Study on the Tautomer Interconversion of 3-Oxo Pentanoate During Gas Chromatography

Enol and keto tautomers of methyl 3-oxo pentanoate could be separated on a HP-5 capillary column. The chromatographic peaks were identified by examining characteristic mass ions arose from the corresponding enol and keto molecular ions. The study showed that the area percentage of enol tautomer is a function of temperature of the column. Treating the column as a reactor, the energy of activation for the on-column tautomerization could be extracted (35.1 kJ mol⁻¹) by monitoring the loss of the enol tautomer, because the reaction is found to obey pseudo first-order kinetics. The enthalpy and the entropy changes (ΔH = −3.98 kJ mol⁻¹, ΔS = −7.89 J K⁻¹mol⁻¹) for the enol-to-keto reaction in the stationary phase were also obtained.     

Palladium salicylaldimine complexes containing boronate esters

Reactions of salicylaldehydes with boronate ester derivatives of aniline have been examined. Addition of these Schiff base ligands to palladium acetate or Na₂PdCl₄ afforded novel boron-containing trans-bis(N-arylsalicylaldiminato) palladium complexes.Condensation of salicylaldehyde (2-HOC₆H₄C(O)H) with H₂NC₆H₄Bpin (pin=1,2-O₂C₂Me₄) afforded the boron-containing Schiff bases, 2-HOC₆H₄C(H)=NC₆H₄Bpin (1–3a). Similar reactivity with 2-hydroxy-5-nitrobenzaldehyde and 2-hydroxy-1-naphthaldehyde gave the corresponding Schiff bases (1-3b) and (1-3c), respectively. Reaction of Schiff bases (2) and (3) with palladium acetate or Na₂PdCl₄ afforded complexes of the type PdL₂ (4,5), where L=deprotonated Schiff base. The molecular structure of the nitro-salicylaldehyde 4-Bpin palladium complex (5b) was characterized by an X-ray diffraction study. All new palladium compounds have been characterized fully and tested for their antifungal activity against Aspergillus niger and Aspergillus flavus.     

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.     

Probing the kinetic landscape of transient peptide-protein interactions by use of peptide (15)n NMR relaxation dispersion spectroscopy: binding of an antithrombin peptide to human prothrombin

Protein-ligand interactions may lead to the formation of multiple molecular complexes in dynamic exchange, affecting the kinetic and thermodynamic characteristics of the binding equilibrium. We followed the dissociation kinetics of the transient and specific complex of an antithrombotic peptide N-acetyl-Asp(55)-Phe-Glu-Glu-Ile-Pro(60)-Glu-Glu-Tyr-Leu-Gln(65) with human prothrombin by use of (15)N NMR relaxation dispersion spectroscopy of the peptide. Every one of the five (15)N-labeled adjacent residues of the peptide exhibited apparently different kinetic exchange and relaxation behaviors, which were especially evident at different concentrations of prothrombin. Binding-induced (15)N relaxation dispersion of residues Phe(56), Glu(57), Glu(58), and Ile(59) can be fitted phenomenologically to a two-site on-and-off exchange mechanism with physically feasible relaxation and kinetic parameters obtained for residues Phe(56), Glu(58), and Ile(59), independent of the prothrombin concentration. The apparent kinetic parameters of Glu(57) show some dependence on the concentration of prothrombin and the extracted transverse relaxation rate for Glu(57) in the bound state was severalfold higher than that expected for a protein-peptide complex with a size of approximately 72 kDa. In addition, the equilibrium population of the bound peptide obtained for Glu(57) was inconsistent with those for Phe(56), Glu(58), and Ile(59) and with the prothrombin/peptide ratios used in the experiments. These discrepancies can be explained by the presence of two conformations for the peptide-protein complex exchanging at a rate of approximately 100 s(-)(1). In all, our study shows that fast dissociation of protein-peptide complexes can be studied quantitatively using peptide (15)N NMR relaxation dispersion measurements without a precise knowledge of the peptide and protein concentrations. In addition, protein titration was found to improve the accuracy of quantitative analysis and may make it possible to determine the rate of conformational changes within the protein-peptide complex.     

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.     

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.     

Experiments in Solving Mixed Integer Programming Problems on a Small Array of Transputers

The time-consuming process of solving large-scale Mixed Integer Programming problems using the branch-and-bound technique can be speeded up by introducing a degree of parallelism into the basic algorithm. This paper describes the development and implementation of a parallel branch-and-bound algorithm created by adapting a commercial MIP solver. Inherent in the design of this software are certain ad hoc methods, the use of which are necessary in the effective solution of real problems. The extent to which these ad hoc methods can successfully be transferred to a parallel environment, in this case an array of at most nine transputers, is discussed. Computational results on a variety of real integer programming problems are reported.