Evaluation of inductively coupled plasma optical emission spectrometers with axially and radially viewed configurations

The analytical performance of two inductively coupled plasma optical emission spectrometers with axially and radially viewed configurations, equipped with charge coupled device solid-state detectors was evaluated using Ar, Ba, Mg, and Ni as test elements. Both instruments have similar Echelle optical arrangements and radio-frequency generators, differing only in the viewing mode and in the diameter of the central injector tube, i.e. 2.3 for the axially and 1.4 mm for the radially viewed ICP. The figures of merit evaluated were: warm-up time, short- and long-term stabilities, UV and VIS spectral resolution and limit of detection (LOD) for Ni in 0.14 mol l⁻¹ HNO₃ and 1000 mg l⁻¹ Cr media, respectively. The influence of residual carbon content on background equivalent concentration (BEC) and sensitivity attained for Al, As, Ca, Cd, Co, Cr, Cu, Fe, Mg, Mn, Se and Zn was also investigated in both viewing modes. The robustness, short- and long-term stabilities, and UV and VIS spectral resolutions were similar for both configurations. For the radially viewed equipment, the warm-up time was at least a factor of 2 shorter than that for the axially viewed configuration. On the other hand, the sensitivity attained for Ni with the axially viewed arrangement was approximately 20 times better than that with the radially viewed. In both viewing modes, and for most of the evaluated elements, the values of BEC and LOD were similar for all studied carbon concentrations (from 10 to 10 000 mg l⁻¹ C) when working with robust plasma conditions. The Mg II/Mg I ratio at an applied power of 1.3 kW and a nebulizer gas flow-rate of 0.90 and 0.70 l min⁻¹ for axially and radially viewed configurations were 10.6 and 13.7, respectively. Quantitative determinations were successfully performed using both systems.     

Copper(II) and nickel(II) metallopolymers derived from polyacylhydrazones

A series of polyacylhydrazones derived from condensing diacetyl with oxalic, malonic, succinic, glutaric and adipic dihydrazides was prepared, characterized and reacted with copper(II) and nickel(II) acetate to give metallopolymers of general formula [Cu₂(L)(AcO)₂(OH)(H₂O)₂] · yH₂O _n , [Cu(L)(AcO)(HO)(H₂O)] · yH₂O _n , [Ni₂(L)(AcO)₂-(HO)₂] · yH₂O _n and [Ni(L)(AcO)(HO)] · yH₂O _n , where L refers to the neutral dihydrazone unit. Magnetic susceptibility measurements in the 4.2–300 K range indicate significant antiferromagnetic coupling between the Cu^II centers in the metallopolymers, which may indicate the presence of two polymer chains crosslinked by bis--acetatocopper(II) bridges. Based on i.r., spectral and magnetic measurements, tentative structures of the Cu^II and Ni^II metallopolymers have been proposed. The dihydrazone units in these polymers are coordinated to the metal(II) via the azomethine nitrogen(s) whereas the amide group remains uncoordinated. Each Cu^II is penta-coordinated in a distorted square pyramidal environment and is neutralized by one bridged acetate and a hydroxide ion, while the fifth coordination site is occupied by a water molecule. In the nickel(II) metallopolymers the metal ions are in a tetrahedral environment and are coordinated to azomethine nitrogen, two bridged acetate oxygens and to the hydroxide ion.     

Stereoselective Synthesis of HIV-1 Protease Inhibitor, DMP 323

DMP 323, a potent HIV-1 protease inhibitor, has been synthesized by an efficient stereoselective process, amenable to large scale preparations. The core C(2) symmetric diol was synthesized by a stereoselective pinacol coupling of CBZ protected D-phenylalanine. Judicious selection of protecting groups allowed cyclic urea formation under mild conditions, enhanced the ease of bis-alkylation, and led to intermediates which were easily purified without chromatography. Additionally, a one-pot, high yield process was developed to prepare the alkylating agent, 4-[(triphenylmethoxy)methyl]benzyl chloride from 1,4-benzenedimethanol.     

119Sn-Mössbauer spectroscopic studies on organoheterobimetallic half sandwich ruthenium–tin containing derivatives

A series of heterobimetallic complexes containing Ru–Sn bonds, of general formula [RuCp(L)₂SnX₂Y] [L = PPh₃, 1/2 dppe = 1,2-bis(diphenylphosphino)ethane; X, Y = F, Cl and Br], was prepared and studied by elemental analysis, ¹¹⁹Sn-Mössbauer spectroscopy, i.r. and ¹H-, ¹³C-, ¹⁹F-, ³¹P- and ¹¹⁹Sn-n.m.r. spectroscopy. ¹¹⁹Sn-Mössbauer studies allowed determination of the coordination number of the Sn^II center as well as the group electronegativity of the organometallic fragment [RuCp(L)₂]⁺. These results, supported by multinuclear n.m.r. data suggested that the electronic charge distribution between the Ru^II and Sn^II centers are strongly dependant upon the nature of L and the electronegativity of X and Y.     

Total synthesis of the thiopeptide antibiotic amythiamicin D

The thiopeptide (or thiostrepton) antibiotics are a class of sulfur containing highly modified cyclic peptides with interesting biological properties, including reported activity against MRSA and malaria. Described herein is the total synthesis of the thiopeptide natural product amythiamicin D, which utilizes a biosynthesis-inspired hetero-Diels-Alder route to the pyridine core of the antibiotic as a key step. Preliminary studies using a range of serine-derived 1-ethoxy-2-azadienes established that hetero-Diels-Alder reaction with N-acetylenamines proceeded efficiently under microwave irradiation to give 2,3,6-trisubstituted pyridines. The thiazole building blocks of the antibiotic were obtained by either classical Hantzsch reactions or by dirhodium(II)-catalyzed chemoselective carbene N-H insertion followed by thionation, and were combined to give the bis-thiazole that forms the left-hand fragment of the antibiotic. The key Diels-Alder reaction of a tris-thiazolyl azadiene with benzyl 2-(1-acetylaminoethenyl)thiazole-4-carboxylate gave the core tetrathiazolyl pyridine, which was elaborated into the natural product by successive incorporation of glycine and bis-thiazole fragments followed by macrocyclization.     

Characterization of dislocation interactions in olivine using electron tomography

We have investigated by electron tomography, in a transmission electronic microscope, the interactions between dislocations in olivine single crystals and polycrystals deformed in axial compression at T < 1000 °C (T < 0.5T_m). Dislocations are mostly of the [0?0?1] type, except in the polycrystal where [1?0?0] and [0?0?1] dislocations have been activated. A few 〈1?0?1〉 junctions have been found and characterized. Many collinear interactions have been identified either involving direct interactions between crossing dislocations of opposite Burgers vectors or indirect interactions between dislocations gliding in parallel planes and sessile dislocation loops. We suggest that collinear interaction, already identified as the primary source of strain hardening in FCC metals, is the main dislocation interaction mechanism in olivine deformed at temperatures below 1000 °C.     

Retention in overloaded columns, an experimental approach

Employing a micro-bore silica capillary coated with Carbowax 20 M, the dependence of chromatographic retention upon operative variables was studied surpassing the sample capacity of the column. Solution thermodynamics in the non-linear range of the absorption isotherm of n-alkanes on poly(ethylene oxide) were analyzed interpreting the experimental data through a retention equation deduced in a preceding theoretical work. At 120 degrees C, and pressures up to 11 bar abs, deviations from the ideal-gas behavior are found to be negligible, either for the fluid dynamics of the carrier-gas, or the thermodynamics of solution of the n-alkanes. Within the experimental error, for all practical purposes the mobile phase can be treated as an ideal gas. This constraint allows studying a solute molecule placed in an environment ranging from solvent monomers only, to a mixture of varying composition of solvent and solute, avoiding effects from significant interactions in the gas phase. In the experimental conditions explored, the absorption isotherm can be represented by taking only two-terms of its power series development.     

New synthesis strategies for effective functionalization of kaolinite and saponite with silylating agents

Functionalization of Brazilian São Simão kaolinite and Spanish Yunclillos saponite with the alkoxysilanes 3-aminopropyltriethoxysilane and 3-mercaptopropyltrimethoxysilane is reported. The resulting hybrids were characterized by X-ray diffraction, thermal analysis, infrared absorption spectroscopy, and scanning electron microscopy, which demonstrated the effectiveness of the interlamellar grafting process. The X-ray diffractograms revealed incorporation of the alkoxide molecules into the interlayer space of the clays. The displacement of the stretching bands of interlayer hydroxyls in the infrared spectra of the modified kaolinites and the increased intensity of the Mg–OH vibrations in the spectra of the modified saponites confirmed the functionalization of the clays. The thermal behavior of the organoclays confirmed the stability of the hybrids, which was dependent on the clay used for preparation of the materials.     

Factors Influence Complexing Selectivity of Lariat Crown Ethers Toward Alkali Metal Ions in Electrospray Ionization Mass Spectrometry

The selectivity of eight lariat crown ethers in the sym‐dibenzo‐16‐crown‐5 series toward alkali metal ions was studied with electrospray ionization mass spectrometry under different conditions. With the exception of 2g , which is equally selective toward Na⁺ and Li⁺, all other lariat crown ethers show the best selectivity toward Li⁺ in methanol. Factors that influence the selectivity include the water content, counterions, nature of the side arms, and the externally added cations. Iodide gives the best Na⁺ selectivity with R_I > R_Br > R_Cl. Increased water content profoundly increases the Na⁺ selectivity when the side arm is hydrophilic and the steric hindrance is small. Externally added cations (Cs⁺ and/or Rb⁺) enhance the Na⁺ selectivity by exchanging the smaller Li⁺ from the cavity.