Search Results (203)

The preparation of stable dispersions of MoS₂ by ultrasonic aqueous and/or organic media containing amphiphilic molecules is an attractive and widely applicable method to form MoS₂ fine particles while suppressing its aggregation. In this study, we developed a series of polymers with pendant sulfide moieties as a new dispersant, under the hypothesis that it would interact with sulfur atoms on MoS₂ surfaces. First, we designed a sulfide group-substituted methacrylate derivative (ESMA) with the hypothesis that it would interact with the MoS₂ surface through sulfur-sulfur interactions. Then, we synthesized well-defined polymers with pendant sulfide groups by living radical polymerization (ATRP). Next, 0.5 wt% MoS₂ was added to a DMSO solution containing 1 wt% of the obtained polymer (polyESMA), and the mixture was treated with a bath-type ultrasonicator for 3 h to obtain a MoS₂ dispersion. We found that stable dispersions of MoS₂ in a fine particle state, although not in the form of single-layer or few-layer nanosheets, could be readily formed in DMSO using polyESMA as a polymeric dispersant. Furthermore, we synthesized polymeric dispersants with different molecular weights and investigated the relationship between the structure of the dispersant and the dispersion stability. Full article

Reducing the ecological impact of dyes through wastewater discharge into the environment is a challenge that must be addressed in textile wastewater pollution prevention. Congo red (CR) dye is widely used in experimental studies for textile wastewater treatment due to its high organic loads used in its preparation. The degradation of organic dyes of the CR type was investigated using the photocatalytic activity of functionalized polymers. We have employed photodegradation procedures for both polymer-supported glycine groups (Code: AP2) and polymer-supported glycine-Zn(II) (Code: AP2-Zn(II)). A photocatalysis efficiency of 89.2% was achieved for glycine pendant groups grafted on styrene-6.7% divinylbenzene copolymer (AP2) and 95.4% for the AP2-Zn(II) sample by using an initial concentration of CR of 15 mg/L, a catalyst concentration of 1 g/L, and 240 min of photocatalysis. The findings provided here have shown that the two materials (AP2 and AP2-Zn(II)) may be effectively employed in the heterogeneous photocatalysis method to remove CR from water. From the perspective of the degradation mechanism of CR, the two photocatalysts act similarly. Full article

This study explores the development and evaluation of a novel series of aromatic co-polyamides featuring diverse pendant groups, including phenyl and pyridinyl derivatives, designed for water desalination membrane applications. These co-polyamides, synthesized with a combination of hexafluoroisopropyl, oxyether, phenyl, and amide groups, exhibited excellent solubility in polar aprotic solvents, thermal stability exceeding 350 °C, and the ability to form robust, flexible films. Membranes prepared via phase inversion demonstrated variable water permeability and NaCl rejection rates, significantly influenced by the pendant group chemistry. Notably, pyridinyl-substituted membranes achieved water fluxes up to 17.7 L m⁻² h⁻¹ and a NaCl rejection of 37.3%, while phenyl-substituted variants provided insights into the interplay of hydrophobicity and porosity. These findings highlight the critical role of pendant group functionality in tailoring membrane performance, offering a foundation for further structural modifications to enhance efficiency in water treatment technologies. Full article

Understanding the adsorption features of polymer microgels with different chemical compositions and structures is crucial in studying the mechanisms of respective emulsion stabilization. Specifically, the use of stimuli-responsive particles can introduce new properties and broaden the application range of such complex systems. Recently, we demonstrated that emulsions stabilized by microgels composed of interpenetrating networks (IPNs) of poly-N-isopropylacrylamide (PNIPAM) and polyacrylic acid (PAA) exhibit higher colloidal stability upon heating compared to PNIPAM homopolymer and other relevant PNIPAM-based copolymer counterparts. In the present work, using pendant drop tensiometry, we studied the evolution of water–tetradecane interfacial tension during the adsorption of PNIPAM-PAA IPN particles, comparing them with single-network P-(NIPAM-co-AA) and PNIPAM microgels. The results showed that, despite having the same chemical composition, copolymer particles exhibit completely different adsorption behavior in comparison to other microgel architectures. The observed disparity can be attributed to the nonuniform distribution of charged acrylic acid groups within the P-(NIPAM-co-AA) network obtained through precipitation polymerization. Oppositely, the presence of IPN architecture provides a uniform distribution of different monomers inside respective microgels. Additionally, hydrogen bonding between PNIPAM and PAA subchains appears to reduce the electrostatic energy barrier, enhancing the ability of IPN particles to successfully cover the liquid interface. Overall, our findings confirm the efficiency of using PNIPAM-PAA IPN microgels for the preparation of oil-in-water emulsions and their stability, even when the temperature rises above the lower critical solution temperature of PNIPAM. Full article

Bacterial contamination is a major public health concern on a global scale. Treatment resistance in bacterial infections is becoming a significant problem that requires solutions. We were interested in obtaining new polymeric functionalized compounds with antibacterial properties. Three components (polymeric amine, aldehyde, and phosphite) were used in the paper in a modified “one-pot” Kabachnik–Fields reaction, in tetrahydrofuran at 60 °C, to create the N-C-P skeleton in aminophosphonate groups. Two copolymers were thus prepared starting from an acrylonitriledivinylbenzene (AN-15%DVB) copolymer containing pendant primary amine groups modified by grafting aminophosphonate groups, i.e., aminobenzylphosphonate (Bz-DVB-AN) and aminoethylphosphonate (Et-DVB-AN). The two copolymers were characterized by FT-IR spectroscopy, SEM-EDX, TGA, and antibacterial properties. It was shown that the novel products have antibacterial qualities against S. aureus and E. coli bacteria. The sample with the strongest antibacterial activity was Et-DVB-AN. We assessed how well the Weibull model and the first-order kinetic model represent the inactivation of microbial cells in our samples. The main advantage of the new antibacterial agents developed in this work is their easy recovery, which helps to avoid environmental contamination. Full article

New derivatives of the closo-decaborate anion [B₁₀H₉–O(CH₂)₂O(CH₂)₃C(O)–L–OCH₃]²⁻ (An) (1: L = Trp; 2: L = His; 3: L = Met; 4: L = Ala(2-oxopyrrolidin-3-yl) (Pld) were synthesized and isolated as tetraphenylphosphonium salts (Ph₄P)₂An. Anions 1²⁻; 2²⁻; 3²⁻, and 4²⁻ contain a pendant functional group from the L-tryptophan methyl ester, L-histidine methyl ester, L-methionine methyl ester, or methyl 2-amino-3-(2-oxopyrrolidin-3-yl)propanoate (-Trp–OCH₃, -His–OCH₃, -Met–OCH₃, or -Pld–OCH₃) residue, respectively, bonded with the boron cluster anion through the oxybis[(ethane-2,1-diyl)oxy] spacer. This pacer is formed as a result of the nucleophilic opening of the attached dioxane molecule in the [B₁₀H₉O(CH₂)₄O]⁻ starting derivative. Sodium salts of the target compounds were isolated and used in biological experiments. It was established that among compounds Na₂An (An = 1–4), not all are capable of inhibiting the cytopathic effect of the virus in vitro. Sodium salts Na₂An have a low toxic effect on a monolayer of continuous canine embryonic kidney (MDCK) cell line. Compounds Na₂1 and Na₂2 had IC₅₀ of 5.0 and 20.0 μg/mL, respectively, while for compounds Na₂3 and Na₂4, IC₅₀ values could not be achieved at the concentrations studied. The studies performed for molecular docking of the anionic part of 1²⁻ and 2²⁻ with the transmembrane domain of viroporin M2 show some differences in the location of these two ligands inside the M2 canal pore. Full article

Organic compounds with 1,3-diketone or 3-amino enone functional groups are extremely important as they can be converted into a plethora of carbo- or heterocyclic derivatives or can be used as ligands in the formation of metal complexes. Here, we have achieved the preparation of a series of non-symmetrical β-ketoenamines (O,N,N proligand) of the type (4-MeOC₆H₄)C(=O)CH=C(R)NH(Q) obtained through the Schiff base condensation of 1,3-diketones (1-anisoylacetone, 1-anisyl-3-(4-cyanophenyl)-1,3-propanedione, and 1-anisyl-3-(4,4,4-trifluorotolyl)-1,3-propanedione) functionalized with electron donor and electron-withdrawing substituents and 8-aminoquinoline (R = CH₃, 4-C₆H₄CN, 4-C₆H₄CF₃; Q = C₉H₇N). Schiff base ketoimines with a pendant quinolyl moiety were isolated as single regioisomers in yields of 22–56% and characterized with FT-IR, ¹H NMR, and UV-visible spectroscopy, as well as single-crystal X-ray crystallography, which allowed for the elucidation of the nature of the isolated regioisomers. The regioselectivity of the condensation of electronically unsymmetrical 1,3-diaryl-1,3-diketones with 8-aminoquinoline was studied by ¹H NMR, providing regioisomer ratios of ~3:1 and ~2:1 in the case of CN and CF₃ substituents, respectively. The electronic effects correlate well with the difference between the Hammett σ⁺ coefficients of the two para substituents on the aryl rings. Full article

Tetraphenylethene (TPE) is known as a molecule that exhibits aggregation-induced emission (AIE). In this study, pendant hydroxyl groups were introduced onto polyfluorene with a TPE moiety. Sol-gel reactions of polydiethoxysiloxane (PDEOS) were carried out in the presence of hydroxyl-functionalized AIE polyfluorene (TPE-PF-OH) and polydimethylsiloxane carrying pendant hydroxyl groups (PDMS-OH) to immobilize AIE polyfluorene into a PDMS/SiO₂ hybrid in an isolated dispersion state. The luminescence intensity from this three-component hybrid increased with the increase in silica content. The luminescence intensity decreased with increasing external temperature. For the control experiment, sol-gel reactions of PDEOS were carried out in the presence of hydroxyl group-free polyfluorene (TPE-PF) and PDMS to obtain ternary composites. We found that the luminescence from this composite was not significantly affected by the silica content or external temperature. We synthesized temperature-responsive AIE materials without changing the concentration or aggregation state of the AIE molecules. Full article

For the first time, we introduced chemomechanical self-oscillating poly(N-isopropylacrylamide)-based gels containing catalytically active Fe or Ru complexes both as crosslinkers and as pendant groups. All the obtained gels exhibited sustained autonomous oscillations driven by the Belousov–Zhabotinsky reaction within their structure. The Ru complex-based gels also demonstrated pronounced chemomechanical oscillations; they periodically swelled/shrunk when the catalyst was reduced/oxidized. It was found that the combination of catalytically active cross-linking and pendant Ru complexes in the same gel led to a change in the structure of the gel and a significant increase in the amplitude of its mechanical oscillations. The proposed approach allowed for increasing the amplitude of the mechanical oscillations of self-oscillating gels and opened up new possibilities for adjusting their characteristics. We believe that these gels hold potential for the development of soft actuators and systems capable of signal processing through propagating and interacting chemical waves. Full article

This study investigates hydrogels based on 2-Acrylamido-2-methyl-1-propanesulfonic acid sodium salt (AMPS) copolymers, incorporating N-hydroxyethyl acrylamide (HEA) and 3-sulfopropyl acrylate potassium salt (SPA). The addition of HEA and SPA is designed to fine-tune the hydrogels’ water absorption and mechanical properties, ultimately enhancing their characteristics and expanding their potential for biomedical applications. A copolymer of AMPS, 2-carboxyethyl acrylate (CEA) combined with methacrylic acid (MAA) as poly(AMPS-stat-CEA-stat-MAA, PACM), was preliminarily synthesized. CEA and MAA were modified with allyl glycidyl ether (AGE) through ring-opening, yielding macromers with pendant allyl groups (PACM-AGE). Copolymers poly(AMPS-stat-HEA-stat-CEA-stat-MAA) (PAHCM) and poly(AMPS-stat-SPA-stat-CEA-stat-MAA) (PASCM) were also synthesized and modified with AGE to produce PAHCM-AGE and PASCM-AGE macromers. These copolymers and macromers were characterized by ¹H NMR, FT-IR, and GPC, confirming successful synthesis and functionalization. The macromers were then photocrosslinked into hydrogels and evaluated for swelling, water content, and mechanical properties. The results revealed that the PASCM-AGE hydrogels exhibited superior swelling ratios and water retention, achieving equilibrium water content (~92%) within 30 min. While the mechanical properties of HEA and SPA containing hydrogels show significant differences compared to PACM-AGE hydrogel (tensile strength 2.5 MPa, elongation 47%), HEA containing PAHCM-AGE has a higher tensile strength (5.8 MPa) but lower elongation (19%). In contrast, SPA in the PASCM-AGE hydrogels led to both higher tensile strength (3.7 MPa) and greater elongation (92%), allowing for a broader range of hydrogel properties. An initial study on drug delivery behavior was conducted using PACM-AGE hydrogels loaded with photosensitizers, showing effective absorption, release, and antibacterial activity under light exposure. These AMPS-based macromers with HEA and SPA modifications demonstrate enhanced properties, making them promising for wound management and drug delivery applications. Full article

The ²⁰³Pb and ²¹²Pb lead radioisotopes are attracting growing interest as they can aid in the development of personalized, targeted radionuclide treatment for advanced and currently untreatable cancers. In the present study, the bonding interactions of Pb²⁺ with twelve macrocyclic ligands, having an octa and nona coordination, were assessed using Density Functional Theory (DFT) calculations. The molecular structures in an aqueous solution were computed utilizing the polarized continuum model. The preference for the twisted square antiprismatic (TSAP) structure was confirmed for ten out of the eleven cyclen-based complexes. The characteristics of the bonding were assessed using a Natural Energy Decomposition Analysis (NEDA). The analysis revealed a strong electrostatic character of the bonding in the complexes, with minor variations in electrical terms. The charge transfer (CT) had a comparable energetic contribution only in the case of neutral ligands, while in general, it showed notable variations regarding the various donor groups. Our data confirmed the general superiority of the carboxylate O and aromatic N donors. The combination of the selected efficient pendant arms pointed out the superiority of the acetate pendant arms and the lack of significant cooperation between the different pendant arms in the probed ligands. Altogether, the combination led only to a marginal enhancement in the total CTs in the complexes. Full article

The aim of this study was to develop new materials with adsorbent properties that can be used for the adsorption recovery of Au(III) from aqueous solutions. To achieve this result, it is necessary to obtain inexpensive adsorbent materials in a granular form. Concomitantly, these materials must have a high adsorption capacity and selectivity. Other desired properties of these materials include a higher physical resistance, insolubility in water, and materials that can be regenerated or reused. Among the methods applied for the separation, purification, and preconcentration of platinum-group metal ions, adsorption is recognised as one of the most promising methods because of its simplicity, high efficiency, and wide availability. The studies were carried out using three supports: cellulose (CE), chitosan (Chi), and diatomea earth (Diat). These supports were functionalised by impregnation with extractants, using the ultrasound method. The extractants are environmentally friendly and relatively cheap amino acids, which contain in their structure pendant groups with nitrogen and sulphur heteroatoms (aspartic acid—Asp, l-glutamic acid—Glu, valine—Val, DL-cysteine—Cys, or serine—Ser). After preliminary testing from 75 synthesised materials, CE-Cys was chosen for the further recovery of Au(III) ions from aqueous solutions. To highlight the morphology and the functionalisation of the material, we physicochemically characterised the obtained material. Therefore, the analysis of the specific surface and porosity showed that the CE-Cys material has a specific surface of 4.6 m²/g, with a porosity of about 3 nm. The FT-IR analysis showed the presence, at a wavelength of 3340 cm⁻¹, of the specific NH bond vibration for cysteine. At the same time, pHpZc was determined to be 2.8. The kinetic, thermodynamic, and equilibrium studies showed that the pseudo-second-order kinetic model best describes the adsorption process of Au(III) ions on the CE-Cys material. A maximum adsorption capacity of 12.18 mg per gram of the adsorbent material was achieved. It was established that the CE-Cys material can be reused five times with a good recovery degree. Full article

Reaction of [Ru(H)₂(CO)(PPh₃)₃] 1 with an equimolar amount of pyrrole-2-carboxylic acid (H₂L₁) leads to the homoleptic chelate derivative k²(O,O)-[RuH(CO)(HL₁)(PPh₃)₂] 2. Prolonged acetonitrile refluxing promotes an unusual k²(O,O)- → k²(N,O)- dynamic chelate conversion, forming a neutral, stable, air- and moisture- insensitive, solvento-species k²(N,O)-[Ru(MeCN)(CO)(L₁)(PPh₃)₂] 3. Analogously, reaction of 1 with the pyrrole-2-carboxyaldehyde (HL₂) affords k²(N,O)-[RuH(CO)(HL₂)(PPh₃)₂] 4, 5, as a couple of functional isomers. Optimized reaction conditions such as temperature and solvent polarity allow the isolation of dominant configurations. Structure 5 is a pyrrolide Ru-carbaldehyde, obtained from cyclization of the pendant CHO function, whereas species 4 can be viewed as an ethanoyl-conjugated Ru-pyrrole. Derivatives 3–5 were characterized by single crystal X-ray diffraction, ESI-Ms, IR, and NMR spectroscopy, indicating distinct features for the Ru-bonded pyrrolyl groups. DFT computational results, coplanarity, bond equalization, and electron delocalization along the fused five-membered rings support aromatic features. In accordance with the antisymbiotic trans-influence, both the isolated isomers 4 and 5 disclose CO ligands opposite to N- or O-anionic groups. The quantitative Mayer bond order evidences a stabilizing backbonding effect. Antibacterial and antifungal trials on Gram-positive (Staphylococcus aureus), Gram-negative (Escherichia coli), and Candida albicans were further carried out. Full article

Functional polymers play an important role in various biomedical applications. From many choices, poly(2-isopropenyl-2-oxazoline) (PIPOx) represents a promising reactive polymer with great potential in various biomedical applications. PIPOx, with pendant reactive 2-oxazoline groups, can be readily prepared in a controllable manner via several controlled/living polymerization methods, such as living anionic polymerization, atom transfer radical polymerization (ATRP), reversible addition–fragmentation transfer (RAFT) or rare earth metal-mediated group transfer polymerization. The reactivity of pendant 2-oxazoline allows selective reactions with thiol and carboxylic group-containing compounds without the presence of any catalyst. Moreover, PIPOx has been demonstrated to be a non-cytotoxic polymer with immunomodulative properties. Post-polymerization functionalization of PIPOx has been used for the preparation of thermosensitive or cationic polymers, drug conjugates, hydrogels, brush-like materials, and polymer coatings available for drug and gene delivery, tissue engineering, blood-like materials, antimicrobial materials, and many others. This mini-review covers new achievements in PIPOx synthesis, reactivity, and use in biomedical applications. Full article