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1.
Sensors (Basel) ; 21(2)2021 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-33467480

RESUMO

More effective methods to detect bovine tuberculosis, caused by Mycobacterium bovis, in wildlife, is of paramount importance for preventing disease spread to other wild animals, livestock, and human beings. In this study, we analyzed the volatile organic compounds emitted by fecal samples collected from free-ranging wild boar captured in Doñana National Park, Spain, with an electronic nose system based on organically-functionalized gold nanoparticles. The animals were separated by the age group for performing the analysis. Adult (>24 months) and sub-adult (12-24 months) animals were anesthetized before sample collection, whereas the juvenile (<12 months) animals were manually restrained while collecting the sample. Good accuracy was obtained for the adult and sub-adult classification models: 100% during the training phase and 88.9% during the testing phase for the adult animals, and 100% during both the training and testing phase for the sub-adult animals, respectively. The results obtained could be important for the further development of a non-invasive and less expensive detection method of bovine tuberculosis in wildlife populations.


Assuntos
Nariz Eletrônico , Nanopartículas Metálicas , Mycobacterium tuberculosis , Tuberculose , Compostos Orgânicos Voláteis , Animais , Animais Selvagens , Bovinos , Fezes , Feminino , Ouro , Humanos , Masculino , Espanha , Sus scrofa , Suínos , Tuberculose/diagnóstico , Tuberculose/veterinária
2.
J Am Chem Soc ; 142(52): 21767-21774, 2020 Dec 30.
Artigo em Inglês | MEDLINE | ID: mdl-33331155

RESUMO

Adsorption of molecules is a fundamental step in all heterogeneous catalytic reactions. Nevertheless, the basic mechanism by which photon-mediated adsorption processes occur on solid surfaces is poorly understood, mainly because they involve excited catalyst states that complicate the analysis. Here we demonstrate a method by which density functional theory (DFT) can be used to quantify photoinduced adsorption processes on transition metal oxides and reveal the fundamental nature of these reactions. Specifically, the photoadsorption of SO2 on TiO2(101) has been investigated by using a combination of DFT and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The combined experimental and theoretical approach gives a detailed description of the photocatalytic desulfurization process on TiO2, in which sulfate forms as a stable surface product that is known to poison the catalytic surface. This work identifies surface-SO42- as the sulfate species responsible for the surface poisoning and shows how this product can be obtained from a stepwise oxidation of SO2 on TiO2(101). Initially, the molecule binds to a lattice O2- ion through a photomediated adsorption process and forms surface sulfite, which is subsequently oxidized into surface-SO42- by transfer of a neutral oxygen from an adsorbed O2 molecule. The work further explains how the infrared spectra associated with this oxidation product change during interactions with water and surface hydroxyl groups, which can be used as fingerprints for the surface reactions. The approach outlined here can be generalized to other photo- and electrocatalytic transition metal oxide systems.

3.
J Infect Dis ; 219(1): 101-109, 2019 01 01.
Artigo em Inglês | MEDLINE | ID: mdl-30016445

RESUMO

Background: Human echinococcosis is a neglected infectious disease affecting more than 1 million people globally. Its diagnosis is expensive and difficult because of lack of adequate resources in low-resource locations, where most cases occur. Methods: A group of volunteers diagnosed with the 2 main types of echinococcosis and corresponding control groups were recruited from hospitals in Tunisia (32 patients with cystic echinococcosis and 43 controls) and Poland (16 patients with alveolar echinococcosis and 8 controls). Breath samples were collected from all patients and analyzed by gas chromatography coupled to mass spectrometry, and a specifically developed electronic nose system. Results: The chemical analysis revealed statistically different concentrations of 2 compounds in the breath of patients with cystic echinococcosis compared to controls, and statistically different concentrations of 7 compounds in the breath of patients with alveolar echinococcosis compared to controls. The discrimination accuracy achieved by the electronic nose system was 100% for cystic echinococcosis and 92.9% for alveolar echinococcosis, while the discrimination accuracy between these 2 patient groups was 92.1%. Conclusion: Here we advocate a noninvasive, fast, easy-to-operate and nonexpensive diagnostic tool for the diagnosis of human echinococcosis disease through exhaled breath analysis, suitable for early diagnosis and population screening.


Assuntos
Testes Respiratórios/métodos , Equinococose/diagnóstico , Técnicas Eletroquímicas/métodos , Expiração , Compostos Orgânicos Voláteis/análise , Adolescente , Adulto , Animais , Biomarcadores/análise , Biomarcadores/química , Testes Respiratórios/instrumentação , Técnicas Eletroquímicas/instrumentação , Nariz Eletrônico , Feminino , Helmintíase/diagnóstico , Helmintos/patogenicidade , Humanos , Masculino , Espectrometria de Massas , Pessoa de Meia-Idade , Técnicas de Diagnóstico Molecular , Polônia , Tunísia , Adulto Jovem
4.
Sensors (Basel) ; 19(15)2019 Aug 01.
Artigo em Inglês | MEDLINE | ID: mdl-31374817

RESUMO

The durability of metal-based constructions, especially those containing reinforced concrete, is mainly limited by corrosion processes. Diamond-like carbon (DLC)-coated silicon (Si) wafers provide a chemically inert and mechanically robust sensing interface for application in aggressive environments. In this study, iron-sensitive dyes, i.e., 2,3-dihydroxypyridine (DHP) and 1,2-dihydroxybenzol (DHB), were coated onto DLC-modified Si wafers for evaluating the potential of detecting corrosion processes via evanescent field absorption spectroscopy using Fourier-transform infrared spectroscopy. The obtained IR spectra reveal discernible changes of the dye layer after exposure to iron solutions, which indicates that indeed corrosion processes may be studied at molecular level detail.

5.
Nanotechnology ; 29(6): 065603, 2018 Feb 09.
Artigo em Inglês | MEDLINE | ID: mdl-29206108

RESUMO

Here, we report for the first time the fabrication of ligand-functionalised ultrapure monodispersed metal nanoparticles (Au, Cu, and Pt) from their pure metal precursors using the advanced gas deposition technique. The experimental conditions during nanoparticle formation were adjusted in order to obtain ultrafine isolated nanoparticles on different substrates. The morphology and surface analysis of the as-deposited metal nanoparticles were investigated using scanning electron microscopy, x-ray diffraction and Fourier transform infra-red spectroscopy, which demonstrated the formation of highly ordered pure crystalline nanoparticles with a relatively uniform size distribution of ∼10 nm (Au), ∼4 nm (Cu) and ∼3 nm (Pt), respectively. A broad range of organic ligands containing thiol or amine functional groups were attached to the nanoparticles to form continuous networks of nanoparticle-ligand nanoassemblies, which were characterised by scanning electron microscopy and x-ray photoelectron spectroscopy. The electrical resistance of the functional nanoassemblies deposited in the gap spacing of two microfabricated parallel Au electrodes patterned on silicon substrates ranged between tens of kΩ and tens of MΩ, which is suitable for use in many applications including (bio)chemical sensors, surface-enhanced Raman spectroscopy and molecular electronic rectifiers.

6.
Anal Bioanal Chem ; 408(14): 3675-80, 2016 05.
Artigo em Inglês | MEDLINE | ID: mdl-27007740

RESUMO

Protein immobilization on functionalized fluorine-terminated nanocrystalline (NCD) films was studied by attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy using an immobilization protocol developed to specifically bind C-reactive protein (CRP). Using an ATR-FTIR spectroscopy method employing a force-controlled anvil-type configuration, three critical steps of the ex situ CRP immobilization were analyzed. First, the NCD surface was passivated by deposition of a copolymer layer consisting of polyethylene oxide and polypropylene oxide. Second, a synthetic modified polypeptide binder with high affinity to CRP was covalently attached to the polymeric film. Third, CRP dissolved in aqueous buffer in concentrations of 10-20 µg/mL was added on the functionalized NCD surface. Both the amide I and II bands, due to the polypeptide binder and CRP, were clearly observed in ATR-FTIR spectra. CRP amide I bands were extracted from difference spectra and yielded bands that agreed well with the reported amide I band of free (non-bonded) CRP in solution. Thus, our results show that CRP retains its secondary structure when it is attached to the polypeptide binders. Compared to previous IR studies of CRP in solution, about 200 times lower concentration was applied in the present study. Graphical Abstract Direct non-destructive ATR-FTIR analysis of C-reactive protein (CRP) selectively bound to functionalized nanocrystalline diamond (NCD) sensor surface.


Assuntos
Técnicas Biossensoriais , Proteína C-Reativa/análise , Diamante , Nanoestruturas , Espectroscopia de Infravermelho com Transformada de Fourier/métodos , Cristalização
7.
Biochem Biophys Res Commun ; 464(1): 336-41, 2015 Aug 14.
Artigo em Inglês | MEDLINE | ID: mdl-26129771

RESUMO

The oxidative stress-related reactive aldehydes 4-hydroxy-2-nonenal (HNE) and 4-oxo-2-nonenal (ONE) have been shown to promote formation of α-synuclein oligomers in vitro. However, the changes in secondary structure of α-synuclein and the kinetics of the oligomerization process are not known and were the focus of this study. Size exclusion chromatography showed that after 1 h of incubation, HNE induced the formation of an oligomeric α-synuclein peak with a molecular weight of about ∼2000 kDa, which coincided with a decreasing ∼50 kDa monomeric peak. With prolonged incubation (up to 24 h) the oligomeric peak became the dominating molecular species. In contrast, in the presence of ONE, a ∼2000 oligomeric peak was exclusively observed after 15 min of incubation and this peak remained constant with prolonged incubation. Western blot analysis of HNE-induced α-synuclein oligomers showed the presence of monomers (15 kDa), SDS-resistant low molecular (30-160 kDa) and high molecular weight oligomers (≥260 kDa), indicating that the oligomers consisted of both covalent and non-covalent protein. In contrast, ONE-induced α-synuclein oligomers only migrated as covalent cross-linked high molecular-weight material (≥300 kDa). Both circular dichroism (CD) and Attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy showed that the formation of HNE- and ONE-induced oligomers coincided with a spectral change from random coil to ß-sheet. However, ONE-induced α-synuclein oligomers exhibited a slightly higher degree of ß-sheet. Taken together, our results indicate that both HNE and ONE induce a change from random coil to ß-sheet structure that coincides with the formation of α-synuclein oligomers; albeit through different kinetic pathways depending on the degree of cross-linking.


Assuntos
Aldeídos/química , alfa-Sinucleína/química , Cromatografia em Gel , Dicroísmo Circular , Humanos , Cinética , Peso Molecular , Oxirredução , Multimerização Proteica , Estrutura Secundária de Proteína , Proteínas Recombinantes/química
8.
Toxicol Appl Pharmacol ; 288(1): 1-11, 2015 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-26163175

RESUMO

The aim of this study was to investigate the inflammatory and immunological responses in airways and lung-draining lymph nodes (LDLNs), following lung exposure to iron oxide (hematite) nanoparticles (NPs). The responses to the hematite NPs were evaluated in both healthy non-sensitized mice, and in sensitized mice with an established allergic airway disease. The mice were exposed intratracheally to either hematite NPs or to vehicle (PBS) and the cellular responses were evaluated on days 1, 2, and 7, post-exposure. Exposure to hematite NPs increased the numbers of neutrophils, eosinophils, and lymphocytes in the airways of non-sensitized mice on days 1 and 2 post-exposure; at these time points the number of lymphocytes was also elevated in the LDLNs. In contrast, exposing sensitized mice to hematite NPs induced a rapid and unspecific cellular reduction in the alveolar space on day 1 post-exposure; a similar decrease of lymphocytes was also observed in the LDLN. The results indicate that cells in the airways and in the LDLN of individuals with established airway inflammation undergo cell death when exposed to hematite NPs. A possible explanation for this toxic response is the extensive generation of reactive oxygen species (ROS) in the pro-oxidative environment of inflamed airways. This study demonstrates how sensitized and non-sensitized mice respond differently to hematite NP exposure, and it highlights the importance of including individuals with respiratory disorders when evaluating health effects of inhaled nanomaterials.


Assuntos
Compostos Férricos/toxicidade , Exposição por Inalação/efeitos adversos , Pulmão/efeitos dos fármacos , Nanopartículas , Pneumonia/imunologia , Animais , Líquido da Lavagem Broncoalveolar/química , Líquido da Lavagem Broncoalveolar/imunologia , Morte Celular/efeitos dos fármacos , Citocinas/metabolismo , Modelos Animais de Doenças , Relação Dose-Resposta a Droga , Eosinófilos/efeitos dos fármacos , Eosinófilos/imunologia , Eosinófilos/metabolismo , Feminino , Cinética , Pulmão/imunologia , Pulmão/metabolismo , Linfonodos/efeitos dos fármacos , Linfonodos/imunologia , Linfonodos/metabolismo , Contagem de Linfócitos , Linfócitos/efeitos dos fármacos , Linfócitos/imunologia , Linfócitos/metabolismo , Camundongos Endogâmicos BALB C , Neutrófilos/efeitos dos fármacos , Neutrófilos/imunologia , Neutrófilos/metabolismo , Ovalbumina , Estresse Oxidativo/efeitos dos fármacos , Pneumonia/induzido quimicamente , Pneumonia/metabolismo , Espécies Reativas de Oxigênio/metabolismo , Medição de Risco , Fatores de Risco
9.
Anal Chem ; 86(16): 8136-41, 2014 Aug 19.
Artigo em Inglês | MEDLINE | ID: mdl-25032789

RESUMO

The first combination of mid-infrared (MIR) tunable quantum cascade lasers (tQCLs) with thin-film diamond strip waveguides (DSWGs) suitable for advanced chemical sensing/biosensing is demonstrated. The sensing system is composed of thin diamond films grown on surface-passivated Si wafers via chemical vapor deposition (CVD) and microstructured using inductively coupled plasma (ICP) etching, serving as photonic waveguides for radiation emitted by a broadly tunable quantum cascade laser (tQCL) in the spectral regime of 5.78-6.35 µm (1570-1730 cm(-1)). The characterization of the free-standing diamond waveguides reveals excellent transmission properties across a broad MIR band. As a proof of concept, the detection of acetone in D2O via evanescent field absorption is demonstrated achieving a limit of detection (LOD) as low as 200 pL, which indicates a significant sensitivity improvement compared to conventional MIR slab/strip waveguides reported to date. Providing characteristic absorption features within the tuning range of the tQCL, studies using anisaldehyde as an analyte further corroborate the potential of tQCL-DSWG-based chemical sensors/biosensors.


Assuntos
Diamante/química , Espectroscopia de Infravermelho com Transformada de Fourier/instrumentação , Acetona/análise , Benzaldeídos/análise , Técnicas Biossensoriais/instrumentação , Técnicas Biossensoriais/métodos , Desenho de Equipamento , Raios Infravermelhos , Espectroscopia de Infravermelho com Transformada de Fourier/métodos
10.
Nat Commun ; 15(1): 5259, 2024 Jun 19.
Artigo em Inglês | MEDLINE | ID: mdl-38898091

RESUMO

Highly sensitive, low-power, and chip-scale H2 gas sensors are of great interest to both academia and industry. Field-effect transistors (FETs) functionalized with Pd nanoparticles (PdNPs) have recently emerged as promising candidates for such H2 sensors. However, their sensitivity is limited by weak capacitive coupling between PdNPs and the FET channel. Herein we report a nanoscale FET gas sensor, where electrons can tunnel between the channel and PdNPs and thus equilibrate them. Gas reaction with PdNPs perturbs the equilibrium, and therefore triggers electron transfer between the channel and PdNPs via trapping or de-trapping with the PdNPs to form a new balance. This direct communication between the gas reaction and the channel enables the most efficient signal transduction. Record-high responses to 1-1000 ppm H2 at room temperature with detection limit in the low ppb regime and ultra-low power consumption of ~ 300 nW are demonstrated. The same mechanism could potentially be used for ultrasensitive detection of other gases. Our results present a supersensitive FET gas sensor based on electron trapping effect in nanoparticles.

11.
Biophys J ; 105(2): 310-9, 2013 Jul 16.
Artigo em Inglês | MEDLINE | ID: mdl-23870252

RESUMO

It is a challenging task to characterize the biodistribution of nanoparticles in cells and tissue on a subcellular level. Conventional methods to study the interaction of nanoparticles with living cells rely on labeling techniques that either selectively stain the particles or selectively tag them with tracer molecules. In this work, Raman imaging, a label-free technique that requires no extensive sample preparation, was combined with multivariate classification to quantify the spatial distribution of oxide nanoparticles inside living lung epithelial cells (A549). Cells were exposed to TiO2 (titania) and/or α-FeO(OH) (goethite) nanoparticles at various incubation times (4 or 48 h). Using multivariate classification of hyperspectral Raman data with partial least-squares discriminant analysis, we show that a surprisingly large fraction of spectra, classified as belonging to the cell nucleus, show Raman bands associated with nanoparticles. Up to 40% of spectra from the cell nucleus show Raman bands associated with nanoparticles. Complementary transmission electron microscopy data for thin cell sections qualitatively support the conclusions.


Assuntos
Núcleo Celular/metabolismo , Células Epiteliais/metabolismo , Compostos Férricos/metabolismo , Nanopartículas Metálicas , Titânio/metabolismo , Transporte Biológico , Linhagem Celular Tumoral , Núcleo Celular/ultraestrutura , Células Epiteliais/ultraestrutura , Humanos , Pulmão/citologia , Análise Multivariada , Análise Espectral Raman
12.
ACS Nanosci Au ; 2(2): 128-139, 2022 Apr 20.
Artigo em Inglês | MEDLINE | ID: mdl-37101663

RESUMO

The ability to control electronic states by utilizing quantum confinement of one of the material components in heterojunctions is a promising approach to perform energy-level matching. In this work, we report the possibility to achieve optimum energy alignment in heterojunctions made from size-controlled quantum dots (Q-dots) of ZnO in combination with three copper oxides: Cu2O, Cu4O3, and CuO. Quantum confinement effects on the ZnO nanoparticles in the diameter range 2.6-7.4 nm showed that the direct optical band gap decreased from 3.99 to 3.41 eV, with a dominating shift occurring in the conduction band (CB) edge, and thus the possibility to obtain close to 0.6 eV CB edge shift by controlling the size of ZnO. The effect was utilized to align the electronic bands in the ZnO Q-dot/copper oxide heterojunctions to allow for charge transfer between the materials and to test the ability to improve the photocatalytic performance for the system, evaluated by the transformation of a dye molecule in water. The catalyst materials were investigated by X-ray diffraction, scanning electron microscopy, ultraviolet-visible (UV-vis), photoluminescence, and Raman spectroscopy. The most promising material combination was found to be the Cu2O copper oxide in combination with an energy aligned ZnO Q-dot system with approximately 7 nm diameter, showing strong synergy effects in good agreement with the energy-level analysis, outperforming the added effect of its individual components, ZnO-Q-dots and Cu2O, by about 140%. The results show that utilization of a heterojunction with controllable energy alignment can provide a drastically improved photocatalytic performance. Apart from increased photocatalytic activity, specific surface states of ZnO are quenched when the heterojunction is created. It is anticipated that the same approach can be utilized in several material combinations with the added benefit of a system with controllable overpotential and thus added specificity for the targeted reduction reaction.

13.
ACS Appl Mater Interfaces ; 14(13): 15756-15764, 2022 Apr 06.
Artigo em Inglês | MEDLINE | ID: mdl-35315635

RESUMO

Most transparent conducting materials are based on Sn:In2O3 (ITO). When applied onto flexible substrates, ITO can be prepared in an oxide-metal-oxide (OMO) configuration, typically ITO/Ag/ITO, where the ductility of the embedded metal layer is intended to reduce the mechanical brittleness and improve the electrical conductivity of the OMO multilayer. Hitherto, the lower limit of the thickness of the Ag layer has been limited by the percolation threshold, which limits the Ag layer to be thicker than ∼10 nm to avoid agglomeration and to ensure conductivity and structural stability. Metal layers of thicknesses below 10 nm are, however, desirable for obtaining OMO coatings with better optical properties. It is known that agglomeration of the metal layer can, to some extent, be suppressed when substituting Ag by an Ag-Pd-Cu (APC) alloy. APC-based OMO films exhibit excellent optical and electrical properties, but still continuous APC films well below 10 nm thickness cannot be achieved. In this work we demonstrate that controlled oxidation of APC results in smooth, ultrathin APC:O continuous coatings (of thickness ∼5 nm) on ITO-coated PET substrates. Moderate oxidation yields superficial PdOx formation, which suppresses Ag agglomeration, while still maintaining excellent conductivity. On the other hand, extensive oxidation of APC leads to extensive Pd oxide nucleation deteriorating the conductivity of the film. The ITO/APC:O/ITO films exhibit low resistivity, attributed to a high Hall mobility associated with suppressed agglomeration, good stability in high humidity/temperature environments, superior transmittance in the visible and infrared region, and excellent mechanical bending properties, thus providing new opportunities for fabricating superior transparent conducting coatings on polymer substrates.

14.
ACS Sens ; 7(10): 3094-3101, 2022 Oct 28.
Artigo em Inglês | MEDLINE | ID: mdl-36121758

RESUMO

The gas sensing properties of graphene back-gated field-effect transistor (GFET) sensors toward acetonitrile, tetrahydrofuran, and chloroform vapors were investigated with the focus on unfolding possible gas detection mechanisms. The FET configuration of the sensor device enabled gate voltage tuning for enhanced measurements of changes in DC electrical characteristics. Electrical measurements were combined with a fluctuation-enhanced sensing methodology and intermittent UV irradiation. Distinctly different features in 1/f noise spectra for the organic gases measured under UV irradiation and in the dark were observed. The most intense response observed for tetrahydrofuran prompted the decomposition of the DC characteristic, revealing the photoconductive and photogating effect occurring in the graphene channel with the dominance of the latter. Our observations shed light on understanding surface processes at the interface between graphene and volatile organic compounds for graphene-based sensors in ambient conditions that yield enhanced sensitivity and selectivity.

15.
Small ; 7(4): 514-23, 2011 Feb 18.
Artigo em Inglês | MEDLINE | ID: mdl-21265017

RESUMO

The cellular uptake and distribution of five types of well-characterized anatase and rutile TiO(2) nanoparticles (NPs) in A549 lung epithelial cells is reported. Static light scattering (SLS), in-vitro Raman microspectroscopy (µ-Raman) and transmission electron spectroscopy (TEM) reveal an intimate correlation between the intrinsic physicochemical properties of the NPs, particle agglomeration, and cellular NP uptake. It is shown that µ-Raman facilitates chemical-, polymorph-, and size-specific discrimination of endosomal-particle cell uptake and the retention of particles in the vicinity of organelles, including the cell nucleus, which quantitatively correlates with TEM and SLS data. Depth-profiling µ-Raman coupled with hyperspectral data analysis confirms the location of the NPs in the cells and shows that the NPs induce modifications of the biological matrix. NP uptake is found to be kinetically activated and strongly dependent on the hard agglomeration size-not the primary particle size-which quantitatively agrees with the measured intracellular oxidative stress. Pro-inflammatory responses are also found to be sensitive to primary particle size.


Assuntos
Células Epiteliais/efeitos dos fármacos , Células Epiteliais/metabolismo , Pulmão/citologia , Nanopartículas/química , Nanopartículas/toxicidade , Titânio/metabolismo , Titânio/toxicidade , Linhagem Celular , Quimiocina CCL2/metabolismo , Humanos , Interleucina-8/metabolismo , Microscopia Eletrônica de Transmissão , Nanopartículas/ultraestrutura , Análise Espectral Raman
16.
J Phys Chem A ; 115(32): 8948-59, 2011 Aug 18.
Artigo em Inglês | MEDLINE | ID: mdl-21711003

RESUMO

Adsorption of trimethyl phosphate (TMP) on well-characterized hematite, maghemite and goethite nanoparticles was studied by in situ DRIFT spectroscopy as a model system for adsorption of organophosphorous (OP) compounds on iron minerals. The iron minerals were characterized by X-ray diffraction (XRD), Raman spectroscopy, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), specific surface area, and pore size distribution. The minerals were found to consist of stoichimetrically and morphologically well-defined maghemite, hematite, and goethite nanoparticles. Analysis of in situ diffuse reflectance Fourier transform (DRIFT) spectroscopy shows that TMP bonds mainly to Lewis acid Fe sites through the O phosphoryl atom (-P═O-Fe) on hematite and maghemite. On goethite most TMP molecules bond to Brønstedt acid surface OH groups and form hydrogen bonded surface complexes. The vibrational mode analysis and uptake kinetics suggest two main reasons for the observed trend of reactivity toward TMP (hematite > maghemite > goethite): (i) larger number of accessible Lewis acid adsorption sites on hematite; (ii) stronger interaction between the Lewis acid Fe sites and the phosphoryl O atom on TMP for hematite and maghemite compared to goethite with concomitant formation of surface coordinated TMP and dimethyl phosphate intermediates. As a result, on the oxides a surface oxidation pathway dominates during the initial adsorption, which results in the formation of surface methoxy and formate. In contrast, on goethite a slower hydrolysis pathway is identified, which eventually yields phosphoric acid. The observed trends of the reactivity and analysis of the corresponding surface structure and particle morphology suggest an intimate relation between the surface chemistry of exposed crystal facets on the iron minerals. These results are important to understand OP surface chemistry on iron minerals.

17.
RSC Adv ; 11(17): 10224-10234, 2021 03 05.
Artigo em Inglês | MEDLINE | ID: mdl-35423477

RESUMO

Heterojunction copper-zinc oxide catalysts were prepared by a hybrid two-step methodology comprising hydrothermal growth of ZnO nanorods (ZnO-NR) followed by deposition of Cu2O nanoparticles using an advanced gas deposition technique (AGD). The obtained bicatalysts were characterized by SEM, AFM, XRD, XPS, PL and spectrophotometry and revealed well-dispersed and crystalline Cu2O nanoparticles attached to the ZnO-NR. The adsorption properties and photocatalytic degradation of Orange II dye in water solutions were measured. It was found that the bicatalysts exhibited a conversion rate and quantum yield that both were about 50% higher compared with ZnO-NR alone, which were attributed to the intrinsic electric field created at the p-n junction formed at the Cu2O/ZnO interface facilitating charge separation of electron-hole pairs formed upon interband photon absorption. The interpretation was evidenced by efficient quenching of characteristic deep level ZnO photoluminescence bands and photoelectron core-level energy shifts. By comparisons with known energy levels in Cu2O and ZnO, the effect was found to be most pronounced for the non-polar ZnO-NR side facets, which accounted for about 95% of the exposed surface area of the catalyst and hence the majority of dye adsorption. It was also found that the dye adsorption capacity of the ZnO nanorods increased considerably after Cu2O deposition thereby facilitating the oxidation of the dye. The results imply the possibility of judiciously aligning band edges on structurally controlled and well-connected low-dimensional semiconductor nanostructures using combined two-step synthesis techniques, where in particular vacuum-based techniques such as AGD allow for growth of well-connected nanocrystals with well developed heterojunction interfaces.

19.
Mater Sci Eng C Mater Biol Appl ; 110: 110665, 2020 May.
Artigo em Inglês | MEDLINE | ID: mdl-32204094

RESUMO

Inflammatory diseases increase has recently sparked the research interest for drugs diagnostic tools development. At therapeutic doses, acetylsalicylic acid (ASA or aspirin) is widely used for these diseases' treatment. ASA overdoses can however give rise to adverse side effects including ulcers, gastric damage. Hence, development of simple, portable and sensitive methods for ASA detection is desirable. This paper reports aspirin analysis in urine, saliva and pharmaceutical tablet using an electrochemical sensor and a voltammetric electronic tongue (VE-Tongue). The electrochemical sensor was fabricated by self-assembling chitosan capped with gold nanoparticles (Cs + AuNPs) on a screen-printed carbon electrode (SPCE). It exhibits a logarithmic-linear relationship between its response and the ASA concentration in the range between 1 pg/mL and 1 µg/mL. A low detection limit (0.03 pg/mL), good selectivity against phenol and benzoic acid interference, and successful practical application were demonstrated. Qualitative analysis was performed using the VE-Tongue based unmodified metal electrodes combined with two chemometric approaches to classify urine samples spiked with different aspirin concentrations. Partial least squares (PLS) method provided prediction models obtained from the data of both devices with a regression correlation coefficient R2 = 0.99. Correspondingly, the SPCE/(Cs + AuNPs) electrochemical sensor and VE-Tongue could be viable tools for biological analysis of drugs.


Assuntos
Aspirina/análise , Técnicas Biossensoriais/instrumentação , Líquidos Corporais/química , Quitosana/química , Técnicas Eletroquímicas/instrumentação , Nariz Eletrônico , Ouro/química , Nanopartículas Metálicas/química , Calibragem , Carbono/química , Análise de Dados , Análise Discriminante , Eletrodos , Humanos , Análise dos Mínimos Quadrados , Nanopartículas Metálicas/ultraestrutura , Análise de Componente Principal , Análise de Regressão , Reprodutibilidade dos Testes , Espectroscopia de Infravermelho com Transformada de Fourier , Comprimidos
20.
Bioelectrochemistry ; 132: 107404, 2020 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-31911357

RESUMO

Malathion (MAL) is an organophosphorus (OP) insecticide. It is a cholinesterase inhibitor, which can pose serious health and environmental problems. In this study, a sensitive and selective molecular imprinted polymer (MIP) based on screen-printed gold electrodes (Au-SPE) for MAL detection in olive oils and fruits, was devised. The MIP sensor was prepared using acrylamide as the functional monomer and MAL as the template. Subsequently, the morphology of the electrode surface was studied by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The electrochemical characterization of the developed MIP sensor was performed by cyclic voltammetry (CV), differential pulse voltammetry (DPV), and electrochemical impedance spectroscopy (EIS) techniques. The operational repeatability and stability of the sensor were studied. It was found to have a dynamic concentration range of (0.1 pg mL-1-1000 pg mL-1) and a low limit of detection (LOD) of 0.06 pg mL-1. Furthermore, the sensor was employed to determine MAL content in olive oil with a recovery rate of 87.9% and a relative standard deviation of 8%. It was successfully applied for MAL determination in real samples and promise to open new opportunities for the detection of OP pesticides residues in various food products, as well as in environmental applications.


Assuntos
Técnicas Eletroquímicas/instrumentação , Contaminação de Alimentos/análise , Inseticidas/análise , Malation/análise , Impressão Molecular , Olea/química , Azeite de Oliva/química , Polímeros/química , Limite de Detecção , Microscopia de Força Atômica , Microscopia Eletrônica de Varredura , Reprodutibilidade dos Testes
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