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1.
Aquat Toxicol ; 272: 106966, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-38815345

RESUMO

The accumulation of plastics waste in the environment has raised a worrisome concern, moving the society to seek out for sustainable solutions, such as the transition from the use of fossil-based, conventional plastics to bioplastics (BPs). However, once in the environment bioplastics have the same probability to accumulate and experience weathering processes than conventional plastics, leading to the formation of microplastics (MPs). However, to date the information on the potential toxicity of MPs originated from the weathering of bioplastics is limited. Thus, this study aimed at investigating the adverse effects induced by the exposure to MPs made of a bioplastic polymer, the polylactic acid (PLA), towards the freshwater cladoceran Daphnia magna. Organisms were exposed for 21 days to three concentrations (0.125 µg/mL, 1.25 µg/mL and 12.5 µg/mL) of PLA microplastics (hereafter PLA-MPs). A multi-level approach was performed to investigate the potential effects through the biological hierarchy, starting from the sub-individual up to the individual level. At the sub-individual level, changes in the oxidative status (i.e., the amount of reactive oxygen species and the activity of antioxidant and detoxifying enzymes) and oxidative damage (i.e., lipid peroxidation) were explored. Moreover, the total caloric content as well as the content of protein, carbohydrate and lipid content assess were used to investigate the effects on energy reserves. At individual level the changes in swimming activity (i.e., distance moved and swimming speed) were assessed. Our results showed that the exposure to PLA-MPs induced a slight modulation in the oxidative status and energy reserves, leading to an increase in swimming behavior of treated individuals compared to control conspecifics. These results suggest that the exposure to MPs made of a bioplastic polymer can induce adverse effects similar to those caused by conventional polymers.


Assuntos
Daphnia , Microplásticos , Poliésteres , Poluentes Químicos da Água , Animais , Poliésteres/toxicidade , Daphnia/efeitos dos fármacos , Microplásticos/toxicidade , Poluentes Químicos da Água/toxicidade , Estresse Oxidativo/efeitos dos fármacos , Daphnia magna
2.
Toxics ; 12(4)2024 Apr 18.
Artigo em Inglês | MEDLINE | ID: mdl-38668523

RESUMO

The implementation of recycling techniques represents a potential solution to the plastic pollution issue. To date, only a limited number of plastic polymers can be efficiently recycled. In the Italian plastic waste stream, the residual, non-homogeneous fraction is called 'Plasmix' and is intended for low-value uses. However, Plasmix can be used to create new materials through mechanical recycling, which need to be tested for their eco-safety. This study aimed to investigate the potential toxicity of two amounts (0.1% and 1% MPs in soil weight) of microplastics (MPs) made of naïve and additivated Plasmix-based materials (Px and APx, respectively) on the earthworm Eisenia foetida. Changes in oxidative status and oxidative damage, survival, gross growth rate and reproductive output were considered as endpoints. Although earthworms ingested both MP types, earthworms did not suffer an oxidative stress condition or growth and reproductive impairments. The results suggested that exposure to low amounts of both MPs can be considered as safe for earthworms. However, further studies testing a higher amount or longer exposure time on different model species are necessary to complete the environmental risk assessment of these new materials.

3.
J Hazard Mater ; 469: 134000, 2024 May 05.
Artigo em Inglês | MEDLINE | ID: mdl-38508107

RESUMO

The ubiquitous presence of water-soluble polymers (WSPs) in freshwater environments raises concerns regarding potential threats to aquatic organisms. This study investigated, for the first time, the effects of widely used WSPs -polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), polyacrylic acid (PAA), and polyethylene glycol (PEG)- using a multi-level approach in the freshwater biological model Daphnia magna. This integrated assessment employed a suite of biomarkers, evaluation of swimming behaviour, and proteomic analysis to investigate the effects of three environmentally relevant concentrations (0.001, 0.5, and 1 mg/L) of the tested WSPs from molecular to organismal levels, assessing both acute and chronic effects. Our findings reveal that exposure to different WSPs induces specific responses at each biological level, with PEG being the only WSP inducing lethal effects at 0.5 mg/L. At the physiological level, although all WSPs impacted both swimming performance and heart rate of D. magna specimens, PAA exhibited the greatest effects on the measured behavioural parameters. Furthermore, proteomic analyses demonstrated altered protein profiles following exposure to all WSPs, with PVA emerging as the most effective.


Assuntos
Poluentes Químicos da Água , Água , Animais , Água/farmacologia , Polímeros/toxicidade , Daphnia magna , Proteoma , Proteômica , Daphnia , Poluentes Químicos da Água/toxicidade
4.
Environ Pollut ; 348: 123868, 2024 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-38556148

RESUMO

A growing number of studies have demonstrated that microplastic (MP) contamination is widespread in terrestrial ecosystems. A wide array of MPs made of conventional, fossil-based polymers differing in size and shape has been detected in soils worldwide. Recently, also MPs made of bioplastics have been found in soils, but there is a dearth of information concerning their toxicity on soil organisms. This study aimed at exploring the potential toxicity induced by the exposure for 28 days to irregular shaped and differently sized MPs made of a fossil-based (polyethylene terephthalate - PET) and a bioplastic (polylactic acid - PLA) polymer on the earthworm Eisenia foetida. Two amounts (1 g and 10 g/kg of soil, corresponding to 0.1% and 1% of soil weight) of both MP types were administered to the earthworms. A multi-level approach was used to investigate the MP-induced effects at sub-individual and individual level. Changes in the activity of antioxidant and detoxifying enzymes, as well as in lipid peroxidation levels, were investigated at specific time-points (i.e., 7, 14, 21 and 28 days) as sub-individual responses. Histological analyses were performed to assess effects at tissue level, while the change in digging activity was considered as a proxy of behavioral effects. Earthworms ingested MPs made of both the polymers. MPs made of PET did not induce any adverse effect at none of the biological levels. In contrast, MPs made of PLA caused the modulation of earthworms' oxidative status as showed by a bell-shaped activity of superoxide dismutase coupled with an increase in glutathione peroxidase activity. However, neither oxidative and tissue damage, nor behavioral alteration occurred. These findings suggest that the exposure to bio-based MPs can cause higher toxicity compared to fossil-based MPs.


Assuntos
Microplásticos , Oligoquetos , Poliésteres , Animais , Microplásticos/toxicidade , Plásticos/toxicidade , Polietilenotereftalatos , Ecossistema , Antioxidantes/farmacologia , Solo , Polietileno/farmacologia
5.
Eur J Pharm Sci ; 195: 106726, 2024 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-38354986

RESUMO

EMA and FDA are upgrading guidelines on assessing the quality and the equivalence of topically applied drug products for developing copies of originator products and supporting post-marketing variations. For topical products having remarkably similar composition, both EMA and FDA accept the equivalence on the bases of the comparison of rheological properties and in vitro drug release constant (k) and skin permeation flux (J) values, instead of clinical studies. This work aims to evaluate the feasibility to expand this approach to variations of the composition of complex semi-solid preparations. Ibuprofen (IB) creams at two different strengths (i.e., 1 % and 10 %) were used as a model formulation. Two formulative changes were performed: (a) the addition of the humectant to simulate a minor post-marketing variation; (b) the substitution of the emulsifying system to simulate a major one. These variations impacted only in 1 % IB formulations where both the equivalences of rheological data and J-values failed. At the highest concentration, the presence of IB crystals broke down the differences in rheological patterns and lead the IB thermodynamic activity at the maximum figuring out an overlapping of the J-values. Such data suggest the combination of these studies, which are thought mainly for the development of copies, could be also applied to the management of post-marketing variations that involve product composition.


Assuntos
Absorção Cutânea , Pele , Pele/metabolismo , Ibuprofeno/metabolismo , Termodinâmica , Reologia
6.
Sci Total Environ ; 893: 164843, 2023 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-37327888

RESUMO

The water-soluble polymers (WSPs) are widely used in many industrial applications and are present in several commonly used products due to their physical-chemical characteristics: as their name indicates, despite being synthetic polymers, they are able to solubilize in water. Because of this peculiar property, both the qualitative-quantitative evaluation in aquatic ecosystems and their potential (eco)toxicological effects have been neglected until now. The aim of this study was to evaluate the possible effects of three of the most widely used WSPs as polyacrylic acid (PAA), polyethylene glycol (PEG) and polyvinyl pyrrolidone (PVP) on the swimming behaviour of zebrafish (Danio rerio) embryos after the exposure to different concentrations (0.001, 0.5, 1 mg/L). The exposure lasted from the eggs' collection up to 120 h post fertilization (hpf) also using three different light intensity (300 lx, 2200 lx, 4400 lx) to better evaluate any effects related to different gradients of light/dark transitions. In order to analyze individual behavioural changes in embryos, their swimming movements were tracked and a number of parameters for locomotion and directionality were quantified. The main results showed that all three WSPs resulted in significant (p ≤ 0.05) variations in different movement parameters, suggesting a possible toxicity scale: PVP > PEG â‰« PAA.


Assuntos
Polímeros , Poluentes Químicos da Água , Animais , Polímeros/toxicidade , Peixe-Zebra , Ecossistema , Água , Locomoção , Poluentes Químicos da Água/toxicidade , Embrião não Mamífero , Larva
7.
Phys Chem Chem Phys ; 24(39): 24514-24523, 2022 Oct 12.
Artigo em Inglês | MEDLINE | ID: mdl-36193719

RESUMO

The heat-induced crystallization of amorphous calcium phosphate (ACP) is an intriguing process not yet well comprehended. This is because most of the works on this topic are based on ex situ studies where the materials are characterized after the heat and cooldown cycles, thus missing transient structural changes. Here, we used time-resolved energy dispersive X-ray diffraction and infrared spectroscopy to study, for the first time, the thermal crystallization of ACP in situ. The thermal crystallization of two kinds of citrate-stabilized carbonated ACP was studied, as they are promising materials for the preparation of advanced bioceramics. The behavior of these samples was compared to that of two citrate-free ACPs, either doped or non-doped with carbonate ions. Our results evinced that several phenomena occur during ACP thermal annealing. Before crystallization, all ACP samples undergo a decrease in the short-range order process, followed by several internal reorganizations. We have assessed that differently from carbonate-free ACP, carbonated ACPs with and without citrate directly crystallize into a biomimetic poorly crystalline carbonated hydroxyapatite. Citrate-stabilized ACPs in comparison to citrate-free ACPs have a faster hydroxyapatite formation kinetics, which is due to their higher specific surface area. This work reveals the necessity and the potentialities of using in situ techniques to effectively probe complex processes such as the heat-induced crystallization of ACPs.


Assuntos
Fosfatos de Cálcio , Durapatita , Fosfatos de Cálcio/química , Cristalização , Durapatita/química , Íons
8.
Molecules ; 27(20)2022 Oct 18.
Artigo em Inglês | MEDLINE | ID: mdl-36296595

RESUMO

The research for alternative administration methods for anticancer drugs, towards enhanced effectiveness and selectivity, represents a major challenge for the scientific community. In the last decade, polymeric nanostructured delivery systems represented a promising alternative to conventional drug administration since they ensure secure transport to the selected target, providing active compounds protection against elimination, while minimizing drug toxicity to non-target cells. In the present research, poly(glycerol sebacate), a biocompatible polymer, was synthesized and then nanostructured to allow curcumin encapsulation, a naturally occurring polyphenolic phytochemical isolated from the powdered rhizome of Curcuma longa L. Curcumin was selected as an anticancer agent in virtue of its strong chemotherapeutic activity against different cancer types combined with good cytocompatibility within healthy cells. Despite its strong and fascinating biological activity, its possible exploitation as a novel chemotherapeutic has been hampered by its low water solubility, which results in poor absorption and low bioavailability upon oral administration. Hence, its encapsulation within nanoparticles may overcome such issues. Nanoparticles obtained through nanoprecipitation, an easy and scalable technique, were characterized in terms of size and stability over time using dynamic light scattering and transmission electron microscopy, confirming their nanosized dimensions and spherical shape. Finally, biological investigation demonstrated an enhanced cytotoxic effect of curcumin-loaded PGS-NPs on human cervical cancer cells compared to free curcumin.


Assuntos
Antineoplásicos , Curcumina , Nanopartículas , Humanos , Curcumina/química , Linhagem Celular Tumoral , Nanopartículas/química , Polímeros/química , Antineoplásicos/química , Água , Tamanho da Partícula , Portadores de Fármacos/química
9.
Sci Total Environ ; 851(Pt 2): 158301, 2022 Dec 10.
Artigo em Inglês | MEDLINE | ID: mdl-36030849

RESUMO

Microplastic (MP) contamination is ubiquitous and widespread in terrestrial and aquatic ecosystems, including remote areas. However, information on the presence and distribution of MPs in high-mountain ecosystems, including glaciers, is still limited. The present study aimed at investigating presence, spatial distribution, and patterns of contamination of MPs on three glaciers of the Ortles-Cevedale massif (Central Alps, Northern Italy) with different anthropic pressures, i.e., the Forni, Cedec and Ebenferner-Vedretta Piana glaciers. Samples of supraglacial debris were randomly collected from the glaciers and MPs were isolated. The mean amount (±SE) of MPs measured in debris from Forni, Cedec and Ebenferner-Vedretta Piana glaciers was 0.033 ± 0.007, 0.025 ± 0.009, and 0.265 ± 0.027 MPs g-1 dry weight, respectively. The level and pattern of MP contamination from the Ebenferner-Vedretta Piana glacier were significantly different from those of the other glaciers. No significant spatial gradient in MP distribution along the ablation areas of the glaciers was observed, suggesting that MPs do not accumulate toward the glacier snout. Our results confirmed that local contamination can represent a relevant source of MPs in glacier ecosystems experiencing high anthropic pressure, while long-range transport can be the main source on other glaciers.


Assuntos
Camada de Gelo , Poluentes Químicos da Água , Microplásticos , Plásticos , Ecossistema , Itália , Monitoramento Ambiental/métodos , Poluentes Químicos da Água/análise
10.
Artigo em Inglês | MEDLINE | ID: mdl-36011719

RESUMO

The environmental accumulation of plastic wastes has become one of the most discussed topics in the scientific community. The development of new strategies to tackle this issue is of crucial importance, and different approaches are being investigated to effectively reduce plastic waste generated by improper or inefficient disposal. In addition to the efforts addressing the development of biodegradable plastics, the research is currently focused on the development of innovative recycling approaches. Indeed, although most plastic materials are potentially recyclable, only 15% of the worldwide plastic waste is currently recycled, while the remaining 85% is usually incinerated to recover thermal energy or landfilled. The hurdles to efficient recycling come from improper management of end-of-life plastic goods. Moreover, the highly heterogeneous nature and versatility of plastic and polymeric materials have led to the development of multilayered materials, composites, blends and many other different species, whose management and/or reprocessing to yield high-value products is extremely challenging. Thus, although these materials are extremely valuable from an industrial point of view, they add a high degree of complexity to the recycling process because each one of them is different from the other, but they cannot be separated efficiently. The aim of the present review is to return a comprehensive overview of environmental and management issues related to the complex and heterogeneous mixture of plastic waste that is generated at the end of the sorting procedures in Italian plastic recycling plants, the so-called 'Plasmix'. This review lists the difficulties and limitations related to the management of non-recyclable Plasmix and highlights the strategies for the proper, sustainable and valuable use of this plastic waste.


Assuntos
Plásticos , Gerenciamento de Resíduos , Indústrias , Polímeros , Reciclagem , Gerenciamento de Resíduos/métodos
11.
Front Chem ; 10: 927563, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-36003614

RESUMO

Aggregation-induced emissive materials are gaining particular attention in the last decades due to their wide application in different fields, from optical devices to biomedicine. In this work, compounds having these kinds of properties, composed of tetraphenylethylene scaffold combined with fatty acids of different lengths, were synthesized and characterized. These molecules were found able to self-assemble into different supramolecular emissive structures depending on the chemical composition and water content. Furthermore, they were used as N-terminus capping agents in the development of peptide-based materials. The functionalization of a 5-mer laminin-derived peptide led to the obtainment of luminescent fibrillary materials that were not cytotoxic and were able to form supramolecular gels in aqueous environment.

12.
Aquat Toxicol ; 248: 106200, 2022 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-35605492

RESUMO

Despite the pollution induced by plastics become a well-known and documented problem, bringing many countries to adopt restrictions about their production, commercialization and use, the impact of another emerging category of synthetic polymers, represented by the Water-Soluble Polymers (WSPs), also known as "liquid plastics", is overlooked by scientific community. WSPs are produced in large quantities and used in a wide plethora of applications such as food packaging, pharmaceuticals and personal care products, cosmetics and detergents, with a consequent continuous release in the environment. The aim of this study was the investigation of the possible toxicity induced by polyvinyl alcohol (PVA), one of the main produced and used WSPs, on two freshwater model organisms, the crustacean Daphnia magna and the teleost Danio rerio (zebrafish). We evaluated the effects of solubilized standard PVA powder and PVA-based commercial bags for carp-fishing, at 3 different concentrations (1 µg/L, 0.5 mg/L and 1 mg/L), through the exposures for 14 days of D. magna (daphnids; age < 24 h) and for 5 days of zebrafish embryos (up to 120 h post fertilization - hpf). As acute effects we evaluated the immobilization/mortality of specimens, while for chronic toxicity we selected several endpoints with a high ecological relevance, as the behavioural alteration on swimming performance, in real-time readout, and the activity of monoamine oxidase (MAO), a neuro-enzyme with a potential implication in the organism movement. The results showed the lack of significant effects induced by the selected substances, at all tested concentrations and in both model organisms. However, considering the wide plethora of available WSPs, other investigations are needed to provide the initial knowledge of risk assessment of these compounds contained in some consumer products.


Assuntos
Plásticos , Poluentes Químicos da Água , Animais , Organismos Aquáticos , Daphnia , Plásticos/toxicidade , Polímeros/farmacologia , Álcool de Polivinil/toxicidade , Água/farmacologia , Poluentes Químicos da Água/toxicidade , Peixe-Zebra
13.
Polymers (Basel) ; 14(6)2022 Mar 14.
Artigo em Inglês | MEDLINE | ID: mdl-35335490

RESUMO

Polyurethane nanocomposites were prepared with a nanosized high surface area graphite (HSAG) functionalized on its edges with hydroxyl groups as a building block. Edge functionalization of HSAG was obtained through reaction with KOH. The addition of OH groups was demonstrated by means of infrared (FTIR) and thermogravimetric analysis (TGA), and the Boehm titration allowed estimation of a level of about 5.0 mmolOH/gHSAG. Results from wide-angle X-ray diffraction (WAXD) and Raman spectroscopy suggested that functionalization of the graphene layers occurred on the edges. The evaluation of the Hansen solubility parameters of G-OH revealed a substantial increase of δP and δH parameters with respect to HSAG. In line with these findings, homogeneous and stable dispersions of G-OH in a polyol were obtained. PU were prepared by mixing a dispersion of G-OH in cis-1,4-butenediol with hexamethylene diisocyanate. A model reaction between catechol, 1,4-butanediol, and hexamethylene diisocyanate demonstrated the reactivity of hydroxylated aromatic rings with isocyanate groups. PU-based G-OH, characterized with WAXD and differential scanning calorimetry (DSC), revealed lower Tg, higher Tc, Tm, and crystallinity than PU without G-OH. These results could be due to the higher flexibility of the polymer chains, likely a consequence of the dilution of the urethane bonds by the carbon substrate. Hence, G-OH allowed the preparation of PU with a larger temperature range between Tg and Tm, with potential positive impact on material applications. The model reaction between butylisocyanate and 1-butanol revealed that HSAG and G-OH promote efficient formation of the urethane bond, even in the absence of a catalyst. The effect of high surface area carbon on the nucleophilic oxygen attack to the isocyanate group can be hypothesized. The results here reported lead us to comment that a reactive nanosized sp2 carbon allotrope, such as G-OH, can be used as a multifunctional building block of PU. Indeed, G-OH is a comonomer of PU, a promoter of the polymerization reaction, and can definitely act as reinforcing filler by tuning its amount in the final nanocomposite leading to highly versatile materials. The larger temperature range between Tg and Tm, together with the presence of G-OH acting as a reinforcing agent, could allow the production of piezoresistive sensing, shape-memory PU with good mechanical features.

14.
Sci Total Environ ; 806(Pt 1): 150495, 2022 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-34844332

RESUMO

From the onset of Covid-19 pandemic, the use of face masks has been adapted as one of the main measures to slow down the transmission of the SARS-CoV-2 virus worldwide. The inadequate handling and management of face masks lead to a massive dispersal in the environment, resulting in a new source of microfibers because of their breakdown and/or degradation. In addition, the laundering of reusable face masks of different polymeric composition can represent an additional sources of microfibers to natural ecosystems, but it was largely neglected. The present study explored the release of synthetic or natural microfibers from reusable and disposable face masks of five different fabrics when subjected to a cycle of laundering in a domestic washing machine. After a single wash, face masks released an average (± SE) of 284.94 ± 73.66 microfibers, independently of the fabrics. Focusing on the fabrics composing the face masks, polyurethane (541.33 ± 51.84 microfibers) and cotton-based (823.00 ± 112.53 microfibers) face masks released the highest amount of synthetic and natural microfibers, respectively. Considering the crucial role of face masks to counteract the pandemic and the increasing trend of their use, further studies represent a priority to estimate the contribution of face mask-derived microfibers to freshwater contamination.


Assuntos
COVID-19 , Lavanderia , Ecossistema , Humanos , Máscaras , Pandemias , SARS-CoV-2
15.
Environ Sci Pollut Res Int ; 29(20): 29455-29466, 2022 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-34312747

RESUMO

Atmospheric pollutants, such as NOx, SO2, and particulate matter, together with water percolation inside the stone pores, represent the main causes of cultural heritage decay. In order to avoid these undesired phenomena, the application of protective coatings represents a reliable solution. In this context, the present study focused on the synthesis of low-fluorine content methacrylic-based (MMA) polymeric resins characterized by seven F atoms (namely F7 monomer) in the lateral chains. Four different percentages (1.0, 2.5, 5.0, and 10.0%) of the present monomer were adopted to obtain a final polymeric structure showing the desired hydrophobicity, processability, and structural and thermal stability (even after accelerated UV aging tests). MMA_F7(1.0) seemed to be the optimal one; therefore, it was further applied onto Candoglia marble. Specifically, the treated substrates showed good surface hydrophobicity, water repellency, and water vapor transpirability. No color variation was observed even after a 1.5-year exposure in a real polluted environment (Monza Cathedral). Interestingly, the application of this coating hindered the atmospheric nitrates penetration inside the stones and, at the same time, it limited the sulfates (gypsum) formation, thus revealing a very promising marbles protection resin.


Assuntos
Carbonato de Cálcio , Flúor , Carbonato de Cálcio/química , Fluoretos , Interações Hidrofóbicas e Hidrofílicas , Material Particulado , Polímeros
16.
Chemistry ; 27(67): 16690-16700, 2021 Dec 01.
Artigo em Inglês | MEDLINE | ID: mdl-34634149

RESUMO

Organic materials with multiple emissions tunable by external stimuli represent a great challenge. TTPyr, crystallizing in different polymorphs, shows a very rich photophyisics comprising excitation-dependent fluorescence and phosphorescence at ambient conditions, and mechanochromic and thermochromic behavior. Transformation among the different species has been followed by thermal and X-ray diffraction analyses and the emissive features interpreted through structural results and DFT/TDDFT calculations. Particularly intriguing is the polymorph TTPyr(HT), serendipitously obtained at high temperature but stable also at room temperature, whose non-centrosymmetric structure guarantees an SHG efficiency 10 times higher than that of standard urea. Its crystal packing, where only the TT units are strongly rigidified by π-π stacking interactions while the Pyr moieties possess partial conformational freedom, is responsible for the observed dual fluorescence. The potentialities of TTPyr for bioimaging have been successfully established.


Assuntos
Luminescência , Pirenos , Cristalografia por Raios X , Conformação Molecular , Temperatura
17.
Polymers (Basel) ; 13(5)2021 Mar 06.
Artigo em Inglês | MEDLINE | ID: mdl-33800816

RESUMO

Despite the poor photochemical stability of capsules walls, polyacrylate is one of the most successful polymers for microencapsulation. To improve polyacrylate performance, the combined use of different acrylate-based polymers could be exploited. Herein butyl methacrylate (BUMA)-based lattices were obtained via free radical polymerization in water by adding (i) methacrylic acid (MA)/methyl methacrylate (MMA) and (ii) methacrylamide (MAC) respectively, as an aqueous phase in Pickering emulsions, thanks to both the excellent polymer shells' stability and the high encapsulation efficiency. A series of BUMA_MA_MMA terpolymers with complex macromolecular structures and BUMA_MAC linear copolymers were synthesized and used as dispersing media of an active material. Rate and yield of encapsulation, active substance adsorption onto the polymer wall, capsule morphology, shelf-life and controlled release were investigated. The effectiveness of the prepared BUMA-based microcapsules was demonstrated: BUMA-based terpolymers together with the modified ones (BUMA_MAC) led to slow (within ca. 60 h) and fast (in around 10 h) releasing microcapsules, respectively.

18.
Nanomaterials (Basel) ; 11(4)2021 Apr 10.
Artigo em Inglês | MEDLINE | ID: mdl-33920319

RESUMO

The synthesis of highly concentrated aqueous silver nanoparticles (NPs), exploiting different types of polymeric stabilizing agents, has been extensively investigated, especially for the stabilization of spherical yellow nanoparticles. In this context, here, a successful and easy wet chemical method was adopted to synthesize concentrated primary colored (yellow, red, blue and green) sols. The influence of polyvinylpyrrolidone (PVP) and polyvinyl alcohol (PVA) in affecting the final stability was finely investigating via UV/Vis spectroscopy, dynamic light scattering, TEM and colorimetric analysis. The next step consisted on the deposition of obtained sols onto a crown-treated polyethylene terephthalate (PET) support to obtain transparent colored micrometric homogeneous films. The fabricated PVP-based Ag films were revealed to be outstandingly UV-stable, contrarily to PVA-based films, probably due to the degradation of the polymer itself. Indeed, after UV aging tests, the PVA macromolecules could be broken and chemically modified (demonstrated by FT-IR analyses). This resulted in there being insufficient macromolecules to efficiently cover the surface of the nanoparticles, meaning that the nanoparticles tended to aggregate with each other, destabilizing the system itself. Hence, the obtained colored films described herein could represent a promising tool for different applications, from color shifting to optoelectronic devices.

19.
Polymers (Basel) ; 13(4)2021 Feb 23.
Artigo em Inglês | MEDLINE | ID: mdl-33672105

RESUMO

Poly(3,4-ethylenedioxythiophene) (PEDOT) plays a key role in the field of electrically conducting materials, despite its poor solubility and processability. Various molecules and polymers carrying sulfonic groups can be used to enhance PEDOT's electrical conductivity. Among all, sulfonated polyarylether sulfone (SPAES), prepared via homogenous synthesis with controlled degree of sulfonation (DS), is a very promising PEDOT doping agent. In this work, PEDOT was synthesized via high-concentration solvent-based emulsion polymerization using 1% w/w of SPAES with different DS as dopant. It was found that the PEDOT:SPAESs obtained have improved solubility in the chosen reaction solvents, i.e., N, N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide, and N-methyl-2-pyrrolidone and, for the first time, the role of doping agent, DS and polymerization solvents were investigated analyzing the electrical properties of SPAESs and PEDOT:SPAES samples and studying the different morphology of PEDOT-based thin films. High DS of SPAES, i.e., 2.4 meq R-SO3-× g-1 of polymer, proved crucial in enhancing PEDOT's electrical conductivity. Furthermore, the DMSO capability to favor PEDOT and SPAES chains rearrangement and interaction results in the formation of a polymer film with more homogenous morphology and higher conductivity than the ones prepared from DMAc, DMF, and NMP.

20.
Soft Matter ; 17(11): 3105-3112, 2021 Mar 21.
Artigo em Inglês | MEDLINE | ID: mdl-33598667

RESUMO

Yield stress materials deform as elastic solids or flow as viscous liquids, depending on the applied stress, which also allows them to trap particles below a certain size or density threshold. To investigate the conditions for such a transition at the microscale, we use an optofluidic microrheometer, based on the scattering of an infrared beam onto a microbead, which reaches forces in the nN scale. We perform creep experiments on a model soft material composed of swollen microgels, determining the limits of linear response and yield stress values, and observe quantitative agreement with bulk measurements. However, the motion of the microbead, both below and above yielding, reflects distinctive microscale features of the surrounding material, whose plastic rearrangements were investigated by us using small, passive tracers.

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