Dual Thermo- and pH-Responsive Polymer Nanoparticle Assemblies for Potential Stimuli-Controlled Drug Delivery.

The development of stimuli-responsive drug delivery systems enables targeted delivery and environment-controlled drug release, thereby minimizing off-target effects and systemic toxicity. We prepared and studied tailor-made dual-responsive systems (thermo- and pH-) based on synthetic diblock copolymers consisting of a fully hydrophilic block of poly[-(1,3-dihydroxypropyl)methacrylamide] (poly(DHPMA)) and a thermoresponsive block of poly[-(2,2-dimethyl-1,3-dioxan-5-yl)methacrylamide] (poly(DHPMA-acetal)) as drug delivery and smart stimuli-responsive materials. The copolymers were designed for eventual medical application to be fully soluble in aqueous solutions at 25 °C.

The influence of bio-based monomers on the structure and thermal properties of polyurethanes.

Most polyurethanes (PU) are currently produced through the polyaddition reaction of polyisocyanates with polyols and chain extenders, using components of petrochemical origin. From an environmental and geopolitical point of view, and with regard to the problems of oil supply and processing, the replacement of petrochemical PU raw materials with renewable resources is highly desirable. It is also one of the principles of sustainable development and an important challenge for chemical companies and market competitiveness.

Vanadium-Containing Ionic Liquids Derived from Complexes of Modified Edta as Catalysts of Epoxy-Anhydride Ring-Opening Copolymerization.

A new type of vanadium-containing ionic liquids (ILs) was synthesized by cation exchange from barium salts of oxidovanadium(IV) complexes stabilized by edta and its congeners (dcta, oedta, and heedta) serving as pentadentate ligands. All starting barium salts and several magnesium and cesium salts, serving as models for the cation exchange, were structurally characterized by single-crystal XRD analysis. The synthesized ILs consisting of organic cations (BuN, Bmim, and BuP) and complex anions ([VO(edta)], [VO(dcta)], [VO(oedta)], and [VO(heedta)]) were characterized by analytical and spectroscopic methods including EPR spectroscopy and cyclic voltammetry.

Microplastics meet micropollutants in a central european river stream: Adsorption of pollutants to microplastics under environmentally relevant conditions.

Microplastics have emerged as pervasive pollutants in aquatic environments, and their interaction with organic contaminants poses a significant environmental challenge. This study aimed to explore the adsorption of micropollutants onto microplastics in a river, examining different plastic materials and the effect of aging on adsorption capacity. Microplastics (low-density polyethylene (LDPE), polyethylene terephthalate (PET), and polyvinyl chloride (PVC)) were introduced into a river stream, and a comprehensive analysis involving 297 organic pollutants was conducted.

Sustainable aerogels based on biobased poly (itaconic acid) for adsorption of cationic dyes.

This work reports the synthesis of poly (itaconic acid) by thermal polymerization mediated by 2,2'-Azobis(2-methylpropionamidine) dihydrochloride. Furthermore, physical hydrogels were prepared by using high molecular weight poly (itaconic acid) characterized by low dispersity and laponite RD. The hydrogels presented porous 3D network structures, with a high-water penetration of almost 2000 g/g of swelling ratio, which can allow the adsorption sites of both poly (itaconic acid) and laponite RD to be easily exposed and facilitate the adsorption of dyes.

Biodegradation of aliphatic polyurethane foams in soil: Influence of amide linkages and supramolecular structure.

Polyurethane (PU) foams are classified as physically nonrecyclable thermosets. The current effort of sustainable and eco-friendly production makes it essential to explore methods of better waste management, for instance by modifying the structure of these frequently used polymers to enhance their microbial degradability. The presence of ester links is known to be a crucial prerequisite for the biodegradability of PU foams.

The effects of formation and functionalization of graphene-based membranes on their gas and water vapor permeation properties.

The gas and water vapor permeabilities of graphene-based membranes can be affected by the presence of different functional groups directly bound to the graphene network. In this work, one type of carboxylated graphene oxide (GO-COOH) and two types of graphene oxide synthesized i) under strong oxidative conditions directly from graphite (GO-1) and ii) under mild oxidative conditions from exfoliated graphene (GO-2) were used as precursors of self-standing membranes prepared with thicknesses in the range of 12-55 μm via slow-vacuum filtration preparation method. It was observed that the permeabilities for all tested gases decreased in order GO-2 > GO-1 > GO-COOH and depended on both the arrangement of graphene sheets and their functionalization.

Intercalation of Ionic Liquids into LDH Structures for Microwave-Accelerated Polymerizations.

Microwave-accelerated ring-opening polymerization (ROP) of cyclic esters catalyzed by ionic liquid (IL) anions, intercalated into layered double hydroxides (LDHs), has been recently described as a fast and environmentally friendly synthetic way to prepare biodegradable polyester/LDH nanocomposites. However, to observe this synergistic catalytic effect between microwaves and IL anions and to achieve a homogeneous structure of the final polymer nanocomposite, the IL anions must be efficiently intercalated inside the LDH structure. Herein, we investigate the effects of various metal compositions of M/Al LDHs (M = Mg, Co, and Ca) and different LDH synthetic routes (one-step direct coprecipitation, two-step coprecipitation/anion exchange, and two-step urea/anion exchange) on the intercalation efficiency of trihexyltetradecylphosphonium bis(2,4,4-trimethylpentyl)phosphinate IL.

In vitro toxicity assessment of polyethylene terephthalate and polyvinyl chloride microplastics using three cell lines from rainbow trout (Oncorhynchus mykiss).

The RTgill-W1 (gill), RTG-2 (gonad), and RTL-W1 (liver) cell lines derived from a freshwater fish rainbow trout (Oncorhynchus mykiss), were used to assess the toxicity of polyethylene terephthalate (PET) and two forms of polyvinyl chloride (PVC). Two size fractions (25-μm and 90-μm particles) were tested for all materials. The highest tested concentration was 1 mg/ml, corresponding to from 70 000 ± 9000 to 620 000 ± 57 000 particles/ml for 25-μm particles and from 2300 ± 100 to 11 000 ± 1000 particles/ml for 90-μm particles (depending on the material).

The Synthesis of Bio-Based Michael Donors from Tall Oil Fatty Acids for Polymer Development.

In this study, the synthesis of a Michael donor compound from cellulose production by-products-tall oil fatty acids-was developed. The developed Michael donor compounds can be further used to obtain polymeric materials after nucleophilic polymerization through the Michael reaction. It can be a promising alternative method for conventional polyurethane materials, and the Michael addition polymerization reaction takes place under milder conditions than non-isocyanate polyurethane production technology, which requires high pressure, high temperature and a long reaction time.

Pharmacokinetics of Intramuscularly Administered Thermoresponsive Polymers.

Aqueous solutions of some polymers exhibit a lower critical solution temperature (LCST); that is, they form phase-separated aggregates when heated above a threshold temperature. Such polymers found many promising (bio)medical applications, including in situ thermogelling with controlled drug release, polymer-supported radiotherapy (brachytherapy), immunotherapy, and wound dressing, among others. Yet, despite the extensive research on medicinal applications of thermoresponsive polymers, their biodistribution and fate after administration remained unknown.

Insight into the aqueous Laponite® nanodispersions for self-assembled poly(itaconic acid) nanocomposite hydrogels: The effect of multivalent phosphate dispersants.

Hypothesis: We hypothesize, that physical network between Laponite® nanoparticles and high molecular weight polyelectrolyte formed by mixing of Laponite® nanodispersion (containing multivalent phosphate dispersant) and polyelectrolyte solution is strongly influenced by the type and content of dispersant, which forms electric double layer (EDL) closely to the Laponite® edges. Thus, optimum dispersant concentration is necessary to overcome clay-clay interactions (excellent clay delamination), but should not be exceeded, what would result in the EDL compression and weakening of attractions forming clay-polyelectrolyte network. Thus, deeper investigation of Laponite® nanodispersions is highly demanded since it would enable to better design the self-assembled clay-polyelectrolyte hydrogels.

Polycyclic aromatic hydrocarbon accumulation in aged and unaged polyurethane microplastics in contaminated soil.

The interaction of microplastics (MPs) and common environmental organic pollutants has been a frequently discussed topic in recent years. Although the estimated contamination caused by MPs in terrestrial ecosystems is one order of magnitude higher than that in the oceans, experiments have been conducted solely in an aqueous matrix. Therefore, an experiment was carried out with two soils differing in their concentrations of polycyclic aromatic hydrocarbons (PAHs) and polyurethane foams used for scent fences along roads and crop fields.

Development and Characterization of "Green Open-Cell Polyurethane Foams" with Reduced Flammability.

This work presents the cell structure and selected properties of polyurethane (PUR) foams, based on two types of hydroxylated used cooking oil and additionally modified with three different flame retardants. Bio-polyols from municipal waste oil with different chemical structures were obtained by transesterification with triethanolamine (UCO_TEA) and diethylene glycol (UCO_DEG). Next, these bio-polyols were used to prepare open-cell polyurethane foams of very low apparent densities for thermal insulation applications.

Effects of Immobilized Ionic Liquid on Properties of Biodegradable Polycaprolactone/LDH Nanocomposites Prepared by In Situ Polymerization and Melt-Blending Techniques.

The high capacity of calcinated layered double hydroxides (LDH) to immobilize various active molecules together with their inherent gas/vapor impermeability make these nanoparticles highly promising to be applied as nanofillers for biodegradable polyester packaging. Herein, trihexyl(tetradecyl)phosphonium decanoate ionic liquid (IL) was immobilized on the surface of calcinated LDH. Thus, the synthesized nanoparticles were used for the preparation of polycaprolactone (PCL)/LDH nanocomposites.

High-Molecular-Weight Polyampholytes Synthesized via Daylight-Induced, Initiator-Free Radical Polymerization of Renewable Itaconic Acid.

Herein, it is reported for the first time that when mixed with choline chloride, itaconic acid (IA), normally a low-reactive vinyl monomer, undergoes initiator-free radical polymerization under normal daylight. Furthermore, the process results in the formation of abnormally high-molecular-weight poly(itaconic acid) derivatives with M greater than ≈800 000 g mol . Detailed 1D/2D NMR studies indicate that the polymers have two types of ionizable moieties, that is, anionic carboxylic and cationic choline ester groups in an average molar ratio of 12:1.

Ionic Liquids as Delaminating Agents of Layered Double Hydroxide during In-Situ Synthesis of Poly (Butylene Adipate--Terephthalate) Nanocomposites.

Currently, highly demanded biodegradable or bio-sourced plastics exhibit inherent drawbacks due to their limited processability and end-use properties (barrier, mechanical, etc.). To overcome all of these shortcomings, the incorporation of lamellar inorganic particles, such as layered double hydroxides (LDH) seems to be appropriate.

Ultrasound exfoliation of graphite in biphasic liquid systems containing ionic liquids: A study on the conditions for obtaining large few-layers graphene.

Herein we describe a successful protocol for graphite exfoliation using a biphasic liquid system (water/dichloromethane, DCM) containing ionic liquids (ILs; 1,3-dibenzylimidazolium benzoate- and 1-naphthoate). The use of (surface active) IL and sonication led to stable DCM/water (O/W) emulsion, which enhanced graphene formation, suppressed its re-aggregation and decreased shear/cavitation damage. The O/W emulsion stabilization by the ILs was studied by dynamic light scattering (DLS), whereas their interaction with the graphene sheets were described by Density Functional Theory (DFT) calculations.

Ionic Liquid-Silica Precursors via Solvent-Free Sol-Gel Process and Their Application in Epoxy-Amine Network: A Theoretical/Experimental Study.

This work describes the solvent-free sol-gel synthesis of epoxy-functionalized silica-based precursors in the presence of 1-butyl-3-methylimidazolium-based ionic liquids (ILs) containing different anions: chloride (Cl) and methanesulfonate (MeSO). The IL-driven sol-gel mechanisms were investigated in detail using experimental characterizations (Si NMR and ATR FTIR spectroscopy) and a theoretical computational method based on density functional theory (DFT). We observed complex IL influence on both hydrolysis and condensation steps, involving especially H-bonding and Coulomb coupling stabilization of the process intermediates.

Characterizing crystal disorder of trospium chloride: a comprehensive,(13) C CP/MAS NMR, DSC, FTIR, and XRPD study.

Analysis of C cross-polarization magic angle spinning (CP/MAS) nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC), Fourier transform infrared (FTIR), and X-ray powder diffraction data of trospium chloride (TCl) products crystallized from different mixtures of water-ethanol [φ(EtOH) = 0.5-1.0] at various temperatures (0°C, 20°C) and initial concentrations (saturated solution, 30%-50% excess of solvent) revealed extensive structural variability of TCl.