The cyclodimerisation of 3-methyl-2-butenenitrile

3-Methyl-2-butenenitrile (1) cyclodimerised on treatment with lithium diisopropylamide in dimethoxyethane at temperatures between ?78°C and 0°C to 3-amino-4-cyano-1,5,5-trimethyl-1,3-cyclohexadiene (2) the structure of which was established by acid hydrolysis to the known 4-cyano-1,5,5-trimethyl-1-cyclohexene-3-one (3).     

Synthesis of hapten-phosphoramidites from 2′-deoxyuridine

A total of 11 novel phosphoramidites, 3a-d, 4a-d and 14a-c were prepared from 2′-deoxyuridine functionalized at 5 and 6-position of the pyrimidine ring with hapten reporter groups, e.g. adamantane, carbazole, dansyl and dabsyl, suitable for use in immunodetection nucleic acid testing assays.     

Measurement of internuclear distances in solid-state NMR by a background-filtered REDOR experiment

A background-filtered version of the rotational-echo double resonance (REDOR) experiment is demonstrated. The experiment combines a traditional REDOR pulse sequence with a double-cross-polarization (DCP) sequence to select only those signals coming from spin pairs of interest. The relatively inefficient DCP sequence, which transfers polarization from (1)H to (15)N and subsequently to (13)C, is improved by the use of adiabatic passages through the (-1) sideband of the Hartmann-Hahn matching condition. The result is an efficient 2D-REDOR pulse sequence that does not require a reference experiment for removal of background signals. The data produced by the experiment are ideally suited to analysis by newly developed dipolar transform methods, such as the REDOR transform. The relevant features of the experiment are demonstrated on simple labeled amino acids. Relative efficiencies of several other potential filtering methods are also compared. Copyright 2000 Academic Press.     

Conical parametric scattering of a single extraordinary beam in BaTiO3 crystal

In this paper, the parametric scattering of a single extraordinary polarized beam of laser in BaTiO₃ photorefractive crystal has been investigated experimentally and theoretically. The resulting pattern consists of beam fanning, isotropic ring, and anisotropic one. Among all parts of scattering pattern, isotropic ring has not been studied as much as beam fanning and anisotropic ring, and there still are some differences in reports about it. Therefore, the study has mainly focused on this part. In this experimental configuration, isotropic ring is just visible in positive angles although the other parts of parametric scattering pattern can be visible from behind and in front of the crystal. In addition to steady state pattern in forward and backward directions, its transient behavior with the rotation of crystal has been studied. The results of experiments have been analyzed carefully, and their theoretical explanations have been presented based on the standard theory of parametric scattering in photorefractive crystals. It has been shown that this configuration corresponds to the so called parametric B-process scattering.     

Infrared radiative transfer in planetary atmospheres—I. Effects of computational and spectroscopic economies on thermal heating/cooling rates

The availability of accurate spectroscopic data and improved knowledge of continuum absorption characteristics has required a further detailed study of i.r. radiative transfer. A sophisticated radiative transfer scheme based upon the Mayer-Goody random band model is developed and the derived transmissivities for H₂O, CO₂ and O₃ are calibrated against laboratory measurements. This calibrated scheme is used to assess the effects on calculated heating/cooling rate profiles of introducing computational and spectroscopic economies.     

Malliavin calculus for the stochastic 2D Navier—Stokes equation

We consider the incompressible, two‐dimensional Navier‐Stokes equation with periodic boundary conditions under the effect of an additive, white‐in‐time, stochastic forcing. Under mild restrictions on the geometry of the scales forced, we show that any finite‐dimensional projection of the solution possesses a smooth, strictly positive density with respect to Lebesgue measure. In particular, our conditions are viscosity independent. We are mainly interested in forcing that excites a very small number of modes. All of the results rely on proving the nondegeneracy of the infinite‐dimensional Malliavin matrix. © 2006 Wiley Periodicals Inc.     

Synthesis of aromatic bisabolene natural products via palladium-catalyzed cross-couplings of organozinc reagents

Aromatic bisabolene derivatives were prepared by two methods involving cross-coupling of organozinc reagents. The first synthesis of (+/-)-glandulone A (10), as well as syntheses of (+/-)-curcuhydroquinone (8) and (+/-)-curcuquinone (9), were accomplished via coupling of a secondary alkyl zinc reagent (1,5-dimethyl-4-hexenylzinc halide, 18) to protected bromohydroquinones using Pd(dppf)Cl(2) as catalyst. Coupling of arylzinc halides with alkenyl triflate 16 using Pd(PPh(3))(4) catalyst provided a number of bisabolene derivatives and led to syntheses of dehydro-alpha-curcumene (2), (+/-)-curcuphenol (3), and (+/-)-elvirol (13). A high-yield synthesis of the (+/-)-heliannuol D precursor 29 is also reported using this method.     

Self-chemical ionization of diethylzinc

The self-chemical ionization of diethylzinc is examined by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry and semiempirical molecular orbital calculations. Electron impact of diethylzinc neutral produces the radical cation, C(4)H(15)Zn(+) (m/z x 122), which reacts further with the neutral (C(2)H(5))(2)Zn to give the following product ions: Zn(+) (m/z x 64), C(2)H(5)Zn(+) (m/z x 93), C(4)H(9)Zn(+) (m/z x 121), C(4)H(11)Zn(2)(+) (m/z x 187), and C(6)H(15)Zn(2)(+) (m/z x 215). To determine the structure and pathways for production of these ions, monoisotopic (12)C(4)H(15)(64)Zn(+), (64)Zn(+) and (12)C(2)H(5)(64)Zn(+) were individually isolated and reacted with the neutral background. We also performed semiempirical molecular orbital calculations (ZINDO/1). The molecular orbital calculations and experimental data are consistent in predicting that the ethyl group on the diethylzinc cation carries the positive charge. Copyright 1999 John Wiley & Sons, Ltd.