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1.
Environ Sci Technol ; 58(22): 9714-9722, 2024 Jun 04.
Artigo em Inglês | MEDLINE | ID: mdl-38780409

RESUMO

Gold nanoparticles (Au-NPs) are used as catalysts for a diverse range of industrial applications. Currently, Au-NPs are synthesized chemically, but studies have shown that plants fed Au deposit, this element naturally as NPs within their tissues. The resulting plant material can be used to make biomass-derived catalysts. In vitro studies have shown that the addition of specific, short (∼10 amino acid) peptide/s to solutions can be used to control the NP size and shape, factors that can be used to optimize catalysts for different processes. Introducing these peptides into the model plant species, Arabidopsis thaliana (Arabidopsis), allows us to regulate the diameter of nanoparticles within the plant itself, consequently influencing the catalytic performance in the resulting pyrolyzed biomass. Furthermore, we show that overexpressing the copper and gold COPPER TRANSPORTER 2 (COPT2) in Arabidopsis increases the uptake of these metals. Adding value to the Au-rich biomass offers the potential to make plant-based remediation and stabilization of mine wastes financially feasible. Thus, this study represents a significant step toward engineering plants for the sustainable recovery of finite and valuable elements from our environment.


Assuntos
Arabidopsis , Ouro , Nanopartículas Metálicas , Ouro/química , Nanopartículas Metálicas/química , Arabidopsis/metabolismo , Catálise , Biomassa , Tamanho da Partícula , Cobre/química
2.
Org Biomol Chem ; 21(5): 1070-1081, 2023 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-36629051

RESUMO

Highly effective acid-catalysed reactions of amines with dimethyl carbonate (DMC) have been conducted with significant yields and selectivity of carboxymethylation or methylation products. Lewis acids (FeCl3, ZnCl2, and AlCl3·6H2O), Brønsted acids (PTSA, acetic, and formic acids), and acids supported on silica (silica sulfuric and silica perchlorate) resulted in carboxymethylation of primary aliphatic amines with high conversions. It was found that the Lewis acid FeCl3 also promoted carboxymethylation of primary aromatic amines and secondary amines. At both 90 °C or an elevated temperature of 150 °C under pressure, AlCl3·6H2O demonstrated highly selective monomethylation of aromatic amines. In addition, both silica sulfuric acid and silica perchlorate at 90 °C exhibited no conversion for secondary amines but enhanced carboxymethylation with high conversions of 80.7-87.5% and selectivity of >99.00% at 150 °C in a pressure reactor. At 1.0 equivalent, both promoted excellent conversion and selectivity of primary aliphatic amines at 90 °C. In addition, they were easily recovered and reused for at least four additional reactions without significant loss of efficiency with consistent conversions and selectivity. Green metrics evaluation for the silica sulfuric acid-catalysed reaction highlighted the sustainability features of the process. Silica-supported catalysts are highly stable, making them ideal alternative catalysts for the methylation and carbonylation of various amines with DMC. Acid-catalysed DMC reactions of amines may expand the substrate scope and offer new opportunities for developing sustainable organic synthetic methodologies.

3.
Org Biomol Chem ; 21(12): 2603-2609, 2023 Mar 22.
Artigo em Inglês | MEDLINE | ID: mdl-36896732

RESUMO

Cross-coupling and cascade reactions typically rely on unsustainable and toxic volatile organic solvents. 2,2,5,5-Tetramethyloxolane (TMO) and 2,5-diethyl-2,5-dimethyloxolane (DEDMO) are both inherently non-peroxide forming ethers, and have been used in this work as effective, more sustainable, and potentially bio-based alternative solvents for Suzuki-Miyaura and Sonogashira reactions. Suzuki-Miyaura reactions demonstrated good yields for a range of substrates, 71-89% in TMO and 63-92% in DEDMO. In addition, a Sonogashira reaction exhibited the excellent yields of 85-99% performed in TMO, which was significantly higher than traditional volatile organic solvents, THF or toluene, and higher than those reported for another non-peroxide forming ether, namely eucalyptol. Cascade Sonogashira reactions utilizing a simple annulation methodology were particularly effective in TMO. Furthermore, a green metric assessment confirmed that the methodology employing TMO was more sustainable and greener than the traditional solvents THF and toluene, thereby demonstrating the promise of TMO as an alternative solvent for Pd-catalyzed cross-coupling reactions.

4.
Faraday Discuss ; 202: 157-173, 2017 09 21.
Artigo em Inglês | MEDLINE | ID: mdl-28661518

RESUMO

Many traditional solvents have drawbacks including sustainability and toxicity issues. Legislation, such as REACH, is driving the move towards less hazardous chemicals and production processes. Therefore, safer bio-based solvents need to be developed. Herein, a 10 step method has been proposed for the development of new bio-based solvents, which utilises a combination of in silico modelling of Hansen solubility parameters (HSPs), experimental Kamlet-Abboud-Taft parameters, a selection of green synthetic routes followed by application testing and toxicity measurements. The challenges that the chemical industry face in the development of new bio-based solvents are highlighted through a case study on methyl(2,2-dimethyl-1,3-dioxolan-4-yl)methyl carbonate (MMC), which can be synthesised from glycerol. Although MMC is an attractive candidate as a replacement solvent, simply being bio-derived is not enough for a molecule to be regarded as green. The methodology of solvent development described here is a broadly applicable protocol that will indicate if a new bio-based solvent is functionally proficient, and will also highlight the importance of early stage Kamlet-Abboud-Taft parameters determination and toxicity testing in the development of a green solvent.


Assuntos
Formiatos/síntese química , Formiatos/química , Estrutura Molecular , Solventes/síntese química , Solventes/química
5.
Faraday Discuss ; 202: 451-464, 2017 09 21.
Artigo em Inglês | MEDLINE | ID: mdl-28660921

RESUMO

The recovery and separation of high value and low volume extractives are a considerable challenge for the commercial realisation of zero-waste biorefineries. Using solid-phase extractions (SPE) based on sustainable sorbents is a promising method to enable efficient, green and selective separation of these complex extractive mixtures. Mesoporous carbonaceous solids derived from renewable polysaccharides are ideal stationary phases due to their tuneable functionality and surface structure. In this study, the structure-separation relationships of thirteen polysaccharide-derived mesoporous materials and two modified types as sorbents for ten naturally-occurring bioactive phenolic compounds were investigated. For the first time, a comprehensive statistical analysis of the key molecular and surface properties influencing the recovery of these species was carried out. The obtained results show the possibility of developing tailored materials for purification, separation or extraction, depending on the molecular composition of the analyte. The wide versatility and application span of these polysaccharide-derived mesoporous materials offer new sustainable and inexpensive alternatives to traditional silica-based stationary phases.


Assuntos
Polissacarídeos/isolamento & purificação , Adsorção , Tamanho da Partícula , Polissacarídeos/química , Porosidade , Extração em Fase Sólida , Propriedades de Superfície
6.
Environ Sci Technol ; 51(5): 2992-3000, 2017 03 07.
Artigo em Inglês | MEDLINE | ID: mdl-28191957

RESUMO

Although a promising technique, phytoextraction has yet to see significant commercialization. Major limitations include metal uptake rates and subsequent processing costs. However, it has been shown that liquid-culture-grown Arabidopsis can take up and store palladium as nanoparticles. The processed plant biomass has catalytic activity comparable to that of commercially available catalysts, creating a product of higher value than extracted bulk metal. We demonstrate that the minimum level of palladium in Arabidopsis dried tissues for catalytic activity comparable to commercially available 3% palladium-on-carbon catalysts was achieved from dried plant biomass containing between 12 and 18 g·kg-1 Pd. To advance this technology, species suitable for in-the-field application: mustard, miscanthus, and 16 willow species and cultivars, were tested. These species were able to grow, and take up, palladium from both synthetic and mine-sourced tailings. Although levels of palladium accumulation in field-suitable species are below that required for commercially available 3% palladium-on-carbon catalysts, this study both sets the target, and is a step toward, the development of field-suitable species that concentrate catalytically active levels of palladium. Life cycle assessment on the phytomining approaches described here indicates that the use of plants to accumulate palladium for industrial applications has the potential to decrease the overall environmental impacts associated with extracting palladium using present-day mining processes.


Assuntos
Mineração , Paládio , Arabidopsis , Catálise , Mostardeira , Poluentes do Solo
7.
J Anal Appl Pyrolysis ; 121: 62-66, 2016 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-27695151

RESUMO

The effect of pyrolysis rate on the properties of alginic acid-derived carbonaceous materials, termed Starbon®, was investigated. Thermal Gravimetry-IR was used to prepare porous carbons up to 800 °C at several rates and highlighted increased CO2 production at higher pyrolysis rates. N2 porosimetry of the resultant carbons shows how pyrolysis rate affects both the mesopore structure and thus surface area and surface energy. Surface capacity of these carbons was analysed by methylene blue dye adsorption. In general, as the rate of pyrolysis increased, the mesopore content and adsorbent capacity decreased. It is considered here that the rapid production of volatiles at these higher rates causes structural collapse of the non-templated pore network. The work here demonstrates that pyrolysis rate is a key variable which needs to be controlled to maximise the textural properties of Starbon® required for adsorption applications.

8.
Int J Mol Sci ; 16(8): 17546-64, 2015 Jul 31.
Artigo em Inglês | MEDLINE | ID: mdl-26263976

RESUMO

To date limited work has focused on assessing the economic viability of scCO2 extraction to obtain waxes as part of a biorefinery. This work estimates the economic costs for wax extraction from maize stover. The cost of manufacture (COM) for maize stover wax extraction was found to be € 88.89 per kg of wax, with the fixed capital investment (FCI) and utility costs (CUT) contributing significantly to the COM. However, this value is based solely on scCO2 extraction of waxes and does not take into account the downstream processing of the biomass following extraction. The cost of extracting wax from maize stover can be reduced by utilizing pelletized leaves and combusting the residual biomass to generate electricity. This would lead to an overall cost of € 10.87 per kg of wax (based on 27% combustion efficiency for electricity generation) and €4.56 per kg of wax (based on 43% combustion efficiency for electricity generation). A sensitivity analysis study showed that utility costs (cost of electricity) had the greatest effect on the COM.


Assuntos
Biomassa , Dióxido de Carbono/química , Ceras/química , Zea mays/química , Dióxido de Carbono/economia , Dióxido de Carbono/isolamento & purificação , Folhas de Planta/química , Ceras/economia
9.
Int J Mol Sci ; 16(8): 17101-59, 2015 Jul 28.
Artigo em Inglês | MEDLINE | ID: mdl-26225963

RESUMO

The global bio-based chemical market is growing in size and importance. Bio-based solvents such as glycerol and 2-methyltetrahydrofuran are often discussed as important introductions to the conventional repertoire of solvents. However adoption of new innovations by industry is typically slow. Therefore it might be anticipated that neoteric solvent systems (e.g., ionic liquids) will remain niche, while renewable routes to historically established solvents will continue to grow in importance. This review discusses bio-based solvents from the perspective of their production, identifying suitable feedstocks, platform molecules, and relevant product streams for the sustainable manufacturing of conventional solvents.


Assuntos
Biocombustíveis , Recuperação e Remediação Ambiental/métodos , Química Verde/métodos , Solventes/efeitos adversos , Solventes/química , Solventes/economia , Tensoativos/efeitos adversos , Tensoativos/química , Tensoativos/economia
10.
RSC Adv ; 14(24): 16921-16934, 2024 May 22.
Artigo em Inglês | MEDLINE | ID: mdl-38799212

RESUMO

Ursolic acid is a triterpene plant extract that exhibits significant potential as an anti-cancer, anti-tumour, and anti-inflammatory agent. Its direct use in the pharmaceutical industry is hampered by poor uptake of ursolic acid in the human body coupled with rapid metabolism causing a decrease in bioactivity. Modification of ursolic acid can overcome such issues, however, use of toxic reagents, unsustainable synthetic routes and poor reaction metrics have limited its potential. Herein, we demonstrate the first reported carboxymethylation and/or methylation of ursolic acid with dimethyl carbonate (DMC) as a green solvent and sustainable reagent under acidic conditions. The reaction of DMC with ursolic acid, in the presence of PTSA, ZnCl2, or H2SO4-SiO2 yielded the carboxymethylation product 3ß-[[methoxy]carbonyl]oxyurs-12-en-28-oic acid, the methylation product 3ß-methoxyurs-12-en-28-oic acid and the dehydration product urs-2,12-dien-28-oic acid. PTSA demonstrated high conversion and selectivity towards the previously unreported carboxymethylation of ursolic acid, while the application of formic acid in the system led to formylation of ursolic acid (3ß-formylurs-12-en-28-oic acid) in quantitative yields via esterification, with DMC acting solely as a solvent. Meanwhile, the methylation product of ursolic acid, 3ß-methoxyurs-12-en-28-oic acid, was successfully synthesised with FeCl3, demonstrating exceptional conversion and selectivity, >99% and 99%, respectively. Confirmed with the use of qualitative and quantitative green metrics, this result represents a significant improvement in conversion, selectivity, safety, and sustainability over previously reported methods of ursolic acid modification. It was demonstrated that these methods could be applied to other triterpenoids, including corosolic acid. The study also explored the potential pharmaceutical applications of ursolic acid, corosolic acid, and their derivatives, particularly in anti-inflammatory, anti-cancer, and anti-tumour treatments, using molecular ADMET and docking methods. The methods developed in this work have led to the synthesis of novel molecules, thus creating opportunities for the future investigation of biological activity and the modification of a wide range of triterpenoids applying acidic DMC systems to deliver novel active pharmaceutical intermediates.

11.
Water Res ; 261: 121994, 2024 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-38955037

RESUMO

Biological activated carbon filter (BAC) is one of the most effective technologies for removing disinfection by-product (DBP) precursors from water. Biochar is a lower-cost medium that has the potential to replace granular activated carbon in BAC applications, thus leading to the development of biological biochar filter (BCF). This study compared BCF with BAC for the removal of DBP precursors using column experiments. Both BCF and BAC achieved the removal of DBP precursors, resulting in concentrations of all DBP formation potential below the World Health Organization guideline values for drinking water. Bromodichloromethane and unknown DBP precursor removal by BCF was comparable to that by BAC. However, BAC removed more chloroform and dichloroacetontrile precursors than BCF. For microbial community analysis, cell numbers in a bottom layer (inlet) of BCF and BAC columns were higher than those in the top layer. The abundances of Nordella and a microbial genus from Burkholderiaceae at the bottom layer showed a strong correlation to the number of DBP precursors removed and were comparable in BCF and BAC. This finding likely contributes to the similarities between DBPs species removed and the removal performances of some known and unknown DBP precursors by BCF and BAC. Overall results from this study revealed that biochar can be served as a low-cost and sustainable replacement of activated carbon in water filter for DBP precursor removal.


Assuntos
Carvão Vegetal , Desinfecção , Filtração , Purificação da Água , Carvão Vegetal/química , Purificação da Água/métodos , Poluentes Químicos da Água , Desinfetantes
12.
Environ Pollut ; 357: 124456, 2024 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-38942273

RESUMO

Triclocarban (TCC), an antibacterial agent commonly used in personal care products, is one of the top ten contaminants of emerging concern in various environmental media, including soil and contaminated water in vadose zone. This study aimed to investigate TCC-contaminated water remediation using biochar-immobilized bacterial cells. Pseudomonas fluorescens strain MC46 (MC46), an efficient TCC-degrading isolate, was chosen, whereas agro-industrial carbonized waste as biochar was directly used as a sustainable cell immobilization carrier. According to the long-term TCC removal performance results (160 d), the biochar-immobilized cells consistently exhibited high TCC removal efficiencies (84-97%), whereas the free MC46 removed TCC for 76-94%. At 100 days, the detachment of the MC46 cells from the immobilized cell column was observed. The micro-Fourier-transform infrared spectroscopy results indicated that extracellular polymeric substance (EPS) was produced, but polysaccharide and protein fractions were washed out of the column. The lipid fraction of EPS adhered to the biochar, promoting TCC sorption for long-term treatment. The shortening of MC46 cells improved the tolerance of TCC toxicity. The TCC-contaminated water was successfully detoxified by the biochar-immobilized MC46 cells. Overall, the waste-derived biochar-immobilized cell system proposed in this study for the removal of emerging contaminants, including TCC, is efficient, economical, and aligned with the sustainable development concept of value-added utilization of waste.


Assuntos
Carbanilidas , Células Imobilizadas , Carvão Vegetal , Pseudomonas fluorescens , Poluentes Químicos da Água , Carvão Vegetal/química , Pseudomonas fluorescens/metabolismo , Poluentes Químicos da Água/metabolismo , Células Imobilizadas/metabolismo , Biodegradação Ambiental
13.
RSC Adv ; 14(1): 29-45, 2024 Jan 02.
Artigo em Inglês | MEDLINE | ID: mdl-38173606

RESUMO

A combination of supercritical carbon dioxide (scCO2) extraction and microwave-assisted pyrolysis (MAP) have been investigated for the valorisation of waste rice straw. ScCO2 extraction of rice straw led to a 0.7% dry weight yield of lipophilic molecules, at elevated temperatures of 65 °C and pressures of 400 bar. Lipid compositions (fatty acids, fatty alcohol, fatty aldehydes, steroid ketones, phytosterols, n-alkanes and wax esters) of the waxes obtained by scCO2 were comparable to those obtained Soxhlet extraction using the potentially toxic solvent n-hexane. ScCO2 extraction positively influenced the pyrolysis heating rate, with a rate of 420 K min-1 for particles of 500-2000 µm, compared to 240 K min-1 for the same particle size of untreated straw. Particle size significantly affected cellulose decomposition and the distribution of pyrolysis products (gaseous, liquid and char), highlighting the importance of selecting an adequate physical pre-treatment. TG and DTG of the original rice straw and resulting biochar produced indicated that cellulose was completely decomposed during the MAP. While a rapid pressure change occurred at ∼120 °C (size > 2000 µm) and ∼130 °C (size 500-2000 µm) during MAP and was associated with the production of incondensable gas during cellulose decomposition, this takes place at significantly lower temperatures than those observed with conventional pyrolysis, 320 °C. Wax removal by scCO2 influences the dielectric properties of the straw, enhancing microwave absorption with rapid heating rates and elevated final pyrolysis temperatures, illustrating the benefits of combining these sustainable technologies within a holistic rice straw biorefinery.

14.
RSC Adv ; 13(4): 2427-2437, 2023 Jan 11.
Artigo em Inglês | MEDLINE | ID: mdl-36741189

RESUMO

Nonpolar, nonperoxide forming, sustainable and potentially bio-based solvents, namely 2,2,5,5-tetramethyloxolane (TMO) and 2,5-diethyl-2,5-dimethyloxolane (DEDMO), were utilized as an alternative to toxic petroleum-based hydrocarbon solvents for extraction of hentriacontane-14,16-dione from waste wheat straw waxes. This work is the first to report the application of DEDMO as a solvent for the extraction of natural products. The sustainable methodology developed in this research provided considerable advantages over previously reported systems in terms of high extraction yields, excellent selectivity towards the ß-diketones and low amounts of waste generated. DEDMO provided the highest recovery yield for all the sustainable solvents investigated, recovering 23.7% of the wax (which is a 68.8% yield of the ß-diketone). The extracted lipophilic hentriacontane-14,16-dione was utilised in combination with the sustainable solvents TMO or DEDMO to facilitate the creation of highly hydrophobic coatings. Moreover, the use of DEDMO was found to aid in the self-assembly of nano-structured tubule formation of both the unrefined wax and isolated ß-diketone. Green metric evaluation using process mass intensity (PMI), E-factor, solvent intensity (SI), and water intensity (WI) demonstrated that the described extraction procedure for hentriacontane-14,16-dione was highly sustainable and safer than the previous methodology. This sustainable manufacturing process may create the potential to valorise agricultural wastes as part of a holistic biorefinery.

15.
RSC Adv ; 13(21): 14712-14728, 2023 May 09.
Artigo em Inglês | MEDLINE | ID: mdl-37197677

RESUMO

Biochar and magnetic biochar prepared from chrysanthemum waste of the beverage industry are effective adsorbents for the removal of the non-steroidal anti-inflammatory drug, ibuprofen (IBP), from aqueous systems. The development of magnetic biochar using iron chloride, overcame poor separation characteristics from the liquid phase of the powdered biochar after adsorption. Characterisation of biochars was achieved through Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), N2 adsorption/desorption porosimetry, scanning electron microscopy (SEM), electron dispersive X-ray analysis (EDX), X-ray photoelectron spectroscopy (XPS), vibrating sample magnetometer (VSM), moisture and ash content, bulk density, pH and zero-point charge (pHpzc). The specific surface area of non-magnetic and magnetic biochars was 220 and 194 m2 g-1, respectively. Adsorption of ibuprofen was optimised with respect to contact time (5-180 min), solution pH (2-12) and initial drug concentration (5-100 mg L-1), with equilibrium being reached in 1 hour, and the maximum ibuprofen removal occurred at pH 2 and 4 for biochar and magnetic biochars, respectively. Investigation of the adsorption kinetics was achieved through application of the pseudo-first order, pseudo-second order, Elovich and intra-particle diffusion models. Adsorption equilibrium was evaluated using Langmuir, Freundlich and Langmuir-Freundlich isotherm models. The adsorption kinetics and isotherms for both biochars are well described by pseudo-second order kinetic and Langmuir-Freundlich isotherm models, respectively, with the maximum adsorption capacity of biochar and magnetic biochar being 167 and 140 mg g-1, respectively. Chrysanthemum derived non-magnetic and magnetic biochars exhibited significant potential as sustainable adsorbents toward the removal of emerging pharmaceutical pollutants such as ibuprofen from aqueous solution.

16.
Chemistry ; 18(42): 13520-30, 2012 Oct 15.
Artigo em Inglês | MEDLINE | ID: mdl-22945297

RESUMO

The preparation and characterization of a set of periodic mesoporous organosilicas (PMOs) that contain different fractions of 1,3-bis(3-trimethoxysilylpropyl)imidazolium chloride (BTMSPI) groups uniformly distributed in the silica mesoporous framework is described. The mesoporous structure of the materials was characterized by powder X-ray diffraction, transmission electron microscopy, and N(2) adsorption-desorption analysis. The presence of propyl imidazolium groups in the silica framework of the materials was also characterized by solid-state NMR spectroscopy and diffuse-reflectance Fourier-transform infrared spectroscopy. The effect of the BTMSPI concentration in the initial solutions on the structural properties (including morphology) of the final materials was also examined. The total organic content of the PMOs was measured by elemental analysis, whereas their thermal stability was determined by thermogravimetric analysis. Among the described materials, it was found that PMO with 10% imidazolium content is an effective host for the immobilization of perruthenate through an ion-exchange protocol. The resulting Ru@PI-10 was then employed as a recyclable catalyst in the highly efficient aerobic oxidation of various types of alcohols.


Assuntos
Álcoois/química , Imidazóis/química , Compostos de Organossilício/química , Compostos de Rutênio/química , Adsorção , Catálise , Líquidos Iônicos/química , Compostos de Organossilício/síntese química , Oxirredução , Porosidade , Dióxido de Silício/química
17.
R Soc Open Sci ; 9(6): 211699, 2022 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-35719880

RESUMO

Demand for cannabinoid is growing, with the global market expected to reach $9.69 billion by 2025. Understanding how chemical composition changes in hemp at different harvest times is crucial to maximizing this industrial crop value. Important compositional changes in three different compound classes (essential oils, cannabinoids, and lipids) from inflorescences (tops), leaves, and stems of hemp (Cannabis sativa L., Finola variety) at different harvesting stages have been investigated. Over 85% of the total extracts from the tops were cannabinoids, while leaves demonstrated the greatest quantities of wax ester and sterols. Essential oil and cannabinoid increased in tops until full flowering (third harvest), reaching 2030 µg g-1 and 39 475 µg g-1, respectively. Cannabinoids decreased at seed maturity (final harvest) to 26 969 µg g-1. This demonstrates the importance of early harvesting to maximize cannabidiol (CBD), which is highly sought after for its therapeutic and pharmacological properties. A total of 21 161 µg g-1 of CBD was extracted from the tops at full flowering (third harvest); however, a significant increase (63%) in the banned psychoactive tetrahydrocannabinol (THC) was observed from budding (157 µg g-1 of biomass) to the full flowering (9873 µg g-1 of biomass). Harvesting the tops after budding is preferable due to the high CBD content and low amounts of THC.

18.
J Hazard Mater ; 424(Pt C): 127691, 2022 02 15.
Artigo em Inglês | MEDLINE | ID: mdl-34775314

RESUMO

Biochar is a low-cost adsorbent with considerable potential for utilization as a water filtration medium; however, organic matter leaching from biochar can lead to the formation of disinfection by-products (DBPs). This study investigated the leaching of dissolved organic carbon (DOC) from eucalyptus-derived biochar and the formation of DBPs generated by chlorination and chloramination. Column experiments with empty bed contact times (EBCTs) of 10 and 30 min were conducted for 200 bed volumes (BVs). The highest DOC concentration (3.5 µg-C/g-biochar) was detected with an EBCT of 30 min. Chloroform (49 µg/L) and dichloroacetonitrile (7 µg/L) because of chlorination were found during the first five BVs, but were reduced thereafter. During the first 10 BVs, unknown chlorinated DBPs generated (CHOCl) by chlorination and chloramination (193 and 152 formulae, respectively) were tentatively identified via an unknown screening analysis. The release of DBP precursors from biochar tentatively identified in this study will impact water filtration applications.


Assuntos
Desinfetantes , Poluentes Químicos da Água , Purificação da Água , Carvão Vegetal , Desinfecção , Matéria Orgânica Dissolvida , Halogenação , Espectrometria de Massas , Poluentes Químicos da Água/análise
19.
Org Biomol Chem ; 9(21): 7420-6, 2011 Nov 07.
Artigo em Inglês | MEDLINE | ID: mdl-21904726

RESUMO

The application of a novel palladium containing ionic liquid based periodic mesoporous organosilica (Pd@PMO-IL) catalyst in the aerobic oxidation of primary and secondary alcohols under molecular oxygen and air atmospheres is investigated. It was found that the catalyst is quite effective for the selective oxidation of several activated and non-activated alcoholic substrates. The catalyst system could be successfully recovered and reused several times without any significant decrease in activity and selectivity. Moreover, the hot filtration test, atomic absorption spectroscopy (AA) and kinetic study with and without selective catalyst poisons showed that the catalyst works in a heterogeneous pathway without any palladium leaching in reaction solution. Furthermore, nitrogen-sorption experiment and transmission electron microscopy (TEM) image proved the superior stability of high-ordered PMO-IL mesostructure during reaction process. TEM image also confirmed the presence of well-distributed Pd-nanoparticles in the uniform mesochannels of the material. These observations can be attributed to the ionic liquid nature of PMO-IL mesostructure which facilitates the reaction through production, chemical immobilization and stabilization of active palladium nanoparticles, as well as preventing Pd-agglomeration during overall process.


Assuntos
Álcoois/química , Imidazóis/química , Cetonas/síntese química , Compostos Organometálicos/química , Compostos de Organossilício/química , Paládio/química , Catálise , Cetonas/química , Estrutura Molecular , Compostos Organometálicos/síntese química , Oxirredução , Tamanho da Partícula , Porosidade , Propriedades de Superfície
20.
Bioresour Technol ; 341: 125832, 2021 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-34461404

RESUMO

Waste Cassia bakeriana seed pods were used for porous carbon production in a facile pyrolysis process. The carbons were highly efficient adsorbents for methylene blue, congo red and ciprofloxacin antibiotic from aqueous media. The experimental results demonstrated that despite moderate surface area of 283.4 m2/g, KOH activated carbon (PSAC-KOH) exhibited the highest adsorption capacity for congo red reported to date for carbon-based adsorbents (970 mg/g). PSAC-KOH also demonstrated a high adsorption capacity at 600 mg/g for ciprofloxacin. Raman spectroscopy, X-ray diffraction and X-ray Photoelectron spectroscopy analysis of the carbons demonstrated an extensive graphitic characteristic, while Fourier transform infrared spectra of PSAC-KOH suggested a high proportion of aromaticity which promotes adsorption mechanisms including electrostatic and π-π interactions. Pseudo-second-order kinetic model fitting suggested a rate-controlling chemisorption mechanism. The utilization of waste Cassia bakeriana seed pods for carbon production may create new opportunities to develop sustainable and highly efficient adsorbents for water remediation.


Assuntos
Cassia , Poluentes Químicos da Água , Adsorção , Antibacterianos , Carvão Vegetal , Ciprofloxacina , Cinética
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