All-Fiber Flexible Electrochemical Sensor for Wearable Glucose Monitoring.

Wearable sensors, specifically microneedle sensors based on electrochemical methods, have expanded extensively with recent technological advances. Today's wearable electrochemical sensors present specific challenges: they show significant modulus disparities with skin tissue, implying possible discomfort in vivo, especially over extended wear periods or on sensitive skin areas. The sensors, primarily based on polyethylene terephthalate (PET) or polyimide (PI) substrates, might also cause pressure or unease during insertion due to the skin's irregular deformation. To address these constraints, we developed an innovative, wearable, all-fiber-structured electrochemical sensor. Our composite sensor incorporates polyurethane (PU) fibers prepared via electrospinning as electrode substrates to achieve excellent adaptability. Electrospun PU nanofiber films with gold layers shaped via thermal evaporation are used as base electrodes with exemplary conductivity and electrochemical catalytic attributes. To achieve glucose monitoring, gold nanofibers functionalized by gold nanoflakes (AuNFs) and glucose oxidase (GOx) serve as the working electrode, while Pt nanofibers and Ag/AgCl nanofibers serve as the counter and reference electrode. The acrylamide-sodium alginate double-network hydrogel synthesized on electrospun PU fibers serves as the adhesive and substance-transferring layer between the electrodes. The all-fiber electrochemical sensor is assembled layer-by-layer to form a robust structure. Given the stretchability of PU nanofibers coupled with a high specific surface area, the manufactured porous microneedle glucose sensor exhibits enhanced stretchability, superior sensitivity at 31.94 µA (lg(mM))-1 cm-2, a broad detection range (1-30 mM), and a significantly low detection limit (1 mM, S/N = 3), as well as satisfactory biocompatibility. Therefore, the novel electrochemical microneedle design is well-suited for wearable or even implantable continuous monitoring applications, thereby showing promising significant potential within the global arena of wearable medical technology.

Impact of screw tip design on screw anchorage: mechanical testing and numerical simulation.

BACKGROUND: Screw loosening is a commonly reported issue following spinal screw fixation and can lead to various complications. The initial cause of screw loosening is biomechanical deterioration. Previous studies have demonstrated that modifications in screw design can impact the local biomechanical environment, specifically the stress distribution on bone-screw interfaces. There are several different designs of screw tips available for clinically used pedicle screws; however, it remains unclear whether these variations affect the local stress distribution and subsequent screw anchorage ability. METHODS: This study conducted comprehensive biomechanical research using polyurethane foam mechanical tests and corresponding numerical simulations to investigate this topic. Models of pedicle screw-fixed osteoporotic polyurethane foam were created with two different clinically used screw tip designs (flat and steep) featuring varying tip lengths, taper angles, and diameters, as well as identical flank overlap areas and thread designs. The anchorage ability of the different models was assessed through toggle and pull-out test. Additionally, numerical mechanical models were utilized to compute the stress distributions at the screw and bone-screw interfaces in the different models. RESULTS: Mechanical tests revealed superior anchorage ability in models utilizing flat-tipped screws. Furthermore, numerical modeling indicated improved anchorage ability and reduced stress concentration tendency in these models. CONCLUSION: Changes in screw tip design can significantly impact the biomechanical anchoring capability of screws. Specifically, flatter tip pedicle screws may mitigate the risk of screw loosening by alleviating stress concentration on bone-screw interfaces.

Implementation of 3D Printing and Modeling Technologies for the Fabrication of Dose Boluses for External Radiotherapy at the CLCC of Sétif, Algeria.

Objective: In external radiotherapy, dose boluses and compensators are used for treatment of irregular facial topography surfaces. In such cases, skewed isodose curves need to be addressed using a bolus that gives the deep dose distribution a shape adapted to the anatomical structures to be protected or irradiated. The combination of 3D modeling and printing technologies is a promising alternative to the conventional inaccurate and uncomfortable bolus fabrication technique. In this work, the proposed technologies will be used in the design and fabrication of high-performance and high-accuracy boluses that respond to the main constraints on metrology, adhesion to the patient's surface, comfort, and dose delivery. Methods: As a first phase in the implementation of the proposed solution, 3D printing materials, to be used in the fabrication of radiotherapy boluses, were selected and characterized to check how they respond to the required criteria on functionality, safety, and quality. Results: The obtained results show that among the studied materials, thermoplastic polyurethane (TPU) was found to be slightly more suitable than polylactic acid (PLA) for the fabrication of 3D printing boluses but for some kinds of treatments, PLA may be preferred despite its relative rigidity. Conclusion: In this work, procedures for dose bolus fabrication were proposed, and necessary data were obtained for some available 3D printing materials (TPU and PLA) that can be used for targeted applications. This achievement is a major step toward the final implementation of 3D modeling and printing technologies for the efficient fabrication of radiotherapy dose boluses.

Sustained release of brimonidine from conjunctival sac insert to reduce intraocular pressure for glaucoma treatment.

BACKGROUND: Glaucoma is one of the major irreversible blinding eye diseases in the world. Reducing intraocular pressure (IOP) is the primary treatment option, and taking eye drops daily is the common method. However, short drug duration and poor bioavailability of eye drops may lead to unsatisfied therapeutic effects and inadequate patient compliance. METHODS: A brimonidine-loaded silicone rubber insert (BRI@SR@PT) was prepared by loading brimonidine into a surface-modified silicone rubber ring, followed by polydopamine/thermoplastic polyurethane coatings. The physical properties, in vitro cytocompatibility and drug release of BRI@SR@PT were investigated. The BRI@SR@PT was administrated in the conjunctival sac of rabbit eyes, and its in vivo drug release, IOP-lowering efficacy and biosafety were assessed. RESULTS: The BRI@SR@PT presented great thermal stability and excellent elasticity. The BRI@SR@PT was able to release BRI sustainably for 28 days with little toxicity in vitro. Compared to BRI eye drops, the BRI@SR@PT effectively lowered IOP for 21 days based on the sustained BRI release with great biosafety when administrated in conjunctival sac of rabbit eyes in a noninvasive fashion. CONCLUSIONS: The conjunctival sac insert (BRI@SR@PT), as a promising drug-delivery platform, may provide a sustained IOP-lowering treatment for patients with ocular hypertension or glaucoma, without the need for invasive procedures.

Enhanced biodegradation of 2, 4-dichlorophenol in packed bed biofilm reactor by impregnation of polyurethane foam with Fe3O4 nanoparticles: Bio-kinetics, process optimization, performance evaluation and toxicity assessment.

In this work, an effort has been made to enhance the efficacy of biological process for the effective degradation of 2, 4-dichlorophenol (2, 4-DCP) from wastewater. The polyurethane foam was modified with Fe3O4 nanoparticles and combined with polyvinyl alcohol, sodium alginate, and bacterial consortium for biodegradation of 2, 4-DCP in a packed bed biofilm reactor. The maximum removal efficiency of 2, 4-DCP chemical oxygen demand, and total organic carbon were found to be 92.51 ± 0.83 %, 86.85 ± 1.32, and 91.78 ± 1.24 %, respectively, in 4 days and 100 mg L-1 of 2, 4-DCP concentration at an influent loading rate of 2 mg L-1h-1 and hydraulic retention time of 50 h. Packed bed biofilm reactor was effective for up to four cycles to remove 2, 4-DCP. Growth inhibition kinetics were evaluated using the Edward model, yielding maximum growth rate of 0.45 day-1, inhibition constant of 110.6 mg L-1, and saturation constant of 62.3 mg L-1.

Evaluation of the effects of temperature and centrifugation time on elimination of uncured resin from 3D-printed dental aligners.

The study investigated the effects of temperature and centrifugation time on the efficacy of removing uncured resin from 3D-printed clear aligners. Using a photo-polymerizable polyurethane resin (Tera Harz TC-85, Graphy Inc., Seoul, Korea), aligners were printed and subjected to cleaning processes using isopropyl alcohol (IPA) or centrifugation (g-force 27.95g) at room temperature (RT, 23 °C) and high temperature (HT, 55 °C) for 2, 4, and 6 min. The control group received no treatment (NT). Cleaning efficiency was assessed through rheological analysis, weight measurement, transparency evaluation, SEM imaging, 3D geometry evaluation, stress relaxation, and cell viability tests. Results showed increased temperature and longer centrifugation times significantly reduced aligner viscosity, weight (P < 0.05), and transmittance. IPA-cleaned aligners exhibited significantly lower transparency and rougher surfaces in SEM images. All groups met ISO biocompatibility standards in cytotoxicity tests. The NT group had higher root mean square (RMS) values, indicating greater deviation from the original design. Stress relaxation tests revealed over 95% recovery in all groups after 60 min. The findings suggest that a 2-min HT centrifugation process effectively removes uncured resin without significantly impacting the aligners' physical and optical properties, making it a clinically viable option.

Efficacy of auxetic lattice structured shoe sole in advancing footwear comfort-From the perspective of plantar pressure and contact area.

Introduction: Designing footwear for comfort is vital for preventing foot injuries and promoting foot health. This study explores the impact of auxetic structured shoe soles on plantar biomechanics and comfort, motivated by the integration of 3D printing in footwear production and the superior mechanical properties of auxetic designs. The shoe sole designs proposed in this study are based on a three-dimensional re-entrant auxetic lattice structure, orthogonally composed of re-entrant hexagonal honeycombs with internal angles less than 90 degrees. Materials fabricated using this lattice structure exhibit the characteristic of a negative Poisson's ratio, displaying lateral expansion under tension and densification under compression. Methods: The study conducted a comparative experiment among three different lattice structured (auxetic 60°, auxetic 75° and non-auxetic 90°) thermoplastic polyurethane (TPU) shoe soles and conventional polyurethane (PU) shoe sole through pedobarographic measurements and comfort rating under walking and running conditions. The study obtained peak plantar pressures (PPPs) and contact area across seven plantar regions of each shoe sole and analyzed the correlation between these biomechanical parameters and subjective comfort. Results: Compared to non-auxetic shoe soles, auxetic structured shoe soles reduced PPPs across various foot regions and increased contact area. The Auxetic 60°, which had the highest comfort ratings, significantly lowered peak pressures and increased contact area compared to PU shoe sole. Correlation analysis showed that peak pressures in specific foot regions (hallux, second metatarsal head, and hindfoot when walking; second metatarsal head, third to fifth metatarsal head, midfoot, and hindfoot when running) were related to comfort. Furthermore, the contact area in all foot regions was significantly associated with comfort, regardless of the motion states. Conclusion: The pressure-relief performance and conformability of the auxetic lattice structure in the shoe sole contribute to enhancing footwear comfort. The insights provided guide designers in developing footwear focused on foot health and comfort using auxetic structures.

Bio-Based Polyurethane Networks Containing Sunflower Oil Based Polyols.

This work focused on the preparation and investigation of polyurethane (SO-PU)-containing sunflower oil glycerides. By transesterification of sunflower oil with glycerol, we synthesized a glyceride mixture with an equilibrium composition, which was used as a new diol component in polyurethanes in addition to poly(ε-caprolactone)diol (PCLD2000). The structure of the glyceride mixture was characterized by physicochemical methods, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS), nuclear magnetic resonance spectroscopy (NMR), and size exclusion chromatography (SEC) measurements. The synthesis of polyurethanes was performed in two steps: first the prepolymer with the isocyanate end was synthesized, followed by crosslinking with an additional amount of diisocyanate. For the synthesis of the prepolymer, 4,4'-methylene diphenyl diisocyanate (MDI) or 1,6-hexamethylene diisocyanate (HDI) were used as isocyanate components, while the crosslinking was carried out using an additional amount of MDI or HDI. The obtained SO-PU flexible polymer films were characterized by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). The so-obtained flexible SO-PU films were proved to be suitable for the preparation of potentially biocompatible and/or biodegradable scaffolds. In addition, the stress versus strain curves for the SO-PU polymers were interpreted in terms of a mechanical model, taking into account the yield and the strain hardening.

The effects of submicron-textured surface topography on antibiotic efficacy against biofilms.

Submicron-textured surfaces have been a promising approach to mitigate biofilm development and control microbial infection. However, the use of the single surface texturing approach is still far from ideal for achieving complete control of microbial infections on implanted biomedical devices. The use of a surface topographic modification that might improve the utility of standard antibiotic therapy could alleviate the complications of biofilms on devices. In this study, we characterized the biofilms of Staphylococcus aureus and Pseudomonas aeruginosa on smooth and submicron-textured polyurethane surfaces after 1, 2, 3, and 7 days, and measured the efficacy of common antibiotics against these biofilms. Results show that the submicron-textured surfaces significantly reduced biofilm formation and growth, and that the efficacy of antibiotics against biofilms grown on textured surfaces was improved compared with smooth surfaces. The antibiotic efficacy appears to be related to the degree of biofilm development. At early time points in biofilm formation, antibiotic treatment reveals reasonably good antibiotic efficacy against biofilms on both smooth and textured surfaces, but as biofilms mature, the efficacy of antibiotics drops dramatically on smooth surfaces, with lesser decreases seen for the textured surfaces. The results demonstrate that surface texturing with submicron patterns is able to improve the use of standard antibiotic therapy to treat device-centered biofilms by slowing the development of the biofilm, thereby offering less resistance to antibiotic delivery to the bacteria within the biofilm community.

New experimental model to evaluate the effect of negative pressure wound therapy and viscosity exudates in foam dressings using confocal microscopy.

Negative pressure wound therapy is currently one of the most popular treatment approaches that provide a series of benefits to facilitate healing, including increased local blood perfusion with reduced localized oedema and control of wound exudate. The porous foam dressing is a critical element in the application of this therapy and its choice is based on its ability to manage exudate. Industry standards often employ aqueous solutions devoid of proteins to assess dressing performance. However, such standardized tests fail to capture the intricate dynamics of real wounds, oversimplifying the evaluation process. This study aims to evaluate the technical characteristics of two different commercial polyurethane foam dressings during negative pressure wound therapy. We introduce an innovative experimental model designed to evaluate the effects of this therapy on foam dressings in the presence of viscous exudates. Our findings reveal a proportional increase in dressing fibre occupancy as pressure intensifies, leading to a reduction in dressing pore size. The tests underscore the pressure system's diminished efficacy in fluid extraction with increasing fluid viscosity. Our discussion points to the need of establishing standardized guidelines for foam dressing selection based on pore size and the necessity of incorporating real biological exudates into industrial standards.

Thermographic analysis of perforations in polyurethane blocks performed with experimental conical drill bit in comparison to conventional orthopedic drill bit: a preliminary study.

OBJECTIVE: Conical orthopedic drill bits may have the potential to improve the stabilization of orthopedic screws. During perforations, heat energy is released, and elevated temperatures could be related to thermal osteonecrosis. This study was designed to evaluate the thermal behavior of an experimental conical drill bit, when compared to the conventional cylindrical drill, using polyurethane blocks perforations. RESULTS: The sample was divided into two groups, according to the method of drilling, including 25 polyurethane blocks in each: In Group 1, perforations were performed with a conventional orthopedic cylindrical drill; while in Group 2, an experimental conical drill was used. No statistically significant difference was observed in relation to the maximum temperature (MT) during the entire drilling in the groups, however the perforation time (PT) was slightly longer in Group 2. Each drill bit perforated five times and number of perforations was not correlated with a temperature increase, when evaluated universally or isolated by groups. The PT had no correlation with an increase in temperature when evaluating the perforations universally (n = 50) and in Group 1 alone; however, Group 2 showed an inversely proportional correlation for these variables, indicating that, for the conical drill bit, drillings with longer PT had lower MT.

Efficacy of 3D printed anatomically equivalent thermoplastic polyurethane guide conduits in promoting the regeneration of critical-sized peripheral nerve defects.

Three-dimensional (3D) printing is an emerging tool for creating patient-specific tissue constructs analogous to the native tissue microarchitecture. In this study, anatomically equivalent 3D nerve conduits were developed using thermoplastic polyurethane (TPU) by combining reverse engineering and material extrusion (i.e. fused deposition modeling) technique. Printing parameters were optimized to fabricate nerve-equivalent TPU constructs. The TPU constructs printed with different infill densities supported the adhesion, proliferation, and gene expression of neuronal cells. Subcutaneous implantation of the TPU constructs for three months in rats showed neovascularization with negligible local tissue inflammatory reactions and was classified as a non-irritant biomaterial as per ISO 10993-6. To performin vivoefficacy studies, nerve conduits equivalent to rat's sciatic nerve were fabricated and bridged in a 10 mm sciatic nerve transection model. After four months of implantation, the sensorimotor function and histological assessments revealed that the 3D printed TPU conduits promoted the regeneration in critical-sized peripheral nerve defects equivalent to autografts. This study proved that TPU-based 3D printed nerve guidance conduits can be created to replicate the complicated features of natural nerves that can promote the regeneration of peripheral nerve defects and also show the potential to be extended to several other tissues for regenerative medicine applications.

Enzyme-Activated Biomimetic Vesicles Confining Mineralization for Bone Maturation.

Inspired by the crucial role of matrix vesicles (MVs), a series of biomimetic vesicles (BVs) fabricated by calcium glycerophosphate (CaGP) modified polyurethane were designed to mediate the mineralization through in situ enzyme activation for bone therapy. In this study, alkaline phosphatase (ALP) was harbored in the porous BVs by adsorption (Ad-BVs) or entrapment (En-BVs). High encapsulation of ALP on En-BVs was effectively self-activating by calcium ions of CaGP-modified PU that specifically hydrolyzed the organophosphorus (CaGP) to inorganic phosphate, thus promoting the formation of the highly oriented bone-like apatite in vitro. Enzyme-catalyzed kinetics confirms the regulation of apatite crystallization by the synergistic action of self-activated ALP and the confined microcompartments of BVs. This leads to a supersaturated microenvironment, with the En-BVs group exhibiting inorganic phosphate (Pi) levels 4.19 times higher and Ca2+ levels 3.67 times higher than those of simulated body fluid (SBF). Of note, the En-BVs group exhibited excellent osteo-inducing differentiation of BMSCs in vitro and the highest maturity with reduced bone loss in rat femoral defect in vivo. This innovative strategy of biomimetic vesicles is expected to provide valuable insights into the enzyme-activated field of bone therapy.

Maturation of human cardiomyocytes derived from induced pluripotent stem cells (iPSC-CMs) on polycaprolactone and polyurethane nanofibrous mats.

Investigating the potential of human cardiomyocytes derived from induced pluripotent stem cells (iPSC-CMs) in in vitro heart models is essential to develop cardiac regenerative medicine. iPSC-CMs are immature with a fetal-like phenotype relative to cardiomyocytes in vivo. Literature indicates methods for enhancing the structural maturity of iPSC-CMs. Among these strategies, nanofibrous scaffolds offer more accurate mimicry of the functioning of cardiac tissue structures in the human body. However, further research is needed on the use of nanofibrous mats to understand their effects on iPSC-CMs. Our research aimed to evaluate the suitability of poly(ε-caprolactone) (PCL) and polyurethane (PU) nanofibrous mats with different elasticities as materials for the maturation of iPSC-CMs. Analysis of cell morphology and orientation and the expression levels of selected genes and proteins were performed to determine the effect of the type of nanofibrous mats on the maturation of iPSC-CMs after long-term (10-day) culture. Understanding the impact of 3D structural properties in in vitro cardiac models on induced pluripotent stem cell-derived cardiomyocyte maturation is crucial for advancing cardiac tissue engineering and regenerative medicine because it can help optimize conditions for obtaining more mature and functional human cardiomyocytes.

XTT assay for detection of bacterial metabolic activity in water-based polyester polyurethane.

Cellular metabolic activity can be detected by tetrazolium-based colorimetric assays, which rely on dehydrogenase enzymes from living cells to reduce tetrazolium compounds into colored formazan products. Although these methods have been used in different fields of microbiology, their application to the detection of bacteria with plastic-degrading activity has not been well documented. Here, we report a microplate-adapted method for the detection of bacteria metabolically active on the commercial polyester polyurethane (PU) Impranil®DLN using the tetrazolium salt 2,3-bis [2-methyloxy-4-nitro-5-sulfophenyl]-2H-tetrazolium-5-carboxanilide (XTT). Bacterial cells that are active on PU reduce XTT to a water-soluble orange dye, which can be quantitatively measured using a microplate reader. We used the Pseudomonas putida KT2440 strain as a study model. Its metabolic activity on Impranil detected by our novel method was further verified by Fourier-transform infrared spectroscopy (FTIR) analyses. Measurements of the absorbance of reduced XTT at 470 nm in microplate wells were not affected by the colloidal properties of Impranil or cell density. In summary, we provide here an easy and high-throughput method for screening bacteria active on PU that can be adapted to other plastic substrates.

Hemodialysis bilayer bionic blood vessels developed by the mechanical stimulation of hepatitis B viral X(HBX) gene- transfected hepatic stellate cells. / é€šè¿‡æœºæ¢°åŠ›åˆºæ¿€ä¹™åž‹è‚ç‚Žç— æ¯’XåŸºå› (HBX)转染的肝星状细胞制备血液透析用双层仿生血管.

Artificial vascular graft (AVG) fistula is widely used for hemodialysis treatment in patients with renal failure. However, it has poor elasticity and compliance, leading to stenosis and thrombosis. The ideal artificial blood vessel for dialysis should replicate the structure and components of a real artery, which is primarily maintained by collagen in the extracellular matrix (ECM) of arterial cells. Studies have revealed that in hepatitis B virus (HBV)-induced liver fibrosis, hepatic stellate cells (HSCs) become hyperactive and produce excessive ECM fibers. Furthermore, mechanical stimulation can encourage ECM secretion and remodeling of a fiber structure. Based on the above factors, we transfected HSCs with the hepatitis B viral X (HBX) gene for simulating the process of HBV infection. Subsequently, these HBX-HSCs were implanted into a polycaprolactone-polyurethane (PCL-PU) bilayer scaffold in which the inner layer is dense and the outer layer consists of pores, which was mechanically stimulated to promote the secretion of collagen nanofiber from the HBX-HSCs and to facilitate crosslinking with the scaffold. We obtained an ECM-PCL-PU composite bionic blood vessel that could act as access for dialysis after decellularization. Then, the vessel scaffold was implanted into a rabbit's neck arteriovenous fistula model. It exhibited strong tensile strength and smooth blood flow and formed autologous blood vessels in the rabbit's body. Our study demonstrates the use of human cells to create biomimetic dialysis blood vessels, providing a novel approach for creating clinical vascular access for dialysis.

Tailorable acrylate-endcapped urethane-based polymers for precision in digital light processing: Versatile solutions for biomedical applications.

Bioengineering seeks to replicate biological tissues exploiting scaffolds often based on polymeric biomaterials. Digital light processing (DLP) has emerged as a potent technique to fabricate tissue engineering (TE) scaffolds. However, the scarcity of suitable biomaterials with desired physico-chemical properties along with processing capabilities limits DLP's potential. Herein, we introduce acrylate-endcapped urethane-based polymers (AUPs) for precise physico-chemical tuning while ensuring optimal computer-aided design/computer-aided manufacturing (CAD/CAM) mimicry. Varying the polymer backbone (i.e. poly(ethylene glycol) (PEG) versus poly(propylene glycol) (PPG)) and photo-crosslinkable endcap (i.e. di-acrylate versus hexa-acrylate), we synthesized a series of photo-crosslinkable materials labeled as UPEG2, UPEG6, UPPG2 and UPPG6. Comprehensive material characterization including physico-chemical and biological evaluations, was followed by a DLP processing parametric study for each material. The impact of the number of acrylate groups per polymer (2 to 6) on the physico-chemical properties was pronounced, as reflected by a reduced swelling, lower water contact angles, accelerated crosslinking kinetics, and increased Young's moduli upon increasing the acrylate content. Furthermore, the different polymer backbones also exerted a substantial effect on the properties, including the absence of crystallinity, remarkably reduced swelling behaviors, a slight reduction in Young's modulus, and slower crosslinking kinetics for UPPG vs UPEG. The mechanical characteristics of DLP-printed samples showcased the ability to tailor the materials' stiffness (ranging from 0.4 to 5.3 MPa) by varying endcap chemistry and/or backbone. The in vitro cell assays confirmed biocompatibility of the material as such and the DLP-printed discs. Furthermore, the structural integrity of 3D scaffolds was preserved both in dry and swollen state. By adjusting the backbone chemistry or acrylate content, the post-swelling dimensions could be customized towards the targeted application. This study showcases the potential of these materials offering tailorable properties to serve many biomedical applications such as cartilage TE.

Construction of sustainable and highly efficient fire-protective nanocoatings based on polydopamine and phosphorylated cellulose for flexible polyurethane foam.

Layer-by-layer (LBL) self-assembly is an effective strategy for constructing fire-resistant coatings on flexible polyurethane foam (FPUF), while the efficiency of fire-resistant coatings remains limited. Therefore, this study proposes an in situ flame retardancy modification combined with LBL self-assembly technology to enhance the efficiency of flame retardant coatings for FPUF. Initially, polydopamine (PDA) and polyethyleneimine (PEI) were employed to modify the FPUF skeleton, thereby augmenting the adhesion on the surface of the skeleton network. Then, the self-assembly of MXene and phosphorylated cellulose nanofibers (PCNFs) via the LBL technique on the foam skeleton network formed a novel, sustainable, and efficient flame retardant system. The final fire-protective coatings comprising PDA/PEI and MXenes/PCNF effectively prevented the collapse of the foam structure and suppressed the melt dripping of the FPUF during combustion. The peak heat release rate, the peak CO production rate and peak CO2 production rate were reduced by 68.6 %, 61.1 %, and 68.4 % only by applying a 10-bilayer coating. In addition, the smoke release rate and total smoke production were reduced by 83.3 % and 57.7 %, respectively. This work offers a surface modification approach for constructing highly efficient flame retardant coatings for flammable polymeric materials.

TME-Triggered Degradable Phototheranostic Nanoplatform for NIR-II Fluorescence Bioimaging-Guided Phototherapies and Immune Activation.

The low therapeutic efficacy and potential long-term toxicity of antitumor treatments seriously limit the clinical application of phototherapies. Herein, we develop a degradable phototheranostic nanoplatform for NIR-II fluorescence bioimaging-guided synergistic photothermal (PTT) and photodynamic therapies (PDT) and immune activation to inhibit tumor growth. The phototheranostic nanoplatform (CX@PSS) consists of multidisulfide-containing polyurethane loaded with a photosensitizer CX, which can be specifically degraded in the GSH overexpressed tumor microenvironment (TME) and exhibits good NIR-II fluorescence, photodynamic, and photothermal properties. Under 808 nm light irradiation, CX@PSS exhibits efficient photothermal conversion and ROS generation, which further induces immunogenic cell death (ICD), releasing tumor-associated antigens and activating the immune response. In vitro and in vivo studies confirm the potential of CX@PSS in NIR II FL imaging-guided tumor treatments by synergistic PTT, PDT, and immune activation. This work is expected to provide a new pathway for clinical applications of imaging-guided tumor diagnosis and treatments.

Understanding visible light and microbe-driven degradation mechanisms of polyurethane plastics: Pathways, property changes, and product analysis.

The accumulation of polyurethane plastics (PU-PS) in the environment is on the rise, posing potential risks to the health and function of ecosystems. However, little is known about the degradation behavior of PU-PS in the environment, especially water environment. To address this knowledge gap, we investigated and isolated a degrading strain of Streptomyces sp. B2 from the surface of polyurethane coatings. Subsequently, a photoreactor was employed to simulate the degradation process of bio-based polyurethane (BPU) and petroleum-based polyurethane (PPU) under three conditions, including single microorganism (SM), single light exposure (SL), and combined light exposure/microorganism action (ML) in aqueous solution. The results indicated that PU-PS mainly relies on biodegradation, with the highest degradation rate observed after 28 d under SM condition (BPU 5.69 %; PPU 5.25 %). SL inhibited microbial growth and degradation, with the least impact on plastic degradation. Microorganisms colonized the plastic surface, secreting relevant hydrolytic enzymes and organic acids into the culture medium, providing a negative charge. The carbon chains were broken and aged through hydrogen peroxide induction or attack by oxygen free radicals. This process promoted the formation of oxidized functional groups such as OH and CO, disrupting the polymer's structure. Consequently, localized fragmentation and erosion of the microstructure occurred, resulting in the generation of secondary microplastic (MPs) particles, weight loss of the original plastic, increased surface roughness, and enhanced hydrophilicity. Additionally, BPU exhibited greater degradability than PPU, as microorganisms could utilize the produced fatty acids, which promoted their reproduction. In contrast, PPU degradation generated a large amount of isocyanate, potentially toxic to cells and inhibiting biodegradation. This study unveils the significant role of microorganisms in plastic degradation and the underlying degradation mechanisms of BPU, providing a novel strategy for polyurethane degradation and valuable information for comprehensive assessment of the behavior and fate of MPs in the environment.