Markierungsexperimente zur fragmentierung von 1,2,3-thiadiazolen

The generation of thiirenes in the thermal and photochemical nitrogen elimination of 1,2,3-thiadiazoles is discussed in relation to oxirene formation. Isotope labelling experiments were performed with 4-phenyl-[4-¹³C]-1,2,3-thiadiazole ( 7 ) as the substrate.     

Über Oxotantalate der Lanthanide des Formeltyps MTaO4 (M = La – Nd,Sm – Lu)

About Lanthanide Oxotantalates with the Formula MTaO₄ (M = La – Nd, Sm – Lu) Besides being a by‐product of solid state syntheses in tantalum ampoules the lanthanide(III) oxotantalates of the formula MTaO₄ can be easily prepared by sintering lanthanide sesquioxide M₂O₃ and tantalum(V) oxide Ta₂O₅ with sodium chloride as flux. Under these conditions two structure types emerge depending upon the M³⁺ cationic radius. For M = La – Pr the MTaO₄‐type tantalates crystallize in the space group P2₁/c with lattice constants of a = 762(±1), b = 553(±4), c = 777(±4) pm, β = 101(±1)° and four formula units per unit cell. With M = Nd, Sm – Lu, the monoclinic cell dimensions (space group P2/c) shrink to the lattice constants like a = 516(±9), b = 551(±9), c = 534(±9) pm, β = 96.5(±0.3)° and there are only two formula units present. Both structures show a coordination sphere of eight oxygen atoms for the lanthanide trications shaped as distorted square antiprism for the structure with the larger lanthanides (in the following referred to as A‐type) and as trigonal dodecahedron for the structure with the smaller ones (called as B‐type in the following). The coordination environment about the Ta⁵⁺ cations can be described as a slightly distorted octahedron (CN = 6) for the A‐type structure of MTaO₄ and a heavily distorted one (CN = 6) for the B‐type. The difference between the two types results from the interconnection of these [TaO₆]^7? octahedra. Whereas they are connected via four vertices to form corrugated layers according to parallel the bc‐plane in the A‐type, the octahedra of the B‐type MTaO₄ structure share edges to built up zig‐zag chains along the c axis.     

Determination of internuclear distances in uniformly labeled molecules by rotational-resonance solid-state NMR

Rotational-resonance magic-angle spinning NMR experiments are frequently used to measure dipolar couplings and to determine internuclear distances. So far most measurements were performed on samples containing isolated spin pairs. Thus, extensive structure elucidation, for example in biomolecules, requires the preparation of a whole set of doubly labeled samples. Here, we describe the analysis of the rotational-resonance polarization-exchange curves obtained from a single, uniformly labeled sample. It is shown experimentally that, at a magnetic field of 14.09 T, the rotational-resonance conditions in uniformly (13)C-labeled threonine are sufficiently narrow to permit the measurement of five distances between the four carbon spins with an accuracy of better than 10%. The polarization-exchange curves are analyzed using a modified two-spin model consisting of the two active spins. The modified model includes an additional offset in the final polarization, which comes from the coupling to the additional, passive, spins. The validity of this approach is experimentally verified for uniformly (13)C-labeled threonine. The broader applicability of such a model is demonstrated by numerical simulations which quantify the errors as a function of the most relevant parameters in the spin system.     

Determination of phenoxy acid herbicides by high-performance liquid chromatography and on-line enrichment

Summary Phenoxy acid herbicides have been determined by use of high-pressure liquid chromatography (HPLC). The separation efficiency of several stationary phases like octadecyl silica and nitril silica has been estimated using different mobile phases. Regarding the necessary experimental conditions for separating phenoxy acids, the enrichment phases for on-line operation have been tested by use of column switching. The method of sample enrichment is described and the enrichment factors have been calculated.

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Bestimmung von Phenoxycarbonsäure-Herbiciden durch HPLC und On-line-AnreicherungI. Möglichkeiten der chromatographischen Trennung durch HPLC unter besonderer Berücksichtigung der On-line-Anreicherung der Herbicid-Verbindungen

     

Thermodynamics of mixed electrolyte solutions. XI. An isopiestic study of the quaternary system NaCl−KCl−CaCl2−H2O at 25°C

Osmotic and activity coefficients in the aqueous quaternary system sodium chloride-potassium chloride-calcium chloride were derived from isopiestic measurements at 25°C. The isopiestic data were treated by the various procedures of Scatchard, Friedman, and Reilly, Wood, and Robinson. The results obtained showed good agreement with those obtained by pseudo-ternary transforms. Interaction parameters obtained indicated the preponderance of pairwise interactions. Excess Gibbs free energies of mixing were calculated.     

The effectiveness of solvents as hydrogen bond donors

Taft and Kamlet's -scale of solvent hydrogen bond donation ability is reexamined with regard to its correlations with three widely used polarity scales: Dimroth and Reichardt's E _T (30), Kosower's Z and Mayer's A _N , as well as with the _m values of the solvents when present as monomeric solutes. The correlation with E _T serves to extend the solvent -scale according to the expression:

Slow water diffusion in micellar solutions

Slowly diffusing water molecules were found by quasi-elastic neutron scattering (QENS) in a sodium dodecyl sulfate (SDS) micellar solution, and both their diffusion coefficient (4.33 x 10(-6) cm2 x s(-1)) and mole fraction (0.057) were determined. After successfully checking the mean slowing down of solvent molecules by the gradient compensated stimulated spin-echo (GCSTE) pulse sequence NMR method, a similar effect was observed with this technique in the solvent phase of dodecyl trimethylammonium bromide (DTAB) and differing chain length (X = 12, 20, 30, and 40) ethoxylated nonyl phenol (9NX) micellar systems. Following the literature, the experimental results are qualitatively explained by assuming that, apart from ionic hydration, H-bonds may form between the solvent molecules and the O or N atoms present in the hydrophilic (head)groups of the micelle-forming monomers.     

Influence of camphorsulfonic acid in nitroxide‐mediated styrene miniemulsion polymerization

The rate‐accelerating effects of camphorsulfonic acid (CSA) on nitroxide‐mediated styrene miniemulsion polymerization were studied. Polymerizations were initiated with benzoyl peroxide (BPO) as an initiator and mediated with either 2,2,6,6‐tetramethylpiperidinyloxy (TEMPO) or 4‐hydroxy‐2,2,6,6‐tetramethylpiperidinyloxy (OH‐TEMPO). Although CSA has been used to accelerate the rate in bulk nitroxide‐mediated polymerizations, it has not been well studied in emulsion/miniemulsion. With dispersed systems, the effectiveness of CSA is likely to be affected by partitioning between the aqueous and organic phases. In styrene miniemulsion experiments performed over a range of conditions, the effect of adding CSA varied from negligible to significantly increasing the final conversion and molecular weight, depending on the nitroxide:BPO ratio. At a ratio of nitroxide:BPO = 1.7, the effect of CSA addition is small, whereas the final conversion and molecular weight are dramatically enhanced by CSA addition when the nitroxide:BPO ratio is 3.6. CSA is most effective in enhancing the rate and molecular weight when the initial free‐nitroxide concentration is higher. The magnitude of the rate and molecular weight enhancement was similar for TEMPO and OH‐TEMPO despite their differences in water solubility. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2828–2841, 2002     

Photochemically catalyzed reaction of ochratoxin A with D- and L-cysteine

The photolysis (>300 nm) of ochratoxin A (OTA, N-[[(3R)-5-chloro-8-hydroxy-3-methyl-1-oxo-7-isochromanyl]carbonyl]-3-phenyl-L-alanine, 1) in the presence of excess (2 and 12 molar equiv) cysteine (CySH) has been investigated and found to yield sulfur adducts 5 and 6 that are characterized by liquid chromatography-mass spectrometry and 1H-NMR spectroscopy. The adduct 5 was ascribed to the Michael addition conjugate resulting from covalent attachment of CySH to the ochratoxin quinone (4) generated by photooxidation of OTA. This species was also formed by photolysis of a synthetic sample of the hydroquinone of OTA (ochratoxin hydroquinone, 3) in the presence of 12 equiv L-CySH. The conjugate 5 derived from photolysis of 3 with L-CySH was used for 1H-NMR analysis. The sulfur adduct 6 was the major species detected from covalent attachment of CySH to photoactivated OTA, and it resulted from direct displacement of the OTA Cl atom by CySH. The implications of the cysteinyl adducts to the in vivo toxicity of OTA are discussed, with particular emphasis given to conjugate 5, as products from the photooxidative pathway may be of relevance to the nephrotoxic properties of OTA.     

NMR spectra of a microcrystalline protein at 30 kHz MAS

Proteins are not always available in amounts desirable for solid-state magic-angle spinning (MAS) nuclear-magnetic resonance (NMR) spectroscopy. To maximize the signal-to-noise ratio achievable with small samples, the filling factor must be optimized by using small-diameter MAS rotors. These rotors have the added benefit of allowing higher radio frequency field amplitudes during polarization transfer steps and during decoupling periods as well as allowing higher spinning frequencies. We demonstrate the advantages of relatively fast MAS (30 kHz using a 2.5 mm rotor) compared to MAS at 12 kHz for the 10.4 kDa model protein Crh with 93 residues and show that the signal-to-noise ratio in two-dimensional correlation spectra can be significantly improved by taking advantage of optimized pulse sequences available with rapid MAS.