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Interfacial polymerization (IP) and self-assembly are two thermodynamically different processes involving an interface in their systems. When the two systems are incorporated, the interface will exhibit extraordinary characteristics and generate structural and morphological transformation. In this work, an ultrapermeable polyamide (PA) reverse osmosis (RO) membrane with crumpled surface morphology and enlarged free volume was fabricated via IP reaction with the introduction of self-assembled surfactant micellar system. The mechanisms of the formation of crumpled nanostructures were elucidated via multiscale simulations. The electrostatic interactions among m-phenylenediamine (MPD) molecules, surfactant monolayer and micelles, lead to disruption of the monolayer at the interface, which in turn shapes the initial pattern formation of the PA layer. The interfacial instability brought about by these molecular interactions promotes the formation of crumpled PA layer with larger effective surface area, facilitating the enhanced water transport. This work provides valuable insights into the mechanisms of the IP process and is fundamental for exploring high-performance desalination membranes.
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Separating oil from water allows us to reuse both fluids for various applications, leading to a more economical process. Membrane separation has been evidenced as a cost-effective process for wastewater treatment. A hollow fiber membrane made of polyacrylonitrile (PAN) is an excellent choice for separating oil from water because of its superior chemical resistance. Its low antifouling ability, however, reduces the effectiveness of its separation. Hence, in this study, we used tannic acid (TA) and FeIII complex to modify the surface of the PAN hollow fiber membrane. To improve membrane performance, different reaction times were investigated. The results demonstrate that even when the TA-FeIII covered the pores of the PAN membrane, the water flux remained constant. However, when an emulsion was fed to the feed solution, the flux increased from 50 to 66 LMH, indicating low oil adhesion on the surface of the modified membrane. When compared to the pristine membrane, the modified membrane had superior antifouling and reusability. As a result, the hydrophilic TA-FeIII complex on PAN surface improves overall membrane performance.
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Transforming biological waste into high-value-added materials is currently attracting extensive research interest in the medical and industrial treatment fields. The design and use of new antibacterial systems are urgently needed. In this study, we used discarded oyster shell powder (OSP) to prepare calcium oxide (CaO). CaO was mixed with silver (Ag), zinc (Zn), and copper (Cu) ions as a controlled release and antibacterial system to test the antibacterial activity. The inhibition zones of various modified metals were between 22 and 29 mm for Escherichia coli (E. coli) and between 21 and 24 mm for Staphylococcus aureus (S. aureus). In addition, linear low-density polyethylene (LLDPE) combined with CaO and metal ion forms can be an excellent alternative to a hybrid composite. The strength modulus at 1% LLDPE to LLDPE/CaO Ag increased from 297 to 320 MPa. In addition, the antimicrobial activity of LLDPE/CaO/metal ions against E. coli had an antibacterial effect of about 99.9%. Therefore, this hybrid composite material has good potential as an antibacterial therapy and biomaterial suitable for many applications.
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In this work, silica nanoparticles were produced in situ, to be embedded eventually in the polyamide layer formed during interfacial polymerization for fabricating thin-film nanocomposite membranes with enhanced performance for dehydrating isopropanol solution. The nanoparticles were synthesized through a sol-gel reaction between 3-aminopropyltrimethoxysilane (APTMOS) and 1,3-cyclohexanediamine (CHDA). Two monomers-CHDA (with APTMOS) and trimesoyl chloride-were reacted on a hydrolyzed polyacrylonitrile (hPAN) support. To obtain optimum fabricating conditions, the ratio of APTMOS to CHDA and reaction time were varied. Field emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM) were used to illustrate the change in morphology as a result of embedding silica nanoparticles. The optimal conditions for preparing the nanocomposite membrane turned out to be 0.15 (g/g) APTMOS/CHDA and 60 min mixing of APTMOS and CHDA, leading to the following membrane performance: flux = 1071 ± 79 gâm-2âh-1, water concentration in permeate = 97.34 ± 0.61%, and separation factor = 85.39. A stable performance was shown by the membrane under different operating conditions, where the water concentration in permeate was more than 90 wt%. Therefore, the embedment of silica nanoparticles generated in situ enhanced the separation efficiency of the membrane.
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In this work, thin-film composite polyamide membranes were fabricated using triethylenetetramine (TETA) and trimesoyl chloride (TMC) following the vacuum-assisted interfacial polymerization (VAIP) method for the pervaporation (PV) dehydration of aqueous isopropanol (IPA) solution. The physical and chemical properties as well as separation performance of the TFCVAIP membranes were compared with the membrane prepared using the traditional interfacial polymerization (TIP) technique (TFCTIP). Characterization results showed that the TFCVAIP membrane had a higher crosslinking degree, higher surface roughness, and denser structure than the TFCTIP membrane. As a result, the TFCVAIP membrane exhibited a higher separation performance in 70 wt.% aqueous IPA solution at 25 °C with permeation flux of 1504 ± 169 gâm-2âh-1, water concentration in permeate of 99.26 ± 0.53 wt%, and separation factor of 314 (five times higher than TFCTIP). Moreover, the optimization of IP parameters, such as variation of TETA and TMC concentrations as well as polymerization time for the TFCVAIP membrane, was carried out. The optimum condition in fabricating the TFCVAIP membrane was 0.05 wt.% TETA, 0.1 wt% TMC, and 60 s polymerization time.
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Wastewater effluents containing high concentrations of dyes are highly toxic to the environment and aquatic organisms. Recycle and reuse of both water and dye in textile industries can save energy and costs. Thus, new materials are being explored to fabricate highly efficient nanofiltration membranes for fulfilling industrial needs. In this work, three diamines, 1,4-cyclohexanediamine (CHD), ethylenediamine (EDA), and p-phenylenediamine (PPD), are reacted with TMC separately to fabricate a thin film composite polyamide membrane for dye desalination. Their chemical structures are different, with the difference located in the middle of two terminal amines. The surface morphology, roughness, and thickness of the polyamide layer are dependent on the reactivity of the diamines with TMC. EDA has a short linear alkane chain, which can easily react with TMC, forming a very dense selective layer. CHD has a cyclohexane ring, making it more sterically hindered than EDA. As such, CHD's reaction with TMC is slower than EDA's, leading to a thinner polyamide layer. PPD has a benzene ring, which should make it the most sterically hindered structure; however, its benzene ring has a pi-pi interaction with TMC that can facilitate a faster reaction between PPD and TMC, leading to a thicker polyamide layer. Among the TFC membranes, TFCCHD exhibited the highest separation efficiency (pure water flux = 192.13 ± 7.11 Lâm-2âh-1, dye rejection = 99.92 ± 0.10%, and NaCl rejection = 15.46 ± 1.68% at 6 bar and 1000 ppm salt or 50 ppm of dye solution). After exposure at 12,000 ppmâh of active chlorine, the flux of TFCCHD was enhanced with maintained high dye rejection. Therefore, the TFCCHD membrane has a potential application for dye desalination process.
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In membrane-based separation, molecular size differences relative to membrane pore sizes govern mass flux and separation efficiency. In applications requiring complex molecular differentiation, such as in natural gas processing, cascaded pore size distributions in membranes allow different permeate molecules to be separated without a reduction in throughput. Here, we report the decoration of microporous polymer membrane surfaces with molecular fluorine. Molecular fluorine penetrates through the microporous interface and reacts with rigid polymeric backbones, resulting in membrane micropores with multimodal pore size distributions. The fluorine acts as angstrom-scale apertures that can be controlled for molecular transport. We achieved a highly effective gas separation performance in several industrially relevant hollow-fibrous modular platform with stable responses over 1 year.
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Nanofluidics derived from low-dimensional nanosheets and protein nanochannels are crucial for advanced catalysis, sensing, and separation. However, polymer nanofluidics is halted by complicated preparation and miniaturized sizes. This work reports the bottom-up synthesis of modular nanofluidics by confined growth of ultrathin metal-organic frameworks (MOFs) in a polymer membrane consisting of zwitterionic dopamine nanoparticles (ZNPs). The confined growth of the MOFs on the ZNPs reduces the chain entanglement between the ZNPs, leading to stiff interfacial channels enhancing the nanofluidic transport of water molecules through the membrane. As such, the water permeability and solute selectivity of MOF@ZNPM are one magnitude improved, leading to a record-high performance among all polymer nanofiltration membranes. Both the experimental work and the molecular dynamics simulations confirm that the water transport is shifted from high-friction-resistance conventional viscous flow to ultrafast nanofluidic flow as a result of rigid and continuous nanochannels in MOF@ZNPM.
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A thin-film composite (TFC) polyurea membrane was fabricated for the dehydration of an aqueous tetrahydrofuran (THF) solution through interfacial polymerization, wherein polyethyleneimine (a water-soluble amine monomer) and m-xylene diisocyanate (an oil-soluble diisocyanate monomer) were reacted on the surface of a modified polyacrylonitrile (mPAN) substrate. Cosolvents were used to tailor the membrane properties and increase the membrane permeation flux. Four types of alcohols that differed in the number of carbon (methanol, ethanol, isopropanol, and tert-butanol) were added as cosolvents, serving as swelling agents, to the aqueous-phase monomer solution, and their effect on the membrane properties and pervaporation separation was discussed. Attenuated total reflection Fourier transform infrared spectroscopy confirmed the formation of a polyurea layer on mPAN. Field emission scanning electron microscopy and surface water contact angle analysis indicated no change in the membrane morphology and hydrophilicity, respectively, despite the addition of cosolvents for interfacial polymerization. The TFC membrane produced when ethanol was the cosolvent exhibited the highest separation performance (permeation flux = 1006 ± 103 g·m-2·h-1; water concentration in permeate = 98.8 ± 0.3 wt.%) for an aqueous feed solution containing 90 wt.% THF at 25 °C. During the membrane formation, ethanol caused the polyurea layer to loosen and to acquire a certain degree of cross-linking. The optimal fabrication conditions were as follows: 10 wt.% ethanol as cosolvent; membrane curing temperature = 50 °C; membrane curing time = 30 min.
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The advancement in membrane science and technology, particularly in nanofiltration applications, involves the blending of functional nanocomposites into the membranes to improve the membrane property. In this study, Ag-polydopamine (Ag-PDA) particles were synthesized through in situ PDA-mediated reduction of AgNO3 to silver. Infusing Ag-PDA particles into polyethersulfone (PES) matrix affects the membrane property and performance. X-ray photoelectron spectroscopy (XPS) analyses confirmed the presence of Ag-PDA particles on the membrane surface. Field emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM) describe the morphology of the membranes. At an optimum concentration of Ag-PDA particles (0.3 wt % based on the concentration of PES), the modified membrane exhibited high water flux 13.33 Lâm-2âh-1 at 4 bar with high rejection for various dyes of >99%. The PESAg-PDA0.3 membrane had a pure water flux more than 5.4 times higher than that of a pristine membrane. Furthermore, in bacterial attachment using Escherichia coli, the modified membrane displayed less bacterial attachment compared with the pristine membrane. Therefore, immobilizing Ag-PDA particles into the PES matrix enhanced the membrane performance and antibacterial property.
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Thin-film composite (TFC) polyamide membranes formed through interfacial polymerization can function more efficiently by tuning the chemical structure of participating monomers. Accordingly, three kinds of diamine monomers were considered to take part in interfacial polymerization. Each diamine was reacted with trimesoyl chloride (TMC) to manufacture TFC polyamide nanofiltration (NF)-like forward osmosis (FO) membranes. The diamines differed in chemical structure; the functional group present between the terminal amines was classified as follows: aliphatic group of 1,3-diaminopropane (DAPE); cyclohexane in 1,3-cyclohexanediamine (CHDA); and aromatic or benzene ring in m-phenylenediamine (MPD). For FO tests, deionized water and 1 M aqueous sodium sulfate solution were used as feed and draw solution, respectively. Interfacial polymerization conditions were also varied: concentrations of water and oil phases, time of contact between the water-phase solution and the membrane substrate, and polymerization reaction time. The resultant membranes were characterized using attenuated total reflectance-Fourier transform infrared spectroscopy, field emission scanning electron microscopy, atomic force microscopy, and surface contact angle measurement to identify the chemical structure, morphology, roughness, and hydrophilicity of the polyamide layer, respectively. The results of FO experiments revealed that among the three diamine monomers, CHDA turned out to be the most effective, as it led to the production of TFC NF-like FO membrane with optimal performance. Then, the following optimum conditions were established for the CHDA-based membrane: contact between 2.5 wt.% aqueous CHDA solution and polysulfone (PSf) substrate for 2 min, and polymerization reaction between 1 wt.% TMC solution and 2.5 wt.% CHDA solution for 30 s. The composite CHDA-TMC/PSf membrane delivered a water flux (Jw) of 18.24 ± 1.33 LMH and a reverse salt flux (Js) of 5.75 ± 1.12 gMH; therefore, Js/Jw was evaluated to be 0.32 ± 0.07 (g/L).
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In this study, cellulose acetate (CA) mixed-matrix membranes were fabricated through the wet-phase inversion method. Two types of montmorillonite (MMT) nanoclay were embedded separately: sodium montmorillonite (Na-MMT) and organo-montmorillonite (O-MMT). Na-MMT was converted to O-MMT through ion exchange reaction using cationic surfactant (dialkyldimethyl ammonium chloride, DDAC). Attenuated total reflectance-Fourier transform infrared (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS) compared the chemical structure and composition of the membranes. Embedding either Na-MMT and O-MMT did not change the crystallinity of the CA membrane, indicating that the nanoclays were dispersed in the CA matrix. Furthermore, nanoclays improved the membrane hydrophilicity. Compared with CANa-MMT membrane, CAO-MMT membrane had a higher separation efficiency and antifouling property. At the optimum concentration of O-MMT in the CA matrix, the pure water flux reaches up to 524.63 ± 48.96 Lâm-2âh-1âbar-1 with over 95% rejection for different oil-in-water emulsion (diesel, hexane, dodecane, and food-oil). Furthermore, the modified membrane delivered an excellent antifouling property.
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The type of organic solvents used in interfacial polymerization affects the surface property, free volume, and separation performance of the thin-film composite (TFC) polyamide membrane. In this study, TFC polyamide membrane was fabricated through interfacial polymerization between diethylenetriamine (DETA) and trimesoyl chloride (TMC). Four types of organic solvent were explored in the preparation of pervaporation membrane. These are tetralin, toluene, hexane, and isopentane. The solubility parameter distance between organic solvents and DETA follows in increasing order: tetralin (17.07 MPa1/2) < toluene (17.31 MPa1/2) < hexane (19.86 MPa1/2) < isopentane (20.43 MPa1/2). Same trend was also observed between the organic solvents and DETA. The larger the solubility parameter distance, the denser and thicker the polyamide. Consequently, field emission scanning electron microscope (FESEM) and positron annihilation spectroscopy (PAS) analysis revealed that TFCisopentane had the thickest polyamide layer. It also delivered the highest pervaporation efficiency (permeation flux = 860 ± 71 g m-2 h-1; water concentration in permeate = 99.2 ± 0.8 wt%; pervaporation separation index = 959,760) at dehydration of 90 wt% aqueous ethanol solution. Furthermore, TFCisopentane also exhibited a high separation efficiency in isopropanol and tert-butanol. Therefore, a suitable organic solvent in preparation of TFC membrane through interfacial polymerization enables high pervaporation efficiency.
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A variety of metal organic frameworks (MOFs) were synthesized and evaluated for their iodine adsorption capacity. Out of the MOFs tested, ZIF-8 showed the most promising result with an iodine vapor uptake of 876.6 mg/g. ZIF-8 was then incorporated into a polymer, polyethersulfone (PES), at different proportions to prepare mixed matrix membranes (MMMs), which were then used to perform further iodine adsorption experiments. With a mixing ratio of 40 wt % of ZIF-8, the iodine adsorption capacity reached 1387.6 mg/g, wherein an astounding 60% improvement in adsorption was seen with the MMMs prepared compared to the original ZIF-8 powder.
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In this study, the basal spacing of montmorillonite (MMT) was modified through ion exchange. Two kinds of MMT were used: sodium-modified MMT (Na-MMT) and organo-modified MMT (O-MMT). These two particles were incorporated separately into the thin-film nanocomposite polyamide membrane through the interfacial polymerization of piperazine and trimesoyl chloride in n-hexane. The membrane with O-MMT (TFNO-MMT) has a more hydrophilic surface compared to that of membrane with Na-MMT (TFNNa-MMT). When various types of MMT were dispersed in the n-hexane solution with trimesoyl chloride (TMC), O-MMT was well-dispersed than Na-MMT. The poor dispersion of Na-MMT in n-hexane led to the aggregation of Na-MMT on the surface of TFNNa-MMT. TFNO-MMT displayed a uniform distribution of O-MMT on the surface, because O-MMT was well-dispersed in n-hexane. In comparison with the pristine and TFNNa-MMT membranes, TFNO-MMT delivered the highest pure water flux of 53.15 ± 3.30 Lâm-2âh-1 at 6 bar, while its salt rejection for divalent ions remained at 95%-99%. Furthermore, it had stable performance in wide operating condition, and it exhibited a magnificent antifouling property. Therefore, a suitable type of MMT could lead to high separation efficiency.
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Water transport rate in network membranes is inversely correlated to thickness, thus superior permeance is achievable with ultrathin membranes prepared by complicated methods circumventing nanofilm weakness and defects. Conferring ultrahigh permeance to easily prepared thicker membranes remains challenging. Here, a tetrakis(hydroxymethyl) phosphonium chloride (THPC) monomer is discovered that enables straightforward modification of polyamide composite membranes. Water permeance of the modified membrane is ≈6 times improved, give rising to permeability (permeance × thickness) one magnitude higher than state-of-the-art polymer nanofiltration membranes. Meanwhile, the membrane exhibits good rejection (RNa2SO4 = 98%) and antibacterial properties under crossflow conditions. THPC modification not only improves membrane hydrophilicity, but also creates additional angstrom-scale channels in polyamide membranes for unimpeded transport of water. This unique mechanism provides a paradigm shift in facile preparation of ultrapermeable membranes with unreduced thickness for clean water and desalination.
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Antibacterianos/química , Antibacterianos/farmacologia , Membranas Artificiais , Nylons/química , Nylons/farmacologia , Compostos Organofosforados/química , Permeabilidade , Água/químicaRESUMO
Separating molecules or ions with sub-Angstrom scale precision is important but technically challenging. Achieving such a precise separation using membranes requires Angstrom scale pores with a high level of pore size uniformity. Herein, we demonstrate that precise solute-solute separation can be achieved using polyamide membranes formed via surfactant-assembly regulated interfacial polymerization (SARIP). The dynamic, self-assembled network of surfactants facilitates faster and more homogeneous diffusion of amine monomers across the water/hexane interface during interfacial polymerization, thereby forming a polyamide active layer with more uniform sub-nanometre pores compared to those formed via conventional interfacial polymerization. The polyamide membrane formed by SARIP exhibits highly size-dependent sieving of solutes, yielding a step-wise transition from low rejection to near-perfect rejection over a solute size range smaller than half Angstrom. SARIP represents an approach for the scalable fabrication of ultra-selective membranes with uniform nanopores for precise separation of ions and small solutes.
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Membrane support properties influence the performance of thin-film composite nanofiltration membranes. We fabricated several polysulfone (PSf) supports. The physicochemical properties of PSf were altered by adding polyethylene glycol (PEG) of varying molecular weights (200â»35,000 g/mol). This alteration facilitated the formation of a thin polyamide layer on the PSf surface during the interfacial polymerization reaction involving an aqueous solution of piperazine containing 4-aminobenzoic acid and an organic solution of trimesoyl chloride. Attenuated total reflectance-Fourier transform infrared validated the presence of PEG in the membrane support. Scanning electron microscopy and atomic force microscopy illustrated that the thin-film polyamide layer morphology transformed from a rough to a smooth surface. A cross-flow filtration test indicated that a thin-film composite polyamide membrane comprising a PSf support (TFC-PEG20k) with a low surface porosity, small pore size, and suitable hydrophilicity delivered the highest water flux and separation efficiency (J = 81.1 ± 6.4 L·m-2·h-1, RNa2SO4 = 91.1% ± 1.8%, and RNaCl = 35.7% ± 3.1% at 0.60 MPa). This membrane had a molecular weight cutoff of 292 g/mol and also a high rejection for negatively charged dyes. Therefore, a PSf support exhibiting suitable physicochemical properties endowed a thin-film composite polyamide membrane with high performance.
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A thermoresponsive chitosan derivative was synthesized by reacting chitosan (CS) with butyl glycidyl ether (BGE) to break the inter- and intramolecular hydrogen bonds of the polymer. An aqueous solution of the thermoresponsive CS derivative exhibits a lower critical solution temperature (LCST) than CS, and it undergoes a phase transition separation when the temperature changes. Successful incorporation of BGE into the CS was confirmed by FTIR and XPS analyses. Varying the BGE content and the concentration of the aqueous solution produced different LCST ranges, as shown by transmittance vs temperature curves. The particle size was observed by scanning electron microscopy, which revealed that the particles were smaller and well dispersed at 15 °C, whereas the particles became larger and tended to aggregate at 60 °C. A similar trend was observed with the mean particle size measured using dynamic light scattering. Positron annihilation lifetime spectroscopy data also revealed the reversibility of the particle properties as a function of temperature. Microstructure analysis showed that the particles had larger free-volume sizes at 15 °C than at 60 °C. The particles were also found to be nontoxic with 92% cell survival. A simple forward osmosis (FO) test for dye dehydration revealed the potential use of the thermoresponsive chitosan derivative as a draw solute with a flux of 8.6 L/m2 h and rejection of 99.8%.
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Quitosana/análogos & derivados , Osmose , Quitosana/química , Tamanho da Partícula , Polímeros/química , SoluçõesRESUMO
Diabetes mellitus may cause vascular endothelial damage via endothelial matrix metalloproteinase-2 (MMP-2). The role of endothelial autophagy in MMP-2-mediated cell injury in response to high-glucose (HG) stimulation was rarely described. In this study, we used HG-treated human umbilical vein endothelial cells (HUVECs) to investigate the effect of autophagy on MMP-2-induced cell transmigration and apoptosis. THP-1 transmigration was detected by the transmigration assay. Light chain 3 (LC3, representing autophagy), MMP-2, and poly (ADP-ribose) polymerase (PARP, representing apoptosis) of HG (33 mM)-treated HUVECs were evaluated by western blot analysis. The MMP-2 activity was also examined by gelatin zymography. We used GM6001 (10 µM, an MMP-2 inhibitor) to investigate the relationship of MMP-2 and THP-1 transmigration. Using 3-methyladenine (3MA, 5 mM, an LC3 inhibitor), we explored the effects of autophagy on MMP-2 expression, THP-1 transmigration, and apoptosis. Our results showed that HG increased LC3-II expression, MMP-2 activity, THP-1 transmigration, and cleaved PARP expression in a time-dependent manner (0-48 h); among them, LC3-II appeared earlier (0-24 h) than the others (24-48 h). GM6001 suppressed MMP-2 activity and ameliorated THP-1 transmigration. 3MA suppressed LC3-II expression and increased MMP-2 expression, THP-1 transmigration, and cleaved PARP expression. From these sequential findings, we demonstrated that autophagy plays a protective role in MMP-2-mediated cell transmigration and cell death in HG-stimulated HUVECs.