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(+)-Plakevulin A (1), an oxylipin isolated from an Okinawan sponge Plakortis sp. inhibits enzymatic inhibition of DNA polymerases (pols) α and δ and exhibits cytotoxicity against murine leukemia (L1210) and human cervix carcinoma (KB) cell lines. However, the half-maximal inhibitory concentration (IC50) value for cytotoxicity significantly differed from those observed for the enzymatic inhibition of pols α and ß, indicating the presence of target protein(s) other than pols. This study demonstrated cytotoxicity against human promyelocytic leukemia (HL60), human cervix epithelioid carcinoma (HeLa), mouse calvaria-derived pre-osteoblast (MC3T3-E1), and human normal lung fibroblast (MRC-5) cell lines. This compound had selectivity to cancer cells over normal ones. Among these cell lines, HL60 exhibited the highest sensitivity to (+)-plakevulin A. (+)-Plakevulin A induced DNA fragmentation and caspase-3 activation in HL60 cells, indicating its role in apoptosis induction. Additionally, hydroxysteroid 17-ß dehydrogenase 4 (HSD17B4) was isolated from the HL60 lysate as one of its binding proteins through pull-down experiments using its biotinylated derivative and neutravidin-coated beads. Moreover, (+)-plakevulin A suppressed the activation of interleukin 6 (IL-6)-induced signal transducer and activator of transcription 3 (STAT3). Because the knockdown or inhibition of STAT3 induces apoptosis and HSD17B4 regulates STAT3 activation, (+)-plakevulin A may induce apoptosis in HL60 cell lines by suppressing STAT3 activation, potentially by binding to HSD17B4. The present findings provide valuable information for the mechanism of its action.
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Apoptosis , Interleucina-6 , Factor de Transcripción STAT3 , Humanos , Factor de Transcripción STAT3/metabolismo , Factor de Transcripción STAT3/antagonistas & inhibidores , Apoptosis/efectos de los fármacos , Células HL-60 , Interleucina-6/metabolismo , Animales , Ratones , Antineoplásicos/farmacología , Antineoplásicos/química , Antineoplásicos/síntesis química , Ensayos de Selección de Medicamentos Antitumorales , Relación Dosis-Respuesta a Droga , Estructura Molecular , Relación Estructura-ActividadRESUMEN
Streptococcus suis, a gram-positive coccus, is recognized as an emerging zoonotic pathogen that causes serious infections in humans, such as bacterial meningitis and sepsis, with poor outcomes. The pathogen is known to be transmitted through the consumption of raw pork or occupational exposure to pigs. A previously healthy 38-year-old woman with occupational exposure to raw pork was presented to our emergency department with a clinical diagnosis of rapidly progressive septic shock. Peripheral blood smears detected chains of cocci inside granulocytes, which led to the early recognition of gram-positive cocci in short chains before the blood culture test results. Blood cultures later tested positive for S. suis serotype 2. The patient's condition deteriorated despite aggressive resuscitative measures including antibiotics, vasopressors, multiple blood transfusions, mechanical ventilation, and renal replacement therapy. Initiation of veno-arterial extracorporeal membrane oxygenation was ineffective, and the patient died 16 h after admission. The identification of bacteria in the peripheral blood smear indicated an overwhelming infection and led to the rapid recognition of bacteremia. Our report aims to raise awareness about fatal zoonotic pathogens and to promote the unique role of peripheral blood smears that could provide preliminary diagnostic information before blood culture results.
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Sepsis , Choque Séptico , Infecciones Estreptocócicas , Streptococcus suis , Humanos , Animales , Porcinos , Adulto , Infecciones Estreptocócicas/microbiología , Sepsis/tratamiento farmacológico , Antibacterianos/uso terapéutico , Choque Séptico/microbiologíaRESUMEN
Epo-C12 is a synthetic derivative of epolactaene, isolated from Penicillium sp. BM 1689-P. Epo-C12 induces apoptosis in human acute lymphoblastoid leukemia BALL-1 cells. In our previous studies, seven proteins that bind to Epo-C12 were identified by a combination of pull-down experiments using biotinylated Epo-C12 (Bio-Epo-C12) and mass spectrometry. In the present study, the effect of Epo-C12 on peroxiredoxin 1 (Prx 1), one of the proteins that binds to Epo-C12, was investigated. Epo-C12 inhibited Prx 1 peroxidase activity. However, it did not suppress its chaperone activity. Binding experiments between Bio-Epo-C12 and point-mutated Prx 1s suggest that Epo-C12 binds to Cys52 and Cys83 in Prx 1. The present study revealed that Prx 1 is one of the target proteins through which Epo-C12 exerts an apoptotic effect in BALL-1 cells.
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Antineoplásicos/farmacología , Apoptosis/efectos de los fármacos , Peroxirredoxinas/antagonistas & inhibidores , Animales , Antineoplásicos/química , Línea Celular Tumoral , Inhibidores Enzimáticos , Compuestos Epoxi/química , Regulación Enzimológica de la Expresión Génica/efectos de los fármacos , Humanos , Estructura Molecular , Mutación , Peroxirredoxinas/genética , Peroxirredoxinas/metabolismo , Polienos/químicaRESUMEN
The acrosome reaction is a multi-step event essential for physiological fertilization. During the acrosome reaction, gamete fusion-related factor IZUMO1 translocates from the anterior acrosome to the equatorial segment and assembles the gamete fusion machinery. The morphological changes in the acrosome reaction process have been well studied, but little is known about the molecular mechanisms of acrosome reorganization essential for physiological gamete membrane fusion. To elucidate the molecular mechanisms of IZUMO1 translocation, the steps of the acrosome reaction during that process must be clarified. In this study, we established a method to detect the early steps of the acrosome reaction and subdivided the process into seven populations through the use of two epitope-defined antibodies, anti-IZUMO1 and anti-SPACA1, a fertilization-inhibiting antibody. We found that part of the SPACA1 C-terminus in the periacrosomal space was cleaved and had begun to disappear when the vesiculation of the anterior acrosome occurred. The IZUMO1 epitope externalized from the acrosomal lumen before acrosomal vesiculation and phosphorylation of IZUMO1 occurred during the translocation to the equatorial segment. IZUMO1 circumvented the area of the equatorial segment where the SPACA1C-terminus was still localized. We therefore propose an IZUMO1 translocation model and involvement of SPACA1.
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Membrana Celular/metabolismo , Isoantígenos/metabolismo , Fusión de Membrana/fisiología , Oocitos/metabolismo , Proteínas de Plasma Seminal/metabolismo , Espermatozoides/metabolismo , Animales , Epítopos/metabolismo , Isoantígenos/genética , Masculino , Ratones , Proteínas de Plasma Seminal/genética , Capacitación Espermática/fisiologíaRESUMEN
Solar-driven catalysts on semiconductors to produce hydrogen are considered as a means to solve environmental issues. In this study, H2 production coupling with oxygen consumption by noble metal-free α-FeOOH was demonstrated even though the conduction band edge was lower than the reduction potential of H+ to H2 . For activation of α-FeOOH, an electron donor, Hg-Xe irradiation, and low pH (ca. 5) were indispensable factors. The H2 production from H2 O was confirmed by GC-MS using isotope-labeled water (D2 O) and deuterated methanol. The α-FeOOH synthesized by coprecipitation method showed 25â times more active than TiO2 . The photocatalytic activity was stable for over 400â h. Our study suggests that α-FeOOH known as rust can produce H2 by light induction.
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Invited for the cover of this issue is Tetsuya Yamada, Ken-ichi Katsumata and co-workers at Tokyo Institute of Technology and Tokyo University of Science. The image depicts rust producing hydrogen and purifying the pollutants at the same time by photocatalytic reaction. Read the full text of the article at 10.1002/chem.201903642.
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There is a need for highly efficient photocatalysts, particularly for water purification. In this study, we fabricated a mesoporous TiO2 thin film on a boron-doped diamond (BDD) layer by a surfactant-assisted sol-gel method, in which self-assembled amphiphilic surfactant micelles were used as an organic template. Scanning electron microscopy revealed uniform mesopores, approximately 20 nm in diameter, that were hexagonally packed in the TiO2 thin film. Wide-angle X-ray diffraction and Raman spectroscopy clarified that the framework crystallized in the anatase phase. Currentâ»voltage (Iâ»V) measurements showed rectification features at the TiO2/BDD heterojunction, confirming that a pâ»n hetero-interface formed. The as-synthesized mesoporous TiO2/BDD worked well as a photocatalyst, even with a small volume of TiO2 (15 mm × 15 mm × c.a. 1.5 µm in thickness). The use of deep UV light (λ = 222 nm) as a light source was necessary to enhance photocatalytic activity, due to photo-excitation occurring in both BDD and TiO2.
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Boro/química , Diamante/química , Procesos Fotoquímicos , Titanio/química , Rayos Ultravioleta , Catálisis , PorosidadRESUMEN
High faradaic efficiencies can be achieved in the production of formic acid (HCOOH) by metal electrodes, such as Sn or Pb, in the electrochemical reduction of carbon dioxide (CO2 ). However, the stability and environmental load in using them are problematic. The electrochemical reduction of CO2 to HCOOH was investigated in a flow cell using boron-doped diamond (BDD) electrodes. BDD electrodes have superior electrochemical properties to metal electrodes, and, moreover, are highly durable. The faradaic efficiency for the production of HCOOH was as high as 94.7 %. Furthermore, the selectivity for the production of HCOOH was more than 99 %. The rate of the production was increased to 473â µmol m-2 s-1 at a current density of 15â mA cm-2 with a faradaic efficiency of 61 %. The faradaic efficiency and the production rate are almost the same as or larger than those achieved using Sn and Pb electrodes. Furthermore, the stability of the BDD electrodes was confirmed by 24â h operation.
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The inactivation of Escherichia coli and Qß phage was examined following their photocatalytic treatment with TiO2 hollows and spheres that had been prepared by electrospray, hydrothermal treatment, and calcination. The crystal structures of the hollows and spheres were assigned to TiO2 anatase, and the surface areas of the hollows and spheres were determined to be 91 and 79 m(2) g(-1), respectively. Interestingly, TiO2 spheres exhibited higher anti-pathogen performance than TiO2 hollows, a difference we ascribe to the prevention of light multi-scattering by microorganisms covering the surfaces of the TiO2 particles. The photocatalytic decomposition of dimethyl sulfoxide (DMSO) in the presence of TiO2 hollows and spheres was examined in order to study the dependence of photocatalytic activity on TiO2 morphology for the size scale of the reactants. TiO2 hollows provided greater photocatalytic decomposition of DMSO than did TiO2 spheres, in contrast to the pattern seen for pathogen inactivation. Fabrication of photocatalysts will need to vary depending on what substance (e.g., organic compound or biological agent) is being targeted for environmental remediation.
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Luz , Nanopartículas del Metal/química , Titanio/química , Allolevivirus/efectos de los fármacos , Catálisis , Dimetilsulfóxido/química , Escherichia coli/efectos de los fármacos , Nanopartículas del Metal/toxicidad , Nanopartículas del Metal/ultraestructura , Azul de Metileno/química , Microscopía Electrónica de Rastreo , Espectrofotometría Ultravioleta , Difracción de Rayos XRESUMEN
In the photocatalysis of porous nano-crystalline materials, the transfer of electrons to O2 plays an important role, which includes the electron transport to photocatalytic active centers and successive interfacial transfer to O2. The slowest of them will determine the overall speed of electron transfer in the photocatalysis reaction. Considering the photocatalysis of porous nano-crystalline TiO2 as an example, although some experimental results have shown that the electron kinetics are limited by the interfacial transfer, we still lack the depth of understanding the microscopic mechanism from a theoretical viewpoint. In the present research, a stochastic quasi-equilibrium (QE) theoretical model and a stochastic random walking (RW) model were established to discuss the electron transport and electron interfacial transfer by taking the electron multi-trapping transport and electron interfacial transfer from the photocatalytic active centers to O2 into consideration. By carefully investigating the effect of the electron Fermi level (EF) and the photocatalytic center number on electron transport, we showed that the time taken for an electron to transport to a photocatalytic center predicated by the stochastic RW model was much lower than that predicted by the stochastic QE model, indicating that the electrons cannot reach a QE state during their transport to photocatalytic centers. The stochastic QE model predicted that the electron kinetics of a real photocatalysis for porous nano-crystalline TiO2 should be limited by electron transport, whereas the stochastic RW model showed that the electron kinetics of a real photocatalysis can be limited by the interfacial transfer. Our simulation results show that the stochastic RW model was more in line with the real electron kinetics that have been observed in experiments, therefore it is concluded that the photoinduced electrons cannot reach a QE state before transferring to O2.
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Since the report of the Honda-Fujishima effect, heterogeneous photocatalysis has attracted much attention around the world because of its potential energy and environmental applications. Although great progresses have been made in recent years, most were focused on preparing highly-active photocatalysts and investigating visible light utilization. In fact, we are still unclear on the thermodynamic and kinetic nature of photocatalysis to date, which sometimes leads to misunderstandings for experimental results. It is timely to give a review and discussion on the thermodynamics and kinetics of photocatalysis, so as to direct future researches. However, there is an absence of a detailed review on this topic until now. In this article, we tried to review and discuss the thermodynamics and kinetics of photocatalysis. We explained the thermodynamic driving force of photocatalysis, and distinguished the functions of light and heat in photocatalysis. The Langmuir-Hinshelwood kinetic model, the ËOH oxidation mechanism, and the direct-indirect (D-I) kinetic model were reviewed and compared. Some applications of the D-I model to study photocatalytic kinetics were also discussed. The electron transport mode and its importance in photocatalysis were investigated. Finally, the intrinsic relation between the kinetics and the thermodynamics of photocatalytic reactions was discussed.
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Termodinámica , Catálisis , Cinética , Procesos Fotoquímicos , SemiconductoresRESUMEN
We report simultaneous photoelectrocatalytic (PEC) glucose sensing and biohydrogen generation for the first time from the direct PEC oxidation of glucose at multifunctional and robust Cu2O-TiO2 photocatalysts. Striking improvement of 30% in overall H2 gas evolution (â¼122 µmol h(-1) cm(-2)) by photoholes assisted glucose oxidation opens a new platform in solar-driven PEC biohydrogen generation.
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Técnicas Biosensibles , Cobre/química , Glucosa/química , Hidrógeno/química , Titanio/química , Catálisis , Electrodos , Oxidación-Reducción , Procesos FotoquímicosRESUMEN
We demonstrate one-step gold nanoparticle (AuNP) coating and the surface nitridation of TiO2 nanowires (TiO2-NWs) to amplify visible-light photon reflection. The surface nitridation of TiO2-NW arrays maximizes the anchoring of AuNPs, and the subsequent reduction of the band gap energy from 3.26 eV to 2.69 eV affords visible-light activity. The finite-difference time-domain (FDTD) simulation method clearly exhibits the enhancement in the strengths of localized electric fields between AuNPs and the nanowires, which significantly improves the photocatalytic (PC) performance. Both nitridation and AuNP decoration of TiO2-NWs result in beneficial effects of high (e(-)/h(+)) pair separation through healing of the oxygen vacancies. The combined effect of harvesting visible-light photons and reducing recombination in Au/N-doped TiO2-NWs promotes the photocatalytic activity towards degradation of methyl orange to an unprecedented level, â¼4 fold (1.1 × 10(-2) min) more than does TiO2-NWs (2.9 × 10(-3) min(-1)). The proposed AuNP decoration of nitridated TiO2-NW surfaces can be applied to a wide range of n-type metal oxides for photoanodes in photocatalytic applications.
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Oro/química , Nanopartículas del Metal/química , Nanoporos/ultraestructura , Nanocables/química , Titanio/química , Catálisis/efectos de la radiación , Oro/efectos de la radiación , Luz , Ensayo de Materiales , Nanopartículas del Metal/efectos de la radiación , Nanocables/efectos de la radiación , Oxidación-Reducción/efectos de la radiación , Dispersión de Radiación , Titanio/efectos de la radiaciónRESUMEN
The lotus plant is recognized as a 'King plant' among all the natural water repellent plants due to its excellent non-wettability. The superhydrophobic surfaces exhibiting the famous 'Lotus Effect', along with extremely high water contact angle (>150°) and low sliding angle (<10°), have been broadly investigated and extensively applied on variety of substrates for potential self-cleaning and anti-corrosive applications. Since 1997, especially after the exploration of the surface micro/nanostructure and chemical composition of the lotus leaves by the two German botanists Barthlott and Neinhuis, many kinds of superhydrophobic surfaces mimicking the lotus leaf-like structure have been widely reported in the literature. This review article briefly describes the different wetting properties of the natural superhydrophobic lotus leaves and also provides a comprehensive state-of-the-art discussion on the extensive research carried out in the field of artificial superhydrophobic surfaces which are developed by mimicking the lotus leaf-like dual scale micro/nanostructure. This review article could be beneficial for both novice researchers in this area as well as the scientists who are currently working on non-wettable, superhydrophobic surfaces.
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Materiales Biomiméticos/química , Nanoestructuras/química , Hojas de la Planta/química , Politetrafluoroetileno/química , Interacciones Hidrofóbicas e Hidrofílicas , Lotus/anatomía & histología , Lotus/química , Microscopía Electrónica de Rastreo , Nanoestructuras/ultraestructura , Hojas de la Planta/anatomía & histología , Propiedades de Superficie , Agua/químicaRESUMEN
The catalytic, electrocatalytic, or photocatalytic conversion of CO2 into useful chemicals in high yield for industrial applications has so far proven difficult. Herein, we present our work on the electrochemical reduction of CO2 in seawater using a boron-doped diamond (BDD) electrode under ambient conditions to produce formaldehyde. This method overcomes the usual limitation of the low yield of higher-order products, and also reduces the generation of H2 . In comparison with other electrode materials, BDD electrodes have a wide potential window and high electrochemical stability, and, moreover, exhibit very high Faradaic efficiency (74%) for the production of formaldehyde, using either methanol, aqueous NaCl, or seawater as the electrolyte. The high Faradaic efficiency is attributed to the sp(3)-bonded carbon of the BDD. Our results have wide ranging implications for the efficient and cost-effective conversion of CO2.
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Dióxido de Carbono/química , Formaldehído/química , Agua de Mar/química , Boro/química , Diamante/química , Técnicas Electroquímicas , Electrodos , Metanol/química , Oxidación-Reducción , Presión , Teoría Cuántica , TemperaturaRESUMEN
In recent years, cells provided by cell banks and medical facilities have been used for cell therapy, regenerative therapy, and fundamental research. Cryopreservation is an effective means of maintaining stable cell quality over a long period of time. The slow freezing method is most suitable for processing many human cells isolated simultaneously from organs and tissues, but it is necessary to develop a freezing solution for this method. In this study, we report the successful development of a dimethyl sulfoxide (DMSO)-free freezing medium for differentiated neuronal cells. Neuronal differentiation results in the differentiation of undifferentiated SK-N-SH cells into neuronal cells. A basic freezing medium (BFM) was prepared using Dulbecco's modified Eagle's medium, 1 M maltose, and 1% sericin as the essential ingredients, supplemented with 5%-40% propylene glycol (PG). Each BFM supplemented with 5%-40% PG was evaluated in undifferentiated cells. After thawing, BFM supplemented with 10% and 20% PG were 83% and 88% viable, respectively. There was no significant difference between the 10% and 20% PG groups. However, a significant difference was observed when the concentration of PG in the BFM decreased by 5% (5% PG vs. 10% PG; p = 0.0026). Each DMSO-free BFM was evaluated using differentiated neuronal cells. There was no significant difference between the 10% PG BFM and stem-CB-free groups. Viability was significantly different in the 10% glycerol BFM (4.8%) and 10% PG BFM (45%) (p = 0.028). The differentiated cells with 10% PG BFM showed higher adherence to culture dishes than those with 10% glycerol BFM. These results show that BFM containing PG was effective in differentiating neuronal cells. DMSO affects the central nervous system at low concentrations. This report indicates that DMSO is unsuitable for neuronal cells with multipotent differentiation potential. Therefore, it is essential for cell banking and transplantation medicine services to select appropriate cell freezing media.
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Dimetilsulfóxido , Glicerol , Humanos , Dimetilsulfóxido/farmacología , Criopreservación/métodos , Congelación , Diferenciación Celular , Supervivencia Celular , Crioprotectores/farmacologíaRESUMEN
The polymeric adsorption of methylene blue (MB) on a TiO(2) surface is reported. The MB molecule on the TiO(2) surface mainly exists as the H-trimeric adsorption state, which results in the MB@TiO(2) polymeric sol. The trimeric adsorption leads to a remarkable "blueshift" of visible-light adsorption of MB. Electrostatic attraction is important for trimeric adsorption of MB on TiO(2) surfaces. The trimer-monomer equilibrium is highly sensitive on temperature changes, showing an interesting reversible thermochromism. The MB@TiO(2) polymeric sol can be photodegraded under UV illumination without destroying the equilibrium of trimer-monomer. Compared with anionic methyl orange, the TiO(2) colloid hydrosol shows highly selective photocatalysis of MB and other cationic dyes, including crystal violet, methylene green, and victoria blue B. The MB@TiO(2) polymeric sol is stable under visible-light illumination because interfacial transfer of electrons does not exist between MB and TiO(2).
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The effective use of human-derived cells that are difficult to freeze, such as parenchymal cells and differentiated cells from stem cells, is crucial. A stable supply of damage-sensitive cells, such as differentiated neuronal cells, neurons, and glial cells can contribute considerably to cell therapy. We developed a serum-free freezing solution that is effective for the cryopreservation of differentiated neuronal cells. The quality of the differentiated and undifferentiated SK-N-SH cells was determined based on cell viability, live-cell recovery rate, and morphology of cultured cells, to assess the efficacy of the freezing solutions. The viability and recovery rate of the differentiated SK-N-SH neuronal cells were reduced by approximately 1.5-folds compared to that of the undifferentiated SK-N-SH cells. The viability and recovery rate of the differentiated SK-N-SH cells were remarkably different between the freezing solutions containing 10% DMSO and that containing 10% glycerol. Cryoprotectants such as fetal bovine serum (FBS), antifreeze proteins (sericin), and sugars (maltose), are essential for protecting against freeze damage in differentiated neuronal cells and parenchymal cells. Serum-free alternatives (sericin and maltose) could increase safety during cell transplantation and regenerative medicine. Considering these, we propose an effective freezing solution for the cryopreservation of neuronal cells.
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A simple water treatment system consisting of a deep UV light (λ = 222 nm) source, a mesoporous TiO2/boron-doped diamond (BDD) photocatalyst, and a BDD electrode was prepared and used to decompose sulfamethoxazole (SMX) in an advanced oxidation process. The mesoporous TiO2/BDD photocatalyst used with the electrochemical treatment promoted SMX decomposition, but the mesoporous TiO2/BDD photocatalyst alone had a similar ability to decompose SMX as photolysis. Fragments produced through photocatalytic treatment were decomposed during the electrochemical treatment and fragments produced during the electrochemical treatment were decomposed during the photocatalytic treatment, so performing the electrochemical and photocatalytic treatments together effectively decomposed SMX and decrease the total organic carbon concentration to a trace.
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Contaminantes Químicos del Agua , Purificación del Agua , Boro , Diamante , Electrodos , Oxidación-Reducción , SulfametoxazolRESUMEN
Poly(ethylene terephthalate) (PET) films with a moth-eye-like surface are coated with TiO(2) particles to form self-cleaning antireflective films. The use of a TiO(2) suspension of high concentration to coat the PET surface produces a thicker TiO(2) layer with smaller pores, whereas a low concentration of a TiO(2) suspension gives a thinner layer of TiO(2) with larger pores. The PET films coated with TiO(2) particles exhibit a high transmittance of 76-95% and almost no absorption in the range of 400-800 nm. The PET films coated with a TiO(2) suspension with a concentration of ≥2 vol % exhibit superhydrophilicity after irradiation with UV light. After irradiation, the superhydrophilic nature is retained for at least 18 days. The TiO(2)-coated PET films showed the ability to decompose methylene blue under UV irradiation.