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1.
J Hazard Mater ; 476: 135016, 2024 Sep 05.
Artigo em Inglês | MEDLINE | ID: mdl-38986407

RESUMO

Formaldehyde (FA) is a hazardous indoor air pollutant with carcinogenic propensity. Oxidation of FA in the dark at low temperature (DLT) is a promising strategy for its elimination from indoor air. In this light, binary manganese-cobalt oxide (0.1 to 5 mol L-1-MnCo2O4) is synthesized and modified in an alkaline medium (0.1-5 mol L-1 potassium hydroxide) for FA oxidation under room temperature (RT) conditions. Accordingly, 1-MnCo2O4 achieves 100 % FA conversion at RT (50 ppm and 7022 h-1 gas hourly space velocity (GHSV)). The catalytic activity of 1-MnCo2O4 is assessed further as a function of diverse variables (e.g., catalyst mass, relative humidity, FA concentration, molecular oxygen (O2) content, flow rate, and time on-stream). In situ diffuse reflectance infrared Fourier-transform spectroscopy confirms that FA molecules are adsorbed onto the active surface sites of 1-MnCo2O4 and oxidized into water (H2O) and carbon dioxide (CO2) through dioxymethylene (DOM) and formate (HCOO-) as the reaction intermediates. According to the density functional theory simulations, the higher catalytic activity of 1-MnCo2O4 can be attributed to the combined effects of its meritful surface properties (e.g., the firmer attachment of FA molecules, lower energy cost of FA adsorption, and lower desorption energy for CO2 and H2O). This work is the first report on the synthesis of alkali (KOH)-modified MnCo2O4 and its application toward the FA oxidative removal at RT in the dark. The results of this study are expected to provide valuable insights into the development of efficient and cost-effective non-noble metal catalysts against indoor FA at DLT.

2.
Nat Commun ; 15(1): 4883, 2024 Jun 07.
Artigo em Inglês | MEDLINE | ID: mdl-38849395

RESUMO

The human methyltransferase and transcriptional coactivator MLL4 and its paralog MLL3 are frequently mutated in cancer. MLL4 and MLL3 monomethylate histone H3K4 and contain a set of uncharacterized PHD fingers. Here, we report a novel function of the PHD2 and PHD3 (PHD2/3) fingers of MLL4 and MLL3 that bind to ASXL2, a component of the Polycomb repressive H2AK119 deubiquitinase (PR-DUB) complex. The structure of MLL4 PHD2/3 in complex with the MLL-binding helix (MBH) of ASXL2 and mutational analyses reveal the molecular mechanism which is conserved in homologous ASXL1 and ASXL3. The native interaction of the Trithorax MLL3/4 complexes with the PR-DUB complex in vivo depends solely on MBH of ASXL1/2, coupling the two histone modifying activities. ChIP-seq analysis in embryonic stem cells demonstrates that MBH of ASXL1/2 is required for the deubiquitinase BAP1 recruitment to MLL4-bound active enhancers. Our findings suggest an ASXL1/2-dependent functional link between the MLL3/4 and PR-DUB complexes.


Assuntos
Proteínas de Ligação a DNA , Histona-Lisina N-Metiltransferase , Ligação Proteica , Proteínas Repressoras , Proteínas Supressoras de Tumor , Ubiquitina Tiolesterase , Proteínas Supressoras de Tumor/metabolismo , Proteínas Supressoras de Tumor/genética , Humanos , Histona-Lisina N-Metiltransferase/metabolismo , Histona-Lisina N-Metiltransferase/genética , Ubiquitina Tiolesterase/metabolismo , Ubiquitina Tiolesterase/genética , Proteínas Repressoras/metabolismo , Proteínas Repressoras/genética , Animais , Proteínas de Ligação a DNA/metabolismo , Proteínas de Ligação a DNA/genética , Camundongos , Elementos Facilitadores Genéticos , Células HEK293 , Dedos de Zinco PHD , Histonas/metabolismo
3.
ACS Appl Mater Interfaces ; 16(26): 33669-33687, 2024 Jul 03.
Artigo em Inglês | MEDLINE | ID: mdl-38912904

RESUMO

To learn more about the behavior of amine (NH2)-functionalized metal-organic framework (MOF)-derived noble metal catalysts in the removal of aromatic volatile organic compounds in air, benzene oxidation at low temperatures has been investigated using 0.2-, 0.8-, and 1.5%-platinum (Pt)/Universitetet i Oslo (UiO)-66-NH2. The benzene conversion (XB) of x%-Pt/UiO-66-NH2-R under dry conditions (175 °C) was 23% (x = 0.2%) < 52% (x = 0.8%) < 100% (x = 1.5%): 'R' suffix denotes reduction pretreatment using a hydrogen (10 vol %) and nitrogen mixture at 300 °C for the generation of metallic Pt (Pt0) sites and simultaneous partial MOF decomposition into carbon- and nitrogen-loaded zirconium dioxide. The prominent role of reduction pretreatment was apparent in benzene oxidation as 1.5%-Pt/UiO-66-NH2 did not exhibit catalytic activity below 175 °C (dry condition). The promotional role of moisture in benzene oxidation by 1.5%-Pt/UiO-66-NH2-R was evident with a rise in the steady-state reaction rate (r) at 110 °C (21 kPa molecular oxygen (O2)) from 1.3 × 10-3 to 5.0 × 10-3 µmol g-1 s-1 as the water (H2O) partial pressure increased from 0 to 1.88 kPa. In contrast, the activity was lowered with increasing RH due to catalyst poisoning by excess moisture (r (110 °C) of 6.6 × 10-04 µmol g-1 s-1 at 2.83 kPa H2O (21 kPa O2)). Kinetic modeling suggests that XB proceeds through the Langmuir-Hinshelwood mechanism on the Pt/UiO-66-NH2-R surface (dissociative O2 chemisorption and the involvement of two oxygen species in benzene oxidation). According to the density functional theory simulation, the carbon and nitrogen impurities are to make the first XB step (i.e., hydrogen migration from the benzene molecule to the substrate) energetically favorable. The second hydrogen atom from the benzene molecule is also extracted effectively, while the oxygen derived from O2 facilitates further XB. The Pt0 sites dissociate the O2 and H2O molecules, while the product of the latter, i.e., free hydrogen and hydroxyl, makes the subsequent XB steps energetically favorable.

4.
Environ Res ; 255: 119186, 2024 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-38777297

RESUMO

The removal of formaldehyde (FA) is vital for indoor air quality management in light of its carcinogenic propensity and adverse environmental impact. A series of copper manganite spinel structures (e.g., CuMn2O4) are prepared using the sol-gel combustion method and treated with reduction or oxidation pretreatment at 300 °C condition. Accordingly, CuMn2O4-O ("O" suffix for oxidation pre-treatment in air) is identified as the best performer to achieve 100% conversion (XFA) of FA (50 ppm) at 90 °C; its performance, if assessed in terms of reaction kinetic rate (r) at XFA = 10%, is 5.02E-03 mmol g-1 h-1. The FA removal performance increases systematically with decreases in flow rate, FA concentration, and relative humidity (RH) or with increases in bed mass. The reaction pathways and intermediates of FA catalytic oxidation on CuMn2O4-A are studied with density functional theory simulations, temperature-programmed characterization experiments, and in-situ diffuse reflectance infrared Fourier transform spectroscopy. The synergistic combination of large quantities of adsorbed oxygen (OA) species and oxidized metal species (e.g., Cu2+) contribute to the enhanced catalytic performance of CuMn2O4-O to oxidize FA into CO2 with the reaction intermediates of H2CO2 (DOM), HCOO-, and CO. The present study is expected to provide valuable insights into the thermocatalytic oxidation of FA over spinel CuMn2O4 materials and their catalytic performances in relation to the key process variables.


Assuntos
Cobre , Formaldeído , Formaldeído/química , Cobre/química , Catálise , Poluentes Atmosféricos/química , Poluentes Atmosféricos/análise , Oxirredução , Temperatura , Temperatura Baixa , Óxido de Alumínio , Óxido de Magnésio
5.
Structure ; 32(6): 706-714.e3, 2024 Jun 06.
Artigo em Inglês | MEDLINE | ID: mdl-38579707

RESUMO

Human mixed lineage leukemia 4 (MLL4), also known as KMT2D, regulates cell type specific transcriptional programs through enhancer activation. Along with the catalytic methyltransferase domain, MLL4 contains seven less characterized plant homeodomain (PHD) fingers. Here, we report that the sixth PHD finger of MLL4 (MLL4PHD6) binds to the hydrophobic motif of ten-eleven translocation 3 (TET3), a dioxygenase that converts methylated cytosine into oxidized derivatives. The solution NMR structure of the TET3-MLL4PHD6 complex and binding assays show that, like histone H4 tail, TET3 occupies the hydrophobic site of MLL4PHD6, and that this interaction is conserved in the seventh PHD finger of homologous MLL3 (MLL3PHD7). Analysis of genomic localization of endogenous MLL4 and ectopically expressed TET3 in mouse embryonic stem cells reveals a high degree overlap on active enhancers and suggests a potential functional relationship of MLL4 and TET3.


Assuntos
Proteínas de Ligação a DNA , Dioxigenases , Histona-Lisina N-Metiltransferase , Ligação Proteica , Humanos , Dioxigenases/metabolismo , Dioxigenases/química , Dioxigenases/genética , Animais , Camundongos , Proteínas de Ligação a DNA/metabolismo , Proteínas de Ligação a DNA/química , Proteínas de Ligação a DNA/genética , Histona-Lisina N-Metiltransferase/metabolismo , Histona-Lisina N-Metiltransferase/química , Histona-Lisina N-Metiltransferase/genética , Sítios de Ligação , Proteínas Proto-Oncogênicas/metabolismo , Proteínas Proto-Oncogênicas/química , Proteínas Proto-Oncogênicas/genética , Modelos Moleculares , Proteína de Leucina Linfoide-Mieloide/metabolismo , Proteína de Leucina Linfoide-Mieloide/química , Proteína de Leucina Linfoide-Mieloide/genética
6.
J Colloid Interface Sci ; 665: 1029-1042, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-38579386

RESUMO

Formaldehyde (FA), a carcinogenic oxygenated volatile organic compound, is present ubiquitously in indoor air. As such, it is generally regarded as a critical target for air quality management. The oxidative removal of FA under dark and room-temperature (RT) conditions is of practical significance. A series of ternary nickel-cobalt-manganese oxide-supported platinum catalysts (Pt/NiCoMnO4) have been synthesized for FA oxidative removal at RT in the dark. Their RT conversion values for 50 ppm FA (XFA) at 5,964 h-1 gas hourly space velocity (GHSV) decrease in the following order: 1 wt% Pt/NiCoMnO4 (100 %) > 0.5 wt% Pt/NiCoMnO4 (25 %) > 0.05 wt% Pt/NiCoMnO4 (14 %) > NiCoMnO4 (6 %). The catalytic performance of 1 wt% Pt/NiCoMnO4 has been examined further under the control of various process variables (e.g., catalyst mass, flow rate, relative humidity, FA concentration, time on stream, and molecular oxygen content). The catalytic oxidation of FA at low temperatures (e.g., RT and 60 °C) is accounted for by Langmuir-Hinshelwood mechanism (single-site competitive-adsorption), while Mars van Krevelen kinetics is prevalent at higher temperatures. In situ diffuse-reflectance infrared Fourier-transform spectroscopy reveals that FA oxidation proceeds through a series of reaction intermediates such as DOM, HCOO-, and CO32-. Based on the density functional theory simulations, the unique electronic structures of the nearest surface atoms (platinum and nickel) are suggested to be responsible for the superior catalytic activity of Pt/NiCoMnO4.

7.
J Hazard Mater ; 470: 134089, 2024 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-38579580

RESUMO

Photocatalytic removal of gaseous hydrogen sulfide (H2S) has been studied through the control of key process variables using a prototype air purifier (AP) fabricated with titanium dioxide (TiO2)-supported mercury. The performance of Hg/TiO2 systems, prepared with different Hg mass proportions over TiO2 (such as 0.1%, 1%, 2%, and 5%), is measured against 5 ppm H2S at 160 L min-1 under UV irradiation. Accordingly, their removal efficiency (RE) values after 360 s are 40.3%, 74.8%, 99.3%, and 99.9%, respectively (relative to 33.5% of AP (TiO2)). An AP with a 2% Hg/TiO2 unit achieves a clean air delivery rate of 32 L min-1 with kinetic reaction rate (r (at 10% RE)) of 0.774 mmol h-1 g-1, quantum yield of 2.19E-02 molecules photon-1, and space-time yield of 1.46E-04 molecules photon-1 mg-1. The superior photocatalytic performance of Hg/TiO2 is supported by superoxide anion and hydroxyl radicals formed in dry air and humid nitrogen (N2) environments, respectively. A density functional theory simulation suggests that the presence of oxygen vacancies should promote the disparities in the electronic structure to subsequently affect the reaction pathways and energetics. The presence of moisture enhances the robust formation of a mercury-OH bond to favorably yield ß-mercury sulfide from H2S.

8.
Chemosphere ; 350: 141114, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-38184080

RESUMO

MXenes are an emerging class of two-dimensional (2D) inorganic materials with great potential for versatile applications such as adsorption and catalysis. Here, we describe the synthesis of a platinized titanium carbide MXene (Pt@Ti3C2) catalyst with varying amounts of platinum (0.1%-2 wt.%) for the low-temperature oxidation of benzene, an aromatic volatile organic compound often found in industrial flue gas. A 1% formulation of Pt@Ti3C2-R allowed near-complete (97%) oxidation of benzene to CO2 at 225 °C with a steady-state reaction rate (r) of 0.119 mol g-1·h-1. This low-temperature catalytic oxidation reaction was promoted by an increase in the lattice oxygen (O*)/Pt2+ species (active sites) of 1%Pt@Ti3C2-R from 45.3/34.6% to 71.0/61.1% through pre-thermal reduction under H2 flow, as revealed by X-ray photoelectron spectroscopy, temperature-programmed reduction, and in situ diffuse reflectance infrared Fourier transform spectroscopy analyses. The cataltyic activity of 1% Pt@Ti3C2-R against benzene was assessed under the control of the key process variables (e.g., catalyst mass, flow rate, benzene concentration, relative humidity, and time-on-stream) to help optimize the oxidation reaction process. The results provide new insights into the use of platinum-based 2D MXene catalysts for low-temperature oxidative removal of benzene from the air.


Assuntos
Benzeno , Nitritos , Platina , Elementos de Transição , Temperatura , Benzeno/química , Platina/química , Oxirredução , Titânio/química , Catálise , Estresse Oxidativo
9.
Sci Total Environ ; 915: 169612, 2024 Mar 10.
Artigo em Inglês | MEDLINE | ID: mdl-38154644

RESUMO

The thermocatalytic oxidative potential of various supported noble metal catalysts (SNMCs) is well-known for hazardous volatile organic compounds (VOCs), e.g., formaldehyde (FA) and toluene. However, little is known about SNMC performance against ambient VOC pollution with low concentration (subppm levels) relative to industrial effuluents with high concentrations (several hundred ppm). Here, the thermocatalytic oxidation performance of a titanium dioxide (TiO2)-supported platinum catalyst (Pt/TiO2) has been evaluated for a low-concentration binary mixture of FA and toluene at low temperatures and in the dark. A sample of TiO2 containing 1 wt% Pt with thermal reduction pre-treatment under hydrogen achieved 100 % conversion of FA (500 ppb) and toluene (100 ppb) at 130 °C and a gas hourly velocity of 59,701 h-1. Its catalytic activity was lowered by either a decrease in catalyst mass or an increase in VOC concentration, relative humidity, or flow rate. In situ diffuse reflectance infrared Fourier transform spectroscopy, density functional theory simulations, and molecular oxygen (O2) temperature-programmed desorption experiments were used to identify possible VOC oxidation pathways, reaction mechanisms, and associated surface phenomena. The present work is expected to offer insights into the utility of metal oxide-supported Pt catalysts for the low-temperature oxidative removal of gaseous VOCs in the dark, primarily for indoor air quality management.

10.
Sci Total Environ ; 904: 166882, 2023 Dec 15.
Artigo em Inglês | MEDLINE | ID: mdl-37678523

RESUMO

Furfural (FF: aldehyde derivable from lignocellulosic biomass) has been widely recognized as a versatile building block for eco-friendly and sustainable applications to reduce industrial reliance on fossil-fuel carbon sources. Hydrogenation of FF, in particular, is recognized as one of the most effective routes for producing various value-added chemicals (e.g., furfuryl alcohol and 2-methylfuran). The gas-phase FF hydrogenation reaction offers economic and environmental advantages over its liquid-phase counterpart in conversion efficiency, product selectivity, and kinetics. The operation of the former does not require high hydrogen pressures or hazardous solvents while not generating undesirable by-products (due to reduced selectivity toward the ring-opening reaction). In this context, the utility of noble and non-noble metal catalyst systems has been recognized for their potential to induce effective FF hydrogenation in the gas phase. The present review addresses current understandings and recent developments in research on gas-phase FF hydrogenation and the factors governing the performance of metal-based catalysts (e.g., materials and surface chemistry; conversion efficiency; product selectivity; and the mechanisms, pathways, and kinetics of the associated reactions). Current shortcomings and research avenues are also discussed to help establish a roadmap for future development of the gas-phase FF hydrogenation technology and associated disciplines. Overall, the present review is expected to offer much-needed insights into the scalability of metal-based catalytic systems for efficient FF hydrogenation in the gas phase.

11.
Elife ; 122023 08 29.
Artigo em Inglês | MEDLINE | ID: mdl-37642294

RESUMO

Mycobacterium tuberculosis (Mtb) is evolutionarily equipped to resist exogenous reactive oxygen species (ROS) but shows vulnerability to an increase in endogenous ROS (eROS). Since eROS is an unavoidable consequence of aerobic metabolism, understanding how Mtb manages eROS levels is essential yet needs to be characterized. By combining the Mrx1-roGFP2 redox biosensor with transposon mutagenesis, we identified 368 genes (redoxosome) responsible for maintaining homeostatic levels of eROS in Mtb. Integrating redoxosome with a global network of transcriptional regulators revealed a hypothetical protein (Rv0158) as a critical node managing eROS in Mtb. Disruption of rv0158 (rv0158 KO) impaired growth, redox balance, respiration, and metabolism of Mtb on glucose but not on fatty acids. Importantly, rv0158 KO exhibited enhanced growth on propionate, and the Rv0158 protein directly binds to methylmalonyl-CoA, a key intermediate in propionate catabolism. Metabolite profiling, ChIP-Seq, and gene-expression analyses indicate that Rv0158 manages metabolic neutralization of propionate toxicity by regulating the methylcitrate cycle. Disruption of rv0158 enhanced the sensitivity of Mtb to oxidative stress, nitric oxide, and anti-TB drugs. Lastly, rv0158 KO showed poor survival in macrophages and persistence defect in mice. Our results suggest that Rv0158 is a metabolic integrator for carbon metabolism and redox balance in Mtb.


Assuntos
Besouros , Mycobacterium tuberculosis , Animais , Camundongos , Mycobacterium tuberculosis/genética , Propionatos , Espécies Reativas de Oxigênio , Homeostase , Oxirredução , Mutagênese
12.
Environ Res ; 216(Pt 2): 114534, 2023 01 01.
Artigo em Inglês | MEDLINE | ID: mdl-36252831

RESUMO

In this work, zinc oxide coupled cadmium tungstate (ZnO-CT) was prepared as a nano-photocatalyst through a green synthesis route using lemon leaf extract and characterized based on diverse microscopic and spectroscopic techniques. To explore the applicabilties of the prepared nanocomposite (NC), its photocatalytic activity has been investigated against Congo red (CR) dye under natural solar light irradiation conditions. ZnO- CT nano-photocatalyst showcases 97% photocatalytic degradation of the CR after 90 min of natural solar light irradiation with quantum yield of 1.16 × 10-8 molecules photon-1. The ZnO-CT NC has shown the enhanced photocatalytic degradation performance against CR when compared to its pristine forms (e.g., ZnO (70%) or CT (44%)). According to the free radical trapping and quenching experiments, the photocatalytic activity of ZnO-CT NC appears to be driven efficiently by superoxide and hydroxyl radicals. The photocatalytic degradation kinetics for CR dye was also studied using the pseudo-first-order, diffusional, and Singh models. The high photocatalytic activity of ZnO-CT NC can be accounted for by the presence of electron-withdrawing functional groups like acids (-COOH) and aldehydes (-CHO) on its surface which helped maintain the prolonged recombination of charge carriers and enhanced stability of ZnO-CT (with moderately low leaching rate of cadmium ions (∼2-5%)).


Assuntos
Nanocompostos , Óxido de Zinco , Óxido de Zinco/química , Cádmio , Catálise , Nanocompostos/química , Corantes/química , Vermelho Congo/química
13.
Adv Colloid Interface Sci ; 305: 102696, 2022 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-35640317

RESUMO

Rapid industrial growth has been accompanied by the pollution of hazardous volatile organic pollutants (VOCs) in air. Among various options available for the treatment of VOCs, the use of metal oxide composites as photocatalysts has been adopted preferably due to their potential to induce the synergistic interactions between the metal nanoparticles (NPs) and metal oxides (especially titanium dioxide (TiO2)). In this context, an in-depth review is offered to describe the fundamental mechanism of metal oxide-based photocatalysis for the oxidation of gaseous benzene as a model VOC. The discussion has been extended further to evaluate their performances in terms of key performance metrics (e.g., quantum yield (QY), space-time yield (STY), and figure of merit (FOM)). The TiO2-based metallic bi-component photocatalysts (e.g., Sr2CeO4/TiO2) generally exhibited better photodegradation efficiency with enhanced light absorption capability than monometallic-TiO2 (e.g., Pd-TiO2) composites or other modified photocatalysts (e.g., metal-organic framework (MOF)-based composites). Finally, we address the current challenges and future perspectives in this highly challenging research field.

14.
J Hazard Mater ; 434: 128857, 2022 07 15.
Artigo em Inglês | MEDLINE | ID: mdl-35429758

RESUMO

Under dark/low temperature (DLT) conditions, the oxidative removal of gaseous formaldehyde (FA) was studied using eggshell waste supported silver (Ag)-manganese dioxide (MnO2) bimetallic catalysts. To assess the synergistic effects between the two different metals, 0.03%-Ag-(0.5-5%)-MnO2/Eggshell catalysts were prepared and employed for DLT-oxidation of FA. The steady-state FA oxidation reaction rate (mmol g-1 h-1), when measured using 100 ppm FA at 80 °C (gas hourly space velocity (GHSV) of 5308 h-1), varied as follows: Ag-1.5%-MnO2/Eggshell-R (9.4) > Ag-3%-MnO2/Eggshell-R (8.1) > Ag-1.5%-MnO2/Eggshell (7.5) > Ag-5%-MnO2/Eggshell-R (7.2) > Ag-1.5%-MnO2/CaCO3-R (6.8) > MnO2-R (6) > Ag-0.5%-MnO2/Eggshell-R (3.2) > Ag/Eggshell-R (2.6). (Here, 'R' denotes hydrogen-based thermochemical reduction pretreatment.) The temperature required for 90% FA conversion (T90) at the same GHSV exhibited a contrary ordering: Ag/Eggshell-R (175 °C) > Ag-0.5%-MnO2/Eggshell-R (123 °C) > Ag-5%-MnO2/Eggshell-R (113 °C) > MnO2-R (99 °C) > Ag-1.5%-MnO2/Eggshell (96 °C) > Ag-3%-MnO2/Eggshell-R (93 °C) > Ag-1.5%-MnO2/Eggshell-R (77 °C). The eggshell catalyst outperformed the ones made of commercial calcium carbonate due to the presence of defects in the former. The MnO2 co-catalyst enhances the catalytic activities through the capture and activation of atmospheric oxygen (O2) with rapid catalytic regeneration. Also, MnO2 favorably captures the hydrogen of the adsorbed FA molecules to make the oxidation pathway thermodynamically more favorable.


Assuntos
Compostos de Manganês , Óxidos , Animais , Catálise , Casca de Ovo , Formaldeído , Gases , Hidrogênio , Compostos de Manganês/química , Estresse Oxidativo , Óxidos/química , Oxigênio/química , Prata/química , Temperatura
15.
Sci Total Environ ; 822: 153605, 2022 May 20.
Artigo em Inglês | MEDLINE | ID: mdl-35114233

RESUMO

The photocatalytic destruction (PCD) of volatile organic compounds (VOC) into environmentally benign compounds is one of the most ideal routes for the management of indoor air quality. It is nevertheless not easy to achieve the mineralization of aromatic VOC through PCD technology because of their recalcitrant structures (i.e., conjugated π benzene ring). In this research, the PCD potential against three model aromatic hydrocarbons (i.e., benzene (B), toluene (T), and m-xylene (X): namely, BTX) has been explored using a titanium dioxide (TiO2) supported platinum (Pt) catalyst after the high-temperature hydrogen (H2)-based reduction (R) pre-treatment (i.e., Pt/TiO2-R). The effects of the key process variables (e.g., relative humidity (RH), oxygen (O2) content, flow rate, VOC concentration, and the co-presence of VOC) on the PCD efficiency and related mechanisms were also assessed in detail. The PCD efficiency is seen to increase with the rise in the increasing number of methyl groups on the benzene ring (in the order of benzene (46.5%), toluene (68.2%), and m-xylene (95.9%)), as the adsorption and activation of the VOC molecule on the photocatalyst surface are promoted by the increased distribution of electrons on the benzene ring. The BTX were oxidated subsequently by the photogenerated reactive oxygen species (ROS), i.e., the hydroxyl radicals (•OH) and superoxide anion radicals (•O2-). The overall results of this study are expected to help expand the applicability of photocatalysis towards air quality management by offering detailed insights into the factors and processes governing the photocatalytic decomposition of aromatic VOCs.


Assuntos
Poluentes Atmosféricos , Compostos Orgânicos Voláteis , Poluentes Atmosféricos/análise , Benzeno , Catálise , Titânio/química , Tolueno , Compostos Orgânicos Voláteis/análise
16.
J Hazard Mater ; 424(Pt B): 127454, 2022 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-34655876

RESUMO

In this research, the adsorptive performance of a starch-magnesium/aluminum layered double hydroxide (S-Mg/Al LDH) composite was investigated for different organic dyes in single-component systems by conducting a series of batch mode experiments. S-Mg/Al LDH composite showed preferential adsorption of anionic dyes than cationic dyes. The marked impact of key process variables (e.g., contact time, adsorbent dosage, pH, and temperature) on its adsorption was investigated. Multiple isotherms, kinetics, and thermodynamic models were applied to describe adsorption behavior, diffusion, and uptake rates of the organic dyes over S-Mg/Al LDH composite. A better fitting of the non-linear Langmuir model reflects the predominance of monolayered adsorption of dye molecules on the composite surface. Partition coefficients (mg g-1 µM-1) for S-Mg/Al LDH were observed in the following descending order: Amaranth (665) > Tartrazine (186) > Sunset yellow (71) > Eosin yellow (65). Furthermore, comparative evaluation of the adsorption enthalpy, entropy, and Gibbs free energy values indicates that the adsorption process is spontaneous and exothermic. S-Mg/Al LDH composite maintained a stable adsorption/desorption recycling process over six consecutive cycles with the advantages of low cost, chemical/mechanical stability, and easy recovery. The results of this study are expected to expand the application of modified LDHs toward wastewater treatment.

17.
Indian J Otolaryngol Head Neck Surg ; 74(Suppl 3): 4706-4712, 2022 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-36742912

RESUMO

In order to diagnose chronic rhinosinusitis (CRS), diagnostic nasal endoscopy (DNE) and computed tomography (CT) scan both are important investigations. But both have their pros and cons, some findings are seen better in DNE and others in CT. Our study aims to correlate DNE and CT findings. 50 patients with CRS were included in this observational prospective study done at tertiary care hospital. Preoperative each patient underwent DNE and got CT scan followed by scoring using Lund Kennedy and Lund Mackay grading respectively. Functional Endoscopic Sinus Surgery (FESS) was performed and intraoperative findings were correlated with CT scan for each of them. The sensitivity of endoscopy was 93.18% and the specificity was 83.33%. Positive predictive value of DNE was 97.62% and negative predictive value was 62.50%. Most of the endoscopy positive patients of CRS were CT positive. Also, the sensitivity of CT PNS was highest for all groups of sinus disease while specificity was high for posterior group of sinuses (81.82%) and frontal sinus (89.19%). Both DNE and CT scan should be used for planning the management of CRS. DNE tells better about middle meatal secretions, condition of mucosa, polyps. But in situations where due to anatomical variation DNE is difficult, CT scan helps us. CT identifies the extent of disease, the anatomical variants and vital relations of PNS. Overdiagnosis through CT is checked by DNE.

18.
Environ Pollut ; 271: 116401, 2021 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-33422746

RESUMO

In this work, ZnO-CdWO4 nanoparticles have been synthesized by the ecofriendly green method with lemon leaf extract to favorably anchor functional groups on their surface. The prepared ZnO-CdWO4 nanoparticles are used as adsorbent to treat Congo red (CR) dye after characterization through FT-IR, UV-Vis, TEM, SEM-EDX, and HRTEM techniques. The equilibrium partition coefficient and adsorption capacity values for CR by ZnO-CdWO4 are estimated as 21.4 mg g-1 µM-1 and 5 mg g-1, respectively (at an initial dye concentration of 10 mg L-1). The adsorption process is found as exothermic and spontaneous, as determined by the ΔG°, ΔS°, and ΔH° values. The Boyd plot has been used as a confirmatory tool to fit the adsorption kinetics data along with intraparticle diffusion and pseudo-second-order models. Based on this research, ZnO-CdWO4 nanoparticles are validated as an effective adsorbent for CR dye in aqueous solutions.


Assuntos
Nanopartículas , Poluentes Químicos da Água , Óxido de Zinco , Adsorção , Corantes , Concentração de Íons de Hidrogênio , Cinética , Espectroscopia de Infravermelho com Transformada de Fourier , Poluentes Químicos da Água/análise
19.
J Hazard Mater ; 401: 123379, 2021 01 05.
Artigo em Inglês | MEDLINE | ID: mdl-33113714

RESUMO

There is a growing demand to protect food products against the hazard of microbes and their toxins. To satisfy such goals, it is important to develop highly sensitive, reliable, sophisticated, rapid, and cost-effective sensing techniques such as electrochemical sensors/biosensors. Although diverse forms of nanomaterials (NMs)-based electrochemical sensing methods have been introduced in markets, the reliability of commercial products is yet insufficient to meet the practical goal. In this review, we focused on: 1) sources of pathogenic microbes and their toxins; 2) possible routes of their entrainment in food, and 3) current development of NM-based biosensors to realize real-time detection of the target analytes. At last, future prospects and challenges in this research field are discussed.


Assuntos
Técnicas Biossensoriais , Nanoestruturas , Bactérias , Técnicas Eletroquímicas , Reprodutibilidade dos Testes
20.
Biochem J ; 477(20): 4001-4019, 2020 10 30.
Artigo em Inglês | MEDLINE | ID: mdl-33000860

RESUMO

The toxin-antitoxin (TA) systems are small operon systems that are involved in important physiological processes in bacteria such as stress response and persister cell formation. Escherichia coli HigBA complex belongs to the type II TA systems and consists of a protein toxin called HigB and a protein antitoxin called HigA. The toxin HigB is a ribosome-dependent endoribonuclease that cleaves the translating mRNAs at the ribosome A site. The antitoxin HigA directly binds the toxin HigB, rendering the HigBA complex catalytically inactive. The existing biochemical and structural studies had revealed that the HigBA complex forms a heterotetrameric assembly via dimerization of HigA antitoxin. Here, we report a high-resolution crystal structure of E. coli HigBA complex that revealed a well-ordered DNA binding domain in HigA antitoxin. Using SEC-MALS and ITC methods, we have determined the stoichiometry of complex formation between HigBA and a 33 bp DNA and report that HigBA complex as well as HigA homodimer bind to the palindromic DNA sequence with nano molar affinity. Using E. coli growth assays, we have probed the roles of key, putative active site residues in HigB. Spectroscopic methods (CD and NMR) and molecular dynamics simulations study revealed intrinsic dynamic in antitoxin in HigBA complex, which may explain the large conformational changes in HigA homodimer in free and HigBA complexes observed previously. We also report a truncated, heterodimeric form of HigBA complex that revealed possible cleavage sites in HigBA complex, which can have implications for its cellular functions.


Assuntos
Antitoxinas/química , Proteínas de Escherichia coli/química , Escherichia coli/metabolismo , Antitoxinas/genética , Antitoxinas/metabolismo , Dicroísmo Circular , Cristalografia por Raios X , Proteínas de Ligação a DNA/química , Proteínas de Ligação a DNA/genética , Proteínas de Ligação a DNA/metabolismo , Escherichia coli/química , Proteínas de Escherichia coli/genética , Proteínas de Escherichia coli/metabolismo , Espectroscopia de Ressonância Magnética , Modelos Moleculares , Simulação de Dinâmica Molecular , Óperon/genética , Regiões Promotoras Genéticas , Ligação Proteica , Domínios Proteicos/genética , Multimerização Proteica , Proteínas Recombinantes , Regulação para Cima
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