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[N-(1,3-dihydroxypropyl)methacrylamide] (poly(DHPMA)) and a thermoresponsive block of poly[N-(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. However, they form well-defined nanoparticles with hydrodynamic diameters of 50-800 nm when heated above the transition temperature of 27-31 °C. This temperature range is carefully tailored to align with the human body's physiological conditions. The formation of the nanoparticles and their subsequent decomposition was studied using dynamic light scattering (DLS), transmission electron microscopy (TEM), isothermal titration calorimetry (ITC), and nuclear magnetic resonance (NMR). 1H NMR studies confirmed that after approximately 20 h of incubation at pH 5, which closely mimics tumor microenvironment, approximately 40% of the acetal groups were hydrolyzed, and the thermoresponsive behavior of the copolymers was lost. This smart polymer response led to disintegration of the supramolecular structures, possibly releasing the therapeutic cargo. By tuning the transition temperature to the values relevant for medical applications, we ensure precise and effective drug release. In addition, our systems did not exhibit any cytotoxicity against any of the three cell lines. Our findings underscore the immense potential of these nanoparticles as eventual advanced drug delivery systems, especially for cancer therapy.
- Klíčová slova
- RAFT polymerization, drug delivery systems, pH-sensitive polymers, self-assembling block copolymers, thermoresponsive polymers,
- MeSH
- antitumorózní látky chemie farmakologie chemická syntéza aplikace a dávkování MeSH
- biokompatibilní materiály chemie farmakologie chemická syntéza MeSH
- doxorubicin chemie farmakologie MeSH
- koncentrace vodíkových iontů MeSH
- lidé MeSH
- molekulární struktura MeSH
- nanočástice * chemie MeSH
- nosiče léků chemie MeSH
- polymery * chemie chemická syntéza farmakologie MeSH
- systémy cílené aplikace léků MeSH
- teplota * MeSH
- testování materiálů * MeSH
- uvolňování léčiv MeSH
- velikost částic * MeSH
- viabilita buněk účinky léků MeSH
- Check Tag
- lidé MeSH
- Publikační typ
- časopisecké články MeSH
- Názvy látek
- antitumorózní látky MeSH
- biokompatibilní materiály MeSH
- doxorubicin MeSH
- nosiče léků MeSH
- polymery * MeSH
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. Current research studies focus mainly on the use of bio-based polyols for PUs, while other PU components, in particular polyisocyanates, remain of petrochemical origin. In this work, a series of PUs have been synthesized by polyaddition reactions of different types of renewable polyols and bio-based polyisocyanates. The effects of the bio-derived components on the structure, thermal stability and phase transformations of the PU were studied using FTIR and NMR spectroscopy, SWAXS, TGA, DSC, DMTA and TGA-FTIR. A full conversion of the bio-based monomers was achieved in all cases, indicating good compatibility and reactivity of all bio-based components. It was observed that bio-based PU exhibited a lower degree of phase separation and slightly lower thermal stability compared to PUs from petrochemical monomers.
- Klíčová slova
- Biomass, Climate change, Natural resource, Polyurethane, Sustainable development,
- Publikační typ
- časopisecké články MeSH
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. Passive samplers were deployed to monitor micropollutant presence in the river. Sixty-four analytes were identified in the river flow, with telmisartan being the most prevalent. Nonaged PVC showed the highest telmisartan concentration at 279 ng/g (168 ng/m2 regarding the microplastic surface), while aged PVC exhibited a fourfold decrease. Conversely, aged LDPE preferentially adsorbed metoprolol and tramadol, with concentrations increasing 12- and 3-fold, respectively, compared to nonaged LDPE. Azithromycin and clarithromycin, positively charged compounds, exhibited higher sorption to PET microplastics, regardless of aging. Diclofenac showed higher concentrations on nonaged PVC compared to aged PVC. Aging induced structural changes in microplastics, including color alterations, smaller particle production, and increased specific surface area. These changes influenced micropollutant adsorption, with hydrophobicity, dissociation constants, and the ionic form of pollutants being key factors. Aged microplastics generally showed different sorption properties. A comparison of microplastics and control sand particles indicated preferential micropollutant sorption to microplastics, underscoring their role as vectors for contaminant transport in aquatic ecosystems. Analysis of river sediment emphasized the significance of contact time in pollutant accumulation. Overall, this study provides insights into the complex interactions between microplastics and organic pollutants under environmental conditions and contributes to a better understanding of the fate and behavior of these two types of contaminants in aquatic ecosystems.
- Klíčová slova
- Low-density polyethylene (LDPE), Pharmaceuticals, Polyethylene terephthalate (PET), Polyvinyl chloride (PVC), Telmisartan, aging,
- MeSH
- adsorpce MeSH
- chemické látky znečišťující vodu * analýza MeSH
- mikroplasty * analýza MeSH
- monitorování životního prostředí * MeSH
- řeky * chemie MeSH
- Publikační typ
- časopisecké články MeSH
- Názvy látek
- chemické látky znečišťující vodu * MeSH
- mikroplasty * MeSH
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 (Bu4N+, Bmim+, and Bu4P+) and complex anions ([VO(edta)]2-, [VO(dcta)]2-, [VO(oedta)]-, and [VO(heedta)]-) were characterized by analytical and spectroscopic methods including EPR spectroscopy and cyclic voltammetry. Then, ILs were tested as catalysts for the ring-opening copolymerization of epoxy resin with cyclic anhydride showing significant catalytic activity, which led to production of highly cross-linked glassy thermosets. A detailed isothermal DSC kinetic study was performed for the most promising IL showing that the progress of cross-linking can be successfully fitted by the Kamal-Sourour model. Based on the DSC and NIR results, the initiation mechanism of the cross-linking in the presence of vanadium-containing IL was suggested. IL had ability to activate a rapid hydrolysis of anhydride cycle and the formed carboxyl groups initiated a polyesterification. In parallel, the role of imidazolium cation of IL for the initiation of chain-growth anionic copolymerization is also discussed.
- Publikační typ
- časopisecké články MeSH
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.
- Klíčová slova
- Amide bond, Biodegradation, Enzymatic activity, Microbial composition, Polyurethane foam, Soil burial, Supramolecular structure,
- MeSH
- amidy * MeSH
- estery MeSH
- polyurethany * chemie MeSH
- půda MeSH
- RNA ribozomální 16S MeSH
- Publikační typ
- časopisecké články MeSH
- Názvy látek
- amidy * MeSH
- estery MeSH
- polyurethane foam MeSH Prohlížeč
- polyurethany * MeSH
- půda MeSH
- RNA ribozomální 16S MeSH
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.
- Klíčová slova
- Aggregation, Cationic dye, Composites, Metachromasy, Polyitaconic acid, Water pollution,
- MeSH
- adsorpce MeSH
- barvicí látky * chemie MeSH
- chemické látky znečišťující vodu * chemie MeSH
- hydrogely chemie MeSH
- kinetika MeSH
- silikáty * MeSH
- sukcináty * MeSH
- voda MeSH
- Publikační typ
- časopisecké články MeSH
- Názvy látek
- barvicí látky * MeSH
- chemické látky znečišťující vodu * MeSH
- hydrogely MeSH
- itaconic acid MeSH Prohlížeč
- laponite MeSH Prohlížeč
- silikáty * MeSH
- sukcináty * MeSH
- voda MeSH
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.
- Klíčová slova
- Carboxylated graphene oxide, Gas permeability, Graphene oxide, Graphene-based membrane,
- Publikační typ
- časopisecké články MeSH
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.
- Publikační typ
- časopisecké články MeSH
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.
- Klíčová slova
- Microplastics, Oncorhynchus mykiss, PET, PVC, Reactive oxygen species, Toxicity,
- MeSH
- buněčné linie MeSH
- chemické látky znečišťující vodu * analýza MeSH
- cytochrom P-450 CYP1A1 metabolismus MeSH
- mikroplasty toxicita MeSH
- Oncorhynchus mykiss * metabolismus MeSH
- plastické hmoty toxicita metabolismus MeSH
- polyethylentereftaláty toxicita metabolismus MeSH
- polyvinylchlorid toxicita metabolismus MeSH
- reaktivní formy kyslíku metabolismus MeSH
- zvířata MeSH
- Check Tag
- zvířata MeSH
- Publikační typ
- časopisecké články MeSH
- Názvy látek
- chemické látky znečišťující vodu * MeSH
- cytochrom P-450 CYP1A1 MeSH
- mikroplasty MeSH
- plastické hmoty MeSH
- polyethylentereftaláty MeSH
- polyvinylchlorid MeSH
- reaktivní formy kyslíku MeSH
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.
- Klíčová slova
- LCST, biodistribution, poly(2,2-difluoroethyl)acrylamide, poly(N,N-diethylacrylamide), poly(N-acryloylpyrolidine), poly(N-isopropylacrylamide), polyacrylamide, rational polymer design,
- MeSH
- myši MeSH
- polymery * MeSH
- teplota MeSH
- tkáňová distribuce MeSH
- uvolňování léčiv MeSH
- voda * MeSH
- zvířata MeSH
- Check Tag
- myši MeSH
- zvířata MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
- Názvy látek
- polymery * MeSH
- voda * MeSH
