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1.
Talanta ; 277: 126279, 2024 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-38810382

RESUMO

N6-methyladenosine (6mA) plays a pivotal role in diverse biological processes, including cancer, bacterial toxin secretion, and bacterial drug resistance. However, to date there has not been a selective, sensitive, and simple method for quantitative detection of 6mA at single base resolution. Herein, we present a series piezoelectric quartz crystal (SPQC) sensor based on the specific recognition of transcription-activator-like effectors (TALEs) for locus-specific detection of 6mA. Detection sensitivity is enhanced through the use of a hybridization chain reaction (HCR) in conjunction with silver staining. The limit of detection (LOD) of the sensor was 0.63 pM and can distinguish single base mismatches. We demonstrate the applicability of the sensor platform by quantitating 6mA DNA at a specific site in biological matrix. The SPQC sensor presented herein offers a promising platform for in-depth study of cancer, bacterial toxin secretion, and bacterial drug resistance.


Assuntos
Adenina , Técnicas Biossensoriais , DNA , Adenina/análogos & derivados , Adenina/análise , Adenina/química , Adenina/metabolismo , DNA/química , DNA/análise , Técnicas Biossensoriais/métodos , Limite de Detecção , Humanos , Quartzo/química
2.
Sensors (Basel) ; 23(24)2023 Dec 14.
Artigo em Inglês | MEDLINE | ID: mdl-38139667

RESUMO

A gas sensor array was developed and evaluated using four high-frequency quartz crystal microbalance devices (with a 30 MHz resonant frequency in fundamental mode). The QCM devices were coated with ethyl cellulose (EC), polymethylmethacrylate (PMMA), Apiezon L (ApL), and Apiezon T (ApT) sensing films, and deposited by the ultrasonic atomization method. The objective of this research was to propose a non-invasive technique for acetone biomarker detection, which is associated with diabetes mellitus disease. The gas sensor array was exposed to methanol, ethanol, isopropanol, and acetone biomarkers in four different concentrations, corresponding to 1, 5, 10, and 15 µL, at temperature of 22 °C and relative humidity of 20%. These samples were used because human breath contains them and they are used for disease detection. Moreover, the gas sensor responses were analyzed using principal component analysis and discriminant analysis, achieving the classification of the acetone biomarker with a 100% membership percentage when its concentration varies from 327 to 4908 ppm, and its identification from methanol, ethanol, and isopropanol.


Assuntos
Diabetes Mellitus , Técnicas de Microbalança de Cristal de Quartzo , Humanos , Acetona/análise , 2-Propanol , Metanol , Biomarcadores , Etanol , Quartzo/química , Diabetes Mellitus/diagnóstico
3.
ACS Appl Mater Interfaces ; 15(14): 17922-17937, 2023 Apr 12.
Artigo em Inglês | MEDLINE | ID: mdl-37010879

RESUMO

Mining practices, chiefly froth flotation, are being critically reassessed to replace their use of biohazardous chemical reagents in favor of biofriendly alternatives as a path toward green processes. In this regard, this study aimed at evaluating the interactions of peptides, as potential floatation collectors, with quartz using phage display and molecular dynamics (MD) simulations. Quartz-selective peptide sequences were initially identified by phage display at pH = 9 and further modeled by a robust simulation scheme combining classical MD, replica exchange MD, and steered MD calculations. Our residue-specific analyses of the peptides revealed that positively charged arginine and lysine residues were favorably attracted by the quartz surface at basic pH. The negatively charged residues at pH 9 (i.e., aspartic acid and glutamic acid) further showed affinity toward the quartz surface through electrostatic interactions with the positively charged surface-bound Na+ ions. The best-binding heptapeptide combinations, however, contained both positively and negatively charged residues in their composition. The flexibility of peptide chains was also shown to directly affect the adsorption behavior of the peptide. While attractive intrapeptide interactions were dominated by a weak peptide-quartz binding, the repulsive self-interactions in the peptides improved the binding propensity to the quartz surface. Our results showed that MD simulations are fully capable of revealing mechanistic details of peptide adsorption to inorganic surfaces and are an invaluable tool to accelerate the rational design of peptide sequences for mineral processing applications.


Assuntos
Peptídeos , Quartzo , Quartzo/química , Peptídeos/química , Sequência de Aminoácidos , Simulação de Dinâmica Molecular , Minerais , Adsorção
4.
Food Chem ; 396: 133669, 2022 Dec 01.
Artigo em Inglês | MEDLINE | ID: mdl-35841682

RESUMO

In this work, dispersive solid-phase extraction procedure was developed for trace cadmium determination before flame atomic absorption spectrometry (FAAS) measurement. Copper(II) based nanoflowers were synthesized to utilize as adsorbent for preconcentration of cadmium. The detection power of the spectrometric system was enhanced by placing a slotted quartz tube (SQT) onto the flame burner which increases the residence time of the analyte atoms in the flame region. The analytical performance of the developed system was evaluated with and without SQT equipment and the enhancement in detection power was calculated by the ratio of detection limits of CuNF-DSPE-FAAS (copper nanoflower based dispersive solid phase extraction-flame atomic absorption spectrometry) and FAAS system. Enhancement was determined as 73 and 104.3 times for CuNF-DSPE-FAAS and CuNF-DSPE-SQT-FAAS (CuNF-DSPE-slotted quartz tube-FAAS), respectively. Percent recovery results indicated the applicability of the developed method for the determination of trace cadmium.


Assuntos
Microextração em Fase Líquida , Quartzo , Cádmio/análise , Cobre/análise , Microextração em Fase Líquida/métodos , Quartzo/química , Extração em Fase Sólida , Espectrofotometria Atômica/métodos
5.
Biosensors (Basel) ; 12(5)2022 May 07.
Artigo em Inglês | MEDLINE | ID: mdl-35624609

RESUMO

Cleaning a quartz crystal microbalance (QCM) plays a crucial role in the regeneration of its biosensors for reuse. Imprecise removal of a receptor layer from a transducer's surface can lead to unsteady operation during measurements. This article compares three approaches to regeneration of the piezoelectric transducers using the electrochemical, oxygen plasma and Piranha solution methods. Optimization of the cleaning method allowed for evaluation of the influence of cleaning on the surface of regenerated biosensors. The effectiveness of cleaning the QCM transducers with a receptor layer in the form of a peptide with the KLLFDSLTDLKKKMSEC-NH2 sequence was described. Preliminary cleaning was tested for new electrodes to check the potential impact of the cleaning on deposition and the transducer's operation parameters. The effectiveness of the cleaning was assessed via the measurement of a resonant frequency of the QCM transducers. Based on changes in the resonant frequency and the Sauerbrey equation, it was possible to evaluate the changes in mass adsorption on the transducer's surface. Moreover, the morphology of the QCM transducer's surface subjected to the selected cleaning techniques was presented with AFM imaging. The presented results confirm that each method is suitable for peptide-based biosensors cleaning. However, the most invasive seems to be the Piranha method, with the greatest decrease in performance after regeneration cycles (25% after three cycles). The presented techniques were evaluated for their efficiency with respect to a selected volatile compound, which in the future should allow reuse of the biosensors in particular applications, contributing to cost reduction and extension of the sensors' lifetime.


Assuntos
Técnicas Biossensoriais , Técnicas de Microbalança de Cristal de Quartzo , Técnicas Biossensoriais/métodos , Eletrodos , Peptídeos , Quartzo/química
6.
Anal Chim Acta ; 1202: 338894, 2022 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-35341511

RESUMO

Multi-gas detection represents a suitable solution in many applications, such as environmental and atmospheric monitoring, chemical reaction and industrial process control, safety and security, oil&gas and biomedicine. Among optical techniques, Quartz-Enhanced Photoacoustic Spectroscopy (QEPAS) has been demonstrated to be a leading-edge technology for addressing multi-gas detection, thanks to the modularity, ruggedness, portability and real time operation of the QEPAS sensors. The detection module consists in a spectrophone, mounted in a vacuum-tight cell and detecting sound waves generated via photoacoustic excitation within the gas sample. As a result, the sound detection is wavelength-independent and the volume of the absorption cell is basically determined by the spectrophone dimensions, typically in the order of few cubic centimeters. In this review paper, the implementation of the QEPAS technique for multi-gas detection will be discussed for three main areas of applications: i) multi-gas trace sensing by exploiting non-interfering absorption features; ii) multi-gas detection dealing with overlapping absorption bands; iii) multi-gas detection in fluctuating backgrounds. The fundamental role of the analysis and statistical tools will be also discussed in detail in relation with the specific applications. This overview on QEPAS technique, highlighting merits and drawbacks, aims at providing ready-to-use guidelines for multi-gas detection in a wide range of applications and operating conditions.


Assuntos
Técnicas Fotoacústicas , Quartzo , Técnicas Fotoacústicas/métodos , Quartzo/química , Análise Espectral/métodos
7.
Anal Sci ; 38(6): 843-849, 2022 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-35347676

RESUMO

A sensitive, accurate and simple analytical method was developed to determine cadmium by slotted quartz tube-flame atomic absorption spectrometry after preconcentration/extraction with polystyrene coated magnetic nanoparticles based dispersive solid phase extraction. The surface of Fe3O4 based magnetic nanoparticles was modified with polystyrene to yield higher selectivity and sensitivity in adsorption efficiency of cadmium. The nanoparticles were dispersed into the aqueous solution to extract/separate cadmium. Significant parameters of the method including magnetic nanoparticle amount, mixing effect, effect of ionic strength, eluent concentration and sonication period were optimized to achieve optimal conditions for the analyte. The limit of detection and quantification values of the developed method were found to be 0.62 and 2.1 ng/mL, respectively. Under the optimum conditions, enhancement of the detection power for cadmium were calculated as 102 folds for the developed method. The developed method was then applied to cigarette ash to test its accuracy and applicability. Total cadmium was found to be between 402 and 450 ng/g in the ashes of different cigarette brands commercially available in Turkey. The accuracy of quantifying cadmium in the complex ash samples was enhanced by using the matrix matching calibration strategy. The developed method provides sensitive and selective determination of cadmium at ng/mL levels even at complex cigarette ash samples. High percent recovery results (90-102%) were obtained from spiked real samples.


Assuntos
Nanopartículas de Magnetita , Produtos do Tabaco , Poluentes Químicos da Água , Cádmio/análise , Limite de Detecção , Nanopartículas de Magnetita/química , Poliestirenos , Quartzo/química , Extração em Fase Sólida/métodos , Espectrofotometria Atômica/métodos , Produtos do Tabaco/análise , Poluentes Químicos da Água/análise
8.
Proc Natl Acad Sci U S A ; 117(45): 27836-27846, 2020 11 10.
Artigo em Inglês | MEDLINE | ID: mdl-33097669

RESUMO

Inhalation of silica particles can induce inflammatory lung reactions that lead to silicosis and/or lung cancer when the particles are biopersistent. This toxic activity of silica dusts is extremely variable depending on their source and preparation methods. The exact molecular moiety that explains and predicts this variable toxicity of silica remains elusive. Here, we have identified a unique subfamily of silanols as the major determinant of silica particle toxicity. This population of "nearly free silanols" (NFS) appears on the surface of quartz particles upon fracture and can be modulated by thermal treatments. Density functional theory calculations indicates that NFS locate at an intersilanol distance of 4.00 to 6.00 Å and form weak mutual interactions. Thus, NFS could act as an energetically favorable moiety at the surface of silica for establishing interactions with cell membrane components to initiate toxicity. With ad hoc prepared model quartz particles enriched or depleted in NFS, we demonstrate that NFS drive toxicity, including membranolysis, in vitro proinflammatory activity, and lung inflammation. The toxic activity of NFS is confirmed with pyrogenic and vitreous amorphous silica particles, and industrial quartz samples with noncontrolled surfaces. Our results identify the missing key molecular moieties of the silica surface that initiate interactions with cell membranes, leading to pathological outcomes. NFS may explain other important interfacial processes involving silica particles.


Assuntos
Silanos/química , Dióxido de Silício/química , Dióxido de Silício/toxicidade , Membrana Celular , Cristalização , Poeira , Tamanho da Partícula , Quartzo/química , Quartzo/toxicidade , Propriedades de Superfície
9.
Part Fibre Toxicol ; 17(1): 20, 2020 06 04.
Artigo em Inglês | MEDLINE | ID: mdl-32498698

RESUMO

BACKGROUND: Talc, a hydrous magnesium silicate, often used for genital hygiene purposes, is associated with ovarian carcinoma in case-control studies. Its potential to cause inflammation, injury, and functional changes in cells has been described. A complication of such studies is that talc preparations may be contaminated with other materials. A previous study by (Beck et al. Toxicol Appl Pharmacol 87:222-34, 1987) used a hamster model to study talc and granite dust exposure effects on various biochemical and cellular inflammatory markers. Our current study accessed key materials used in that 1987 study; we re-analyzed the original talc dust with contemporary scanning electron microscopy and energy dispersive x-ray analysis (SEM/EDX) for contaminants. We also examined the original bronchoalveolar lavage (BAL) cells with polarized light microscopy to quantify cell-associated birefringent particles to gain insight into the talc used. RESULTS: SEM/EDX analyses showed that asbestos fibers, quartz, and toxic metal particulates were below the limits of detection in the original talc powder. However, fibers with aspect ratios ≥3:1 accounted for 22% of instilled material, mostly as fibrous talc. Talc (based on Mg/Si atomic weight % ratio) was the most abundant chemical signature, and magnesium silicates with various other elements made up the remainder. BAL cell counts confirmed the presence of acute inflammation, which followed intratracheal instillation. Measurements of cell associated birefringent particles phagocytosis revealed significant differences among talc, granite, and control exposures with high initial uptake of talc compared to granite, but over the 14-day experiment, talc phagocytosis by lavaged cells was significantly less than that of granite. Phagocytosis of talc fibers by macrophages was observed, and birefringent particles were found in macrophages, neutrophils, and multinucleate giant cells in lavaged cells from talc-exposed animals. CONCLUSION: Our data support the contention that talc, even without asbestos and other known toxic contaminants, may elicit inflammation and contribute to lung disease. Our findings support the conclusions of (Beck et al. Toxicol Appl Pharmacol 87:222-34, 1987) study. By analyzing particulate exposures with polarized light microscopy and SEM/EDX, fibrous talc was identified and a distinctive pattern of impaired particulate ingestion was demonstrated.


Assuntos
Exposição por Inalação/efeitos adversos , Pulmão/efeitos dos fármacos , Macrófagos/efeitos dos fármacos , Silicatos de Magnésio/toxicidade , Neutrófilos/efeitos dos fármacos , Talco/toxicidade , Animais , Líquido da Lavagem Broncoalveolar/química , Líquido da Lavagem Broncoalveolar/citologia , Células Cultivadas , Cricetinae , Poeira , Exposição por Inalação/análise , Pulmão/metabolismo , Pulmão/patologia , Macrófagos/metabolismo , Macrófagos/ultraestrutura , Silicatos de Magnésio/química , Silicatos de Magnésio/farmacocinética , Masculino , Microscopia Eletrônica de Varredura , Neutrófilos/metabolismo , Neutrófilos/ultraestrutura , Tamanho da Partícula , Quartzo/química , Quartzo/farmacocinética , Quartzo/toxicidade , Dióxido de Silício/química , Dióxido de Silício/farmacocinética , Dióxido de Silício/toxicidade , Espectrometria por Raios X , Propriedades de Superfície , Talco/química , Talco/farmacocinética
10.
J Hazard Mater ; 388: 121743, 2020 04 15.
Artigo em Inglês | MEDLINE | ID: mdl-31836372

RESUMO

Surface acoustic wave (SAW)-based formaldehyde gas sensor using bi-layer nanofilms of bacterial cellulose (BC) and polyethyleneimine (PEI) was developed on an ST-cut quartz substrate using sol-gel and spin coating processes. BC nanofilms significantly improve the sensitivity of PEI films to formaldehyde gas, and reduces response and recovery times. The BC films have superfine filamentary and fibrous network structures, which provide a large number of attachment sites for the PEI particles. Measurement results obtained using in situ diffuse reflectance Fourier transform infrared spectroscopy showed that the primary amino groups of PEI strongly adsorb formaldehyde molecules through nucleophilic reactions, thus resulting in a negative frequency shift of the SAW sensor due to the mass loading effect. In addition, experimental results showed that the frequency shifts of the SAW devices are determined by thickness of PEI film, concentration of formaldehyde and relative humidity. The PEI/BC sensor coated with three layers of PEI as the sensing layer showed the optimal sensing performance, which had a frequency shift of 35.6 kHz for 10 ppm formaldehyde gas, measured at room temperature and 30 % RH. The sensor also showed good selectivity and stability, with a low limit of detection down to 100 ppb.


Assuntos
Poluentes Atmosféricos/análise , Celulose/química , Monitoramento Ambiental/instrumentação , Formaldeído/análise , Polietilenoimina/química , Quartzo/química , Som , Adsorção , Monitoramento Ambiental/métodos , Desenho de Equipamento , Modelos Teóricos , Nanoestruturas/química , Sensibilidade e Especificidade
11.
Methods Mol Biol ; 2003: 31-52, 2019.
Artigo em Inglês | MEDLINE | ID: mdl-31218612

RESUMO

Extensive studies on the spontaneous collapse of phospholipid vesicles into supported lipid bilayers (SLBs) have led to procedures which allow SLB formation on a wealth of substrates and lipid compositions. SLBs provide a widely accepted and versatile model system which mimics the natural cell membrane separating the extracellular and intracellular fluids of the living cell. The quartz crystal microbalance with dissipation monitoring (QCM-D) has been central in both the understanding of vesicle collapse into SLBs on various substrates but also in probing the kinetics and mechanisms of biomolecular interactions with SLBs in real time. We describe a robust procedure to form SLBs of zwitterionic and charged lipids on SiO2 sensor crystals which subsequently can be exploited to probe the interaction between proteins and peptides with the SLB.


Assuntos
Membrana Celular/química , Proteínas/química , Técnicas de Microbalança de Cristal de Quartzo/métodos , Quartzo/química , Cinética , Bicamadas Lipídicas/química , Peptídeos/química , Dióxido de Silício/química
12.
Magn Reson Imaging ; 56: 77-85, 2019 02.
Artigo em Inglês | MEDLINE | ID: mdl-30316982

RESUMO

Asphaltene adsorption on solid surfaces is a standing problem in petroleum industry. It has an adverse effect on reservoir production and development by changing rock wettability, plugging pore throats, and affects oil transport through pipelines. Asphaltene chemistry constitutes important part of the ageing process as part of petrophysical studies and core analysis. The mechanisms and contribution of various oil components to adsorption processes is not fully understood. To investigate the kinetics of the ageing process and address the relative contribution of different oil components, we prepared three sets of sandstone core plugs aged in different oil mixtures over various time intervals. Cores were then re-saturated with decane to evaluate their wetting state using low-field NMR relaxometry by monitoring a change of surface relaxivity. Adsorbed deposits were then extracted from cores for solution-state NMR analysis. Their 1H and 1H-13C correlation spectra obtained using heteronuclear single quantum coherence (HSQC) technique were matched to spectra of four SARA (saturates, aromatics, resins and asphaltenes) components of oil mixtures to deduce components of deposits and inter-component interactions. We notice that wettability reversal of rock is inversely proportional to initial asphaltene concentration. Analysis of deposits reveals an increase in their aliphatic content over ageing time, which is accompanied by a change of the morphology of the pore space due to cluster aggregates forming a network. Results suggest that the ageing process in respect to the wetting state of rock samples consists of three distinctive stages: (i) an early-time period, when the fraction of most polar asphaltenes creates a discontinuous layer corresponding to mixed-wet state; (ii) an intermediate-time interval, at which the full grain coverage may be achieved (at favourable chemical environment) corresponding to strong oil-wetting; (iii) a late-time stage, where intense macro-aggregates accumulation occurs, changing the pore space integrity. It is likely asphaltene-aliphatic interactions leading to growth of sub-micron size macro-aggregates.


Assuntos
Silicatos de Alumínio/química , Caulim/química , Imageamento por Ressonância Magnética/métodos , Espectroscopia de Ressonância Magnética/métodos , Hidrocarbonetos Policíclicos Aromáticos/química , Compostos de Potássio/química , Quartzo/química , Adsorção , Alcanos , Gases , Cinética , Microscopia Eletrônica de Varredura , Permeabilidade , Porosidade , Propriedades de Superfície , Molhabilidade , Microtomografia por Raio-X
13.
Magn Reson Imaging ; 56: 86-89, 2019 02.
Artigo em Inglês | MEDLINE | ID: mdl-30336200

RESUMO

We have applied diffusion and relaxation Nuclear Magnetic Resonance experiments to investigate the translational and rotational mobility of adsorbents on quartz and calcite mineral surfaces. On both surfaces it was found that water is the dominant molecule. On the quartz surface the majority of water molecules have a relatively high degree of both rotational and translational mobility, while a minor fraction of water molecules, and all hydrocarbon molecules, have a significantly lower mobility. On the calcite surface the translational mobility is very low for all the adsorbed molecules, while there is a large diversity in rotational mobility, indicating that the hydrocarbon molecules are strongly attached to the surface, but that some part of each molecule still have a large degree of rotational mobility. Diffusion and relaxation experiments give a detailed description of both the molecular mobility of adsorbed species on these mineral surfaces, which leads to new insight with respect to aging processes on a molecular level.


Assuntos
Hidrocarbonetos/química , Espectroscopia de Ressonância Magnética/métodos , Minerais/química , Petróleo , Água/química , Adsorção , Difusão , Imageamento por Ressonância Magnética , Pós , Quartzo/química , Rotação , Software
14.
Braz. oral res. (Online) ; 33: e027, 2019. tab, graf
Artigo em Inglês | LILACS | ID: biblio-1011658

RESUMO

Abstract Nowadays, demand for esthetic restorations has risen considerably; thus, nonmetal esthetic posts made of either high-strength ceramics or reinforced resins, such as fiber-reinforced resin posts, have become more and more popular. Important characteristics of fiber-reinforced posts involve a modulus of elasticity similar to dentin and their ability to be cemented by an adhesive technique. A total of 36 maxillary incisors were divided into four groups. In this study, four adhesively luted fiber-reinforced (glass fiber, quartz glass fiber, zirconia glass fiber and woven polyethylene fiber ribbon) post systems were used. Post spaces were prepared by employing drills according to the protocol established for each group, and each post was adhesively luted with one of three adhesive systems. Three segments per root apical to the cementoenamel junction (CEJ) were obtained by sectioning the root under distilled water with a carbon spare saw. The samples (total of 108 sections) were 2.0±0.1 mm in thickness and they were stored individually in black film canisters with sterile distilled water. In order to determine the bond strength, the bonding area of each specimen was measured, and specimens were attached to a device to test microtensile strength at a speed of 1 mm/min. The analyses revealed no statistically significant differences between the adhesive systems and fiber-reinforced posts. (P> 0.05). However, the coronal portion of the root dentin had the highest bond strength. Adhesive systems used along with fiber-reinforced resin posts demonstrated reliable bonding.


Assuntos
Humanos , Colagem Dentária/métodos , Adesivos Dentinários/química , Resinas Compostas/química , Cimentos de Resina/química , Coroas , Quartzo/química , Resistência à Tração , Zircônio , Esmalte Dentário , Cavidade Pulpar , Análise do Estresse Dentário , Dentina , Vidro
15.
Part Fibre Toxicol ; 15(1): 23, 2018 05 21.
Artigo em Inglês | MEDLINE | ID: mdl-29783987

RESUMO

Human exposure to (certain forms of) crystalline silica (CS) potentially results in adverse effects on human health. Since 1997 IARC has classified CS as a Group 1 carcinogen [1], which was confirmed in a later review in 2012 [2]. The genotoxic potential and mode of genotoxic action of CS was not conclusive in either of the IARC reviews, although a proposal for mode of actions was made in an extensive review of the genotoxicity of CS by Borm, Tran and Donaldson in 2011 [3]. The present study identified 141 new papers from search strings related to genotoxicity of respirable CS (RCS) since 2011 and, of these, 17 relevant publications with genotoxicity data were included in this detailed review.Studies on in vitro genotoxic endpoints primarily included micronucleus (MN) frequency and % fragmented DNA as measured in the comet assay, and were mostly negative, apart from two studies using primary or cultured macrophages. In vivo studies confirmed the role of persistent inflammation due to quartz surface toxicity leading to anti-oxidant responses in mice and rats, but DNA damage was only seen in rats. The role of surface characteristics was strengthened by in vitro and in vivo studies using aluminium or hydrophobic treatment to quench the silanol groups on the CS surface.In conclusion, the different modes of action of RCS-induced genotoxicity have been evaluated in a series of independent, adequate studies since 2011. Earlier conclusions on the role of inflammation driven by quartz surface in genotoxic and carcinogenic effects after inhalation are confirmed and findings support a practical threshold. Whereas classic in vitro genotoxicity studies confirm an earlier no-observed effect level (NOEL) in cell cultures of 60-70 µg/cm2, transformation frequency in SHE cells suggests a lower threshold around 5 µg/cm2. Both levels are only achieved in vivo at doses (2-4 mg) beyond in vivo doses (> 200 µg) that cause persistent inflammation and tissue remodelling in the rat lung.


Assuntos
Dano ao DNA , Exposição por Inalação/efeitos adversos , Micronúcleos com Defeito Cromossômico/induzido quimicamente , Mutagênicos/toxicidade , Dióxido de Silício/toxicidade , Animais , Linhagem Celular , Cricetulus , Humanos , Mesocricetus , Mutagênicos/química , Nível de Efeito Adverso não Observado , Quartzo/química , Quartzo/toxicidade , Medição de Risco , Dióxido de Silício/química
16.
Bull Environ Contam Toxicol ; 100(5): 715-719, 2018 May.
Artigo em Inglês | MEDLINE | ID: mdl-29411047

RESUMO

In this study, dispersive liquid-liquid microextraction was systematically optimized for the preconcentration of nickel after forming a complex with diphenylcarbazone. The measurement output of the flame atomic absorption spectrometer was further enhanced by fitting a custom-cut slotted quartz tube to the flame burner head. The extraction method increased the amount of nickel reaching the flame and the slotted quartz tube increased the residence time of nickel atoms in the flame to record higher absorbance. Two methods combined to give about 90 fold enhancement in sensitivity over the conventional flame atomic absorption spectrometry. The optimized method was applicable over a wide linear concentration range, and it gave a detection limit of 2.1 µg L-1. Low relative standard deviations at the lowest concentration in the linear calibration plot indicated high precision for both extraction process and instrumental measurements. A coal fly ash standard reference material (SRM 1633c) was used to determine the accuracy of the method, and experimented results were compatible with the certified value. Spiked recovery tests were also used to validate the applicability of the method.


Assuntos
Poluentes Ambientais/análise , Níquel/análise , Espectrofotometria Atômica/métodos , Poluentes Ambientais/química , Concentração de Íons de Hidrogênio , Microextração em Fase Líquida/métodos , Níquel/química , Quartzo/química
17.
J AOAC Int ; 101(3): 843-847, 2018 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-28903806

RESUMO

A dispersive liquid-liquid microextraction (DLLME) technique based on a solidification-of-floating-organic-drop (SFOD) procedure was developed for the determination of trace amounts of cadmium (Cd) by using a flame atomic absorption spectrometer (FAAS) fitted with a slotted quartz tube (SQT). The extraction of Cd was achieved by forming a complex with diphenylcarbazone. Parameters affecting the formation of complex and extraction outputs were carefully optimized to obtain high-absorbance signals to achieve lower LODs. An SQT was fitted on top of the flame burner head to further enhance the absorbance of the signals recorded by the FAAS. Coupling the DLLME-SFOD procedure with SQT-FAAS produced an enhancement factor of about 183. The LOD of the method was 0.23 µg/L with an RSD of 3.8%. Matrix-matching was used to overcome any low recovery results obtained with tap water and municipal wastewater.


Assuntos
Cádmio/análise , Microextração em Fase Líquida/métodos , Espectrofotometria Atômica/métodos , Complexos de Coordenação/química , Química Verde/métodos , Ligantes , Limite de Detecção , Quartzo/química , Semicarbazonas/química
18.
Spectrochim Acta A Mol Biomol Spectrosc ; 192: 146-152, 2018 Mar 05.
Artigo em Inglês | MEDLINE | ID: mdl-29128748

RESUMO

Oxidative stress biomarkers, including glutathione (GSH) and related compounds, are involved in a variety of interactions enabling redox potential maintenance in living cells and protection against radicals. Since the oxidative stress is promoting and, in many cases, inducing serious illnesses, monitoring of GSH levels can aid in diagnostics and disease prevention. Herein, we report on the discovery of the formation of a supramolecular ensemble of GSH with fluorone black (9-phenyl fluorone, FB) which is optically active and enables sensitive determination of GSH by resonance elastic light scattering (RELS). We have found that supramolecular interactions of GSH with FB can be probed with spectroscopic, RELS, and electrochemical methods. Our investigations show that RELS intensity for FB solutions increases with GSH concentration while fluorescence emission of FB is not affected, as quenching begins only above 0.8mM GSH. The UV-Vis difference spectra show a positive peak at 383nm and a negative peak at 458nm, indicating a higher-energy absorbing complex in comparison to the non-bonded FB host. Supramolecular interactions of FB with GSH have also been corroborated by electrochemical measurements involving two configurations of FB-GSH ensembles on electrodes: (i) an inverted orientation on Au-coated quartz crystal piezoelectrode (Au@SG-FB), with strong thiolate bonding to gold, and (ii) a non-inverted orientation on glassy carbon electrode (GCE@FB-GS), with weak π-π stacking attachment and efficient charge mediation through the ensemble. The formation of a supramolecular ensemble with hydrogen bonding has also been confirmed by quantum mechanical calculations. The discovery of supramolecular FB-GSH ensemble formation enables elucidating the mechanisms of strong RELS responses, changes in UV-Vis absorption spectra, and the electrochemical reactivity. Also, it provides new insights to the understanding of the efficient charge-transfer in redox potential homeostasis which is likely based on an intermediate formation of a similar type of supramolecular ensembles.


Assuntos
Biomarcadores/metabolismo , Fluoresceínas/metabolismo , Glutationa/metabolismo , Estresse Oxidativo , Biomarcadores/química , Carbono/química , Técnicas Eletroquímicas , Eletrodos , Fluoresceínas/química , Vidro/química , Glutationa/química , Ouro/química , Ligação de Hidrogênio , Modelos Moleculares , Conformação Molecular , Quartzo/química , Espalhamento de Radiação , Espectrometria de Fluorescência , Espectrofotometria Ultravioleta
19.
Environ Monit Assess ; 189(10): 513, 2017 Sep 20.
Artigo em Inglês | MEDLINE | ID: mdl-28932958

RESUMO

In this study, solidified floating organic drop microextraction (SFODME) by 1-undecanol was combined with slotted quartz tube flame atomic absorption spectrometry (SQT-FAAS) for the determination of cadmium at trace levels. Formation of a complex with 4,4'-dimethyl-2,2'-bipyridine facilitated the extraction of cadmium from aqueous solutions. Several chemical variables were optimized in order to obtain high extraction outputs. Parameters such as concentration of the ligand, pH, and amount of buffer solution were optimized to enhance the formation of cadmium complex. The SFODME method was assisted by dispersion of extractor solvent into aqueous solutions using 2-propanol. Under the optimum extraction and instrumental conditions, the limit of detection and limit of quantitation values obtained for cadmium using the combined methods (SFODME-SQT-FAAS) were found to be 0.4 and 1.3 µg L-1, respectively. Matrix effects on the method were also examined for tap water and wastewater, and spiked recovery results were found to be very satisfactory. Graphical Abstract SFODME-SQT-FAAS system for sensitive determination of cadmium.


Assuntos
Cádmio/análise , Monitoramento Ambiental/métodos , Microextração em Fase Líquida/métodos , Quartzo/química , Espectrofotometria Atômica/métodos , Poluentes Químicos da Água/análise , Água Potável/análise , Concentração de Íons de Hidrogênio , Sensibilidade e Especificidade , Soluções , Solventes/química , Águas Residuárias/análise
20.
Ecotoxicol Environ Saf ; 145: 483-489, 2017 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-28780447

RESUMO

Reducing the concentration of heavy metals including lead (Pb) and nickel (Ni) in organic contaminants such as municipal wastes and sewage sludge is of health and environmental importance. Nanoscale zero-valent iron (NZVI) particles can effectively remove heavy metals from contaminated aqueous and solid media. It was accordingly hypothesized that it is possible to recycle and detoxify organic waste materials containing heavy metals using NZVI and NZVI fixed on quartz (QNZVI). The objective was to investigate the effects of NZVI type, concentration (2% and 5%) and contact time on the removal of Pb and Ni from raw compost, compost fermented with beet molasses, and leachate using a factorial design. The results indicated the significant reduction of DTPA- Pb and DTPA-Ni concentration, in all the organic compounds treated with NZVI and QNZVI (P= 0.01), compared with control. Increased concentration of NZVI in all treatments, increased the rate of DTPA-Pb and DTPA-Ni (P= 0.01) at 113.1% and 180% for Pb (NZVI at 2% and 5%), and at 16.3% and 23.3% for Ni, irrespective of the NZVI type. The reducing trend of extractable Pb and Ni in all the organic compounds was the same, quick reduction at the beginning, followed by a negligible rate. The highest reduction rates for Pb (at one hour) and Ni (at 672h) were equal to 72.93% and 23.27%, respectively. NZVI at 2% was more efficient than NZVI at 5%. There were not any significant differences between NZVI and QNZVI on the removal of Pb and Ni from the organic contaminants. It is possible to immobilize and reduce the concentration of heavy metals such as Pb and Ni in organic contaminants using NZVI, which is affected by NZVI properties, concentration, and contact time, as well as by organic contaminant type.


Assuntos
Ferro/química , Chumbo/análise , Nanoestruturas/química , Níquel/análise , Quartzo/química , Esgotos/análise , Resíduos Sólidos/análise , Gerenciamento de Resíduos
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