Search Results (114)

The removal of pharmaceutical contaminants like the anticonvulsant carbamazepine (CBZ) from water sources is a growing environmental challenge. This study explores the development of molecularly imprinted polymers (MIPs) tailored for CBZ adsorption using a bulk polymerization approach. Initially, this study focused on selecting the optimal cross-linker, comparing a trifunctional (trimethylolpropane triacrylate, TRIM) and a bifunctional cross-linker (ethylene glycol dimethacrylate, EGDMA) in combination with two common monomers (2-vinylpyridine and methacrylic acid). TRIM-based MIPs demonstrated superior adsorption efficiency and stability due to their higher cross-linking density. To improve sustainability, six bio-based monomers were investigated; of these, eugenol (EUG) and coumaric acid (COU) showed the best CBZ affinity due to π-π interactions and hydrogen bonding. Adsorption tests conducted in pharmaceutical-spiked real wastewater demonstrated that MIPs exhibit a high selectivity for CBZ over other pharmaceuticals like the anti-inflammatory drugs diclofenac (DCF) and ibuprofen (IBU), even at high concentrations. Reaction conditions were further optimized by adjusting the reaction time and the ratio between reagents to enhance selectivity and adsorption performance. These results highlight the potential of bio-based MIPs as efficient and selective materials for the removal of pharmaceutical pollutants from wastewater. Full article

A simple, fast, and low-cost pre-concentration methodology based on the application of multi-template molecularly imprinted polymers (mt-MIP) in a solid-phase extraction system coupled with capillary electrophoresis was developed for the determination of naproxen, diclofenac, and ibuprofen in environmental water samples. A systematic study of the mt-MIP composition was conducted using a second-order simplex lattice experiment design (fraction of the functional monomer methacrylic acid (MAA), the total moles of functional monomers, and the total moles of the cross-linker agent). The optimal mt-MIP, consisting of 0.025 mmol of each analyte, with 2.40 mmol of methacrylic acid (MAA) and 3.60 mmol of 4-vinylpyridine (4VP) and 23.00 mmol of the cross-linker agent (EGDMA), was coupled to an SPE system under the optimal conditions: pH = 3.5; 20 mg of mt-MIP; and an eluent (MeOH/NaOH [0.001]). This methodology provides limits of detection from 3.00 to 12.00 µg L⁻¹ for the studied NSAIDs. The methodology’s precision was evaluated in terms of inter- and intra-day repeatability, with %RSD < 10% in all cases. Finally, the proposed method can be successfully applied in the analysis of environmental water samples (bottle, tap, cistern, well, and river water samples), which demonstrates the developed method’s robustness. Full article

Block copolymer (BCP) lithography is widely regarded as a promising next-generation nanolithography technique. However, achieving rapid assembly with defect-free morphology remains a significant challenge for its practical application. In this study, we presented a facile and efficient solvent annealing method for fabricating well-ordered BCP thin films within minutes on both flat and topographically patterned substrates. By accelerating the swelling process, rapid film swelling was observed within just 10 s of annealing, leading to well-ordered morphologies in 1~3 min. Furthermore, we systematically investigated the influence of swelling ratio (SR) on film morphology by precisely tuning solvent vapor pressure. For cylinder-forming poly(styrene-block-2-vinylpyridine) (PS-b-P2VP) films, we identified three distinct SR-dependent ordering regimes: (I) Excessive SR led to a disordered morphology; (II) near-optimal SR balanced long-range and short-range orders, and a slight increase in SR enhanced the long-range order but introduced short-range defects. (III) Insufficient SR failed to provide adequate chain mobility, limiting long-range order development. These findings highlight the critical role of SR in controlling defect density in nanopatterned surfaces. Long-range-ordered BCP nanopatterns can only be achieved under optimal SR conditions that ensure sufficient chain mobility. We believe this rapid annealing strategy, which is also applicable to other solvent-based annealing systems for BCP films, may contribute to next-generation nanolithography for microfabrication. Full article

Resorcinarenes are polyhydroxylated platforms consisting of 4, 5, 8, or more units of resorcinol. The numbers refer to the number of resorcinol units, with 4-unit platforms being the most stable. Investigation into their use in pharmaceutical applications has increased due to high versatility and functionalization. They exhibit significant flexibility due to their methylene bridges and to the interactions of hydrogen bridges and van der Waals forces. These platforms can be used in an increasing number of applications, which include the functionalization of nanoparticles and relevant materials, the synthesis of catalysts, the removal of contaminants, and analytical separations in analytes such as benzodiazepines and norepinephrine. For this last application, resorcinarenes are functionalized with specific important functional groups. Polymers were developed in the 20th century for the development of materials with significant improvements in thermal and mechanical properties. They are cross-linked polymeric structures, mainly made up of monomers such as styrene, divinylbenzene acrylate, vinylpyridine, and vinyl acetate, among others. They often have a homogeneous, porous structure, but this structure can vary significantly depending on the type of solvent used. Therefore, they have been applied in the functionalization of the polyhydroxylated platforms. In this review, the structure, properties, and synthesis of resorcinarenes, as well as the use of polymeric matrices, are analyzed, emphasizing the functionalization of organic polymers using resorcinarenes. Furthermore, the respective applications in controlled drug delivery, pharmaceutical transport, and therapeutics, which are diverse and show promising growth, will be explored. Full article

In this work, we have employed an advanced method of solvent vapor annealing to expose spin-cast thin films made from various lamellar and micellar block copolymers to generous amounts of different types of solvent vapors, with the final goal of stimulating the films’ self-assembly into (hierarchically) ordered structures. As revealed by atomic force microscopy measurements, periodic lamellar nanostructures of molecular dimensions based on poly(4-vinylpyridine)-b-polybutadiene and poly(2-vinylpyridine)-b-polybutadiene, as well as micellar structures further packed into either (parallel) stripe-like or honeycomb-resembling configurations based on poly(2-vinylpyridine)-b-poly(tert-butyl methacrylate)-b-poly(methacrylate cyclohexyl), were successfully produced through processing. Full article

Mechanically improved polymeric membranes with high ionic conductivity (IC) and good permeability are highly desired for next-generation anion exchange membranes (AEMs) in order to reduce Ohmic losses and enhance water management in alkaline membrane fuel cells. To move towards the fabrication of such high-performance membranes, the creation of hydrophilic ion-conducting double gyroid (DG) nanochannels within block copolymer (BCP) AEMs is a promising approach. However, this attractive solution remains difficult to implement due to the complexity of constructing a well-developed ion-conducting DG morphology across the entire membrane thickness. To deal with this issue, water permeable polystyrene-block-poly(2-vinylpyridine)-block-poly(ethylene oxide) membranes with ion-conducting DG nanochannels were produced by combining a solvent vapor annealing (SVA) treatment with a methylation process. Here, the SVA treatment enabled the manufacture of DG-forming BCP AEMs while the methylation process allowed for the conversion of pyridine sites to N-methylpyridinium (NMP⁺) cations via a Menshutkin reaction. Following this SVA-methylation method, the IC value of water-permeable (~384 L h⁻¹ m⁻² bar⁻¹) DG-structured BCP AEMs in their OH⁻counter anion form was measured to be of ~2.8 mS.cm⁻¹ at 20 °C while a lower IC value was probed, under the same experimental conditions, from as-cast NMP⁺-containing analogs with a non-permeable disordered phase (~1.2 mS.cm⁻¹). Full article

This study investigated the properties of a novel polymeric membrane based on cellulose acetate, polyethylene glycol/poly(styrene)-b-poly(4-vinylpyridine), and embedded with TiO₂ nanoparticles (CA/PEG/PS₁₅₄-b-P4VP₃₈₁/TiO₂ membrane) obtained by wet-phase inversion method. The TiO₂ nanoparticles fabricated by a hydrothermal method were characterized by XRD, SEM, EDX, and UV-Vis analyses to determine the purity, morphology, and optical band gap energy. The prepared polymeric membranes with and without TiO₂ nanoparticles (CA/PEG/PS₁₅₄-b-P4VP₃₈₁/TiO₂ and CA/PEG/PS₁₅₄-b-P4VP₃₈₁ membranes) were characterized by FTIR, SEM, EDXS, and TGA to observe the effect of TiO₂ nanoparticles added to the polymeric membrane matrix and to analyze the chemical structure, morphology, and thermal stability of the obtained polymeric membranes. The contact angle, SFE, water retention, and porosity were also determined. The results showed that adding the TiO₂ nanoparticles into the polymeric membrane (CA/PEG/PS₁₅₄-b-P4VP₃₈₁/TiO₂) significantly reduced the pore size and the water contact angle, increasing the water retention and the porosity. The lower value of the water contact angle of 15.57 ± 0.45° for the CA/PEG/PS₁₅₄-b-P4VP₃₈₁/TiO₂ membrane indicates a pronounced hydrophilic character. The investigations performed showed that the CA/PEG/PS₁₅₄-b-P4VP₃₈₁/TiO₂ membrane presents excellent properties and can be a promising material for water and waste-water treatment through membrane processes (e.g., electrodialysis, ultrafiltration, nanofiltration, reverse osmosis) in the future. Full article

Zwitterionic polymers have garnered significant attention for their distinctive properties, such as biocompatibility, antifouling capabilities, and resistance to protein adsorption, making them promising candidates for a wide range of applications, including drug delivery, oil production inhibitors, and water purification membranes. This study reports the synthesis and characterization of zwitterionic monomers and polymers through the modification of linear, vinyl, and aromatic heterocyclic functional groups via reaction with 1,3-propanesultone. Four zwitterionic polymers with varying molecular structures—ranging from linear to five and six membered ring systems—were synthesized: poly(sulfobetaine methacrylamide) (pSBMAm), poly(sulfobetaine-1-vinylimidazole) (pSB1VI), poly(sulfobetaine-2-vinylpyridine) (pSB2VP), and poly(sulfobetaine-4-vinylpyridine) (pSB4VP). Their molecular weights, thermal behavior, and self-assembly properties were analyzed using gel permeation chromatography (GPC), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), transmission electron microscopy (TEM), and zeta potential measurements. The glass transition temperatures (Tg) ranged from 276.52 °C for pSBMAm to 313.69 °C for pSB4VP, while decomposition temperatures exhibited a similar trend, with pSBMAm degrading at 301.03 °C and pSB4VP at 387.14 °C. The polymers’ self-assembly behavior was strongly dependent on pH and their surface charge, particularly under varying pH conditions: spherical micelles were observed at neutral pH, while fractal aggregates formed at basic pH. These results demonstrate that precise modifications of the chemical structure, specifically in the linear, imidazole, and pyridine moieties, enable fine control over the thermal properties and self-assembly behavior of polyzwitterions. Such insights are essential for tailoring polymer properties for targeted applications in filtration membranes, drug delivery systems, and solid polymer electrolytes, where thermal stability and self-assembly play crucial roles. Full article

The linear diblock copolymer polystyrene-b-poly(4-vinylpyridine) (PS-P4VP) is an important copolymer recently used in many applications such as optoelectronics, sensors, catalysis, membranes, energy conversion, energy storage devices, photolithography, and biomedical applications. (1) Background: The surface thermodynamic properties of PS-P4VP copolymers are of great importance in many chemical and industrial processes. (2) Methods: The inverse gas chromatography (IGC) at infinite dilution was used for the experimental determination of the retention volumes of organic solvents adsorbed on copolymer surfaces as a function of temperature. This led to the variations in the free energy of interaction necessary to the evaluation of the London dispersive and polar acid–base surface energies, the polar enthalpy and entropy, the Lewis acid–base constants, and the transition temperatures of the PS-P4VP copolymer. (3) Results: The application of the thermal Hamieh model led to an accurate determination of the London dispersive surface energy of the copolymer that showed non-linear variations versus the temperature, highlighting the presence of two transition temperatures. It was observed that the Lewis acid–base parameters of the copolymer strongly depend on the temperature, and the Lewis base constant of the solid surface was shown to be higher than its acid constant. (4) Conclusions: An important effect of the temperature on the surface thermodynamic properties of PS-P4VP was proven and new surface correlations were determined. Full article

Starting from poly(4-vinylpyridine) ((P4VP)_n), poly(2-vinylpyridine) ((P2VP)_n), and [N=P(O₂CH₂CF₃)]_m-b-P2VP₂₀ block copolymers, a series of metal-containing homopolymers, (P4VP)_n⊕MX_m, (P2VP)_n⊕MX_m, and [N=P(O₂CH₂CF₃)]_m-b-P2VP₂₀]⊕MX_m MX_m = PtCl₂, ZnCl₂, and Eu(NO₃)₃, have been successfully prepared by using a direct and simple solution methodology. Solid-state pyrolysis of the prepared metal-containing polymeric precursors led to the formation of a variety of different metallic and metal oxide nanoparticles (Pt, ZnO, Eu₂O₃, and EuPO₄) depending on the composition and nature of the polymeric template precursor. Thus, whereas Eu₂O₃ nanostructures were obtained from europium-containing homopolymers ((P4VP)_n⊕MX_m and (P2VP)_n⊕MX_m), EuPO₄ nanostructures were achieved using phosphorus-containing block copolymer precursors, [N=P(O₂CH₂CF₃)]_m-b-P2VP₂₀]⊕MX_m with MX_m = Eu(NO₃)₃. Importantly, and although both Eu₂O₃ and EuPO₄ nanostructures exhibited a strong luminescence emission, these were strongly influenced by the nature and composition of the macromolecular metal-containing polymer template. Thus, for P2VP europium-containing homopolymers ((P4VP)_n⊕MX_m and (P2VP)_n⊕MX_m), the highest emission intensity corresponded to the lowest-molecular-weight homopolymer template, [P4VP(Eu(NO₃)₃]₆₀₀₀, whereas the opposite behavior was observed when block copolymer precursors, [N=P(O₂CH₂CF₃)]_m-b-P2VP₂₀]⊕MX_m MX_m= Eu(NO₃)₃, were used (highest emission intensity corresponded to [N=P(O₂CH₂CF₃)]₁₀₀-b-[P2VP(Eu(NO₃)₃)_x]₂₀). The intensity ratio of the emission transitions: ⁵D₀ → ⁷F₂/⁵D₀ → ⁷F₁, suggested a different symmetry around the Eu³⁺ ions depending on the nature of the polymeric precursor, which also influenced the sizes of the prepared Pt°, ZnO, Eu₂O₃, and EuPO₄ nanostructures. Full article

The microphase separation of high-molecular-weight block copolymers into nanostructured films is strongly dependent on the surface fields. Both, the chain mobility and the effective interaction parameters can lead to deviations from the bulk morphologies in the structures adjacent to the substrate. Resolving frustrated morphologies with domain period L₀ above 100 nm is an experimental challenge. Here, solvothermal annealing was used to assess the contribution of elevated temperatures of the vapor T_v and of the substrate T_s on the evolution of the microphase-separated structures in thin films symmetric of polystyrene-b-poly(2vinylpyridine) block copolymer (PS-PVP) with L₀ about 120 nm. Pronounced topographic mesh-like and stripe patterns develop on a time scale of min and are attributed to the perforated lamella (PL) and up-standing lamella phases. By setting T_v/T_s combinations it is possible to tune the sizes of the resulting PL patterns by almost 10%. Resolving chemical periodicity using selective metallization of the structures revealed multiplication of the topographic stripes, i.e., complex segregation of the component within the topographic pattern, presumably as a result of morphological phase transition from initial non-equilibrium spherical morphology. Reported results reveal approaches to tune the topographical and chemical periodicity of microphase separation of high-molecular-weight block copolymers under strong confinement, which is essential for exploiting these structures as functional templates. Full article

There has been an increasing interest in pH sensors based on nanomaterials in environmental and biological sensing. This work addresses persistent challenges in the development of stable and sensitive pH measurements. We present a CNT-FET-based pH sensor with a hybrid encapsulation stack consisting of poly(4-vinylpyridine)/HfO₂ layers. The resulting liquid-gated sensors feature an excellent sensitivity of up to 50 mV/pH in an operation regime below 1 V, which is within the electrochemical window of most biological species. Moreover, the P4VP encapsulation results in a 1000× higher on-off-current ratio and nearly 83% smaller drift compared to devices encapsulated in only HfO₂. Full article

In this article, ABA triblock copolymer (tri-BCP) thermoplastic elastomers with poly(ethylene oxide) (PEO) middle block and polyzwitterionic poly(4-vinylpyridine) propane-1-sulfonate (PVPS) outer blocks were synthesized. The PVPS-b-PEO-b-PVPS tri-BCPs were doped with lithium bis-(trifluoromethane-sulfonyl) imide (LiTFSI) and used as solid polyelectrolytes (SPEs). The thermal properties and microphase separation behavior of the tri-BCP/LiTFSI hybrids were studied. Small-angle X-ray scattering (SAXS) results revealed that all tri-BCPs formed asymmetric lamellar structures in the range of PVPS volume fractions from 12.9% to 26.1%. The microphase separation strength was enhanced with increasing the PVPS fraction (f_PVPS) but was weakened as the doping ratio increased, which affected the thermal properties of the hybrids, such as melting temperature and glass transition temperature, to some extent. As compared with the PEO/LiTFSI hybrids, the PVPS-b-PEO-b-PVPS/LiTFSI hybrids could achieve both higher modulus and higher ionic conductivity, which were attributed to the physical crosslinking and the assistance in dissociation of Li⁺ ions by the PVPS blocks, respectively. On the basis of excellent electrical and mechanical performances, the PVPS-b-PEO-b-PVPS/LiTFSI hybrids can potentially be used as solid electrolytes in lithium-ion batteries. Full article

We report on the effect of a hydrocarbon (n-dodecane) on the rheological properties and shapes of the hybrid wormlike micelles (WLMs) of a surfactant potassium oleate with an embedded polymer poly(4-vinylpyridine). With and without hydrocarbon solutions, the hybrid micelles exhibit the same values of viscosity at shear rates typical for hydraulic fracturing (HF) tests, as solutions of polymer-free WLMs. Therefore, similar to WLMs of surfactants, they could be applied as thickeners in HF fluids without breakers. At the same time, in the presence of n-dodecane, the hybrid micelles have much higher drag-reducing efficiency compared to microemulsions formed in polymer-free systems since they form “beads-on-string” structures according to results obtained using cryo-transmission electron microscopy (cryo-TEM), dynamic-light scattering (DLS), and small-angle X-ray scattering (SAXS). Consequently, they could also act as drag-reducing agents in the pipeline transport of recovered oil. Such a unique multi-functional additive to a fracturing fluid, which permits its concurrent use in oil production and oil transportation, has not been proposed before. Full article

The energy level offset at inorganic layer–organic layer interfaces and the mismatch of hole/electron mobilities of the individual layers greatly limit the establishment of balanced charge carrier injection inside the emissive layer of halide perovskite light-emitting diodes (PeQLEDs). In contrast with other types of light-emitting devices, namely OLEDs and QLEDs, various techniques such as inserting an electron suppression layer between the emissive and electron transport layer have been employed as a means of establishing charge carrier injection into their respective emissive layers. Hence, in this study, we report the use of a thin layer of Poly(4-vinylpyridine) (PVPy) (an electron suppression material) placed between the emissive and electron transport layer of a halide PeQLEDs fabricated with an inverted configuration. With ZnO as the electron transport material, devices fabricated with a thin PVPy interlayer between the ZnO ETL and CsPbBr₃ -based green QDs emissive layer yielded a 4.5-fold increase in the maximum observed luminance and about a 10-fold increase in external quantum efficiency (EQE) when compared to ones fabricated without PVPy. Furthermore, the concentration and coating process conditions of CsPbBr₃ QDs were altered to produce various thicknesses and film properties which resulted in improved EQE values for devices fabricated with QDs thin films of lower surface root-mean-square (RMS) values. These results show that inhibiting the excessive injection of electrons and adjusting QDs layer thickness in perovskite-inverted QLEDs is an effective way to improve device luminescence and efficiency, thereby improving the carrier injection balance. Full article