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1.
Nanotechnology ; 35(32)2024 May 24.
Artigo em Inglês | MEDLINE | ID: mdl-38710177

RESUMO

This study investigates the fabrication process of copper thin films via thermal evaporation, with precise control over film thickness achieved throughZ-position adjustment. Analysis of the as-fabricated copper films reveals a discernible relationship between grain size (〈D〉) andZ-position, characterized by a phenomenological equation〈D〉XRDn(Z)=〈D〉0n1+32rZ2+158rZ4, which is further supported by a growth exponent (n) of 0.41 obtained from the analysis. This value aligns well with findings in the literature concerning the growth of copper films, thus underlining the validity and reliability of our experimental outcomes. The resulting crystallites, ranging in size from 20 to 26 nm, exhibit a resistivity within the range of 3.3-4.6µΩ · cm. Upon thermal annealing at 200 °C, cuprite Cu2O thin films are produced, demonstrating crystallite sizes ranging from ∼9 to ∼24 nm with increasing film thickness. The observed monotonic reduction in Cu2O crystallites relative to film thickness is attributed to a recrystallization process, indicating amorphization when oxygen atoms are introduced, followed by the nucleation and growth of newly formed copper oxide phase. Changes in the optical bandgap of the Cu2O films, ranging from 2.31 to 2.07 eV, are attributed mainly to the quantum confinement effect, particularly important in Cu2O with size close than the Bohr exciton diameter (5 nm) of the Cu2O. Additionally, correlations between refractive index and extinction coefficient with film thickness are observed, notably a linear relationship between refractive index and charge carrier density. Electrical measurements confirm the presence of a p-type semiconductor with carrier concentrations of ∼1014cm-3, showing a slight decrease with film thickness. This phenomenon is likely attributed to escalating film roughness, which introduces supplementary scattering mechanisms for charge carriers, leading to a resistivity increase, especially as the roughness approaches or surpasses the mean free path of charge carriers (8.61 nm). Moreover,ab-initiocalculations on the Cu2O crystalline phase to investigate the impact of hydrostatic strain on its electronic and optical properties was conducted. We believe that our findings provide crucial insights that support the elucidation of the experimental results. Notably, thinner cuprite films exhibit heightened sensitivity to ethanol gas at room temperature, indicating potential for highly responsive gas sensors, particularly for ethanol breath testing, with significant implications for portable device applications.

2.
J Environ Manage ; 310: 114805, 2022 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-35240565

RESUMO

The present study analyzed the performance of photochemical and electrochemical techniques in the degradation and mineralization of the pesticide carbendazim (CBZ). Direct photolysis (DP), heterogeneous photocatalysis (HP), photoelectrocatalysis (PEC), and electrochemical oxidation (EO) were tested, and the influence of UV radiation, current density (j), and supporting electrolyte concentration were evaluated. The results suggest that CBZ is only degraded by DP when UV-C254nm is used. For HP, the CBZ degradation was observed both when UV-A365nm or UV-C254nm were used, which is related to the reactive oxygen species (ROS) formed by the photocatalytic activity (photon-ROS). Neither DP nor HP were able to mineralize CBZ, demonstrating its resistance to photomediated processes. For EO, regardless of the j, there were higher CBZ degradation and mineralization than those observed when using DP and HP. The increase in the supporting electrolyte concentration (Na2SO4) did not affect the levels of degradation and mineralization of CBZ. Concerning the PEC, a CBZ mineralization of 52.2% was accomplished. These findings demonstrate that the EO is the main pathway for CBZ mineralization, suggesting an additional effect of the electro-ROS on the photon-ROS and UV-C254nm. The values of mineralization, kinetics, and half-life show that PEC UV-C254nm with a j of 15 mA cm-2 was the best setting for the degradation and mineralization of CBZ. However, when the values of specific energy consumption were considered for industrial applications, the use of EO with a j of 3 mA cm-2 and 4 g L-1 of Na2SO2 becomes more attractive. The assessment of by-products formed after this best cost-efficient treatment setting revealed the presence of aromatic and aliphatic compounds from CBZ degradation. Acute phytotoxicity results showed that the presence of sodium sulfate can be a representative factor regarding the toxicity of samples treated in electrochemical systems.


Assuntos
Poluentes Químicos da Água , Benzimidazóis , Carbamatos , Oxirredução , Fotólise , Raios Ultravioleta , Poluentes Químicos da Água/química
3.
Phys Chem Chem Phys ; 22(6): 3702-3714, 2020 Feb 14.
Artigo em Inglês | MEDLINE | ID: mdl-32003381

RESUMO

In this work, we present a coupled experimental and theoretical first-principles investigation on one of the more promising oxide-diluted magnetic semiconductors, the Sn1-xCoxO2 nanoparticle system, in order to see the effect of cobalt doping on the physical and chemical properties. Our findings suggest that progressive surface enrichment with dopant ions plays an essential role in the monotonous quenching of the surface disorder modes. That weakening is associated with the passivation of the oxygen vacancies as the Co excess at the surface becomes larger. Room-temperature 119Sn Mössbauer spectroscopy data analysis revealed the occurrence of a distribution of isomer shifts, related to the different non-equivalent surroundings of Sn4+ ions and the coexistence of Sn2+/Sn4+ at the particle surfaces provoked by the inhomogeneous distribution of Co ions, in agreement with the X-ray photoelectron spectroscopy measurements. Magnetic measurements revealed a paramagnetic behavior of the Co ions dispersed in the rutile-type matrix with antiferromagnetic correlations, which become stronger as the Co content is increased. Theoretical calculations show that a defect with two Co mediated by a nearby oxygen vacancy is the most likely defect. The predicted effects of this defect complex are in accordance with the experimental results.

4.
Nanotechnology ; 23(12): 125701, 2012 Mar 30.
Artigo em Inglês | MEDLINE | ID: mdl-22397807

RESUMO

We report on the strong temperature-dependent thermal expansion, α(D), in CdS quantum dots (QDs) embedded in a glass template. We have performed a systematic study by using the temperature-dependent first-order Raman spectra, in CdS bulk and in dot samples, in order to assess the size dependence of α(D), and where the role of the compressive strain provoked by the glass host matrix on the dot response is discussed. We report the Grüneisen mode parameters and the anharmonic coupling constants for small CdS dots with mean radius R âˆ¼ 2.0 nm. We found that γ parameters change, with respect to the bulk CdS, in a range between 20 and 50%, while the anharmonicity contribution from two-phonon decay channel becomes the most important process to the temperature-shift properties.

5.
Chemosphere ; 268: 128858, 2021 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-33187661

RESUMO

Heterogeneous photocatalysis was used for the degradation and mineralization of erythromycin (ERY), with a consequent production of carboxylic acids. For that, a series of TiO2 and Ti1-xSnxO2 structured catalysts, namely M1 to M5, was prepared using the washcoating method, with the catalytic coatings being deposited onto stainless steel meshes. Besides, the catalytic activity of the prepared systems was compared to that of the commercial mesh (CM). The results showed that the prepared TiO2 structured catalyst (M1) presented better ERY oxidation than the CM one, what was associated to the higher catalyst load and to the anatase/rutile ratio. Considering the Sn-doped structured catalysts, for M2, M4 and M5 catalysts, lower ERY mineralization and high formation of carboxylic acids were found, when compared to the M3 catalyst. The improved M3 activity was attributed to the formation of a staggered gap (type II heterojunction), providing better charge separation. In this situation, a high generation of hydroxyl radicals is obtained, resulting on a higher ERY mineralization. By the obtained results it is possible to determine that the addition order and the type of Sn compound added in the washcoating process, affects the catalytic activity due to the formation of a solid solution and to the type of produced heterostructures. The M3 catalyst also showed high stability in long-term tests up to 44 h of reaction. The results provide insights into the development of an inexpensive structured catalyst production method and its influence in the stability of the photocatalyst, as well as in its applicability on water/wastewater treatment.


Assuntos
Eritromicina , Titânio , Catálise , Compostos de Estanho
6.
Sci Rep ; 7(1): 7175, 2017 08 03.
Artigo em Inglês | MEDLINE | ID: mdl-28775257

RESUMO

In this study Surface Enhanced Raman Spectroscopy (SERS) data recorded from mouse mammary glands cancer cells (4T1 cell line) was used to assess information regarding differences between control, death and viable cells after Photodynamic Therapy (PDT) treatment. The treatment used nanoemulsions (NE/PS) loaded with different chloroaluminumphthalocyanine (ClAlP) photosensitizer (PS) contents (5 and 10 µmol × L-1) and illumination (660 nm wavelength) at 10 J × cm-2 (10 minutes). The SERS data revealed significant molecular alterations in proteins and lipids due to the PDT treatment. Principal Component Analysis (PCA) was applied to analyze the data recorded. Three-dimensional and well reproductive PCA scatter plots were obtained, revealing that two clusters of dead cells were well separated from one another and from control cluster. Overlap between two clusters of viable cells was observed, though well separated from control cluster. Moreover, the data analysis also pointed out necrosis as the main cell death mechanism induced by the PDT, in agreement with the literature. Finally, Raman modes peaking at 608 cm-1 (proteins) and 1231 cm-1 (lipids) can be selected for follow up of survival rate of neoplastic cells after PDT. We envisage that this finding is key to contribute to a quick development of quantitative infrared thermography imaging.


Assuntos
Neoplasias da Mama/tratamento farmacológico , Indóis/farmacologia , Compostos Organometálicos/farmacologia , Fotoquimioterapia/métodos , Fármacos Fotossensibilizantes/farmacologia , Animais , Morte Celular/efeitos dos fármacos , Linhagem Celular Tumoral , Sobrevivência Celular/efeitos dos fármacos , Indóis/administração & dosagem , Camundongos , Nanotecnologia , Compostos Organometálicos/administração & dosagem , Fármacos Fotossensibilizantes/administração & dosagem , Análise de Componente Principal , Análise Espectral Raman/métodos
7.
J Phys Condens Matter ; 27(9): 095301, 2015 Mar 11.
Artigo em Inglês | MEDLINE | ID: mdl-25679305

RESUMO

In this study, we report on the structural and hyperfine properties of Al-doped SnO2 nanoparticles synthesized by a polymer precursor method. The x-ray diffraction data analysis carried out using the Rietveld refinement method shows the formation of only rutile-type structures in all samples, with decreasing of the mean crystallite size as the Al content. A systematic study of the unit cell, as well as the vicinity of the interstitial position show strong evidence of two doping regimes in the rutile-type structure of SnO2. Below 7.5 mol% doping a dominant substitutional solution of Al(+3) and Sn(4+)-ions is determined. However, the occupation of both substitutional and interstitial sites is determined above 7.5 mol% doping. These findings are in good agreement with theoretical ab initio calculations.

8.
Biomol Eng ; 17(2): 41-9, 2001 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-11163750

RESUMO

In this work Raman spectroscopy was used to investigate uncoated magnetic fluids (UMF's) and coated magnetic fluids (CMF's). The coating agents were N-oleoylsarcosine, dodecanoic acid, and ethoxylated polyalcohol. The Raman probe is the hydroxyl (OH) group chemisorbed at the magnetic nanoparticle surface and the measurements were performed in the typical OH bending and OH stretching regions. The room temperature Raman data obtained from the UMF's and CMF's are compared to each other and with the data obtained from liquid water. Suppression of Raman modes from the MF's are discussed in terms of symmetry reduction and in terms of the interaction between the chemisorbed OH-group and the surrounding medium. The relative grafting coefficient associated to different coatings are estimated from the Raman data. The highest grafting coefficient is achieved with a single coating of dodecanoic acid in the hydrocarbon-based MF. The surface-grafting coefficient of the N-oleoylsarcosine-coated MF reduces when the polar liquid carrier replaces the non-polar liquid carrier. In comparison to liquid water, it was found that the hydrogen bonding between the chemisorbed OH-group and the solvent was enhanced in UMF's and reduced in CMF's.


Assuntos
Magnetismo , Análise Espectral Raman/métodos , Álcoois/química , Fenômenos Biofísicos , Biofísica , Temperatura Alta , Ligação de Hidrogênio , Ácidos Láuricos/química , Sarcosina/química , Termodinâmica , Água/química
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