Strukturelle Abwandlungen anN-Acetylneuraminsäure, 3

From methyl-5-acetylamino-7,8-anhydro-4,9-O-bis-(t-butyldimethylsilyl)-3,5-dideoxy--D-glycero-D-galacto-2-nonulopyranosidonic acid methylester (1) the derivatives1 a and1 b were obtained by removing the 9-O-(t-butyldimethylsilyl)group withBu ₄NF, followed by acetylation. Treatment of1 b with 80% acetic acid and acetanhydride/pyridine yields the 8-epi-N-acetylneuraminic acid derivative2 a and the 7-epi-N-acetylneuraminic acid derivative3 a in a ratio of 3:1 (Scheme 1). The structure elucidation of2 b was achieved by converting2 b via the 4,9-bis-O-(tBDMSi)-8-O-tosyl-derivative2 d into the epoxide1 (Scheme 2). Using the same sequence the epoxides4 and5 were transformed into theN-acetylneuraminic acid derivative6 a and the 7,8-bis-epi-N-acetylneuraminic acid derivative7 a (Scheme 3). After treatment with sodium hydroxide and 0.025m HCl and Dowex 50 H⁺ the 8-epi-, 7-epi- and 7,8-bis-epi-N-acetylneuraminic acids2,3, and7 were obtained. These three compounds were tested withCMP-N-acetylneuraminic acid synthetase.

Herrn KollegenK. Schlögl mit den besten Wünschen zum 60. Geburtstag.     

Molecule-Responsive Fluorescent Sensors of α-Helix Peptides Bearing α-Cyclodextrin, Pyrene and Nitrobenzene Units in Their Side Chains

-Helix peptides bearing one unit of -cyclodextrin (-CD), one unit of pyrene and one unit of nitrobenzene (NB) in their side chains have been designed and synthesized as novel molecule-responsive devices.In both the CD-peptides, -PR17 and -PL17, the NB unit is separated from the CD unit by two turns of the helix. Two reference peptides (PL17, and -P17,) have also been synthesized. The circular dichroism studies in the peptide absorption region (200–250 nm)of -PR17 and -PL17 suggestthat the CD-peptides form stable-helixstructures (83–77%), which was destabilized by accommodating guest molecules (e.g., n-pentanol) into the CD cavity. It suggests that formation of intramolecular host–guest(CD–NB) complex stabilized thehelical structure and exogenous guest molecule excluded the appending NB moiety from inside to outside of the CD cavity, thereby causing destabilization of the helical structure and increasing the random coil content. The ICD spectra of the peptides in the pyrene and nitrobenzene absorption region (250–40 nm) suggest that NB forms inclusion complex with CD. The fluorescence studies revealed that the fluorescence of the pyrene unit is quenched by the NB unit in -PR17 and -PL17. The fluorescence intensity increases with increasing guest concentration for the CD-peptides.This guest-responsiveenhancement in the fluorescence intensity can be explained in terms of increased distance between the pyrene and NB moieties, which is caused by exclusion of the NB moiety from the CD cavity by guest accommodation. Using the guest-responsive fluorescence quenching properties of the CD-peptides, we have obtained binding constants for various short chain alkanols. -PL17 has higher binding affinity to the guest molecules than its isomer, -PR17, indicating that the location of functional groups on the peptide scaffold is important in molecule detection.     

Preparation and characterization of theβ-cyclodextrin inclusion complex with sulfafurazole

The 1 : 1 inclusion complex involving sulfafurazole (SF) and-cyclodextrin (-CD) is prepared by the freeze-drying method and characterized on the basis of its chemical analysis, thermal behavior, infrared spectrum, X-ray powder pattern and¹³C NMR spectrum in DMSO-d₆ solution. The stability constant of the inclusion complex was determined by the solubility method. The effect of cyclodextrin on the UV absorption spectrum of sulfafurazole was also observed.     

Lack of dissipativity is not symplecticness

We show that, when numerically integrating Hamiltonian problems, nondissipative numerical methods do not in general share the advantages possessed by symplectic integrators. Here a numerical method is called nondissipative if, when applied with a small stepsize to the test equationdy/dt = iy, real, has amplification factors of unit modulus. We construct a fourth order, nondissipative, explicit Runge-Kutta-Nyström procedure with small error constants. Numerical experiments show that this scheme does not perform efficiently in the numerical integration of Hamiltonian problems.This research has been supported by project DGICYT PB92-254.     

Thermodynamic properties of the spin-Peierls transition in CuGeO3

We present an investigation of the spin-Peierls transition atT _SP=14.5 K in polycrystalline CuGeO₃ through specific-heat and thermal-expansion measurements. Clear second-order phase-transition anomalies are found in both properties atT _SP, although only a small entropy of S0.1 Rn2 is released at the transition. Most of the entropy is released atT _SP<T<150 K, where the temperature dependence of the magnetic contribution to the specific heat as well as the thermal expansion exhibit extrema atT ^*40 K. These are caused by one-dimensional antiferromagnetic fluctuations along the Cu chains, possibly accompanied by structural fluctuations. Using Ehrenfest's relation, a hydrostatic pressure coefficient (T _SP/_p)_p0 (0.45±0.06) K/kbar is derived.     

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.     

Pattern transfer and photoluminescence damage assessment of deep-submicrometer features etched by photon-induced cryoetching

We present a study of pattern-transfer and etch-induced damage in photon-induced cryoetching. Features with effective radii as small as 100 nm have been formed in both bulk and layered GaAs/AlGaAs materials. A measurement of the photoluminescence of etch-defined deep- submicrometer structures material suggests that this form of etching results in minimal process-induced damage. Modeling of the luminescence vs feature size for these features shows that the luminescence is limited only by carrier diffusion and non-radiative surface recombination.     

The Boolean Prime Ideal Theorem Plus Countable Choice Do Not Imply Dependent Choice

Two Fraenkel-Mostowski models are constructed in which the Boolean Prime Ideal Theorem is true. In both models, AC for countable sets is true, but AC for sets of cardinality 2 and the 2m = m principle are both false. The Principle of Dependent Choices is true in the first model, but false in the second. Mathematics Subject Classification: 03E25, 03E35, 04A25.     

Composition and properties of freeze-dried products of nicotinic acid withβ-cyclodextrin and heptakis (2,6-0-dimethyl)-β-cyclodextrin

The purpose of the study was to examine the formation of inclusion compounds in the freeze-dried products obtained from aqueous solutions of nicotinic acid and -cyclodextrin (-CD), or heptakis (2,6-0-dimethyl)--cyclodextrin (DIMEB). The molar ratios used were 1:1 and 2:1. In addition two freezing temperatures (–40 and –196°C) and different secondary drying temperatures (+50 and +80°C) were used. Freeze-dried products with -CD obtained after low temperature freezing are of the same crystallographic structure as seen in a pure inclusion compound prepared by coprecipitation. Amorphous products were formed after fast freezing. The molar ratios of included nicotinic acid in the freeze-dried products vary — dependent on the preparation conditions — between 0.75:1 and 1:1. A factorial design proves that the included drug amount can be increased by enhancement of the amount of nicotinic acid used, by faster freezing, and by the combination of these two factors. The proof of inclusion formation was given by a combination of X-ray diffractography, differential scanning calorimetry, thermogravimetry and thermofractography.The freeze-dried preparations obtained with DIMEB were amorphous mixtures of the two components. No proof for inclusion of the nicotinic acid in the cyclodextrin cavity could be given. Higher (–40°C) or lower (–196°C) freezing temperatures and the running of the secondary drying process could not influence these results. The very low stability constant of the complex and steric reasons are responsible for this behavior.     

K3 et formules de Riemann-Hurwitzp-adiques

The well-known formula of Riemann-Hurwitz gives the change of genuses in ann-fold covering of compact connected Riemann surfaces. In Iwasawa theory, there existp-adic analogues which give the change of certain ^±-invariants in ap-extension ofCM number fields. Using functorial and arithmetical properties ofK ₃, we extend such Riemann-Hurwitzp-adic formulas to non-CM fields, assuming some restrictive hypotheses on the capitulation ofK ₂.