Your browser doesn't support javascript.
Mostrar: 20 | 50 | 100
Resultados 1 - 20 de 20.055
Filtrar
1.
Phys Chem Chem Phys ; 22(9): 5057-5069, 2020 Mar 07.
Artigo em Inglês | MEDLINE | ID: mdl-32073000

RESUMO

Graph theory-based reaction pathway searches (ACE-Reaction program) and density functional theory calculations were performed to shed light on the mechanisms for the production of [an + H]+, xn+, yn+, zn+, and [yn + 2H]+ fragments formed in free radical-initiated peptide sequencing (FRIPS) mass spectrometry measurements of a small model system of glycine-glycine-arginine (GGR). In particular, the graph theory-based searches, which are rarely applied to gas-phase reaction studies, allowed us to investigate reaction mechanisms in an exhaustive manner without resorting to chemical intuition. As expected, radical-driven reaction pathways were favorable over charge-driven reaction pathways in terms of kinetics and thermodynamics. Charge- and radical-driven pathways for the formation of [yn + 2H]+ fragments were carefully compared, and it was revealed that the [yn + 2H]+ fragments observed in our FRIPS MS spectra originated from the radical-driven pathway, which is in contrast to the general expectation. The acquired understanding of the FRIPS fragmentation mechanism is expected to aid in the interpretation of FRIPS MS spectra. It should be emphasized that graph theory-based searches are powerful and effective methods for studying reaction mechanisms, including gas-phase reactions in mass spectrometry.


Assuntos
Teoria da Densidade Funcional , Radicais Livres/química , Oligopeptídeos/química , Análise de Sequência de Proteína/métodos , Sequência de Aminoácidos , Óxidos N-Cíclicos/química , Gases/química , Cinética , Espectrometria de Massas , Simulação de Dinâmica Molecular , Termodinâmica
2.
J Phys Chem Lett ; 11(5): 1636-1643, 2020 Mar 05.
Artigo em Inglês | MEDLINE | ID: mdl-32013435

RESUMO

High efficiency of light harvesting in photosynthetic pigment-protein complexes is governed by evolutionary-perfected protein-assisted tuning of individual pigment properties and interpigment interactions. Due to the large number of spectrally overlapping pigments in a typical photosynthetic complex, experimental methods often fail to unambiguously identify individual chromophore properties. Here, we report a first-principles-based modeling protocol capable of predicting properties of pigments in protein environment to a high precision. The technique was applied to successfully uncover electronic properties of the Fenna-Matthews-Olson (FMO) pigment-protein complex. Each of the three subunits of the FMO complex contains eight strongly coupled bacteriochlorophyll a (BChl a) pigments. The excitonic structure of FMO can be described by an electronic Hamiltonian containing excitation (site) energies of BChl a pigments and electronic couplings between them. Several such Hamiltonians have been developed in the past based on the information from various spectroscopic measurements of FMO; however, fine details of the excitonic structure and energy transfer in FMO, especially assignments of short-lived high-energy sites, remain elusive. Utilizing polarizable embedding quantum mechanics/molecular mechanics with the effective fragment potentials, we computed the electronic Hamiltonian of FMO that is in general agreement with previously reported empirical Hamiltonians and quantitatively reproduces experimental absorption and circular dichroism spectra of the FMO protein. The developed computational protocol is sufficiently simple and can be utilized for predictive modeling of other wild-type and mutated photosynthetic pigment-protein complexes.


Assuntos
Proteínas de Bactérias/metabolismo , Complexos de Proteínas Captadores de Luz/metabolismo , Simulação de Dinâmica Molecular , Teoria Quântica , Proteínas de Bactérias/química , Bacterioclorofila A/química , Bacterioclorofila A/metabolismo , Chlorobi/metabolismo , Dicroísmo Circular , Transferência de Energia , Gases/química , Complexos de Proteínas Captadores de Luz/química , Fotossíntese
3.
Environ Sci Technol ; 54(5): 3022-3031, 2020 03 03.
Artigo em Inglês | MEDLINE | ID: mdl-32045525

RESUMO

Sulfuric acid aerosol (SAA) can considerably deteriorate air visibility, which poses a threat to human health. Pretreatment methods that enlarge SAA sizes are crucial to enhanced emission control from industrials. This study provides an insight into SAA growth in terms of aerosol dynamics simulation and growth experiments under simulated flue gas conditions. Results show that SAA growth dynamics are dominated by coagulation and condensation mechanisms for small and large aerosols, respectively. The two mechanisms are coupled mainly in SAA sizes smaller than 0.05 µm. A large amount of time was allotted for the SAA distribution to grow into an approximately log-normal form without the use of any activation methods. Cooling gas and corona discharge can both enhance SAA growth. Cooling gas is in charge of condensation, whereas corona discharge mainly acts on coagulation. They exhibited 14.3% and 12.3% increases in mean diameter and 12.3% and 69.1% decreases in number concentration. In contrast, adding vapor led to a 1.58% decrease in mean diameter and a 9.4% increase in number concentration. Findings suggest that combining cooling gas and corona discharge to simultaneously promote coagulation and condensation and reduce SAA emission from humid flue gas is possible.


Assuntos
Poluentes Atmosféricos , Aerossóis , Gases , Humanos , Tamanho da Partícula , Ácidos Sulfúricos
4.
Bioresour Technol ; 304: 122960, 2020 May.
Artigo em Inglês | MEDLINE | ID: mdl-32062500

RESUMO

Unlike light torrefaction at 200 °C (B200), the mild (250 °C) and severe (300 °C) torrefaction pretreatments (B250 and B300) significantly increased the calorific value, reduced the oxygen content and improved the surface morphology for bamboo residues (BR). The main oxygen-removing carriers of BR during torrefaction were CO2 and carbonyl compounds. Their torrefaction delayed the start and burnout temperatures of the BR combustions, increased CO2 emission and decreased NH3 and NO emissions significantly. The torrefaction reduced their activation energy in zone II (200-350 °C) and led to a transition from a nucleation to a diffusion mechanism. All the combustions in zone III (350-500 °C) were best explained by a reaction order model whose order rose with the elevated torrefaction temperature. Overall, BR appeared to be more suitable for the torrefaction at 250-300 °C. Our results can provide practical insights into how to turn BR into efficient and clean bioenergy.


Assuntos
Florestas , Gases , Biomassa , Cinética , Temperatura Ambiente
5.
Bioresour Technol ; 304: 122735, 2020 May.
Artigo em Inglês | MEDLINE | ID: mdl-32086037

RESUMO

The catalytic activity of biochar for tar removal was evaluated in a bench-scale combined fixed bed reactor by comparison of gaseous tar catalytic cracking behaviors over land (Corn stalks, Cs), coastal (Reed, Re) and marine (Sargassum horneri, Sh) char catalyst. The experiments demonstrated that the tar yield after addition of the biochar was reduced significantly; the tar conversion efficiency reached to 94.6% for catalytic at 850 °C with 50 mm char bed length using Re char. And the yield and composition of gas also changed markedly. The percentage of H2 and CO in the product gas were obviously increased. Sh has a higher H2 content (49.3% of the total gas content), whereas, CO dominated in the gas products for Cs (45.4%) and Re (48.1%). The results from GC-MS analysis illustrated that the increase in temperature promoted the tar cracking and also promotes the polymerization of some tar components.


Assuntos
Eliminação de Resíduos , Alcatrões , Biomassa , Catálise , Gases
6.
Environ Monit Assess ; 192(3): 166, 2020 Feb 06.
Artigo em Inglês | MEDLINE | ID: mdl-32030517

RESUMO

Gas flaring is a major activity in oil exploration processes in Nigeria with concerns on its effects on the oil communities. This study investigated the contribution of flare gases to pollution burden of Anieze and Okwuibome communities. Water samples were displayed at 10-m, 50-m, and 100-m locations from gas-flaring stations, and control samples were taken in another location. After a month, the water samples were examined for heavy metals, polycyclic aromatic hydrocarbons, and physico-chemical parameters. Pb was found only in the 50-m location and above the WHO standard. Fe, Zn, and Cr were detected in the order 10 m > 50 m > 100 m > control whereas Cd was detected in the order 100 m > 50 m > 10 m > control. Fe, Zn, Cr, and Cd were linked to gas-flaring activities. The total PAHs were found in the order 10 m (1929.43 µg/L) > 100 m (1759.64 µg/L) > 50 m (620.27 µg/L) > control (389.37 µg/L). The signature ratio related the PAH sources to combination of petroleum and combustion sources. The sources of the PAHs were linked to the flare gas. The study implicates gas-flaring activities for the increased pollution burden in the communities and suggests policies that guide its reduction in petroleum explorations.


Assuntos
Água Subterrânea , Metais Pesados , Campos de Petróleo e Gás , Hidrocarbonetos Policíclicos Aromáticos , Poluentes Químicos da Água , Monitoramento Ambiental , Gases , Nigéria
7.
J Environ Radioact ; 214-215: 106183, 2020 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-32063288

RESUMO

Extensive vadose zone metals and organic contamination remains at many former industrial and defense manufacturing sites, and effective remedial solutions are needed to slow or prevent its migration to groundwater. In this study, the application of gaseous substrates to stimulate microbial respiratory reduction of comingled radioisotopes and nitrate under unsaturated conditions was examined for possible application at the Hanford Site, a former nuclear production facility in southeastern WA, USA. First, screening studies were performed to qualitatively measure the sediment respiratory response to 14 gaseous or volatile organic substrates at two moisture contents, 4% and 8%. Volatile substrates produced the strongest respiratory response, among them were butyrate, pentane, butyl acetate. Ethane and butane were the most effective gaseous substrates but only at 8% water content. Hanford sediment from two waste sites with distinctive chemistries were wetted to 7% moisture content, packed into columns, and treated with ethane or butane. After 4 weeks, columns were then leached to quantify retardation in the mobility of aqueous contaminant concentrations compared to no gas control columns. Treatment with both gases resulted in >80% removal of Cr from the aqueous phase. However, NO3 concentration and a waste sites exposure history to NO3 had a major effect on U and Tc reduction. Incomplete nitrate reduction outcompeted U and Tc in waste site sediments having limited prior exposure to NO3. Conversely, waste site sediments co-contaminated with NO3 were able to achieve highly reduced conditions resulting in complete denitrification of NO3, and delayed leaching of U and Tc. This implied effective reduction of both contaminants to less mobile species. This study demonstrates that unsaturated vadose sediments at Hanford waste sites have the capacity for a sustained respiratory response to gaseous substrate injection, which could potentially be deployed as part of an overall strategy to reduce the flux of long-lived radionuclides to groundwater at Hanford and other legacy waste sites.


Assuntos
Gases/química , Monitoramento de Radiação , Sedimentos Geológicos , Água Subterrânea , Radioisótopos , Poluentes Radioativos da Água
8.
Chemosphere ; 244: 125529, 2020 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-32050333

RESUMO

Fluidized bed bioreactors can overcome the limitations of packed bed bioreactors such as clogging, which has been observed in the industrial application for decades. The key to establish a gaseous fluidized bed bioreactor for treatment of volatile organic compounds is to achieve microbial growth on a light packing material. In this study, Two fungal species and two bacterial species were isolated to build a fungal fluidized-bed reactor (FFBR). A light packing material with wheat bran coated on expended polystyrene was used. The FFBR was operated for 65 days for gaseous ethanol removal and obtained elimination capacities of 500-1800 g∙m-3∙h-1 and removal efficiencies of 20-50%. The pressure drops was well controlled with values around 400 Pa∙m-1. Stress tolerant genera including Aureobasidium, Stenotrophomonas and Brevundimonas were dominant. Meyerozyma, whose species were present in an initial inoculated isolate, was detected among the dominant species with 28.70% relative abundance; they were reported to degrade complicated compounds under similarly stressful environments.


Assuntos
Reatores Biológicos/microbiologia , Etanol/metabolismo , Fungos , Gases
9.
Bioresour Technol ; 301: 122780, 2020 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-31978702

RESUMO

In this study, horticultural waste (HW) and sewage sludge (SS) with different mass ratios were co-gasified with steam at different temperatures to investigate the product distribution, gas synergistic interaction, and optimal design for gas products from co-gasification process. Results showed that with the increase of SS ratio in blends, the H2 content was increased and the syngas yield was decreased. The synergistic interaction was more significant at higher temperature which promoted the H2 production probably due to the reduction and steam oxidation of Fe species in SS during co-gasification process. The optimized highest effective gas content (82.92 vol%) was achieved with the highest HHV (11.40 MJ/m3) at the conditions of SS ratio = 0.80 and temperature of 900 °C. It indicates that steam co-gasification of HW and SS is a promising technology to produce desired syngas towards a clean and efficient waste management process.


Assuntos
Vapor , Gerenciamento de Resíduos , Gases , Esgotos , Temperatura Ambiente
10.
Phys Chem Chem Phys ; 22(9): 4896-4904, 2020 Mar 04.
Artigo em Inglês | MEDLINE | ID: mdl-31930249

RESUMO

Ibuprofen is a well-established non-steroidal anti-inflammatory drug, inhibiting the prostaglandin-endoperoxide synthase. One of the key features defining the ibuprofen structure is the doubly intermolecular O-HO[double bond, length as m-dash]C hydrogen bond in cyclic dimers as know from carboxylic acids and confirmed by X-ray analysis. Until now, there was neither information about the vaporization enthalpy of ibuprofen nor about how this thermal property is determined by the subtle balance between different types of intermolecular interaction. In this study we derive the vaporization enthalpy of ibuprofen from thermochemical experiments to be . We dissected the hydrogen bond energy, EHB = 45.0 kJ mol-1, exclusively from measured vaporization enthalpies of related aliphatic carboxylic acids, their homomorph methyl esters and alkyl acetates, respectively. This contribution from hydrogen bonding could be confirmed almost quantitatively from quantum chemical calculations of ibuprofen clusters, which also suggest dispersion interaction of similar order (Edisp = 47 kJ mol-1). Following the full analysis of the gas-vapor transition enthalpy, we studied the changing structural components from the solid to the liquid phase of ibuprofen by means of Attenuated Total Reflection Infrared (ATR-IR) spectroscopy. The cyclic dimers as observed in the X-ray patterns are essentially preserved in the liquid state just above the melting point. However, with increasing temperature the doubly hydrogen-bonded cyclic dimers are replaced by singly hydrogen-bonded linear dimers in the liquid ibuprofen. The transfer enthalpy from the temperature-dependent equilibria of both dimers as obtained from the IR intensity ratios of the vibrational bands quantifies for the first time the energy of the released, single hydrogen bond to be EHB = 21.0 kJ mol-1. Overall, we show that a combination of thermodynamics, infrared spectroscopy and quantum chemistry provides quantification and detailed understanding of structure and molecular interaction in ibuprofen and related compounds.


Assuntos
Gases/química , Ibuprofeno/química , Teoria da Densidade Funcional , Dimerização , Ligações de Hidrogênio , Espectrofotometria Infravermelho , Termodinâmica
11.
J Phys Chem Lett ; 11(4): 1215-1221, 2020 Feb 20.
Artigo em Inglês | MEDLINE | ID: mdl-31978303

RESUMO

Site-selective dissociation induced by core photoexcitation of biomolecules is of key importance for the understanding of radiation damage processes and dynamics and for its promising use as "chemical scissors" in various applications. However, identifying products of site-selective dissociation in large molecules is challenging at the carbon, nitrogen, and oxygen edges because of the high recurrence of these atoms and related chemical groups. In this paper, we present the observation of site-selective dissociation at the sulfur L-edge in the gas-phase peptide methionine enkephalin, which contains only a single sulfur atom. Near-edge X-ray absorption mass spectrometry has revealed that the resonant S 2p → σ*C-S excitation of the sulfur contained in the methionine side chain leads to site-selective dissociation, which is not the case after core ionization above the sulfur L-edge. The prospects of such results for the study of charge dynamics in biomolecular systems are discussed.


Assuntos
Gases/química , Peptídeos/química , Enxofre/química , Espectroscopia por Absorção de Raios X , Encefalinas/química , Metionina/química , Prótons , Teoria Quântica
12.
Food Chem ; 313: 126062, 2020 May 30.
Artigo em Inglês | MEDLINE | ID: mdl-31931422

RESUMO

In sparkling wine, foam characteristics are one of the major attributes. The foam quality depends on wine components. Bentonite is added to the base wine to facilitate the riddling process, but causes a loss of foamability. Acacia gum can be used as additive in wine. We have studied if the addition of Acacia senegal gum (AsenG), Acacia seyal gum (AseyG) and different AsenG fractions could improve the foamability of different base wines treated with bentonite. The foamability differs depending on the gum or the gum fraction treatment but also on the wine, being these differences linked to some aspects of their respective compositions and molecular parameters. AsenG and AseyG increase the foamability (by Mosalux - sparging procedure), respectively, in five and seven out of eight base wines treated with bentonite. Therefore, AsenG and AseyG are potential treatments increasing the foamability of these wines.


Assuntos
Goma Arábica/química , Vinho/análise , Bentonita/química , Cromatografia Líquida de Alta Pressão , Gases/química
13.
Sci Total Environ ; 714: 136819, 2020 Apr 20.
Artigo em Inglês | MEDLINE | ID: mdl-31986393

RESUMO

The problems of determining the protective properties of barrier materials used for the production of body surface protection products of an isolative type are very actual. These garments are expected to have long-term resistance against permeation of toxic substances. The paper deals with the study of the effect of organic solvent vapours on the changes in protective properties of selected anti-gas protective garments commonly used by the North Atlantic Treaty Organization armed forces. Permeation measurements of selected gases with integral permeameter were performed to verify their barrier properties, surface changes after exposure to selected solvents by using a 3D optical profilometer, permeation measurements for vapours of these solvents with differential permeameter, and experimental simulating the possible influence of barrier properties of garments within permeation of air. It has been shown that in the case of gases, the permeability of the studied materials increases with decreasing kinetic diameter of the penetrant molecule used. In the case of acetonitrile and isooctane vapours, permeability increased with increasing vapour concentration due to interactions between polymeric materials and molecules of organic compounds. The permeation measurements of pure vapours and air/vapour mixtures indicate that the level of interactions between the molecules of the penetrant and the material of the protective garment is not strong enough to degrade the material of the garment in such a way as to allow a greater penetration of the pollutants through it. The results of permeation experiments for gases and organic vapours showed very good barrier properties of studied chemical isolated garments.


Assuntos
Militares , Gases , Humanos , Permeabilidade , Roupa de Proteção , Solventes
14.
Phys Chem Chem Phys ; 22(5): 2999-3007, 2020 Feb 07.
Artigo em Inglês | MEDLINE | ID: mdl-31957771

RESUMO

Infrared multiple photon dissociation (IRMPD) spectroscopy has been used to probe the structures of the three protonated base-pair mismatches containing 9-ethylguanine (9eG) in the gas phase. Computational chemistry has been used to determine the relative energies and compute the infrared spectra of these complexes. By comparing the IRMPD spectra with the computed spectra, in all cases, it was possible to deduce that what was observed experimentally were the lowest energy computed structures. The protonated complex between 9eG and 1-methylthymine (1mT) is protonated at N7 of 9eG-the most basic site of all three bases in this study-and bound in a Hoogsteen type structure with two hydrogen bonds. The experimental IRMPD spectrum for the protonated complex between 9eG and 9-methyladenine (9mA) is described as arising from a combination of the two lowest energy structures, both which are protonated at N1 of adenine and each containing two hydrogen bonds with 9eG being the acceptor of both. The protonated dimer of 9eG is protonated at N7 with an N7-H+-N7 ionic hydrogen bond. It also contains an interaction between a C-H of protonated guanine and the O6 carbonyl of neutral guanine which is manifested in a slight red shift of that carbonyl stretch. The protonated 9eG/9mA structures have been previously identified by X-ray crystallography in RNA and are contained within the protein database.


Assuntos
Gases/química , Guanina/análogos & derivados , Espectrofotometria Infravermelho , Adenina/análogos & derivados , Adenina/química , Adenina/metabolismo , Pareamento Incorreto de Bases , Cristalografia por Raios X , Guanina/química , Guanina/metabolismo , Ligações de Hidrogênio , Modelos Moleculares , Fótons , Timina/análogos & derivados , Timina/química , Timina/metabolismo
15.
Environ Sci Technol ; 54(3): 2022-2030, 2020 02 04.
Artigo em Inglês | MEDLINE | ID: mdl-31909975

RESUMO

Mercury emission from industrial activities is a great threat to public health and ecosystems. Developing new strategies and materials to remove mercury still remains a serious task. Herein, selenide-decorated copper foam prepared by a heating-stirring method (Cu-hs) was used as a monolithic mercury adsorption material. The Cu-hs exhibited much better adsorption of elemental mercury (Hg0) compared with the selenide-decorated cordierite honeycomb prepared by the same method (Cordierite-hs). Nearly 100% Hg0 adsorption efficiency was obtained under a high gaseous hourly space velocity of 6.0 × 104. Excellent Hg0 adsorption capacity was obtained in a wide range of reaction temperatures from 40 to 120 °C, suggesting the good adaptability of Cu-hs in different operating conditions. The Cu-hs exhibited high selectivity for Hg0 against H2O and SO2, which is advantageous for real applications in industrial flue gas. The Hg0 adsorption capacity of Cu-hs reached 3743 g/m3, about 14 times higher than the 243 g/m3 of Cordierite-hs. The excellent Hg0 adsorption performance of Cu-hs was attributed to the high affinity of the selenium in Cu2Se for mercury, the homogeneous distribution of Cu2Se, and the superior fluid characteristics of the Cu foam substrate. The adsorption performance of the spent Cu-hs could be effectively recovered by HCl solution leaching and subsequent reselenization. The utilization of recyclable Cu-hs provides a cost-effective and environmentally friendly method for removing mercury from industrial flue gas.


Assuntos
Mercúrio , Adsorção , Cobre , Ecossistema , Gases
16.
Environ Sci Technol ; 54(3): 1857-1866, 2020 02 04.
Artigo em Inglês | MEDLINE | ID: mdl-31913027

RESUMO

The present work aims to develop a novel and sustainable approach to adsorb and recover low-concentration Hg0 in the off-gas downstream a distillation/condensation system in the recycling processes for waste Hg-containing devices. Hg0 adsorption and regeneration efficiencies of raw and HNO3-treated activated carbon fiber cloth (ACFC) were examined. The adsorption experiments were conducted with an initial Hg0 concentration of 260-300 µg/m3 at room temperature. The regeneration of ACFC was done by an electrothermal swing process with 20, 40, and 60 W direct currents. The experimental results showed that the Hg0 adsorption efficiency of raw ACFC increased to approximately 90% after the 60 W electrothermal regeneration. After HNO3 treatment, the content of oxygen functional groups on HNO3-treated ACFC increased, which enhanced the Hg0 adsorption performance and resulted in over 90% adsorption efficiency for the samples before and after electrothermal regeneration. Importantly, both raw and HNO3-treated ACFCs retained the high adsorption efficiency after nine cycles of adsorption/regeneration, indicating that both raw and HNO3-treated ACFCs were effective and renewable adsorbents for low-concentration Hg0 adsorption and recovery. A Hg adsorption/regeneration mechanism was proposed to explain the increasing adsorption efficiency after electrothermal regeneration and the great adsorption efficiency of HNO3-treated ACFC.


Assuntos
Carvão Vegetal , Mercúrio , Adsorção , Fibra de Carbono , Gases
17.
Environ Sci Technol ; 54(3): 1730-1739, 2020 02 04.
Artigo em Inglês | MEDLINE | ID: mdl-31940195

RESUMO

We report elevated levels of gaseous inorganic chlorinated and nitrogenated compounds in indoor air while cleaning with a commercial bleach solution during the House Observations of Microbial and Environmental Chemistry field campaign in summer 2018. Hypochlorous acid (HOCl), chlorine (Cl2), and nitryl chloride (ClNO2) reached part-per-billion by volume levels indoors during bleach cleaning-several orders of magnitude higher than typically measured in the outdoor atmosphere. Kinetic modeling revealed that multiphase chemistry plays a central role in controlling indoor chlorine and reactive nitrogen chemistry during these periods. Cl2 production occurred via heterogeneous reactions of HOCl on indoor surfaces. ClNO2 and chloramine (NH2Cl, NHCl2, NCl3) production occurred in the applied bleach via aqueous reactions involving nitrite (NO2-) and ammonia (NH3), respectively. Aqueous-phase and surface chemistry resulted in elevated levels of gas-phase nitrogen dioxide (NO2). We predict hydroxyl (OH) and chlorine (Cl) radical production during these periods (106 and 107 molecules cm-3 s-1, respectively) driven by HOCl and Cl2 photolysis. Ventilation and photolysis accounted for <50% and <0.1% total loss of bleach-related compounds from indoor air, respectively; we conclude that uptake to indoor surfaces is an important additional loss process. Indoor HOCl and nitrogen trichloride (NCl3) mixing ratios during bleach cleaning reported herein are likely detrimental to human health.


Assuntos
Poluentes Atmosféricos , Poluição do Ar em Ambientes Fechados , Cloro , Gases , Humanos , Ácido Hipocloroso , Ventilação
18.
Top Curr Chem (Cham) ; 378(1): 14, 2020 Jan 13.
Artigo em Inglês | MEDLINE | ID: mdl-31933069

RESUMO

Classical molecular simulations can provide significant insights into the gas adsorption mechanisms and binding sites in various metal-organic frameworks (MOFs). These simulations involve assessing the interactions between the MOF and an adsorbate molecule by calculating the potential energy of the MOF-adsorbate system using a functional form that generally includes nonbonded interaction terms, such as the repulsion/dispersion and permanent electrostatic energies. Grand canonical Monte Carlo (GCMC) is the most widely used classical method that is carried out to simulate gas adsorption and separation in MOFs and identify the favorable adsorbate binding sites. In this review, we provide an overview of the GCMC methods that are normally utilized to perform these simulations. We also describe how a typical force field is developed for the MOF, which is required to compute the classical potential energy of the system. Furthermore, we highlight some of the common analysis techniques that have been used to determine the locations of the preferential binding sites in these materials. We also review some of the early classical molecular simulation studies that have contributed to our working understanding of the gas adsorption mechanisms in MOFs. Finally, we show that the implementation of classical polarization for simulations in MOFs can be necessary for the accurate modeling of an adsorbate in these materials, particularly those that contain open-metal sites. In general, molecular simulations can provide a great complement to experimental studies by helping to rationalize the favorable MOF-adsorbate interactions and the mechanism of gas adsorption.


Assuntos
Gases/isolamento & purificação , Estruturas Metalorgânicas/química , Adsorção , Dióxido de Carbono/isolamento & purificação , Simulação por Computador , Hidrogênio/isolamento & purificação , Modelos Químicos , Modelos Moleculares , Método de Monte Carlo , Eletricidade Estática , Termodinâmica
19.
Chem Soc Rev ; 49(3): 708-735, 2020 Feb 10.
Artigo em Inglês | MEDLINE | ID: mdl-31993598

RESUMO

Covalent organic frameworks (COFs) are an emerging class of crystalline porous polymers with highly tuneable structures and functionalities. COFs have been proposed as ideal materials for applications in the energy-intensive field of molecular separation due to their notable intrinsic features such as low density, exceptional stability, high surface area, and readily adjustable pore size and chemical environment. This review attempts to highlight the key advancements made in the synthesis of COFs for diverse separation applications such as water treatment or the separation of gas mixtures and organic molecules, including chiral and isomeric compounds. Methods proposed for the fabrication of COF-based columns and continuous membranes for practical applications are also discussed in detail. Finally, a perspective regarding the remaining challenges and future directions for COF research in the field of separation has also been presented.


Assuntos
Estruturas Metalorgânicas/química , Gases/isolamento & purificação , Isomerismo , Estrutura Molecular , Compostos Orgânicos/isolamento & purificação , Porosidade , Relação Estrutura-Atividade , Propriedades de Superfície , Purificação da Água/métodos
SELEÇÃO DE REFERÊNCIAS
DETALHE DA PESQUISA