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Type I photosensitizers offer an advantage in photodynamic therapy (PDT) due to their diminished reliance on oxygen levels, thus circumventing the challenge of hypoxia commonly encountered in PDT. In this study, we present the synthesis and comprehensive characterization of a novel type I photosensitizer derived from a cyclometalated Ir(III)-rhodamine complex. Remarkably, the complex exhibits a shift in absorption and fluorescence, transitioning from "off" to "on" states in aprotic and protic solvents, respectively, contrary to initial expectations. Upon exposure to light, the complex demonstrates the effective generation of O2- and ·OH radicals via the type I mechanism. Additionally, it exhibits notable photodynamic antibacterial activity against both Gram-positive and Gram-negative bacteria, demonstrated through in vitro and in vivo experiments. This research offers valuable insights for the development of novel type I photosensitizers.
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Antibacterianos , Bactérias Gram-Negativas , Bactérias Gram-Positivas , Irídio , Testes de Sensibilidade Microbiana , Fotoquimioterapia , Fármacos Fotossensibilizantes , Rodaminas , Fármacos Fotossensibilizantes/farmacologia , Fármacos Fotossensibilizantes/química , Fármacos Fotossensibilizantes/síntese química , Antibacterianos/farmacologia , Antibacterianos/química , Antibacterianos/síntese química , Bactérias Gram-Negativas/efeitos dos fármacos , Rodaminas/química , Rodaminas/farmacologia , Irídio/química , Irídio/farmacologia , Bactérias Gram-Positivas/efeitos dos fármacos , Complexos de Coordenação/farmacologia , Complexos de Coordenação/química , Complexos de Coordenação/síntese química , Animais , Raios Infravermelhos , Estrutura Molecular , CamundongosRESUMO
In this article, a triple-band wearable monopole antenna fed by a coplanar waveguide (CPW) with an integrated electromagnetic bandgap (EBG) array is proposed. The monopole antenna consists of an asymmetric inverted U-shaped strip, a horizontal branch, and an L-shaped ground stub, which can generate the 2.45/5.8 GHz wireless local area network (WLAN) band and the 3.5 GHz worldwide interoperability for microwave access (WiMAX) band. To reduce the influence of antenna radiation on the human body, a triple-band 3 × 3 EBG array has been integrated into the back of the monopole antenna. The EBG unit is composed of two rectangular rings and a circular ring, and the operating frequencies correspond to the triple bands of the monopole antenna. In this paper, the impedance and radiation performances of the stand-alone monopole antenna and the integrated antenna are analyzed, and the safety for the human body is evaluated based on specific absorption rate (SAR) values. The proposed triple-band antenna can be used in wearable devices in wireless body area networks (WBANs).
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Zeolite SAPO-34 has been widely used in the industry because of its special pore structure and wide distribution of acid sites in the pore channel. However, traditional SAPO-34 with a small pore size suffers from carbon deposition and deactivation in catalytic reactions, and its inability to catalytically convert bulky organic molecules limits its industrial application. Meanwhile, impurities of SAPO-5, which have weak acidity leading to rapid catalyst deactivation, appear in SAPO-34 zeolite. Therefore, it is of great significance to synthesize SAPO-34 zeolite with a mesoporous pore structure, which can significantly improve the transfer of molecules in zeolites. In this paper, SAPO-34 zeolite with a hierarchical pore structure was synthesized, and its hydrodesulfurization performance for 4,6-dimethyldibenzothiophene (4,6-DMDBT) was studied in a fixed bed reactor. The characteristic results show that BET-specific surface area, micropore volume, and mesoporous volume of synthesized SAPO-34 are 754 m2 g-1, 0.25, and 0.23 cm3 g-1 respectively, and the pore size is mainly concentrated at 4 nm. The catalytic conversion of 4,6-DMDMT with Co- and Mo-supported SAPO-34 is about 83%, which is much higher than the catalytic performance of Al2O3.
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In this work, an innovative technology by using ferrous sulfate combined with digestate, was applied to the Cr (VI) reduction. In the combined process, 3% ferrous sulfate, 5% digestate, 2% glucose, 30 °C and 50% moisture content were proved to be the optimal operating conditions. The combined process achieved 100% reduction of 3000 mg/Kg Cr (VI) within 10 days. Ferrous sulfate and digestate had a synergistic effect on Cr (VI) reduction. XPS analysis showed that Cr (VI) was reduced to Cr (III) in the combined treatment group. Functional microorganisms in digestate played an important role in the reduction of Cr (VI). Sulfate and Fe(III) could be reduced by microorganisms in digestate, and the reduction products accelerated the reduction of Cr (VI). The combined treatment improved the relative abundance of Clostridium, Acinetobacter, and Tissierella, which were of great significance for the reduction of Cr (VI).
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Cromo , Solo , Cromo/análise , Compostos Férricos , Compostos Ferrosos , OxirreduçãoRESUMO
In this study, indoor simulation experiments were performed to elucidate the effects of migration and transformation of dissolving organic matter (DOM) during the decay of algal blooms. Based on ultraviolet-visible spectra (UV-vis) and excitation-emission matrix spectroscopy (EEMs), spectral characterizations of dissolved organic matter (DOM) in overlying water were evaluated with analyses of the physical and chemical indexes, variation in dissolved organic carbon (DOC), and variation in dissolved inorganic carbon (DIC). Results showed that at the early stage of decay, a large amount of organic matter was released, and dissolved oxygen (DO) decreased sharply. With the extension of reaction time, DOC gradually changed into DIC, which further changed the oxidation-reduction and acid-base characteristics of the water. UV-vis spectra showed that a large amount of DOM was released with high aromaticity and a high degree of humification, and the released DOM was gradually degraded. With the application of parallel factor analysis in excitation-emission matrix spectroscopy (EEM-PARAFAC), three fluorescence components were analyzed:refractory humic-like substances (C1), protein-like tryptophan substances (C2) produced by algae, and fulvic-like substances (C3) related to microbial activities. Most protein-like tryptophan substances were degraded into fulvic-like substances by microorganisms during the decaying process. Heterotrophic microorganisms promoted the release of algae-derived DOM and accelerated the degradation of DOM. The DOM born during algae blooms decaying process was eventually converted into humic-like substance, which was difficult to be degraded. We analyzed correlations of water quality, UV-vis spectrum, and EEMs parameters. Results showed that ORP was positively correlated (P<0.05) with DO. There was a significant negative correlation (P<0.05) between pH and DOC, which was consistent with the trend of the transformation to from DOC to DIC; C1 was positively correlated (P<0.05) with Fn355; and C2 was significantly positively correlated (P<0.05) with DOC and Fn280; C3 was positively correlated (P<0.05) with FI, BIX and ß:α. The variation trend of these spectral parameters was consistent with that of DOM components. In summary, with the analyses of water quality characteristics and spectral characteristics of DOM in overlying water during algae blooms decaying process, it was expected that our results could contribute to the further exploration of the dynamic migration and transformation of lake DOM and the changes of carbon cycling.
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Substâncias Húmicas , Água , Eutrofização , Substâncias Húmicas/análise , Lagos , Espectrometria de FluorescênciaRESUMO
Construction of two-dimensional (2D) metal-organic frameworks (MOFs) for energy storage and conversion has attracted great attention due to the synergistic advantages of 2D nanostructures and MOFs. Herein, a Co-MOF material with different 2D morphologies of vertical nanoplate arrays and faveolate nanosheets are in-situ fabricated on Ni foam with and without using polyvinylpyrrolidone (PVP) as a regulator. Toward the application in energy storage, both of two morphologies of the Co-MOF exhibit good electrochemical properties. In particular, the vertical Co-MOF nanoplate arrays deliver a high areal capacity of 8.56 C/cm2 at the current density of 5 mA/cm2, which is much higher than that of faveolate Co-MOF nanosheets (2.39 C/cm2 at 5 mA/cm2). Moreover, a hybrid supercapacitor (HSC) device using the Co-MOF nanoplate arrays positive electrode and activated carbon (AC) negative electrode is assembled, which delivers a volumetric capacitance of 17.9 F/cm3 at 10 mA/cm2, a high energy density of 7.2 mW h cm-3 and a good cyclic stability (retaining over 88.0% of initial capacitance after 3000 cycles). These findings demonstrate that the as-fabricated 2D Co-MOFs possess a huge potential in energy storage.
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With the demand of energy and re-utilization of wastes, the renewable lignocellulosic biomass, has attracted increasing and significant attention for alleviating the growing energy crisis and environment problems. As main components of lignocellulosic biomass, lignin, cellulose, and hemicellulose are connected by hydrogen bond to form a compact skeleton structure, resulting the trenchant condition of biomass pyrolysis. Also, pyrolysis products of above three main constituents contain a large amount of oxygenates that cause low heating value, high corrosiveness, high viscosity, and instability. Meanwhile, zeolites are of considerable significance to the conversion of lignocellulosic biomass to desirable chemical products on account of fine shape selectivity and moderate acid sites and strength. Among numerous zeolites, ZSM-5-based catalysts have been most extensively studied, and the acidity and porosity of ZSM-5 can be tuned by changing the content of Si or Al in zeolite. Beyond that, doping of other metal elements, such as Mn, Co, Ni, Ga, Ce, Pt, into ZSM-5 is also an efficient way to regulate the strength and density of acid sites in zeolite precisely. This review focused on the recent investigation of Ni-modified microporous ZSM-5 used in catalytic pyrolysis of lignin and cellulose. The application of metal-modified hierarchical ZSM-5 is also covered.
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Tight junctions are important structures that form the barrier of cells and tissues, and they play key roles in maintaining homeostasis of our body. The backbone of the tight junction proteins are claudins, which composed more than twenty members. The tight junction protein 1 (TJP1), also called ZO-1 (Zonula Occludens-1), is one of the tight junction related proteins, and it is widely used in literature to label tight junctions. Here we showed that TJP1 (ZO-1) is highly expressed in cancerous HeLa cells, fibroblast cells, HUVEC as well as MDCK cells, while claudin-1 is highly expressed in HUVEC and MDCK cells, but not expressed in HeLa and fibroblast cells. We aimed to investigate whether tight junction is present in HeLa and fibroblast cells. We used transepithelial/transendothelial electrical resistance (TEER) to measure tight junction dynamics in these cells. The results showed that there is no TEERs in HeLa and fibroblast cells, while there is relatively high TEER in HUVEC and MDCK cells. Importantly, the TEER in MDCK cells is dramatically reduced after knockdown of TJP1 (ZO-1). These results suggest that TJP1 (ZO-1) cannot be used as a marker of tight junctions in a variety of cells, while TJP1 (ZO-1) may play an important role in regulation of tight junctions in MDCK cells.
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An eight-element multiple-input multiple-output (MIMO) frame antenna array in the 3.5 GHz band (3400-3600 MHz) for 5G mobile terminal systems was presented. By using the adjacent grounding and electromagnetic coupling feeding technology, the loop antenna element could generate two resonant frequencies, thus effectively expanding its bandwidth. By adopting double-sided parallel strip line (DSPSL) technology, the electromagnetic coupling inside the loop antenna could be adjusted, and the size of the loop antenna could be effectively reduced so that the MIMO antenna array could obtain a low-profile structure. The total size of the MIMO array was 150 mm × 75 mm × 5.3 mm. Without additional isolation measures, the measured -6 dB impedance bandwidth (BW) was 3400-3660 MHz, and the minimum isolation between antenna elements was better than -20 dB. The proposed antenna was expected to be applied to 5G mobile terminals based on its low-profile, high-isolated characteristics, and good MIMO performance.
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Nanomaterials with graphene-like structures have many excellent properties different from bulk materials and have become one of the most popular international frontiers in recent years. In this paper, graphene-like molybdenum disulfide materials are prepared by ultrasonic exfoliation method assisted with 1-Dodecanethiol. Double solvent ultrasonic exfoliation is realized by introducing chloroform. In addition, the optimal preparation conditions for the preparation of graphene-based molybdenum disulfide are investigated from the aspects of ultrasonic processing time and volume ratio of 1-Dodecanethiol and chloroform. Ultrasonic cleaning instrument is used in the experiment, it's type is KQ3200E (40KHz, 150 W). Results show that the prepared graphene-like molybdenum disulfide has the highest concentration when the volume ratios of 1-Dodecanethiol and chloroform is 1:1 and ultrasonic processing time is 12 h. The dispersion of graphene-like molybdenum disulfide in low-boiling organic solvents, such as chloroform, tetrahydrofuran (THF), isopropanol (IPA), acetone, acetonitrile (CH3CN) and ethanol, is realized by solvent exchange method. Characterized by transmission electron microscopy, a relatively thin sheet material is obtained. In addition, the latest methods for preparing graphene-like molybdenum disulfide nanosheet are discussed in view of micromechanical exfoliation, lithium ion intercalation, chemical vapor deposition and chemical synthesis, the advantages and limitations of various preparation methods are compared, the applications of graphene-like molybdenum disulfide nanosheets are also investigated.
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A compact broadband implantable patch antenna is designed for the field of biotelemetry and experimentally demonstrated using the Medical Device Radiocommunications Service (MedRadio) band (401â»406 MHz). The proposed antenna can obtain a broad impedance bandwidth by exciting dual-resonant frequencies, and has a compact structure using bent metal radiating strips and a short strategy. The total volume of the proposed antenna, including substrate and superstrate, is about 479 mm³ (23 × 16.4 × 1.27 mm³). The measured bandwidth is 52 MHz (382â»434 MHz) at a return loss of -10 dB. The resonance, radiation and specific absorption rate (SAR) performance of the antenna are examined and characterized.
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Through the manipulation of co-polarized reflection and cross-polarized reflection from a periodic array of metal-dielectric-metal resonators, a plethora of unprecedented metamaterial devices have been successfully demonstrated, such as perfect absorber and polarization converter. Recently, some broadband absorbers based on anisotropic resonators have been reported, which are actually poor absorbers when the cross-polarized reflection is considered. Here, we demonstrate that an ultra-wideband and high-efficiency reflective cross-polarization convertor can be achieved by breaking the symmetry of the resonator unit of a perfect absorber. Simulation results show that the polarization conversion ratio of the proposed metasurface is above 90% in the frequency range from 6.67 to 17.1 GHz and the relative bandwidth reaches 87.7%. The experimental results are in good agreement with the simulation results. The method paves a new way for the design of broadband polarization convertor, which can also be extended to the terahertz band.
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We report the design, fabrication, and measurement of an ultra-broadband wide-angle reflective cross-polarization convertor using the compact H-shaped metasurface. The significant bandwidth expansion is attributed to the four electromagnetic resonances generated in an H-shaped unit. The simulation results show that the polarization conversion ratio (PCR) of the proposed metasurface is above 90% in the frequency range from 7 to 19.5 GHz and the relative bandwidth reaches 94%. The proposed metasurface is valid for a wide range of incident angles, and the mean polarization conversion ratio remains 80% even though the incident angle reaches 41.5°. The experimental results are in good agreement with the simulation results. Compared with the previous designs, the proposed linear polarization converter has a simple geometry but an excellent performance and hence has potential applications in microwave communications, remote sensors, and imaging systems.
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The self-assembly of carboxylated fullerene with poly(styrene-b-2-vinylpyridine) (PS-b-P2VP) with different molecular weights, poly-2-vinylpyridine, and amine-terminated polystyrene, at the interface between toluene and water was investigated. For all values of the pH, the functionalized fullerene interacted with the polymers at the water/toluene interface, forming a nanoparticle network, reducing the interfacial tension. At pH values of 4.84 and 7.8, robust, elastic films were formed at the interface, such that hollow tubules could be formed in situ when an aqueous solution of the functionalized fullerene was jetted into a toluene solution of PS-b-P2VP at a pH of 4.84. With variation of the pH, the mechanical properties of the fullerene/polymer assemblies can be varied by tuning the strength of the interactions between the functionalized fullerenes and the PS-b-P2VP.
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Properties of binary surfactant systems of nonionic surfactants poly(ethylene oxide) (PEO) lauryl ethers (C(12)E(10), C(12)E(23), C(12)E(42)) with a cationic gemini surfactant, butanediyl-α,ω-bis(tetradecyldimethylammonium bromide) (14-4-14), have been investigated by Steady-state Fluorescence (FL), zeta potential, Dynamic Light Scattering (DLS), Transmission Electron Microscopy (TEM), Cryogenic Transmission Electron Microscopy (CryoTEM), and X-ray Diffraction (XRD). Through FL measurements, critical micelle concentration (CMC) of the three binary systems for different mixing mole fractions is determined and the values fall between those of pure constituent surfactants. Ideal CMC (CMC(ideal)), mole fraction in aggregates (X), interaction parameter (ß), activity coefficients (f(1) and f(2)), and excess free energy of mixing (ΔG(ex)) have been calculated. All these parameters indicate nonideal behavior and synergistic interactions between the constituent surfactants, which is explained in terms of electrostatic attraction between headgroups of constituent surfactants and reduction of electrostatic repulsion between headgroups of 14-4-14 due to the presence of nonionic surfactants. DLS, TEM and CryoTEM results show that nonionic surfactants facilitate the formation of larger aggregates. Micelles and vesicles in larger size compared with those of 14-4-14 coexist in the mixed solutions. Both surfactant composition and PEO chain length are found to play a strong effect on the properties of the binary systems.
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Micelas , Polietilenoglicóis/química , Compostos de Amônio Quaternário/química , Tensoativos/química , Cátions/química , Microscopia Eletrônica de Transmissão , Água/químicaRESUMO
A novel class of amphiphilic cationic polyelectrolytes, poly(A-co-G)s, comprising of gemini type surfactant segment 1,3-bis(N,N-dimethyl-N-dodecylammonium)-2-propylacrylate dibromide (G) and acryloyloxyethyl trimethyl ammonium chloride (A), were synthesized. Their aggregation properties were investigated by employing fluorescence spectroscopy, dynamic light scattering, transmission electron microscopy, and ζ-potential measurements. For comparison, a series of polyelectrolytes containing a traditional single alkyl chain surfactant unit (acryloyloxyethyl-N,N-dimethyl-N-dodecylammonium bromide (D)), poly(A-co-D)s, were also synthesized and investigated. It was found that the critical aggregation concentration (cac) of poly(A-co-G)s is much lower than that of poly(A-co-D)s. The huge interpolymer aggregates (with a hydrodynamic radius of >450 nm) occur in poly(A-co-G)s aqueous solution, and the size of aggregates increases with the increase of the molar content of the gemini-type surfmer segment and the concentration of the copolymer. The size of aggregates in poly(A-co-D)s aqueous solution is much smaller than poly(A-co-G)s, which also increases with the increase of the molar content of the single alkyl chain surfmer segment and the concentration of the copolymer. The results of aggregation number and charge density of aggregate in poly(A-co-G)s and poly(A-co-D)s indicate that the copolymers have a strong tendency toward interpolymer aggregation and the aggregates in poly(A-co-G)s are much more compact than those of poly(A-co-D)s. These results are interpreted in terms of the synergistic effects of double hydrophobic chains on the gemini surfactant unit.
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OBJECTIVE: To explore an ideal method for comprehensive correcting of the unilateral cleft lip nasal defomity. METHODS: The operation includes replacement of the displaced tissue, excision of the deviated septum, and correction of the deviated septum and the deformity of the lower nose. The excised nasal septum was grafted on the alar base, the nasal columella and the nasal tip. RESULTS: 32 patients were treated with this method from 1994 to 1999. Postoperative fellow-up for 1-3 years demonstrated satisfactory results. CONCLUSION: Through excision and grafting of the nasal septum, the deviated septum and the deformity of the lower nose are effectively corrected. Complete undermining and replacement of the displaced structure are the basis of correcting the cleft lip nasal deformity.