Search Results (18)

In this paper, we report a metal-driven structural tuning strategy with the L-histidine (His) ligand to modulate peroxidase-like nanozyme performance. Although the His coordinates with gold(III) ions to form an extended helical coordination polymer, its interaction with Cu(II) ions results in quantum-confined, ultrasmall nanoclusters. Based on the optical, structural, and surface analysis, the blue-emitting cores are stabilized by His ligands through imidazole nitrogen coordination, consistent with a Cu-centered coordination environment involved in the observed catalytic activity. According to the catalytic measurements, the His-Cu clusters outperformed the His-Au coordination polymer reference system. Steady-state kinetic modeling and 3D profiling revealed a pronounced shift in the pH optimum: low-valent Cu-containing His-Cu NCs enable efficient peroxide-dependent catalysis under nearly neutral conditions (pH 7.4), whereas His-Au CP exhibits its maximum activity under acidic conditions. Based on these findings, this work highlights nanoscale engineering for tailor-made biomimetic applications. Full article

Plasma polymerization offers a solvent-free route to functional polymer materials, but the structural integrity and accessibility of functional groups in plasma-derived networks remain insufficiently validated. Herein, N-vinylimidazole (NVI) was polymerized using atmospheric-pressure dielectric barrier discharge (DBD) plasma in a liquid-film configuration to generate a chemically heterogeneous poly(N-vinylimidazole)-like material that could be recovered and evaluated in aqueous solution. ATR–FTIR and ¹H NMR spectroscopy indicate substantial vinyl-group consumption with retention of imidazole functionality. Functional behavior was probed using chromium(III) (Cr³⁺) as a model metal ion. UV–Vis spectroscopy revealed systematic changes in the Cr³⁺ d–d transition region (~580–600 nm) with increasing polymer concentration, consistent with ligand-field perturbation arising from interactions with imidazole donor sites. A monotonic increase in absorbance with an increasing ligand-to-metal ratio was observed, followed by plateau behavior at higher ratios, indicating saturation of accessible coordination environments. These results demonstrate that plasma-polymerized material retains chemically accessible imidazole functionalities capable of coordinating transition-metal ions in solution, establishing atmospheric-pressure plasma polymerization as a viable route to functional imidazole-containing materials. Full article

Textile dye effluents containing toxic organic compounds pose serious environmental challenges. In this study, novel Poly(1-vinyl imidazole)-Bis[2-(methacryloyloxy)ethyl] phosphate (PVIB) polymers were synthesized with crosslinker molar fractions ranging from 5% to 80% and were subsequently investigated as advanced adsorbents for textile dye removal. Procion Red (PR), a widely used reactive dye, was selected as the model pollutant. The materials were characterized using FTIR, TGA, DTG, SEM-EDX, WD-XRF, TEM, and BET analyses. Adsorption mechanisms were examined through kinetic, isotherm, and thermodynamic models. Among the synthesized formulations, PVIB20% achieved the best dye removal, reaching an experimental adsorption capacity of 330 mg g⁻¹ within 60 min under acidic to neutral conditions. The kinetic modeling studies identified the pseudo-first-order model as the best fit, indicating a surface-controlled process involving both physical and chemical interactions. Isotherm studies showed that the Langmuir and Redlich–Peterson models provided the best fit, yielding a maximum monolayer adsorption capacity of 765 mg g⁻¹. Thermodynamic analysis revealed that the adsorption was spontaneous, endothermic, and entropy-driven. Overall, PVIB20% demonstrated superior adsorption capacity, rapid kinetics, and strong dye–polymer interactions compared with many conventional and modified adsorbents, which highlights its potential as an efficient and durable material for anionic dye removal from wastewater. Full article

Owing to multiple non-covalent interactions, ionic groups impart unique chemical and physical properties into polymers including ion conductivity/mobility, permeation, and intrinsic healability. Ionenes contain ionic groups in their polymer backbone, which offer great versatility in polymer design. Herein, selected aliphatic and aromatic imidazoles were synthesized, which were used as monomeric building blocks for the preparation of thermoplastic ionenes by following a Sn2 step growth reaction across organic halides. The structure and molecular weight of the polymers was characterized by Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR) techniques. Once polymerized, anion-exchange reactions were carried out to replace the halides with four other counter-anions. Subsequently, the effect of the nature of the anion and the cation on the polymers’ thermal and hygroscopic properties was studied in detail by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and FTIR spectroscopy. Depending on the chemical structures of the polymeric cations and the related anions, tailored polymers with a glass transition temperature (T_g) in the range of 30 °C to 131 °C and a thermal stability varying between 170 °C and 385 °C were obtained. Full article

Nowadays, nitrate ions and azo dyes are a significant source of water pollution due to their high toxicity, persistence, and potential to be carcinogenic. Both contaminants are the result of anthropogenic sources, such as sewage or industrial wastewater discharge; the first one results also as a consequence of the intensive use of fertilizers. In this work we report the use of a new quaternized pentablock copolymer (PTBr) for the removal of nitrate ions and methyl orange (MO) dye from water by adsorption processes. Morphological, chemical, and thermal properties of the pentablock copolymer were investigated, respectively, by scanning electron microscopy (SEM), Attenuated Total Reflectance Infrared Spectroscopy (ATR-FTIR) (FT-IR), and X-ray photoelectron spectroscopy (XPS), thermal gravimetric analysis (TGA), and differential scanning calorimetry (DSC) analyses. Anionic removal ability and adsorption rate in water solutions containing either a single contaminant species or a mix of the two contaminants were studied by UV–VIS absorbance spectroscopy as a function of time and initial concentration. The presence of imidazole groups confers on PTBr a positive charge and a hydrophilic character that are responsible for an effective removal of anions from water. PTBr film reports an adsorption efficiency of 10.15 mg/g for nitrate removal and this value is in line with others reported in the literature. In the case of the simultaneous presence of nitrate and MO, it is found that nitrate ions removal is slightly affected by the presence of the dye, since both contaminants compete for electrostatic interaction with imidazole groups. On the contrary, the dye removal does not show significant change with or without the presence of nitrate ions, probably due to other kinds of interaction that it can establish with the polymer surface (π-π interaction). The adsorption process and the related mechanisms are described using kinetic and isothermal models. Despite a certain reduction in the adsorption efficiency for one of the investigated contaminants, the results confirm the possibility of using the quaternized pentablock copolymer for the co-adsorption of both inorganic and organic anions. Full article

A series of new Ag(I) complexes with 2,6-bis[(imidazol-2-yl)thiomethyl]naphthalene (L) and a range of counterions (X⁻) such as PF₆⁻ (1, 2), SbF₆⁻ (3), and CF₃SO₃⁻ (4) was prepared. As shown by SCXRD studies, all of these are 1D coordination polymers with a waved chain motive and general formula {[AgL]X}_n. Two methanol solvates containing PF₆⁻ (1) and SbF₆⁻ (3) counterions are isostructural. The triflate counterion leads to the formation of a topologically equivalent structural motive, with a different conformation of the ligand in the 1D chain and a different crystal packing as a result of the presence of another set of intermolecular interactions. The presence of water in 2 leads to a significant change in the conformation of the ligand. The naphthalene rings show a different orientation towards the imidazole rings, which is energetically less favorable but is stabilized by an extended net of intermolecular interactions with the counterion, which leads to an efficient crystal packing. Full article

Some original poly(tetrasubstituted imidazole)s incorporating different units were synthesized and characterized. These materials were obtained via a cascade polycondensation process assisted by microwave irradiation that was developed by our team. This time, we integrated two well-known chromophore structures into the macromolecular backbone, which were benzothiadiazole (BTD) and diketopyrrolopyrrole (DKPP). These new polymers were fully characterized: their chemical structures were confirmed using NMR spectroscopy and their thermal, optical and electrochemical properties were investigated and compared with a reference polymer containing a phenyl spacer instead of the mentioned chromophore units. These materials were found to exhibit a large Stokes shift of up to 350 nm. Furthermore, a polymer presenting large absorption on the UV–visible range and an emission close to the near-infrared region was obtained by coupling the mentioned moieties. According to the established properties of this latter polymer, it presents a potential for applications in biological imaging or optoelectronic devices. Full article

ZIF-67@ATP was prepared by the in situ growth of the zeolite imidazole frame (ZIF-67) on the surface of attapulgite (ATP). The structure and surface morphology of ZIF-67@ATP were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Different mass fractions of ATP and ZIF-67@ATP were added to ethylene vinyl acetate (EVA)/magnesium hydroxide (MH) composites as flame retardant synergists. The flame retardancy of EVA composites was evaluated by the limiting oxygen index (LOI) test, UL-94 test and cone calorimeter test. Composites containing 3 wt% of ZIF-67@ATP reached an LOI value of 43% and a V-0 rating in the UL-94 test, and the ignition time of the composite increased from 38 s to 56 s. The tensile strength and impact strength of the composites did not change significantly, but the elongation at break increased greatly. Typically, for composites containing 4 wt% of ZIF-67@ATP, the elongation at break of the composites increased from 69.5% to 522.2% compared to the samples without the synergist. This study provides novel insights into the application of attapulgite in the field of flame retardant polymer materials. Full article

Two Ag(I) complexes with 1,3-bis(imidazol-1-ylmethyl)benzene (bib) and counterions BF₄^¯ (1) and PF₆^¯ (2) were synthesized in order to check their behavior in forming molecular/crystal structures. This allows comparison with the final products of analogous syntheses performed with similar bidentate ligands containing methyl substituents on the benzene ring, namely 1,3-bis(imidazol-1-ylmethyl)-5-methylbenzene (bimb) and 1,3-bis(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene (bitmb). The Ag(I) complexes obtained with the methylated ligands mentioned above form isostructural pairs of waved 1D chains or dinuclear boxes, of general formula {[Ag(bimb)]X}_n and [Ag₂(btmb)₂]X₂, respectively (X = BF₄^¯, PF₆^¯), under the same reaction conditions. SCXRD analyses of 1 and 2 revealed the formation of polymeric coordination compounds of formula {[Ag₂(bib)₃](BF₄)₂}_n and {[Ag(bib)]PF₆}_n, respectively, different from those observed for bimb. The 3D coordination polymer 1 forms a unique 5,5-c net of 5,5T188 topological type, observed for the very first time for a coordination compound, with silver cations adopting a trigonal geometry, whereas 2 shows the presence of 1D single-stranded cationic helices with linear coordination of the metal centers. Interestingly, these complexes differ not only from the mentioned isostructural pairs of related Ag(I) complexes, but also from the isostructural pair of compounds obtained as the final product when reacting bib and bimb with the larger counterion CF₃SO₃^¯. Hirshfeld surface analyses indicate a higher contribution of F···H intermolecular contacts in 2 than in 1, with H^…H contacts being dominant in the latter. Full article

New donor–acceptor conjugated alternating or random copolymers containing 1-methyl-2-phenylbenzimidazole and benzothiadiazole (P1), diketopyrrolopyrrole (P4), or both acceptors (P2) are reported. The specific feature of these copolymers is the presence of a permanent dipole-bearing moiety (1-methyl-2-phenyl imidazole (MPI)) fused with the 1,4-phenylene ring of the polymer main chain. For comparative reasons, polymers of the same main chain but deprived of the MPI group were prepared, namely, P5 with diketopyrrolopyrrole and P3 with both acceptors. The presence of the permanent dipole results in an increase of the optical band gap from 1.51 eV in P3 to 1.57 eV in P2 and from 1.49 eV in P5 to 1.55 eV in P4. It also has a measurable effect on the ionization potential (IP) and electrochemical band gap (E_g^CV), leading to their decrease from 5.00 and 1.83 eV in P3 to 4.92 and 1.79 eV in P2 as well as from 5.09 and 1.87 eV in P5 to 4.94 and 1.81 eV in P4. Moreover, the presence of permanent dipole lowers the exciton binding energy (E_b) from 0.32 eV in P3 to 0.22 eV in P2 and from 0.38 eV in P5 to 0.26 eV in P4. These dipole-induced changes in the polymer properties should be beneficial for photovoltaic applications. Bulk heterojunction solar cells fabricated from these polymers (with PC₇₁BM acceptor) show low series resistance (r_s), indicating good electrical transport properties. The measured power conversion efficiency (PCE) of 0.54% is limited by the unfavorable morphology of the active layer. Full article

Implementing new methods to prepare magnetite nanoparticles with a covered or uncovered surface has been, and still is, a significant challenge. In this work, we describe a very clear and effortless way for the preparation of magnetite nanoparticles using two types of bases, namely: 1-(3-aminopropyl)imidazole and sodium hydroxide. Fourier transform infrared spectroscopy (FTIR) served as a tool for the structural investigation of the as-prepared magnetite nanoparticles. The morphology of the samples was investigated using Transmission Electron Microscopy (TEM). Comprehensive high-resolution X-ray photoelectron spectroscopy investigations (XPS) were applied as an effective tool for analyzing the composition of the various types of magnetic nanoparticles. Further polymer linkage was accomplished with poly(benzofuran-co-arylacetic acid) on the amino-functionalized surface of aminopropylimidazole-containing magnetic nanoparticles. The findings are promising for biomedicine, catalysis, and nanotechnology applications. Full article

Bio-nanocomposites-based packaging materials have gained significance due to their prospective application in rising areas of packaged food. This research aims to fabricate biodegradable packaging films based upon polyvinyl alcohol (PVA) and starch integrated with metal-organic frameworks (MOFs) or organic additives. MOFs offer unique features in terms of surface area, mechanical strength, and chemical stability, which make them favourable for supporting materials used in fabricating polymer-based packaging materials. zeolitic imidazolate frameworks (ZIFs) are one of the potential candidates for this application due to their highly conductive network with a large surface area and high porosity. Present research illustrates a model system based on ZIF-67 (C₈H₁₀N₄Co) bearing 2–10 wt.% loading in a matrix of PVA/starch blend with or without pyrolysis to probe the function of intermolecular interaction in molecular packing, tensile properties, and glass transition process. ZIF-67 nanoparticles were doped in a PVA/starch mixture, and films were fabricated using the solution casting method. It was discovered through scanning electron microscopy (SEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), and Fourier transform infrared spectroscopy (FTIR) that addition of ZIF-67 and pyrolyzed ZIF-67 changed and enhanced the thermal stability of the membrane. Moreover, 2–10 wt.% loading of ZIF-67 effected the thermal stability, owing to an interlayer aggregation of ZIF-67. The membranes containing pyrolyzed ZIF-67 showed mechanical strength in the order of 25 MPa in a moderate loading of pyrolyzed ZIF-67 (i.e., at 4 wt.%). The crystallinity enhanced by an increment in ZIF-67 loading. On the other hand, pyrolyzed ZIF-67 carbon became amorphous because of the inert environment and elevated temperature. The surface area also increased after the pyrolysis, which helped to increase the strength of the composite films. Full article

Currently, a lot of attention is paid to polymer inclusion membranes (PIMs). Their particular advantages include effective support fixation, easy preparation, versatility, stability, good mechanical properties and good chemical resistance. The paper presents a review of the literature related to the applications of polymer inclusion membranes containing alkylimidazole derivatives as carriers in the processes of transporting ions of heavy and toxic metals, such as Zn(II), Cu(II), Cd(II), Co(II), Ni(II), and Mn(II). It has been proven that alkylimidazoles exhibit varying complex-forming properties towards metal ions, and that their properties (hydrophobic and alkaline) can be modified easily by changing the size of the alkyl group and its position in the imidazole ring, which allows obtaining efficiently working metal ion carriers. The stability of an imidazole derivative-metal ion complex determines the speed and selectivity of the process of transporting metal ions across polymer inclusion membranes. Also, the morphological structure of polymer inclusion membranes impacts the efficiency of the process involving the release and separation of metal ions. Full article

Metal-organic frameworks (MOFs) have shown great potential in flame retardant applications; however, strategies for fully exploiting the advantages of MOFs in order to further enhance the flame retardant performance are still in high demand. Herein, a novel MOF composite was designed through the generated cooperative role of MOF (NH₂-MIL-101(Al)) and a phosphorus-nitrogen-containing ionic liquid ([DPP-NC₃bim][PMO]). The ionic liquid (IL) was composed of imidazole cation modified with diphenylphosphinic group (DPP) and phosphomolybdic acid (PMoA) anions, which can trap the degrading polymer radicals and reduce the smoke emission. The MOF acts as a porous host and can avoid the agglomeration of ionic liquid. Meanwhile, the -NH₂ groups of NH₂-MIL-101(Al) can increase the compatibility with epoxy resin (EP). The framework is expected to act as an efficient insulating barrier to suppress the flame spread. It was demonstrated that the MOF composite (IL@NH₂-MIL-101(Al)) is able to effectively improve the fire safety of EP at low additions (3 wt. %). The LOI value of EP/IL@NH₂-MIL-101(Al) increased to 29.8%. The cone calorimeter results showed a decreased heat release rate (51.2%), smoke production rate (37.8%), and CO release rate (44.8%) of EP/IL@NH₂-MIL-101(Al) with respect to those of neat EP. This strategy can be extended to design other advanced materials for flame retardant. Full article

Polyelectrolyte hydrogels bearing l-phenylalanine (PHE), l-valine (AVA), and l-histidine (Hist) residues were used as scaffolds for the formation of silver nanoparticles by reduction of Ag⁺ ions with NaBH₄. The interaction with the metal ion allowed a prompt collapse of the swollen hydrogel, due to the neutralization reaction of basic groups present on the polymer. The imidazole nitrogen of the hydrogel with Hist demonstrated greater complexing capacity with the Ag⁺ ion compared to the hydrogels with carboxyl groups. The subsequent reduction to metallic silver allowed for the restoration of the hydrogel’s degree of swelling to the starting value. Transmission electron microscopy (TEM) and spectroscopic analyses showed, respectively, a uniform distribution of the 15 nm spherical silver nanoparticles embedded on the hydrogel and peak optical properties around a wavelength of 400 nm due to the surface plasmonic effect. Unlike native hydrogels, the composite hydrogels containing silver nanoparticles showed good antibacterial activity as gram+/gram− bactericides, and higher antifungal activity against S. cerevisiae. Full article