Biodegradable Nanofiber/Metal-Organic Framework/Cotton Air Filtration Membranes Enabling Simultaneous Removal of Toxic Gases and Particulate Matter.

The typical filters that protect us from harmful components, such as toxic gases and particulate matter (PM), are made from petroleum-based materials, which need to be replaced with other environmentally friendly materials. Herein, we demonstrate a route to fabricate biodegradable and dual-functional filtration membranes that effectively remove PM and toxic gases. The membrane was integrated using two layers: (i) cellulose-based nanofibers for PM filtration and (ii) metal-organic framework (MOF)-coated cotton fabric for removal of toxic gases. Zeolitic imidazolate framework (ZIF-8) was grown from the surface of the cotton fabric by the treatment of cotton fabric with an organic precursor solution and subsequent immersion in an inorganic precursor solution. Cellulose acetate nanofibers (NFs) were deposited on the MOF-coated cotton fabric via electrospinning. At the optimal thickness of the NF layer, the quality factor of 18.8 × 10-2 Pa-1 was achieved with a filtration efficiency of 93.1%, air permeability of 19.0 cm3/cm2/s, and pressure drop of 14.2 Pa. The membrane exhibits outstanding gas adsorption efficiencies (>99%) for H2S, formaldehyde, and NH3. The resulting membrane was highly biodegradable, with a weight loss of 62.5% after 45 days under standard test conditions. The proposed strategy should provide highly sustainable material platforms for practical multifunctional membranes in personal protective equipment.

CuBTC Metal-Organic Framework Decorated with FeBTC Nanoparticles with Enhance Water Stability for Environmental Remediation Applications.

Metal-organic frameworks (MOFs) based on Cu-benzene tricarboxylate (CuBTC) are widely used for gas storage and removal applications. However, they readily lose their crystal structures under humid conditions, limiting their practical applications. This structural decomposition reduces the specific surface area, gas adsorption capability, and recyclability of CuBTC considerably. In this study, a stable MOF against water exposure was designed based on FeBTC nanoparticle-covered CuBTC (FeCuBTC). A simple one-pot solvothermal process that enables the epitaxial growth of FeBTC on the CuBTC surface was proposed. Structural and morphological analyses after water exposure revealed that the water stability of FeCuBTC was better than that of CuBTC, which completely lost its crystallinity. This observed improvement in the water stability of the synthesized MOF proved to be beneficial for the adsorption of formaldehyde under humid conditions. The proposed strategy herein is simple yet highly effective in the design of hetero-bimetallic MOFs with considerably improved water resistance and extended applicability for environmental remediation processes.

Reactive oxygen species scavenging nanofibers with chitosan-stabilized Prussian blue nanoparticles for enhanced wound healing efficacy.

Chronic inflammatory wounds pose therapeutic challenges in the biomedical field. Polymeric nanofibrous matrices provide extracellular-matrix-like structures to facilitate wound healing; however, wound infection and the subsequent accumulation of reactive oxygen species (ROS) delay healing. Therefore, we herein developed electrospun nanofibers (NFs), composed of chitosan-stabilized Prussian blue (PBChi) nanoparticles (NPs) and poly(vinyl alcohol) (PVA), with ROS scavenging activity to impart antioxidant and wound healing properties. The PBChi NPs were prepared using chitosan with different molecular weights, and their weight ratio with respect to PVA was optimized to yield PBChi-NP-coated PVA NFs with well-defined NF structures. In situ and in vitro antioxidant activity assays showed that the PBChi/PVA NFs could effectively remove ROS. Particularly, PBChi/PVA NFs with a lower chitosan molecular weight exhibited greater antioxidant activity. The hydroxyl radical scavenging activity of PBChi10k/PVA NFs was 60.4 %, approximately two-fold higher than that of PBChi100k/PVA NFs. Further, at the concentration of 10 µg/mL, they could significantly lower the in vitro ROS level by up to 50.7 %. The NFs caused no significant reduction in cell viability, owing to the excellent biocompatibility of PVA with PBChi NPs. Treatment using PBChi/PVA NFs led to faster cell proliferation in in vitro scratch wounds, reducing their size from 202 to 162 µm. The PBChi/PVA NFs possess notable antioxidant and cell proliferation properties as ROS-scavenging wound dressings.

Rational Process Design for Facile Fabrication of Dual Functional Hybrid Membrane of MOF and Electrospun Nanofiber towards High Removal Efficiency of PM2.5 and Toxic Gases.

The application of nanofiber (NF) and porous metal-organic framework (MOF) has increasingly attracted attention for the protection of public health. This composite platform provides the physical sieving of particulate matters (PMs) and capturing gases, serving as an outstanding filtering medium with lightweight and multifunctionality. Herein, process design and optimization are performed to produce a multifunctional membrane comprised NFs and MOF particles. Electrospinning/electrospray techniques are used to fabricate a hybrid membrane of poly(vinyl alcohol) NF and Fe-BTC as an adsorptive MOF on a macroporous nonwoven (NW). Three types of filters are prepared by varying the order of processing steps, that is, MOF/NF/NW, MOF+NF/NW, and NF/MOF/NW, to elucidate the effect of the fabrication process in the filtration of air pollutant. The optimal filtration performance is achieved in MOF+NF/NW system: the highest filtration efficiency (97%) and outstanding gas capturing efficiencies (≈60% and ≈35% decreases from initial NH3 and H2 S concentrations, respectively). However, when air permeability and filtration efficiency are considered, the most desirable configuration for personal protection equipment (PPE) is NF/MOF/NW system, which effectively enabled comfortable breathing without compromising the lightweight and multifunctional performance.

Coloration and Chromatic Sensing Behavior of Electrospun Cellulose Fibers with Curcumin.

The effective approach for coloration and chromatic sensing of electrospun cellulose fabrics with a natural colorant, curcumin, is demonstrated. To achieve high surface area, the morphology of fiber was controlled to have rough and porous surface through an electrospinning of a cellulose acetate (CA) solution under optimized electrospinning parameters and solvent system. The resulting CA fibers were treated with a curcumin dye/NaOH ethanol solution, in which deacetylation of the CA fiber and high-quality coloration with curcumin were simultaneously achieved. As a control, a cotton fiber with similar diameter and smooth surface morphology was treated by the same method, resulting in poor coloration quality. The difference can be attributed to high surface area as well as trapping of dye molecules inside of cellulose fiber during deacetylation. Both fibers were further utilized for a chromatic sensing application for specific toxic gases. The incorporated curcumin dye responded to hydrogen chloride and ammonia gases reversibly via keto-enol tautomerism, and, as a consequence, the color was reversibly changed between reddish-brown and yellow colors. The cellulose fiber fabricated by the electrospinning showed ten times higher and two times quicker responsiveness compared to curcumin-colored cotton fiber sample prepared with the same immersion method.

Electrospinning/Electrospray of Ferrocene Containing Copolymers to Fabricate ROS-Responsive Particles and Fibers.

We demonstrate an electrospray/electrospinning process to fabricate stimuli-responsive nanofibers or particles that can be utilized as stimuli-responsive drug-loaded materials. A series of random copolymers consisting of hydrophobic ferrocene monomers and hydrophilic carboxyl groups, namely poly(ferrocenylmethyl methacrylate-r-methacrylic acid) [poly(FMMA-r-MA)] with varied composition, was synthesized with free radical copolymerization. The morphologies of the resulting objects created by electrospray/electrospinning of the poly(FMMA-r-MA) solutions were effectively varied from particulate to fibrous structures by control of the composition, suggesting that the morphology of electrosprayed/electrospun copolymer objects was governed by its composition and hence, interaction with the solvent, highlighting the significance of the balance of hydrophilicity/hydrophobicity of the copolymer chain to the assembled structure. Resulting particles and nanofibers exhibited largely preserved responsiveness to reactive oxygen species (ROS) during the deposition process, opening up the potential to fabricate ROS-sensitive material with various desirable structures toward different applications.

Fabrication of ZnO Nanoparticle-Decorated Nanofiber Mat with High Uniformity Protected by Constructing Tri-Layer Structure.

We demonstrate a sequential electrospinning process involving the adsorption of ZnO nanoparticles on the surface of bio-based polyester, which is a terpolyester of a renewable isosorbide (ISB) monomer, ethylene glycol, 1,4-cyclohexane dimethanol, and terephthalic acid, the-so-called PEICT, to fabricate stable ZnO nanoparticles/PEICT nanofiber composite system protected with other two PEICT nanofiber mats. We found that post-electrospinning treatment with a particular solvent was effective to remove a residual solvent molecule in the PEICT nanofibers, which induced significant aggregation of the nanoparticles, leading to non-uniform distribution of the particles on the surface. Sequential electrospinning of the PEICT solution to sandwich ZnO nanoparticle-decorated PEICT nanofiber mat enabled to attain protected the inorganic/organic hybrid nanofiber mat, improving the long-term stability, and the reproducibility of the inorganic particles decorated nanofiber fabrication.

Recent Advances on Nanofiber Fabrications: Unconventional State-of-the-Art Spinning Techniques.

In this review, we describe recent relevant advances in the fabrication of polymeric nanofibers to address challenges in conventional approaches such as electrospinning, namely low throughput and productivity with low size uniformity, assembly with a regulated structure and even architecture, and location with desired alignments and orientations. The efforts discussed have mainly been devoted to realize novel apparatus designed to resolve individual issues that have arisen, i.e., eliminating ejection tips of spinnerets in a simple electrospinning system by effective control of an applied electric field and by using mechanical force, introducing a uniquely designed spinning apparatus including a solution ejection system and a collection system, and employing particular processes using a ferroelectric material and reactive precursors for atomic layer deposition. The impact of these advances to ultimately attain a fabrication technique to solve all the issues simultaneously is highlighted with regard to manufacturing high-quality nanofibers with high- throughput and eventually, practically implementing the nanofibers in cutting-edge applications on an industrial scale.

X-ray-Based Spectroscopic Techniques for Characterization of Polymer Nanocomposite Materials at a Molecular Level.

This review provides detailed fundamental principles of X-ray-based characterization methods, i.e., X-ray photoelectron spectroscopy, energy-dispersive X-ray spectroscopy, and near-edge X-ray absorption fine structure, and the development of different techniques based on the principles to gain deeper understandings of chemical structures in polymeric materials. Qualitative and quantitative analyses enable obtaining chemical compositions including the relative and absolute concentrations of specific elements and chemical bonds near the surface of or deep inside the material of interest. More importantly, these techniques help us to access the interface of a polymer and a solid material at a molecular level in a polymer nanocomposite. The collective interpretation of all this information leads us to a better understanding of why specific material properties can be modulated in composite geometry. Finally, we will highlight the impacts of the use of these spectroscopic methods in recent advances in polymer nanocomposite materials for various nano- and bio-applications.

Thiol-functionalized cellulose nanofiber membranes for the effective adsorption of heavy metal ions in water.

This work reports the fabrication of a thiol-functionalized cellulose nanofiber membrane that can effectively adsorb heavy metal ions. Thiol was incorporated onto the surface of cellulose nanofibers, which were fabricated by the deacetylation of electrospun cellulose acetate nanofibers and subsequent esterification of a thiol precursor molecule. Adsorption mechanism was investigated using adsorption isotherms. Adsorption capacity as a function of adsorbate concentration was described well with Langmuir isotherm, suggesting that metal ions form a surface monolayer with a homogenously distributed adsorption energy. Maximum adsorption capacities in the Langmuir isotherm for Cu(II), Cd(II), and Pb(II) ions were 49.0, 45.9, and 22.0 mg·g-1, respectively. The time-dependent adsorption capacities followed a pseudo-second-order kinetic model, suggesting that chemisorption of each doubly charged metal ion occurs with two thiol groups on the surface. These results highlight the significance of surface functionality on biocompatible, nontoxic, and sustainable cellulose materials to expand their potential and applicability towards water remediation applications.

Thiol-based chemistry as versatile routes for the effective functionalization of cellulose nanofibers.

We demonstrate effective functionalization chemistry for cellulose nanofiber modification using thiol functionality. Electrospun cellulose acetate nanofibers were deacetylated to obtain cellulose nanofibers, which were modified further to incorporate thiol on their surface by the esterification of hydroxyl groups with 3,3'-dithiodipropionic acid and further reductive cleavage of the disulfide bond. The thiol functionality was highly versatile to bring simple and efficient chemical reactions to attain (i) Ag nanoparticle-adsorbed cellulose nanofibers by Ag ion reduction at surface, (ii) various amine (primary amine and quaternary amine) functionalized cellulose nanofibers by Michael addition, and (iii) complex polymer functionalized cellulose nanofibers by a radical-based thiol-ene reaction, under mild conditions, i.e. in any reaction media, at room temperature, and under ambient atmosphere, evidenced by a variety of characterization methods including a quantitative analysis with X-ray photoemission spectroscopy. These scalable thiol-based chemistries should offer a new generation of well-tailored cellulose nanofiber materials with complex inorganic, organic, and polymeric functionalities, potentially expanding to functionalized surfaces of other carbohydrate-based materials to achieve the desired properties.

Tunichrome-inspired pyrogallol functionalized chitosan for tissue adhesion and hemostasis.

The nature-inspired fabrication of tissue adhesive and hemostatic hydrogels holds great potential for restoring damaged internal tissue in regenerative medicine. However, feeble adhesion, multifaceted systems, prohibitive costs, and toxicity impede their applications in the medical field. In order to solve this problem, we fabricated chitosan-based wet tissue adhesive with hemostatic functions inspired by the self-healing mechanism of the tunicate. In order to introduce pyrogallol moiety, gallic acids, which are broadly distributed in nature, were incorporated into chitosan backbone, a key residue for the self-healing process of tunichrome in tunicates. The in vitro adhesion test results of the tunicate-inspired hydrogel exhibited two-fold greater adhesion ability in wet condition than did fibrin glue, a commercially available surgical glue. Further, the tunicate-inspired hydrogel exhibited significantly more platelet adhesion and blood clotting ability than the parent polymer. We also demonstrated the ability of the derivative to completely mimic the tunicate's fibrous structure by fabricating an electrospun mat. The hemostatic function vis-à-vis the wet adhesiveness of the synthesized chitosan-based material may be useful for facilitating the shortcomings of the restorative tissue medicine. Additionally, the electrospinning capability will enable the modulate of the structure-property relationship and a three-dimensional design for its application site.

Readily Functionalizable and Stabilizable Polymeric Particles with Controlled Size and Morphology by Electrospray.

Electrospraying is an effective and facile technique for the production of micro- or nanoparticles with tailored sizes, shapes, morphologies, and microstructures. We synthesized functionalizable poly(styrene-random-glycidyl methacrylate) copolymers and used them to fabricate microparticles via the electrospray technique. The sizes and morphologies of the electrosprayed particles are controlled by altering the process parameters (feed rate and applied voltage), and the composition and thermodynamic properties of the polymer (i.e., compatibility of the polymer with the solvent). We further investigated modifying the surfaces of the electrosprayed particles with 3-mercaptopropionic acid by a simple and efficient thiol-epoxy "click" reaction as a proof-of-concept demonstration that desired functionality can be introduced onto the surfaces of these particles; the outcome was confirmed by various spectroscopic techniques. In addition, the epoxides within the particles easily undergo crosslinking reactions, enabling further effective particle stabilization. The results reveal that the structure and properties of the polymer can be used to fine-tune the structural parameters of the electrosprayed particles, such as their sizes and morphologies, which opens up the possibility of imparting a variety of desired chemical functionalities into the structures of stable organic materials via post-electrospray modification processes.

Fabrication of Two Polyester Nanofiber Types Containing the Biobased Monomer Isosorbide: Poly (Ethylene Glycol 1,4-Cyclohexane Dimethylene Isosorbide Terephthalate) and Poly (1,4-Cyclohexane Dimethylene Isosorbide Terephthalate).

The thermal and mechanical properties of two types of polyester nanofiber, poly (1,4-cyclohexanedimethylene isosorbide terephthalate) (PICT) copolymers and the terpolyester of isosorbide, ethylene glycol, 1,4-cyclohexane dimethanol, and terephthalic acid (PEICT), were investigated. This is the first attempt to fabricate PICT nanofiber via the electrospinning method; comparison with PEICT nanofiber could give greater understanding of eco-friendly nanofibers containing biomass monomers. The nanofibers fabricated from each polymer show similar smooth and thin-and-long morphologies. On the other hand, the polymers exhibited significantly different mechanical and thermal properties; in particular, a higher tensile strength was observed for PICT nanofiber mat than for that of PEICT. We hypothesized that PICT has more trans-configuration than PEICT, resulting in enhancement of its tensile strength, and demonstrated this by Fourier transform infrared spectroscopy. In addition, PICT nanofibers showed clear crystallization behavior upon increased temperature, while PEICT nanofibers showed completely amorphous structure. Both nanofibers have better tensile properties and thermal stability than the typical polyester polymer, implying that they can be utilized in various industrial applications.

Effective Formation of Well-Defined Polymeric Microfibers and Nanofibers with Exceptional Uniformity by Simple Mechanical Needle Spinning.

The fabrication of nanofibers with a mechanical force has attracted increasing attention owing to its facile and easy fabrication. Herein, we demonstrate a novel and facile fabrication technique with the mechanical force, needle spinning, which utilizes a needle tip to draw a polymer solution to form fibrous structures. We studied the effect of the processing parameters to the nanofiber structure, namely, the pulling away speed, pulling away distances, needle size, and polymer concentration, which were systemically controlled. As the needle spinning provides an effective route to adjust those parameters, highly uniform nanofibers can be achieved. There are clear tendencies in the diameter; it was increased as the polymer concentration and needle size were increased, and was decreased as the pulling away distance and pulling away speed were increased. Needle spinning with a precise control of the processing parameter enables us to readily fabricate well-defined nanofibers, with controlled dimensions in diameter and length; plus, single nanofibers also can be easily formed. Those features cannot be realized in common spinning process such as electrospinning. Therefore, this technique will lead to further development of the use of mechanical force for nanofiber fabrication and will expand the range of nanofibers applications.

Antibacterial efficacy of poly(vinyl alcohol) composite nanofibers embedded with silver-anchored silica nanoparticles.

Silver has been widely used as an effective antibacterial agent especially for treating burns and wounds. However, release of silver from materials often arouse side effects due to toxicity of silver towards mammalian cells. Argyria and argyrosis are well known problems of acute toxicity of silver towards human body. Immobilization of silver is an effective approach to reduce silver release. Herein, we present poly(vinyl alcohol) (PVA) composite nanofibers embedded with silver-anchored silica nanoparticles (SSNs) as a novel antibacterial material. Silver nanoparticles anchored on silica nanoparticles were prepared and incorporated into PVA nanofibers to fabricate silver-silica embedded PVA nanofibers (SSN-PVA) by electrospinning. Incorporation of SSNs into PVA was confirmed by TEM and SEM results revealed regular nanofibers whose diameter increased with successive addition of SSNs. The SSN-PVA nanofibers showed significant antibacterial efficacy against both Gram-negative and Gram-positive bacteria. Our research results demonstrated SSN-embedded polymeric nanofibers can open up a promising prospect for the prevention of bacterial infection in diverse biomedical fields including wound dressing. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 106B: 1121-1128, 2018.

Fabrication and characterization of nanofibers of honey/poly(1,4-cyclohexane dimethylene isosorbide trephthalate) by electrospinning.

We report the fabrication of novel nanofibers using naturally occurring antimicrobial honey incorporated in poly(1,4-cyclohexane dimethylene isosorbide trephthalate) (PICT) for the potential wound dressing applications. We fabricated PICT/honey using three blend ratios 90:10, 85:15 and 80:20 respectively. Morphology of PICT nanofibers and PICT/honey nanofibers was observed under Scanning Electron Microscope and it showed bead-free nanofibers. Fourier Transform Infrared Spectroscope was used to confirm the presence of honey in PICT electrospun nanofibers. Tensile strength of PICT/honey nanofibers was slightly reduced with variation in effect of elongation. Water contact angle measurements were done with the static contact angle by a contact angle meter, which showed that hydrophobicity was decreased by adding the honey. The XPS spectra showed that honey was present in the PICT/honey nanofibers. The release behavior of honey was investigated by UV-visible Spectrophotometer. The release was complete in 15min and the maximum release of honey was 72mg/L in 10min. Therefore, PICT/honey nanofibers having 15% concentration of honey are suitable for good elastic behavior and tensile strength as compared to other concentrations of honey.

Electrospun tri-layered zein/PVP-GO/zein nanofiber mats for providing biphasic drug release profiles.

Simple sequential electrospinning was utilized to create a functional tri-layered nanofiber mesh that achieves time-regulated biphasic drug release behavior. A tri-layered nanofiber mesh -composed of zein and poly(vinylpyrrolidone) (PVP) as the top/bottom and middle layers, respectively - was constructed through sequential electrospinning with ketoprofen (KET) as the model drug. PVP was blended with graphene oxide (GO) to improve the drug release functionality of PVP nanofiber as well as its mechanical properties. Scanning electron microscopy confirmed that the resultant nanofibers had a linear morphology, smooth surface, and tri-layered structure. In addition, X-ray diffraction patterns, differential scanning calorimetric analyses, and Fourier transform infrared spectra verified that the drugs were uniformly dispersed throughout the nanofiber due to good compatibility between the polymer and KET induced by hydrogen interaction. In vitro release test of the tri-layered structure, each component of which had distinct release features, successfully demonstrated time-regulated biphasic drug release. Also, it was confirmed that the drug release rate and duration can be controlled by designing a morphological feature - namely, mesh thickness - which was achieved by simply regulating the spinning time of the first and third layer. This multilayered electrospun nanofiber mesh fabricated by sequential electrospinning could provide a useful method of controlling drug release behavior over time, which will open new routes for practical applications and stimulate further research in the development of effective drug release carriers.

Dyeing and characterization of regenerated cellulose nanofibers with vat dyes.

Recent advancement in dyeing of nanofibers has been accelerated to improve their aesthetic properties, however, achieving good color fastness remains a challenge. Therefore, we attempt to improve the color fastness properties nanofibers. Vat dyes are known for better color fastness and their application on nanofibers has not been investigated to date. Herein, we report dyeing of regenerated cellulose nanofibers (RCNF) that were produced from precursor of cellulose acetate (CA) followed by deacetylation process. The resultant RCNF was dyed with two different vat dyes and the color attributes were examined under spectrophotometer which showed outstanding color build-up. Morphological of CA before and after deacetylation and before and after vat dyeing was investigated under TEM, FE-SEM and SEM respectively. The vat dyed RCNF were further characterized by FTIR and WAXD. Excellent color fastness results demonstrate that vat dyed RCNF can potentially be considered for advanced apparel applications.

Enhanced Wettability and Thermal Stability of a Novel Polyethylene Terephthalate-Based Poly(Vinylidene Fluoride) Nanofiber Hybrid Membrane for the Separator of Lithium-Ion Batteries.

In this study, a novel membrane for the separator in a lithium-ion (Li-ion) battery was proposed via a mechanically pressed process with a poly(vinylidene fluoride) (PVDF) nanofiber subject and polyethylene terephthalate (PET) microfiber support. Important physical properties, such as surface morphology, wettability, and heat stability were considered for the PET-reinforced PVDF nanofiber (PRPN) hybrid separator. Images of scanning electron microscopy (SEM) showed that the PRPN hybrid separator had a homogeneous pore size and high porosity. It can wet out in battery electrolytes completely and quickly, satisfying wettability requirements. Moreover, the electrolyte uptake was higher than that of dry-laid and wet-laid nonwovens. For heat stability, no shrink occurred even when the heating temperature reached 135 °C, demonstrating thermal and dimensional stability. Moreover, differential scanning calorimetry (DSC) showed that the PRPN hybrid separator possessed a shutdown temperature of 131 °C, which is the same as conventional separators. Also, the meltdown temperature reached 252 °C, which is higher than the shutdown temperature, and thus can protect against internal cell shorts. The proposed PRPN hybrid separator is a strong candidate material for utilization in Li-ion batteries.