One-pot synthesis of 5-(substituted-amino)pyrazoles

An efficient and mild one-pot synthesis of substituted 5-alkylamino and/or 5-(arylamino)pyrazoles is described. A suitably decorated β-ketoamide, an aryl or alkyl hydrazine and Lawesson's reagent are suspended in THF/Py and gently heated to yield the requisite 5-aminopyrazoles.     

TheQ EC dependence of evidence for a 17-keV neutrino from the55Fe radiative decay

The internal bremsstrahlung spectrum of⁵⁵Fe was studied using HPGe detector in low background and reduced pileup conditions. The data show that the conclusion on the presence of a heavy mass neutrino strongly depends from the experimental decay energy value taken in the analysis. The decay energy was found to beQ _EC =231.37 ± 0.10 keV. The obtained results also show the need for the higher accuracyQ _EC used in the analysis of the existence of a 17-keV neutrino in the⁵⁵Fe decay.The authors would like to thank A. Plochocki and J. ylicz for helpful discussion and assistance.     

Large-scale collisional energy transfer in laser-pumped metastable Ca atoms: Excitation of resonance states of Ca II

We report the first experimental observation of the excitation of the 4p ² P _{3/2, 1/2} resonance states of Ca II (located at 74 720.4 and 74 497.5 cm^–1 above the ground state of Ca I) following pulsed-laser pumping of the 4s ^{2 1} S _O–4s4p ³P₁ intercombination transition of Ca I (E _ex = 15 210 cm^–1). Large scale collisional transfer of energy between the laser-excited atoms is believed to be responsible for this. This is possibly because sufficient time is available (_rad of the 4s4p ³ P ₁ state is approximately 350 µs) for collisions to build such a high level of excitation. Some interesting additional features of the fluorescence spectra of the laser-pumped Ca vapor, such as temperature dependence of the fluorescence intensities and evolution in time of some selected states, are also presented.     

On input/output stabilization of singular integrodifferential systems

In this paper we consider a class of systems described by singular integrodifferential equations. This type of systems appear, for example, in the modeling of certain aeroelastic control problems. We study these systems in frequency domain framework and show the existence of finite-dimensional stabilizing controllers. An algorithmic procedure is outlined for the construction of such controllers. In order to illustrate the numerical aspects of this algorithm, we present an example involving the classical Theodorsen model of an airfoil, which fits in the class of systems considered here.This work was supported in part by the National Science Foundation under Grants DMS-8907019 and MSS-9203418.     

Real-time measurement and control of particle-number density and size of the detonation products of lead azide

Time-resolved measurement and modeling of the number density and size of lead particles produced following the detonation of Lead Azide (LA) are presented. Particles expanding freely into vacuum through a supersonic nozzle or interacting with a barrier placed above the LA sample are monitored via attenuation of laser beams at 0.67, 1.3 and 10.6 µm. The attenuation depends on the conditions of expansion, but is always much more pronounced at 0.67 µm and 1.3 µm. From the ratio between the attenuations at 0.67 µm and 10.6 µm, the radius and number density of the particles are calculated applying Beer's law and Mie's theory. It is found that 20–90 µs following the detonation the attenuation at 32–36 mm above the LA sample is due to particles with radii of 0.9, 0.7 and 0.1 µm for free expansion into vacuum through the nozzle or near the barrier, respectively. Also, the expansion through the nozzle results in a transparent medium above the nozzle exit for the first few µs following the detonation. The effect of the nozzle is attributed to the fact that the velocity of the expanding detonation products is supersonic, which leads to compression and heating in the throat region, in contrast to the more familiar phenomenon of cooling at subsonic velocities. The dynamics of particles expanding under the different conditions and the mechanism of size reduction and elimination of particles is discussed.     

Spectroscopic properties of the photoproducts of pyridoxal-5′-P irradiation: Catalytic site recognition of ribonuclease A

Photoproducts of pyridoxal-5-P, i.e., 4-pyridoxic-5-P and bis-pyridoxal-5-P, have been studied by spectroscopic methods. The spectroscopic properties of bis-pyridoxal-5-P (bis-PLP) resemble those of pyridoxal-5-P (PLP) under similar experimental conditions. The coupling of methylen hydrogens to the phosphorus atom has been shown by NMR spectroscopy. The singlet in the³¹P-NMR spectra and the triplet in¹H-undecoupled experiments confirm the presence of the phosphate group in the 5 position of the structure of the vitamin. The effect of pH and solvent composition on the relative distribution of species of bis-pyridoxine-5-P (bis-PNP) has been investigated by absorption and fluorescence spectroscopy. The acid-base dissociation of the phosphate group is easily detected by emission spectroscopy. Bis-PNP and bis-PLP bind to the enzyme RNase A and they behave as competitive inhibitors with respect to the substrate cytidine-2-3-cyclic phosphate. The natural forms of vitamin B₆, pyridoxine, and pyridoxine-5-P have no effect on the catalytic activity of the protein. Experimental evidence derived from fluorescence and inhibition experiments is consistent with the hypothesis that bis-PNP recognizes the catalytic site of RNase A.     

Alternating iteration and elliptic variational inequalities

Summary Free boundary value problems, too complicated for formulation as a variational inequality, are broken up into two problems on overlapping regions. On one region the problem is treated as an ordinary boundary value problem; on the second region, the free boundary part of the problem is reduced to a variational inequality. By solving the two problems successively it is shown that under certain conditions the successive solutions converge to a single function that gives a solution of the original problem. Application to a filtration problem is given.     

Fluorinated triazinones from hexafluoroacetone ethoxycarbonylimine

The behavior of hexafluoroacetone ethoxycarbonylimine in cyclocondensation with different binucleophiles of the amidine type, viz., amino derivatives of N- and N,S-heterocycles, was studied. A preparative method for the synthesis of previously unknown annelated 2,2-bis(trifluoromethyl)-1,3,5-triazinones was developed.     

Enantioselective synthesis of functionalized γ-butyrolactones

Sharpless asymmetric dihydroxylation and aminohydroxylation of (E)-dimethyl-2-alkylidene glutarates 2 were shown to afford enantio-enriched or enantiopure highly functionalized γ-butyrolactones 3 and 7.     

Alkylation of 6-(3-Indolyl)indolo[2,3-b]carbazole

The methylation and allylation of 6-(3-indolyl)indolo[2,3-b]carbazole were studied, and its trimethyl and mono-, di-, and triallyl derivatives were obtained.