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.     

Neue Synthesen von 4,4′-Äthinylendiphenol (4,4′-Dihydroxytolan)

Zusammenfassung Es werden zwei neue Wege zur herstellung des 4,4-Äthinylendiphenols beschrieben. Der erste beruht auf der Entmethylierung des Bis-(4-methoxyphenyl)acetylens, der zweite auf der Oxydation des 4,4-Dihydroxybenzildihydrazons nach derCurtiusschen Methode.

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Two new syntheses of 4.4-ethynylene diphenol

Two new syntheses of 4.4-ethynylene diphenol are described: demethylation of bis-(4-methoxyphenyl)-acetylene, and oxidation of 4.4-dihydroxybenzildihydrazone according toCurtius.

     

A second-quantization representation of the Epstein-Nesbet partitioning of the full hamiltonian

A second-quantization representation of the Epstein-Nesbet partitioning of the total electronic hamiltonian is suggested. In this approach, the unperturbed hamiltonian contains not only the one-particle orbital energies but also the Coulomb and corresponding exchange two-particle terms. Such a hamiltonian can advantageously be used in all branches of the many-body diagrammatic perturbation theory for simple and correct inclusion of the diagonal ladder and ring diagrams in all orders of perturbation theory.     

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.     

Mathematical modeling of physico-chemical characteristics of cement-waste composites in radioactive waste management

An optimization of mortar (as matrix), improved with bentonite clay, used for immobilization of radionuclides⁶⁰Co,¹³⁷Cs,⁸⁵Sr and⁵⁴Mn, is presented. A relatively simple mathematical model is given, which permits minimization of leach rate and permeability and maximization of compressive strength. An optimal solution, based on experimental data, is given. These results will be used for a future Yugoslav radioactive waste storing center.     

Continuous electrophoretic separation of106Ru species in sea water and uptake of the separated fractions by sea algae

¹⁰⁶Ru chloro and nitrosyl-nitrato complexes in sea water were separated into several species by continuous electrophoresis on a filter paper curtain. Biological uptake experiments were carried out on sea algae Fucus virsoides with fractionated¹⁰⁶Ru chloro and nitrosyl-nitrato complex species in sea water. The biological uptake of¹⁰⁶Ru chloro complex species was about 8 times higher than the uptake of¹⁰⁶Ru nitrosyl-nitrato species. Electrophoretically most mobile electrically positively charged cationic species in both systems also showed about 8 times higher biological uptake than the most mobile negatively charged anionic species. A close relation of the biological uptake to the sign of the electrical charge and the electrophoretic mobility of the species is demonstrated. The results are discussed with respect to possible danger to the biological environment as a consequence of the aging of ruthenium species in sea water resulting from¹⁰⁶Ru waste disposal to the sea from a nuclear reprocessing plant. On leave of absence from the National Institute of Radiological Sciences, 9-1, 4-chome, Anagawa, Chiba-shi, Japan, on a fellowship from The Science and Technology Agency of the Japanese Govemment.     

Synthesis of 5-(4,6-dimethyl-2-pyrimidinyl)-1,3,4-oxadiazole-2-thione and its alkylation,aminomethylation, and acylation

The reaction of the hydrazide of 4,6-dimethyl-2-pyrimidinecarboxylic acid with potassium ethylxnthate gave 5-(4,6-dimethyl-2-pyrimidinyl)-1,3,4-oxadiazole-2-thione. The alkylation of this product in an alkaline medium proceeds at the sulfur atom, while the aminomethylation and acylation proceed at the nitrogen atom. The major criterion for the structure of the S- and N-derivatives is the chemical shift of C₍₂₎ in the 1,3,4-oxadiazole ring in the ¹³C NMR spectra.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 700–705, May, 1993.