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1.
Small ; : e2403453, 2024 Jun 08.
Artigo em Inglês | MEDLINE | ID: mdl-38850189

RESUMO

Upcoming energy-autonomous mm-scale Internet-of-things devices require high-energy and high-power microbatteries. On-chip 3D thin-film batteries (TFBs) are the most promising option but lack high-rate anode materials. Here, Li4Ti5O12 thin films fabricated by atomic layer deposition (ALD) are electrochemically evaluated on 3D substrates for the first time. The 3D Li4Ti5O12 reveals an excellent footprint capacity of 20.23 µAh cm-2 at 1 C. The outstanding high-rate capability is demonstrated with 7.75 µAh cm-2 at 5 mA cm-2 (250 C) while preserving a remarkable capacity retention of 97.4% after 500 cycles. Planar films with various thicknesses exhibit electrochemical nanoscale effects and are tuned to maximize performance. The developed ALD process enables conformal high-quality spinel (111)-textured Li4Ti5O12 films on Si substrates with an area enhancement of 9. Interface engineering by employing ultrathin AlOx on the current collector facilitates a required crystallization time reduction which ensures high film and interface quality and prospective on-chip integration. This work demonstrates that 3D Li4Ti5O12 by ALD can be an attractive solution for the microelectronics-compatible fabrication of scalable high-energy and high-power Li-ion 3D TFBs.

2.
Photochem Photobiol Sci ; 23(5): 823-837, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38568410

RESUMO

Titanium dioxide (TiO2) is a well-known material for its biomedical applications, among which its implementation as a photosensitizer in photodynamic therapy has attracted considerable interest due to its photocatalytic properties, biocompatibility, high chemical stability, and low toxicity. However, the photoactivation of TiO2 requires ultraviolet light, which may lead to cell mutation and consequently cancer. To address these challenges, recent research has focused on the incorporation of metal dopants into the TiO2 lattice to shift the band gap to lower energies by introducing allowed energy states within the band gap, thus ensuring the harnessing of visible light. This study presents the synthesis, characterization, and application of TiO2 nanoparticles (NPs) in their undoped, doped, and co-doped forms for antimicrobial photodynamic therapy (APDT) against Candida albicans. Blue light with a wavelength of 450 nm was used, with doses ranging from 20 to 60 J/cm2 and an NP concentration of 500 µg/ml. It was observed that doping TiO2 with Cu, Fe, Ag ions, and co-doping Cu:Fe into the TiO2 nanostructure enhanced the visible light photoactivity of TiO2 NPs. Experimental studies were done to investigate the effects of different ions doped into the TiO2 crystal lattice on their structural, optical, morphological, and chemical composition for APDT applications. In particular, Ag-doped TiO2 emerged as the best candidate, achieving 90-100% eradication of C. albicans.


Assuntos
Antifúngicos , Candida albicans , Luz , Nanopartículas , Titânio , Titânio/química , Titânio/farmacologia , Antifúngicos/farmacologia , Antifúngicos/química , Antifúngicos/síntese química , Candida albicans/efeitos dos fármacos , Nanopartículas/química , Testes de Sensibilidade Microbiana , Fármacos Fotossensibilizantes/química , Fármacos Fotossensibilizantes/farmacologia , Fármacos Fotossensibilizantes/síntese química , Fotoquimioterapia
3.
J Nanobiotechnology ; 22(1): 158, 2024 Apr 08.
Artigo em Inglês | MEDLINE | ID: mdl-38589901

RESUMO

In the context of wound healing and tissue regeneration, precise control of cell migration direction is deemed crucial. To address this challenge, polydimethylsiloxane (PDMS) platforms with patterned 10 nm thick TiOx in arrowhead shape were designed and fabricated. Remarkably, without tall sidewall constraints, MC3T3-E1 cells seeded on these platforms were constrained to migrate along the tips of the arrowheads, as the cells were guided by the asymmetrical arrowhead tips which provided large contact areas. To the best of our knowledge, this is the first study demonstrating the use of thin TiOx arrowhead pattern in combination with a cell-repellent PDMS surface to provide guided cell migration unidirectionally without tall sidewall constraints. Additionally, high-resolution fluorescence imaging revealed that the asymmetrical distribution of focal adhesions, triggered by the patterned TiOx arrowheads with arm lengths of 10, 20, and 35 µm, promoted cell adhesion and protrusion along the arrowhead tip direction, resulting in unidirectional cell migration. These findings have important implications for the design of biointerfaces with ultrathin patterns to precisely control cell migration. Furthermore, microelectrodes were integrated with the patterned TiOx arrowheads to enable dynamic monitoring of cell migration using impedance measurement. This microfluidic device integrated with thin layer of guiding pattern and microelectrodes allows simultaneous control of directional cell migration and characterization of the cell movement of individual MC3T3-E1 cells, offering great potential for the development of biosensors for single-cell monitoring.


Assuntos
Dimetilpolisiloxanos , Adesões Focais , Adesão Celular , Movimento Celular
4.
Arch Toxicol ; 98(4): 1061-1080, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38340173

RESUMO

We present a novel lung aerosol exposure system named MALIES (modular air-liquid interface exposure system), which allows three-dimensional cultivation of lung epithelial cells in alveolar-like scaffolds (MatriGrids®) and exposure to nanoparticle aerosols. MALIES consists of multiple modular units for aerosol generation, and can be rapidly assembled and commissioned. The MALIES system was proven for its ability to reliably produce a dose-dependent toxicity in A549 cells using CuSO4 aerosol. Cytotoxic effects of BaSO4- and TiO2-nanoparticles were investigated using MALIES with the human lung tumor cell line A549 cultured at the air-liquid interface. Experiments with concentrations of up to 5.93 × 105 (BaSO4) and 1.49 × 106 (TiO2) particles/cm3, resulting in deposited masses of up to 26.6 and 74.0 µg/cm2 were performed using two identical aerosol exposure systems in two different laboratories. LDH, resazurin reduction and total glutathione were measured. A549 cells grown on MatriGrids® form a ZO-1- and E-Cadherin-positive epithelial barrier and produce mucin and surfactant protein. BaSO4-NP in a deposited mass of up to 26.6 µg/cm2 resulted in mild, reversible damage (~ 10% decrease in viability) to lung epithelium 24 h after exposure. TiO2-NP in a deposited mass of up to 74.0 µg/cm2 did not induce any cytotoxicity in A549 cells 24 h and 72 h after exposure, with the exception of a 1.7 fold increase in the low exposure group in laboratory 1. These results are consistent with previous studies showing no significant damage to lung epithelium by short-term treatment with low concentrations of nanoscale BaSO4 and TiO2 in in vitro experiments.


Assuntos
Nanopartículas , Aerossóis e Gotículas Respiratórios , Humanos , Células A549 , Células Cultivadas , Nanopartículas/toxicidade , Linhagem Celular , Aerossóis
5.
Drug Chem Toxicol ; : 1-11, 2024 Sep 03.
Artigo em Inglês | MEDLINE | ID: mdl-39227360

RESUMO

Due to its antioxidant action, the carotenoid lycopene has been demonstrated to have a protective effect in several disease models; however, its effect on the nanoform of titanium oxide (nano-TiO2)-induced neurotoxicity has not yet been determined. The purpose of this study was to evaluate how lycopene affects neuronal damage brought on by nano-TiO2 and the mechanisms involved. SH-SY5Y cells were treated with different concentrations of nano-TiO2 for 48 hours, the MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) test was used after that to evaluate cell viability. IC50 of nano-TiO2 was determined and the results revealed that IC50 is equal 40 µM/mL, lycopene (10 µM) was applied to SH-SY5Y human neuroblastoma cells an hour before exposure to 40 µM nano-TiO2. Reactive oxygen species, lipid peroxidation, nitric oxide, glutathione, superoxide dismutase, and catalase, tumor necrosis factor-alpha, interleukin 1 beta, nuclear factor kappa B, and apoptotic markers (Bcl2, Bax, and caspase-3), were measured to determine the anti-oxidant effect of lycopene. In SH-SY5Y neuroblastoma cells, pretreatment with 10 µM lycopene significantly reduced the toxicity brought on by exposure to nano-TiO2, according to MTT assay findings and lactate dehydrogenase (LDH) cytotoxicity assessment. In cells exposed to nano-TiO2, lycopene pretreatment significantly boosted the activity of antioxidative enzymes and reduced oxidative stress. Furthermore, when SH-SY5Y cells were subjected to nano-TiO2, lycopene pretreatment stopped neuroinflammation and apoptosis. The findings of this study suggest that lycopene may be an effective neuroprotective against oxidative stress and neuroinflammation and may be used to stop neuronal death or injury in a variety of neurological illnesses.

6.
Int J Mol Sci ; 25(2)2024 Jan 16.
Artigo em Inglês | MEDLINE | ID: mdl-38256151

RESUMO

Cardiovascular diseases (CVDs) increasingly burden health systems and patients worldwide, necessitating the improved awareness of current treatment possibilities and the development of more efficient therapeutic strategies. When plaque deposits narrow the arteries, the standard of care implies the insertion of a stent at the lesion site. The most promising development in cardiovascular stents has been the release of medications from these stents. However, the use of drug-eluting stents (DESs) is still challenged by in-stent restenosis occurrence. DESs' long-term clinical success depends on several parameters, including the degradability of the polymers, drug release profiles, stent platforms, coating polymers, and the metals and their alloys that are employed as metal frames in the stents. Thus, it is critical to investigate new approaches to optimize the most suitable DESs to solve problems with the inflammatory response, delayed endothelialization, and sub-acute stent thrombosis. As certain advancements have been reported in the literature, this review aims to present the latest updates in the coatings field for cardiovascular stents. Specifically, there are described various organic (e.g., synthetic and natural polymer-based coatings, stents coated directly with drugs, and coatings containing endothelial cells) and inorganic (e.g., metallic and nonmetallic materials) stent coating options, aiming to create an updated framework that would serve as an inception point for future research.


Assuntos
Doenças Cardiovasculares , Células Endoteliais , Humanos , Doenças Cardiovasculares/terapia , Artérias , Ligas , Polímeros
7.
Int J Mol Sci ; 25(10)2024 May 13.
Artigo em Inglês | MEDLINE | ID: mdl-38791348

RESUMO

Hybrid nanomaterials have attracted considerable interest in biomedicine because of their fascinating characteristics and wide range of applications in targeted drug delivery, antibacterial activity, and cancer treatment. This study developed a gelatin-coated Titanium oxide/palladium (TiO2/Pd) hybrid nanomaterial to enhance the antibacterial and anticancer capabilities. Morphological and structural analyses were conducted to characterize the synthesized hybrid nanomaterial. The surface texture of the hybrid nanomaterials was examined by high-resolution transmission electron microscopy (HR-TEM) and field-emission scanning electron microscopy (FE-SEM). The FE-SEM image revealed the bulk of the spherically shaped particles and the aggregated tiny granules. Energy dispersive X-ray spectroscopy (EDS) revealed Ti, Pd, C, and O. X-ray diffraction (XRD) revealed the gelatin-coated TiO2/Pd to be in the anatase form. Fourier transform infrared spectroscopy examined the interactions among the gelatin-coated TiO2/Pd nanoparticles. The gelatin-coated TiO2/Pd nanomaterials exhibited high antibacterial activity against Escherichia coli (22 mm) and Bacillus subtilis (17 mm) compared to individual nanoparticles, confirming the synergistic effect. More importantly, the gelatin-coated TiO2/Pd hybrid nanomaterial exhibited remarkable cytotoxic effects on A549 lung cancer cells which shows a linear increase with the concentration of the nanomaterial. The hybrid nanomaterials displayed higher toxicity to cancer cells than the nanoparticles alone. Furthermore, the cytotoxic activity against human cancer cells was verified by the generation of reactive oxygen species and nuclear damage. Therefore, gelatin-coated TiO2/Pd nanomaterials have potential uses in treating cancer and bacterial infections.


Assuntos
Antibacterianos , Antineoplásicos , Escherichia coli , Gelatina , Nanoestruturas , Paládio , Titânio , Titânio/química , Titânio/farmacologia , Antibacterianos/farmacologia , Antibacterianos/química , Humanos , Antineoplásicos/farmacologia , Antineoplásicos/química , Gelatina/química , Paládio/química , Paládio/farmacologia , Escherichia coli/efeitos dos fármacos , Nanoestruturas/química , Células A549 , Bacillus subtilis/efeitos dos fármacos , Testes de Sensibilidade Microbiana , Difração de Raios X , Nanopartículas Metálicas/química
8.
Molecules ; 29(10)2024 May 19.
Artigo em Inglês | MEDLINE | ID: mdl-38792253

RESUMO

Preparing high-performance oxygen evolution reaction (OER) catalysts with low precious metal loadings for water electrolysis applications (e.g., for green hydrogen production) is challenging and requires electrically conductive, high-surface-area, and stable support materials. Combining the properties of stable TiO2 with those of active iridium oxide, we synthesized highly active electrodes for OER in acidic media. TiO2 powders (both commercially available Degussa P-25® and hydrothermally prepared in the laboratory from TiOSO4, either as received/prepared or following ammonolysis to be converted to titania black), were decorated with IrO2 by UV photodeposition from Ir(III) aqueous solutions of varied methanol scavenger concentrations. TEM, EDS, FESEM, XPS, and XRD measurements demonstrate that the optimized version of the photodeposition preparation method (i.e., with no added methanol) leads to direct deposition of well-dispersed IrO2 nanoparticles. The electroactive surface area and electrocatalytic performance towards OER of these catalysts have been evaluated by cyclic voltammetry (CV), Linear Sweep Voltammetry (LSV), and Electrochemical Impedance Spectroscopy (EIS) in 0.1 M HClO4 solutions. All TiO2-based catalysts exhibited better mass-specific (as well as intrinsic) OER activity than commercial unsupported IrO2, with the best of them (IrO2 on Degussa P-25® ΤiO2 and laboratory-made TiO2 black) showing 100 mAmgIr-1 at an overpotential of η = 243 mV. Chronoamperometry (CA) experiments also proved good medium-term stability of the optimum IrO2/TiO2 electrodes during OER.

9.
Nanotechnology ; 34(48)2023 Sep 12.
Artigo em Inglês | MEDLINE | ID: mdl-37619535

RESUMO

Worldwide, dyes are significant pollutants present in water because of their huge consumption for industrial purposes. These dyes as pollutants cause serious health issues in human beings and cause the loss of aquatic biodiversity. So, remediation of pollutants like dyes from wastewater is the need of the hour. In the present study, we greenly synthesizedSpirulina-mediated titanium oxide nanoparticles (STONPs) for the adsorptive remediation of methyl orange (MO) (anionic) and malachite green (MG) (cationic) dyes. The characterization of STONPs was performed by Field emission scanning electron microscopy (FESEM) with EDX, FT-IR, XRD, Zeta Potential and particle size analyzer, Raman spectroscopy, and UV-vis. The various parameter effects like pH, nano-adsorbent dose, the concentration of dye, contact time, and temperature were also examined. Adsorption isotherms like Langmuir, Freundlich, and Temkin, and Kinetics models like Elovich Model, Pseudo 1st, intraparticle diffusion model (IPDM), Pseudo 2nd order, and the thermodynamic model were applied for a stronger interpretation. Theqmaxattained utilizing the Langmuir adsorption model was 272.4795 mg g-1and 209.6436 mg g-1for MO and MG correspondingly. The regeneration study of synthesized nanomaterials up to five cycles was also done. We found that greenly synthesized STONPs have great potential for adsorptive remediation for both MG and MO dyes.


Assuntos
Poluentes Ambientais , Nanopartículas , Humanos , Corantes , Adsorção , Espectroscopia de Infravermelho com Transformada de Fourier , Cátions , Extratos Vegetais
10.
Environ Res ; 227: 115786, 2023 06 15.
Artigo em Inglês | MEDLINE | ID: mdl-37004858

RESUMO

Various pesticides and organic compounds generated as a result of rapid industrialization and pharmaceutical companies pose a major threat to the environment. Novel photocatalysts based on zinc oxide and titanium oxide exhibit great potential towards absorption of these organic pollutants from wastewater. The photocatalysts possess various extraordinary properties like photocatalytic degradation potential, non-toxic and high stability. However, several limitations are also associated with the applications of these photocatalysts like poor affinity, particle agglomeration, high band gap and recovery issues. Hence, optimization is required to enhance their efficiency and at the same time make them cost effective and sustainable. The review covers the mechanism for water treatment, limitations and development of different modification strategies that improve the removal efficiency of titanium and zinc oxide based photocatalysts. Thus, further research in the field of photocatalysts can be encouraged for carrying out water remediation.


Assuntos
Nanoestruturas , Óxido de Zinco , Desinfecção , Titânio , Catálise
11.
Sensors (Basel) ; 23(17)2023 Aug 29.
Artigo em Inglês | MEDLINE | ID: mdl-37687950

RESUMO

This numerical research presents a simple hybrid structure comprised of TiO2-Cu-BaTiO3 for a modified Kretschmann configuration that exhibits high sensitivity and high resolution for biosensing applications through an angular interrogation method. Recently, copper (Cu) emerged as an exceptional choice as a plasmonic metal for developing surface plasmon sensors (SPR) with high resolution as it yields finer, thinner SPR curves than Ag and Au. As copper is prone to oxidation, especially in ambient conditions, the proposed structure involves the utilization of barium titanate (BaTiO3) film as a protection layer that not only preserves Cu film from oxidizing but enhances the performance of the sensor to a great extent. Numerical results also show that the utilization of a thin adhesive layer of titanium dioxide (TiO2) between the prism base and Cu film not only induces strong interaction between them but also enhances the performance of the sensor. Such a configuration, upon suitable optimization of the thickness of each layer, is found to enhance sensitivity as high as 552°/RIU with a figure of merit (FOM) of 136.97 RIU-1. This suggested biosensor design with enhanced sensitivity is expected to enable long-term detection with greater accuracy and sensitivity even when using Cu as a plasmonic metal.


Assuntos
Cobre , Ressonância de Plasmônio de Superfície , Filmes Cinematográficos
12.
Nano Lett ; 22(1): 433-440, 2022 Jan 12.
Artigo em Inglês | MEDLINE | ID: mdl-34964640

RESUMO

An all-solid-state lithium-sulfur battery (ASSLSB) is a promising candidate for post-Li-ion battery technologies with high energy densities and good safety performance. However, the intrinsic insulating nature of sulfur requires triple-phase contact with an ionic conductor and an electronic conductor for electrochemical reactions, which decreases the amount of active surface and lowers the charge-transfer efficiency. In this work, a double-phase interface constructed from a mixed ionic/electronic conductor is proposed to enhance the solid-state electrochemical reaction of sulfur. By employing lithium lanthanum titanium oxide/carbon (LLTO/C) nanofibers with mixed ionic/electronic conductivity, enhanced charge-transfer behavior is realized at the sulfur-LLTO/C double-phase interface, compared to the traditional triple-phase interface. As a result, high sulfur utilization and excellent rate performance are achieved. And the facilitated charge transfer shows great potential to lower the operating temperature and improve the sulfur content for practical applications of ASSLSBs. Cycle performance is also enhanced due to the suppressed shuttle effect of polysulfides by the incorporation of the LLTO/C nanofibers.

13.
Int J Mol Sci ; 24(17)2023 Aug 26.
Artigo em Inglês | MEDLINE | ID: mdl-37686076

RESUMO

Bacterial infection has traditionally been treated with antibiotics, but their overuse is leading to the development of antibiotic resistance. This may be mitigated by alternative approaches to prevent or treat bacterial infections without utilization of antibiotics. Among the alternatives is the use of photo-responsive antimicrobial nanoparticles and/or nanocomposites, which present unique properties activated by light. In this study, we explored the combined use of titanium oxide and polydopamine to create nanoparticles with photocatalytic and photothermal antibacterial properties triggered by visible or near-infrared light. Furthermore, as a proof-of-concept, these photo-responsive nanoparticles were combined with mussel-inspired catechol-modified hyaluronic acid hydrogels to form novel light-driven antibacterial nanocomposites. The materials were challenged with models of Gram-negative and Gram-positive bacteria. For visible light, the average percentage killed (PK) was 94.6 for E. coli and 92.3 for S. aureus. For near-infrared light, PK for E. coli reported 52.8 and 99.2 for S. aureus. These results confirm the exciting potential of these nanocomposites to prevent the development of antibiotic resistance and also to open the door for further studies to optimize their composition in order to increase their bactericidal efficacy for biomedical applications.


Assuntos
Anti-Infecciosos , Nanocompostos , Escherichia coli , Staphylococcus aureus , Antibacterianos/farmacologia , Raios Infravermelhos
14.
Int J Mol Sci ; 24(7)2023 Apr 03.
Artigo em Inglês | MEDLINE | ID: mdl-37047671

RESUMO

The cytocompatibility of titanium oxides (TiO2) and oxynitrides (N-TiO2, TiOxNy) thin films depends heavily on the surface topography. Considering that the initial relief of the substrate and the coating are summed up in the final topography of the surface, it can be expected that the same sputtering modes result in different surface topography if the substrate differs. Here, we investigated the problem by examining 16 groups of samples differing in surface topography; 8 of them were hand-abraded and 8 were machine-polished. Magnetron sputtering was performed in a reaction gas medium with various N2:O2 ratios and bias voltages. Abraded and polished uncoated samples served as controls. The surfaces were studied using atomic force microscopy (AFM). The cytocompatibility of coatings was evaluated in terms of cytotoxicity, adhesion, viability, and NO production. It has been shown that the cytocompatibility of thin films largely depends on the surface nanostructure. Both excessively low and excessively high density of peaks, high and low kurtosis of height distribution (Sku), and low rates of mean summit curvature (Ssc) have a negative effect. Optimal cytocompatibility was demonstrated by abraded surface with a TiOxNy thin film sputtered at N2:O2 = 1:1 and Ub = 0 V. The nanopeaks of this surface had a maximum height, a density of about 0.5 per 1 µm2, Sku from 4 to 5, and an Ssc greater than 0.6. We believe that the excessive sharpness of surface nanostructures formed during magnetron sputtering of TiO2 and N-TiO2 films, especially at a high density of these structures, prevents both adhesion of endothelial cells, and their further proliferation and functioning. This effect is apparently due to damage to the cell membrane. At low height, kurtosis, and peak density, the main factor affecting the cell/surface interface is inefficient cell adhesion.


Assuntos
Células Endoteliais , Nanoestruturas , Titânio/química , Nanoestruturas/química , Microscopia de Força Atômica
15.
Pak J Med Sci ; 39(5): 1249-1254, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-37680828

RESUMO

Objective: To evaluate antagonistic role of titanium oxide nanoparticles against selected dental caries promoting bacteria. Methods: This in vitro-experimental study was conducted at Pakistan Institute of Engineering and Applied Sciences (PIEAS), National Institute of Health (NIH) and School of Dentistry (SOD), Islamabad for the period of one year from February 2022 to January 2023. Modified hydrothermal heating method was used to prepare titanium oxide nanoparticles (TiO2Nps). Size, shape, phase, band gap energy, surface and elemental composition of Nps were deciphered by application of various modern techniques including x-ray diffraction spectroscopy (XRD), scanning electron microscopy (SEM), dynamic light scattering (DLS), UV-Vis diffuse reflectance spectroscopy (DRS), atomic force microscopy (AFM), energy dispersive x-ray spectroscopy (EDX). Antimicrobial action of nanoparticles was evaluated against representatives of gram-positive (mono-derm) and Gram negative bacteria (di-derm) responsible for promoting dental caries. The zones of inhibition were calculated by disc diffusion method for each bacterial strain. Results: Characterization revealed that TiO2Nps were having an average size of 54nm, showing anatase-rutile phase having spherical, with very few- irregularly shaped particles. TiO2Nps contained only pure titanium and oxygen in the EDX image but organic compounds in FTIR scan. Results of antimicrobial action indicated their potent bactericidal action against Pseudomonas aeruginosa (20mm), Escherichia coli (19mm) and Lactobacillus acidophilus (19nm) while comparatively less activity against Staphylococcus aureus (16mm).. Conclusion: TiO2Nps fabricated by modified protocol displayed an effective antimicrobial activity and can be used as an alternative to the contemporary chemotherapeutics against selected bacterial pathogens to prevent dental caries.

16.
Angew Chem Int Ed Engl ; 62(37): e202309440, 2023 Sep 11.
Artigo em Inglês | MEDLINE | ID: mdl-37507344

RESUMO

Traditional mechanochemically controlled reversible-deactivation radical polymerization (RDRP) utilizes ultrasound or ball milling to regenerate activators, which induce side reactions because of the high-energy and high-frequency stimuli. Here, we propose a facile approach for tribochemically controlled atom transfer radical polymerization (tribo-ATRP) that relies on contact-electro-catalysis (CEC) between titanium oxide (TiO2 ) particles and CuBr2 /tris(2-pyridylmethylamine (TPMA), without any high-energy input. Under the friction induced by stirring, the TiO2 particles are electrified, continuously reducing CuBr2 /TPMA into CuBr/TPMA, thereby conversing alkyl halides into active radicals to start ATRP. In addition, the effect of friction on the reaction was elucidated by theoretical simulation. The results indicated that increasing the frequency could reduce the energy barrier for the electron transfer from TiO2 particles to CuBr2 /TPMA. In this study, the design of tribo-ATRP was successfully achieved, enabling CEC (ca. 10 Hz) access to a variety of polymers with predetermined molecular weights, low dispersity, and high chain-end fidelity.

17.
Plant J ; 105(4): 1123-1133, 2021 02.
Artigo em Inglês | MEDLINE | ID: mdl-33220116

RESUMO

Imaging mass spectrometry (IMS) is a powerful technique that enables analysis of various molecular species at a high spatial resolution with low detection limits. In contrast to the matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) approach, surface-assisted laser desorption/ionization (SALDI) can be more effective in the detection of small molecules due to the absence of interfering background signals in low m/z ranges. We developed a functionalized TiO2 nanowire as a solid substrate for IMS of low-molecular-weight species in plant tissues. We prepared TiO2 nanowires using an inexpensive modified hydrothermal process and subsequently functionalized them chemically with various silane analogs to overcome the problem of superhydrophilicity of the substrate. Chemical modification changed the selectivity of imprinting of samples deposited on the substrate surface and thus improved the detection limits. The substrate was applied to image distribution of the metabolites in very fragile specimens such as the petal of Catharanthus roseus. We observed that the metabolites are distributed heterogeneously in the petal, which is consistent with previous results reported for the C. roseus plant leaf and stem. The intermediates corresponding to the biosynthesis pathway of some vinca alkaloids were clearly shown in the petal. We also performed profiling of petals from five different cultivars of C. roseus plant. We verified the semi-quantitative capabilities of the imprinting/imaging approach by comparing results using the LC-MS analysis of the plant extracts. This suggested that the functionalized TiO2 nanowire substrate-based SALDI is a powerful technique complementary to MALDI-MS.


Assuntos
Catharanthus/metabolismo , Flores/metabolismo , Nanofios , Espectrometria de Massas por Ionização e Dessorção a Laser Assistida por Matriz/métodos , Titânio , Alcaloides de Vinca/metabolismo , Metabolismo Secundário , Espectrometria de Massas por Ionização e Dessorção a Laser Assistida por Matriz/instrumentação
18.
Chemphyschem ; 23(15): e202200029, 2022 Aug 03.
Artigo em Inglês | MEDLINE | ID: mdl-35604808

RESUMO

This study reports a noble metal-free robust inorganic photocatalyst for H2 O2 synthesis via two-electron oxygen reduction reaction (ORR). Antimony-doped tin oxide nanorods were heteroepitaxially grown from rutile TiO2 seed crystals with an orientation of (001)ATO //(001)TiO2 (ATO-NR//TiO2 ,//denotes heteroepitaxial junction) by a hydrothermal method. UV-light irradiation of ATO-NR//TiO2 particles stably and continuously produces H2 O2 from aerated aqueous solution of ethanol. Electrochemical measurements using rotating electrodes show that Sb-doping into SnO2 greatly enhances the electrocatalytic activity for two-electron ORR. The striking photocatalytic activity of ATO-NR//TiO2 stems from the effective charge separation, electrocatalytic activity for two-electron ORR, low catalytic activity for H2 O2 decomposition, and extraordinary robustness.

19.
Eur Arch Otorhinolaryngol ; 279(9): 4425-4433, 2022 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-35249130

RESUMO

PURPOSE: We report the manufacture of particles containing a mixture of hydroxyapatite-argentum-titanium oxide (HAT), followed by attachment to nonwoven polyester fabrics to produce HAT-coated sheets (HATS) for use in masks. The purpose of the present study was to perform cellular, in vivo, and clinical studies to further examine the safety of HATS for use in masks to improve nasal allergy. METHODS: Reverse mutation tests for HAT were performed using five bacterial strains. A cellular toxicity test was performed using a Chinese hamster cell line incubated with the HATS extracts. Skin reactions after intradermal administration were examined in rabbits. Skin sensitization tests in guinea pigs were performed using the HATS extracts. HAT was administered to the nasal cavity and conjunctival sac of the rabbits. An oral administration study was performed in rats. Finally, a human skin patch test was performed using the HATS. RESULTS: Reverse mutation tests showed negative results. The cellular toxicity test showed that the HATS extract had moderate cytotoxicity. The intradermal skin reaction and skin sensitization tests were all negative. The administration of HAT to the nasal cavity and intraocular administration showed negative results. No toxicity was observed after oral administration of HAT powder up to a dose of 2000 mg/kg. Finally, the skin patch test result was negative. CONCLUSION: Although HAT showed moderate cytotoxicity, in vivo results indicated that HAT is safe because it does not come in direct contact with cells in normal usage, and HATS is safe when used in masks.


Assuntos
Cosméticos , Hipersensibilidade , Animais , Cricetinae , Durapatita , Cobaias , Humanos , Máscaras , Coelhos , Ratos , Titânio
20.
Int J Mol Sci ; 23(7)2022 Apr 04.
Artigo em Inglês | MEDLINE | ID: mdl-35409363

RESUMO

The desire to harness solar energy to address current global environmental problems led us to investigate two-dimensional (2D) core-shell hybrid photocatalysts in the form of a 2D-TiO2-surfactant, mainly composed of fatty acids. The bulk products, prepared by two slightly different methods, consist of stacked host-guest hybrid sheets held together by van der Waals forces between alkyl carboxylate moieties, favoring the synergistic conjugation of the photophysical properties of the core and the hydrophobicity of the self-assembled surfactant monolayer of the shell. X-ray diffraction and the vibrational characteristics of the products revealed the influence of synthesis strategies on two types of supramolecular aggregates that differ in the core chemical structure, guest conformers of alkyl surfactant tails and type, and the bilayer and monolayer of the structure of nanocomposites. The singular ability of the TiO2 core to anchor carboxylate leads to commensurate hybrids, in contrast to both layered clay and layered double-hydroxide-based ion exchangers which have been previously reported, making them potentially interesting for modeling the role of fatty acids and lipids in bio-systems. The optical properties and photocatalytic activity of the products, mainly in composites with smaller bandgap semiconductors, are qualitatively similar to those of nanostructured TiO2 but improve their photoresponse due to bandgap shifts and the extreme aspect-ratio characteristics of two-dimensional TiO2 confinement. These results could be seen as a proof-of-concept of the potential of these materials to create custom-designed 2D-TiO2-surfactant supramolecular photocatalysts.


Assuntos
Nanocompostos , Tensoativos , Catálise , Ácidos Graxos , Nanocompostos/química , Titânio/química
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