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Passerini polymerization using naturally occurring α-lipoic acid as a raw material yields polyamides with 1,2-dithiolane functional groups in a one-step reaction. The polyamide exhibits characteristics of an adaptable dynamically crosslinked network through reversible ring-opening reaction of 1,2-dithiolane, enabling self-healing, reusable strong adhesion, and regeneration through decrosslinking and re-crosslinking.
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Nanofibers are some of the most attractive materials that can modify functionalities for developing new kinds of specific applications and are mainly used as a biomedical material. Herein, we designed and prepared antibacterial nonwoven fiber mats of PLA and PLA composited with Ag nanoparticles by electrospinning. The effects of varying filler contents on their chemical, surface morphology, thermal, water absorbency, and antibacterial properties were investigated using FTIR, SEM/EDS, DSC, swelling ratio, and qualitative and quantitative antibacterial tests. FTIR and EDS spectra indicated that Ag nanoparticles were incorporated in the PLA without chemical bonding. SEM revealed that the average diameter of the PLA nanofibers containing the Ag nanoparticles was more significant than those without those particles. In addition, fiber diameters are proportional to the amount of Ag nanoparticle contents. DSC indicated that the Ag nanoparticles can be incorporated within the PLA matrix without strongly affecting their thermal properties. Moreover, the crystallinity of the composite nonwoven fiber mats was higher than those of fiber mats in the neat PLA. However, TGA revealed that the loaded Ag can improve the thermal stability of the PLA electrospun fiber mats. Accordingly, the antibacterial activities revealed that all the composite nanofiber mats exhibited excellent resistance against S. aureus and E. coli bacterial strains. In addition, in the cell toxicity study, all produced hybrids of nonwoven fiber mats induced a reduction in cell viability for the L929 fibroblast cells. Our results suggest that the designed and prepared nonwoven fiber mats may have good potential for use in the biomedical field, particularly in wound dressing applications.
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Due to their diverse and unique physical properties, miktoarm star copolymers (µ-SCPs) have garnered significant attention. In our study, we employed α-monobomoisobutyryl-terminated polydimethylsiloxane (PDMS-Br) to carry out styrenics-assisted atom transfer radical coupling (SA ATRC) in the presence of 4-vinylbenzyl alcohol (VBA) at 0 °C. By achieving high coupling efficiency (χc = 0.95), we obtained mid-chain functionalized PDMS-VBAm-PDMS polymers with benzylic alcohols. Interestingly, matrix-assisted laser desorption/ionization time of flight mass spectrometry (MALDI-TOF MS) analysis revealed the insertion of only two VBA coupling agents (m = 2). Subsequently, the PDMS-VBA2-PDMS products underwent mid-chain extensions using ε-caprolactone (ε-CL) through ring-opening polymerization (ROP) with an efficient organo-catalyst at 40 °C, resulting in the synthesis of novel (PDMS)2-µ-(PCL)2 µ-SCPs. Eventually, novel (PDMS)2-µ-(PCL)2 µ-SCPs were obtained. The obtained PDMS-µ-PCL µ-SCPs were further subjected to examination of their solid-state self-assembly through small-angle X-ray scattering (SAXS) experiments. Notably, various nanostructures, including lamellae and hexagonally packed cylinders, were observed with a periodic size of approximately 15 nm. As a result, we successfully developed a simple and effective reaction combination (Ð) strategy (i.e., SA ATRC-Ð-ROP) for the synthesis of well-defined PDMS-µ-PCL µ-SCPs. This approach may open up new possibilities for fabricating nanostructures from siloxane-based materials.
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A simple and compact intensity-interrogated terahertz (THz) relative humidity (RH) sensing platform is successfully demonstrated in experiments on the basis of combining a porous polymer sensing membrane and a continuous THz electronic system. The RH-sensing membrane is fabricated by surface modification of a porous polymer substrate with hydrophilic and photosensitive copolymer brushes via a UV-induced graft-polymerization process. The intensity interrogation sensing scheme indicated that the power reduction of the 0.4 THz wave is dependent on the grafting density of the copolymer brushes and proportional to the RH percent levels in the humidity-controlled air-sealed chamber. This finding was verified by the water contact angle measurement. Based on the slope of the proportional relation, the best sensitivity of the hydrophilic surface-modified sensing membrane was demonstrated at 0.0423 mV/% RH at the copolymer brush density of 1.57 mg/mm3 grafted on the single side of the sensing membrane. The sensitivity corresponds to a detection limit of approximately 1% RH. The THz RH sensing membrane was proven to exhibit the advantages of low loss, low cost, flexibility, high sensitivity, high RH resolution, and a wide RH working range of 25-99%. Thus, it is a good candidate for novel applications of wearable electronics, water- or moisture-related industrial and bio-sensing.
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Terahertz (THz) plasmonic metamaterial, based on a metal-wire-woven hole array (MWW-HA), is investigated for the distinct power depletion in the transmittance spectrum of 0.1-2 THz, including the reflected waves from metal holes and woven metal wires. Woven metal wires have four orders of power depletion, which perform sharp dips in a transmittance spectrum. However, only the first-order dip at the metal-hole-reflection band dominates specular reflection with a phase retardation of approximately π. The optical path length and metal surface conductivity are modified to study MWW-HA specular reflection. This experimental modification shows that the first order of MWW-HA power depletion is sustainable and sensitively correlated with a bending angle of the woven metal wire. Specularly reflected THz waves are successfully presented in hollow-core pipe wave guidance specified from MWW-HA pipe wall reflectivity.
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A hole array was fabricated via photolithography to wet the bottoms of holes using oxygen plasma. Amide-terminated silane, a water immiscible compound before hydrolysis, was evaporated for deposition on the plasma-treated hole template surface. The silane compound was hydrolyzed along the edges of circular sides of the hole bottom to form a ring of an initiator after halogenation. Poly(methacrylic acid) (PMAA) was grafted from the ring of the initiator to attract Ag clusters (AgCs) as AgC-PMAA hybrid ring (SPHR) arrays via alternate phase transition cycles. The SPHR arrays were modified with a Yersinia pestis antibody (abY) to detect the antigen of Yersinia pestis (agY) for plague diagnosis. The binding of the agY onto the abY-anchored SPHR array resulted in a geometrical change from a ring to a two-humped structure. The reflectance spectra could be used to analyze the AgC attachment and the agY binding onto the abY-anchored SPHR array. The linear range between the wavelength shift and agY concentration from 30 to 270 pg mL-1 was established to obtain the detection limit of ~12.3 pg mL-1. Our proposed method provides a novel pathway to efficiently fabricate a ring array with a scale of less than 100 nm, which demonstrates excellent performance in preclinical trials.
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Chitosan is a naturally derived biodegradable polymer with abundancy, sustainability, and ease of chemical modification. Polyurethanes are a family of elastic biocompatible polymers, and composites of polyurethanes have versatile properties and applications. Chitosan-polyurethane composites were recently developed but had insufficient strength and limited stretchability. In the current study, cellulose nanofibers (CNFs) were integrated in chitosan-polyurethane composites to prepare stretchable and anisotropic materials. A biodegradable polyurethane was first synthesized, end-capped with aldehyde to become dialdehyde polyurethane (DP) nanoparticles, and added with CNFs to prepare the DP-CNF composite crosslinker (DPF). The waterborne DPF crosslinker was then blended with chitosan solution to make polyurethane-CNF-chitosan (DPFC) composites. After blending, DPFC may form hydrogel in ~33 min at room temperature, which confirmed crosslinking. Composite films cast and dried from the blends showed good elongation (~420.2 %) at 60 °C. Anisotropic films were then generated by tension annealing with pre-strain. The annealed films with 200 % pre-strain exhibited large elastic anisotropy with ~4.9 anisotropic ratio. In situ SAXS/WAXS analyses unveiled that rearrangement and alignment of the microstructure during tension annealing accounted for the anisotropy. The anisotropic composite films had the ability to orient the growth of neural stem cells and showed the potential for biomimetic and tissue engineering applications.
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Quitosano , Nanofibras , Nanofibras/química , Quitosano/química , Celulosa/química , Poliuretanos/química , Anisotropía , Dispersión del Ángulo Pequeño , Difracción de Rayos X , PolímerosRESUMEN
A series of di-functional benzoxazine (BZ) monomers was synthesized, specifically the double-decker silsesquioxane (DDSQ) cage structure (DDSQ-BZ). Comparative analyses were conducted between DDSQ-BZ monomers and the most commonly utilized bisphenol A-functionalized bifunctional benzoxazine (BPA-BZ) monomer. DDSQ-BZ compounds possess better thermal properties such as high char yield and high thermal decomposition temperature (Td10) after thermal ring-opening polymerization (ROP) because the inorganic DDSQ cage nanostructure features a nano-reinforcement effect. In addition, blending inorganic DDSQ-BZ compounds with epoxy resin was explored to form organic/inorganic hybrids with enhanced thermal and mechanical properties following thermal ROP. The improvement in mechanical properties is primarily attributed to the network structure formed by the cross-linking between DDSQ-BZ and the epoxy resin during thermal ROP, as well as hydrogen bonding interactions formed between the hydroxyl groups generated during thermal ROP and the Si-O-Si bonds in the DDSQ structure.
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This research focuses on the mechanical properties of polypropylene (PP) blended with recycled PP (rPP) at various concentrations. The rPP can be added at up to 40 wt% into the PP matrix without significantly affecting the mechanical properties. MFI of blended PP increased with increasing rPP content. Modulus and tensile strength of PP slightly decreased with increased rPP content, while the elongation at break increased to up to 30.68% with a 40 wt% increase in rPP content. This is probably caused by the interfacial adhesion of PP and rPP during the blending process. The electrical conductivity of materials was improved by adding carbon black into the rPP matrices. It has a significant effect on the mechanical and electrical properties of the composites. Stress-strain curves of composites changed from ductile to brittle behaviors. This could be caused by the poor interfacial interaction between rPP and carbon black. FTIR spectra indicate that carbon black did not have any chemical reactions with the PP chains. The obtained composites exhibited good performance in the electrical properties tested. Finally, DSC results showed that rPP and carbon black could act as nucleating agents and thus increase the degree of crystallinity of PP.
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In this study, we synthesized three hybrid microporous polymers through Heck couplings of octavinylsilsesquioxane (OVS) with 2,5-bis(4-bromophenyl)-1,3,4-oxadiazole (OXD-Br2), tetrabromothiophene (Th-Br4), and 2,5-bis(4-bromophenyl)-3,4-diphenylthiophene (TPTh-Br2), obtaining the porous organic-inorganic polymers (POIPs) POSS-OXD, POSS-Th, and POSS-TPTh, respectively. Fourier transform infrared spectroscopy and solid state 13C and 29Si NMR spectroscopy confirmed their chemical structures. Thermogravimetric analysis revealed that, among these three systems, the POSS-Th POIP possessed the highest thermal stability (T5: 586 °C; T10: 785 °C; char yield: 90 wt%), presumably because of a strongly crosslinked network formed between its OVS and Th moieties. Furthermore, the specific capacity of the POSS-TPTh POIP (354 F g-1) at 0.5 A g-1 was higher than those of the POSS-Th (213 F g-1) and POSS-OXD (119 F g-1) POIPs. We attribute the superior electrochemical properties of the POSS-TPTh POIP to its high surface area and the presence of electron-rich phenyl groups within its structure.
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We conducted Passerini-type multicomponent polymerizations (P-MCPs) with various monomers and afforded a series of functional poly(carbamoyl ester)s (PCEs). We demonstrated an efficient, diverse, and facile approach through P-MCPs to produce these novel PCEs with dual-cleavable linkages of ester and disulfide groups and the aggregation-induced emission (AIE) luminogen tetraphenylethylene (TPE).
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Nanopartículas , Polímeros , Polimerizacion , ÉsteresRESUMEN
Cellulose nanofibers functionalized with multiple aldehyde group were synthesized as the crosslinker to produce composite self-healing hydrogel and shape memory cryogel from chitosan. The hydrogel possessed effective self-healing (â¼100% efficiency) and shear-thinning properties. The cryogel had macroporous structure, large water absorption (>4300%), and high compressibility. Both hydrogel and cryogel were injectable. In particular, the cryogel (nanocellulose/chitosan 1:6) revealed thermally induced shape memory, the mechanism of which was elucidated by in situ small-angle X-ray scattering (SAXS) and wide-angle X-ray scattering (WAXS) as changes in orientation of the induced crystalline structure during the shape memory program. The shape memory cryogel with a large size (15 mm × 10 mm × 1.1 mm) injected through a 16 G syringe needle was recoverable in 37 °C water. Moreover, the cryogel was cytocompatible and promoted cell growth. The nanocellulose-chitosan composite hydrogel and cryogel are injectable and degradable biomaterials with adjustable mechanical properties for potential medical applications.
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Quitosano , Nanofibras , Celulosa/química , Quitosano/química , Criogeles/química , Hidrogeles/química , Nanofibras/química , Dispersión del Ángulo Pequeño , Agua/química , Difracción de Rayos XRESUMEN
As bromate removal and reduction can be also achieved using metals, aluminum (Al) appears as the most promising one for reduction of bromate because Al is abundant element and exhibits a high reduction power. Reactions between bromate and Al shall be even enhanced through ultrasound (US) process because US can facilitate mass transfer on liquid/solid interfaces and clean surfaces via generating microscale turbulence to facilitate reactions. Therefore, the aim of this study is for the first time to investigate the effect of US on bromate removal by Al metal. Specifically, Al particle would be treated by HCl to afford HCl-treated Al (HCTAL), which is capable of removing bromate and even reducing it to bromide. Such a mechanism is also validated by density function theory calculation through determining adsorption energy as -152.8 kJ/mole, and oxygen atoms of bromate would be extracted and reacted with Al atoms, releasing bromide ion. US not only facilitated bromate removal by further increasing removal capacity under the acidic condition but also suppressed the inhibitive effect from basicity at relatively high pH. The spent HCTAL could still remove bromate and convert it to bromide after regeneration. These features indicate that US considerably enhances bromate removal by Al. PRACTITIONER POINTS: Bromate removed by Al is elucidated by DFT calculation with Eabsorption = -152.8 kJ/mole. Oxygen atoms of bromate are extracted and reacted with Al atoms, releasing bromide ion. A higher power of ultrasound would substantially enhance bromate removal efficiency. Ultrasound also suppresses the inhibitive effect from basicity at relatively high pH. With ultrasound, the interference of co-existing anions on bromate removal is lessened.
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Contaminantes Químicos del Agua , Purificación del Agua , Aluminio , Bromatos , Bromuros , Desinfección , Oxígeno , Agua , Contaminantes Químicos del Agua/análisisRESUMEN
Applications of cellulose nanofibers currently match the demands of biodegradable and renewable constituent biocomposites. In this study, we studied the process of preparing TEMPO-oxidized cellulose nanofibers (TOCNs). These nano-sized cellulose fibers (ca. 11 nm) can be fabricated to high transmittance and optically transparent paper (OP) films. Then the OP films can be facilely immobilized initiating sites for the subsequent surface-initiated atom transfer radical polymerization (SI ATRP). We investigated SI ATRP with styrene (St) kinetics and monitored chemical structure changes of the OP surfaces. The obtained OP-g-PSt significantly led to enhance thermal stability and alter the OP surface with hydrophobic compared to that of pristine OP film. Characterization was studied by Fourier transform infrared spectroscopy (FT-IR), powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), UV-Vis spectroscopy, thermogravimetric analyzer (TGA), and water contact angle (WCA) measurements.
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Functionalities of 3D printing filaments have gained much attention owing to their properties for various applications in the last few years. Innovative biocomposite 3D printing filaments based on polylactic acid (PLA) composited with ZnO nanoflowers at varying contents were successfully fabricated via a single-screw extrusion technique. The effects of the varying ZnO nanoflower contents on their chemical, thermal, mechanical, and antibacterial properties were investigated using Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and tensile testing, as well as qualitative and quantitative antibacterial tests, respectively. It was found that the ZnO nanoflowers did not express any chemical reactions with the PLA chains. The degrees of the crystallinity of the PLA/ZnO biocomposite filaments increased when compared with those of the neat PLA, and their properties slightly decreased when increasing the ZnO nanoflower contents. Additionally, the tensile strength of the PLA/ZnO biocomposite filaments gradually decreased when increasing the ZnO nanoflower contents. The antibacterial activity especially increased when increasing the ZnO nanoflower contents. Additionally, these 3D printing filaments performed better against Gram-positive (S. aureus) than Gram-negative (E. coli). This is probably due to the difference in the cell walls of the bacterial strains. The results indicated that these 3D printing filaments could be utilized for 3D printing and applied to medical fields.
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Gelatin was immobilized selectively on the amide groups-modified bottom of a trench array of a photoresist template with 2 µm resolution by the ethyl(dimethylaminopropyl) carbodiimide/N-hydroxysuccinimide reaction. The gelatin-immobilized line array was brominated to generate a macroinitiator for atom transfer radical polymerization. Poly(methacrylic acid) (PMAA) brushes were grafted from the macroinitiator layer as line arrays of one-dimensional diffraction gratings (DGs) for various grafting polymerization times. A laser beam system was employed to analyze the optical feature with a characteristic diffraction effect of the PMAA DGs at a 45° incident angle along the transverse magnetic and transverse electric polarization. The growth of the PMAA brush lines increased both their heights and widths, leading to a change in the reflective diffraction intensity. The PMAA brushes under various grafting polymerization times were cleaved from the substrate by digestion of gelatin with trypsin, and their molecular weights were obtained by gel permeation chromatography. The change degree of the diffraction intensity varied linearly with the molecular weight of the PMAA brushes over a wide range, from 135 to 1475 kDa, with high correlation coefficients. Molecular weight determination of polymer brushes using the reflective diffraction intensity provides a simple method to monitor their growth in real time without polymer brush cleavage.
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The dual-functional Bi2WO6/polydopamine (PDA)-modified gauze membrane has been developed for applications in photocatalytic degradation and solar steam generation. Two types of membrane were prepared by changing the growth sequence of Bi2WO6 nanomaterials and PDA on gauze substrates. The spatial distribution of Bi2WO6 and polydopamine has a great influence on light absorption, photocatalytic degradation, and solar steam generation performances. Bi2WO6 photocatalysts can absorb short-wavelength light for the photocatalytic decoloration of organic dyes. The photothermal polydopamine can convert light into heat for water evaporation. Besides, the gauze substrate provides water transport channels to facilitate water evaporation. The morphology, surface chemistry, and optical properties of Bi2WO6-PDA modified gauzes were characterized by scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and diffuse reflectance spectra. The photothermal properties, wetting properties, and solar steam generation rates of the composite films were also studied. Degradation of 96% of indigo carmine was achieved after being irradiated for 120 min in the presence of G/PDA/BWNP. The water evaporation rates of the G/BWP/PDA sample under the irradiation of an Xe lamp (light intensity = 1000 W/m2) reached 1.94 kg·m-2·h-1.
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Reversible-deactivation radical polymerization (RDRP) serves as a powerful tool nowadays for the preparations of unique linear and non-linear macromolecules. In this study, enhanced spin capturing polymerizations (ESCPs) of styrene (St) and tert-butyl acrylate (tBA) monomers were, respectively, conducted in the presence of difunctional (1Z,1'Z)-1,1'-(1,4-phenylene) bis (N-tert-butylmethanimine oxide) (PBBN) nitrone. Four-arm (PSt)4 and (PtBA)4 star macroinitiators (MIs) can be afforded. By correspondingly switching the second monomer (i.e., tBA and St), miktoarm star copolymers (µ-stars) of (PSt)2-µ-(PtBA-b-PSt)2 and (PtBA)2-µ-(PSt-b-PtBA)2) were thus obtained. We further conducted hydrolysis of the PtBA segments to PAA (i.e., poly(acrylic acid)) in µ-stars to afford amphiphilic µ-stars of (PSt)2-µ-(PAA-b-PSt)2 and (PAA)2-µ-(PSt-b-PAA)2. We investigated each polymerization step and characterized the obtained two sets of "sequence-isomeric" µ-stars by FT-IR, 1H NMR, differential scanning calorimeter (DSC), and thermogravimetric analysis (TGA). Interestingly, we identified their physical property differences in the case of amphiphilic µ-stars by water contact angle (WCA) and atomic force microscopy (AFM) measurements. We thus proposed two microstructures caused by the difference of polymer chain sequences. Through this polymerization transformation (T) approach (i.e., ESCP-T-NMP), we demonstrated an interesting and facile strategy for the preparations of µ-stars with adjustable/switchable interior and exterior polymer structures toward the preparations of various nanomaterials.
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Concentrated polymer brushes (CPBs) and semi-dilute polymer brushes (SDPBs) of poly(2-hydroxyethyl methacrylate), poly(2-hydroxyethyl acrylate), poly[poly(ethylene glycol)methyl ether methacrylate] (PPEGMA) and poly(2-methoxyetyl acrylate) were prepared on silica particles and silicon wafers by surface-initiated atom transfer radical polymerization (SI-ATRP). In order to evaluate in vitro blood compatibility, plasma protein adsorption on the brushes was quantified with a BCA protein assay, and the adsorbed proteins on the brushes were identified using high-performance liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). All four CPBs displayed much less protein adsorption than their corresponding SDPBs. Interestingly, the number and type of identified proteins differed on the brushes. Platelet adhesion was then examined on the brushes, whereby CPBs suppressed platelet adhesion to a greater extent than the corresponding SDPBs, although platelet activation was observed on all surfaces. As a result, the CPBs of PPEGMA prevented platelet adhesion the most. After screening the polymers by in vitro evaluation, CPBs of PPEGMA were then grafted on a catheter by SI-ATRP. The catheter with the CPBs was implanted into the jugular vein of a rabbit. The in vivo assessment after three weeks of implantation confirmed that the CPBs caused little coagulation or inflammation, whereas the pristine catheter exhibited inflammation and encapsulation.
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Proteínas Sanguíneas/efectos de los fármacos , Polímeros/farmacología , Adsorción , Animales , Humanos , Masculino , Adhesividad Plaquetaria/efectos de los fármacos , Polímeros/síntesis química , Polímeros/química , ConejosRESUMEN
Transmembrane serine protease (TMPRSS2) plays an oncogenic role in prostate cancer as the fusion gene with ERG, and has also been demonstrated to be essential for the cellular entry of severe acute respiratory syndrome coronaviruses (SARS-CoV). Thus, targeting TMPRSS2 is a promising strategy for therapies against both prostate cancer and coronavirus infection. Although Nafamostat and Camostat have been identified as TMPRSS2 inhibitors, severe side effects such as cerebral hemorrhage, anaphylactoid reaction, and cardiac arrest shock greatly hamper their clinical use. Therefore, more potent and safer drugs against this serine protease should be further developed. In this study, we developed a fluorescence resonance energy transfer (FRET)-based platform for effectively screening of inhibitors against TMPRSS2 protease activity. The disruption of FRET between green and red fluorescent proteins conjugated with the substrate peptide, which corresponds to the cleavage site of SARS-CoV-2 Spike protein, was measured to determine the enzymatic activity of TMPRSS2. Through an initiate pilot screening with around 100 compounds, Flupirtine, a selective neuronal potassium channel opener, was identified as a potential TMPRSS2 inhibitor from an FDA-approved drug library by using this screening platform, and showed inhibitory effect on the TMPRSS-dependent infection of SARS-CoV-2 Spike-pseudotyped lentiviral particles. This study describes a platform proven effective for rapidly screening of TMPRSS2 inhibitors, and suggests that Flupirtine may be worthy of further consideration of repurposing to treat COVID-19 patients.