Crystal structure of a seven-coordinate cobalt(II) complex with a new polyfunctional hydrazonic ligand, [Co(H4dapis)(OH2)2]Cl2·9/2H2O

A seven-coordinate cobalt(II) complex has been synthesized with a new hydrazonic ligand, H₄dapis, and its crystal structure determined by X-ray diffraction methods and refined toR 0.0564 for 2763 independent reflections. The structure consists of [Co(H₄dapis)(OH₂)2] cations, Cl anions, and lattice H₂O molecules interlinked by hydrogen bonds. The cobalt atom has a distorted pentagonal bipyramidal environment with two axial H₂O molecules and the H₄dapis ligand forming the basal plane.     

Quadratic estimates for the number of integer points in convex bodies

We give bounds for the mean square deviation with respect to arbitrary probability measures of the number of integer points in translated or dilated convex bodies. The proofs are based on Fourier analytic methods.     

Contrasting chemoselectivities in the ultrasound and microwave assisted bromination reactions of substituted alkylaromatics with N-bromosuccinimide

Ultrasound and microwave assisted bromination reactions of various alkylaryls with N-bromosuccinimide, either neat or in water, shows diverse chemoselectivity. Thus, ring substitution occurs in water with ultrasound, whereas with microwaves both side-chain α-bromination and ring substitution occur. With neat reactants, side-chain α-bromination predominates for microwave assisted reactions. In the presence of water the chemoselectivity with microwave-promoted bromination is similar to that observed using classical methods.     

Synthesis and spectroscopic characterization of new triorganotin(IV) complexes with the bis(1‐methyl‐1H‐imidazol‐2‐ylthio)acetate ligand: effects on trout erythrocyte components

Triorganotin(IV) derivatives containing the anionic ligand bis(1‐methyl‐1H‐imidazol‐2‐ylthio)acetate [(S‐tim)₂CHCO₂]⁻ were synthesized from the reaction between R₃SnCl acceptors (R = Me and Ph) and the sodium salt of the ligand. Mono‐nuclear complexes of the type [(S‐tim)₂CHCO₂]SnR₃ were obtained, which were fully characterized by elemental analyses and FT‐IR in the solid state, and by NMR (¹H, ¹³C and ¹¹⁹Sn) spectroscopy and electrospray ionization mass in solution. The toxic effects shown by these compounds on trout erythrocyte components showed that the toxicity of the organotin(IV) complexes depends on the nature and on the lipophilicity of the substituents on the metal centre. Copyright © 2007 John Wiley & Sons, Ltd.     

Toward a Greener World—Cyclodextrin Derivatization by Mechanochemistry

Cyclodextrin (CD) derivatives are a challenge, mainly due to solubility problems. In many cases, the synthesis of CD derivatives requires high-boiling solvents, whereas the product isolation from the aqueous methods often requires energy-intensive processes. Complex formation faces similar challenges in that it involves interacting materials with conflicting properties. However, many authors also refer to the formation of non-covalent bonds, such as the formation of inclusion complexes or metal–organic networks, as reactions or synthesis, which makes it difficult to classify the technical papers. In many cases, the solubility of both the starting material and the product in the same solvent differs significantly. The sweetest point of mechanochemistry is the reduced demand or complete elimination of solvents from the synthesis. The lack of solvents can make syntheses more economical and greener. The limited molecular movements in solid-state allow the preparation of CD derivatives, which are difficult to produce under solvent reaction conditions. A mechanochemical reaction generally has a higher reagent utilization rate. When the reaction yields a good guest co-product, solvent-free conditions can be slower than in solution conditions. Regioselective syntheses of per-6-amino and alkylthio-CD derivatives or insoluble cyclodextrin polymers and nanosponges are good examples of what a greener technology can offer through solvent-free reaction conditions. In the case of thiolated CD derivatives, the absence of solvents results in significant suppression of the thiol group oxidation, too. The insoluble polymer synthesis is also more efficient when using the same molar ratio of the reagents as the solution reaction. Solid reactants not only reduce the chance of hydrolysis of multifunctional reactants or side reactions, but the spatial proximity of macrocycles also reduces the length of the spacing formed by the crosslinker. The structure of insoluble polymers of the mechanochemical reactions generally is more compact, with fewer and shorter hydrophilic arms than the products of the solution reactions.     

A Plane-Strain Formulation of Elastic-Plastic Constitutive Laws

ABSTRACT

Constitutive laws for elastic-plastic materials are derived by eliminating the transverse stress component on the basis of the plane-strain constraint. This leads to a fictitious hardening and temperature dependence of the loading function. For standard elastic-plastic materials the resulting laws are associated; however, the plastic strain state is represented by equivalent plastic-strain measures, which also account for transverse yielding. The new constitutive laws, together with the standard reduced form of the equilibrium and compatibility equations, permit the formulation of the plane-strain elastic-plastic analysis problem in terms of the in-plane stress components only. In the case of perfectly plastic materials, the subsequent plane-strain yield surfaces are contained within a domain bounded by a limit surface which represents the yield condition normally adopted in plane-strain limit analysis.     

Adulteration of Essential Oils: A Multitask Issue for Quality Control. Three Case Studies: Lavandula angustifolia Mill., Citrus limon (L.) Osbeck and Melaleuca alternifolia (Maiden & Betche) Cheel

The quality control of essential oils (EO) principally aims at revealing the presence of adulterations and at quantifying compounds that are limited by law by evaluating EO chemical compositions, usually in terms of the normalised relative abundance of selected markers, for comparison to reference values reported in pharmacopoeias and/or international norms. Common adulterations of EO consist of the addition of cheaper EO or synthetic materials. This adulteration can be detected by calculating the percent normalised areas of selected markers or the enantiomeric composition of chiral components. The dilution of the EO with vegetable oils is another type of adulteration. This adulteration is quite devious, as it modifies neither the qualitative composition of the resulting EO nor the marker’s normalised percentage abundance, which is no longer diagnostic, and an absolute quantitative analysis is required. This study aims at verifying the application of the two above approaches (i.e., normalised relative abundance and absolute quantitation) to detect EO adulterations, with examples involving selected commercial EO (lavender, bergamot and tea tree) adulterated with synthetic components, EO of different origin and lower economical values and heavy vegetable oils. The results show that absolute quantitation is necessary to highlight adulteration with heavy vegetable oils, providing that a reference quantitative profile is available.     

Multivariate analysis of fMRI time series: classification and regression of brain responses using machine learning

Machine learning and pattern recognition techniques are being increasingly employed in functional magnetic resonance imaging (fMRI) data analysis. By taking into account the full spatial pattern of brain activity measured simultaneously at many locations, these methods allow detecting subtle, non-strictly localized effects that may remain invisible to the conventional analysis with univariate statistical methods. In typical fMRI applications, pattern recognition algorithms "learn" a functional relationship between brain response patterns and a perceptual, cognitive or behavioral state of a subject expressed in terms of a label, which may assume discrete (classification) or continuous (regression) values. This learned functional relationship is then used to predict the unseen labels from a new data set ("brain reading"). In this article, we describe the mathematical foundations of machine learning applications in fMRI. We focus on two methods, support vector machines and relevance vector machines, which are respectively suited for the classification and regression of fMRI patterns. Furthermore, by means of several examples and applications, we illustrate and discuss the methodological challenges of using machine learning algorithms in the context of fMRI data analysis.     

A new approach to the decontamination of asbestos-polluted waters by treatment with oxalic acid under power ultrasound

A suspension of chrysotile asbestos fibres in aqueous 0.5M oxalic acid was subjected to power ultrasound with the aim to disrupt and detoxify the mineral by the leaching action of oxalic acid on its structural cations acting simultaneously with a vigorous acoustic cavitation. Sonication was performed in a "cavitating tube", a vertical hollow vibrating cylinder made of titanium, operating at 19.2 kHz and 150 W. Treatment lasted from 2.5 to 21 h. Scanning electron microscopy (SEM) showed that the joint action of the chelating agent and ultrasound (though not of either when applied independently) mostly converted asbestos fibres into micrometric aggregates and nano-sized debris, whose morphology totally differed from asbestos fibres. When treated suspensions were filtered through CA membranes (pore size 0.20 microm), more than half of the asbestos went through the filter because it had either been brought in solution or dispersed in the form of extremely small particles. Most of the structural metal ions were brought into solution (ICP-AES). After the treatment the BET surface area of the recovered solid was tenfold greater than the original. The crystalline fraction of residual solids, though resembling the original sample in XRD, was shown by micro-Raman spectra to be made of antigorite, a polymorph form of serpentine. Furthermore, as the length of these antigorite fibrils lay outside the fibre range rated as a health hazard under worldwide regulations, our procedure can be employed for the decontamination of chrysotile-polluted waters and sediments.     

Structural insights into methyl‐ or methoxy‐substituted 1‐(α‐aminobenzyl)‐2‐naphthol structures: the role of C—H…π interactions

Aminobenzylnaphthols are a class of compounds containing a large aromatic molecular surface which makes them suitable candidates to study the role of C—H…π interactions. We have investigated the effect of methyl or methoxy substituents on the assembling of aromatic units by preparing and determining the crystal structures of (S,S)‐1‐{(4‐methylphenyl)[(1‐phenylethyl)amino]methyl}naphthalen‐2‐ol, C₂₆H₂₅NO, and (S,S)‐1‐{(4‐methoxyphenyl)[(1‐phenylethyl)amino]methyl}naphthalen‐2‐ol, C₂₆H₂₅NO₂. The methyl group influenced the overall crystal packing even if the H atoms of the methyl group did not participate directly either in hydrogen bonding or C—H…π interactions. The introduction of the methoxy moiety caused the formation of new hydrogen bonds, in which the O atom of the methoxy group was directly involved. Moreover, the methoxy group promoted the formation of an interesting C—H…π interaction which altered the orientation of an aromatic unit.