Detection of Amadori compounds by capillary electrophoresis coupled to tandem mass spectrometry

Capillary electrophoresis coupled to mass spectrometry (CE-MS) is reported for the first time as an alternative and powerful analytical method for the characterization and monitoring of N-substituted 1-amino-1-deoxyketoses (Amadori compounds). It allows rapid separation and identification of Amadori compounds, while benefiting from the well-known advantages of MS, such as specificity and sensitivity. Amadori compounds of several amino acids, such as glycine, valine, isoleucine, methionine, proline, and phenylalanine, as well as a cysteine-derived compound, were separated and/or discriminated using CE-MS/MS under standard conditions. The technique may also be useful to study the stability and degradation kinetics of other labile charged Maillard intermediates that play an important role in food and medical science.     

Synthesis of corroles bearing up to three different meso substituents

[reaction: see text] We have developed a new method that affords regioisomerically pure corroles possessing up to three different substituents at the meso positions. The corrole formation reaction involves the acid-catalyzed condensation of a dipyrromethane-dicarbinol with pyrrole followed by oxidation with DDQ. ABC-Type corroles were synthesized for the first time according to this procedure.     

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.     

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.     

Carbon-13 kinetic isotope effect of the decarbonylation of oxalic acid

Carbon-13 intramolecular kinetic isotope effects in the decarbonylation of oxalic acid dihydrate of natural isotopic composition by SO₃ and by fuming sulphuric acid at room temperature and decarbonylation of oxalic acid dihydrate by 100% H₃PO₄ in the temperature interval 80–150°C have been determined. The obtained isotopic and kinetic results have been compared with the earlier¹³C experimental and theoretical studies in other solvents.     

A quantitative evaluation of the electrostatic theory for ion pair chromatography

Summary A quantitative model for ion pair chromatography based on the electrostatic theory is described. The model is based on the solution of the linearised Poisson-Boltzmann equation in a cylinder. The obtained equations are compared with experimental data from a number of different systems. The agreement between theory and experiments is satisfactorily. Systematic deviations due to the use of the linearised equation and ion correlation effects are discussed.     

On the determination of crystallinity and cellulose content in plant fibres

A comparative study of cellulose crystallinity based on the sample crystallinity and the cellulose content in plant fibres was performed for samples of different origin. Strong acid hydrolysis was found superior to agricultural fibre analysis and comprehensive plant fibre analysis for a consistent determination of the cellulose content. Crystallinity determinations were based on X-ray powder diffraction methods using side-loaded samples in reflection (Bragg-Brentano) mode. Rietveld refinements based on the recently published crystal structure of cellulose Iβ followed by integration of the crystalline and amorphous (background) parts were performed. This was shown to be straightforward to use and in many ways advantageous to traditional crystallinity determinations using the Segal or the Ruland–Vonk methods. The determined cellulose crystallinities were 90–100 g/100 g cellulose in plant-based fibres and 60–70 g/100 g cellulose in wood based fibres. These findings are significant in relation to strong fibre composites and bio-ethanol production.     

Redox thermochemistry of SrFe1-xCoxO3-d

The enthalpy of oxidation of SrFe_1-xCo_xO_3-d with x=0.33 and 0.67 has been determined by adiabatic calorimetry; average values for x=0.33 and 0.67 are -67±11 and -49.5±9 kJ (mol O₂)^-1. These data and the previously reported value for SrFeO_3-d suggest that the enthalpy of oxidation for pure (perovskite-type) SrCoO_3-d is close to zero. Earlier reported composition - partial pressure data for SrFe_0.67Co_0.33O_3-d are reproduced when preferential oxidation of iron is assumed for low partial pressures of oxygen. This revised version was published online in August 2006 with corrections to the Cover Date.     

Synthesis and characterization of an Al(69)(3-) cluster with 51 naked Al atoms: analogies and differences to the previously characterized Al(77)(2-) cluster

A disproportionation process of a metastable AlCl solution with a simultaneous ligand exchange-Cl is substituted by N(SiMe(3))(2)-leads to a [Al(69)[N(SiMe(3))(2)](18)](3-) cluster compound that can be regarded as an intermediate on the way to bulk metal formation. The cluster was characterized by an X-ray crystal structural analysis. Regarding its structure and the packing within the crystal, this metalloid cluster with 4 times more Al atoms than ligands is compared to the [Al(77)N(SiMe(3))(2)](20)](2-) cluster that has been published four years ago. Although there is a similar packing density of the Al atoms in both clusters as well as in Al metal, the X-ray structural analysis shows significant differences in topology and distance proportions. The differences between these-at a first glance almost identical-Al clusters demonstrate that results of physical measuring, e.g., of nanostructured surfaces which carry supposedly identical cluster species, have to be interpreted with great caution.     

Photoelectron spectra of cyclopolysilanes

Summary He (I) PE spectra of cyclopentasilane and cyclohexasilane show excellent agreement with STO-3 G + ab initio calculations. The HOMO in both compounds is of (SiSi) 3 p character. First IP's appear at 9.4 and 9.6 eV respectively.

---

Photoelektronenspektren von Cyclopolysilanen (Kurze Mitt.)

Zusammenfassung Die He (I) PE-Spektren der Cyclosilane Si₅H₁₀ und Si₆H₁₂ zeigen ausgezeichnete Übereinstimmung mit STO-3 G + ab initio Rechnungen. Beide Ringe besitzen HOMO's mit (SiSi) 3 p Charakter. Die ersten Ionisierungspotentiale liegen bei 9.4 bzw. 9.6 eV.