Optical Spectroscopy and Theoretical Studies in Calixarene Chemistry

This review summarizes different applications of optical spectroscopic methods in calixarene chemistry including UV/Vis spectrometry, vibrational spectroscopic techniques (FTIR and Raman spectroscopy), luminescence spectroscopy (including fluorescence and phosphorescence), ellipsometry and various optical microscopic methods. Moreover, the results of theoretical studies (AM1, PM3, DFT, ab initio, etc.) are summarized based on selected papers in the field of conformational studies, thermodynamics and complexation features. About 300 references are processed systematically from the results reported mainly in the recent years with emphasis on the potential of practical application of these molecules.     

Magnetic properties of HITPERM-type alloys at high temperature

(Fe,Co)–Zr,Hf)–Cu–B (HITPERM-type) alloys with variable Hf, Zr and Co content were isothermally crystallised at 500–650 °C for 1 h, and the optimum nanocrystallisation temperature was selected on the basis of the minimum coercive field at room temperature. The quasistatic hysteresis loops were measured at temperature from 20 to 650 °C. Subsequently, the optimally annealed alloys were subjected to long-term annealing at 500, 550 and 600 °C. Working temperature of 600°C is too high for the investigated alloys to maintain stable magnetic properties. Temperature of 550 or 500 °C permits the material to be magnetically stable for a long period. The magnetic hysteresis loops recorded for the nanocrystalline alloys, where Fe:Co ratio is close to 1 and refractory metals content is 7 at.%, prove that coercive field increases slightly with temperature, but remains in the range of 20–40 A/m (depending on the alloy composition) from 20 to 550 °C. This proves that the investigated alloys, after optimisation of chemical composition, may be suitable for high temperature use.     

Synthesis of cephalosporins carrying isoxazolyl acetamido and related side chains

Starting from 3,5-dimethylisoxazole the carboxylic acids I and V, the amino acids VIII (L-) and IX (D-), and the ureido acids X (L-) and XI (D-) were prepared, which were used for the synthesis of the new cephalosporins XVIIb, XXa-c (L-), and XXIb (D-). Thein vitro antibacterial activity of these semi-synthetic antibiotics was studied. The resorption of XVIIb was investigated in mice.Research Group for Antibiotics of the Hungarian Academy of Sciences, H-4010 Debrecen, P.O. Box 70, Hungary. Published in Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1524–1535, November, 1998.     

Conflict resolution in fuzzy environment

Conflict resolution methodology is discussed with fuzzified Pareto frontier. Four solution concepts, namely, the Nash solution, the generalized Nash solution, the Kalai-Smorodinsky concept, and a solution method based on a special bargaining process are examined. The solutions are also fuzzy, the corresponding payoff values are fuzzy numbers, the membership functions of which are determined. Three particular cases are considered in the paper. Linear, quadratic, and general nonlinear Pareto frontiers with known shape are examined.     

Maskierung mit Kaliumjodid bei direkten Titrationen von Kupfer(II) mit Äthylendiamintetraessigsäure

Zusammenfassung Die Jodidoxydation durch Cu(II) wird in Anwesenheit von Ammoniak, Natriumtartrat, citrat oder -oxalat infolge Komplexbildung verhindert. Daher kann man z. B. Quecksüber(II) in Anwesenheit der genannten Komplexbildner mit Kaliumjodid maskieren und Kupfer(II) durch direkte Titration mit ÄDTA gegen Murexid, Brenzcatechinviolett, Chromazurol S, PAN oder PAR als Indikator bestimmen.

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Masking with potassium iodide in direct titrations of copper(II) with ethylenediamine tetraacetic acid

Summary The formation of a complex prevents the iodide oxidation by Cu(II) in the presence of ammonia, sodium tartrate, citrate, or oxalate. Hence mercury(II) for instance, can be masked against potassium iodide in the presence of these complex formers, and Cu(II) can be determined by direct titration with EDTA in the presence of murexide, pyrocatechol violet, chromazurol, PAN or PAR as indicator.

     

Change of geometry of polyacetylene upon charge transfer

Crystal orbital calculations on cis- and trans-polyacethylene chains indicate two kinds of geometry changes on charge transfer. (1) increase (decrease) of the CC bond lenght and CCC bond angles in the trans conformer taking up (losing) electrons, and $\text{(u)}\text{?}$ a tendency towards bond-length equalization on electron uptake and loss for both conformers.     

Characterisation of combinatorial libraries of mucin-2 antigen peptides by high-resolution mass spectrometry

An epitope motif, TX(1)TX(2)T, of mucin-2 glycoprotein was identified by means of a mucin-2-specific monoclonal antibody, mAb 994, raised against a synthetic mucin-derived 15-mer peptide conjugate. For determination of the epitope sequence recognised with highest affinity by mAb 994, a combinatorial approach was applied using the portioning-mixing technique excluding Cys. Antibody binding of libraries was most profound when Gln was at the X(1) position. Analytical characterisation of the TQTX(2)T library was conducted by amino acid analysis and matrix-assisted laser desorption/ionisation time-of-flight (MALDI-TOF) and electrospray ionisation Fourier transform ion cyclotron resonance (ESI-FTICR) mass spectrometric methods. Control libraries were prepared by mixing 19 individual peptides corresponding to the TQTX(2)T sequence. Thus, mixtures of 6, 10 and 19 pentapeptides were analysed and compared with the combinatorial mixture. MALDI-TOFMS was able to detect only partially the components in the 6- and 10-member mixtures, but failed to characterise a more complex 19-member mixture. In contrast, ESI-FTICRMS resolved all mixtures of higher complexity and provided direct identification at monoisotopic resolution, such as for a peptide library containing 'isobaric' lysine and glutamine (Delta m = 0.0364 Da). The results of this study suggest that ESI-FTICRMS is a powerful tool for characterisation of combinatorial peptide libraries of higher complexity.     

Stereochemical studies—76 saturated heterocycles—63 : synthesis of cis- and trans-n-methyl- and n-benzyl-4.5- and 5,6-tetramethylenetetrahydro-1,3-oxazines; an x-ray study of n-benzyl-cis-4,5-tetramethylenetetrahydro-1,-3-oxazinium- picrate

- The corresponding $\text{cis}$- and $\text{trans-N}$-methyl- and $\text{N}$-benzyl-5,6- and 4,5-tetramethylenetetrahydro-l,3-oxazines $\text{(5a,b-8a,b)}$were synthesized from $\text{cis}$- and $\text{trans-N}$-methyl and$\text{N}$-benzyl-2- aminomethyl-1-cyclohexanols $\text{1a,b,2a,b}$, from $\text{cis}$- and $\text{trans-N}$-methyl- and $\text{N}$benzyl -2-hydroxymethyl-1-cyclohexylamines$\text{(3a,b,4a,b)}$ by reaction with formaldehyde. The aminoalcohols $\text{1a,2a,3a,b}$and $\text{4a,b}$ were prepared in considerably higher yields than in earlier procedures. NMR spectroscopy showed that the $\text{cis}$ isomers of the synthesized oxazines were conformationally homogeneous in solution, and their preferred conformation (inside or outside) depended on the steric requirement of the groups attached to the anellation points, whereas a bulky C-2 substituent had no influence on the predominant conformation. The structure of $\text{N}$-benzyl-$\text{cis}$-4,5-tetramethylenetetrahydro-1,3-oxaziniumpicrate $\text{(7b)}$. determined by X-ray diffraction analysis, was in agreement with the predominant N-outside conformation of the corresponding base, established by means of NMR spectroscopy.     

Selective hydrogenations of steroids catalyzed by heterogenized Ru complexes

Summary [RuCl₂(PPh₃)₃], [{RuCl₂(TPPMS)₂}₂] and their heterogenized analogs were applied in the selective hydrogenation of 17-keto- and α,β-unsaturated ketosteroids. In basic conditions these complexes selectively hydrogenated the C=O bonds, similarly to the results obtained in the case of α,β-unsaturated aldehydes. A new method was developed for the synthesis of an expensive steroid alcohol, which can be prepared traditionally in a more complicated way.