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Cellulose fiber-based textiles are ubiquitous in daily life for their processability, biodegradability, and outstanding flexibility. Integrating cellulose textiles with functional coating materials can unlock their potential functionalities to engage diverse applications. Metal-organic frameworks (MOFs) are ideal candidate materials for such integration, thanks to their unique merits, such as large specific surface area, tunable pore size, and species diversity. However, achieving scalable fabrication of MOFs-textiles with high mechanical durability remains challenging. Here, we report a facile and scalable strategy for direct MOF growth on cotton fibers grafted via the diazonium chemistry. The as-prepared ZIF-67-Cotton textile (ZIF-67-CT) exhibits excellent ultraviolet (UV) resistance and organic contamination degradation via the peroxymonosulfate activation. The ZIF-67-CT is also used to encapsulate essential oils such as carvacrol to enable antibacterial activity against E. coli and S. aureus. Additionally, by directly tethering a hydrophobic molecular layer onto the MOF-coated surface, superhydrophobic ZIF-67-CT is achieved with excellent self-cleaning, antifouling, and oil-water separation performances. More importantly, the reported strategy is generic and applicable to other MOFs and cellulose fiber-based materials, and various large-scale multi-functional MOFs-textiles can be successfully manufactured, resulting in vast applications in wastewater purification, fragrance industry, and outdoor gears.
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Personal protective equipment pays attention exclusively to external safety protection and ignores the internal thermoregulation of physiological state in association with sweating. Herein, a super-hygroscopic calcium-doped poly(sodium 4-styrenesulfonate) and superhydrophobic metal-organic-framework-overlayed wearables (Ca-PSS/MOF) integrated cooling wearable is proposed for special personal thermal management (PTM). Compared to the pristine fabric, the superhydrophobic MOF wearables exhibit anti-fouling and antibacterial capabilities, and the antibacterial efficiency is up to 99.99% and 98.99% against E. coli and S. aureus, respectively. More importantly, Ca-PSS/MOF demonstrate significant heat index changes up to 25.5 °C by reducing relative humidity dramatically from 91.0% to 60.0% and temperature from 36.5 to 31.6 °C during the running test. The practical feasibility of the Ca-PSS/MOF cooling wearables is well proved with the protective suit of the fireman. Owing to these multifunctional merits, the sandwich-structured cooling Ca-PSS/MOF are expected to provide new insights for designing the next-generation multifunctional apparel for PTM.
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Estruturas Metalorgânicas , Dispositivos Eletrônicos Vestíveis , Zinco , Zinco/química , Estruturas Metalorgânicas/química , Humanos , Escherichia coli , Staphylococcus aureus/efeitos dos fármacos , Antibacterianos/química , Antibacterianos/farmacologia , Temperatura , Interações Hidrofóbicas e HidrofílicasRESUMO
Hollow polymer microfibers with variable microstructural and hydrophilic properties were proposed as building elements to create axon-mimicking phantoms for validation of diffusion tensor imaging (DTI). The axon-mimicking microfibers were fabricated in a mm-thick 3D anisotropic fiber strip, by direct jet coaxial electrospinning of PCL/polysiloxane-based surfactant (PSi) mixture as shell and polyethylene oxide (PEO) as core. Hydrophilic PCL-PSi fiber strips were first obtained by carefully selecting appropriate solvents for the core and appropriate fiber collector rotating and transverse speeds. The porous cross-section and anisotropic orientation of axon-mimicking fibers were then quantitatively evaluated using two ImageJ plugins-nearest distance (ND) and directionality based on their scanning electron microscopy (SEM) images. Third, axon-mimicking phantom was constructed from PCL-PSi fiber strips with variable porous-section and fiber orientation and tested on a 3T clinical MR scanner. The relationship between DTI measurements (mean diffusivity [MD] and fractional anisotropy [FA]) of phantom samples and their pore size and fiber orientation was investigated. Two key microstructural parameters of axon-mimicking phantoms including normalized pore distance and dispersion of fiber orientation could well interpret the variations in DTI measurements. Two PCL-PSi phantom samples made from different regions of the same fiber strips were found to have similar MD and FA values, indicating that the direct jet coaxial electrospun fiber strips had consistent microstructure. More importantly, the MD and FA values of the developed axon-mimicking phantoms were mostly in the biologically relevant range.
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Fabrics have been used broadly in daily life for an enormous variety of applications due to their intrinsic advantages, such as flexibility, renewability, and good processability. Integrating natural fabrics with metal-organic frameworks (MOFs) is an effective strategy to improve the added value of textiles with special functionalities. Here, a facile, low-cost, and scalable technology is reported for the in situ growth of MOFs on cotton fabrics. A uniform and dense coating of regular octahedral Cu-1,3,5-benzenetricarboxylic acid (CuBTC) crystals was formed on the fiber surface, followed by treatment with 1H,1H,2H,2H-perfluorooctyltriethoxysilane and triethoxyoctylsilane to create a superhydrophobic CuBTC@cotton fabric (SMCF), which greatly improved its water stability and extended superhydrophobic CuBTC's potential applications. The as-prepared MCF has a specific surface area of 229 m2/g, which is 11 times that of pristine fabrics (21 m2/g). This high porosity further endows the fabric with enhanced loading capacity of essential oils to enable excellent antibacterial ability. Moreover, the SMCF also exhibits excellent self-cleaning, UV shielding, and anti-icing performances. In addition, we performed COMSOL simulations to investigate the dynamic freezing process of water on the surface of samples, which agrees well with our experimental observations. By combining the merits of both fabrics and MOFs, the MCF is expected to extend the applications of traditional textiles in antifouling, safety, the fragrance industry, and healthcare for the next-generation multifunctional fabrics.
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Objective. The use of diffusion magnetic resonance imaging (dMRI) opens the door to characterizing brain microstructure because water diffusion is anisotropic in axonal fibres in brain white matter and is sensitive to tissue microstructural changes. As dMRI becomes more sophisticated and microstructurally informative, it has become increasingly important to use a reference object (usually called an imaging phantom) for validation of dMRI. This study aims to develop axon-mimicking physical phantoms from biocopolymers and assess their feasibility for validating dMRI measurements.Approach. We employed a simple and one-step method-coaxial electrospinning-to prepare axon-mimicking hollow microfibres from polycaprolactone-b-polyethylene glycol (PCL-b-PEG) and poly(D, L-lactide-co-glycolic) acid (PLGA), and used them as building elements to create axon-mimicking phantoms. Electrospinning was firstly conducted using two types of PCL-b-PEG and two types of PLGA with different molecular weights in various solvents, with different polymer concentrations, for determining their spinnability. Polymer/solvent concentration combinations with good fibre spinnability were used as the shell material in the following co-electrospinning process in which the polyethylene oxide polymer was used as the core material. Following the microstructural characterization of both electrospun and co-electrospun fibres using optical and electron microscopy, two prototype phantoms were constructed from co-electrospun anisotropic hollow microfibres after inserting them into water-filled test tubes.Main results. Hollow microfibres that mimic the axon microstructure were successfully prepared from the appropriate core and shell material combinations. dMRI measurements of two phantoms on a 7 tesla (T) pre-clinical scanner revealed that diffusivity and anisotropy measurements are in the range of brain white matter.Significance. This feasibility study showed that co-electrospun PCL-b-PEG and PLGA microfibre-based axon-mimicking phantoms could be used in the validation of dMRI methods which seek to characterize white matter microstructure.
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Biomimética , Imagem de Difusão por Ressonância Magnética , Imagens de Fantasmas , Polímeros , Substância BrancaRESUMO
In this study, fluorinated polycaprolactone (PCL) block polymers with different fluorine contents were synthesized via atom transfer radical polymerization (ATRP). An electrospraying technique was used to prepare fluorinated PCL microspheres with different microstructures. In contrast to the golf ball shape of unmodified PCL microspheres displaying porous pits on the surface, block polymer PCL-PTFOA(2 h) and PCL-PTFOA(6 h) microsphere surfaces displayed regular honeycomb-like pore structures. Thermally induced and evaporation-induced phase separations are proposed as the main mechanisms involved in the formation of the porous microstructures. The micro-phase separation between the two blocks of the fluorinated PCL copolymer is another factor that promoted the uniform collapse on the microsphere surface and the formation of its rugged wall. The surface roughness of the porous microspheres significantly improved their hydrophobicity, generating coating contact angles on aluminium foil substrates that measured as high as 162.4 ± 1.5°, which revealed that the surfaces were super-hydrophobic. Lastly, cotton fabric was directly coated with the fluorinated polymer microspheres via electrospraying, resulting in super-hydrophobic surfaces and CAs reaching 160.0 ± 1.3°. The results demonstrate that electrospraying is a simple, innovative and cost-effective method for preparing polymer microspheres with controllable microstructures for fabric coating applications.
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Highly hydrophilic hollow polycaprolactone (PCL) microfibres were developed as building elements to create tissue-mimicking test objects (phantoms) for validation of diffusion magnetic resonance imaging (MRI). These microfibres were fabricated by the co-electrospinning of PCL-polysiloxane-based surfactant (PSi) mixture as shell and polyethylene oxide as core. The addition of PSi had a significant effect on the size of resultant electrospun fibres and the formation of hollow microfibres. The presence of PSi in both co-electrospun PCL microfibre surface and cross-section, revealed by X-ray energy dispersive spectroscopy (EDX), enabled water to wet these fibres completely (i.e., zero contact angle) and remained active for up to 12 months after immersing in water. PCL and PCL-PSi fibres with uniaxial orientation were constructed into water-filled phantoms. MR measurement revealed that water molecules diffuse anisotropically in the PCL-PSi phantom. Co-electrospun hollow PCL-PSi microfibres have desirable hydrophilic properties for the construction of a new generation of tissue-mimicking dMRI phantoms.
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A major block in the development of small diameter vascular grafts is achieving suitable blood vessel regeneration while minimizing the risk of thrombosis, intimal hyperplasia, suture retention, and mechanical failure. Silk-based tubular vessels for tissue engineering have been prepared by molding, dipping, electrospinning, or gel spinning, however, further studies are needed to improve the mechanical and blood compatibility properties. In the present study a bilayered vascular graft based on silk fibroin (SF) was developed. The graft was composed of an inner silk fiber-reinforced SF tube containing heparin and a highly porous SF external layer. Compared with previously fabricated SF tubes the fiber-reinforcement provided a comparable or higher mechanical strength, burst pressure, and suture retention strength, as well as mechanical compliance, to saphenous veins for vascular grafts. Heparin release was sustained for at least 1 month, affording blood compatibility to the grafts. The outer layer of the grafts prepared through lyophilization had a highly porous structure in which the macropore walls were composed of nanofibers similar to extracellular matrix, which offered an excellent environment for cell growth. In vitro studies showed good cytocompatibility and hemocompatibility.