Glycol Dimethacrylate Research Articles

Pharmacokinetics of pulmonary indacaterol in rat lung using molecular imprinting solid-phase extraction coupled with RP-UPLC

Indacaterol, a β2 agonist prescribed for long-term management of patients with chronic obstructive pulmonary disease and asthma. In this study the first MISPE cartridges was developed using indacaterol as a template for its selective extraction from rat lung tissues, enabling precise pharmacokinetic evaluation at the drug’s site of action. A molecular imprinting polymer was synthesized using indacaterol as a template, methacrylic acid as a functional monomer and ethylene glycol dimethacrylate as a cross-linker with a molar ratio (1: 4: 20). The polymer was characterized by a high binding capacity of 9840 ± 0.86 and high selectivity with an imprinting factor of 4.53 ± 0.12. The synthesized polymer was utilized as a sorbent in solid-phase extraction to purify and extract indacaterol from lung tissue matrix. The optimum molecularly imprinted solid-phase extraction (MISPE) conditions were 20.0 mg of molecular imprinting polymer and non-imprinting polymer, acetonitrile as the loading solvent, acetonitrile: water (20: 80; by volume) as the washing solvent, and methanol: acetic acid (90: 10; by volume) as the eluting solvent. A pharmacokinetic study was performed for indacaterol in rat lungs using the synthesized and optimized MISPE cartridge as a tool for sample purification. These parameters were determined in the lung tissues of rats emphasizing the local exposure of indacaterol to its target organ. The Cmax and Tmax were 51.020 ± 2.810 µg mL− 1 and 0.083 ± 0.001 h, respectively. The AUC 0−24 and AUC0 − inf were 175.920 ± 1.053 and 542.000 ± 5.245 µg h mL− 1, respectively. The elimination rate constant was 0.014 ± 0.00012 h− 1 and the half-life time was 48.510 ± 0.012 h. This study successfully developed and optimized MISPE cartridges using indacaterol as a template, enabling precise pharmacokinetic evaluation in rat lung tissues. The cartridges demonstrated high binding capacity and selectivity, providing crucial insights into the local exposure of indacaterol at its site of action.

Poly(ethylene glycol) dimethacrylate (PEGDMA) multi-functional pillar-patterned surface for osteogenic differentiation of pre-osteoblast and anti-bacterial effects to Escherichia coli and Staphylococcus aureus

Cells are sensitive to the surface topographical environment, which can subsequently induce changes in cell morphology, cytoskeleton, and differentiation. Therefore, the topological environment in bone implant devices is known to influence the cell behavior, adhesion, and differentiation of osteoblasts. Furthermore, bone implant devices with anti-bacterial properties could be necessary to prevent surgical site infections (SSIs). Consequently, there is a demand for research into multi-functional surfaces that can facilitate osteoblast differentiation while also possessing an anti-bacterial effect. In this study, we fabricated and assessed the poly(ethylene glycol) dimethacrylate (PEGDMA) nano/micro pillar-patterned surface to find the optimized dimensional characteristics of the pillar pattern for multi-functional effect. Results observed that the pillar pattern enhanced differentiation to osteoblast on the pillar-patterned surface (D1S0.5) having pillars with 0.5 μm height, 1 μm diameter, and 0.5 μm spacing between pillars and pillar-patterned surface (D1S1) having pillars with 0.5 μm height, 1 μm diameter, and 1 μm spacing between pillars. Subsequently, results of evaluating anti-bacterial effect revealed that the optimized pillar-patterned surface exhibited remarkable antibacterial effect, with the D1S0.5 pillar-patterned surface showing the highest antibacterial effect. Consequently, this study proposed and verified a multi-functional pillar-patterned surface capable of promoting osteoblast differentiation with anti-bacterial effects.

A highly sensitive and selective molecularly imprinted sensor for the determination of atorvastatin

In this study, we developed a highly sensitive carbon paste sensor that combines a molecularly imprinted polymer (MIP) with specific recognition capabilities to monitor atorvastatin (ATV). In the MIP synthesis, designed especially for ATV, ethylene glycol dimethacrylate (EGDMA) was utilized as a cross-linking monomer and methacrylic acid (MAA) as a functional monomer. This non-covalent method made use of polymerization by free radicals. After that, this MIP was added to a carbon paste electrode (CPE), which served as both a selective detection element and a preconcentration agent for ATV analysis. The improved CPE was characterized using scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS). To investigate ATV, the anodic peak signal was assessed using square wave stripping voltammetry (SWSV).The calibration curve exhibited two linear regions encompassing dosages from 0.005 to 1 µM and 1 to 20 µM, with a 1.5 nM calculated detection limit. The designed MIP electrode was successfully utilized to assess ATV in tablet and human blood serum samples, demonstrating its usefulness in practical analysis.

UV Filter NanoCapsule with Broad‐Spectrum UV Protection

AbstractIn this study, nanocapsules encapsulating avobenzone (AVB) compounded with isooctyl p‐dimethylaminobenzoate (OD‐PABA) were prepared via miniemulsion polymerization using methyl methacrylate (MMA) as the monomer, ethylene glycol dimethacrylate (EGDMA) as the cross‐linker, and poly(styrene‐co‐methacrylic acid) (P(St‐co‐MAA)) as the polymeric emulsifier. When a solid ultraviolet radiation A (UVA) filter, AVB, was encapsulated in nanocapsules (A‐UVNCs), the encapsulation and loading rates were 67.6% and 9.7%, respectively. When a liquid ultraviolet radiation B (UVB) filter, OD‐PABA, was combined with AVB, the encapsulation and loading rates of the nanocapsules (A/O‐UVNCs) of AVB and OD‐PABA increased to 90.0% and 15.6%, respectively, and 71.5% and 14.0%, respectively. The A/O‐UVNCs realized broad‐spectrum ultraviolet (UV) protection with an SPF value of 46.3. The A/O‐UVNCs have raspberry‐like nanostructures. These submicron particles can scatter and reflect a portion of the UV radiation and synergistically enhance UV protection. After exposure to simulated sunlight for four hours, the UVAPF of a sunscreen containing A‐UVNCs or A/O‐UVNCs decreased to a smaller extent than that of the sunscreen containing free AVB. Cell toxicity experiments showed that the cell viability of A‐UVNCs and A/O‐UVNCs was 85.9% and 83.0%, respectively. Therefore, UVNCs not only enhance UV protection but also improve photostability and safety.

Effect of binary porogen mixtures on polymer monoliths prepared by gamma-radiation initiated polymerization

Gamma-radiation initiated polymerization is an easy-to-use and simple technique for the preparation of porous polymer monoliths widely used as active materials in separation columns. Herein, binary porogen mixtures of ethyl acetate/acetone/acetonitrile with methanol were used to synthesize diethylene glycol dimethacrylate monoliths with this technique. Systematic studies have been performed to determine the effect of the composition of the solvent mixture on the morphology and the reaction kinetics, including the growth mechanism and the growth rate. The irradiation dose-dependent conversion profiles showed that with binary solvents the polymerization is much faster than with the same compounds used as single solvents. Depending on the type and the composition of the solvent one-, two- and three-dimensional, and fractal growth mechanisms were identified.

Photopolymerization of Imprinted Polymer with Dummy Template for the Recognition of Hydroquinone in Aqueous Medium

This study' purposes are to synthesize molecularly imprinted polymer (MIP) with hydroxyethyl methacrylate (HEMA) and triethylene glycol dimethacrylate (TEGDMA) using p-xylene under ultraviolet curing at 405 nm for the recognition of hydroquinone (HQ) in aqueous medium. The template was extracted from the polymer with a mixture of methanol and acetic acid (9:1) by volume (v/v). The Fourier transform infrared (FTIR) spectrum of MIP (after wash) showed the absence of peak at the range of 840–860 cm−1, which represented the stretching outside the aromatic plane C–H at the para position (p-xylene). Field emission scanning electron microscope (FESEM) micrograph showed that the MIP had cavities compared to non-imprinted polymer (NIP). The MIP (MIP-Pxy) with ratio (monomer:crosslinker) 0.25 and 1.00% template gave the highest uptake of hydroquinone (HQ) in aqueous solution, which implied more specific recognition (highest KD value). The rebinding of HQ onto MIP-Pxy was best described by both isotherm (Langmuir and Freundlich) and kinetic model (pseudo-first and -second). The MIP was successfully synthesized using p-xylene, able to recognize HQ and was very selective to p-CP. Implication of the study, the synthesized MIP can be used for recognition and sensing materials for HQ and any similar molecules.

Long-Lasting, Transparent Antibacterial Shield: A Durable, Broad-Spectrum Anti-Bacterial, Non-Cytotoxic, Transparent Nanocoating for Extended Wear Contact Lenses.

The increasing incidence of serious bacterial keratitis, a sight-threatening condition often exacerbated by inadequate contact lens (CLs) care, highlights the need for innovative protective technology. This study introduces a long-lasting antibacterial, non-cytotoxic, transparent nanocoating for CLs via a solvent-free polymer deposition method, aiming to prevent bacterial keratitis. The nanocoating comprises stacked polymer films, with poly(dimethylaminomethyl styrene-co-ethylene glycol dimethacrylate) (pDE) as a biocompatible, antibacterial layer atop poly(2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane) (pV4D4) as an adhesion-promoting layer. The pD6E1-grafted (g)-pV4D4 film shows non-cytotoxicity toward two human cell lines and antibacterial activity of >99% against four bacteria, including methicillin-resistant Staphylococcus aureus (MRSA), an antibiotic-resistant bacteria and Pseudomonas aeruginosa, which causes ocular diseases. Additionally, the film demonstrates long-lasting antibacterial activity greater than 96% against MRSA for 9 weeks in phosphate-buffered saline. To the best knowledge, this duration represents the longest reported long-term stability with less than 5% decay of antibacterial performance among contact-killing antibacterial coatings. The film exhibits exceptional mechanical durability, retaining its antibacterial activity even after 15 washing cycles. The pD6E1-g-pV4D4-coated CL maintains full optical transmittance compared to that of pristine CL. It is expected that the unprecedentedly prolonged antibacterial performance of the coating will significantly alleviate the risk of infection for long-term CL users.

Influence of Poly(Ethylene Glycol) Dimethacrylates’ Chain Length on Electrical Conductivity and Other Selected Physicochemical Properties of Thermally Sensitive N-isopropylacrylamide Derivatives

Thermosensitive polymers P1–P6 of N-isopropylacrylamide (PNIPA) and poly(ethylene glycol) dimethacrylates (PEGDMAs), av. Mn 550–20,000, were synthesized via surfactant-free precipitation polymerization (SFPP) using ammonium persulfate (APS) at 70 °C. The polymerization course was monitored by the conductivity. The hydrodynamic diameters (HDs) and the polydispersity indexes (PDIs) of the aqueous dispersion of P1–P6 in the 18–45 °C range, assessed via dynamic light scattering (DLS), were at 18° as follows (nm): 73.95 ± 19.51 (PDI 0.57 ± 0.08), 74.62 ± 0.76 (PDI 0.56 ± 0,01), 69.45 ± 1.47 (PDI 0.57 ± 0.03), 196.2 ± 2.50 (PDI 0.53 ± 0.04), 194.30 ± 3.36 (PDI 0.56 ± 0.04), 81.99 ± 0.53 (PDI 0.56 ± 0.01), 76.87 ± 0.30 (PDI 0.54 ± 0.01), respectively. The electrophoretic mobilities estimated the zeta potential (ZP) in the 18–45 °C range, and at 18 °C they were as follows (mV): −2.57 ± 0.10, −4.32 ± 0.67, −5.34 ± 0.95, −-3.02 ± 0.76, −4.71 ± 2.69, −2.30 ± 0.36, −2.86 ± 0.42 for polymer dispersion P1–P6. The polymers were characterized by attenuated total reflectance–Fourier transform infrared spectroscopy (ATR-FTIR), H nuclear magnetic resonance (1H NMR), thermogravimetric analysis (TG/DTA), Differential Scanning Calorimetry (DSC), and powder X-ray diffraction analysis (PXRD). The length of the cross-linker chain influences the physicochemical properties of the obtained polymers.

Innovative Poly(lactic Acid) Blends: Exploring the Impact of the Diverse Chemical Architectures from Itaconic Acid

Environment-friendly polymer blends of poly(lactic acid) (PLA) and itaconic acid (IA), poly(itaconic acid) (PIA), poly(itaconic acid)-co-poly(methyl itaconate) (Cop-IA), and net-poly(itaconic acid)-ν-triethylene glycol dimethacrylate (Net-IA) were performed via melt blending. The compositions studied were 0.1, 1, 3, and 10 wt% of the diverse chemical architectures. The research aims to study and understand the effect of IA and its different architectures on the mechanical, rheological, and thermal properties of PLA. The PLA/IA, PLA/PIA, PLA/Cop-IA, and PLA/Net-IA blends were characterized by dynamic mechanical thermal analysis, rotational rheometer (RR), thermogravimetric analysis, differential scanning calorimetry, X-ray diffraction, and scanning electron microscopy. The complex viscosity, storage module, and loss module for the RR properties were observed in the following order: PLA/Cop-IA, PLA/Net-IA, and PLA/PIA > PLA > PLA/IA. Thermal stability improved with increasing concentrations of Cop-IA and Net-IA. In the same way, the mechanical properties were enhanced. In addition, the micrographs illustrated the formation of fibrillar structures for all blends. The crystallinity degree displayed higher values for the blends that contain Net-IA > Cop-IA than IA > PIA. Therefore, IA and its architectures can influence these studied properties, which have potential applications in disposable food packing.

Adsorption and detection of praseodymium ion by ion-imprinted polymer with ultra-low sensitivity.

A novel kind of carbon dot (CD) was prepared by one-step hydrothermal microwave assisted method using L-tryptophan and L-tartaric acid as raw materials. Monodisperse poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate) microspheres were utilized as the matrix, with praseodymium (Pr) ion (Pr3+) as the template, methacrylic acid as the functional monomer, and 5-amino-8-hydroxyquinoline (5-AHQ) acts as the ligand. A composite microsphere of ion-imprinted polymer (IIP) and CD (noted CD@IIP) was prepared by surface-initiated atom transfer radical polymerization (SI-ATRP). For comparison, IIP without CD (Pr-IIP) and non-imprinted polymer (NIP) were also prepared. Through static adsorption experiments, it was determined that the saturated adsorption amount of CD@IIP is 47.19mgg-1, that of Pr-IIP is 54.49mgg-1, while that of NIP is only 24.32mgg-1. Dynamic adsorption experiments showed that the equilibrium of three kinds of materials wasreached within 30min. Particularly, CD@IIP could emit two fluorescence peaks at 325nm and 421nm under ultraviolet irradiation, and exhibited excellent selectivity and fluorescence quenching effect on Pr3+. The fluorescence response of Pr3+ in the range 0-400μmol L-1 was determined by ratiometric fluorescence method, offering a two-stage model and robust linear regression coefficient. These results demonstrated that CD@IIP exhibited selective adsorption ability for Pr3+, and a sensitive, rapid and simple method for detection of Pr3+ was successfully developed.

Rh nanoparticles confined in triphenylphosphine oxide-functionalized core-crosslinked micelles with a polyanionic shell: Synthesis, characterization, and application in aqueous biphasic hydrogenation

Core-crosslinked micelles (CCMs) with a hydrophilic polyanionic shell made of poly(sodium styrene sulfonate) chains, P(SS−Na+), a triphenylphosphine oxide-functionalized polystyrene core (TPPO@PSt) and crosslinked at the inner end of the polystyrene chains by diethylene glycol dimethacrylate (DEGDMA) were synthesized by reversible addition-fragmentation chain-transfer (RAFT) polymerization as a stable TPPO@CCM-A latex. One-pot synthesis of rhodium nanoparticles (RhNPs) by the reduction of [Rh(COD)(μ-Cl)]2 in the aqueous TPPO@CCM-A latex yielded a stable RhNP-TPPO@CCM-A latex without the need of additional stabilizer or base. This Rh-loaded latex was applied to the catalytic biphasic hydrogenation of styrene under mild conditions with complete selectivity towards ethylbenzene and corrected turnover frequencies (cTOFs) ranging from 3250 to 10,010 h−1 based on the surface atoms of the RhNPs. Importantly, the catalytic phase proved recyclable after product extraction, owing to the efficient retention of the RhNPs by the core TPPO ligands.

SYNTHESIS AND CHARACTERIZATIONS OF NOVEL MISWAK POWDER-BASED DENTAL COMPOSITES

This study aimed to synthesize a novel miswak based dental composite by incorporating miswak powder, chlorhexidine (CHX), and silica fillers in different proportions into a resinous mixture and assess the influence of these fillers on the physical, mechanical, and biological properties of newly developed composites. The stock monomer solution was synthesized using urethane dimethacrylate, triethylene glycol dimethacrylate, and hydroxyethyl methacrylate. Four experimental groups (A, B, C, D) were prepared using 30% stock monomer with 70% filler formulations, while two commercial composites were used as control groups (E, F). The highest value of degree of conversion was shown by Group D, whereas the lowest – by Group A. Compressive strength evaluation showed Group E had the highest value, while the lowest value was recorded for Group B. Furthermore, cytotoxicity assessment showed that all the groups of composites had a biocompatible nature, except Groups A and B, having slight cytotoxicity. Thus, the experimental groups can be used as restorative materials as they exhibited optimum properties.

Selective apigenin assay in plant extracts and herbal supplement with molecularly imprinted polymer-based electrochemical sensor

This study is the first successful application of a nanomaterial-supported molecularly imprinted polymer (MIP)-based electrochemical sensor for the sensitive and selective determination of apigenin (API), which is a naturally occurring product of the flavone class that is an aglycone of several glycosides. Secondary metabolites are biologically active substances produced by plants in response to various environmental factors. The levels of these compounds can vary depending on factors such as climate, soil conditions and the season in which the plants are grown. Therefore, the analysis of these compounds is essential to properly understand the biological effects of plant extracts and to ensure their safe use. To increase the glassy carbon electrode (GCE) surface's active surface area and porosity, zinc oxide nanoparticles (ZnO NPs) were integrated into the MIP-based electrochemical sensor design. Tryptophan methacrylate (TrpMA) was selected as the functional monomer along with other MIP components such as 2-hydroxyethyl methacrylate (HEMA, basic monomer), 2-hydroxy-2-methylpropiophenone (initiator), and ethylene glycol dimethacrylate (EGDMA, crosslinking agent). The morphological and electrochemical characterizations of the developed API/ZnO NPs/TrpMA@MIP-GCE sensor were performed with scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The indirect measurement approach via 5.0 mM [Fe(CN)6]3–/4– solution was utilized to determine API in the linear range of 1.0x10−13 M − 1.0x10−12 M. The limit of detection (LOD) and limit of quantification (LOQ) for standard solutions were found to be 2.47x10−14 and 8.23x10−14 M, respectively. In addition, the extraction processes were carried out using ultrasound-assisted extraction (UAE) and maceration (MCR) procedures. For Apium graveolens L., Petroselinum crispum (Mill.) Fuss and herbal supplement, the API recoveries varied from 98.79 % to 102.71 %, with average relative standard deviations (RSD) less than 2.25 % in all three cases. The sensor's successful performance in the presence of components with chemical structures similar to the API was also demonstrated, revealing its unique selectivity.

Design and fabrication of acorn-like Janus molecularly imprinted materials for highly specific separation and enrichment of oxytetracycline from restaurant oily wastewater

Molecularly imprinted polymer (MIP) is dedicated to the adsorption of target substances in the aqueous phase, but ignores the adsorption in a more complex environment (oily wastewater). In order to explore the application field of existing MIPs, acorn-like Janus particles were fabricated by photo-initiated seed swelling polymerization. A novel amphiphilic Janus-MIP was prepared with the acorn-like Janus particles as matrix, methacrylic acid, ethylene dimethacrylate and oxytetracycline (OTC) as functional monomers, crosslinking agents and template molecules via surface initiated-atom transfer radical polymerization (SI-ATRP). For comparison, the poly (glycidyl methacrylate-co-ethylene glycol dimethacrylate) (poly (GMA-co-EDMA)) microspheres were also utilized as the matrix to prepare common spherical-MIP. The adsorption capacity of Janus-MIP for OTC was 23.8 mg g−1 in oil-water system, while the adsorption capacity of spherical-MIP for OTC was only 12.6 mg g−1 in the same system. At the same time, through high performance liquid chromatography (HPLC) analysis, Janus-MIP can specifically recognize and adsorb trace OTC in restaurant oily wastewater samples, and the proposed method exhibited a lower limit of detection (LOD, 3 ng mL−1) and a higher OTC recovery rate (94.2 %–98.4 %). This work demonstrated great potential for the detection and control of OTC contamination from real samples in an oil-water mixed environment.

Assessment of Acrylamide Levels by Advanced Molecularly Imprinted Polymer-Imprinted Surface Plasmon Resonance (SPR) Sensor Technology and Sensory Quality in Homemade Fried Potatoes.

This study evaluated acrylamide (AA) levels and various quality parameters in homemade fried potatoes prepared in different sizes by integrating principles from the Slow Food Movement with advanced sensor technology. To this aim, a surface plasmon resonance (SPR) sensor based on a molecularly imprinted polymer (MIP) was first developed for the determination of AA in homemade fried potatoes at low levels, and the AA levels in the samples were established. First of all, monolayer formation of allyl mercaptane on the SPR chip surface was carried out to form double bonds that could polymerize on the chip surface. AA-imprinted SPR chip surfaces modified with allyl mercaptane were prepared via UV polymerization using ethylene glycol dimethacrylate (EGDMA) as a cross-linker, N,N'-azobisisobutyronitrile (AIBN) as an initiator, and methacryloylamidoglutamicacid (MAGA) as a monomer. The prepared AA-imprinted and nonimprinted surfaces were characterized by atomic force microscopy (AFM) and Fourier transform infrared (FTIR) spectroscopy methods. The SPR sensor indicated linearity in the range of 1.0 × 10-9-5.0 × 10-8 M with a detection limit (LOD) of 3.0 × 10-10 M in homemade fried potatoes, and the SPR sensor demonstrated high selectivity and repeatability in terms of AA detection. Additionally, the highest AA level was observed in the potato sample belonging to the T1 group, at 15.37 nM (p < 0.05), and a strong and positive correlation was found between AA levels and sensory parameters, the a* value, the ΔE value, and the browning index (BI) (p < 0.05).

Mechanical Properties of Newly Developed Flowable Composite Derived from Rice Husk at Different Monomer Ratios

An ideal flowable composite (FC) requires good mechanical properties to fulfill its role as a dental restorative material and ensure durability and clinical efficacy, with these properties being influenced by different monomer ratios. The study aimed to evaluate the mechanical properties of the newly developed FC on Vickers hardness, flexural strength, and flexural modulus at different monomer ratios. The newly developed FC employed nanohybrid silica from rice husk and zirconia as fillers, and the ratio of urethane dimethacrylate to triethylene glycol dimethacrylate (UDMA:TEGDMA) at 20:80, 30:70, 50:50, 60:40, 80:20 and 90:10 as monomers. Filtek Supreme Ultra Flowable Restorative, Revolution Formula 2, and G-aenial Universal Flo served as control groups. The data were statistically analyzed using one-way ANOVA with post-hoc Bonferroni test. Generally, the higher UDMA ratio in the newly developed FCs exhibited higher mechanical properties. All newly developed FCs demonstrated a significant decrease in Vickers hardness than control groups. The flexural strength values at ratios of 50:50, 60:40, 80:20, and 90:10 were comparable with control groups and passed the International Organization for Standardization 4049 requirement. Meanwhile, the flexuralmodulus of the newly developed FC at the ratio of 90:10 was comparable to Revolution Formula 2. In summary, the differences in monomer ratios affect the mechanical properties of the newly developed FCs. The improved mechanical properties at ratios of 80:20 and 90:10 could potentially substitute sustainable dental restorative materials, subjected to further investigations.

Sensitive Coatings Based on Molecular-Imprinted Polymers for Triazine Pesticides' Detection.

Triazine pesticide (atrazine and its derivatives) detection sensors have been developed to thoroughly check for the presence of these chemicals and ultimately prevent their exposure to humans. Sensitive coatings were designed by utilizing molecular imprinting technology, which aims to create artificial receptors for the detection of chlorotriazine pesticides with gravimetric transducers. Initially, imprinted polymers were developed, using acrylate and methacrylate monomers containing hydrophilic and hydrophobic side chains, specifically for atrazine, which shares a basic heterocyclic triazine structure with its structural analogs. By adjusting the ratio of the acid to the cross-linker and introducing acrylate ester as a copolymer, optimal non-covalent interactions were achieved with the hydrophobic core of triazine molecules and their amino groups. A maximum sensor response of 546 Hz (frequency shift/layer height equal to 87.36) was observed for a sensitive coating composed of 46% methacrylic acid and 54% ethylene glycol dimethacrylate, with a demonstrated layer height of 250 nm (6.25 kHz). The molecularly imprinted copolymer demonstrated fully reversible sensor responses, not only for atrazine but also for its metabolites, like des-ethyl atrazine, and structural analogs, such as propazine and terbuthylazine. The efficiency of modified molecularly imprinted polymers for targeted analytes was tested by combining them with a universally applicable quartz crystal microbalance transducer. The stable selectivity pattern of the developed sensor provides an excellent basis for a pattern recognition procedure.

Reusable pyrene-based fluorescent organogels for polychlorinated biphenyl detection and removal

Highly toxic hydrophobic polychlorinated biphenyls (PCBs) pollutants are resistant to degradation, and limited methods are available for their elimination, leading to their long-term persistence in ecosystems, which can harm humans and the environment. Therefore, early detection, removal, and continuous monitoring of PCBs are crucial. In this study, a novel fluorescent polymeric probe (P1) to detect PCB congeners (77, 118, and 126) in water was developed. P1 was synthesized by incorporating N,N’-dimethylacrylamide (DMAA) and pyren-1-ylmethyl methacrylate (PyMMA) to form p(DMAA-co-PyMMA). P1 demonstrated high sensitivity toward the most toxic coplanar PCB congeners, 77 and 126, via a fluorescence turn-on mechanism. This sensitivity was attributed to hydrophobic and π–π interactions between the PCBs and PyMMA units of P1. The detection limits for PCB congeners 77 and 126 were determined to be 0.028 and 0.039 mM, respectively. However, PCB 118, a mixed planar congener, exhibited less detection sensitivity than PCB 77 and 126. A porous three-dimensional polymeric organogel (OG) comprising butyl acrylate, PyMMA, and a cross-linker ethylene glycol dimethacrylate was synthesized for practical application. The OG selectively removed PCBs compared to other competing pollutants due to the high hydrophobicity of the PCBs, achieving removal rates of 63 % for PCB 77 and 55 % for PCB 126. The large surface area of the OG facilitated enhanced hydrophobic and π-π interactions between the PCBs and pyrene units. This work emphasizes the efficacy of P1 in detecting PCBs and the potential of using OG in eliminating PCBs, offering a viable method for monitoring and remedying PCB-contaminated environments.

Ultrafine Network-Like Monolayer Structures of Amphiphilic Hyperbranched Copolymers Revealed by the Relative Aggregation Number Method.

The aggregation behavior of two amphiphilic hyperbranched copolymers of poly[oligo(ethylene glycol) methacrylate-co-lauryl methacrylate] (H-[P(OEGMA-co-LMA)]) at the air/water interface was investigated by using the Langmuir film balance technique and atomic force microscopy (AFM). At the air/water interface, H-[P(OEGMA-co-LMA)] copolymers spontaneously form the ultrafine network-like monolayer structures of micelles; each micelle consists of a tiny hydrophobic core of one or two carbon backbones and lauryl side groups and a short hydrophilic shell of oligo(ethylene glycol) (OEG) side groups, and the micellar cores are connected by the branching agent ethylene glycol dimethacrylate (EGDMA). These ultrafine micellar structures are successfully revealed by our relative aggregation number method presented in this work, which is based on our previous relative mass method and methylene number method. The surface pressure-molecular area isotherms of POEGMA29%-PLMA71% (weight percent) and POEGMA69%-PLMA31% are condensed and expanded, respectively, because the density/number of OEG side groups in the former shells is smaller than that in the latter case. Upon monolayer compression, the isotherms of the former are classified into regions I-IV, whereas those of the latter are classified into regions II and III based on their different variation trends of surface pressure. Subphase pH has little influence on the isotherms of the two copolymers because the stretching degrees of hydrophilic OEG side groups in the shells are probably limited by the connected cores, which is different from the large effects in our previous block copolymers containing POEGMA or poly[oligo(ethylene glycol) acrylate] blocks. Under neutral and alkaline conditions, in region III, the mean molecular area (mmA) values of the isotherms of the two copolymers at 20 °C are smaller than those at 10 °C due to the collapse of the OEG side groups above 15 °C. Furthermore, the isotherms of POEGMA69%-PLMA31% move to larger mmA values at 30 °C due to the increased thermal mobility and stretching degrees of more OEG side groups.

Selective solid phase extraction of folic acid from tomato as a biological source with a magnetic molecularly imprinted polymer measured by fluorescence spectroscopy

AbstractA novel magnetic molecular-imprinted polymer (MMIP) was used to selectively extract folic acid directly from real samples. Folic acid was used as template molecule, Fe3O4/SiO2-3-triethoxysilyl-propyl-acrylamide as functional monomer, azobisisobutyronitrile as initiation, ethylene glycol dimethacrylate as crosslinker agent, and acrylamide as the secondary monomer in a mixed ethanol-water solvent. The effect of different parameters on the extraction efficiency was studied, and the optimum conditions were established as follows: the concentrations of crosslinking and template were fixed at 0.05 and 0.06 g, absorption percentage was 96.5, pH was adjusted to 8, and extraction time was 8 h with a temperature of 25 °C. By examining the effect of pH, we tried to investigate the effect of the amide groups that present in MMIP and its intermolecular hydrogen interaction with folic acid. After optimising the effective parameters in polymer synthesis and adsorption rate, a magnetic imprinting dispersive solid-phase extraction method combined with fluorescence spectrophotometry at λem = 367 nm (MMIP-DSPE-FL) was constructed for sensitive determination of folic acid in tomato samples. The limit of quantification (LOQ) and limit of detection (LOD) values were 30.00 ± 0.01 μg L−1 and 10.00 ± 0.03 μg L−1, respectively, after the MMIP-DSPE preconcentration. Three tomato samples were analysed to give recoveries in the range of 80.2–81.6%, with relative standard deviation values below 0.6% (n = 3). The prepared MMIP-DSPE showed high selectivity toward folic acid, which could be used six times without changing adsorption capacity. The adsorption isotherm of the folic acid-imprinted polymer pursued the Langmuir model (RL = 0.029), and the kinetics model followed pseudo-first-order (R2 = 0.9974).