Improved method for the determination of sulfur components in natural gas

Determination of trace concentrations of sulfur components in natural gas is a true analytical challenge. Only analytical procedures based on gas chromatography can meet the sensitivity and accuracy requirements dictated by environmental regulation institutions and modern chemical industry. In the present contribution the sample pretreatment and chromatographic separation steps have been evaluated and optimized based on the use of a flamebased sulfur chemiluminescence detector (SCD) for target compound detection. The proposed instrument consists of a programmed temperature vaporizing (PTV) injector employing a liner packed with Chromosorb 104, a 4 μm thick film apolar column and a flame-based SCD. Using a 13 mL sample loop the detection limit achievable with the new method is 3 μg S/m³. The precision of replicate measure. ments is generally in the range of 5–15% relative standard deviation. Lower detection limits can be achieved by preconcentrating larger sample volumes, e.g. 100 mL.     

Synthesis, structural, spectroscopic, and electrochemical characterization of high oxidation state diruthenium complexes containing four identical unsymmetrical bridging ligands

Six Ru2(6+) derivatives of the form Ru2(L)4(C[triple bond]CC6H5)(2), where L = 2-Fap, 2,3-F(2)ap, 2,4-F(2)ap, 2,5-F(2)ap, 3,4-F(2)ap, or 2,4,6-F(3)ap, are synthesized and characterized as to their electrochemical, spectroscopic, and/or structural properties. These compounds are synthesized from a reaction between LiC[triple bond]CC6H5 and Ru2(L)4Cl. Two of the investigated complexes exist in a (4,0) isomeric form while four adopt a (3,1) geometric conformation. These two series of geometric isomers are compared with previously characterized (4,0) Ru2(ap)4(C[triple bond]CC6H5)(2), (4,0) Ru2(F5ap)4(C[triple bond]CC6H5)(2), and (3,1) Ru2(F5ap)4(C[triple bond]CC6H5)(2). The overall data on the nine compounds thus provide an opportunity to systematically examine how the electrochemical and structural properties of these Ru2(6+) complexes vary with respect to isomer type and electronic properties of the bridging ligands.     

μ‐{N,N′‐Bis[2‐(dimethyl­amino)ethyl]oxamidato(2–)}‐1κ2O,O′:2κ4N,N′,N′′,N′′′‐bis­(4,4′‐dimethyl‐2,2′‐bipyridine‐1κ2N,N′)dinickel(II) bis­(perchlorate)

In the crystal structure of the title complex, [Ni₂(C₁₀H₂₀N₄O₂)(C₁₂H₁₂N₂)₂](ClO₄)₂ or [Ni(dmaeoxd)Ni(dmbp)₂](ClO₄)₂ {H₂dmaeoxd is N,N′‐bis­[2‐(dimethyl­amino)ethyl]oxamide and dmbp is 4,4′‐dimethyl‐2,2′‐bipyridine}, the deprotonated dmaeoxd²⁻ ligand is in a cis conformation and bridges two Ni^II atoms, one of which is located in a slightly distorted square‐planar environment, while the other is in an irregular octa­hedral environment. The cation is located on a twofold symmetry axis running through both Ni atoms. The dmaeoxd²⁻ ligands inter­act with each other via C—H⋯O hydrogen bonds and π–π inter­actions, which results in an extended chain along the c axis.     

Electrochemical and spectroelectrochemical characterization of Ru(2)(4+) and Ru(2)(3+) complexes under a CO atmosphere

Eleven different Ru(2)(4+) and Ru(2)(3+) derivatives are characterized by thin-layer FTIR and UV-visible spectroelectrochemistry under a CO atmosphere. These compounds, which were in-situ electrogenerated from substituted anilinopyridine complexes with a Ru(2)(5+) core, are represented as Ru(2)(L)(4)Cl where L = 2-CH(3)ap, ap, 2-Fap, 2,3-F(2)ap, 2,4-F(2)ap, 2,5-F(2)ap, 3,4-F(2)ap, 3,5-F(2)ap, 2,4,6-F(3)ap, or F(5)ap. The Ru(2)(5+) complexes do not axially bind CO while mono- and bis-CO axial adducts are formed for the Ru(2)(4+) and Ru(2)(3+) derivatives, respectively. Six of the eleven investigated compounds exist in a (4,0) isomeric form while five adopt a (3,1) geometric conformation. These two series of compounds thus provide a large enough number of derivatives to examine trends and differences in the spectroscopic data of the two types of isomers in their lower Ru(2)(4+) and Ru(2)(3+) oxidation states. UV-visible spectra of the Ru(2)(4+) derivatives and IR spectra of the Ru(2)(3+) complexes under CO are both isomer dependent, thus suggesting that these data can be used to reliably predict the isomeric form, i.e., (3,1) or (4,0), of diruthenium complexes containing four unsymmetrical substituted anilinopyridinate bridging ligands; this was confirmed by X-ray crystallographic data for seven compounds whose structures were available.     

Direct determination of rare earth impurities in high purity erbium oxide dissolved in nitric acid by inductively coupled plasma mass spectrometry

A novel method was developed for the direct determination of trace quantities of rare earth elements (REEs) in high purity erbium oxide dissolved in nitric acid by inductively coupled plasma mass spectrometry (ICP-MS) in this work. The mass spectra overlap interferences arose from Er matrix on the neighbouring and monoisotopic analytes of ¹⁶⁵Ho(100) and ¹⁶⁹Tm(100) were eliminated by adjusting instrumental peak resolution value from 0.7 to 0.3 amu. The matrix suppression effect of Er on the ion peak signals of REEs impurities was effectively compensated with spiking In as internal standard element. The limit of quantitation (LOQ) of REEs impurities was from 0.0090 to 0.025 μg g⁻¹, the recoveries of spiked sample for REEs were found to be in the range of 90.3-107% through using the proposed method and relative standard deviation (R.S.D.) varied between 2.5% and 6.7%. The novel methodology had been found to be suitable for the direct determination of trace REEs impurities in 99.999-99.9999% high purity Er₂O₃ and the results obtained from this method keep in good agreement with that acquired from high resolution ICP-MS.     

Monitoring intracellular proteins using fluorescence techniques: from protein synthesis and localization to activity

The recent breakthroughs in genomics and proteomics and improvements of optical methods have made it possible to obtain localized, real-time information on intracellular proteins dynamics, through dynamic three-dimensional (3D) maps of the living cell with nanometric resolution of individual molecules. On one side, brighter variants of the Green Fluorescence Protein (GFP) have been engineered that have different excitation and/or emission spectra that better match available light sources. Like their parent molecule, these variants retain their fluorescence when fused to heterologous proteins on the N- and C- terminals, and this binding generally does not affect the functionality of the tagged protein leading the way to their use as an intracellular reporter. On the other side, optical methods have been improved to allow reaching the level of single-molecule detection inside living cells. Nevertheless some limitations exist for the use of GFP variants for probing 3D conformational changes of proteins. First, these variants are fused to the N and/or C terminals of the studied protein, which are generally not the best location to detect conformational changes resulting from the binding to other proteins or enzyme substrates. Then their own relatively large size makes them unusable for tagging small proteins. These limitations suggest that new tagging processes, permitting the location of the right fluorescent markers at the right places, must be found to built up inter- and/or intra-molecular rulers allowing one to monitor conformational changes resulting from intracellular protein-protein, protein-membrane, and enzyme-substrate binding. These specific locations can be obtained from in vitro studies of 3D conformational changes that occur during protein docking.     

Pyrrolopyridine analogs of nalidixic acid. 1. Pyrrolo[2,3-b]pyridines

A series of 4,7-dihydro-4-oxo-1H-pyrrolo[2,3-b]pyridine-5-carboxylic acids was synthesized from ethyl 5-methyl(or 5H)-2-aminopyrrole-3-carboxylate. The starting pyrroles were obtained by reaction of carbethoxyacetamidine with bromoacetone or chloroacetaldehyde. One compound ( 10 ) showed antibacterial activity in vitro.     

Conversion of 3-benzoyl-1-methyl-4-phenyl-γ-piperidol by arylamines and arylhydrazines. Synthesis of 3-arylamino-1-oxo-1-phenylpropanes and 1,3-diarylpyrazoles and their fragmentation under electron impact

It has been established that on heating, 3-benzoyl-4-hydroxy-1-methyl-4-phenylpiperidine is ring-opened in the presence of arylamines by a type of retroaldol reaction, with subsequent transamination of the intermediate Mannich base and the formation of 3-arylamino-1-oxo-1-phenylpropanes. When using arylhydrazines this γ-piperidol is recyclized with the formation of 1,3-diarylpyrazoles and their 4,5-dihydro derivatives. The mass spectral behavior of a series of 3-arylamino-substituted 1-phenylpropanones has been studied. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1486–1495, October, 2007.     

用硼酸作催化剂一锅法合成双（二氢化嘧啶酮-4-基）苯

A simple effective synthesis of bis(dihydropyrimidinone-4-yl)benzene derivatives, using boric acid as catalyst,from isophthalic aldehyde or terephthalic aldehyde, 1,3-dicarbonyl compounds and urea or thiourea in glacial acetic acid was described. As the expansion of the classical Biginelli reaction, this method has the advantage of excellent yields 83%-94% and short reaction time 0.5-1.5 h.