Coordination Chemistry of the (eta(6)-p-Cymene)ruthenium(II) Fragment with Bis-, Tris-, andTetrakis(pyrazol-1-yl)borate Ligands: Synthesis, Structural, Electrochemical, and CatalyticDiastereoselective Nitroaldol Reaction Studies

Novel [Ru(eta(6)-p-cymene)(kappa(2)-L)X] and [Ru(eta(6)-p-cymene)(kappa(3)-L)]X center dot nH(2)O complexes (L = bis-, tris-, or tetrakis-pyrazolylborate; X = Cl, N-3, PF6, or CF3SO3) are prepared by treatment of [Ru(eta(6)-p-cymene)Cl-2](2) with poly-(pyrazolyl)borate derivatives [M(L)] (L in general; in detail L = Ph(2)Bp = diphenylbis-(pyrazol-1-yl)borate; L = Tp = hydrotris(pyrazol-1-yl)borate; L = pzTp = tetrakis(pyrazol-1-yl)borate; L = Tp(4Bo) = hydrotris(indazol-1-yl)borate, L = T-p4Bo,T-5Me = (5-methylindazol-1-yl)borate; L = Tp(Bn,4Ph) = hydrotris(3-benzyl-4-phenylpyrazol-1-yl)borate; M = Na, K, or TI) and characterized by analytical and spectral data (IR, ESIMS, H-1 and C-13 NMR). The structures of [Ru(eta(6)-p-cymene)(Ph(2)Bp)Cl] (1) and [Ru(eta(6)-p-cymene)(Tp)Cl] (3) have been established by single-crystal X-ray diffraction analysis. Electrochemical studies allowed comparing the electron-donor characters of Tp and related ligands and estimating the corresponding values of the Lever E-L ligand parameter. The complexes [Ru(eta(6)-p-cymene)-(kappa(2)-L)X] and [Ru(eta(6)-p-cymene)(kappa(3)-L)]X center dot nH(2)O act as catalyst precursors for the diastereoselective nitroaldol reaction of benzaldehyde and nitroethane to the corresponding beta-nitroalkanol (up to 82% yield, at room temperature) with diastereoselectivity toward the formation of the threo isomer.

Comparison of Py-GC/FID and Wet Chemistry Analysis for Lignin Determination in Wood and Pulps from Eucalyptus globulus

The kraft pulps produced from heartwood and sapwood of Eucalyptus globulus at 130 degrees C, 150 degrees C, and 170 degrees C were characterized by wet chemistry (total lignin as sum of Klason and soluble lignin fractions) and pyrolysis (total lignin denoted as py-lignin). The total lignin content obtained with both methods was similar. In the course of delignification, the py-lignin values were higher (by 2 to 5%) compared to Klason values, which is in line with the importance of soluble lignin for total lignin determination. Pyrolysis analysis presents advantages over wet chemical procedures, and it can be applied to wood and pulps to determine lignin contents at different stages of the delignification process. The py-lignin values were used for kinetic modelling of delignification, with very high predictive value and results similar to those of modelling using wet chemical determinations.

Physical-chemical and mineralogical characterization of fine aggregates from construction and demolition waste recycling plants

Construction and demolition waste (CDW) represents around 31% of all waste produced in the European Union. It is today acknowledged that the consumption of raw materials in the construction industry is a non-sustainable activity. It is thus necessary to reduce this consumption, and the volume of CDW dumped, by using this waste as a source of raw materials for the production of recycled aggregates. One potential use of these aggregates is their incorporation in reinforced concrete as a replacement of natural aggregates. A concrete that incorporates these aggregates and still performs well requires them to be fully characterized so that their behaviour within the concrete can be predicted. Coarse recycled aggregates have been studied quite thoroughly, because they are simpler to reintroduce in the market as a by-product, and so has the performance of concrete made with them. This paper describes the main results of research designed to characterize the physical and chemical properties of fine recycled aggregates for concrete production and their relationship with mineralogical composition and preprocessing. The constraints of the incorporation of fine aggregates in reinforced concrete are discussed. It is shown that, unless a developed processing diagram is used, this application is not feasible. (C) 2013 Elsevier Ltd. All rights reserved.

A New Method to Determine the Density and Water Absorption of Fine Recycled Aggregates

The construction industry keeps on demanding huge quantities of natural resources, mainly minerals for mortars and concrete production. The depletion of many quarries and environmental concerns about reducing the dumping of construction and demolition waste in quarries have led to an increase in the procuring and use of recycled aggregates from this type of waste. If they are to be incorporated in concrete and mortars it is essential to know their properties to guarantee the adequate performance of the end products, in both mechanical and durability-related terms. Existing regulated tests were developed for natural aggregates, however, and several problems arise when they are applied to recycled aggregates, especially fine recycled aggregates (FRA). This paper describes the main problems encountered with these tests and proposes an alternative method to determine the density and water absorption of FRA that removes them. The use of sodium hexametaphosphate solutions in the water absorption test has proven to improve its efficiency, minimizing cohesion between particles and helping to release entrained air.

Concrete with fine recycled aggregates: a review

This paper presents a review of the literature published so far on the use of fine aggregates from construction demolition waste used as a partial or total replacement of fine natural aggregates in concrete production. The review presents the initial works on this subject and an overview of the existing regulations. It goes on to describe the production, treatment and properties of the fine recycled aggregates (FRA). The most suitable mixing techniques for concrete with this type of aggregates are then discussed. The properties of these concrete mixes are analysed in detail, after which a few examples of structures with this type of concrete are described and compared. The acquisition of fine natural aggregates and the dumping of the fine fraction of construction and demolition waste are two serious environmental problems that can be solved simultaneously by using FRA in concrete production, a subject that is lagging behind the use of the corresponding coarse fraction.

The effect of superplasticizers on the mechanical performance of concrete made with fine recycled concrete aggregates

It is considered that using crushed recycled concrete as aggregate for concrete production is a viable alternative to dumping and would help to conserve abiotic resources. This use has fundamentally been based on the coarse fraction because the fine fraction is likely to degrade the performance of the resulting concrete. This paper presents results from a research work undertaken at Institut Superior Tecnico (IST), Lisbon, Portugal, in which the effects of incorporating two types of superplasticizer on the mechanical performance of concrete containing fine recycled aggregate were evaluated. The purpose was to see if the addition of superplasticizer would offset the detrimental effects associated with the use of fine recycled concrete aggregate. The experimental programme is described and the results of tests for splitting tensile strength, modulus of elasticity and abrasion resistance are presented. The relative performance of concrete made with recycled aggregate was found to decrease. However, the same concrete with admixtures in general exhibited a better mechanical performance than the reference mixes without admixtures or with a less active superplasticizer. Therefore, it is argued that the mechanical performance of concrete made with fine recycled concrete aggregates can be as good as that of conventional concrete, if superplasticizers are used to reduce the water-cement ratio of the former concrete.

The effect of superplasticizers on the workability and compressive strength of concrete made with fine recycled concrete aggregates

The reuse of structural concrete elements to produce new concrete aggregates is accepted as an alternative to dumping them and is favourable to the sustainability of natural reserves. Even though the construction sector is familiar with the use of coarse recycled concrete aggregates, the recycled concrete fines are classified as less noble resources. This research sets out to limit the disadvantages associated with the performance of concrete containing fine recycled concrete aggregates through the use of superplasticisers. Two types of latest generation superplasticisers were used that differ in terms of water reduction capacity and robustness, and the workability, density and compressive strength of each of the compositions analysed were then compared: a reference concrete, with no plasticisers, and concrete mixes with the superplasticisers. For each concrete family mixes with 0%, 10%, 30%, 50% and 100% replacement ratios of fine natural aggregates (FNA) by fine recycled concrete aggregates (FRA) were analysed. Concrete with incorporation of recycled aggregates was found to have poorer relative performance. The mechanical performance of concrete with recycled aggregates and superplasticisers was generally superior to that of the reference concrete with no admixtures and of conventional concrete with lower performance superplasticisers.

Physical, chemical and mineralogical properties of fine recycled aggregates made from concrete waste

This paper assesses the physical, chemical and mineralogical characteristics of fine recycled aggregates obtained from crushed concrete waste, comparing them with two types of natural fine aggregates from different origins. A commercial concrete was jaw crushed, and the effect of different aperture sizes on the particle size distribution of the resulting aggregates was evaluated. The density and water absorption of the recycled aggregates was determined and a model for predicting water absorption over time is proposed. Both natural and recycled aggregates were characterized regarding bulk density and fines content. Recycled aggregates were additionally characterized by XRD, SEM/EDS and DTA/TG of individual size fractions. The results show that natural and recycled fine aggregates have very different characteristics. This should be considered in potential applications, both in terms of the limits for replacing amounts and of the rules and design criteria of the manufactured products. (C) 2015 Elsevier Ltd. All rights reserved.

Rheological behaviour of concrete made with fine recycled concrete aggregates - Influence of the superplasticizer

This paper evaluates the influence of two superplasticizers (SP) on the rheological behaviour of concrete made with fine recycled concrete aggregates (FRCA). Three families of concrete were tested: family CO made without SP, family Cl made with a regular superplasticizer and family C2 made with a high-performance superplasticizer. Five replacement ratios of natural sand by FRCA were tested: 0%, 10%, 30%, 50% and 100%. The coarse aggregates were natural gravels. Three criteria were established to design the concrete mixes' composition: keep the same particle size distribution curves, adjust the water/cement ratio to obtain a similar slump and no pre-saturation of the FRCA. All mixes had the same cement and SP content. The results show that the incorporation of FRCA significantly increased the shrinkage and creep deformation. The FRCA's effect was influenced by the curing age. The reference concrete made with natural sand stabilizes the creep deformation faster than the mixes made with FRCA. The incorporation of superplasticizer increased the shrinkage at early ages and decreased the shrinkage at 91 days of age. The regular superplasticizer did not improve the creep deformation while the high-performance superplasticizer highly improved this property. The incorporation of FRCA jeopardized the SP's effectiveness. This study demonstrated that to use FRCA and superplasticizer for concrete production it is necessary to take into account the different rheological behaviour of these mixes. (C) 2015 Elsevier Ltd. All rights reserved.

Study of the rheology of self-compacting concrete with fine recycled concrete aggregates

This work studies the effect of incorporating fine recycled aggregates on the rheology of self-compacting concrete over time (at 15,45 and 90 min). The fine fraction of the natural aggregates was replaced at 0%, 20%, 50% and 100% with recycled sand. The fresh-state properties were studied by empirical tests (slump-flow, J-Ring, L-Box) and fundamental ones in an ICAR rheometer. The mixes with 50% and 100% recycled sand lost their SCC characteristics at 90 min. Contrarily the mix with 20% replacement maintained suitable passing and filling ability. The causes of this trend were an initial increase of plastic viscosity and afterwards an increase of yield stress. The compressive strength of the 50% and 100% replacement mixes decreased significantly and that of the 20% replacement mix less than 10%. (C) 2015 Elsevier Ltd. All rights reserved.

Temperature-induced structural transitions in self-assembling magnetic nanocolloids

With the help of a unique combination of density functional theory and computer simulations, we discover two possible scenarios, depending on concentration, for the hierarchical self-assembly of magnetic nanoparticles on cooling. We show that typically considered low temperature clusters, i.e. defect-free chains and rings, merge into more complex branched structures through only three types of defects: four-way X junctions, three-way Y junctions and two-way Z junctions. Our accurate calculations reveal the predominance of weakly magnetically responsive rings cross-linked by X defects at the lowest temperatures. We thus provide a strategy to fine-tune magnetic and thermodynamic responses of magnetic nanocolloids to be used in medical and microfluidics applications.

Influence of Soil Chemistry and Plant Physiology in the Phytoremediation of Cu, Mn, and Zn

Different anthropogenic sources of metals can result from agricultural, industrial, military, mining and urban activities that contribute to environmental pollution. Plants can be grown for phytoremediation to remove or stabilize contaminants in water and soil. Copper (Cu), manganese (Mn) and zinc (Zn) are trace essential metals for plants, although their role in homeostasis in plants must be strictly regulated to avoid toxicity. In this review, we summarize the processes involved in the bioavailability, uptake, transport and storage of Cu, Mn and Zn in plants. The efficiency of phytoremediation depends on several factors including metal bioavailability and plant uptake, translocation and tolerance mechanisms. Soil parameters, such as clay fraction, organic matter content, oxidation state, pH, redox potential, aeration, and the presence of specific organisms, play fundamental roles in the uptake of trace essential metals. Key processes in the metal homeostasis network in plants have been identified. Membrane transporters involved in the acquisition, transport and storage of trace essential metals are reviewed. Recent advances in understanding the biochemical and molecular mechanisms of Cu, Mn and Zn hyperaccumulation are described. The use of plant-bacteria associations, plant-fungi associations and genetic engineering has opened a new range of opportunities to improve the efficiency of phytoremediation. The main directions for future research are proposed from the investigation of published results.

Chromone: A valid scaffold in medicinal chemistry

Chromones are a group of naturally occurring compounds that are ubiquitous in nature, especially in plants. The word chromone is derived from the Greek word chroma, meaning “color”, which point out that many chromone derivatives can exhibit a diversity of colors.

Role of a novel disulfide bridge within the all-beta fold of soluble Rieske proteins

Journal of Biological Inorganic Chemistry (2010)15: 271-281