Synthesis and Spectroscopic Characterization of N2-(N-Acetyl-6-O-stearoyl-α-D-muramoyl)-L-alanyl-D-isoglutamine

Title compound 1 was synthesized by a published route which had to be modified (seven steps from readily obtainable starting materials). Characterization of 1 was achieved by spectroscopic means (FAB-MS, ¹H-NMR, including 2D-COSY). Furthermore, commercially available reference material purchased for comparison, was unequivocally established to be 10 , i.e. incompletely deprotected 1 .     

Effect of stabilizers in the thermal treatment of PVC—IX. An investigation of the loss of Ba and Cd stearates from their equimolar mixture during static thermal stress of PVC—IX

Thermal degradation at 180° in air of PVC stabilized with an equimolar mixture of Ba and Cd stearates has been studied. The “unreacted” stearates were separated by filtering tetrahydrofuran solutions of samples. The filtration and thermal degradation were examined by means of infrared spectroscopy in the range 1400–1800 cm^?1. It has been demonstrated that, during the thermal stress, CdCl₂ is accumulated in the sample and that the presence of Ba stearate supports only the consumption of Cd stearate.     

Stereospecific fragmentations in the mass spectra of stereoisomeric isoindoloquinazolines

The mass spectrometric behavior of stereo- and regioisomeric, partially saturated isoindoloquinazolines was studied by positive-ion electron ionization (EI) and fast-atom bombardment (FAB/LSIMS) mass spectrometry combined with collision-induced dissociation (CID). A highly stereospecific retro-Diels-Alder process was observed in the cyclohexene-fused isomers under the EI conditions, and a corresponding (although less specific) fragmentation was observed in their FAB spectra. In the absence of RDA fragmentations, regio- and stereoisomers of the cyclohexane-fused heterocycles could be distinguished based on their FAB/CID spectra.     

Covalent chemistry and conformational dynamics of topologically chiral amide-based molecular knots

The readily available in gram quantities tris(allyloxy)knot of the amide-type 5 (knotane) can be completely and partially deprotected with nBu(3)SnH in the presence of a palladium catalyst resulting in hydroxyknotanes 7-9. These, in turn, react with diethylchlorophosphate giving rise to knotanes equipped with between one and three phosphoryl groups. Sulfonylation of bis(allyloxy)monohydroxyknotane 8 with p-toluenesulfonyl chloride and, following removal of one or two allyl groups from the intermediate monosulfonate 13, give rise to sulfonyloxy-allyloxy-hydroxy- and sulfonyloxy-dihydroxy-knotanes 15 and 14, respectively. This provides a convenient method for the preparation of knotanes with any substitution pattern. All new knotanes have been isolated in preparative amounts and as highly pure substances with an exception of allyloxy-dihydroxyknotane 9. This compound could only be obtained as a mixture with the corresponding monohydroxy-derivative 8. The structures of all synthesized compounds were established by means of FAB and MALDI TOF mass spectrometry, (1)H and (31)P NMR spectroscopy. The triphosphorylated knotane 10 exhibits high solubility in alcohols, allowing its complete enantiomeric resolution with a commercially available chiral HPLC column. (1)H,(1)H DQF-COSY correlation spectroscopy along with H/D exchange experiments and ab initio calculations provided the first detailed (1)H NMR signal assignments of knotanes in [D(6)]DMSO solution. The combination of variable temperature (1)H and (31)P NMR spectroscopy and molecular modeling has been applied to study the conformational behavior of the new knotanes in different solvents. It has been shown that in DMSO solution at room temperature knotanes exist in a relatively rigid nonsymmetrical conformation similar to that found in the solid state while faster conformational exchange leading to the average D(3) symmetrical structure was detected in a number of other solvents.     

Metallkomplexe des Hexamethyl-trisila-tetraphospha-nortricyclen P4 (Sime2)3

Transition Metal Complexes of the Hexamethyl-trisila-tetraphospha-nortricyclene P₄ (Sime ₂) ₃ P₄(Sime₂)₃ 1 reacts with Mo(CO)₆, Cr(CO)₅THF, and Mn(η-C₅H₅)(CO)₂THF to give crystalline complexes in which 1 functions as a monodentate ligand. In each compound one phophorus atom of the cyclotriphosphane ring coordinates to the metal atom. Using Mn(η-C₅H₅)(CO)₂THF, two different P atoms of the P₃ Cr(CO)₄ norbornadiene and 1 react, yielding the dimeric, red, crystalline compound (CO) ₄Cr[μ-P₄(Sime₂)₃]₂Cr(CO)₄. In this complex the two molecules of 1 are both bonded by two P atoms of the P ₃ ring to the two Cr(CO)₄ Units, forming a six-memered (CrP₂)₂ring.     

Form fluctuations of carbosilane dendrimers in dilute solution: a study using neutron spin echo spectroscopy

A series of carbosilane dendrimers with perfluorinated end groups has been prepared. The structure of these molecules in dilute solution is studied using small angle neutron scattering. For generations g<3 we find a non-spherical shape of the particles and a tendency for aggregation. This result is supported by the analysis of the diffusion coefficient obtained from photon correlation spectroscopy. The overall shape of the molecules is that of a core-shell particle. The generation 4 molecule is obtained as a compact sphere. Neutron spin echo spectroscopy reveals a relaxation time which is attributed to the form fluctuations of this particle.     

Chiroptical detection during liquid chromatography,part 5: On-line measurement of circular dichroism spectra Δε(λ) during stops of chromatographic flow

Summary A procedure is described which serves to measure circular dichrograms () on line during stops of flow in liquid chromatography. Since the concentration of substrate in the spectrometer cell during the stop is not known, the differential absorption coefficients are calculated from the experimental differential absorbances A by means of UV absorption (i. e. photomultiplier voltage) data. Verifications of the procedure are obtained by its application to three substrates (Table 1), the () spectra of which were known. The present on-line technique is compared with a corresponding off-line method.The N,N-dimethylthiobenzamides1 and2 as well as the 9,10-phenanthrenequinone7 consist of interconvertible enantiomers because their planar states are destabilized by steric overcrowding of groups. The unknown dichrograms () of1, 2 and7 are obtained (Figs. 2 and 4) and discussed with reference to the helicities of these molecules.In memory of the late Professor Dr. Dr. h. c. Günther Snatzke.     

Ion-exclusion chromatography with conductimetric detection of aliphatic carboxylic acids on a weakly acidic cation-exchange resin by elution with benzoic acid-beta-cyclodextrin

In this study, an aqueous solution consisting of benzoic acid with low background conductivity and beta-cyclodextrin (beta-CD) of hydrophilic nature and the inclusion effect to benzoic acid were used as eluent for the ion-exclusion chromatographic separation of aliphatic carboxylic acids with different pKa values and hydrophobicity on a polymethacrylate-based weakly acidic cation-exchange resin in the H+ form. With increasing concentration of beta-cyclodextrin in the eluent, the retention times of the carboxylic acids decreased due to the increased hydrophilicity of the polymethacrylate-based cation-exchange resin surface from the adsorption of OH groups of beta-cyclodextrin. Moreover, the eluent background conductivity decreased with increasing concentration of beta-cyclodextrin in 1 mM benzoic acid, which could result in higher sensitivity for conductimetric detection. The ion-exclusion chromatographic separation of carboxylic acids with high resolution and sensitivity was accomplished successfully by elution with a 1 mM benzoic acid-10 mM cyclodextrin solution without chemical suppression.     

Image analysis in the electron microscopy of cellulose protofibrils II. Digital correlation methods

Electron micrographs of parallel arrays of negatively stained ramie cellulose protofibrils were analyzed using the two-dimensional digital autocorrelation function (ACF). The method is based upon the statistical analysis of images in real space. The ACF shows strong parallel streaks of high correlation, and the lateral distance between adjacent streaks allows the mean interfibrillar distance to be estimated as 3.7 nm. The intensity profile along the streaks shows a weak modulation with peaks occurring at integral multiples of 3 or 6 nm. These results provide direct evidence that there is a regular axial texture in the protofibrils, and corroborate the conclusions previously drawn from optical diffraction analysis. Using the difference vectors found in the ACF it has been possible to reduce the picture noise level by linear integration, thereby obtaining an enhanced image. A preliminary result obtained in this way suggests that the projected protofibril morphology associated with the observed axial periodicity is a ribbon-like zigzag structure. Possible applications of the method for future work are discussed.