Novel carbon-carbon bond formation reaction of methoxyallene oxide promoted by TiI(4)

Methoxyallene oxide was readily prepared in situ by epoxidation of methoxyallene with 3-chloroperbenzoic acid, and the subsequent reaction with aldehydes or acetals was promoted by titanium tetraiodide and additives to give 2,3-dialkoxy- or 3-hydroxy-2-methoxy ketones in good yields.     

Modeling 1/f noise using moving averages

A model of 1/f noise is considered, based on moving averages of ordern. The coefficientsα _k defining the model are calculated numerically using Seidel iteration which turns out to converge rapidly. The convergence is independent ofn which seems to be caused by the fact that the nonlinear problem solved is defined by a self-similar matrix. The coefficientsα _k appear to approach, with indefinitely growingn, valuesα _k =1/√k and thus the model has a kind of Fourier invariance. Physical interpretation of the invariance is suggested as well as of coefficientsα _k describing long-range correlations. Fractal sets of dimensiond=2.5 are proposed to play certain role in explaining the latter. This work was partly supported by the Scientific Grant Agency of the Ministry of Education of Slovak Republic (VEGA) under the Grant No. 1/3143/96 and by the Slovak Literary Fund.     

Synthesis of novel liquid crystals having the perfluoropyrrolidino group

Novel liquid crystals which have the perfluoropyrrolidino group, a heterocyclic perfluoroalkyl group, and which show smectic phases have been synthesized with perfluoro-(2-pyrrolidinopropionyl fluoride) as one of the starting materials. Analogues with a polymerizable functional group also have been prepared and polymerized to give side chain liquid crystal polymers.     

Low-frequency and high-frequency relaxations in dynamic electric birefringence of poly(γ-benzyl-L-glutamate) in m-cresol

The dc component Δn of the electric birefringence of poly(γ-benzyl-L -glutamate) in m-cresol is measured under an ac electric field at frequencies from 0.5 Hz to 200 kHz for solutions covering the dilute and semidilute regions. The dispersion curve indicates that at low frequencies Δn decreases with increasing frequency (low-frequency relaxation). For high-molecular-weight polymers at high concentration, Δn becomes negative at high frequency and its absolute value decreases with further increase in frequency (high-frequency relaxation). A unified theory for the two relaxations is developed on the basis of a model in which, in the semidilute regime, the rodlike polymer is confined in a cage formed by neighboring polymers and the lifetime of the cage lies between relaxation times of the two relaxations. The low-frequency relaxation is ascribed to end-over-end rotation of the polymer and the high-frequency relaxation to the rotation within a limited angle in the cage. The dependences of relaxation parameters on polymer concentration and molecular weight are reasonably explained by the theory.     

The decay of 101Ag

The decay of ¹⁰¹Ag have been studied using β- and γ-spectrometers in singles and coincidence modes. A half-life of 11.4 ± 0.3 min was obtained and a decay scheme was proposed. The first excited state was established at 80.3 keV and a half-life of 4.8 ± 0.5 ns was suggested. The resultant level structure of ¹⁰¹Pd is compared to a theoretical calculation with strong band mixing.     

Stereospecific photocyclization of α-bisulfenylated keto compounds. Cis-dihydrobenzothiophenes

Irradiation of α-bisulfenylated keto compounds in acetonitrile affords the cis-fused dihydrobenzothiophenes which are dehydrated to benzothiophenes in high yields.     

Bounds on mass transport of flow on an inclined plate

Zusammenfassung In der vorliegenden Arbeit wird das Variationsproblem, welches die Schranken für den Durchfluss in turbulenter Strömung auf einer geneigten Platte bestimmt, nach Busse [2] abgeleitet. Es wird die symmetrische Natur der Lösung des Variationsproblems für die ebene Poiseuille-Strömung geprüft. Dies zeigt einerseits Ähnlichkeit und andrerseits Unterschiede zwischen dem Problem der ebenen Poiseuille-Strömung und der Strömung auf einer geneigten Platte.     

Improved sensitivity for insulin in matrix-assisted laser desorption/ionization time-of-flight mass spectrometry by premixing alpha-cyano-4-hydroxycinnamic acid matrix with transferrin

This report describes an enhancement of the signal intensities of proteins and peptides in matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS). When alpha-cyano-4-hydroxycinnamic acid (CHCA) premixed with human transferrin (Tf) was used as a matrix, the signal intensity of insulin was amplified to more than ten times that of the respective control in CHCA without Tf. The detection limit of insulin was 0.39 fmol on-probe in the presence of Tf, while it was 6.3 fmol in the absence of Tf. The signal intensity of insulin was also enhanced when the CHCA matrix was premixed with proteins other than Tf (80 kDa), such as horse ferritin (20 kDa), bovine serum albumin (BSA, 66 kDa), or human immunoglobulin G (150 kDa). The optimum spectrum of insulin was obtained when the added amount of protein was in the range 0.26-0.62 pmol, regardless of the molecular weight of the added protein. Tf and BSA outperformed the other tested proteins, as determined by improvements in the resulting spectra. When the mass spectra of several peptides and proteins were recorded in the presence of Tf or BSA, the signal intensities of large peptides such as glucagon were enhanced, though those of smaller peptides were not enhanced. In addition, the signal enhancement achieved with Tf and BSA was more pronounced for the proteins, including cytochrome C, than for the large peptides. This enhancement effect could be applied to improve the sensitivity of MALDI-TOFMS to large peptides and proteins.     

Anomalous behavior of the coefficient of normal restitution in oblique impact

The coefficient of normal restitution in an oblique impact is theoretically studied. Using a two-dimensional lattice model for an elastic disk and an elastic wall, we demonstrate that the coefficient of normal restitution can exceed unity and has a peak against the incident angle in our simulation. We also explain this behavior based upon a phenomenological theory.     

Synthesis of Bioactive Organic-Inorganic Hybrids with γ-Methacryloxypropyltrimethoxysilane

Bioactive organic-inorganic hybrids were synthesized through sol-gel processing starting from -methacryloxypropyltrimethoxysilane. NMR-spectroscopic studies showed the presence of silanol groups (Si–OH) and Si–O–Si bonds. In vitro tests of the hybrids for bioactivity with a simulated body fluid (Kokubo solution) indicated that only calcium-containing hybrids could form apatite on their surfaces. Thus the presence of calcium ions was no less important to deposit apatite than the formation of silanol groups or Si–O–Si bonds.