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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 (ãDã) andZ-position, characterized by a phenomenological equationãDãXRDn(Z)=ãDã0n1+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 â¼9 to â¼24 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 â¼1014cm-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.
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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.
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Neoplasias de la Mama/tratamiento farmacológico , Indoles/farmacología , Compuestos Organometálicos/farmacología , Fotoquimioterapia/métodos , Fármacos Fotosensibilizantes/farmacología , Animales , Muerte Celular/efectos de los fármacos , Línea Celular Tumoral , Supervivencia Celular/efectos de los fármacos , Indoles/administración & dosificación , Ratones , Nanotecnología , Compuestos Organometálicos/administración & dosificación , Fármacos Fotosensibilizantes/administración & dosificación , Análisis de Componente Principal , Espectrometría Raman/métodosRESUMEN
We present a systematic study of core-shell Au/Fe3O4 nanoparticles produced by thermal decomposition under mild conditions. The morphology and crystal structure of the nanoparticles revealed the presence of Au core of d = (6.9 ± 1.0) nm surrounded by Fe3O4 shell with a thickness of ~3.5 nm, epitaxially grown onto the Au core surface. The Au/Fe3O4 core-shell structure was demonstrated by high angle annular dark field scanning transmission electron microscopy analysis. The magnetite shell grown on top of the Au nanoparticle displayed a thermal blocking state at temperatures below TB = 59 K and a relaxed state well above TB. Remarkably, an exchange bias effect was observed when cooling down the samples below room temperature under an external magnetic field. Moreover, the exchange bias field (HEX) started to appear at T~40 K and its value increased by decreasing the temperature. This effect has been assigned to the interaction of spins located in the magnetically disordered regions (in the inner and outer surface of the Fe3O4 shell) and spins located in the ordered region of the Fe3O4 shell.
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In this work, we report experimental and theoretical investigations performed in anti-spin ice structures, composed by square lattice of elongated antidots, patterned in nickel thin film. The magnetic vortex crystal state was obtained by micromagnetic simulation as the ground state magnetization, which arises due to the magnetic stray field at the antidot edges inducing chirality in the magnetization of platters among antidots. Ferromagnetic resonance (FMR) and magnetoresistance (MR) measurements were utilized to investigate the vortex crystal magnetization dynamics and magnetoelectric response. By using FMR, it was possible to detect the spin wave modes and vortex crystal resonance, in good agreement with dynamic micromagnetic simulation results. The vortex crystal magnetization configuration and its response to the external magnetic field, were used to explain the isotropic MR behaviour observed.
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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.
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Photoacoustic spectroscopy (PAS) has revolutionized the fields of biological, environmental, and agricultural sciences. It is a very simple, sensitive, and non-destructive technique that allows the determination of optical properties of bio-samples. The in vivo chlorophylls of the leaf have a recorded maximum absorption peak at 675 nm as against 665 nm of the in vitro chlorophylls. The intensity of purple pigmentation in leaves of Blepharocalyx salicifolius (Kunt) O. Berg, is inversely correlated to the soil moisture levels, leaf water content and leaf water potentials. The applicability of PAS to biological samples was discussed. It allows the validation of existing emission models which are important for atmospheric process. A portable device for photoacoustic spectroscopy of plants and other photosynthetic tissues, cells and organelles is provided. Further, there is provided a method to measure photosynthesis of such tissues, cells and organelles.
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Myrtaceae/química , Técnicas Fotoacústicas/métodos , Absorción , Hojas de la Planta/química , Espectrofotometría Infrarroja , TemperaturaRESUMEN
Photoacoustic spectroscopy was used to investigate magnetic nanocomposites incorporating nanosized maghemite particles into styrene-divinylbenzene copolymer template. Typical photoacoustic features were observed in bands C, S and L in the wavelength region of 300-1000 nm. The relative intensity of band-C scaled with the nominal concentration of nanosized maghemite incorporated into the polymeric template whereas the lowest relative intensity of band-S was found in the sample in which the template polymerization took place in the presence of the highest polar-like reaction medium. X-ray diffraction and transmission electron microscopy were used to characterize the magnetic nanosized phase as maghemite, with average particle diameter of 6.9 nm (sample Est34), 7.0 nm (sample H30), and 7.9 nm (sample Em15).
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Compuestos Férricos/química , Nanocompuestos/química , Técnicas Fotoacústicas/métodos , Nanocompuestos/ultraestructura , Tamaño de la Partícula , Análisis Espectral , Temperatura , Difracción de Rayos XRESUMEN
The chemical stability of magnetic particles is of great importance for their applications in medicine and biotechnology. The most challenging problem in physics of disordered systems of magnetic nanoparticles is the investigation of their dynamic properties. The chemical coprecipitation process was used to synthesize spherical magnetite nanoparticles of 14 nm. The as-prepared magnetite nanoparticles have been aged in the matrix. Magnetic properties and aging effect were studied by Mössbauer spectroscopy at temperatures ranging from 77 to 300 K, and X-ray diffraction. At room temperature, the Mössbauer spectrum showed superparamagnetic behavior of the particles, while well-defined sextets were observed at 77K, indicating a blocked regime. The superparamagnetic magnetite nanoparticles can be used as microbead biosensors.
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Compuestos Férricos/química , Fenómenos Magnéticos , Nanopartículas de Magnetita/química , Nanocompuestos/química , Polímeros/química , Polímeros/síntesis química , Espectroscopía de Mossbauer , Temperatura , Difracción de Rayos XRESUMEN
This work was developed with an aqueous suspension of maghemite nanoparticles and colloidal emulsions with nanoparticles of magnetite. The nanoparticles were synthesized by co-precipitation method. The first was the magnetic emulsion nanoparticles of maghemite dispersed in the aqueous extract obtained from the leaf embauba (Cecropia Obtusifolia), whose tree is native to Central and South America. Thereby achieving the magnetic fluid extract embauba stabilized with ionic buffer solution pH 7.4. A second emulsion was prepared with colloidal magnetite nanoparticles with surfaces previously coated with oleic acid as a means of dispersing and using the oil extracted from in nature seed Andiroba (Carapa Guianensis), tree of the Brazilian Amazon. These new magnetic fluids the nanoparticles were characterized by Photoacoustic spectroscopy (PAS) to determine the coating layer of molecules on the surfaces of nanoparticles. In aqueous ionic magnetic fluid Cecropia Obtusifolia (MFCO) chlorogenic acid contributes to the electron density in the presence of four groups alcohols, a ketone group and a carboxylic group. In magnetic fluid-based oil andiroba MFAD PAS spectra show that oleic acid molecules are tightly linked on the surface of the nanoparticles.
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Materiales Biocompatibles/química , Compuestos Férricos/química , Nanopartículas de Magnetita/química , Compuestos Orgánicos/química , Aceites de Plantas/síntesis química , Soluciones/síntesis química , Campos Magnéticos , Nanopartículas de Magnetita/ultraestructura , Ensayo de MaterialesRESUMEN
Loaded microspheres with a silicon (IV) phthalocyanine derivative (NzPC) acting as a photosensitizer were prepared from polyhydroxybutyrate-co-valerate (PHBHV) and poly(ecaprolactone) (PCL) polymers using the emulsification solvent evaporation method (EE). The aim of our study was to prepare two systems of these biodegradable PHBHV/PCL microspheres. The first one containing only photosensitizer previously incorporated in the PHBHV and poly(ecaprolactone) (PCL) microspheres and the second one with the post magnetization of the DDS with magnetic nanoparticles. Magnetic fluid is successfully used for controlled incorporation of nanosized magnetic particles within the micron-sized template. This is the first time that we could get a successful pos incorporation of nanosized magnetic particles in a previously-prepared polymeric template. This procedure opens a great number of possibilities of post-functionalization of polymeric micro or nanoparticles with different bioactive materials. The NzPC release profile of the systems is ideal for PDT, the zeta potential and the size particle are stable upon aging in time. In vitro studies were evaluated using gingival fibroblastic cell line. The dark citotoxicity, the phototoxicity and the AC magnetic field assays of the as-prepared nanomagnetic composite were evaluated and the cellular viability analyzed by the classical test of MTT.
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Fibroblastos/fisiología , Hipertermia Inducida/métodos , Indoles/administración & dosificación , Nanocápsulas/administración & dosificación , Nanocápsulas/química , Fotoquimioterapia/métodos , Materiales Biocompatibles , Línea Celular , Fibroblastos/citología , Humanos , Isoindoles , Campos Magnéticos , Microesferas , Fármacos FotosensibilizantesRESUMEN
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 â¼ 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.
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Superparamagnetic iron-oxide (SPIO) particles were synthesized by the co-precipitation method and the oleic acid-coated SPIO (OA-SPIO) was then obtained by a surface grafting procedure. A stock sample of magnetic oil (MO) with 1.6% particle volume fraction (VF) was obtained by dispersing the OA-SPIO in insulating naphthenic oil. The MO stock sample was diluted in the same naphthenic oil to yield MO with 0.1, 0.04, 0.02, and 0.01% VF. Moreover, the 0.04% VF MO sample was manipulated to yield MO samples with water content of 26, 37, and 63 mg L(-1). The spinel structure of OA-SPIO was assessed by XRD and the average diameter of 8.3 nm was provided by TEM analysis. The saturation magnetization at room temperature (RT) was 70 emu/g and no remanence or coercivity was observed. The average hydrodynamic diameter (D(H)) of the colloidal particles suspended within the 0.04% VF MO sample was 58 nm. After aging for 30 days at RT no change was observed for the lowest water content MO sample (26 mg L(-1)). However, D(H) equals to 270 nm was observed for the highest water content MO sample (63 mg L(-1)). The MO samples with 26 mg L(-1) water content were found stable under heating at 90 degrees C for all VF investigated. We found the insulation resistance dropping significantly as VF and temperature increases. The lowest value found was 11 GOhms for the 0.1% VF at 60 degrees C, which is an acceptable value for MO.
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The field dependence of the optical transmission of tartrate-coated and polyaspartate-coated magnetite-based aqueous colloids was studied. The colloidal stock samples were diluted to prepare a series of samples containing different particle volume fractions ranging from 0.17% up to 1.52% and measured at distinct times after preparation (1, 30, 120, 240, and 1460 days). We show that the magneto-transmissivity behavior is mainly described by the rotation of linear chains, at the low-field range, whereas the analysis of the data provided the measurement of the average chain length. Results also reveal that the optical transmissivity has a minimum at a particular critical field, whose origin is related to the onset of columns of chains built from isolated particle chains, i.e., due to a columnar phase transition. We found the critical field reducing as the particle volume fraction increases and as the sample's aging time increases. To investigate the origin of this phenomenon we used phase condensation models and Mie's theory applied to a chain of spheres and to an infinite cylinder. Possible implications for magnetophotonic colloidal-based devices and biomedical applications were discussed.
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Materiales Biocompatibles/química , Materiales Biocompatibles/efectos de la radiación , Óxido Ferrosoférrico/química , Óxido Ferrosoférrico/efectos de la radiación , Modelos Químicos , Simulación por Computador , Impedancia Eléctrica , Campos Electromagnéticos , Magnetismo , Transición de Fase/efectos de la radiaciónRESUMEN
In this study photoacoustic spectroscopy was used to investigate the effect of dilution of an oil-based magnetic fluid sample on the magnetic nanoparticle surface-coating. Changes of the photoacoustic signal intensity on the band-L region (640 to 830 nm) upon dilution of the stock magnetic fluid sample were discussed in terms of molecular surface desorption. The model proposed here assumes that the driving force taking the molecules out from the nanoparticle surface into the bulk solvent is the gradient of osmotic pressure. This gradient of osmotic pressure is established between the nanoparticle surface and the bulk suspension. It is further assumed that the photoacoustic signal intensity (area under the photoacoustic spectra) scales linearly with the number of coating molecules (surface grafting) at the nanoparticle surface. This model picture provides a non-linear analytical description for the reduction of the surface grafting coefficient upon dilution, which was successfully-used to curve-fit the photoacoustic experimental data.
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Spatially resolved photoluminescence has been used to investigate the details of the carrier capture and recombination dynamics in InAs/AlGaAs self-assembled quantum dots. The spatial PL distribution displays a Gaussian-like profile, whose width depends upon the temperature and detection energy being analyzed. The results give evidence of carrier thermalization between dots with different sizes. The effects of carrier transport in the quantum dot (QD) structure and carrier capture cannot be separated. The results can be modeled by assuming a carrier hopping process.
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In this study, oral carcinoma cells were used to evaluate chloroaluminum-phthalocyanine encapsulated in liposomes as the photosensitizer agent in support of photodynamic therapy (PDT). The genotoxicity and cytotoxicity behavior of the encapsulated photosensitizer in both dark and under irradiation using the 670-nm laser were investigated with the classical trypan blue cell viability test, the acridine orange/ethidium bromide staining organelles test, micronucleus formation frequency, DNA fragmentation, and cell morphology. The cell morphology investigation was carried out using light and electronic microscopes. Our findings after PDT include reduction in cell viability (95%) associated with morphologic alterations. The neoplastic cell destruction was predominantly started by a necrotic process, according to the assay with acridine orange and ethidium bromide, and this was confirmed by electronic microscopy analysis. Neither the PDT agent nor laser irradiation alone showed cytotoxicity, genotoxicity, or even morphologic alterations. Our results reinforce the efficiency of light-irradiated chloroaluminum-phthalocyanine in inducing a positive effect of PDT.
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Indoles/uso terapéutico , Queratinocitos/efectos de los fármacos , Neoplasias de la Boca/tratamiento farmacológico , Compuestos Organometálicos/uso terapéutico , Fotoquimioterapia/métodos , Fármacos Sensibilizantes a Radiaciones/uso terapéutico , Naranja de Acridina , Supervivencia Celular/efectos de los fármacos , Colorantes , Fragmentación del ADN/efectos de los fármacos , Etidio , Colorantes Fluorescentes , Humanos , Queratinocitos/patología , Microscopía/métodos , Neoplasias de la Boca/patología , Necrosis , Resultado del Tratamiento , Azul de TripanoRESUMEN
Room-temperature measurements of the magnetic susceptibility of Bovine Serum Albumin-based nanocapsules (50 to 300 nm in size) loaded with different amounts of maghemite nanoparticles (7.6 nm average diameter) have been carried out in this study. The field (H) dependence of the imaginary peak susceptibility (fp) of the nanocomposite samples was investigated in the range of 0 to 4 kOe. From the analysis of the fp x H curves the concentration (N) dependence of the effective maghemite magnetocrystalline energy barrier (E) was obtained. Analysis of the E x N data was performed using a modified Mørup-Tronc [Phys. Rev. Lett. 72, 3278 (1994)] model, from which a huge contribution from the magnetocrystalline surface anisotropy was observed.
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Compuestos Férricos/química , Nanopartículas , Albúmina Sérica Bovina/química , Magnetismo , Microscopía Electrónica de RastreoRESUMEN
In this study the interaction between magnetic nanoparticles (MNPs) surface-coated with meso-2,3-dimercaptosuccinic acid (DMSA) with both bovine serum albumin (BSA) and human serum albumin (HSA) was investigated. The binding of the MNP-DMSA was probed by the fluorescence quenching of the BSA and HSA tryptophan residue. Magnetic resonance and light microscopy analyses were carried out in in vivo tests using female Swiss mice. The binding constants (Kb) and the complex stoichiometries (n) indicate that MNP-DMSA/BSA and MNP-DMSA/HSA complexes have low association profiles. After five minutes following intravenous injection of MNP-DMSA into mice's blood stream we found the lung firstly target by the MNP-DMSA, followed by the liver in a latter stage. This finding suggests that the nanoparticle's DMSA-coating process probably hides the thiol group, through which albumin usually binds. This indicates that biocompatible MNP-DMSA is a very promising material system to be used as a drug delivery system (DDS), primarily for lung cancer treatment.
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Cristalización/métodos , Portadores de Fármacos/química , Compuestos Férricos/química , Magnetismo , Nanomedicina/métodos , Nanoestructuras/química , Albúmina Sérica/química , Succímero/química , Adsorción , Sitios de Unión , Materiales Biocompatibles Revestidos/química , Sustancias Macromoleculares/química , Ensayo de Materiales , Conformación Molecular , Nanoestructuras/ultraestructura , Tamaño de la Partícula , Unión Proteica , Propiedades de SuperficieRESUMEN
We investigate a magnetic fluid composed of magnetite nanoparticles surfacted with dodecanoic acid molecules and stably dispersed in a hydrocarbon solvent. A comparison between Monte Carlo simulation and different experimental techniques allows us to validate our methodology and investigate the behavior of the surfactant molecules. Our analysis, based on the Langmuir model, suggests that the surfactant grafting number on isolate nanoparticles increases with the nanoparticle concentration, while the grafting on agglomerated nanoparticles presents a more complicated behavior. Our results suggests that, if properly coated and at a certain concentration range, colloids can become stable even in the presence of agglomerates. The role of the Hamaker constant, which controls the van der Waals interaction intensity, was also investigated. We have found that the ratio between grafting and Hamaker constant governs the level of nanoparticle agglomeration.
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The aim of this study was to prepare bovine serum albumin-based beads containing maghemite nanoparticles incorporated via ionic magnetic fluid and to evaluate the cell toxicity of this biocompatible system using the J774-A1 cell line. Transmission electron micrographs obtained from the magnetic fluid sample were used to estimate the average particle diameter around 7.6 nm and diameter dispersion of 0.22. The BSA-based magnetic beads were prepared using the heat protein denaturation route. The nanoparticle concentration in the magnetic fluid sample used for the synthesis of the magnetic beads was in the range of 1.2 x 10(16) to 2.3 x 10(17) particle/ml. The methodology used to investigate the cell toxicity of the magnetic beads was the classical MTT assay. Our observation showed that the toxicity against the J774-A1 cell line depends upon the amount of magnetic material incorporated into the magnetic nanobeads and was found to be 14, 11, 9, 5, and 3% for 2.3 x 10(17), 1.2 x 10(17), 4.6 x 10(16), 2.3 x 10(16), and 1.2 x 10(16) particle/ml, respectively.