Petru Poni Institute of Macromolecular Chemistry

Optically birefringent polymers have found utility in numerous applications, especially in liquid crystal displays. This work is focused on inducing molecular ordering in polyvinyl alcohol films in different conditions. The samples were modified by new mixed approaches: drawing, rubbing before drying, rubbing before drying followed by drawing, and combined rubbing, drawing and then parallel scratching. The level of chain alignment in the samples was quantified by birefringence measurements using several experimental techniques, namely interferometry, polarization ellipse approach, channeled spectra and polarized light refractometry. The produced anisotropy was correlated with the sample morphology examined via optical microscopy under crossed polarizers. Optical retardation was found to be larger as the generated birefringence of mechanically deformed polyvinyl alcohol foils was higher. It was found the new proposed approach of ordering polymer sample by combined rubbing, drawing and then scratching is most suitable as retardation layer for compensating light leakage in display devices.

In this study, suspension polymerization technique is used to obtain three‐dimensional porous networks based on two monofunctional monomers (glycidyl methacrylate and N‐vinylimidazole) and one of the following difunctional monomers known as crosslinking agents: mono‐, di‐ and triethylene glycol dimethacrylate or divinylbenzene. The influence of various operational parameters like: monomer molar ratio, amount and type of crosslinkers, composition of stabilization system, stirring speed, amount of porogenic agent on the reaction yield, surface morphologies, particle size distribution and porous characteristics are investigated in order to find the optimal conditions for the synthesis of microparticles possessing the desired properties for further chemical modification. Crosslinked porous microparticles are structurally characterized by FTIR spectroscopy, X‐ray photoelectron spectroscopy and elemental analysis by determination of nitrogen and epoxy groups. The microparticle morphologies as a function of investigated parameters are revealed by scanning electron microscopy whereas the porous structure is highlighted by mercury porosimetry and dynamic water vapor sorption methods. All the crosslinked networks exhibit porous structures with different surface morphologies and specific surface area values (1.15 – 48.32 m ² g ⁻¹ ) depending on the operational parameters. These microparticles can be considered precursors for the preparation of various functional polymeric materials. This article is protected by copyright. All rights reserved

The asymmetric units of the isostructural compounds (1,4,8,11-tetraazacyclotetradecane-κ ⁴ N )nickel(II) tetraiodidocadmate(II), [Ni(C 10 H 24 N 4 )][CdI 4 ] ( I ), and triiodido-1κ ³ I -μ-iodido-(1,4,8,11-tetraazacyclotetradecane-2κ ⁴ N )cadmium(II)zinc(II), [CdZnI 4 (C 10 H 24 N 4 )] ( II ) (C 10 H 24 N 4 = 1,4,8,11-tetraazacyclotetradecane, cyclam, L ), consist of the centrosymmetric macrocyclic cation [ M ( L )] ²⁺ [ M = Ni II or Zn II ] with the metal ion lying on a twofold screw axis, and the tetraiodocadmate anion [CdI 4 ] ²⁻ located on the mirror plane. In I , the anion acts as an uncoordinated counter-ion while in II it is bound to the Zn II atom via one of the iodide atoms, thus forming an electroneutral heterobimetallic complex [Zn( L )(CdI 4 )]. The Ni II and Zn II ions are coordinated in a square-planar manner by the four secondary N atoms of the macrocyclic ligand L , which adopts the most energetically stable trans -III conformation. The [CdI 4 ] ²⁻ anions in I and II are structurally very similar and represent slightly deformed tetrahedrons with average Cd—I bond lengths and I—Cd—I angles of ca 2.79 Å and 109.6°, respectively. The supramolecular organization of the complexes under consideration in the crystals is very similar and is determined by the hydrogen-bonding interactions between the secondary amino groups of the ligand L in the [ M ( L )] ²⁺ cations and iodide atoms of the [CdI 4 ] ²⁻ anion. In particular, the alternating cations and anions form chains running along the b- axis direction that are arranged into di-periodic sheets oriented parallel to the (101) and (\overline{1}01) planes. Because both kinds of sheets are built from the same cations and anions, this feature provides the three-dimensional coherence of the crystals of I and II .

Environmental contamination with pesticides occurs at a global scale as a result of prolonged usage and, therefore, their removal by low-cost and environmentally friendly systems is actively demanded. In this context, our study was directed to investigate the feasibility of using some self-assembled hydrogels, comprising chitosan (CS) and carboxymethylcellulose (CMC) or dialdehyde (DA)-CMC, for the removal of four complex fungicide formulations, namely Melody Compact (MC), Dithane (Dt), Curzate Manox (CM), and Cabrio®Top (CT). Porous CS/CMC and CS/DA-CMC hydrogels were prepared as discs by combining the semi-dissolution acidification sol-gel transition method with a freeze-drying approach. The obtained CS/CMC and CS/DA-CMC hydrogels were characterized by gel fraction yield, FTIR, SEM, swelling kinetics, and uniaxial compression tests. The batch-sorption studies indicated that the fungicides’ removal efficiency (RE%) by the CS/CMC hydrogels was increased significantly with increasing sorbent doses reaching 94%, 93%, 66% and 48% for MC, Dt, CM and CT, respectively, at 0.2 g sorbent dose. The RE values were higher for the hydrogels prepared using DA-CMC than for those prepared using non-oxidized CMC when initial fungicide concentrations of 300 mg/L or 400 mg/L were used. Our results indicated that CS/DA-CMC hydrogels could be promising biosorbents for mitigating pesticide contamination of aqueous environments.

Wood-polymer composites (WPCs) are a class of materials intensively studied and promoted in the context of sustainable development, mainly when aspects related to the increasing awareness of environmental issues and waste management are considered. Feasible opportunities for producing WPCs with value-added properties intended for common applications emerge when polymers, either synthetic or from renewable resources, raw or waste, are employed in re-/up-cycling approaches. In this context, some examples of easily achievable WPCs are presented herein, namely, formulations based on different wood waste and polymer matrices (synthetic: polypropylene and malleated polypropylene as a compatibilizer; natural: plasticized starch). Their level of performance was assessed through different characterization methods (FTIR, WAXD, TGA, DSC, mechanical test, etc.). The benefits and limitations of this approach are also discussed.

It is acknowledged that the presence of antioxidants boosts the wound-healing process. Many biopolymers have been explored over the years for their antioxidant potential in wound healing, but limited research has been performed on gum structures and their derivatives. This review aims to evaluate whether the antioxidant properties of gellan and guar gums and wound healing co-exist. PubMed was the primary platform used to explore published reports on the antioxidant wound-healing interconnection, wound dressings based on gellan and guar gum, as well as the latest review papers on guar gum. The literature search disclosed that some wound-healing supports based on gellan gum hold considerable antioxidant properties, as evident from the results obtained using different antioxidant assays. It has emerged that the antioxidant properties of guar gum are overlooked in the wound-healing field, in most cases, even if this feature improves the healing outcome. This review paper is the first that examines guar gum vehicles throughout the wound-healing process. Further research is needed to design and evaluate customized wound dressings that can scavenge excess reactive oxygen species, especially in clinical practice.

The paper presents the synthesis and thermal behavior of novel epoxy resins prepared from epoxidized castor oil in the presence of or without trimethylolpropane triglycidyl ether (TMP) crosslinked with 3-hexahydro-4-methylphtalic anhydride (MHHPA) and their comparison with a petroleum-based epoxy resin (MHHPA and TMP). Epoxidized castor oil (ECO) was obtained via in situ epoxidation of castor oil with peroxyacetic acid. The chemical structures of castor oil (CO), ECO, and epoxy matrix were confirmed using FT-IR and 1H-NMR spectroscopy. The morphological and thermal behavior of the resulting products have been investigated. Compared to petroleum-based resins, castor oil-based ones have a lower Tg. Anyway, the introduction of TMP increases the Tg of the resins containing ECO. The morphological behavior is not significantly influenced by using ECO or by adding TMP in the synthesis of resins. The dielectric properties of epoxy resins have been analyzed as a function of frequency (1 kHz–1 MHz) and temperature (−50 to 200 °C). The water absorption test showed that as Tg increased, the percent mass of water ingress decreased.

The wound healing process is often slowed down as a result of complications from bacterial infections and inflammatory reactions. Therefore, it is necessary to develop dressings with fast antibacterial and anti-inflammatory activity that shorten the wound healing period by promoting cell migration and proliferation. Chitosan (CS)-based hydrogels have been widely studied for their antibacterial and wound healing capabilities. Herein, we developed a composite hydrogel based on CS and PVA embedding silver nanoparticles (AgNPs) with antibacterial properties and ibuprofen (Ib) as an anti-inflammatory agent. The hydrogel prepared by double physical cross-linking, with oxalic acid and by freeze–thawing, loaded with 0.225 wt.% AgNPs and 0.264 wt.% Ib, displayed good mechanical properties (compressive modulus = 132 kPa), a high swelling degree and sustained drug delivery (in simulated skin conditions). Moreover, the hydrogel showed strong antibacterial activity against S. aureus and K. pneumoniae due to the embedded AgNPs. In vivo, this hydrogel accelerated the wound regeneration process through the enhanced expression of TNF alpha IP8, by activating downstream cascades and supporting the healing process of inflammation; Cox2, which enhances the migration and proliferation of cells involved in re-epithelialization and angiogenesis; MHCII, which promotes immune cooperation between local cells, eliminating dead tissue and controlling infection; the intense expression of Col I as a major marker in the tissue granulation process; and αSMA, which marks the presence of myofibroblasts involved in wound closure and indicates ongoing re-epithelialization. The results reveal the potential healing effect of CS/PVA/AgNPs/Ib hydrogels and suggest their potential use as wound dressings

Aim: A series of new hybrid molecules with two iodine atoms on the sides were synthesized. Methods: A one-pot, two-component method with trifluoroacetic acid as an effective catalyst to obtain dihydro-pyrrol-2-one compounds was developed. Short reaction times, a cheap catalyst, high yields and clean work-up are benefits of this method. Results: The chemical structures of the newly synthesized compounds were verified through spectroscopic techniques. Their antimicrobial activity against S. aureus, P. aeruginosa and C. albicans was tested in vitro. Conclusion: NC- and OH- radicals confer broad-spectrum antimicrobial activity, including against Gram-positive and Gram-negative bacteria and yeasts. Compounds 3g >7 and >9 were most active on the two bacterial species, while 3l >9 and >3i were most active against the fungal strain.

In recent years, multidrug-resistant bacteria have developed the ability to resist multiple antibiotics, limiting the available options for effective treatment. Raising awareness and providing education on the appropriate use of antibiotics, as well as improving infection control measures in healthcare facilities, are crucial steps to address the healthcare crisis. Further, innovative approaches must be adopted to develop novel drug delivery systems using polymeric matrices as carriers and support to efficiently combat such multidrug-resistant bacteria and thus promote wound healing. In this context, the current work describes the use of two biocompatible and non-toxic polymers, poly(vinyl alcohol) (PVA) and xanthan gum (XG), to achieve hydrogel networks through cross-linking by oxalic acid following the freezing/thawing procedure. PVA/XG-80/20 hydrogels were loaded with different quantities of neomycin sulfate to create promising low-class topical antibacterial formulations with enhanced antimicrobial effects. The inclusion of neomycin sulfate in the hydrogels is intended to impart them with powerful antimicrobial properties, thereby facilitating the development of exceptionally efficient topical antibacterial formulations. Thus, incorporating higher quantities of neomycin sulfate in the PVA/XG-80/20-2 and PVA/XG-80/20-3 formulations yielded promising cycling characteristics. These formulations exhibited outstanding removal efficiency, exceeding 80% even after five cycles, indicating remarkable and consistent adsorption performance with repeated use. Furthermore, both PVA/XG-80/20-2 and PVA/XG-80/20-3 formulations outperformed the drug-free sample, PVA/XG-80/20, demonstrating a significant enhancement in maximum compressive stress.

New composite materials were prepared via cross-linking of polyethylene glycol/2-hydroxypropyl-β-cyclodextrins polyrotaxane (PEG/HPβCD) and polyisoprene/HPβCD semi-polyrotaxane (PI/HPβCD SR) with 1,6-hexamethylene diizocyanate (HMDI). Advanced instrumental methods (such WAXS (wide angle X-ray scattering), AFM (atomic force microscopy), SEM (scanning electron microscopy), and thermal and dynamic vapor sorption) were employed for the structural, morphological and thermal characterization of the resulting composite materials. The roughness parameters calculated using AFM indicate a smoother surface for the composite material with 10 wt% of PI/HPβCD SR, denoting that a homogeneous film was obtained. SEM analysis reveals porous morphologies for both composite materials and the pore sizes increase with the increasing concentration of PI/HPβCD SR in the matrix. Dynamic vapor sorption/desorption measurements and type IV isotherms confirmed the hydrophilic and porous materials, which are in agreement with SEM analysis. The composite with a higher PI/HPβCD SR concentration in the matrix showed increased thermal stability than that of the pure cross-linked material. This material was further tested as a sorbent for methylene blue (MB) dye removal from an aqueous solution. The adsorption capacity of the composite film was found to be 2.58 mg g−1 at 25 °C.

A 30% (w/w) [ImCl][EDA]-based deep eutectic solvent (DES) in water has demonstrated superior gravimetric CO2 uptake with desirable kinetics, lower regeneration enthalpy, and lesser degradation than the industrially-popular 30% monoethanolamine...

Advanced manufacturing technologies for efficient catalytic materials have triggered the rational design of catalysts as well as extensive investigation into preparative methodologies. Herein, we report the preparation of new versatile cellulose acetate/polyurethane (CA/PU) blends for efficient immobilization of CeO2 nanoparticles, the appropriate composition of polymer mixture being chosen after rigorous analysis (SEM, FTIR, optical, mechanical). The band gap energy for hybrid films ranged between 3.02 eV and 2.05 eV, the lowest value being measured for the film with Co-doped CeO2 NPs (B3 film). The best results in photodegradation of methylene blue under visible-light irradiation was attained after 50 min for B3 film (rate constant k = 45.34× 10-3 min-1), while the total mineralization of MB in the same conditions as evaluated by HPLC-ESI MS and TOC analyses was achieved after 90 min. Effect of co-ions (SO42-, Cl- or NO3-) on photocatalytic performance was studied, and scavenger tests were used to identify the active species involved in the photocatalytic mechanism. Also, the photocatalytic efficiency of B3 sample was tested for rhodamine B, metronidazole and 4-nitrophenol degradation. Evaluation of the stability and integrity of hybrid film after 5 catalysis cycles reveal that the photocatalytic potential is retained with no substantial structural changes.

The aim of the study was to evaluate the antibacterial activity and surface hardness of a light-activated microhybrid composite resin modified with green silver nanoparticles (AgNPs). AgNPs were synthesized using an Equisetum sylvaticum extract and characterized through different methods such as UV-Vis, EDX, and FTIR. The obtained AgNPs were mixed with a microhybrid composite resin (Herculite XRV, Kerr Corp., Orange, CA, USA) in different concentrations: 0% (group A-control); 0.5% (group B); 1% (group C); and 1.5% (group D). A total of 120 composite resin disk-shaped samples were obtained and divided into 4 groups (n = 30) according to AgNP concentration. Each group was then divided into 2 subgroups: subgroup 1—samples were not soaked in 0.01 M NaOH solution; and subgroup 2—samples were soaked in 0.01 M NaOH solution. The antibacterial activity against Streptococcus mutans was determined using a direct contact test. A digital electronic hardness tester was used to determine the composite resin’s Vickers surface hardness (VH). Statistical analysis was performed using the Mann–Whitney U and Kruskal–Wallis nonparametric tests with a confidence level of 95%. Groups C and D showed higher antibacterial activity against S. mutans when compared to the control group (p < 0.05). No significant differences were recorded between VH values (p > 0.05). The use of AgNPs synthesized from Equisetum sylvaticum as a composite resin filler in 1% wt. and 1.5% wt. reduced the activity of Streptococcus mutans. Soaking of the experimental composite resin decreased the antibacterial efficacy. The loading of a microhybrid composite resin with AgNPs in concentrations of 0.5% wt., 1% wt., and 1.5% wt. did not influence the surface hardness.

The design and manufacture of innovative multifunctional materials possessing superior characteristics, quality and standards, rigorously required for future development of existing or emerging advanced technologies, is of great importance. These materials should have a very low degree of influence (or none) on the environmental and human health. Adjusting the properties of epoxy resins with organophosphorus compounds and silver-containing additives is key to the simultaneous improvement of the flame-resistant and antimicrobial properties of advanced epoxy-based materials. These environmentally friendly epoxy resin nanocomposites were manufactured using two additives, a reactive phosphorus-containing bisphenol derived from vanillin, namely, (4-(((4-hidroxyphenyl)amino)(6-oxido-6H-dibenzo[c,e][1,2]oxaphosphinin-6-yl)methyl)-2-methoxyphenyl) phenylphosphonate (BPH), designed as both cross-linking agent and a flame-retardant additive for epoxy resin; and additional silver-loaded zeolite L nanoparticles (Ze–Ag NPs) used as a doping additive to impart antimicrobial activity. The effect of BPH and Ze–Ag NPs content on the structural, morphological, thermal, flame resistance and antimicrobial characteristics of thermosetting epoxy nanocomposites was investigated. The structure and morphology of epoxy nanocomposites were investigated via FTIR spectroscopy and scanning electron microscopy (SEM). In general, the nanocomposites had a glassy and homogeneous morphology. The samples showed a single glass transition temperature in the range of 166–194 °C and an initiation decomposition temperature in the range of 332–399 °C. The introduction of Ze–Ag NPs in a concentration of 7–15 wt% provided antimicrobial activity to epoxy thermosets.

The European methodology for plastics, as a feature of the EU's circular economy activity plan, ought to support the decrease in plastic waste. The improvement of recycled plastics' economics and quality is one important part of this action plan. Additionally, achieving the requirement that all plastic packaging sold in the EU by 2030 be recyclable or reusable is an important objective. This means that food packaging materials should be recycled in a closed loop at the end. One of the most significant engineering polymers is polyethylene terephthalate (PET), which is widely used. Due to its numerous crucial qualities, it has a wide variety of applications, from packaging to fibers. The thermoplastic polyolefin, primarily polyethylene and polypropylene (PP), is a popular choice utilized globally in a wide range of applications. In the first phase of the current experiment, the materials were obtained by hot pressing with the press machine. The reinforcer is made of Al nanopowder 800 nm and Fe nanopowder 790 nm and the quality of the recycled polymer was examined using Fourier transform infrared spectroscopy (FTIR), a scanning electron microscope (SEM), and differential scanning calorimetry (DSC). From DSC variation curves as a function of temperature, the values from the transformation processes (glass transition, crystallization, and melting) are obtained. SEM measurements revealed that the polymer composites with Al have smooth spherical particles while the ones with Fe have bigger rough spherical particles.

Low-dimensional structures, such as two-dimensional (2D) Janus films, can be useful in studying fundamental interactions or in applications at the nanoscale. In this work, we report the fabrication of 2D polymer Janus films consisting of one smooth and another nanostructured facet on which silica nanoparticles (NPs) are self-assembled in a compact monolayer shield. The 2D films are made from Pickering emulsions of monomers in water, stabilized by NPs, which are spread over the surface of the water in a Langmuir–Blodgett trough. Following the spreading of the colloidosomes, oil droplets stabilized by NPs collapse, and the interfaces reorganize such that the NP monolayer is found exclusively at the oil/water interface. Upon compression followed by UV polymerization, a 2D solid film is formed, with one smooth and another nanostructured face. The film can be removed from the surface of the water and handled with tweezers. The 2D films exhibit different surface properties on the two sides, such as differences in water wettability. On the nanostructured side, water wettability can be tuned by tuning the surface energy of the nanoparticles, namely by changing their surface functional groups. Upon removal of NPs, the surface can be patterned with an array of circular traces.