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1.
Appl Environ Microbiol ; 90(4): e0147723, 2024 Apr 17.
Artigo em Inglês | MEDLINE | ID: mdl-38445906

RESUMO

Plastic degradation by biological systems emerges as a prospective avenue for addressing the pressing global concern of plastic waste accumulation. The intricate chemical compositions and diverse structural facets inherent to polyurethanes (PU) substantially increase the complexity associated with PU waste management. Despite the extensive research endeavors spanning over decades, most known enzymes exhibit a propensity for hydrolyzing waterborne PU dispersion (i.e., the commercial Impranil DLN-SD), with only a limited capacity for the degradation of bulky PU materials. Here, we report a novel cutinase (CpCut1) derived from Cladosporium sp. P7, which demonstrates remarkable efficiency in the degrading of various polyester-PU materials. After 12-h incubation at 55°C, CpCut1 was capable of degrading 40.5% and 20.6% of thermoplastic PU film and post-consumer foam, respectively, while achieving complete depolymerization of Impranil DLN-SD. Further analysis of the degradation intermediates suggested that the activity of CpCut1 primarily targeted the ester bonds within the PU soft segments. The versatile performance of CpCut1 against a spectrum of polyester-PU materials positions it as a promising candidate for the bio-recycling of waste plastics.IMPORTANCEPolyurethane (PU) has a complex chemical composition that frequently incorporates a variety of additives, which poses significant obstacles to biodegradability and recyclability. Recent advances have unveiled microbial degradation and enzymatic depolymerization as promising waste PU disposal strategies. In this study, we identified a gene encoding a cutinase from the PU-degrading fungus Cladosporium sp. P7, which allowed the expression, purification, and characterization of the recombinant enzyme CpCut1. Furthermore, this study identified the products derived from the CpCut1 catalyzed PU degradation and proposed its underlying mechanism. These findings highlight the potential of this newly discovered fungal cutinase as a remarkably efficient tool in the degradation of PU materials.


Assuntos
Hidrolases de Éster Carboxílico , Cladosporium , Poliuretanos , Poliuretanos/química , Poliuretanos/metabolismo , Cladosporium/genética , Cladosporium/metabolismo , Estudos Prospectivos , Biodegradação Ambiental , Poliésteres/metabolismo , Plásticos
2.
Biomacromolecules ; 25(3): 1810-1824, 2024 Mar 11.
Artigo em Inglês | MEDLINE | ID: mdl-38360581

RESUMO

Polyurethanes (PUs) have adjustable mechanical properties, making them suitable for a wide range of applications, including in the biomedical field. Historically, these PUs have been synthesized from isocyanates, which are toxic compounds to handle. This has encouraged the search for safer and more environmentally friendly synthetic routes, leading today to the production of nonisocyanate polyurethanes (NIPUs). Among these NIPUs, polyhydroxyurethanes (PHUs) bear additional hydroxyl groups, which are particularly attractive for derivatizing and adjusting their physicochemical properties. In this paper, polyether-based NIPU elastomers with variable stiffness are designed by functionalizing the hydroxyl groups of a poly(propylene glycol)-PHU by a cyclic carbonate carrying a pendant unsaturation, enabling them to be post-photo-cross-linked with polythiols (thiol-ene). Elastomers with remarkable mechanical properties whose stiffness can be adjusted are obtained. Thanks to the unique viscous properties of these PHU derivatives and their short gel times observed by rheology experiments, formulations for light-based three-dimensional (3D) printing have been developed. Objects were 3D-printed by digital light processing with a resolution down to the micrometer scale, demonstrating their ability to target various designs of prime importance for personalized medicine. In vitro biocompatibility tests have confirmed the noncytotoxicity of these materials for human fibroblasts. In vitro hemocompatibility tests have revealed that they do not induce hemolytic effects, they do not increase platelet adhesion, nor activate coagulation, demonstrating their potential for future applications in the cardiovascular field.


Assuntos
Elastômeros , Poliuretanos , Humanos , Poliuretanos/farmacologia , Poliuretanos/química , Elastômeros/química , Isocianatos/química , Próteses e Implantes , Supuração
3.
Biomacromolecules ; 25(3): 1724-1737, 2024 Mar 11.
Artigo em Inglês | MEDLINE | ID: mdl-38421316

RESUMO

Stimuli-responsive amphiphilic polymers are known to be precursors to forming promising nanoarchitectonics with tunable properties for application in biomedical sciences. Currently, self-immolative polymers are widely recognized as an emerging class of responsive materials with excellent degradability, which is one of the crucial criteria for designing a robust drug delivery vehicle. Here, we design an amphiphilic polyurethane endowed with a redox-responsive self-immolative linker and a pH-responsive tertiary amine on the backbone, which forms entropy-driven nanoscale supramolecular assemblies (average hydrodynamic diameter ∼110 nm) and is programmed to disassemble in a redox environment (GSH) due to the degradation of the polymer in a self-immolative fashion. The nanoassembly shows efficient drug sequestration and release in a controlled manner in response to glutathione (10 mM). The tertiary amine residing on the surface of the nanoassembly becomes protonated in the tumor microenvironment (pH ∼ 6.4-6.8) and generates positively charged nanoassembly (ζ-potential = +36 mV), which enhances the cancer cell-selective cellular uptake. The biological evaluation of the drug-loaded nanoassembly revealed triple-negative breast cancer (MDAMB-231) selective internalization and cell death while shielding normal cells (RBCs or PBMCs) from off-targeting toxicity. We envision that polyurethane with a redox-responsive self-immolative linker might open up new opportunities for a completely degradable polyurethane-based nanocarrier for drug delivery and diagnosis applications.


Assuntos
Neoplasias da Mama , Polímeros , Humanos , Feminino , Polímeros/química , Poliuretanos/química , Neoplasias da Mama/tratamento farmacológico , Sistemas de Liberação de Medicamentos , Glutationa , Aminas , Portadores de Fármacos/química , Liberação Controlada de Fármacos , Microambiente Tumoral
4.
Biomacromolecules ; 25(7): 4233-4245, 2024 Jul 08.
Artigo em Inglês | MEDLINE | ID: mdl-38838045

RESUMO

In the area of drug delivery aided by stimuli-responsive polymers, the biodegradability of nanocarriers is one of the major challenges that needs to be addressed with the utmost sincerity. Herein, a hydrogen sulfide (H2S) responsive hydrophobic dansyl-based trigger molecule is custom designed and successfully incorporated into the water-soluble polyurethane backbone, which is made of esterase enzyme susceptible urethane bonds. The amphiphilic polyurethanes, PUx (x = 2 and 3) with a biotin chain end, formed self-assembled nanoaggregates. A hemolysis and cytotoxicity profile of doxorubicin (DOX)-loaded biotinylated PU3 nanocarriers revealed that it is nonhemolytic and has excellent selectivity toward HeLa cells (biotin receptor-positive cell lines) causing ∼60% cell death while maintaining almost 100% cell viability for HEK 293T cells (biotin receptor-negative cell lines). Furthermore, better cellular internalization of DOX-loaded fluorescent nanocarriers in HeLa cells than in HEK 293T cells confirmed receptor-mediated endocytosis. Thus, this work ensures that the synthesized polymers serve as biodegradable nanocarriers for anticancer therapeutics.


Assuntos
Doxorrubicina , Sistemas de Liberação de Medicamentos , Poliuretanos , Humanos , Poliuretanos/química , Células HeLa , Doxorrubicina/farmacologia , Doxorrubicina/química , Células HEK293 , Sistemas de Liberação de Medicamentos/métodos , Portadores de Fármacos/química , Nanomedicina Teranóstica/métodos , Biotinilação , Biotina/química , Sobrevivência Celular/efeitos dos fármacos , Nanopartículas/química
5.
Biomacromolecules ; 25(8): 5068-5080, 2024 Aug 12.
Artigo em Inglês | MEDLINE | ID: mdl-39041235

RESUMO

Enzyme-responsive self-assembled nanostructures for drug delivery applications have gained a lot of attention, as enzymes exhibit dysregulation in many disease-associated microenvironments. Azoreductase enzyme levels are strongly elevated in many tumor tissues; hence, here, we exploited the altered enzyme activity of the azoreductase enzyme and designed a main-chain azobenzene-based amphiphilic polyurethane, which self-assembles into a vesicular nanostructure and is programmed to disassemble in response to a specific enzyme, azoreductase, with the help of the nicotinamide adenine dinucleotide phosphate (NADPH) coenzyme in the hypoxic environment of solid tumors. The vesicular nanostructure sequesters, stabilizes the hydrophobic anticancer drug, and releases the drug in a controlled fashion in response to enzyme-triggered degradation of azo-bonds and disruption of vesicular assembly. The biological evaluation revealed tumor extracellular matrix pH-induced surface charge modulation, selective activated cellular uptake to azoreductase overexpressed lung cancer cells (A549), and the release of the anticancer drug followed by cell death. In contrast, the benign nature of the drug-loaded vesicular nanostructure toward normal cells (H9c2) suggested excellent cell specificity. We envision that the main-chain azobenzene-based polyurethane discussed in this manuscript could be considered as a possible selective chemotherapeutic cargo against the azoreductase overexpressed cancer cells while shielding the normal cells from off-target toxicity.


Assuntos
Antineoplásicos , Compostos Azo , Nitrorredutases , Poliuretanos , Compostos Azo/química , Compostos Azo/farmacologia , Humanos , Poliuretanos/química , Antineoplásicos/farmacologia , Antineoplásicos/química , Células A549 , Nitrorredutases/metabolismo , NADH NADPH Oxirredutases/metabolismo , Liberação Controlada de Fármacos , Nanoestruturas/química , Sistemas de Liberação de Medicamentos/métodos
6.
Biomacromolecules ; 25(6): 3795-3806, 2024 Jun 10.
Artigo em Inglês | MEDLINE | ID: mdl-38781116

RESUMO

Biodegradable polymers with shape memory effects (SMEs) offer promising solutions for short-term medical interventions, facilitating minimally invasive procedures and subsequent degradation without requiring secondary surgeries. However, achieving a good balance among desirable SMEs, mechanical performance, degradation rate, and bioactivities remains a significant challenge. To address this issue, we established a strategy to develop a versatile biodegradable polyurethane (PPDO-PLC) with tunable hierarchical structures via precise chain segment control. Initial copolymerization of l-lactide and ε-caprolactone sets a tunable Tg close to body temperature, followed by block copolymerization with poly(p-dioxanone) to form a hard domain. This yields a uniform microphase-separation morphology, ensuring robust SME and facilitating the development of roughly porous surface structures in alkaline environments. Cell experiments indicate that these rough surfaces significantly enhance cellular activities, such as adhesion, proliferation, and osteogenic differentiation. Our approach provides a methodology for balancing biodegradability, SMEs, three-dimensional (3D) printability, and bioactivity in materials through hierarchical structure regulation.


Assuntos
Poliuretanos , Poliuretanos/química , Poliuretanos/farmacologia , Proliferação de Células/efeitos dos fármacos , Materiais Biocompatíveis/química , Materiais Biocompatíveis/farmacologia , Animais , Porosidade , Adesão Celular/efeitos dos fármacos , Osteogênese/efeitos dos fármacos , Camundongos , Poliésteres/química , Diferenciação Celular/efeitos dos fármacos , Lactonas/química , Lactonas/farmacologia , Humanos , Caproatos/química , Dioxanos/química , Polímeros
7.
Nanotechnology ; 35(32)2024 May 23.
Artigo em Inglês | MEDLINE | ID: mdl-38648780

RESUMO

Flexible piezoresistive pressure sensors are gaining significant attention, particularly in the realm of flexible wearable electronic skin. Here, a flexible piezoresistive pressure sensor was developed with a broad sensing range and high sensitivity. We achieved this by curing polydimethylsiloxane (PDMS) on sandpaper, creating a PDMS film as the template with a micro-protrusion structure. The core sensing layer was formed using a composite of silver nanowires (AgNWs) and waterborne polyurethane (WPU) with a similar micro-protrusion structure. The sensor stands out with its exceptional sensitivity, showing a value of 1.04 × 106kPa-1with a wide linear range from 0 to 27 kPa. It also boasts a swift response and recovery time of 160 ms, coupled with a low detection threshold of 17 Pa. Even after undergoing more than 1000 cycles, the sensor continues to deliver stable performance. The flexible piezoresistive pressure sensor based on AgNWs/WPU composite film (AWCF) can detect small pressure changes such as pulse, swallowing, etc, which indicates that the sensor has great application potential in monitoring human movement and flexible wearable electronic skin.


Assuntos
Dimetilpolisiloxanos , Nanofios , Poliuretanos , Pressão , Prata , Dispositivos Eletrônicos Vestíveis , Poliuretanos/química , Nanofios/química , Prata/química , Humanos , Dimetilpolisiloxanos/química , Monitorização Fisiológica/instrumentação , Monitorização Fisiológica/métodos , Movimento
8.
Macromol Rapid Commun ; 45(14): e2400108, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-38639216

RESUMO

Various acoustic materials are developed to resolve noise pollution problem in many industries. Especially, materials with porous structure are broadly used to absorb sound energy in civil construction and transportation area. Polyurethane (PU) porous materials possess excellent damping properties, good toughness, and well-developed pore structures, which have a broad application prospect in sound absorption field. This work aims to summarize the recent progress of fabrication and structure for PU porous materials in sound absorption application. The sound absorption mechanisms of porous materials are introduced. Different kinds of structure for typical PU porous materials in sound absorption application are covered and highlighted, which include PU foam, modified PU porous materials, aerogel, templated PU, and special PU porous materials. Finally, the development direction and existing problems of PU material in sound absorption application are briefly prospected. It can be expected that porous PU with high sound absorption coefficient can be obtained by using some facile methods. The design and accurate regulation of porous structures or construction of multilayer sound absorption structure is favorably recommended to fulfill the high demand of industrial and commercial applications in the future work.


Assuntos
Poliuretanos , Poliuretanos/química , Porosidade , Som
9.
Macromol Rapid Commun ; 45(12): e2300724, 2024 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-38485136

RESUMO

Luminescent solar concentrators (LSCs) are spectral conversion devices offering interesting opportunities for the integration of photovoltaics into the built environment and portable systems. The Förster-resonance energy transfer (FRET) process can boost the optical response of LSCs by reducing energy losses typically associated to non-radiative processes occurring within the device under operation. In this work, a new class of FRET-based thin-film LSC devices is presented, in which the synthetic versatility of linear polyurethanes (PU) is exploited to control the photophysical properties and the device performance of the resulting LSCs. A series of luminescent linear PUs are synthesized in the presence of two novel bis-hydroxyl-functionalized luminophores of suitable optical properties, used as chain extenders during the step-growth polyaddition reaction for the formation of the linear macromolecular network. By synthetically tuning their composition, the obtained luminescent PUs can achieve a high energy transfer efficiency (≈90%) between the covalently linked luminophores. The corresponding LSC devices exhibit excellent photonic response, with external and internal photon efficiencies as high as ≈4% and ≈37%, respectively. Furthermore, their optimized power conversion efficiency combined with their enhanced average visible-light transmittance highlight their suitability for potential use as transparent solar energy devices.


Assuntos
Transferência de Energia , Transferência Ressonante de Energia de Fluorescência , Poliuretanos , Energia Solar , Poliuretanos/química , Luminescência , Estrutura Molecular
10.
Macromol Rapid Commun ; 45(13): e2400014, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-38575152

RESUMO

The permeability for gases through polyurethane (PUR) aerogels prepared from unsorted PUR scraps by means of a recycling technique is measured with a dynamic pressure method. The permeabilities are in the range of 10-15 to 10-13 m2 and thus reflect the pore morphology observed with scanning electron microscopy. The permeability depends on the envelope density and microstructural features of the aerogels and decreases with increasing inner surface area. The comparison of the permeability with the Porod constant, which is obtained independently via small-angle X-ray scattering (SAXS), yields a high consistency with the expected theoretical relationship. However, a calculation of inner surface area based on permeability yields lower results than expected from data based on the established SAXS technique, revealing that the famous Carman-Kozeny law correlates only by trend, which is attributed to additional gas transport through the micro- and mesopores. A possible approach for the correlation of this behavior to the tortuosity is given. Several models accounting for the combined action of viscous flow, Knudsen diffusion, and molecular slip along pore walls are fitted to the experimental data, effectively qualifying the permeability measurement as time-efficient and inexpensive technique for the characterization of structural features of aerogels.


Assuntos
Gases , Géis , Permeabilidade , Poliuretanos , Poliuretanos/química , Porosidade , Géis/química , Gases/química , Espalhamento a Baixo Ângulo , Difração de Raios X , Propriedades de Superfície , Estrutura Molecular
11.
Macromol Rapid Commun ; 45(15): e2400098, 2024 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-38862122

RESUMO

Cellulose nanopaper is a material structure that possesses high mechanical performance and is widely regarded as a promising 2D reinforcement for polymer matrix composites. This work explores the use of low grammage bacterial cellulose (BC) nanopaper as reinforcement for poly(acrylated urethane) interlayer adhesive to increase the impact performance of multilayer acrylic composites. The BC nanopaper is impregnated with an acrylated urethane resin and laminated between acrylic sheets to create BC/acrylic composites consisting of one, three, and five layers of BC nanopaper-reinforced poly(acrylated urethane) interlayer adhesive(s). Both the poly(acrylated urethane)-filled BC nanopaper interlayer adhesive and the resulting laminated acrylic composites are optically transparent. The incorporation of BC nanopaper into the poly(acrylated urethane) interlayer adhesive improves the tensile modulus by eightfold and the single-edge notched fracture toughness by 60% compared to neat poly(acrylated urethane). It is also found that using poly(acrylated urethane)-filled BC nanopaper interlayer adhesive proves beneficial to the impact properties of the resulting laminated acrylic composites. In Charpy impact testing, the impact strength of the multilayer acrylic composites increases by up to 130% compared to the "gold-standard" impact-modified monolithic acrylic, with a BC loading of only 1.6 wt%.


Assuntos
Celulose , Celulose/química , Poliuretanos/química , Resinas Acrílicas/química , Papel , Resistência à Tração , Teste de Materiais
12.
Macromol Rapid Commun ; 45(11): e2400057, 2024 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-38471478

RESUMO

Bis-carbonylimidazolide (BCI) functionalization enables an efficient synthetic strategy to generate high molecular weight segmented nonisocyanate polyurethanes (NIPUs). Melt phase polymerization of ED-2003 Jeffamine, 4,4'-methylenebis(cyclohexylamine), and a BCI monomer that mimics a 1,4-butanediol chain extender enables polyether NIPUs that contain varying concentrations of hard segments ranging from 40 to 80 wt. %. Dynamic mechanical analysis and differential scanning calorimetry reveal thermal transitions for soft, hard, and mixed phases. Hard segment incorporations between 40 and 60 wt. % display up to three distinct phases pertaining to the poly(ethylene glycol) (PEG) soft segment Tg, melting transition, and hard segment Tg, while higher hard segment concentrations prohibit soft segment crystallization, presumably due to restricted molecular mobility from the hard segment. Atomic force microscopy allows for visualization and size determination of nanophase-separated regimes, revealing a nanoscale rod-like assembly of HS. Small-angle X-ray scattering confirms nanophase separation within the NIPU, characterizing both nanoscale amorphous domains and varying degrees of crystallinity. These NIPUs, which are synthesized with BCI monomers, display expected phase separation that is comparable to isocyanate-derived analogues. This work demonstrates nanophase separation in BCI-derived NIPUs and the feasibility of this nonisocyanate synthetic pathway for the preparation of segmented PU copolymers.


Assuntos
Poliuretanos , Poliuretanos/química , Poliuretanos/síntese química , Polímeros/química , Polímeros/síntese química , Imidazóis/química , Estrutura Molecular , Polimerização , Varredura Diferencial de Calorimetria
13.
Macromol Rapid Commun ; 45(11): e2400010, 2024 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-38458610

RESUMO

This work presents a new method for 4D fabrication of two-way shape memory materials that are capable of reversible shapeshifting right after manufacturing, upon application of proper heating and cooling cycles. The innovative solution presented here consists in the combination of highly stretched electrospun shape memory polymer (SMP) nanofibers with a melt electrowritten elastomer. More specifically, the stretched nanofibers are made of a biocompatible thermoplastic polyurethane (TPU) with crystallizable soft segments, undergoing melt-induced contraction and crystallization-induced elongation upon heating and cooling, respectively. Reversible actuation during crystallization becomes possible due to the elastic recovery of the elastomer component, obtained by melt electrowriting of a commercial TPU filament. Thanks to the design freedom offered by additive manufacturing, the elastomer structure also has the role of guiding the shape transformation. Electrospinning and melt electrowriting process parameters are set up so to obtain smart 4D objects capable of two-way shape memory effect (SME), and the possibility of reversible and repeatable actuation is demonstrated. The two components are then combined in different proportions with the aim of tailoring the two-way SME, taking into account the effect of design parameters such as the SMP content, the elastomer pattern, and the composite thickness.


Assuntos
Nanofibras , Polímeros , Polímeros/química , Nanofibras/química , Poliuretanos/química , Elastômeros/química , Materiais Inteligentes/química , Materiais Biocompatíveis/química
14.
Macromol Rapid Commun ; 45(13): e2400022, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-38704741

RESUMO

The preparation of self-healing polyurethane elastomers (PUEs) incorporating dynamic bonds is of considerable practical significance. However, developing a PUE with outstanding mechanical properties and high self-healing efficiency poses a significant challenge. Herein, this work has successfully developed a series of self-healing PUEs with various outstanding properties through rational molecular design. These PUEs incorporate m-xylylene diisocyanate and reversible dimethylglyoxime as hard segment, along with polytetramethylene ether glycol as soft segment. A significant amount of dynamic oxime-carbamate and hydrogen bonds are formed in hard segment. The microphase separated structure of the PUEs enables them to be colorless with a transparency of >90%. Owing to the chemical composition and multiple dynamic interactions, the PUEs are endowed with ultra-high tensile strength of 34.5 MPa, satisfactory toughness of 53.9 MJ m-3, and great elastic recovery both at low and high strains. The movement of polymer molecular chains and the dynamic reversible interactions render a self-healing efficiency of 101% at 70 °C. In addition, this self-healing polyurethane could still maintain high mechanical properties after recycling. This study provides a design strategy for the preparation of a comprehensive polyurethane with superior overall performance, which holds wide application prospects in the fields of flexible displays and solar cells.


Assuntos
Carbamatos , Elastômeros , Ligação de Hidrogênio , Oximas , Poliuretanos , Resistência à Tração , Poliuretanos/química , Oximas/química , Elastômeros/química , Carbamatos/química , Estrutura Molecular , Elasticidade
15.
Macromol Rapid Commun ; 45(14): e2400068, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-38593218

RESUMO

With the advantages of lightweight and low thermal conductivity properties, polymeric foams are widely employed as thermal insulation materials for energy-saving buildings but suffer from inherent flammability. Flame-retardant coatings hold great promise for improving the fire safety of these foams without deteriorating the mechanical-physical properties of the foam. In this work, four kinds of sulfur-based flame-retardant copolymers are synthesized via a facile radical copolymerization. The sulfur-containing monomers serve as flame-retardant agents including vinyl sulfonic acid sodium (SPS), ethylene sulfonic acid sodium (VS), and sodium p-styrene sulfonate (VSS). Additionally, 2-hydroxyethyl acrylate (HEA) and 4-hydroxybutyl acrylate are employed to enable a strong interface adhesion with polymeric foams through interfacial H-bonding. By using as-synthesized waterborne flame-retardant polymeric coating with a thickness of 600 µm, the coated polyurethane foam (PUF) can achieve a desired V-0 rating during the vertical burning test with a high limiting oxygen index (LOI) of >31.5 vol%. By comparing these sulfur-containing polymeric fire-retardant coatings, poly(VS-co-HEA) coated PUF demonstrates the best interface adhesion capability and flame-retardant performance, with the lowest peak heat release rate of 166 kW m-2 and the highest LOI of 36.4 vol%. This work provides new avenues for the design and performance optimization of advanced fire-retardant polymeric coatings.


Assuntos
Retardadores de Chama , Polímeros , Poliuretanos , Enxofre , Poliuretanos/química , Polímeros/química , Enxofre/química , Retardadores de Chama/análise , Incêndios
16.
Macromol Rapid Commun ; 45(14): e2400105, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-38623606

RESUMO

Intelligent materials derived from green and renewable bio-based materials garner widespread attention recently. Herein, shape memory polyurethane composite (PUTA/Fe) with fast response to near-infrared (NIR) light is successfully prepared by introducing Fe3+ into the tannic acid-based polyurethane (PUTA) matrix through coordination between Fe3+ and tannic acid. The results show that the excellent NIR light response ability is due to the even distribution of Fe3+ filler with good photo-thermal conversion ability. With the increase of Fe3+ content, the NIR light response shape recovery rate of PUTA/Fe composite films is significantly improved, and the shape recovery time is reduced from over 60 s to 40 s. In addition, the mechanical properties of PUTA/Fe composite film are also improved. Importantly, owing to the dynamic phenol-carbamate network within the polymer matrix, the PUTA/Fe composite film can reshape its permanent shape through topological rearrangement and show its good NIR light response shape memory performance. Therefore, PUTA/Fe composites with high content of bio-based material (TA content of 15.1-19.4%) demonstrate the shape memory characteristics of fast response to NIR light; so, it will have great potential in the application of new intelligent materials including efficient and environmentally friendly smart photothermal responder.


Assuntos
Carbamatos , Raios Infravermelhos , Ferro , Poliuretanos , Taninos , Taninos/química , Poliuretanos/química , Ferro/química , Carbamatos/química , Fenóis/química , Fenol/química , Materiais Inteligentes/química , Polifenóis
17.
Environ Res ; 249: 118468, 2024 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-38354881

RESUMO

Microorganisms have the potential to be applied for the degradation or depolymerization of polyurethane (PU) and other plastic waste, which have attracted global attention. The appropriate strain or enzyme that can effectively degrade PU is the key to treat PU plastic wastes by biological methods. Here, a polyester PU-degrading bacterium Bacillus sp. YXP1 was isolated and identified from a plastic landfill. Three PU substrates with increasing structure complexities, including Impranil DLN, poly (1,4-butylene adipate)-based PU (PBA-PU), and polyester PU foam, were used to evaluate the degradation capacity of Bacillus sp. YXP1. Under optimal conditions, strain YXP1 could completely degrade 0.5% Impranil DLN within 7 days. After 30 days, the weight loss of polyester PU foam by strain YXP1 was as high as 42.1%. In addition, PBA-PU was applied for degradation pathway analysis due to its clear composition and chemical structure. Five degradation intermediates of PBA-PU were identified, including 4,4'-methylenedianiline (MDA), 1,4-butanediol, adipic acid, and two MDA derivates, indicating that strain YXP1 could depolymerize PBA-PU by the hydrolysis of ester and urethane bonds. Furthermore, the extracellular enzymes produced by strain YXP1 could hydrolyze PBA-PU to generate MDA. Together, this study provides a potential bacterium for the biological treatment of PU plastic wastes and for the mining of functional enzymes.


Assuntos
Bacillus , Biodegradação Ambiental , Poliuretanos , Poliuretanos/química , Bacillus/metabolismo , Bacillus/isolamento & purificação , Bacillus/genética , Poliésteres/metabolismo
18.
Environ Res ; 252(Pt 3): 118953, 2024 Jul 01.
Artigo em Inglês | MEDLINE | ID: mdl-38636643

RESUMO

Gas separation membranes are critical in a variety of environmental research and industrial applications. These membranes are designed to selectively allow some gases to flow while blocking others, allowing for the separation and purification of gases for a variety of applications. Therefore, the demand for fast and energy-efficient gas separation techniques is of central interest for many chemical and energy production diligences due to the intensified levels of greenhouse and industrial gases. This encourages the researchers to innovate techniques for capturing and separating these gases, including membrane separation techniques. Polymeric membranes play a significant role in gas separations by capturing gases from the fuel combustion process, purifying chemical raw material used for plastic production, and isolating pure and noncombustible gases. Polyurethane-based membrane technology offers an excellent knack for gas separation applications and has also been considered more energy-efficient than conventional phase change separation methodologies. This review article reveals a thorough delineation of the current developments and efforts made for PU membranes. It further explains its uses for the separation of valuable gases such as carbon dioxide (CO2), hydrogen (H2), nitrogen (N2), methane (CH4), or a mixture of gases from a variety of gas spillages. Polyurethane (PU) is an excellent choice of material and a leading candidate for producing gas-separating membranes because of its outstanding chemical chemistry, good mechanical abilities, higher permeability, and variable microstructure. The presence of PU improves several characteristics of gas-separating membranes. Selectivity and separation efficiency of PU-centered membranes are enhanced through modifications such as blending with other polymers, use of nanoparticles (silica, metal oxides, alumina, zeolite), and interpenetrating polymer networks (IPNs) formation. This manuscript critically analyzes the various gas transport methods and selection criteria for the fabrication of PU membranes. It also covers the challenges facing the development of PU-membrane-based separation procedures.


Assuntos
Gases , Membranas Artificiais , Poliuretanos , Poliuretanos/química , Gases/química , Poluentes Atmosféricos/análise , Poluentes Atmosféricos/química
19.
J Nanobiotechnology ; 22(1): 244, 2024 May 12.
Artigo em Inglês | MEDLINE | ID: mdl-38735969

RESUMO

Biomaterials can modulate the local immune microenvironments to promote peripheral nerve regeneration. Inspired by the spatial orderly distribution and endogenous electric field of nerve fibers, we aimed to investigate the synergistic effects of electrical and topological cues on immune microenvironments of peripheral nerve regeneration. Nerve guidance conduits (NGCs) with aligned electrospun nanofibers were fabricated using a polyurethane copolymer containing a conductive aniline trimer and degradable L-lysine (PUAT). In vitro experiments showed that the aligned PUAT (A-PUAT) membranes promoted the recruitment of macrophages and induced their polarization towards the pro-healing M2 phenotype, which subsequently facilitated the migration and myelination of Schwann cells. Furthermore, NGCs fabricated from A-PUAT increased the proportion of pro-healing macrophages and improved peripheral nerve regeneration in a rat model of sciatic nerve injury. In conclusion, this study demonstrated the potential application of NGCs in peripheral nerve regeneration from an immunomodulatory perspective and revealed A-PUAT as a clinically-actionable strategy for peripheral nerve injury.


Assuntos
Macrófagos , Regeneração Nervosa , Traumatismos dos Nervos Periféricos , Poliuretanos , Ratos Sprague-Dawley , Células de Schwann , Animais , Regeneração Nervosa/efeitos dos fármacos , Poliuretanos/química , Ratos , Macrófagos/efeitos dos fármacos , Células de Schwann/efeitos dos fármacos , Nanofibras/química , Nervo Isquiático/efeitos dos fármacos , Regeneração Tecidual Guiada/métodos , Masculino , Materiais Biocompatíveis/química , Materiais Biocompatíveis/farmacologia , Alicerces Teciduais/química , Camundongos , Células RAW 264.7
20.
Luminescence ; 39(5): e4753, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38698700

RESUMO

A simple and environmentally friendly method was developed for smart and efficient waterborne polyurethane (PUR) paint. Sugarcane bagasse was recycled into reduced graphene oxide nanosheets (rGONSs). Both lanthanide-doped aluminate nanoparticles (LAN; photoluminescent agent, 7-9 nm) and rGONSs (reinforcement agent) were integrated into a waterborne polyurethane to produce a novel photoluminescent, hydrophobic, and anticorrosive nanocomposite coating. Using ferrocene-based oxidation under masked circumstances, graphene oxide nanosheets were produced from sugarcane bagasse. The oxidized semicarbazide (SCB) nanostructures were integrated into polyurethane coatings as a drying, anticorrosion, and crosslinking agent. Polyurethane coatings with varying amounts of phosphor pigment were prepared and subsequently applied to mild steel. The produced paints (LAN/rGONSs@PUR) were tested for their hydrophobicity, hardness, and scratch resistance. Commission Internationale de l'éclairage (CIE) Laboratory parameters and photoluminescence analysis established the opacity and colourimetric properties of the nanocomposite coatings. When excited at 365 nm, the luminescent transparent paints emitted a strong greenish light at 517 nm. The anticorrosion characteristics of the coated steel were investigated. The phosphor-containing (11% w/w) polyurethane coatings displayed the most pronounced anticorrosion capability and long-persistent luminosity. The prepared waterborne polyurethane paints were very photostable and durable.


Assuntos
Grafite , Interações Hidrofóbicas e Hidrofílicas , Nanocompostos , Pintura , Poliuretanos , Poliuretanos/química , Grafite/química , Nanocompostos/química , Luminescência , Corrosão , Química Verde
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