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1.
ACS Appl Mater Interfaces ; 16(15): 19480-19495, 2024 Apr 17.
Artigo em Inglês | MEDLINE | ID: mdl-38581369

RESUMO

Light-driven soft actuators based on photoresponsive materials can be used to mimic biological motion, such as hand movements, without involving rigid or bulky electromechanical actuations. However, to our knowledge, no robust photoresponsive material with desireable mechanical and biological properties and relatively simple manufacture exists for robotics and biomedical applications. Herein, we report a new visible-light-responsive thermoplastic elastomer synthesized by introducing photoswitchable moieties (i.e., azobenzene derivatives) into the main chain of poly(ε-caprolactone) based polyurethane urea (PAzo). A PAzo elastomer exhibits controllable light-driven stiffness softening due to its unique nanophase structure in response to light, while possessing excellent hyperelasticity (stretchability of 575.2%, elastic modulus of 17.6 MPa, and strength of 44.0 MPa). A bilayer actuator consisting of PAzo and polyimide films is developed, demonstrating tunable bending modes by varying incident light intensities. Actuation mechanism via photothermal and photochemical coupling effects of a soft-hard nanophase is demonstrated through both experimental and theoretical analyses. We demonstrate an exemplar application of visible-light-controlled soft "fingers" playing a piano on a smartphone. The robustness of the PAzo elastomer and its scalability, in addition to its excellent biocompatibility, opens the door to the development of reproducible light-driven wearable/implantable actuators and lightweight soft robots for clinical applications.


Assuntos
Elastômeros , Robótica , Elastômeros/química , Poliuretanos , Ureia
2.
Biosens Bioelectron ; 254: 116222, 2024 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-38518560

RESUMO

Materials that have the ability to manipulate shapes in response to stimuli such as heat, light, humidity and magnetism offer a means for versatile, sophisticated functions in soft robotics or biomedical implants, while such a reactive transformation has certain drawbacks including high operating temperatures, inherent rigidity and biological hazard. Herein, we introduce biodegradable, self-adhesive, shape-transformable poly (L-lactide-co-ε-caprolactone) (BSS-PLCL) that can be triggered via thermal stimulation near physiological temperature (∼38 °C). Chemical inspections confirm the fundamental properties of the synthetic materials in diverse aspects, and study on mechanical and biochemical characteristics validates exceptional stretchability up to 800 % and tunable dissolution behaviors under biological conditions. The integration of the functional polymer with a bioresorbable electronic system highlights potential for a wide range of biomedical applications.


Assuntos
Técnicas Biossensoriais , Elastômeros , Elastômeros/química , Materiais Biocompatíveis/química , Implantes Absorvíveis , Polímeros/química , Poliésteres/química
3.
ACS Appl Mater Interfaces ; 16(13): 16880-16892, 2024 Apr 03.
Artigo em Inglês | MEDLINE | ID: mdl-38506556

RESUMO

To meet the demands of challenging usage scenarios, there is an increasing need for flexible electronic skins that can operate properly not only in terrestrial environments but also extend to complex aquatic conditions. In this study, we develop an elastomer by incorporating dynamic urea bonds and hydrogen bonds into the polydimethylsiloxane backbone, which exhibits excellent autonomous self-healing and reversible adhesive performance in both dry and wet environments. A multifunctional flexible sensor with excellent sensing stability, amphibious self-healing capacity, and amphibious self-adhesive performance is fabricated through solvent-free 3D printing. The sensor has a high sensing sensitivity (GF = 45.1) and a low strain response threshold (0.25%) and can be used to detect small human movements and physiological activities, such as muscle movement, joint movement, respiration, and heartbeat. The wireless wearable sensing system assembled by coupling this device with a bluetooth transmission system is suitable for monitoring strenuous human movement in amphibious environments, such as playing basketball, cycling, running (terrestrial environments), and swimming (aquatic environments). The design strategy provides insights into enhancing the self-healing and self-adhesive properties of soft materials and promises a prospective avenue for fabricating flexible electronic skin that can work properly in amphibious environments.


Assuntos
Elastômeros , Dispositivos Eletrônicos Vestíveis , Humanos , Elastômeros/química , Cimentos de Resina , Adesivos , Estudos Prospectivos , Eletrônica , Impressão Tridimensional
4.
J Am Chem Soc ; 146(15): 10699-10707, 2024 Apr 17.
Artigo em Inglês | MEDLINE | ID: mdl-38518116

RESUMO

Ultralow temperature-tolerant electronic skins (e-skins) can endow polar robots with tactile feedback for exploring in extremely cold polar environments. However, it remains a challenge to develop e-skins that enable sensitive touch sensation and self-healing at ultralow temperatures. Herein, we describe the development of a sensitive robotic hand e-skin that can stretch, self-heal, and sense at temperatures as low as -78 °C. The elastomeric substrate of this e-skin is based on poly(dimethylsiloxane) supramolecular polymers and multistrength dynamic H-bonds, in particular with quadruple H-bonding motifs (UPy). The structure-performance relationship of the elastomer at ultralow temperatures is investigated. The results show that elastomers with side-chain UPy units exhibit higher stretchability (∼3257%) and self-healing efficiency compared to those with main-chain UPy units. This is attributed to the lower binding energy variation and lower potential well. Based on the elastomer with side-chain UPy and man-made electric ink, a sensitive robotic hand e-skin for usage at -78 °C is constructed to precisely sense the shape of objects and specific symbols, and its sensation can completely self-recover after being damaged. The findings of this study contribute to the concept of using robotic hands with e-skins in polar environments that make human involvement limited, dangerous, or impossible.


Assuntos
Elastômeros , Dispositivos Eletrônicos Vestíveis , Humanos , Elastômeros/química , Elasticidade , Pele , Eletricidade
5.
Chem Soc Rev ; 53(8): 4086-4153, 2024 Apr 22.
Artigo em Inglês | MEDLINE | ID: mdl-38465517

RESUMO

Degradable biomedical elastomers (DBE), characterized by controlled biodegradability, excellent biocompatibility, tailored elasticity, and favorable network design and processability, have become indispensable in tissue repair. This review critically examines the recent advances of biodegradable elastomers for tissue repair, focusing mainly on degradation mechanisms and evaluation, synthesis and crosslinking methods, microstructure design, processing techniques, and tissue repair applications. The review explores the material composition and cross-linking methods of elastomers used in tissue repair, addressing chemistry-related challenges and structural design considerations. In addition, this review focuses on the processing methods of two- and three-dimensional structures of elastomers, and systematically discusses the contribution of processing methods such as solvent casting, electrostatic spinning, and three-/four-dimensional printing of DBE. Furthermore, we describe recent advances in tissue repair using DBE, and include advances achieved in regenerating different tissues, including nerves, tendons, muscle, cardiac, and bone, highlighting their efficacy and versatility. The review concludes by discussing the current challenges in material selection, biodegradation, bioactivation, and manufacturing in tissue repair, and suggests future research directions. This concise yet comprehensive analysis aims to provide valuable insights and technical guidance for advances in DBE for tissue engineering.


Assuntos
Materiais Biocompatíveis , Elastômeros , Medicina Regenerativa , Engenharia Tecidual , Humanos , Elastômeros/química , Materiais Biocompatíveis/química , Animais
6.
Acta Biomater ; 177: 165-177, 2024 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-38354873

RESUMO

Four-dimensional (4D) printing unlocks new potentials for personalized biomedical implantation, but still with hurdles of lacking suitable materials. Herein, we demonstrate a bioresorbable shape memory elastomer (SME) with high elasticity at both below and above its phase transition temperature (Ttrans). This SME can be digital light 3D printed by co-polymerizing glycerol dodecanoate acrylate prepolymer (pre-PGDA) with acrylic acid monomer to form crosslinked Poly(glycerol dodecanoate acrylate) (PGDA)-Polyacrylic acid (PAA), or PGDA-PAA network. The printed complex, free-standing 3D structures with high-resolution features exhibit shape programming properties at a physiological temperature. By tuning the pre-PGDA weight ratios between 55 wt% and 70 wt%, Ttrans varies between 39.2 and 47.2 ℃ while Young's moduli (E) range 40-170 MPa below Ttrans with fractural strain (εf) of 170 %-200 %. Above Ttrans, E drops to 1-1.82 MPa which is close to those of soft tissue. Strikingly, εf of 130-180 % is still maintained. In vitro biocompatibility test on the material shows > 90 % cell proliferation and great cell attachment. In vivo vascular grafting trials underline the geometrical and mechanical adaptability of these 4D printed constructs in regenerating the aorta tissue. Biodegradation of the implants shows the possibility of their full replacement by natural tissue over time. To highlight its potential for personalized medicine, a patient-specific left atrial appendage (LAA) occluder was printed and implanted endovascularly into an in vitro heart model. STATEMENT OF SIGNIFICANCE: 4D printed shape-memory elastomer (SME) implants particularly designed and manufactured for a patient are greatly sought-after in minimally invasive surgery (MIS). Traditional shape-memory polymers used in these implants often suffer from issues like unsuitable transition temperatures, poor biocompatibility, limited 3D design complexity, and low toughness, making them unsuitable for MIS. Our new SME, with an adjustable transition temperature and enhanced toughness, is both biocompatible and naturally degradable, particularly in cardiovascular contexts. This allows implants, like biomedical scaffolds, to be programmed at room temperature and then adapt to the body's physiological conditions post-implantation. Our studies, including in vivo vascular grafts and in vitro device implantation, highlight the SME's effectiveness in aortic tissue regeneration and its promising applications in MIS.


Assuntos
Elastômeros , Tecidos Suporte , Humanos , Elastômeros/química , Tecidos Suporte/química , Glicerol , Implantes Absorvíveis , Lauratos , Impressão Tridimensional , Acrilatos
7.
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
8.
ACS Appl Bio Mater ; 7(2): 863-878, 2024 Feb 19.
Artigo em Inglês | MEDLINE | ID: mdl-38207114

RESUMO

A pair of alkyne- and thiol-functionalized polyesters are designed to engineer elastomeric scaffolds with a wide range of tunable material properties (e.g., thermal, degradation, and mechanical properties) for different tissues, given their different host responses, mechanics, and regenerative capacities. The two prepolymers are quickly photo-cross-linkable through thiol-yne click chemistry to form robust elastomers with small permanent deformations. The elastic moduli can be easily tuned between 0.96 ± 0.18 and 7.5 ± 2.0 MPa, and in vitro degradation is mediated from hours up to days by adjusting the prepolymer weight ratios. These elastomers bear free hydroxyl and thiol groups with a water contact angle of less than 85.6 ± 3.58 degrees, indicating a hydrophilic nature. The elastomer is compatible with NIH/3T3 fibroblast cells with cell viability reaching 88 ± 8.7% relative to the TCPS control at 48 h incubation. Differing from prior soft elastomers, a mixture of the two prepolymers without a carrying polymer is electrospinnable and UV-cross-linkable to fabricate elastic fibrous scaffolds for soft tissues. The designed prepolymer pair can thus ease the fabrication of elastic fibrous conduits, leading to potential use as a resorbable synthetic graft. The elastomers could find use in other tissue engineering applications as well.


Assuntos
Poliésteres , Polímeros , Poliésteres/química , Polímeros/química , Elastômeros/química , Tecidos Suporte/química , Compostos de Sulfidrila
9.
Int J Biol Macromol ; 264(Pt 1): 129768, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38296130

RESUMO

Fabrication of biodegradable shape memory polymer with remotely controllable shape actuation is of great significance in the biomedical field but remains challenging. Herein, we present a simple strategy to fabricate a monolayer-based stretchable and mechanically robust polycaprolactone/polydopamine elastomer via efficient thiol-ene click chemistry. The resultant elastomers exhibit desirable photothermal transfer efficiency and can enable rapid temperature increase over the melting temperature of polymeric matrix, and quantitative results demonstrate that the crosslinked film exhibited excellent shape memory properties with shape fixity (Rf) and shape recovery ratios (Rr) approaching 92.3 % and 95.6 %, respectively. Combined with photo stimuli, anisotropic polymer chain relaxation of the prestretched film can generate asymmetric contractions and eventually give rise to ut out-of-plane bending actuations upon photo stimulation, meanwhile, numerical simulation reveals the interaction mechanism of light with film. Beyond this, we further demonstrate that the bending angle is correlated with the parameters of prestretch strain, film thickness as well as irradiation time, and the maximum value can reach 158° with prestretch strain of 200 % and film thickness of 0.3 mm. In particular, the bent structures could be reversibly deformed into plane state via photo-directed corresponding opposite surfaces. Remarkably, the in vitro degradation properties of the elastomers on PBS-T buffer solutions demonstrated that the degradation was composed of induction stage and acceleration stage. This work will pave way for designing biodegradable light-induced shape memory materials toward biomedical device fields and so on.


Assuntos
Elastômeros , Indóis , Polímeros , Elastômeros/química , Polímeros/química , Poliésteres
10.
Microbiol Spectr ; 12(2): e0206323, 2024 Feb 06.
Artigo em Inglês | MEDLINE | ID: mdl-38230930

RESUMO

Meropenem has an excellent activity against gram-positive and gram-negative bacteria, including multi-resistant microorganisms. Even though meropenem is a great candidate for outpatient parenteral antimicrobial therapy (OPAT), its physicochemical stability is a major challenge. This work aimed to demonstrate the suitability of including meropenem in OPAT by elucidating its physicochemical stability in a range of commonly prescribed concentrations within portable elastomeric infusion devices. Physical and chemical stability were evaluated at two concentrations commonly used in clinical practice (2 and 25 mg/mL), and three temperatures (2°C-8°C, 25°C, and 32°C) using Accufuser portable elastomeric infusion devices. Drug adsorption onto portable elastomeric infusion devices was also determined at the end of the experiment. Meropenem stability significantly decreased at higher temperatures and when higher drug solution concentrations were used. Meropenem solutions at 2 mg/mL kept the drug content above 95% over 24 h at 2°C-8°C but just for 8 h at 25°C. Nevertheless, solutions containing 25 mg/mL of meropenem showed a dramatic decrease in chemical stability after 8 h 2°C-8°C and just after 4 h at 25°C or 32°C. However, physical stability was kept favorable during this period. The drug adsorption on the material of the elastomeric infusion device was below 1%, indicating the suitability of the chosen device. We propose several administration protocols for meropenem in portable elastomeric infusion devices in clinical practice, according to the results obtained in our study. The results obtained in this study open up the possibility of administering meropenem in an OPAT setting despite its short stability.IMPORTANCEAlthough outpatient parenteral antibiotic therapy can be a good approach to treating infections, a lack of data regarding antibiotic stability in portable elastomeric infusion devices restricts its safe and effective use. Actually, meropenem is used for prolonged periods above 24 h, and it is not physicochemically stable, which can compromise efficacy and toxicity. This work is of high importance to show the clinicians the real shelf life of meropenem when administered in portable elastomeric infusion devices. We propose several administration protocols for meropenem in portable elastomeric infusion devices in clinical practice, according to the stability drug results obtained in our study.


Assuntos
Antibacterianos , Anti-Infecciosos , Meropeném , Antibacterianos/química , Elastômeros/química , Bombas de Infusão , Bactérias Gram-Negativas , Bactérias Gram-Positivas
11.
ACS Appl Mater Interfaces ; 16(5): 6356-6366, 2024 Feb 07.
Artigo em Inglês | MEDLINE | ID: mdl-38262045

RESUMO

Biodegradable electronic devices have gained significant traction in modern medical applications. These devices are generally desired to have a long enough working lifetime for stable operation and allow for active control over their degradation rates after usage. However, current biodegradable materials used as encapsulations or substrates for these devices are challenging to meet the two requirements due to the constraints of inadequate water resistance, poor mechanical properties, and passive degradation characteristics. Herein, we develop a novel biodegradable elastomer named POC-SS-Res by introducing disulfide linkage and resveratrol (Res) into poly(1,8-octanediol-co-citrate) (POC). Compared to POC, POC-SS-Res exhibits good water resistance and excellent mechanical properties in PBS, providing effective protection for devices. At the same time, POC-SS-Res offers the unique advantage of an active-controllable degradation rate, and its degradation products express low biotoxicity. Good biocompatibility of POC-SS-Res is also demonstrated. Bioelectronic components encapsulated with POC-SS-Res have an obvious prolongation of working lifetime in PBS compared to that encapsulated with POC, and its degradation rate can be actively controlled by the addition of glutathione (GSH).


Assuntos
Materiais Biocompatíveis , Polímeros , Polímeros/química , Materiais Biocompatíveis/química , Engenharia Tecidual , Elastômeros/química , Citratos/química
12.
Macromol Rapid Commun ; 45(4): e2300568, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-37956305

RESUMO

Fibrous strain sensing materials with both high sensitivity and high linearity are of significant importance for wearable sensors, yet they still face great challenges. Herein, a photo-spun reaction encapsulation strategy is proposed for the continuous fabrication of fibrous strain sensor materials (AMGF) with a core-sheath structure. Metallogels (MOGs) formed by bacterial cellulose (BC) nanofibers and Ag nanoparticles (AgNPs), and thermoplastic elastomers (TPE) are employed as the core and sheath, respectively. The in situ ultraviolet light reduction of Ag+ ensured AgNPs to maintain the interconnections between the BC nanofibers and form electron conductive networks (0.31 S m-1 ). Under applied strain, the BC nanofibers experience separation, bringing AMGF a high sensitivity (gauge factor 4.36). The concentration of free ions in the MOGs uniformly varies with applied deformation, endowing AMGF with high linearity and a goodness-of-fit of 0.98. The sheath TPE provided AMGF sensor with stable working life (>10 000 s). Furthermore, the AMGF sensors are demonstrated to monitor complex deformations of the dummy joints in real-time as a wearable sensor. Therefore, the fibrous hybrid conductive network fibers fabricated via the photo-spun reaction encapsulation strategy provide a new route for addressing the challenge of achieving both high sensitivity and high linearity.


Assuntos
Nanopartículas Metálicas , Dispositivos Eletrônicos Vestíveis , Nanopartículas Metálicas/química , Elétrons , Prata/química , Elastômeros/química
13.
Macromol Rapid Commun ; 45(3): e2300526, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-37877649

RESUMO

Nature with its abundant source offers numerous inspirations for structural and engineering designs. The oriented membranes stacked with bouligand structures in the fish scales show an outstanding combination of high strength and crack resistance. Although the applications of hard biomimetic composites are reported, the structures are rarely utilized in soft materials. Inspired by the scales of various fishes, electrospun membranes are used and stacked to fabricate bouligand elastomers, including orthogonal-plywood, single-bouligand, and double-bouligand structures. The effects of different structures on the properties of elastomers are systematically investigated and possible mechanism is explained using finite element analysis (FEA). The stiffness and fatigue characteristics of these biomimetic elastomers with the above structures are improved compared with the original membranes, especially the elastomers with a single-bouligand structure, which can undergo 5 000 cycles at a maximum strain of 35% without complete failure. The crack only propagates to half of the width of the elastomer with remaining strength of 50% of its original strength. Moreover, the mechanical performance can be adjusted by regulating the proportion of the components. The excellent crack-resistant properties and transparency promote its various potential applications.


Assuntos
Elastômeros , Peixes , Animais , Elastômeros/química
14.
Macromol Rapid Commun ; 45(1): e2300240, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-37289949

RESUMO

The physical blending of high-mobility conjugated polymers with ductile elastomers provides a simple way to realize high-performance stretchable films. However, how to control the morphology of the conjugated polymer and elastomer blend film and its response to mechanical fracture processes during stretching are not well understood. Herein, a sandwich structure is constructed in the blend film based on a conjugated polymer poly[(5-fluoro-2,1,3-benzothiadiazole-4,7-diyl)(4,4-dihexadecyl-4H-cyclopenta[2,1-b:3,4-b″]dithiophene-2,6-diyl)(6-fluoro-2,1,3-benzothiadiazole-4,7-diyl)(4,4-dihexadecyl-4H-cyclopenta[2,1-b:3,4-b″]dithiophene-2,6-diyl)] (PCDTFBT) and an elastomer polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene (SEBS). The sandwich structure is composed of a PCDTFBT:SEBS mixed layer laminated with a PCDTFBT-rich layer at both the top and bottom surfaces. During stretching, the external strain energy can be effectively dissipated by the deformation of the crystalline PCDTFBT domains and amorphous SEBS phases and the recrystallization of the PCDTFBT chains. This endows the blend film with excellent ductility, with a large crack onset strain exceeding 1100%, and minimized the electrical degradation of the blend film at a large strain. This study indicates that the electrical and mechanical performance of conjugated polymer/elastomer blend films can be improved by manipulating their microstructure.


Assuntos
Polímeros , Tiadiazóis , Elastômeros/química , Polímeros/química , Poliestirenos , Tiadiazóis/química , Tiofenos/química
15.
Molecules ; 28(24)2023 Dec 09.
Artigo em Inglês | MEDLINE | ID: mdl-38138515

RESUMO

Polyester elastomers are highly flexible and elastic materials that have demonstrated considerable potential in various biomedical applications including cardiac, vascular, neural, and bone tissue engineering and bioelectronics. Polyesters are desirable candidates for future commercial implants due to their biocompatibility, biodegradability, tunable mechanical properties, and facile synthesis and fabrication methods. The incorporation of bioactive components further improves the therapeutic effects of polyester elastomers in biomedical applications. In this review, novel structural modification methods that contribute to outstanding mechanical behaviors of polyester elastomers are discussed. Recent advances in the application of polyester elastomers in tissue engineering and bioelectronics are outlined and analyzed. A prospective of the future research and development on polyester elastomers is also provided.


Assuntos
Elastômeros , Poliésteres , Elastômeros/química , Poliésteres/química , Engenharia Tecidual/métodos , Materiais Biocompatíveis/química
16.
ACS Appl Bio Mater ; 6(10): 4100-4104, 2023 10 16.
Artigo em Inglês | MEDLINE | ID: mdl-37782232

RESUMO

Myocardial tissue engineering strategies such as fabrication of cardiac patches for tissue regeneration offer various solutions for the loss of function developed due to myocardial infarction. Here, we combined the hybrid structure (previously obtained and combined decellularized myocardium grafts with poly(glycerol-sebacate) polymer) with multiwalled carbon nanotubes (MWCNTs) to provide the essential characteristics for cardiac tissue regeneration. MWCNTs were doped in the cross-linked structure, and the conductivity and Young's modulus of the composite elastomer were found as 5 × 10-3 ± 1 × 10-3 S/m and 374 ± 75.8 kPa, respectively. The cell-material interaction was evaluated, and composite structures supported cell adhesion and showed no cytotoxic effect.


Assuntos
Nanotubos de Carbono , Nanotubos de Carbono/toxicidade , Nanotubos de Carbono/química , Miocárdio , Elastômeros/química , Engenharia Tecidual , Matriz Extracelular
17.
Biomacromolecules ; 24(9): 4123-4137, 2023 09 11.
Artigo em Inglês | MEDLINE | ID: mdl-37584644

RESUMO

Citrate-based polymers are commonly used to create biodegradable implants. In an era of personalized medicine, it is highly desired that the degradation rates of citrate-based implants can be artificially regulated as required during clinical applications. Unfortunately, current citrate-based polymers only undergo passive degradation, which follows a specific degradation profile. This presents a considerable challenge for the use of citrate-based implants. To address this, a novel citrate-based polyester elastomer (POCSS) with artificially regulatable degradation rate is developed by incorporating disulfide bonds (S-S) into the backbone chains of the crosslinking network of poly(octamethylene citrate) (POC). This POCSS exhibits excellent and tunable mechanical properties, notable antibacterial properties, good biocompatibility, and low biotoxicity of its degradation products. The degradation rate of the POCSS can be regulated by breaking the S-S in its crosslinking network using glutathione (GSH). After a period of subcutaneous implantation of POCSS scaffolds in mice, the degradation rate eventually increased by 2.46 times through the subcutaneous administration of GSH. Notably, we observed no significant adverse effects on its surrounding tissues, the balance of the physiological environment, major organs, and the health status of the mice during degradation.


Assuntos
Elastômeros , Poliésteres , Camundongos , Animais , Elastômeros/química , Poliésteres/química , Ácido Cítrico , Tecidos Suporte/química , Materiais Biocompatíveis/química , Engenharia Tecidual , Polímeros/química , Citratos/química
18.
Macromol Rapid Commun ; 44(21): e2300354, 2023 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-37572076

RESUMO

Adopting only a small amount of azobenzene molecular to design liquid crystal photo-responsive materials capable of quick response and flexible adjustability is in high demand but is challenging. Herein, azobenzenemolecules into polyurethane elastomer containing crystalline structure for preparing azobenzene liquid-crystal elastomers (ALCEs) are demonstrated and this phenomenon of the synergistic effects between liquid crystal and crystalline phase is discovered. The key point of the work is that the synthetic ALCEs can utilize the reversible isomerism capability of azobenzene molecules under light irradiation, which can pry the motion of the macromolecular crystalline region in system to realize the large macroscopic deformation of the photo-responsive behavior. Obviously, the ALCEs sample containing azobenzene molecule and polyethylene glycol crystallization can quickly bend, illuminated by ultraviolet light and rapidly straighten under green light. Under the same ultraviolet irradiation, the bending speed, final bending angle, recovery rate and recovery ratio of ALCEs are larger than that of ALCEs without any crystalline structure. This ALCEs based on the synergistic effects between liquid crystal and crystalline phase can break through the current dilemma that the application of traditional azobenzene photo-responsive materials is limited by their concentration, greatly expanding the design thought and their scope of application.


Assuntos
Elastômeros , Cristais Líquidos , Elastômeros/química , Cristais Líquidos/química , Compostos Azo/química , Polietilenoglicóis
19.
Biomacromolecules ; 24(8): 3647-3656, 2023 08 14.
Artigo em Inglês | MEDLINE | ID: mdl-37462907

RESUMO

A series of cellulose-graft-diblock bottlebrush copolymer elastomers (cellulose-graft-poly(n-butyl acrylate)-block-poly(methyl methacrylate) (Cell-g-PBA-b-PMMA)) with short side chains were synthesized via successive atom transfer radical polymerization (ATRP) to study the influence of varying compositions and lengths of the graft diblock side chains on microphase morphologies and properties. The microphase-separated morphologies from misaligned spheres to cylinders were observed by atomic force microscopy (AFM) and small-angle X-ray scattering (SAXS) measurements. These bottlebrush copolymer elastomers possessed thermal stability and enhanced mechanical properties because the PMMA outer block could self-assemble into hard microdomains, which served as physical cross-links. The viscoelastic responses of these bottlebrush copolymers within the linear viscoelastic (LVE) regime were carried out by the oscillatory shear rheology. The time-temperature superposition (tTs) principle was applied to construct the master curves of the dynamic moduli, and the sequential relaxation of dense bottlebrush copolymers with different PMMA hard outer block lengths was analyzed. The rheological behaviors in this work could be utilized to build up the connection of microstructures and properties for the application of these bottlebrush copolymers as high-performance thermoplastic elastomers.


Assuntos
Elastômeros , Nanoestruturas , Elastômeros/química , Celulose/química , Polimetil Metacrilato/química , Espalhamento a Baixo Ângulo , Difração de Raios X , Polímeros/química , Nanoestruturas/química , Reologia
20.
Molecules ; 28(13)2023 Jul 07.
Artigo em Inglês | MEDLINE | ID: mdl-37446926

RESUMO

Elastomeric materials are utilized for the short-term protection of products and structures operating under extreme conditions in the aerospace, marine, and oil and gas industries. This research aims to study the influence of functionally active structures on the physical, mechanical, thermophysical, and fire- and heat-protective characteristics of elastomer compositions. The physical and mechanical properties of elastomer samples were determined using Shimazu AG-Xplus, while morphological research into microheterogeneous systems and coke structures was carried out on a scanning electronic microscope, Versa 3D. Differential thermal and thermogravimetric analyses of the samples were conducted on derivatograph Q-1500D. The presence of aluminosilicate microspheres, carbon microfibers, and a phosphor-nitrogen-organic modifier as part of the aforementioned structures contributes to the appearance of a synergetic effect, which results in an increase in the heat-protective properties of a material due to the enhancement in coke strength and intensification of material carbonization processes. The results indicate an 8-17% increase in the heating time of the unheated surface of a sample and a decrease in its linear burning speed by 6-17% compared to known analogues. In conclusion, microspheres compensate for the negative impact of microfibers on the density and thermal conductivity of a composition.


Assuntos
Coque , Incêndios , Elastômeros/química , Temperatura Alta , Teste de Materiais
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