to mechanical stress, such as automotive components or packaging materials. Blends of PP/EOC were produced using 20 and 30 wt% of EOC and 0.5 phr trimethylolpropane trimethacrylate (TMPTMA) monomer. To evaluate the efficiency of branching in both solid and molten states, irradiated samples and samples mixed with dicumyl peroxide (DCP) were selected. The rheological properties of the molten blends in shear and extensional modes were assessed, and their morphology was examined using scanning electron microscopy. The existence of LCB in all samples was confirmed through dynamic viscoelastic measurements. It was concluded that although the irradiation promoted chain scission within the backbone, which resulted in long chain branching, DCP created LCB on the backbone chains of PP through chemical reaction in the melt state. Additionally, the strain hardening constant (n) was calculated, and its value for the irradiated sample PP/EOC 80/20 was 0.19, whereas its value for this blend when employing DCP was 0.14. While the complex viscosity of irradiated blend (8764 Pa.s) was greater than that of melt state branched blend (8377 Pa.s) at 0.1 rad/s, in the higher frequencies it became smaller due to the more effective creation of long chain branches through peroxide grafting in the molten state. The results of the study verified the presence of LCB in the materials by observing longer relaxation time and strain hardening behavior.Highlights The chain branching of PP/EOC blends was investigated in both the melt state and solid state through the presence of TMPTMA monomer. The effectiveness of TMPTMA monomer in grafting was mostly notable in the molten state. The steady state viscosity of LCB‐(PP/EOC) was higher in the presence of dicumyl peroxide compared to irradiated PP/EOC. The samples containing 80 wt% of PP exhibited longer side branches compared to the sample with 70 wt% of PP according to shear and extensional rheometry. The induced side chain branches resulting from irradiation and the use of dicumyl peroxide help increase the miscibility of the polymers to a similar extent.

Rheological behaviors and foaming behaviors of crosslinked ethylene–vinyl acetate with polyfunctional monomers

AbstractTo produce ethylene–vinyl acetate (EVA) foams with a higher foaming ratio and stable cell size, the efficiency of the crosslinking reaction is required to conduct simultaneously with the blowing reaction. Hence, the multifunctional monomer trimethylolpropane trimethacrylate (TMP) as a crosslinking promoter and a crosslinking agent dicumyl peroxide are used together as a crosslinking system to EVA foaming, when chemical blowing agent azodicarbonamide (ADC) is used. The TMP concentration of approximately 1.0 phr (per hundred resin) is most effective for balancing the expansion ratio and fine cell size. In the SEM diagram and expansion ratio results, it can be found that when the concentration of TMP ranges from 0 to 1.0 phr, the cell mean size is reduced from 360.3 to 140.5 μm and the expansion ratio is reduced from 13.6 to 9.1 at 170°C. The results of time‐sweep experiment of thermogravimetric analysis (TGA) show that the foaming time of ADC in the melt increases with the addition of TMP. Capillary rheometer and rotational rheometer tests show that the viscosity and the crosslinking efficiency of the melt are improved with the TMP addition. The curing time has been reduced from 2.93 to 2.22 min for 170°C.

Selective capture of uranium and zirconium from strong HNO3 solution by ethenylphosphonic acid copolymerized polymer

The nuclear fuel rod contains mainly uranium (U) as the fuel and zirconium (Zr) as the cladding material. Improper disposition of the dissolved solution of the exhausted fuel rod releases radioactive acidic aqueous solution, which is a waste of U and Zr resources and also poses a great threat to the environment and living beings. The present work aims to selectively capture U and Zr from a 4 mol/L HNO3 aqueous solution in the presence of competing ions including La, Zn, Cd, Gd, Ce, Sr, Mn, Cu and Ba. Trimethylolpropane trimethacrylate (TMPTMA) copolymerized with ethenylphosphonic acid (EPA). TMPTMA improved the mesoporous character and adsorption ability of the adsorbent towards U and Zr. The synthesized polymer adsorbent was characterized by SEM, EDS, FT-IR, TGA, XRD, BET, XPS, and NMR to study the adsorption. The results indicated that the EPA-POP-2 adsorbent showed considerable adsorption capacity towards U(VI) (374.1 mg g−1) and Zr(IV) (217.4 mg g−1) in a strong HNO3 medium. Langmuir isotherm model fitted well to the experimental data, indicating that the monolayer adsorption process was dominating. The fitted pseudo-second-order (PSO) model represents that the adsorption mechanism is chemisorption. XPS, FT-IR, and DFT calculation results revealed that this adsorption capacity towards U and Zr was because of the P = O ligands present in the adsorbent. Van’t Hoff graph for U and Zr were also drawn to calculate the enthalpy, entropy, and Gibb’s free energy of the reaction. The reusability test showed that the adsorption capacity of synthesized adsorbent was high enough towards the U and Zr even after five consecutive cycles of adsorption and desorption.

Synthesis of molecularly printed methyl methacrylate-based polymers for the detection of di(2-ethylhexyl) phthalate and dibutyl phthalate

Molecularly imprinted polymers (MIP) were obtained by precipitation polymerization for the detection of DEHP and DBP from polymer packaging in drinking water. MIP was obtained by cross-linking DEHP and DBP with methyl methacrylate (MMA) and trimethylolpropane trimethacrylate (TRIM). FTIR, SEM-EDS, UV-Vis and SAA were used to determine properties of polymers (MIP_DEHP, MIP_DBP). The obtained materials were characterized by a mesoporous structure with small, uniform, and porous grains. The surface area and total pore volume of MIP_DEHP were more than twice smaller than MIP_DBP, with a slightly larger pore diameter. Lower C content may indicate the formation of MIP_DEHP and MIP_DBP. The FTIR method confirmed the presence of functional groups –CH, –CO, –C=C and –C=O. The adsorption capacity of MIP_DEHP and MIP_DBP was 0.68 mg/g and 1.06 mg/g, respectively, and was consistent with the Freundlich isothermal adsorption model.

Improved direct current electrical properties of XLPE modified by graftable antioxidant and crosslinking coagent at a wide temperature range

AbstractTo enhance the DC electrical performance of cross‐linked polyethylene (XLPE), the graftable antioxidant methacrylic acid 2‐hydroxy‐3‐(4‐anilinoanilino) propyl ester (GA), which contains carbonyl and amino groups, and the crosslinking coagent trimethylolpropane trimethacrylate (TMPTMA), which contains carbonyl groups, are individually or co‐grafted onto XLPE. The slightly higher deep trap density introduced by higher grafting concentration of TMPTMA results in more significant suppression effect of conductance current and enhanced breakdown strength at a lower temperature, while the suppression effect for the conductance current at 90°C becomes weakened due to limited trap energy. Meanwhile, the deeper energy level introduced by GA suppresses the conductance current and improves the electrical strength of XLPE at 90°C more significantly. By co‐grafting, the conductance current of XLPE in a wide range temperature can be significantly reduced, especially for the temperature dependence of conductance current, which is beneficial to suppress the field strength reversal. The results of thermally stimulated current and molecular simulation show that the polar groups of two monomers introduce deep charge traps in XLPE. The co‐grafting system ensures the rationality of the crosslinking reaction kinetics and does not affect the cable manufacturing.

Multivariate design and application of novel molecularly imprinted polymers selective for triazole fungicides in juice and water samples

In the present study, novel molecularly imprinted polymers were prepared using penconazole as template and different combinations of functional monomers (acrylic acid (AA) and N-isopropylacrylamide (NIPAM)) and cross-linkers (ethylene glycol dimethacrylate (EGDMA) and trimethylolpropane trimethacrylate (TRIM)), according to a Plackett-Burman design of experiments. Materials were fully characterized by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM) and nitrogen adsorption analysis. Rebinding behaviors in solution were studied both at the equilibrium (Langmuir, Freundlich and Temkin models), and at the non-equilibrium (pseudo-first, pseudo-second order kinetics). Materials were further tested as sorbents for dispersive solid phase extraction (d-SPE) on apple juice for multicomponent recovery of triazole fungicides at trace level, testing several variations of extraction parameters (juice pH, amount of sorbent, adsorption time, desorption solvent, desorption time) leading to the selection of the best materials and simultaneously of the best extraction conditions. MIPs synthesized with NIPAM showed significatively higher affinity for triazole pesticides in apple juice than the ones synthesized with AA, while no differences emerged for the two cross-linkers employed (EGDMA, TRIM). Selectivity was also assessed, testing MIPs as d-SPE sorbents in undiluted apple juice spiked with triazole pesticides concurrently with other interfering compounds. The newly developed NIPAM-based penconazole-imprinted MIPs showed an excellent recognition mechanism towards compounds containing the triazole ring, and significatively lower recoveries for other compounds. The developed analytical procedure based on molecularly imprinted polymer dispersive solid phase extraction and liquid chromatography coupled with mass spectrometry (MIP-d-SPE-LC-MS) was validated for selective enrichment and determination of triazole compounds in apple juice samples and river water samples with good recoveries (94.67%–109.03% for river water, 89.79%–110.23%, for apple juice), high repeatability (RSD% < 3.97 for river water, RSD% < 4.85 for apple juice), and reproducibility (RSD% < 5.95 for river water and RSD% < 7.14 for apple juice).

A Label-Free Electrochemical Biosensor for Homocysteine Detection Using Molecularly Imprinted Polymer and Nanocomposite-Modified Electrodes.

An essential biomarker for the early detection of cardiovascular diseases is serum homocysteine (Hcy). In this study, a molecularly imprinted polymer (MIP) and nanocomposite were used to create a label-free electrochemical biosensor for reliable Hcy detection. A novel Hcy-specific MIP (Hcy-MIP) was synthesized using methacrylic acid (MAA) in the presence of trimethylolpropane trimethacrylate (TRIM). The Hcy-MIP biosensor was fabricated by overlaying the mixture of Hcy-MIP and the carbon nanotube/chitosan/ionic liquid compound (CNT/CS/IL) nanocomposite on the surface of a screen-printed carbon electrode (SPCE). It showed high sensitivity, with a linear response of 5.0 to 150 µM (R2 of 0.9753) and with a limit of detection (LOD) at 1.2 µM. It demonstrated low cross-reactivity with ascorbic acid, cysteine, and methionine. Recoveries of 91.10-95.83% were achieved when the Hcy-MIP biosensor was used for Hcy at 50-150 µM concentrations. The repeatability and reproducibility of the biosensor at the Hcy concentrations of 5.0 and 150 µM were very good, with coefficients of variation at 2.27-3.50% and 3.42-4.22%, respectively. This novel biosensor offers a new and effective method for Hcy assay compared with the chemiluminescent microparticle immunoassay at the correlation coefficient (R2) of 0.9946.

Core-shell magnetic molecularly imprinted polymers: nanoparticles targeting selective androgen receptor modulators (sarms) and steroidal models

Super paramagnetic iron oxide nanoparticles (SPIONs) (∼12 nm) were synthesized as the magnetic core for an imprinted polymer (MIP) shell using 4-vinylpyridine as the functional monomer and trimethylolpropane trimethacrylate (TRIM) as the cross-linker, bringing the average size up to ∼45 nm. Five targets were imprinted—the Selective Androgen Receptor Modulators (SARMs) andarine, ligandrol and RAD-140; and the steroids estradiol and gestrinone. All MMIPs produced good selectivity when loaded with a non-target molecule, with all calculated selectivity factors above the 1.2 recommended threshold and also demonstrated good affinity/capacity. The rebinding of the target molecules from a complex matrix was also explored by using spiked river water samples. The SARMs-based MMIPs were able to rebind 99.56, 87.63 and 72.78% of their target molecules (andarine, ligandrol and RAD-140, respectively), while the steroidal-based MMIPs were able to rebind 64.54 and 55.53% of their target molecules (estradiol and gestrinone, respectively) at a nominal loading of 20 ≈μg in 50 mg of NPs. This work highlights the potential of these bi-functional materials for trace material clean-up of complex samples and/or subsequent analysis and opens up possibilities for further simple, rapid-to-synthesise materials for targeted clean-up.