Stereoselective sp-sp bond formation via Negishi cross-coupling of vinylic tellurides and 2-heteroarylzinc chlorides

The Negishi cross-coupling reaction of vinylic- and aryltellurides with heteroarylzinc chlorides catalyzed by PdCl₂/CuI is described. This cross-coupling reaction is general and permits the formation of a new sp²-sp² carbon bond in good yields and high stereoselectivity.     

Chemical Approach to the Optimization of Conditions Using HS-SPME/GC–MS for Characterization of Volatile Compounds in Eugenia brasiliensis Fruit

Grumixama (Eugenia brasiliensis Lam.) is a native fruit of the Brazilian Atlantic Forest, belonging to the Myrtaceae family, which designatesthe most significant number of species with food potential. It stands out due to its phytochemical characteristics because of the presence of polyphenols and volatile organic compounds. Volatile compounds are substances released by foods that give off an aroma and influence flavor. Solid-phase microextraction is a technique that allows for low-cost, fast, and solvent-free extraction, has an affinity for numerous analytes, and is easily coupled to gas chromatography. The objectives of this work were to evaluate the efficiency of different fibers of SPME (solid-phase microextraction) in the extraction of volatile organic compounds from grumixama pulp; optimize a method for extraction time, temperature, and sample weight; and to determine the characteristic volatile profile of this fruit. For the extraction of volatile compounds, three fibers of different polarities were used: polar polyacrylate (PA) fibers, divinylbenzene/carboxyne/polydimethylsiloxane (DVB/CAR/PDMS) semipolar fibers, and polydimethylsiloxane/divinylbenzene (PDMS/DVB). Fourteen volatile organic compounds (VOCs) were identified by DVB/CAR/PDMS, six by PA, and seven by PDMS/DVB through solid-phase microextraction in the headspace mode (SPME-HS). Considering the total number of compounds identified, regardless of the fiber used, and the optimization of the method, Eugenia brasiliensis presented sesquiterpene fractions (85.7%, 83.3%, and 85.7% of total VOCs) higher than the monoterpene fractions (14.3%, 16.7%, and 14.3%) for DVB/CAR/PDMS, PA, and PDMS/DVB, respectively in its composition. In addition, it was possible to verify that the fiber DVB/CAR/PDMS presented a better efficiency due to the larger chromatographic area observed when the grumixama pulp was subjected to conditions of 75 °C, 2.0 g, and an adsorption time of 20 min.     

Pulsed Nd:YAG laser welding of AISI 304 to AISI 420 stainless steels

The technique to weld AISI 304 stainless steel to AISI 420 stainless steel with a pulsed Nd:YAG laser has been investigated. The main objective of this study was to determine the influence of the laser beam position, with respect to the joint, on weld characteristics. Specimens were welded with the laser beam incident on the joint and moved 0.1 and 0.2 mm on either side of the joint. The joints were examined in an optical microscope for cracks, pores and to determine the weld geometry. The microstructure of the weld and the heat affected zones were observed in a scanning electron microscope. An energy dispersive spectrometer, coupled to the scanning electron microscope, was used to determine variations in (weight %) the main chemical elements across the fillet weld. Vickers microhardness testing and tensile testing were carried out to determine the mechanical properties of the weld. The results of the various tests and examinations enabled definition of the best position for the incident laser beam with respect to the joint, for welding together the two stainless steels.     

Optical studies of ZnO nanocrystals doped with Eu3+ ions

Synthetic ZnO nanocrystals have been intentionally doped with Eu³⁺ ions. Structural analysis performed on the nanocrystals showed wurtzite-ZnO as the only phase present in the samples. Photoluminescence in emission and excitation modes allows the assignment of the intra-4f⁶ transitions for the Eu³⁺ ions. From the analysis of the optical data we are able to demonstrate that multiple Eu-related optical centres are present in the studied samples. Oxygen vacancies are likely candidates to be responsible for the ion accommodation in the ZnO lattice and from the photoluminescence excitation data we tentatively assign a trap level at ∼200 meV below the conduction band to this intrinsic defect. PACS 78.66.Hf; 78.67.-n; 82.80.Yc     

Ion synthesis and optical properties of gold nanoparticles in an Al2O3 matrix

Single-crystal Al₂O₃(0001) and Al₂O₃(1120) substrates are implanted by 160-keV Au⁺ ions with doses from 10¹⁵ to 10¹⁷ cm^?2. Some of the implanted samples are air-annealed at 800–1200°C. The properties of the synthesized composite layers are studied by Rutherford backscattering and linear optical reflection measurements, and their nonlinear optical characteristics are examined by RZ-scanning using a picosecond Nd: YAG laser operating at a wavelength of 1064 nm. The Rutherford backscattering spectra indicate that the implanted impurity concentrates near the surface of the Al₂O₃. The formation of gold nanoparticles in the Al₂O₃ can be judged from the characteristic optical plasmon resonance band in the reflectance spectra of the samples irradiated to a dose higher than 6.0 × 10¹⁶ cm^?2. The synthesized particles are shown to be responsible for nonlinear optical refraction in the samples. The nonlinear refractive index, n ₂, and the real part of the third-order susceptibility, Rex⁽³⁾, of the composite layers are determined.     

The structure of crystallographic damage in GaN formed during rare earth ion implantation with and without an ultrathin AlN capping layer

The crystallographic nature of the damage created in GaN implanted by rare earth ions at 300 keV and room temperature has been investigated by transmission electron microscopy versus the fluence, from 7×10¹³ to 2×10¹⁶ at/cm², using Er, Eu or Tm ions. The density of point defect clusters was seen to increase with the fluence. From about 3×10¹⁵ at/cm², a highly disordered ‘nanocrystalline layer’ (NL) appears on the GaN surface. Its structure exhibits a mixture of voids and misoriented nanocrystallites. Basal stacking faults (BSFs) of I₁, E and I₂ types have been noticed from the lowest fluence, they are I₁ in the majority. Their density increases and saturates when the NL is observed. Many prismatic stacking faults (PSFs) with Drum atomic configuration have been identified. The I₁ BSFs are shown to propagate easily through GaN by folding from basal to prismatic planes thanks to the PSFs.When implanting through a 10 nm AlN cap, the NL threshold goes up to about 3×10¹⁶ at/cm². The AlN cap plays a protective role against the dissociation of the GaN up to the highest fluences. The flat surface after implantation and the absence of SFs in the AlN cap indicate its high resistance to the damage formation.     

Voltammetric studies of the interaction between lead metal ion and the methyl parathion pesticide

Journal of Solid State Electrochemistry - In this work, the interaction of the pesticide methyl parathion (MP) with the lead metal ion was evaluated using a carbon electrode reused from a zinc...     

13C NMR quantification of mono and diacylglycerols obtained through the solvent‐free lipase‐catalyzed esterification of saturated fatty acids

In the present investigation, we studied the enzymatic synthesis of monoacylglycerols (MAG) and diacylglycerols (DAG) via the esterification of saturated fatty acids (stearic, palmitic and an industrial residue containing 87% palmitic acid) and glycerol in a solvent‐free system. Three immobilized lipases (Lipozyme RM IM, Lipozyme TL IM and Novozym 435) and different reaction conditions were evaluated. Under the optimal reaction conditions, esterifications catalyzed by Lipozyme RM IM resulted in a mixture of MAG and DAG at high conversion rates for all of the substrates. In addition, except for the reaction of industrial residue at atmospheric pressure, all of these products met the World Health Organization and European Union directives for acylglycerol mixtures for use in food applications. The products were quantified by ¹³C NMR, with the aid of an external reference signal which was generated from a sealed coaxial tube filled with acetonitrile‐d3. After calibrating the area of this signal using the classical external reference method, the same coaxial tube was used repeatedly to quantify the reaction products. Copyright © 2012 John Wiley & Sons, Ltd.