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 M2+/Al3+ 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. The most effective IL anion intercalation was observed for Ca2+/Al3+ LDH prepared using the two-step method consisting of coprecipitation and subsequent anion exchange. After optimization, this synthetic pathway led to the production of LDHs with intercalated IL anions and a reduced amount of intercalated water (<0.6 wt %). The catalytic ability of thus optimized LDH particles was demonstrated on the microwave-assisted ROP of ε-caprolactone, showing rapid progress of polymerization. Within minutes, the polycaprolactones with an average molecular mass in the range of 20 000-50 000 g/mol containing fully delaminated and exfoliated LDH nanoparticles were obtained.

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 Mw greater than ≈800 000 g mol-1 . 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. Potentiometric titration shows polyampholyte behavior of the polymers. Tentative mechanistic studies reveal that the daylight-induced polymerization is initiated by species generated via interactions of near UV light with IA. However, EPR findings show that choline also participates in secondary radical reactions. The obtained polyampholytes are useful bio-based materials for fast and straightforward fabrication of polymer-clay nanocomposite hydrogels with excellent mechanical properties.

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. However, the impact of other hydrolysable groups (urethane, urea and amide) occurred in PU materials, as well as the supramolecular structure of the PU network and the cellular morphology of PU foams, is still relatively unexplored. In this work, fully aliphatic PU foams with and without hydrolyzable amide linkages were prepared and their aerobic biodegradation was investigated using a six-month soil burial test. Besides the variable chemical composition of the PU foams, the influence of their different supramolecular arrangement and cellular morphologies on the extent of biodegradation was also evaluated. Throughout the soil burial test, the release of carbon dioxide, and enzyme activities of proteases, esterases, and ureases were measured. At the same time, phospho-lipid fatty acids (PLFA) analysis was conducted together with an assessment of microbial community composition achieved by analysing the genetic information from the 16S rRNA gene and ITS2 region sequencing. The results revealed a mineralization rate of 30-50 % for the PU foams, indicating a significant level of degradation as well as indicating that PU foams can be utilized by soil microorganisms as a source of both energy and nutrients. Importantly, microbial biomass remained unaffected, suggesting that there was no toxicity associated with the degradation products of the PU foams. It was further confirmed that ester linkages in PU foam structure were easily enzymatically cleavable, while amide linkages were not prone to degradation by soil microorganisms. In addition, it was shown that the presence of amide linkages in PU foam leads to a change in the supramolecular network arrangement due to increased content of hard segments, which in turn reduces the biodegradability of PU foam. These findings show that it is important to consider both chemical composition and supramolecular/macroscopic structure when designing new PU materials in an effort to develop environmentally friendly alternatives.

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. The water adsorption followed Schott's pseudo-second-order model. The mechanism of the adsorption process was investigated using 1H and 31P NMR. The hydrogel is able to fast adsorb by a combination of electrostatic interactions and hydrogen bonding by the synergic effect of the clay and poly (itaconic acid). Moreover, the prepared aerogels exhibited a fast removal of Basic Fuchsin, with an adsorption capacity of 67.56 mg/g and a high removal efficiency (~99 %). The adsorption followed the pseudo-second-order kinetic model and Langmuir isotherm model. Furthermore, the thermodynamic parameters showed that the BF process of adsorption was spontaneous and feasible, endothermic, and followed physisorption. These results indicated that the PIA/laponite-based aerogel can be considered a promising adsorbent material in textile wastewater treatment.

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). Toxicity differences between commercial PVC dry blend powder and secondary microplastics created from a processed PVC were newly described. After a 24-h exposure, the cells were analyzed for changes in viability, 7-ethoxyresorufin-O-deethylase (EROD) activity, and reactive oxygen species (ROS) generation. In addition to the microplastic suspensions, leachates and particles remaining after leaching resuspended in fresh exposure medium were tested. The particles were subjected to leaching for 1, 8, and 15 days. The PVC dry blend (25 µm and 90 µm) and processed PVC (25 µm) increased ROS generation, to which leached chemicals appeared to be the major contributor. PVC dry blend caused substantially higher ROS induction than processed PVC, showing that the former is not suitable for toxicity testing, as it can produce different results from those of secondary PVC. The 90-µm PVC dry blend increased ROS generation only after prolonged leaching. PET did not induce any changes in ROS generation, and none of the tested polymers had any effect on viability or EROD activity. The importance of choosing realistic extraction procedures for microplastic toxicity experiments was emphasized. Conducting long-term experiments is crucial to detect possible environmentally relevant effects. In conclusion, the tested materials showed no acute toxicity to the cell lines.

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. The GO-1 membrane with a high content of oxygen-containing groups showed the best performance for water vapor permeability. The GO-2 membrane with a thickness of 43 µm exhibited a disordered GO sheet morphology and, therefore, unique gas-separation performance towards H2/CO2 gas pair, showing high hydrogen permeability while keeping extremely high H2/CO2 ideal selectivity that exceeds the Robeson 2008 upper bound of polymer membranes.

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. Different polyols, the precursors for Michael donor components, were synthesized from epoxidized tall oil fatty acids by an oxirane ring-opening and esterification reaction with different alcohols (trimethylolpropane and 1,4-butanediol). The addition of functional groups necessary for the Michael reaction was carried out by a transesterification reaction of polyol hydroxyl groups with tert-butyl acetoacetate ester. The following properties of the developed polyols and their acetoacetates were analyzed: hydroxyl value, acid value, moisture content and viscosity. The chemical structure was analyzed using Fourier transform infrared spectroscopy, gel permeation chromatography, size-exclusion chromatography and nuclear magnetic resonance. Matrix-assisted laser desorption/ionization analysis was used for structure identification for this type of acetoacetate for the first time.

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. EXPERIMENTS: To study clay interparticle interactions in the presence of various multivalent phosphates, complementary methods providing wide nanodispersion characterization have been applied: zeta potential measurement and SAXS technique (electrostatic interactions), oscillatory rheology (nanodispersion physical state) and NMR experiments (ion immobilization degree). FINDINGS: It was found that multivalent phosphates induce and tune strength of clay-polyelectrolyte interactions forming hydrogel network in terms of varying EDL on the Laponite® edges. Moreover, phosphate dispersing efficiency depends on the molecular size, chemical structure, and valence of the anion; its potential as efficient dispersant for hydrogel preparation can be evaluated by estimation of anion charge density.

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. Thus, herein, they studied the pharmacokinetics of four different thermoresponsive polyacrylamides after intramuscular administration in mice. In vivo, these thermoresponsive polymers formed depots that subsequently dissolved with a two-phase kinetics (depot maturation, slow redissolution) with half-lives 2 weeks to 5 months, as depot vitrification prolonged their half-lives. Additionally, the decrease of TCP of a polymer solution increased the density of the intramuscular depot. Moreover, they detected secondary polymer depots in the kidneys and liver; these secondary depots also followed two-phase kinetics (depot maturation and slow dissolution), with half-lives 8 to 38 days (kidneys) and 15 to 22 days (liver). Overall, these findings may be used to tailor the properties of thermoresponsive polymers to meet the demands of their medicinal applications. Their methods may become a benchmark for future studies of polymer biodistribution.

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. Two types of polyurethane foam (biodegradable and conventional in aged and unaged form) were exposed to soils containing PAHs that originated from historically contaminated localities. The exposure lasted 28 days, and a newly developed three-step procedure to separate MPs from soil was then applied. Biodegradable polyurethane MPs exhibited a strong tendency to accumulate PAHs after 7 days, and their concentrations significantly grew over time. In contrast, the sorption of PAHs on conventional polyurethane MPs was substantially lower (a maximum of 3.6 times higher concentration than that in the soil). Neither type of foam changed their sorption behaviors after the aging procedure. The results indicate that the flexibility of the polyurethane polymeric network could be the main driving factor for the sorption.

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. Two different methods of nanocomposite preparation were used and compared: microwave-assisted in situ ring opening polymerization (ROP) of ε-caprolactone (εCL) and melt-blending. The in situ ROP of εCL in the presence of LDH nanoparticles with the immobilized IL led to homogenous nanofiller dispersion in the PCL matrix promoting formation of large PCL crystallites, which resulted in the improved mechanical, thermal and gas/water vapor barrier properties of the final nanocomposite. The surface-bonded IL thus acted as nanofiller surfactant, compatibilizer, as well as thermal stabilizer of the PCL/LDH nanocomposites. Contrary to that, the melt-blending caused a partial degradation of the immobilized IL and led to the production of PCL nanocomposites with a heterogenous nanofiller dispersion having inferior mechanical and gas/water vapor barrier properties.

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. In order to obtain foams with reduced flammability, the PUR systems were modified with different amounts (10-30 parts per hundred polyol by weight-php) of flame retardants: TCPP (tris(1-chloro-2-propyl)phosphate), TEP (triethyl phosphate), and DMPP (dimethyl propylphosphonate). The flame retardants caused a decrease of the PUR formulations reactivity. The apparent densities of all the foams were comparable in the range 12-15 kg/m3. The lowest coefficients of thermal conductivity were measured for the open-cell PUR foams modified with DMPP. The lowest values of heat release rate were found for the foams based on the UCO_TEA and UCO_DEG bio-polyols that were modified with 30 php of DMPP.

Ionic Liquids as Delaminating Agents of Layered Double Hydroxide during In-Situ Synthesis of Poly (Butylene Adipate-co-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. However, LDH delamination and homogenous dispersion in a polymer matrix without use of harmful solvents, remains a challenging issue, which explains why LDH-based polymer nanocomposites have not been scaled-up yet. In this work, LDH with intercalated ionic liquid (IL) anions were synthesized by a direct co-precipitation method in the presence of phosphonium IL and subsequently used as functional nanofillers for in-situ preparation of poly (butylene adipate-co-terephthalate) (PBAT) nanocomposites. The intercalated IL-anions promoted LDH swelling in monomers and LDH delamination during the course of in-situ polycondensation, which led to the production of PBAT/LDH nanocomposites with intercalated and exfoliated morphology containing well-dispersed LDH nanoplatelets. The prepared nanocomposite films showed improved water vapor permeability and mechanical properties and slightly increased crystallization degree and therefore can be considered excellent candidates for food packaging applications.

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. Moreover, a comprehensive investigation on cavitation-based exfoliation in the O/W systems was performed to assess the importance of operational parameters, including, the type of ultrasound processor, ultrasound power and insonation, and the influence of the exfoliation medium.

Ionic Liquids as Surfactants for Layered Double Hydroxide Fillers: Effect on the Final Properties of Poly(Butylene Adipate-Co-Terephthalate).

In this work, phosphonium ionic liquids (ILs) based on tetra-alkylphosphonium cations combined with carboxylate, phosphate and phosphinate anions, were used for organic modification of layered double hydroxide (LDH). Two different amounts (2 and 5 wt %) of the organically modified LDHs were mixed with poly(butylene adipate-co-terephthalate) (PBAT) matrix by melt extrusion. All prepared PBAT/IL-modified-LDH composites exhibited increased mechanical properties (20-50% Young's modulus increase), decreased water vapor permeability (30-50% permeability coefficient reduction), and slight decreased crystallinity (10-30%) compared to the neat PBAT.

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 (MeSO3-). The IL-driven sol-gel mechanisms were investigated in detail using experimental characterizations (29Si 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. The obtained IL-silica precursors and their further xerogels were widely characterized (rheology measurements, MALDI TOF, 29Si NMR, ATR FTIR, and DFT simulation), which allowed observation of their precise silica structures and established their most energetically favorable conformations. The detected silica structures were dependent on the IL type and varied from highly condensed 3D cage-like to branched ladder-like and cyclic ones. The application of prepared IL-silica precursors as reinforcing additives into the epoxy-amine network led to an improvement in the organic/inorganic interphase interactions through chemical and physical bonding. Uniform and well-dispersed silica aggregates, in the size of ∼30 nm, were formed when ≤6.8 wt % of each IL-silica precursor was applied into the epoxy-amine network. The use of imidazolium-based ILs contributed to a significant improvement in thermomechanical properties of hybrids and reduced their UV absorption ability compared to that of the reference matrix. All hybrids exhibited an increase in energy to break (up to ∼53%), elongation at break (up to ∼43%), shear storage modulus in the rubbery region (up to 4 times), and thermo-oxidative stability.

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. Although (13) C CP/MAS NMR spectra indicated broad variety of structural phases arising from molecular disorder, temperature-modulated DSC identified presence of two distinct components in the products. FTIR spectra revealed alterations in the hydrogen bonding network (ionic hydrogen bond formation), whereas the X-ray diffraction reflected unchanged unit cell parameters. These results were explained by a two-component character of TCl products in which a dominant polymorphic form is accompanied by partly separated nanocrystalline domains of a secondary phase that does not provide clear Bragg reflections. These phases slightly differ in the degree of molecular disorder, in the quality of crystal lattice and hydrogen bonding network. It is also demonstrated that, for the quality control of such complex products, (13) C CP/MAS NMR spectroscopy combined with factor analysis (FA) can satisfactorily be used for categorizing the individual samples: FA of (13) C CP/MAS NMR spectra found clear relationships between the extent of molecular disorder and crystallization conditions. © 2013 Wiley Periodicals, Inc. and the American Pharmacists Association J Pharm Sci 102:1235-1248, 2013.