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1.
Bioorg Chem ; 149: 107531, 2024 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-38850779

RESUMEN

Nitroreductase (NTR) overexpression often occurs in tumors, highlighting the significance of effective NTR detection. Despite the utilization of various optical methods for this purpose, the absence of an efficient tumor-targeting optical probe for NTR detection remains a challenge. In this research, a novel tumor-targeting probe (Cy-Bio-NO2) is developed to perform dual-modal NTR detection using near-infrared fluorescence and photoacoustic techniques. This probe exhibits exceptional sensitivity and selectivity to NTR. Upon the reaction with NTR, Cy-Bio-NO2 demonstrates a distinct fluorescence "off-on" response at 800 nm, with an impressive detection limit of 12 ng/mL. Furthermore, the probe shows on-off photoacoustic signal with NTR. Cy-Bio-NO2 has been successfully employed for dual-modal NTR detection in living cells, specifically targeting biotin receptor-positive cancer cells for imaging purposes. Notably, this probe effectively detects tumor hypoxia through dual-modal imaging in tumor-bearing mice. The strategy of biotin incorporation markedly enhances the probe's tumor-targeting capability, facilitating its engagement in dual-modal imaging at tumor sites. This imaging capacity holds substantial promise as an accurate tool for cancer diagnosis.


Asunto(s)
Colorantes Fluorescentes , Nitrorreductasas , Imagen Óptica , Animales , Humanos , Ratones , Colorantes Fluorescentes/química , Colorantes Fluorescentes/síntesis química , Ratones Endogámicos BALB C , Ratones Desnudos , Estructura Molecular , Neoplasias/diagnóstico por imagen , Neoplasias Experimentales/diagnóstico por imagen , Neoplasias Experimentales/metabolismo , Nitrorreductasas/metabolismo , Nitrorreductasas/análisis , Técnicas Fotoacústicas , Dióxido de Nitrógeno/síntesis química , Dióxido de Nitrógeno/química
2.
Int J Mol Sci ; 25(10)2024 May 17.
Artículo en Inglés | MEDLINE | ID: mdl-38791510

RESUMEN

α-CD:N2O "host-guest" type complexes were formed by a simple solid-gas reaction (N2O sorption into α-CD) under different gas pressures and temperatures. The new N2O inclusion method applied in the present study was compared with the already known technique based on the crystallization of clathrates from a water solution of α-CD saturated with N2O. A maximum storage capacity of 4.5 wt.% N2O was achieved when charging the cyclodextrin from a gas phase. The amount of included gas decreases to 1.3 wt.% when the complex is stored in air at 1 atm and room temperature, analogous to that achieved by the crystallization of α-CD:N2O. Furthermore, it was shown that the external coordination of N2O to either the upper or lower rim of α-CD without hydration water displacement is the preferred mode of binding, due to hydrogen bonds with neighboring -OH groups from the host macrocycle and three of the hydration water molecules nearby. The capacity of α-CD to store N2O and the thermal stability of the α-CD:N2O complex demonstrated promising applications of these types of complexes in food and beverages.


Asunto(s)
alfa-Ciclodextrinas , alfa-Ciclodextrinas/química , Enlace de Hidrógeno , Temperatura , Dióxido de Nitrógeno/química , Agua/química , Adsorción
3.
Int J Mol Sci ; 25(8)2024 Apr 17.
Artículo en Inglés | MEDLINE | ID: mdl-38674006

RESUMEN

The aim of this study was to obtain nitrogen-enriched activated carbons from orthocoking coal. The initial material was subjected to a demineralisation process. The demineralised precursor was pyrolysed at 500 °C and then activated with sodium hydroxide at 800 °C. Activated carbon adsorbents were subjected to the process of ammoxidation using a mixture of ammonia and air at two different temperature variants (300 and 350 °C). Nitrogen introduction was carried out on stages of demineralised precursor, pyrolysis product, and oxidising activator. The elemental composition, acid-base properties, and textural parameters of the obtained carbon adsorbents were determined. The activated carbons were investigated for their ability to remove nitrogen dioxide. The results demonstrated that the ammoxidation process incorporates new nitrogen-based functional groups into the activated carbon structure. Simultaneously, the ammoxidation process modified the acid-base characteristics of the surface and negatively affected the textural parameters of the resulting adsorbents. Furthermore, the study showed that all of the obtained carbon adsorbents exhibited a distinct microporous texture. Adsorption tests were carried out against NO2 and showed that the carbon adsorbents obtained were highly effective in removing this gaseous pollutant. The best sorption capacity towards NO2 was 23.5 mg/g under dry conditions and 75.0 mg/g under wet conditions.


Asunto(s)
Carbón Orgánico , Dióxido de Nitrógeno , Nitrógeno , Adsorción , Dióxido de Nitrógeno/química , Nitrógeno/química , Carbón Orgánico/química , Carbono/química , Temperatura , Carbón Mineral
4.
Environ Sci Technol ; 58(18): 7904-7915, 2024 May 07.
Artículo en Inglés | MEDLINE | ID: mdl-38661303

RESUMEN

Nitrogen dioxide (NO2) hydrolysis in deliquesced aerosol particles forms nitrous acid and nitrate and thus impacts air quality, climate, and the nitrogen cycle. Traditionally, it is considered to proceed far too slowly in the atmosphere. However, the significance of this process is highly uncertain because kinetic studies have only been made in dilute aqueous solutions but not under high ionic strength conditions of the aerosol particles. Here, we use laboratory experiments, air quality models, and field measurements to examine the effect of the ionic strength on the reaction kinetics of NO2 hydrolysis. We find that high ionic strengths (I) enhance the reaction rate constants (kI) by more than an order of magnitude compared to that at infinite dilution (kI=0), yielding log10(kI/kI=0) = 0.04I or rate enhancement factor = 100.04I. A state-of-the-art air quality model shows that the enhanced NO2 hydrolysis reduces the negative bias in the simulated concentrations of nitrous acid by 28% on average when compared to field observations over the North China Plain. Rapid NO2 hydrolysis also enhances the levels of nitrous acid in other polluted regions such as North India and further promotes atmospheric oxidation capacity. This study highlights the need to evaluate various reaction kinetics of atmospheric aerosols with high ionic strengths.


Asunto(s)
Aerosoles , Aerosoles/química , Hidrólisis , Concentración Osmolar , Dióxido de Nitrógeno/química , Cinética , Atmósfera/química , Contaminantes Atmosféricos/química
5.
ACS Sens ; 9(4): 1967-1977, 2024 04 26.
Artículo en Inglés | MEDLINE | ID: mdl-38494643

RESUMEN

Bimetallic nanocrystals (NCs) have obtained significant attention due to their unique advantages of the intrinsic properties of individual metals and synergistic enhancements resulting from the electronic coupling between two constituent metals. In this work, Pd@Pt core-shell NCs were prepared through a facile one-pot solution-phase method, which had excellent dispersion and uniform size. Concurrently, ZnO nanosheets were prepared via a hydrothermal method. To explore their potential in nitrogen dioxide (NO2) gas sensing applications, sensitive materials based on ZnO nanosheets with varying mass percentages of Pd@Pt NCs were generated through an impregnation process. The sensor based on 0.3 wt % Pd@Pt-ZnO exhibited remarkable performance, demonstrating a substantial response (Rg/Ra = 60.3) to 50 ppb of NO2 at a low operating temperature of 80 °C. Notably, this sensor reached an outstanding low detection limit of 300 ppt. The enhancement in gas sensing capabilities can be attributed to the sensitization and synergistic effects imparted by the exceptional catalytic activity of Pd@Pt NCs, which significantly promoted the reaction. This research introduces a novel approach for the utilization of core-shell structured bimetallic nanocrystals as modifiers in metal-oxide-semiconductor (MOS) materials for NO2 detection.


Asunto(s)
Dióxido de Nitrógeno , Paladio , Platino (Metal) , Óxido de Zinc , Óxido de Zinc/química , Dióxido de Nitrógeno/análisis , Dióxido de Nitrógeno/química , Paladio/química , Platino (Metal)/química , Nanopartículas del Metal/química , Límite de Detección
6.
ACS Sens ; 9(5): 2372-2382, 2024 05 24.
Artículo en Inglés | MEDLINE | ID: mdl-38401047

RESUMEN

Rapid and ultrasensitive detection of toxic gases at room temperature is highly desired in health protection but presents grand challenges in the sensing materials reported so far. Here, we present a gas sensor based on novel zero dimensional (0D)/two dimensional (2D) indium oxide (In2O3)/titanium carbide (Ti3C2Tx) Schottky heterostructures with a high surface area and rich oxygen vacancies for parts per billion (ppb) level nitrogen dioxide (NO2) detection at room temperature. The In2O3/Ti3C2Tx gas sensor exhibits a fast response time (4 s), good response (193.45% to 250 ppb NO2), high selectivity, and excellent cycling stability. The rich surface oxygen vacancies play the role of active sites for the adsorption of NO2 molecules, and the Schottky junctions effectively adjust the charge-transfer behavior through the conduction tunnel in the sensing material. Furthermore, In2O3 nanoparticles almost fully cover the Ti3C2Tx nanosheets which can avoid the oxidation of Ti3C2Tx, thus contributing to the good cycling stability of the sensing materials. This work sheds light on the sensing mechanism of heterojunction nanostructures and provides an efficient pathway to construct high-performance gas sensors through the rational design of active sites.


Asunto(s)
Indio , Dióxido de Nitrógeno , Temperatura , Titanio , Dióxido de Nitrógeno/análisis , Dióxido de Nitrógeno/química , Titanio/química , Indio/química , Porosidad
7.
Environ Pollut ; 334: 122134, 2023 Oct 01.
Artículo en Inglés | MEDLINE | ID: mdl-37414123

RESUMEN

Mineral particles in air could provide atmospheric chemical reaction interface for gaseous substances and participate in atmospheric chemical reaction process, and affecting the status and levels of gaseous pollutants in air. However, differences of the heterogenous reaction on the surface minerals particles are not very clear. Considering main mineral composition of ambient particles was from dust emission, therefore, typical clay minerals (chlorite, illite) and desert particles (Taklimakan Desert) were selected to analysize chemical reaction of NO2, one of major gaseous pollutants, on mineral particles by using of In-situ DRIFTS (diffuse reflectance infrared Fourier transform spectroscopy) under different condition. And In situ near-ambient pressure X-ray photoelectron spectroscopy (In situ NAP-XPS) was employed to investigate iron (one of the major metals) species variation on the surface of mineral dust particles during the heterogeneous reactions. Our data show that humidity controlled by deuterium oxide (D2O) has a greater effect on chemical reactions compared to light and temperature. Under dry conditions, the amount of heterogeneous reaction products of NO2 on the particles shows Xiaotang dust > chlorite > illite > Tazhong dust regardless of dark or light conditions. In contrast, under humidity conditions, the order of nitrate product quantity under moderate conditions was chlorite > illite > Xiaotang dust > Tazhong dust. In situ NAP-XPS results demonstrate that specie variation of the Fe could promote the heterogenous reactions. These data could provide useful information for understanding the formation mechanism of nitrate aerosols and removal of nitrogen oxides in the atmosphere.


Asunto(s)
Polvo , Contaminantes Ambientales , Polvo/análisis , Arcilla , Dióxido de Nitrógeno/química , Nitratos , Minerales/química , Gases , Aerosoles/química
8.
Chembiochem ; 24(12): e202200731, 2023 06 15.
Artículo en Inglés | MEDLINE | ID: mdl-36944581

RESUMEN

Kinetic studies revealed that nitrate radicals (NO3 ⋅), which are formed through reaction of the noxious air pollutants nitrogen dioxide (NO2 ⋅) and ozone (O3 ), very rapidly oxidize phenylalanine residues in an aqueous environment, with overall rate coefficients in the 108 -109  M-1 s-1 range. With amino acids and dipeptides as model systems, the data suggest that the reaction proceeds via a π-complex between NO3 ⋅ and the aromatic ring in Phe, which subsequently decays into a charge transfer (CT) complex. The stability of the π-complex is sequence-dependent and is increased when Phe is at the N terminus of the dipeptide. Computations revealed that the considerably more rapid radical-induced oxidation of Phe residues in both neutral and acidic aqueous environments, compared to acetonitrile, can be attributed to stabilization of the CT complex by the protic solvent; this clearly highlights the health-damaging potential of exposure to combined NO2 ⋅ and O3 .


Asunto(s)
Nitratos , Dióxido de Nitrógeno , Nitratos/química , Dióxido de Nitrógeno/química , Fenilalanina/química , Cinética , Oxidación-Reducción , Dipéptidos/química
9.
Sci Total Environ ; 838(Pt 1): 155973, 2022 Sep 10.
Artículo en Inglés | MEDLINE | ID: mdl-35588848

RESUMEN

Urban grime represents an important environmental surface for heterogeneous reactions in urban environment. Here, we assess the physical and chemical properties of urban grime collected during six consecutive months in downtown of Guangzhou, China. There is a significant variation of the uptake coefficients of NO2 on the urban grime as a function of the relative humidity (RH). In absence of water molecules (0% RH), the light-induced uptake coefficients of NO2 on urban grime samples collected during six months are very similar in order of ≈10-6. At 80% RH, depending on the sampling month the light-induced uptake coefficient of NO2 can reach one order of magnitude higher values (1.5 × 10-5, at 80% RH) compared to those uptakes at 0% RH. In presence of 80% RH, there are strong correlations between the measured NO2 uptakes and the concentrations of the water soluble carbon, soluble anions, polycyclic aromatic hydrocarbons and n-alkanes depicted in the urban grime. These correlations, demonstrate that surface adsorbed water on urban grime play an important role for the uptakes of NO2. The heterogeneous conversion of NO2 on two-month old urban grime under sunlight irradiation (68 W m-2, 300 nm < λ < 400 nm) at 60% RH leads to the formation of unprecedented HONO surface flux of 4.7 × 1010 molecules cm-2 s-1 which is higher than all previously observed HONO fluxes, thereby affecting the oxidation capacity of the urban atmosphere. During the heterogeneous chemistry of NO2 with urban grime, the unsaturated and N-containing organic compounds are released in the gas phase which can affect the air quality in the urban environment.


Asunto(s)
Atmósfera , Dióxido de Nitrógeno , Atmósfera/química , China , Dióxido de Nitrógeno/química , Luz Solar , Agua/química
10.
Environ Pollut ; 304: 119124, 2022 Jul 01.
Artículo en Inglés | MEDLINE | ID: mdl-35367103

RESUMEN

Responses to COVID-19 altered environmental exposures and health behaviours associated with non-communicable diseases. We aimed to (1) quantify changes in nitrogen dioxide (NO2), noise, physical activity, and greenspace visits associated with COVID-19 policies in the spring of 2020 in Barcelona (Spain), Vienna (Austria), and Stockholm (Sweden), and (2) estimated the number of additional and prevented diagnoses of myocardial infarction (MI), stroke, depression, and anxiety based on these changes. We calculated differences in NO2, noise, physical activity, and greenspace visits between pre-pandemic (baseline) and pandemic (counterfactual) levels. With two counterfactual scenarios, we distinguished between Acute Period (March 15th - April 26th, 2020) and Deconfinement Period (May 2nd - June 30th, 2020) assuming counterfactual scenarios were extended for 12 months. Relative risks for each exposure difference were estimated with exposure-risk functions. In the Acute Period, reductions in NO2 (range of change from -16.9 µg/m3 to -1.1 µg/m3), noise (from -5 dB(A) to -2 dB(A)), physical activity (from -659 MET*min/wk to -183 MET*min/wk) and greenspace visits (from -20.2 h/m to 1.1 h/m) were largest in Barcelona and smallest in Stockholm. In the Deconfinement Period, NO2 (from -13.9 µg/m3 to -3.1 µg/m3), noise (from -3 dB(A) to -1 dB(A)), and physical activity levels (from -524 MET*min/wk to -83 MET*min/wk) remained below pre-pandemic levels in all cities. Greatest impacts were caused by physical activity reductions. If physical activity levels in Barcelona remained at Acute Period levels, increases in annual diagnoses for MI (mean: 572 (95% CI: 224, 943)), stroke (585 (6, 1156)), depression (7903 (5202, 10,936)), and anxiety (16,677 (926, 27,002)) would be anticipated. To decrease cardiovascular and mental health impacts, reductions in NO2 and noise from the first COVID-19 surge should be sustained, but without reducing physical activity. Focusing on cities' connectivity that promotes active transportation and reduces motor vehicle use assists in achieving this goal.


Asunto(s)
Contaminantes Atmosféricos , Contaminación del Aire , COVID-19 , Accidente Cerebrovascular , Contaminantes Atmosféricos/análisis , Contaminación del Aire/análisis , COVID-19/epidemiología , Ciudades/epidemiología , Exposición a Riesgos Ambientales/análisis , Conductas Relacionadas con la Salud , Humanos , Salud Mental , Dióxido de Nitrógeno/análisis , Dióxido de Nitrógeno/química , Pandemias , Material Particulado/análisis
11.
Sci Total Environ ; 823: 153649, 2022 Jun 01.
Artículo en Inglés | MEDLINE | ID: mdl-35158289

RESUMEN

In this study, heterogeneous formation of nitrate from O3 reaction with NO2 on black carbon (BC) and KCl-treated BC surface in the presence of NH3 was simulated under 30-90% RH conditions by using a laboratory smog chamber. We found that O3 and NO2 in the chamber quickly reacted into N2O5 in the gas phase, which subsequently hydrolyzed into HNO3 and further neutralized with NH3 into NH4NO3 on the BC surface, along with a small amount of N2O5 decomposed into NO and NO2 through a reaction with the BC surface active site. Meanwhile, the fractal BC aggregates restructured and condensed to spherical particles during the NH4NO3 coating process. Compared to that during the exposure to NO2 or O3 alone, the presence of strong signals of CH2O+, CH2O2+ and CH4NO+ during the simultaneous exposure to both NO2 and O3 suggested a synergetic oxidizing effect of NO2 and O3, which significantly activated the BC surface by forming carbonyl, carboxylic and nitro groups, promoted the adsorption of water vapor onto the BC surface and enhanced the NH4NO3 formation. Under <75 ± 2% RH conditions the coating process of NH4NO3 on the BC surface consisted of a diffusion of N2O5 onto the surface and a subsequent hydrolysis, due to the limited number of water molecules adsorbed. However, under 90 ± 2% RH conditions N2O5 directly hydrolyzed on the aqueous phase of the BC surface due to the multilayer water molecules adsorbed, which caused an instant NH4NO3 formation on the surface without any delay. The coating rate of NH4NO3 on KCl-treated BC particles was 3-4 times faster than that on the pure BC particles at the initial stage, indicating an increasing formation of NH4NO3, mainly due to an enhanced hygroscopicity of BC by KCl salts.


Asunto(s)
Dióxido de Nitrógeno , Esmog , Carbono , Humedad , Dióxido de Nitrógeno/química , Hollín
12.
Anal Bioanal Chem ; 414(15): 4347-4358, 2022 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-35013806

RESUMEN

Gas-phase ozone (O3) and nitrogen dioxide (NO2) can react with environmentally exposed proteins to induce chemical modifications such as the formation of nitrotyrosine (NTyr). Certain proteins with these modifications have also been shown to promote adverse health effects and can trigger an immune response. It is hypothesized that proteinaceous material suspended in the atmosphere as particulate matter, e.g., embedded in pollen, can undergo heterogenous reactions to produce chemically modified proteins that impact human health, especially in urban areas. To investigate the protein modification process under ambient outdoor reaction conditions, bovine serum albumin (BSA) protein samples were loaded onto filters and exposed to urban air in Denver, Colorado (USA). Losses and measurement artifacts were measured independently to calculate nitration effects on the protein via high-performance liquid chromatography and to support the experimental methodology. O3 loss from inlet lines using three commonly used particulate filters was quantified, showing a range of ambient O3 concentration losses from 3.2% for Kynar® (polyvinylidene fluoride) filters to > 60% for commonly used HEPA filters. Protein mass extraction efficiency was calculated as a function of filter material and protein mass using both native and nitrated BSA. Finally, we show examples of BSA samples nitrated by exposure to urban air as a proof-of-concept for future studies, highlighting the potential for atmospherically relevant NTyr formation. The methodology vetted here provides support for a wide variety of experimental efforts related to exposure of analytes to O3 and more broadly to an expanding field of protein modification in ambient air.


Asunto(s)
Contaminantes Atmosféricos , Ozono , Albúmina Sérica Bovina , Contaminantes Atmosféricos/análisis , Nitratos/química , Dióxido de Nitrógeno/química , Óxidos de Nitrógeno/química , Ozono/química , Material Particulado/análisis , Albúmina Sérica Bovina/química
13.
Indoor Air ; 32(1): e12971, 2022 01.
Artículo en Inglés | MEDLINE | ID: mdl-34866244

RESUMEN

To better understand the impact of molds on indoor air quality, we studied the photochemistry of microbial films made by Aspergillus niger species, a common indoor mold. Specifically, we investigated their implication in the conversion of adsorbed nitrate anions into gaseous nitrous acid (HONO) and nitrogen oxides (NOx ), as well as the related VOC emissions under different indoor conditions, using a high-resolution proton transfer reaction-time of flight-mass spectrometer (PTR-TOF-MS) and a long path absorption photometer (LOPAP). The different mold preparations were characterized by the means of direct injection into an Orbitrap high-resolution mass spectrometer with a heated electrospray ionization (ESI-Orbitrap-MS). The formation of a wide range of VOCs, having emission profiles sensitive to the types of films (either doped by potassium nitrate or not), cultivation time, UV-light irradiation, potassium nitrate concentration and relative humidity was observed. The formation of nitrous acid from these films was also determined and found to be dependent on light and relative humidity. Finally, the reaction paths for the NOx and HONO production are proposed. This work helps to better understand the implication of microbial surfaces as a new indoor source for HONO emission.


Asunto(s)
Contaminación del Aire Interior , Contaminación del Aire Interior/análisis , Dióxido de Nitrógeno/química , Óxidos de Nitrógeno , Ácido Nitroso/análisis
14.
J Phys Chem Lett ; 12(32): 7708-7716, 2021 Aug 19.
Artículo en Inglés | MEDLINE | ID: mdl-34355897

RESUMEN

NOx emission heavily affects our environment and human health. Photocatalytic denitrification (deNOx) attracted much attention because it is low-cost and nonpolluting, but undesired nitrite and nitrate were produced in reality, instead of harmless N2. Unveiling the active sites and the photocatalytic mechanism is very important to improve the process. Herein, we have employed a combinational scenario to investigate the reaction mechanism of NO2 and H2O on anatase TiO2(101). On the one hand, a polaron-corrected GGA functional (GGA + Lany-Zunger) was applied to improve the description of electronic states in photoassisted processes. On the other hand, a reaction phase diagram (RPD) was established to understand the (quasi) activity trend over both perfect and defective surfaces. It was found that a perfect surface is more active via the Eley-Rideal mechanism without NO2 adsorption, while the activity on defective surfaces is limited by the sluggish recombinative desorption. A photogenerated hole can weaken the OH* adsorption energies and circumvents the scaling relation of the dark reaction, eventually enhancing the deNOx activity significantly. The insights gained from our work indicate that tuning the reactivity by illumination-induced localized charge and diverse reaction pathways are two methods for improving adsorption, dissociation, and desorption processes to go beyond the conventional activity volcano plot limit of dark conditions.


Asunto(s)
Dióxido de Nitrógeno/química , Titanio/química , Adsorción , Catálisis/efectos de la radiación , Cinética , Modelos Químicos , Termodinámica , Titanio/efectos de la radiación , Rayos Ultravioleta , Agua/química
15.
Int J Mol Sci ; 22(13)2021 Jun 26.
Artículo en Inglés | MEDLINE | ID: mdl-34206928

RESUMEN

Brush-like α-Fe2O3-ZnO heterostructures were synthesized through a sputtering ZnO seed-assisted hydrothermal growth method. The resulting heterostructures consisted of α-Fe2O3 rod templates and ZnO branched crystals with an average diameter of approximately 12 nm and length of 25 nm. The gas-sensing results demonstrated that the α-Fe2O3-ZnO heterostructure-based sensor exhibited excellent sensitivity, selectivity, and stability toward low-concentration NO2 gas at an optimal temperature of 300 °C. The α-Fe2O3-ZnO sensor, in particular, demonstrated substantially higher sensitivity compared with pristine α-Fe2O3, along with faster response and recovery speeds under similar test conditions. An appropriate material synergic effect accounts for the considerable enhancement in the NO2 gas-sensing performance of the α-Fe2O3-ZnO heterostructures.


Asunto(s)
Compuestos Férricos/química , Nanoestructuras/química , Dióxido de Nitrógeno/análisis , Óxido de Zinc/química , Técnicas de Química Analítica/métodos , Dióxido de Nitrógeno/química , Sensibilidad y Especificidad
16.
Int J Mol Sci ; 22(14)2021 Jul 16.
Artículo en Inglés | MEDLINE | ID: mdl-34299235

RESUMEN

The allergenic and inflammatory potential of proteins can be enhanced by chemical modification upon exposure to atmospheric or physiological oxidants. The molecular mechanisms and kinetics of such modifications, however, have not yet been fully resolved. We investigated the oligomerization and nitration of the grass pollen allergen Phl p 5 by ozone (O3), nitrogen dioxide (NO2), and peroxynitrite (ONOO-). Within several hours of exposure to atmospherically relevant concentration levels of O3 and NO2, up to 50% of Phl p 5 were converted into protein oligomers, likely by formation of dityrosine cross-links. Assuming that tyrosine residues are the preferential site of nitration, up to 10% of the 12 tyrosine residues per protein monomer were nitrated. For the reaction with peroxynitrite, the largest oligomer mass fractions (up to 50%) were found for equimolar concentrations of peroxynitrite over tyrosine residues. With excess peroxynitrite, the nitration degrees increased up to 40% whereas the oligomer mass fractions decreased to 20%. Our results suggest that protein oligomerization and nitration are competing processes, which is consistent with a two-step mechanism involving a reactive oxygen intermediate (ROI), as observed for other proteins. The modified proteins can promote pro-inflammatory cellular signaling that may contribute to chronic inflammation and allergies in response to air pollution.


Asunto(s)
Phleum/metabolismo , Proteínas de Plantas/metabolismo , Rinitis Alérgica Estacional/metabolismo , Alérgenos/química , Cinética , Nitratos/metabolismo , Dióxido de Nitrógeno/química , Óxidos de Nitrógeno , Oxidantes , Ozono/química , Ácido Peroxinitroso/química , Proteínas de Plantas/análisis , Poaceae/metabolismo , Polen/metabolismo , Proteínas/química , Rinitis Alérgica Estacional/fisiopatología
17.
Int J Mol Sci ; 22(7)2021 Apr 04.
Artículo en Inglés | MEDLINE | ID: mdl-33916642

RESUMEN

The available tooth whitening products in the market contain high concentrations of hydrogen peroxide (H2O2) as an active ingredient. Therefore, in order to curb the high H2O2 concentration and instability of liquid H2O2, this study evaluated the efficacy and cytotoxicity of the bleaching gel composed of 10% calcium peroxide (CaO2) and visible-light-activating nitrogen-doped titanium dioxide (N-TiO2) with methyl cellulose as a thickener. Extracted bovine teeth were discolored using coffee and black tea stain solution and were divided into two groups (n = 6). Bleaching was performed thrice on each tooth specimen in both the groups, with one minute of visible light irradiation during each bleaching time. The CIELAB L*a*b* values were measured pre- and post-bleaching. The N-TiO2 calcinated at 350 °C demonstrated a shift towards the visible light region by narrowing the band gap energy from 3.23 eV to 2.85 eV. The brightness (ΔL) and color difference (ΔE) increased as bleaching progressed each time in both the groups. ANOVA results showed that the number of bleaching significantly affected ΔE (p < 0.05). The formulated bleaching gel exhibits good biocompatibility and non-toxicity upon exposure to 3T3 cells. Our findings showed that CaO2-based bleaching gel at neutral pH could be a stable, safe, and effective substitute for tooth whitening products currently available in the market.


Asunto(s)
Luz , Metilcelulosa , Dióxido de Nitrógeno , Peróxidos , Titanio , Blanqueamiento de Dientes , Células 3T3 , Animales , Bovinos , Metilcelulosa/química , Metilcelulosa/farmacología , Ratones , Dióxido de Nitrógeno/química , Dióxido de Nitrógeno/farmacología , Peróxidos/química , Peróxidos/farmacología , Titanio/química , Titanio/farmacología
18.
PLoS One ; 16(3): e0249236, 2021.
Artículo en Inglés | MEDLINE | ID: mdl-33765068

RESUMEN

Challenges arise in researching health effects associated with chemical mixtures. Several methods have recently been proposed for estimating the association between health outcomes and exposure to chemical mixtures, but a formal simulation study comparing broad-ranging methods is lacking. We select five recently developed methods and evaluate their performance in estimating the exposure-response function, identifying active mixture components, and identifying interactions in a simulation study. Bayesian kernel machine regression (BKMR) and nonparametric Bayes shrinkage (NPB) were top-performing methods in our simulation study. BKMR and NPB outperformed other contemporary methods and traditional linear models in estimating the exposure-response function and identifying active mixture components. BKMR and NPB produced similar results in a data analysis of the effects of multipollutant exposure on lung function in children with asthma.


Asunto(s)
Exposición a Riesgos Ambientales/análisis , Modelos Estadísticos , Contaminantes Atmosféricos/toxicidad , Asma/etiología , Asma/patología , Teorema de Bayes , Niño , Volumen Espiratorio Forzado/efectos de los fármacos , Humanos , Dióxido de Nitrógeno/química , Ozono/química , Material Particulado/química , Material Particulado/toxicidad , Plaguicidas/toxicidad
19.
Int J Mol Sci ; 22(4)2021 Feb 03.
Artículo en Inglés | MEDLINE | ID: mdl-33546504

RESUMEN

Since the discovery in 1922 of 2,2-diphenyl-1-(2,4,6-trinitrophenyl) hydrazyl stable free radical (DPPH·), the chemistry of such open-shell compounds has developed continuously, allowing for both theoretical and practical advances in the free radical chemistry area. This review presents the important, general and modern aspects of the chemistry of hydrazyl free radicals and the science behind it.


Asunto(s)
Radicales Libres/química , Modelos Químicos , Espectroscopía de Resonancia por Spin del Electrón , Halógenos/química , Estructura Molecular , Dióxido de Nitrógeno/química
20.
Curr Drug Targets ; 22(4): 379-398, 2021.
Artículo en Inglés | MEDLINE | ID: mdl-33371845

RESUMEN

Neglected tropical diseases (NTDs) are responsible for over 500,000 deaths annually and are characterized by multiple disabilities. Leishmaniasis and Chagas diseases are among the most severe NTDs, and are caused by the Leishmania sp and Trypanosoma cruzi, respectively. Glucantime, pentamidine, and miltefosine are commonly used to treat leishmaniasis, whereas nifurtimox, benznidazole are current treatments for Chagas disease. However, these treatments are associated with drug resistance and severe side effects. Hence, the development of synthetic products, especially those containing N02, F, or Cl, are known to improve biological activity. The present work summarizes the information on the antileishmanial and antitrypanosomal activity of nitro-, chloro-, and fluorosynthetic derivatives. Scientific publications referring to halogenated derivatives in relation to antileishmanial and antitrypanosomal activities were hand-searched in databases such as SciFinder, Wiley, Science Direct, PubMed, ACS, Springer, Scielo, and so on. According to the literature information, more than 90 compounds were predicted as lead molecules with reference to their IC50/EC50 values in in vitro studies. It is worth mentioning that only active compounds with known cytotoxic effects against mammalian cells were considered in the present study. The observed activity was attributed to the presence of nitro-, fluoro-, and chloro-groups in the compound backbone. All in all, nitro and halogenated derivatives are active antileishmanial and antitrypanosomal compounds and can serve as the baseline for the development of new drugs against leishmaniasis and Chagas disease. However, efforts in in vitro and in vivo toxicity studies of the active synthetic compounds is still needed. Pharmacokinetic studies and the mechanism of action of the promising compounds need to be explored. The use of new catalysts and chemical transformation can afford unexplored halogenated compounds with improved antileishmanial and antitrypanosomal activity.


Asunto(s)
Antiprotozoarios , Enfermedad de Chagas , Cloruros/química , Fluoruros/química , Leishmaniasis , Dióxido de Nitrógeno/química , Animales , Antiprotozoarios/química , Antiprotozoarios/farmacología , Enfermedad de Chagas/tratamiento farmacológico , Diseño de Fármacos , Humanos , Leishmaniasis/tratamiento farmacológico , Trypanosoma cruzi
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