A simple stereoselective one-pot synthesis of C-nucleosides by 1,3-dipolar cycloaddition of chiral azomethine imines prepared in situ

The NH,NH-dihydrocycloadduct 1 (6-chloro-9,9-dimethyl-7,8-dihydro-9H-pyrazolo[4,3-d]tetrazolo[1,5-b]-pyridazine) obtained by the cycloaddition of 2-diazopropane to 6-chlorotetrazolo[1,5-b]pyridazine, is transformed with protected or unprotected carbohydrates 2, 5, 7,9, 11, 13 and 15 in the presence of methyl acrylate ( 3 ) into the corresponding C-nucleosides 4,6,8,10,12,14 and 16 . In this one-pot synthesis two new chiral centers are formed stereoselectively, dependent on the chirality at C-atom next to aldehydo group in the carbohydrate.     

Potential for micromachined actuation of ultra-wide continuously tunable optoelectronic devices

Tailored scaling represents a principle of success that, both in nature and in technology, allows the effectiveness of physical effects to be enhanced. Mutation and selection in nature are imitated in technology, e.g. by model calculation and design. Proper scaling of dimensions in natural photonic crystals and our fabricated artificial 1D photonic crystals (DBRs, distributed Bragg reflectors) enable efficient diffractive interaction in a specific spectral range. For our optical microsystems we illustrate that tailored miniaturization may also increase the mechanical stability and the effectiveness of spectral tuning by thermal and electrostatic actuation, since the relative significance of the fundamental physical forces involved considerably changes with scaling. These basic physical principles are rigorously applied in micromachined 1.55-μm vertical-resonator-based devices. We modeled, implemented and characterized 1.55-μm micromachined optical filters and vertical-cavity surface-emitting laser devices capable of wide, monotonic and kink-free tuning by a single control parameter. Tuning is achieved by mechanical actuation of one or several air-gaps that are part of the vertical resonator including two ultra-highly reflective DBR mirrors of strong refractive index contrast: (i) Δn=2.17 for InP/air-gap DBRs (3.5 periods) using GaInAs sacrificial layers and (ii) Δn=0.5 for Si₃N₄/SiO₂ DBRs (12 periods) with a polymer sacrificial layer to implement the air-cavity. In semiconductor multiple air-gap filters, a continuous tuning of >8% of the absolute wavelength is obtained. Varying the reverse voltage (U=0–5 V) between the membranes (electrostatic actuation), a tuning range of >110 nm was obtained for a large number of devices. The correlation of the wavelength and the applied voltage is accurately reproducible without any hysteresis. In two filters, tuning of 127 and 130 nm was observed for about ΔU=7 V. The extremely wide tuning range and the very small voltage required are record values to the best of our knowledge. For thermally actuated dielectric filters based on polymer sacrificial layers, Δλ/ΔU=-7 nm/V is found. Received: 10 May 2002 / Published online: 8 August 2002     

Runge–Kutta Methods for Itô Stochastic Differential Equations with Scalar Noise

A general class of stochastic Runge–Kutta methods for Itô stochastic differential equation systems w.r.t. a one-dimensional Wiener process is introduced. The colored rooted tree analysis is applied to derive conditions for the coefficients of the stochastic Runge–Kutta method assuring convergence in the weak sense with a prescribed order. Some coefficients for new stochastic Runge–Kutta schemes of order two are calculated explicitly and a simulation study reveals their good performance.     

Enhancing calibration models for non-invasive near-infrared spectroscopical blood glucose determination

Partial least-squares regression (PLS) and radial basis function (RBF) networks are used to compute calibration models for non-invasive blood glucose determination by NIR diffuse reflectance spectroscopy. A model computation shows that even extremely small deviations of the spectra induce increased prediction errors. Since the spectral contribution of blood glucose is much smaller than deviations resulting from the non-invasive measuring process a method based on Pearson’s correlation coefficient can be used for evaluating the quality of the recorded spectra during the prediction step. Another method is based on the leverage values from the hat matrix of the RBF network. Both methods lead to a significant decrease in prediction error.     

Heterocyclic diazo compounds as starting materials in organic synthesis (review)

Data on the structures and reactions of heterocyclic diazo compounds that lead to the formation of new heterocyclic systems as a result of intra- or intermolecular cyclization and rearrangements are systematized.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 579–603, May, 1980.     

Fast proton conductivity of polycrystalline titanoniobates

The proton conductivity of three layer-type compounds was studied: H₃OTi₂NbO₇. H₂O, HTiNbO₅ and HTiTaO₅. Measurements were made between 20 °C and 90°C on pellets pressed from crystalline powders and soaked with pure water. The hydrated compound had the highest conductivity, (20°C)-6.3–6.9·10^–4 (cm)^–1. Acid ions from the exchange process were quite firmly retained in its layer structure and contributed significantly to the measured conductivity. Consistent results were obtained after prolonged washing with water.Dedicated to Professor Harry Thomas on the occasion of his 60th birthday     

Photoelectron spectroscopy of heterocycles. Azaindenes and azaindolizines

The HeI photoelectron (PE) spectra of indole ( 1 ), benzimidazole ( 2 ), indazole ( 3 ), 3-chloro-indazole ( 4 ), imidazo[1,2-b]pyridazine ( 5 ), 6-chloroimidazo[1,2-b]pyridazine ( 6 ), 2-phenyl-imidazo[1,2-b]pyridazine ( 7 ), 2-phenyl-6-chloroimidazo[1,2-b]pyridazine ( 8 ), tetrazolo[1,2-a]-pyridine ( 9 ) and 8-cyanotetrazolo[1,5-a]pyridine ( 10 ) have been recorded. The spectra of 2–10 are of special interest for studying lone pair interactions. The assignment of the PE spectra submitted here, conjointly with the electronic structure of the studied compounds is discussed on the basis of molecular orbital calculations.     

Pyridazines. LXV. Reactions of some I-phenacylazolopyridazinium halides with 2,3-diphenylcyclopropenone, -thione,or hydrazine

I-Phenacylazolopyridazinium bromides reacted with 2,3-diphenylcyclopropenone or -thione in the presence of triethylaminc to give 3,4,6-triphenyl-2-pyrone or -2-thiopyrone and the corresponding azolopyridazine. Quaternized azolopyridazines reacted with hydrazine to give either 3,6-diphenylpyridazine and the corresponding azoloazine or hy ring opening of the azine part to give 1-methyl-2-(pyrazolyl-5′)imidazole.     

Kraftfeldrechnungen an linearen Oligopyrrolen: 2,2′-Bipyrrol, 2,2′-Furylpyrrol und Prodigiosen

Using a specific force field model, relative stabilities of 2,2-bipyrrole and 2,2-furylpyrrole conformers as well as of prodigiosene tautomers, configurations, and conformations, are studied. 2,2-Bipyrrole adopts anantiperiplanar conformation in accord with other theoretical calculations and experimental findings. Its rotational barrier calculated by this method compares favourably to the one derived by other means. For the parent prodigiosene the (Z)sp,sp arrangement is found to be the most stable one. The two possible tautomers within its dipyrrin fragment do not show a significant energy difference.