Structural Aspects of Copper‐Mediated Atom Transfer Radical Polymerization with a Novel Tetradentate Bisguanidine Ligand

This contribution reports the synthesis of the novel tetradentate bisguanidine ligand 2′,2′‐[ethane‐1, 2‐diylbis(methylazanediyl)]bis(ethane‐2, 1‐diyl)bis(1, 1, 3, 3‐tetramethylguanidine) ( L1 , TMG₂dmtrien), which combines two weak amine and two strong guanidine donor functions. Two new copper(II) complexes were isolated and structurally characterized as complexes [Cu(TMG₂dmtrien)][Br]₂ · 3MeCN ( C1 [Br]₂ · 3MeCN) and [Cu(TMG₂dmtrien)][Cl]₂ · 3MeCN ( C2 [Cl]₂ · 3MeCN). The cations C1 and C2 [Cu(TMG₂dmtrien)]²⁺ show a square‐planar coordination environment and are chiral with both enantiomers being observed in the unit cell. We investigated the application of L1 in copper‐mediated styrene ATRP. L1 shows with CuBr and PEBr as initiator a high polymerization activity according to the polymerization rate. First order kinetics confirm the living character of the polymerization. However, the deviation of molecular weights from theoretical molecular weights and the broad molecular weight distributions hint for a low controlled ATRP. The ATRP with further copper(I) salts {CuCl, [Cu(MeCN)₄]BF₄ and [Cu(MeCN)₄]PF₆} and PECl and PEBr as initiators were investigated as well. Herein the use of [Cu(MeCN)₄]PF₆ with PECl led to promising results.     

Determination of quinolones in milk samples using a combination of magnetic solid-phase extraction and capillary electrophoresis

A magnetic solid-phase extraction (MSPE) method combined with capillary electrophoresis for the simultaneous determination of seven quinolones (QNs) (danofloxacin, ciprofloxacin, marbofloxacin, enrofloxacin, difloxacin, oxolinic acid, and flumequine), using (S)-(+)-6-methoxy-α-methyl-2-naphthaleneacetic acid as internal standard, in milk samples was developed. The variables involved in the preconcentration magnetic procedure were: the composition of the magnetic support composition, the sample pH, and the weight of magnetic adsorbent used. The variables were optimized using a simplex-lattice design. Different magnetite covered with octyl-phenyl silica adsorbents were synthesized by varying the molar ratio of phenyltrimethylsilane and octyltrimethoxysilane; the solids were evaluated for QN preconcentration. Under optimal conditions, a linear range was obtained from 27 to 1000 μg L(-1) with limits of detection ranging from 9 to 12 μg L(-1) for the seven QNs. The absolute recoveries of the seven QNs at three different spiked levels (40, 150, and 400 μg L(-1) ) ranged from 74% to 98% with a relative standard deviation less than 10% in all cases. The proposed method was applied to analyze 20 whole milk samples of different brands. All samples were positive for the presence of QN residues; in some cases, extract dilution was required. The concentrations found are in the range from 31.1 to 5047.3 μg L(-1) . Marbofloxacin was the most frequently found. The method proposed offers advantages in terms of simplicity, sensitivity, efficiency, cost, and analysis time making it an alternative for the analysis of QNs in whole milk samples.     

Characterization of Polyurethanes from Vegetable Oils by TG/DTG,DMA and FT-IR

Summary: Given the demand for renewable resources by industries and the promising potential of vegetable oils for this purpose, the current study aims to evaluate the properties of polyurethanes (PUs) obtained from linseed (Linum usitatissimun L.) oil (PULO) and passion fruit (Passiflora edulis Sims f. flavicarpa Degener) oil (PUPFO), by thermogravimetry (TG), derivative thermogravimetry (DTG), dynamic mechanical analysis (DMA) and Fourier transform infrared (FT-IR). The results showed that PULO is more thermally stable than PUPFO, suggesting that the first presents more urethane linkages. The DMA analysis showed that both prepared PUs have uneven porosity, causing the loss of the elastic plateau. It was found as well that PUPFO exhibits a higher value of glass transition temperature (T_g), signifying that it seems to be more crosslinked than PULO. The analysis by FT-IR showed that the curing reaction of PUs was successful.     

Electrochemical Determination of Inorganic Contaminants in Automotive Fuels

This article critically reviews the electroanalytical methods developed for the determination of inorganic contaminants in automotive fuels. Topics include the methods applied to the analysis of liquid biofuels and liquid fossil fuels for which different strategies were developed based on analytes and sample matrices. Special attention is given to electrodes, detection techniques, and sample preparation protocols (when required). Analytes include anions such as chloride, sulfate and phosphate, and mainly metallic species such as sodium, potassium, magnesium, calcium, cadmium, copper, iron, lead, manganese, mercury, nickel, platinum, tin, vanadium, and zinc. Suggestions for future research are also presented.     

Super impact strength of blends prepared from regular HIPS and poly(butyl acrylate)‐block‐poly(styrene) obtained by RAFT polymerization

S‐allyl‐4‐methyldithiobenzoate was synthesized and used as a chain transfer agent for the RAFT polymerization of butyl acrylate to produce a functionalized acrylic rubber. A solution of 8 wt% of this functionalized rubber was prepared in styrene and polymerized to generate a material called acrylic rubber‐modified polystyrene (AMP) constituted by well‐dispersed particles of poly(butyl acrylate)‐block‐poly(styrene) into a polystyrene matrix. Impact strength of injection‐molded samples of AMP was measured and compared with the general purpose polystyrene (GPPS) and the high impact polystyrene (HIPS). AMP itself showed an impact strength value similar to GPPS; however, when AMP was blended with conventional HIPS, the resulting material exhibited an improvement of 76–91% as compared to HIPS by itself, without affecting negatively tensile properties. Transmission electron microscopy analysis revealed both kinds of dispersed phases, i.e. the typical salami particles of polybutadiene coming from HIPS (size: 0.5–2 µ) and small particles from poly(butyl acrylate)‐block‐poly(styrene) (size: ～50 nm). We clearly showed that such a bimodality of the particle size distribution caused the positive synergistic effect on impact strength. Copyright © 2011 John Wiley & Sons, Ltd.     

TOF‐SIMS study of cystine and cholesterol stones

Two different human stones, cystine and cholesterol from the kidney and gall bladder, were examined by time‐of‐flight secondary ion mass spectrometry using Ga⁺ primary ions as bombarding particles. The mass spectra of kidney stone were compared with those measured for the standard compounds, cystine and cysteine. Similar spectra were obtained for the stone and cystine. The most important identification was based on the existence of the protonated molecules [M + H]⁺ and deprotonated molecules [M‐H]^‐. The presence of cystine salt was also revealed in the stone through the sodiated cystine [M + Na]⁺ and the associated fragments, which might be due to the patient treatment history. In the gallstone, the deprotonated molecules [M‐H]⁺ of cholesterol along with relatively intense characteristic fragments [M‐OH]⁺ were detected. Copyright © 2012 John Wiley & Sons, Ltd.     

Performance of Compton suppression system (CSS) and applicability in food matrices

As a non-destructive and multi-element technique, with high-level metrological properties, instrumental neutron activation analysis (INAA) has an important role to determine chemical elements in food. However, its use may be limited when looking for mass fractions near the detection limits. The Compton scattering of higher energy gamma-rays raised the spectrum baseline thus impairing the determination of several elements. Therefore, the gamma-ray spectrometry with Compton suppression becomes an alternative for improving the performance of INAA, since it can reduce the uncertainty of measurements and the detection limits by increasing the proportion between photopeak area and baseline. Here the performance of a Compton suppression system set by Ortec, with 50% relative efficiency and 2.04?keV resolution (FWHM) for the 1,332?keV photopeak, was evaluated for food analysis. Samples of beans, chickpeas, lentils, peas, and rice were irradiated with neutrons and measured in the suppression system. Detection limits calculated from suppressed and unsuppressed spectra were compared. The suppression factor achieved by the system for ¹³⁷Cs was 5.88?±?0.11 (n?=?20) in the plateau region (358 to 382?keV), which was stable along a 20?week period and similar to the data provided in literature for other systems. Amongst fifteen elements determined, the detection limits for Br, Co, La, Na, Sc, and Se were not improved by the use of Compton suppression. On the other hand, the variable improvement obtained for As, Ca, Cd, Cr, Fe, Hg, K, Rb, and Zn corroborated the idea that the performance of the Compton suppressor must be individually assessed for each type of sample.     

Synthesis, magnetostructural correlation, and catalytic promiscuity of unsymmetric dinuclear copper(II) complexes: models for catechol oxidases and hydrolases

Herein, we report the synthesis and characterization, through elemental analysis, electronic spectroscopy, electrochemistry, potentiometric titration, electron paramagnetic resonance, and magnetochemistry, of two dinuclear copper(II) complexes, using the unsymmetrical ligands N',N',N-tris(2-pyridylmethyl)-N-(2-hydroxy-3,5-di-tert-butylbenzyl)-1,3-propanediamin-2-ol (L1) and N',N'-bis(2-pyridylmethyl)-N,N-(2-hydroxybenzyl)(2-hydroxy-3,5-di-tert-butylbenzyl)-1,3-propanediamin-2-ol (L2). The structures of the complexes [Cu(2)(L1)(μ-OAc)](ClO(4))(2)·(CH(3))(2)CHOH (1) and [Cu(2)(L2)(μ-OAc)](ClO(4))·H(2)O·(CH(3))(2)CHOH (2) were determined by X-ray crystallography. The complex [Cu(2)(L3)(μ-OAc)](2+) [3; L3 = N-(2-hydroxybenzyl)-N',N',N-tris(2-pyridylmethyl)-1,3-propanediamin-2-ol] was included in this study for comparison purposes only (Neves et al. Inorg. Chim. Acta2005, 358, 1807-1822). Magnetic data show that the Cu(II) centers in 1 and 2 are antiferromagnetically coupled and that the difference in the exchange coupling J found for these complexes (J = -4.3 cm(-1) for 1 and J = -40.0 cm(-1) for 2) is a function of the Cu-O-Cu bridging angle. In addition, 1 and 2 were tested as catalysts in the oxidation of the model substrate 3,5-di-tert-butylcatechol and can be considered as functional models for catechol oxidase. Because these complexes possess labile sites in their structures and in solution they have a potential nucleophile constituted by a terminal Cu(II)-bound hydroxo group, their activity toward hydrolysis of the model substrate 2,4-bis(dinitrophenyl)phosphate and DNA was also investigated. Double electrophilic activation of the phosphodiester by monodentate coordination to the Cu(II) center that contains the phenol group with tert-butyl substituents and hydrogen bonding of the protonated phenol with the phosphate O atom are proposed to increase the hydrolase activity (K(ass.) and k(cat.)) of 1 and 2 in comparison with that found for complex 3. In fact, complexes 1 and 2 show both oxidoreductase and hydrolase/nuclease activities and can thus be regarded as man-made models for studying catalytic promiscuity.     

A scheme for synchronizing clocks connected by a packet communication network

Consider a communication system in which a transmitter equipment sends fixed-size packets of data at a uniform rate to a receiver equipment. Consider also that these equipments are connected by a packet-switched network, which introduces a random delay to each packet. Here we propose an adaptive clock recovery scheme able of synchronizing the frequencies and the phases of these devices, within specified limits of precision. This scheme for achieving frequency and phase synchronization is based on measurements of the packet arrival times at the receiver, which are used to control the dynamics of a digital phase-locked loop. The scheme performance is evaluated via numerical simulations performed by using realistic parameter values.     

The Moduli Space of Complex Geodesics in the Complex Hyperbolic Plane

We consider the space M\mathcal{M} of ordered m-tuples of distinct complex geodesics in complex hyperbolic 2-space, H_\mathbbC²{\rm\bf H}_{\mathbb{C}}^{2}, up to its holomorphic isometry group PU(2,1). One of the important problems in complex hyperbolic geometry is to construct and describe the moduli space for M\mathcal{M}. This is motivated by the study of the deformation space of groups generated by reflections in complex geodesics. In the present paper, we give the complete solution to this problem.