Bulk Polymerization Research Articles

Biobased and biodegradable polyester amides based on nylon 6,6 and polybutylene adipate via straightforward bulk polymerization

Aliphatic polyesters are generally known for their limited thermal and mechanical properties, but are prone to biodegradation. On the other hand, aliphatic polyamides, mainly represented by nylons, feature high thermal transition points and enhanced mechanical strength, but are usually classified as nonbiodegradable. In this work, the properties of the aliphatic polyester polybutylene adipate and nylon 6,6 were combined by synthesizing polyester amides. Relatively low- and high-molecular weight series, Mn¯ 7000 and 14400 g/mol, respectively, were synthesized via a straightforward bulk polymerization process by utilizing biobased starting materials: butanediol, adipic acid and nylon 6,6 salt. The amide-to-ester ratio was varied to analyze the influence of the amide content on the molecular structure, thermal properties, mechanical properties, hydrophilicity and biodegradability. Strong relationships between the amide content and the Tg, Tm, degree of crystallinity, and mechanical properties were observed. Water contact angle measurements revealed that all the polyester amides were hydrophilic. Finally, the biodegradation experiments demonstrated that all polyester amides are prone to biodegradation in activated sludge and that the amide content had a major influence on the biodegradation rate. This work supports the high potential of biobased polyester amides for applications in numerous fields due to their versatility in terms of polymeric properties and sustainable character.

On the Activation Energy of Termination in Radical Polymerization, as Studied at Low Conversion.

The chain-length-dependent nature of the termination reaction in radical polymerization (RP) renders the overall termination rate coefficient, <kt>, a complex parameter in the usual situation where the radical chain-length distribution is non-uniform. This applies also for the activation energy of termination, Ea(<kt>), which we subject to detailed mechanistic investigation for the first time. The experimental side of this work measures Ea(<kt>) for the dilute-solution, low-conversion, chemically initiated homopolymerization of styrene (ST), methyl methacrylate (MMA), butyl methacrylate, and dodecyl methacrylate. Values of 25-39 kJ mol-1 are obtained, consistent with strong chain-length-dependent termination (CLDT) for short chains. On other hand, the reanalysis of analogous bulk polymerization data for ST and MMA finds Ea(<kt>) values of 18-24 kJ mol-1, consistent with weak CLDT for long chains. Both these results are as expected from the so-called composite model for CLDT. A simple analytic framework for understanding and predicting Ea(<kt>) values is presented for the standard RP situation of continuous initiation. All the results of this work can be rationalized via this framework, which clearly establishes that Ea(<kt>) is determined by far more than just the Ea of radical diffusion. This framework is extended to activation energy for the number-average degree of polymerization, Ea(DPn), which we measure and successfully scrutinize via our CLDT model. In the final section of this work, we make interesting, testable predictions about Ea(<kt>) and/or Ea(DPn) in various RP systems of different natures to those studied here, most notably, systems involving acrylates, continuous photoinitiation, or dominant chain transfer.

Removal of pyrene from domestic water supply using styrene-based imprinted polymer

Pyrene removal from domestic water supply (DWS) is important due to its mutagenicity, toxicity, and carcinogenicity. Use of molecularly imprinted polymer for pyrene removal is scarce, therefore the study developed polystyrene to complement conventional water treatment methods for pyrene removal. Bulk polymerisation was used to synthesise Pyrene imprinted polystyrene (PIP) and its non-imprinted analogue (NIP). Monoliths were characterised using SEM–EDX, FT-IR, and XRD. Extraction and concentration of pyrene were determined using GC–MS. Adsorption experiments on simulated solutions of pyrene with different concentrations, pH, adsorbent dosage, time, and temperature using PIP and NIP with equilibrium studies were done. Recovery was performed, while pyrene was adsorbed using simulated experiment best conditions. Used PIP and NIP were characterised. Pre-adsorption characterisation confirmed PIP and NIP while post-adsorption showed a clogged surface for NIP, but PIP was pyrene-selective. Pyrene concentration (0.05 mg/L) in DWS was > WHO standard (0.0002 mg/L) with 100% recovery. Adsorption efficiencies ranged from 25–100% and 15–100% with varied parameters for PIP and NIP respectively. However, best adsorption conditions are pH-9, time-1 h, adsorbent dosage-0.8 g, concentration-0.001 mgL−1, and temperature-27 °C with ΔG° (KJmol−1)13.48, 13.70, 13.94 for NIP and 21.24, 21.60, 21.95 for PIP. NIP ΔH° -0.3233 KJmol−1 and ΔS, 0.046 KJmol−1 k−1, while PIP ΔH° -0.0717KJmol−1 and ΔS, 0.071 KJmol−1 k−1. Adsorption fits Langmuir isotherm compared to others with R2 of 0.9140 and 0.9540 for PIP and NIP respectively. The study showed that both PIP and NIP removed pyrene from DWS with excellent efficiencies. However, PIP showed greater selectivity for pyrene removal.Graphical

Comb-grafted poly(vinyl phosphate)-based molybdovanadate heteropoly acid for efficient deep oxidative desulfurization using ionic liquid extractants under mild conditions

The development of simple and efficient desulfurization catalysts has garnered increasing attention in the field of desulfurization. In this study, comb-grafted polyethylene phosphomolybdenum-vanadium heteropoly acid catalysts (P-VPA-MomVn) were synthesized via the bulk polymerization method. The structure and morphology of the catalysts were investigated by FTIR, GPC, 1H NMR, XRD, XPS and SEM. By incorporating ionic liquid as an extractant, the P-VPA-Mo10V2 demonstrates high activity in oxidative desulfurization, removing all DBT from the model oil with a low O/S molar ratio under mild conditions. It is noteworthy that when the reaction temperature is 30 °C, the O/S molar ratio is 3, and the reaction time is 60 min, the catalyst exhibits excellent recycling lifetime of 10 cycles without a significant decline in activity. The incorporation of the ionic liquid further enhances its extraction efficiency, indicating that the catalyst not only possesses a stable structure but also holds strong prospects for industrial application.

Bright Nanocomposites based on Quantum Dot‐Initiated Photocatalysis

AbstractIntegrating quantum dots (QDs) into polymer matrix to form nanocomposites without compromising the QD photoluminescence (PL) is crucial to emerging QD light‐emitting and solar energy conversion fields. However, the most widely‐used bulk polymerization technique, where monomers serve as the QD solvent, usually leads to QD PL quenching caused by radical initiators. Here we demonstrate high‐brightness nanocomposites with near‐unity PL quantum yield (QY), through a novel QDs‐catalyzed (‐initiated) bulk polymerization without using any radical initiators. Different from previous reports where QDs were designed as photo‐sensitizers/catalysts (always with cocatalysts) and hence non‐emissive in catalytic conditions, our QDs combine high brightness with highly effective catalysis, a combination that was previously considered to be hardly possible. In our case, apart from emitting light (at a large probability), the photoexcited QDs act as ‘overall reaction’ catalysts by simultaneously employing photoexcited electrons and holes to produce active radicals without the need of any sacrificial agents. These active radicals, though with a small amount, are sufficient to initiate effective chain reaction‐dominated bulk polymerization, eliminating the requirement of extra radical initiators. This study provides new insights for understanding and development of QDs for energy applications.

Bright Nanocomposites based on Quantum Dot-Initiated Photocatalysis.

Integrating quantum dots (QDs) into polymer matrix to form nanocomposites without compromising the QD photoluminescence (PL) is crucial to emerging QD light-emitting and solar energy conversion fields. However, the most widely-used bulk polymerization technique, where monomers serve as the QD solvent, usually leads to QD PL quenching caused by radical initiators. Here we demonstrate high-brightness nanocomposites with near-unity PL quantum yield (QY), through a novel QDs-catalyzed (-initiated) bulk polymerization without using any radical initiators. Different from previous reports where QDs were designed as photo-sensitizers/catalysts (always with cocatalysts) and hence non-emissive in catalytic conditions, our QDs combine high brightness with highly effective catalysis, a combination that was previously considered to be hardly possible. In our case, apart from emitting light (at a large probability), the photoexcited QDs act as 'overall reaction' catalysts by simultaneously employing photoexcited electrons and holes to produce active radicals without the need of any sacrificial agents. These active radicals, though with a small amount, are sufficient to initiate effective chain reaction-dominated bulk polymerization, eliminating the requirement of extra radical initiators. This study provides new insights for understanding and development of QDs for energy applications.

Chromoionophores decorated silica-polymer hybrid monolith as the solid-state optical sensor for the simultaneous detection of Pb2+, Hg2+, and Cd2+ in aqueous and cigarette samples

This work reports on fabricating a flexible and reliable three-in-one solid-phase ocular sensor to perceive and confiscate the trace Pb2+, Hg2+, and Cd2+ using a structurally customized probe-anchored porous hybrid monolithic sensor. The dual combination of silica/polymer hybrid monolith was achieved from the bulk polymerization of 3-(trimethoxysilyl) propyl methacrylate (TSPM) and pentaerythritol trimethacrylate (PETMA), i.e., poly(TSPM-co-PETMA). The monolithic template delivered a well-ordered porous structure and greater surface area that enabled the regular impregnation of chromophoric probe (TAN), i.e., (E)-1-(thiazol-2-yldiazenyl) naphthalene-2-ol onto monolith surface for sensing target analytes under lower ppb levels. FE-SEM, HR-TEM, EDAX, SAED, p-XRD, FT-IR, TGA and N2 isotherm were deployed to characterize the structural and exterior topographies of the hybrid sensor. The geometrically frozen TAN molecules onto the hybrid monolith form a charge transfer complex with the target ions, thereby rendering a consecutive color shift from light orange to brown for Pb2+, reddish maroon for Hg2+, and purplish pink for Cd2+. The sensor offered a linear response with metal ion concentrations ranging from 0.2 to 100 ppb with lower detection limit values of 0.42, 0.50, and 0.48 ppb for Pb2+, Hg2+, and Cd2+, respectively. The hybrid sensor affords distinct ion sensitivity and selectivity towards Pb2+, Hg2+, and Cd2+ with a quick response time of ≤ 80 s of contact. Furthermore, the sensor was tested with natural samples like environmental water and cigarette samples to validate the method’s real-time monitoring ability. The resultant statistical data demonstrated that the proposed colorimetric sensor was renewable and more feasible for practical application.

Mechanical and Dimensional Stability of Gelatin-Based Hydrogels Through 3D Printing-Facilitated Confined Space Assembly.

Hydrogels have emerged as promising biomaterials for tissue regeneration; yet, their inherent swelling can cause deformation and reduced mechanical properties, posing challenges for practical applications in biomedical engineering. Traditional methods to reduce hydrogel swelling often involve complex synthesis procedures with limited flexibility. Inspired by nature's efficient designs, we present here the approach to improve hydrogel performance using 3D printing-assisted microstructure engineering. By utilizing polymerization-induced phase separation of hydrogel from copolymerization of gelatin methacrylate and hydroxyethyl methacrylate (poly(GelMA-co-HEMA)) in the confined space during vat photopolymerization (VPP) 3D printing, we replicate the cuttlebone-like microstructure of hydrogels with enhanced mechanical properties and swelling resistance. We demonstrate here a 4-fold increase in elastic modulus compared to bulk polymerization of poly(GelMA-co-HEMA), together with improved mechanical and dimensional stability. This method offers promising opportunities for practical biomedical and tissue engineering applications, overcoming previous limitations in the design and performance.

Preparation and application of a new ion-imprinted polymer for nanomolar detection of mercury(II) in environmental waters

This study introduces a novel ion-imprinted polymer for the ultrasensitive detection of mercury(II) in water. The ion-imprinted polymer was synthesized via a simple bulk polymerization process using methacrylic acid as the functional monomer, ethylene glycol dimethacrylate as the cross-linker, morpholine-4-carbodithioic acid phenyl ester as the chelating agent, and ammonium persulfate as the initiator. The electrochemical mercury(II) sensing capability of the ion-imprinted polymer was studied via the modification of a cost-effective carbon paste electrode. A stripping voltammetric technique was utilized to quantify the analyte ions following open-circuit enrichment. Critical experimental parameters, including the nature and concentration of the eluent, solution pH, preconcentration duration, ion-imprinted polymer dosage, sample solution volume and reduction potential, were systematically studied and optimized. Under optimal conditions, the sensor exhibited a linear response in the range of 1.0 to 240.0 nM, with a low detection limit of 0.2 nM. The sensor demonstrated remarkable selectivity against potential interfering ions, including lead(II), cadmium(II), copper(II), zinc(II), manganese(II), iron(II), magnesium(II), calcium(II), sodium(I) and cobalt(II). The practical applicability of the developed method was successfully validated through the analysis of real water samples, suggesting its potential for environmental monitoring applications.

Kinetics and scale inhibition application studies towards bulk and RAFT copolymerization of maleic anhydride and acrylic acid

Poly(maleic anhydride) (PMA) is commonly reckoned as a better water scale inhibitor than poly(acrylic acid) (PAA) since each maleic anhydride unit can supply two carboxylic acid groups. However, pure PMA is difficult to achieve because the steric effect of its monomer MA. Herein, we synthesize copoly(MA-AA) copolymer by bulk polymerization method (bulk-copoly(MA-AA)), which avoids the use of any solvents which have to be removed afterwards. In addition, we also synthesize copoly(MA-AA) by reversible addition-fragmentation chain transfer (RAFT) polymerization method to afford RAFT-copoly(MA-AA) with low polydispersity index (PDI) less than 1.2, and the performance of RAFT-copoly(MA-AA) in water scale inhibition is more excellent relative to bulk-copoly(MA-AA). We also synthesize other copoly(MA-AA) copolymers by varying the molar ratio of MA to AA to study the polymerization mechanism. Through the static scale inhibition experiment, it is concluded that when the concentration of copoly(MA-AA) is 80 mg/L, the scale inhibition performance of RAFT-copoly(MA-AA) can reach 96.50 % which is the best among the control samples. It is also found that only 1:1 alternating copolymerization of MA and AA could be achieved as demonstrated by 1H nuclear magnetic resonance spectra of the copolymers, evidencing the strong steric hindrance of MA for its homo-polymerization.

An entropy- TOPSIS approach to find PMMA/cellulose based biocomposite with optimum mechanical and bio-degradation properties

Poly methyl methacrylate based biocomposite has been manufactured using nanocellulose as reinforcement, which has been extracted from bagasse. The biocomposites are formed by bulk polymerization using benzoyl peroxide as initiator. The composites are evaluated by FTIR, X-ray diffraction, mechanical properties, UV analysis, scanning electron microscope, polarizing light microscope and thermo-gravimetric analysis. Variation in properties is an inherent drawback of natural fibers, for which this MCDM technique is very effective to decipher, the biocomposite with optimum properties. It has been found that when the bagasse fiber is treated with 3.5 % of sodium chlorite solution, it can produce biocomposite with PMMA. It has been observed that, cellulose grafting takes place in the PMMA chain in presence of benzoyl peroxide. Further the work has been extended with loading variation of the said cellulose fibers and 1.5 % loading has been found as the best. The novelty of the work lies in the fact that these evaluations have been substantiated by Multi-Criteria Decision Making (MCDM) technique involving ENTROPY and TOPSIS approach and successfully selected 1.5 wt % loading to fabricate the optimum biocomposite. This composite exhibited around 13.5 % biodegradation within 90 days. This film can find application in packaging field.

Microwave-assisted supramolecular double crosslinked chitosan-based molecularly imprinted polymer for synergistic recognition and selective recovery of Cd(II) and As(V) from water: Performance and mechanistic insights

A novel model of the sustainable double crosslinked molecularly imprinted polymer (D-Crosslinked MIP) represented as a supramolecular imprinted polymer was synthesized via the bulk polymerization method. The primary crosslinking was fabricated using biomacromolecule chitosan as a functional monomer and glutaraldehyde as a crosslinker. The primary crosslinked was subjected to dynamic interactions in a secondary crosslinking by binding Al2O3-NPs and TiO2-NPs, forming the supramolecular D-Crosslinked-MIP. The dually crosslinked formed from combining three distinct crosslinkers in one system for the interaction with As(V) and Cd(II). A microwave was employed to evaluate the performance of the designed material in selectivity and extraction of metal ions from water. The FT-IR, XRD, TG/DTA, SEM-EDX, TEM, and XPS were used to verify the characteristics of (D-nano-Al2O3@Crosslinked Chitosan@D-nano-TiO2). The type of solvents, selectivity, interferences, microwave-contact time, pH, temperatures, concentrations, and regeneration were investigated. By using the D-Crosslinked-MIP, at 15 s, Cd(II) revealed a recovery capacity of 99.03 %, Qmax 862.07 mg/g, while As(V) demonstrated a recovery capacity of 99.06 %, Qmax 850.75 mg/g. The D-Crosslinked-MIP exhibited BETs of 69.01 m2/g with a pore volume of 0.2340 cm3/g owing to polymeric crosslinking by metal oxide NPs. The kinetics, isotherm models, and mechanisms of dually crosslinking and extraction of toxic metals were discussed.

Selective Methylation of Cyclic Ether Towards Highly Elastic Solid Electrolyte Interphase for Silicon-based Anodes.

Silicon (Si)-based anodes offer high theoretical capacity for lithium-ion batteries but suffer from severe volume changes and continuous solid electrolyte interphase (SEI) degradation. Here, we address these challenges by selective methylation of 1,3-dioxolane (DOL), thus shifting the unstable bulk polymerization to controlled interfacial reactions and resulting in a highly elastic SEI. Comparative studies of 2-methyl-1,3-dioxolane (2MDOL) and 4-methyl-1,3-dioxolane (4MDOL) reveal that 4MDOL, with its larger ring strain and more stable radical intermediates due to hyperconjugation effect, promotes the formation of high-molecular-weight polymeric species at the electrode-electrolyte interface. This elastic, polymer-rich SEI effectively accommodates volume changes of Si and inhibits continuous side reactions. Our designed electrolyte enables Si-based anode to achieve 85.4 % capacity retention after 400 cycles at 0.5 C without additives, significantly outperforming conventional carbonate-based electrolytes. Full cells also demonstrate stable long-term cycling. This work provides new insights into molecular-level electrolyte design for high-performance Si anodes, offering a promising pathway toward next-generation lithium-ion batteries with enhanced energy density and longevity.

Eco-friendly covalently connected silicone hydrogel with negatively charged surface for marine anti-biofouling

In this study, a silicone hydrogel (Gel-TA-Si-x) with amphiphilic and negatively charged surfaces was prepared by combining low surface free energy silicone with highly hydrophilic hydrogel materials using the method of one-step solvent-free bulk polymerization. The hydrogel films exhibited good mechanical properties. This was primarily reflected in the high tensile strength (1 MPa) and elongation at break (358.1 %). Notably, the film exhibited increased hydrophobicity, higher water contact angle and gradual decline in water absorption rate as the mPDMS monomer dosage increased. Despite this, the surface free energy remained low at 22.1 mJ m−2, indicating effective fouling release capability (removal strength against pseudobarnacles was 0.16 MPa). In addition, the surface zeta potential of the hydrogel was as low as −86 mV (at pH = 10). Laboratory antifouling performance tests indicated that the surface negativity of the material enhanced its static antifouling performance and the hydrogel with a negatively charged surface exhibited high bacterial adhesion resistance of 93 % and good resistance to Chlorella adherence and biofilm inhibition. Favorable anti-fouling performance was observed after 180 d of marine field testing. Moreover, the covalent connection of silicone monomers with hydrogel monomers through copolymerization create a stable three-dimension crosslinking network, thereby improving the durability of materials in complex marine environments. This study provides a new idea for developing efficient and environmentally friendly silicone hydrogel antifouling materials.

Selective Methylation of Cyclic Ether Towards Highly Elastic Solid Electrolyte Interphase for Silicon‐based Anodes

Silicon (Si)‐based anodes offer high theoretical capacity for lithium‐ion batteries but suffer from severe volume changes and continuous solid electrolyte interphase (SEI) degradation. Here, we address these challenges by selective methylation of 1,3‐dioxolane (DOL), thus shifting the unstable bulk polymerization to controlled interfacial reactions and resulting in a highly elastic SEI. Comparative studies of 2‐methyl‐1,3‐dioxolane (2MDOL) and 4‐methyl‐1,3‐dioxolane (4MDOL) reveal that 4MDOL, with its larger ring strain and more stable radical intermediates due to hyperconjugation effect, promotes the formation of high‐molecular‐weight polymeric species at the electrode‐electrolyte interface. This elastic, polymer‐rich SEI effectively accommodates volume changes of Si and inhibits continuous side reactions. Our designed electrolyte enables Si‐based anode to achieve 85.4% capacity retention after 400 cycles at 0.5 C without additives, significantly outperforming conventional carbonate‐based electrolytes. Full cells also demonstrate stable long‐term cycling. This work provides new insights into molecular‐level electrolyte design for high‐performance Si anodes, offering a promising pathway toward next‐generation lithium‐ion batteries with enhanced energy density and longevity.

Surface coupling of molecularly imprinted polymers as strategy to improve sulfamethoxazole removal from water by carbons produced from spent brewery grain

This work aims to assess the surface coupling of molecularly imprinted polymers (MIP) on carbon adsorbents produced from spent brewery grain, namely biochar (BC) and activated carbon (AC), as a strategy to improve selectivity and the adsorptive removal of the antibiotic sulfamethoxazole (SMX) from water. BC and AC were produced by microwave-assisted pyrolysis, and MIP was obtained by fast bulk polymerization. Two different methodologies were used for the molecular imprinting of BC and AC, the resulting materials being tested for SMX adsorption. Then, after selecting the most favourable molecular imprinting methodology, different mass ratios of MIP:BC or MIP:AC were used to produce and evaluate eight different materials. Molecular imprinting was shown to significantly improve the performance of BC for the target application, and one of the produced composites (MIP1-BC-s(1:3)) was selected for further kinetic and equilibrium studies and comparison with individual MIP and BC. The kinetic behaviour was properly described by both the pseudo-first and pseudo-second order models. Regarding equilibrium isotherms, they fitted the Freundlich and Langmuir models, with MIP1-BC-s(1:3) reaching a maximum adsorption capacity (qm) of 25 ± 1 μmol g-1, 19 % higher than BC. In comparison with other seven pharmaceuticals, the adsorption of SMX onto MIP1-BC-s(1:3) was remarkably higher, as for the specific recognition of this antibiotic by the coupled MIP. The pH study evidenced that SMX removal was higher under acidic conditions. Regeneration experiments showed that MIP1-BC-s(1:3) provided good adsorption performance, which was stable during five regeneration-reutilization cycles. Overall, this study has demonstrated that coupling with MIP may be a suitable strategy to improve the adsorption properties and performance of biochar for antibiotics removal from water, increasing its suitability for practical applications.

Changes in amorphous structure and reaction acceleration during bulk polymerization of methacrylates

Changes in amorphous structure and reaction acceleration during bulk polymerization of methacrylates

Ultrasound‐assisted liquid phase exfoliation of boron nitride nanosheets as fillers for polyacrylate pressure‐sensitive adhesives with enhanced thermal conductivity

AbstractHexagonal boron nitride (h‐BN) is widely used as a filler to improve the thermal conductivity of polymers due to the high thermal conductivity, electrical insulation, and chemical stability. However, the small lateral‐size and poor compatibility limit h‐BN's performances and applications in thermal management. Here, boron nitride nanosheets (BNNSs) were prepared by liquid‐phase ultrasonic exfoliation using isopropanol (IPA) as solvent. Specifically, the BNNSs obtained by ultrasonication for 8 h with an initial concentration of h‐BN of 8 mg/mL have the best exfoliation effect and a high yield of 19.8%, showing a large lateral‐size of 1–2 μm and an ultra‐thin thickness. Then, the resulting BNNSs can be modified by grafting silane coupling agent of KH560 (m‐BNNSs), their micromorphology and chemical composition are characterized by various microscopies and spectrometers. Subsequently, polyacrylate pressure‐sensitive adhesives (PSAs) composites are prepared using m‐BNNSs as a thermally conductive filler by UV bulk polymerization, their thermal conductivity can be greatly improved by 250% compared with that of pure PSAs. For comparison, the thermal conductivity of m‐BNNSs/PSAs composites with filler content of 25 wt% is as high as 0.4382 W/(m K), which is 1.6 times higher than that of h‐BN/PSAs composites. In addition, the incorporation of BNNSs will improve the thermal stability, hardness, and 180° peeling force of the PSAs composites, which will stimulate the practical application of PSAs materials.

Computer simulation‐guided template selection for a molecularly imprinted polymer for selective trifluralin adsorption

AbstractTo meet selective adsorption toward trifluralin, a novel molecularly imprinted polymer (MIP) was fabricated by the dummy template molecular imprinting technology. First, computational simulation was performed to select a suitable dummy template, 3,5‐dinitro‐4‐methylbenzoic acid (T1), based on the maximum basis set superposition error (BSSE)‐corrected binding interaction energy (ΔE) of the monomer N‐vinylpyrrolidone (NVP)‐T1 complex and its structural overlap with trifluralin. Then, the MIP was prepared via the bulk polymerization. The adsorption experiments showed the MIP exhibited a trifluralin adsorption capacity of 5.1 mg g−1, an imprinting factor (IF) of 2.2, and short adsorption equilibrium time of 5 min. The adsorption of trifluralin conformed to the Freundlich adsorption (R2 = 0.985) and pseudo‐second‐order model (R2 = 0.999). In addition, the MIP exhibited selectivity to trifluralin over other adsorbents, including structural analogs (pendimethalin and oryzalin), pesticide (carbendazim), and nitrocompounds (nitrofurantoin, furazolidone, and furaltadone), with the selectivity factor (β) in the range of 1.2–3.0, respectively. In trifluralin/oryzalin mixture, the IF toward oryzalin was still as high as 1.9. The removal rate of the MIP to trifluralin in environmental water samples ranged from 90.08% to 99.04%. This study provides theoretical and experimental insights for the preparation of MIP using dummy templates.

Development of a Molecularly Imprinted Polymer for Determination of Atenolol Based on Selective Solid Phase Extraction and Application in Pharmaceutical Samples

This paper demonstrates the synthesis and storage of molecular-imprinted polymers (MIP) at room temperature using bulk polymerization of atenolol (Ate), which is characterized by high sensitivity, low costs, and high stability. The research used 0.99:6:20 mmol ratios of template, monomer, and cross-linking agents for the polymerization in order to ensure an appropriate adsorption capacity. By making MIP for atenolol as Ate-MIP, which could be looked at with a UV-VIS spectrophotometer at 276 nm, Fourier- transform infrared spectroscopy (FT-IR), and scanning electron microscopy (SEM), a functional monomer of allyl chloride with cross-linking ethylene glycol dimethyl acrylate was made. Mass spectrometric (MS) detection may use allyl chloride to determine atenolol levels in pharmaceutical preparations. The GC/MS methods developed in this study are accurate, sensitive, and precise and can be easily applied to (NOVATEN/India and ATENOIOI/U.K.) tablets in pharmaceutical preparation. The elution process was applied to the template (Ate) from the Ate-MIP, which developed cavities, caused by using porogenic solutions of methanol, chloroform, and acetic acid (70:20:10, respectively). The maximum adsorption capacity of Ate-MIP was 2.9957 µmol/g, and the ratio of template to monomer was 1:1 in adherence to the Langmuir isotherm model. A solid-phase extraction (SPE) syringe packed with molecular imprinted polymers (MIPs) was used to selectively separate and pre-concentrate Ate from aqueous solutions and estimations of atenolol.