2,009 research outputs found
Zeolites and related materials as catalyst supports for hydrocarbon oxidation reactions
Catalytic oxidation is a key technology for the conversion of petroleum-based feedstocks into useful chemicals (e.g., adipic acid, caprolactam, glycols, acrylates, and vinyl acetate) since this chemical transformation is always involved in synthesis processes. Millions of tons of these compounds are annually produced worldwide and find applications in all areas of chemical industries, ranging from pharmaceutical to large-scale commodities. The traditional industrial methods to produce large amounts of those compounds involve over-stoichiometric quantities of toxic inorganic reactants and homogeneous catalysts that operate at high temperature, originating large amounts of effluents, often leading to expensive downstream processes, along with nonrecovery of valuable catalysts that are loss within the reactant effluent. Due to the increasingly stringent environmental legislation nowadays, there is considerable pressure to replace these antiquate technologies, focusing on heterogeneous catalysts that can operate under mild reactions conditions, easily recovered, and reused. Parallelly, recent advances in the synthesis and characterization of metal complexes and metal clusters on support surfaces have brought new insights to catalysis and highlight ways to systematic catalysts design. This review aims to provide a comprehensive bibliographic examination over the last 10 years on the development of heterogeneous catalysts, i.e., organometallic complexes or metal clusters immobilized in distinct inorganic supports such as zeolites, hierarchical zeolites, silicas, and clays. The methodologies used to prepare and/or modify the supports are critically reviewed, as well as the methods used for the immobilization of the active species. The applications of the heterogenized catalysts are presented, and some case-studies are discussed in detail.info:eu-repo/semantics/publishedVersio
Efficient cyclohexane oxidation with hydrogen peroxide catalysed by a C-scorpionate iron(II) complex immobilized on desilicated MOR zeolite
The hydrotris(pyrazol-1-yl)methane iron(II) complex [FeCl2{eta(3)-HC(pz)(3)}] (Fe, pz = pyrazol-1-yl) immobilized on commercial (MOR) or desilicated (MOR-D) zeolite, catalyses the oxidation of cyclohexane with hydrogen peroxide to cyclohexanol and cyclohexanone, under mild conditions. MOR-D/Fe (desilicated zeolite supported [FeCl2{eta(3)-HC(pz)(3)}] complex) provides an outstanding catalytic activity (TON up to 2.90 x 10(3)) with the concomitant overall yield of 38%, and can be easy recovered and reused. The MOR or MOR-D supported hydrotris(pyrazol-1-yl)methane iron(II) complex (MOR/Fe and MOR-D/Fe, respectively) was characterized by X-ray powder diffraction, ICP-AES, and TEM studies as well as by IR spectroscopy and N-2 adsorption at -196 degrees C. The catalytic operational conditions (e.g., reaction time, type and amount of oxidant, presence of acid and type of solvent) were optimized. (C) 2013 Elsevier B.V. All rights reserved
Effect of copper on antioxidant enzyme activities and mineral nutrition of white lupin plants grown in nutrient solution
We analyzed the effect of different copper (Cu) concentrations (0.10, 0.15, 0.20 and
0.35 mM) and time (1 day to 9 days) on several growth and biochemical parameters
of roots and shoots of white lupin plants (Lupinus albus cv Estoril) grown in nutrient
solution. A significant decrease in leaf fresh weight and leaf area was detected. Copper
accumulated in the roots, and an impairment of nutrient translocation was only observed
after six days at the highest Cu concentrations applied. A transient increase in the
activity of polyphenoloxidase (EC 1.10.3.1) enforces a role for lignification as a defense
strategy under enhanced Cu levels. The activities of several antioxidative enzymes were
enhanced after Cu application. Our results indicate that Lupinus albus cv ‘Estoril’ is a
rather resistant plant that can cope with moderate concentrations of copper, mostly by
controlling up to a certain point, the uptake of excessive amounts of this meta
Characterization of plant antioxidative system in response to abiotic stresses: a focus on heavy metal toxicity
During their life span, plants can be subjected to a number of abiotic stresses, like drought,
temperature (both high and low), radiation, salinity, soil pH, heavy metals, lack of essential
nutrients, air pollutants, etc. When affected by one, or a combination of abiotic stresses, a
response is induced by changes in the plant metabolism, growth and general development.
Reactive Oxygen Species (ROS) are a natural consequence of the aerobic metabolism, and
plants have mechanisms to deal with them in normal conditions, controlling the formation and
removal rates. Under stress conditions, cell homeostasis is disrupted and ROS production can
increase a lot putting a heavy burden on the those antioxidative mechanisms, some of which
are activated in order to eliminate the excess ROS (Mittler et al., 2004).
Trace element contamination cause abiotic stress in plants and it can affect crop production
and quality. Certain metals, like copper, are essential for plants, but at high concentrations
(depending on plant species) can be considered toxic. Other elements like cadmium and
arsenic (a metalloid), while not essential elements for plants, are widespread pollutants that
are present in nature due to both natural and manmade activities.
Plants have developed different strategies to cope with these stresses. Some use an
avoidance strategy to reduce trace element assimilation while others use internal defence
mechanisms to cope with the increasing levels of the toxic species. Phytotoxic amounts of
trace elements are known to affect several physiological processes and can cause oxidative
stress. Plants have developed several trace element defence mechanisms, that allow them to
grow despite the presence of variable concentrations of trace elements, but the threshold
concentrations as well as the different response mechanisms strongly depend on plant
species and on the type of metal. Metal toxicity can cause a redox imbalance and induce the
increase of ROS concentration, activating the antioxidant defence mechanisms of plants
(Sharma & Dietz, 2009). These mechanisms are very dependent on the metal and the plant
but usually include the involvement of the ascorbate-glutathione cycle enzymes which is a
major antioxidative defence mechanism, and of other antioxidant enzymes like catalase,
peroxidases, and superoxide dismutase. Other non-enzymatic substances with reported
antioxidant properties can also be involved in plant defence mechanisms, like ascorbate,
glutathione, alkaloids, phenolic compounds, non-proteic amino-acids and carotenoid
Highly active and selective supported rhenium catalysts for aerobic oxidation of n-Hexane and n-Heptane
A series of derivative C-scorpionate rhenium complexes, i.e., [ReCl2{NNC(O)C6H5} (Hpz)(PPh3)2] (A) (where Hpz is pyrazole), [ReCl2{NNC(O)C6H5}(Hpz)2(PPh3)] (B), [ReClF {NNC(O)C6H5}(Hpz)2(PPh3)] (C), and their precursor [ReOCl3(PPh3)2] (D), immobilized on 3-aminopropyl-functionalized silica have been prepared and used for neat O2 oxidation of n-hexane and n-heptane mainly to the corresponding alcohols and, in lower amounts, ketones. The supported catalyst C, with fluoro- and diazenido-ligands, exhibits the highest activity for both alkanes (overall turnover numbers (TONs) up to 3.8 _ 103 and 2.5 _ 103, for n-hexane and n-heptane, respectively) and can be reused in consecutive catalytic cycles. Improved conversion was observed after addition of hetero-carboxylate co-catalysts. A free-radical-based mechanism is proposed to explain the product formation.info:eu-repo/semantics/publishedVersio
Physiological responses of Lupinus luteus to different copper concentrations
Yellow lupin (Lupinus luteus L.) plants were grown in hydroponic solution for 15 d under different copper
concentrations (0.1, 0.5, 1.0, 10, 25 and 50 μM). With increasing Cu concentration total biomass was not affected, leaf
area slightly decreased, while chlorophyll content decreased considerably. Cu content increased significantly both in
roots and in leaves, but the contents of other ions were only slightly affected at the highest Cu concentration (Mn
content decreased both in roots and in leaves, P content decreased only in leaves and Zn content increased in roots).
Superoxide dismutase (SOD) activity increased up to day 7 after copper application. Peroxidase (GPOD) and
polyphenol oxidase (PPO) activities also increased, while catalase (CAT) activity remained constan
Influence of enzymes and technology on virgin olive oil composition
This work aims at presenting the state-of-the-art about the influence of the activity of olive endogenous
enzymes, as well as of the application of adjuvants in olive oil technology, discussing their influence on
the composition of virgin olive oil, especially in phenols and volatile compoundsinfo:eu-repo/semantics/publishedVersio
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