Rapid separation of phenylthiohydantoin amino acids: ambient pressure ion-mobility mass spectrometry (IMMS)

An electrospray ionization (ESI) ambient pressure ion-mobility spectrometer (APIMS) interfaced to an orthogonal reflector time-of-flight mass spectrometer (TOFMS) was evaluated for the first time as a detector for the identification of phenylthiohydantoin (PTH)-derivatized amino acids, the final products in the Edman sequencing process of peptides and proteins. The drift and flight times of the twenty common PTH amino acids were characterized by a well-defined 2-D mobility/mass spectral pattern. The combination of mobility/mass modes of analysis gave rise to a unique trend-line formation for the series of PTH amino acids. In addition, each PTH amino acid had a unique reduced mobility constant K(o), thus enabling the differentiation of all the amino acid derivatives including the PTH-leucine and PTH-isoleucine isomers. More importantly it was shown that it was possible to resolve a complete reference mixture of PTH amino acids in a single experimental run in less than 1 min. Detection limits for the PTH amino acids were found to range from 1.04 to 3.52 ng; indicating that the limits of detection were less than 17.0 pmol for all of the PTH amino acids.     

Synthesis,crystal structure and luminescent property of a novel H<Subscript>2</Subscript>O-bridged cobalt(II) polymer with one-dimensional chain structure

The coordination compound [Co(C₁₀H₇COO)₂(H₂O)₃]_2n · 4nH₂O was prepared by the reaction of 1-naphthoic acid and cobalt(II) acetate tetrahydrate in basic solution, and was fully characterized by X-ray diffraction, element analysis, FTIR, TG-DTA and luminescent spectra. In the crystal the six-coordinated Co(II) centers are linked into one-dimensional zigzag chains by water molecules, which are further assembled into a two-dimensional network through weak inter-chain C–H···π interactions. The solid complex exhibits favorable fluorescent properties similar to those of free ligand at room temperature, which can be assigned to the intraligand electronic transfer.     

Voltammetry and electrocatalytic properties of cobalt (1,4,8,12-tetraazacyclopentadecane) in aqueous solution

Summary The spectrochemical, electrochemical and electrocatalytic properties of Co[15]aneN₄ ([15]aneN₄ = 1,4,8,12-tetraazacyclopentadecane) have been investigated. The results show that, in aqueous solution, this compound mainly exists as three species whose axial coordination positions are occupied by water and/or hydroxy ligands; it is marginal whether other substrates such as Cl^– and NO _inf3 ^sup– interact with the central ion in acid-base solutions. The approximate Pourbaix diagram of Co^III/II[15]ane N₄ was determined. There is an electrochemically-induced isomerization between two trans conformational isomers of the Co[15]aneN₄ complexes in acid and netural solutions. The Co[15]aneN₄ complex has electrocatalytic properties for reduction of nitrate and nitrite only in strong alkaline solution.     

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.     

Chitosan-mediated and spatially selective electrodeposition of nanoscale particles

Nanoscale particles offer a variety of interesting properties, and there is growing interest in their assembly into higher ordered structures. We report that the pH-responsive aminopolysaccharide chitosan can mediate the electrodeposition of model nanoparticles. Chitosan is known to electrodeposit at the cathode surface in response to a high localized pH. To demonstrate that chitosan can mediate nanoparticle deposition, we suspended fluorescently labeled latex nanoparticles (100 nm diameter spheres) in a chitosan solution (1%) and performed electrodeposition (0.05 mA/cm2 for several minutes). Results demonstrate that chitosan is required for nanoparticle electrodeposition; chitosan confers spatial selectivity to electrodeposition; and nanoparticles distribute throughout the electrodeposited chitosan film. Additionally, we observed that the deposited films reversibly swell upon rehydration. This work indicates that chitosan provides a simple means to assemble nanoparticles at addressable locations and provides further evidence that stimuli-responsive biological materials may facilitate fabrication at the microscale.     

The Effect of Alkane Chain Length on the Liquid–Liquid Critical Temperatures of Oligostyrene/Linear-Alkane Mixtures

Summary. Upper critical solution temperatures (UCSTs) for liquid–liquid demixing in a set of mixtures of linear alkanes (pentane (N ₁=5) to pentacontane (N ₁=50)) with an oligostyrene (1241amu, N ₂=12) are reported. We find strong correlation between the Hildebrand solubility parameters of the alkanes and the UCST. Correlations are developed which enable predictions concerning the miscibility of mixtures of compounds with longer chains.     

A Substituted Tetraazaporphyrinogen as an Electroactive Component for a Polymeric Membrane Anion-Selective Electrode

A novel anion-selective electrode has been prepared by usingtetraazaporphyrinogen as the electroactive component and o-nitrophenyloctylether as the plasticizer. The electrode exhibits almost Nernstian responsecharacteristics for Pic^-, ReO ₄ ^- ,SCN^-, ClO ₄ ^- and TPB^-. The linearresponse ranges towards the above-mentioned anions are 10^-6 10^-2, 10^-5 10^-2,10^-5 10^-2, 10^-5 10^-1, and 10^-5 10^-2mol/Land the corresponding slopes are -56.8, -57.1, -56.3, -56.1, and -59.9mV/decade with correlation coefficients of -0.99978, -0.99987, -0.99999,-0.99998, and -0.99998, respectively. The electrode shows an anti-Hofmeisterselectivity sequence: Pic^- > SCN^- >ReO ₄ ^- > ClO ₄ ^- > I^- >Br^- > BF ₄ ^- > Sal^->NO ₃ ^- > Cl^-. The unusual responsemechanism of the novel anion-selective electrode was investigated byexperimental observations and calculation with the MNDO method. Theelectrode was used as a TPB^- and a Pic^-sensitiveelectrode, respectively, and applied to the assay of levamisolehydrochloride tablets by potentiometric titration and Gran's methods. Theresults obtained are in excellent agreement with that determined by thestandard pharmacopoeia method based on nonaqueous titration.     

Sorption and desorption of radiostrontium on powdered bentonite: Effect of pH and fulvic acid

The effect of pH and fulvic acid on the sorption of Sr on bentonite was investigated by using batch experiments. The sorption and desorption isotherms of Sr on bentonite were determined at room temperature, at pH 6.0±0.2 and in presence of 0.1M NaCl. It was found that the sorption of Sr is independent at pH<8, and then increases slightly with increasing pH. Fulvic acid increases the sorption of Sr significantly on bentonite at low pH, but decreases the sorption of Sr at pH>8. The sorption of Sr on bentonite can be described by a reversible sorption process and the sorption mechanism consists mainly of ion exchange. This revised version was published online in July 2006 with corrections to the Cover Date.