Simultaneous analysis of 13C‐glutathione as its dimeric form GSSG and its precursor [1‐13C]glycine using liquid chromatography/isotope ratio mass spectrometry

Determination of glutathione kinetics using stable isotopes requires accurate measurement of the tracers and tracees. Previously, the precursor and synthesized product were measured with two separate techniques, liquid chromatography/isotope ratio mass spectrometry (LC/IRMS) and gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). In order to reduce sample volume and minimize analytical effort we developed a method to simultaneously determine ¹³C‐glutathione as its dimeric form (GSSG) and its precursor [1‐¹³C]glycine in a small volume of erythrocytes in one single analysis. After having transformed ¹³C‐glutathione into its dimeric form GSSG, we determined both the intra‐erythrocytic concentrations and the ¹³C‐isotopic enrichment of GSSG and glycine in 150 µL of whole blood using liquid chromatography coupled to LC/IRMS. The results show that the concentration (range of µmol/mL) was reliably measured using cycloleucine as internal standard, i.e. with a precision better than 0.1 µmol/mL. The ¹³C‐isotopic enrichment of GSSG and glycine measured in the same run gave reliable values with excellent precision (standard deviation (sd) <0.3‰) and accuracy (measured between 0 and 5 APE). This novel method opens up a variety of kinetic studies with relatively low dose administration of tracers, reducing the total cost of the study design. In addition, only a minimal sample volume is required, enabling studies even in very small subjects, such as preterm infants. Copyright © 2009 John Wiley & Sons, Ltd.     

Kinetic theory of hydrodynamic flows,III. the torque on a rotating sphere or cylinder1

The extended Boltzmann equation introduced in previous papers is used to compute the torque exerted on a macroscopic sphere or cylinder placed in a dilute gas, when the mean free path of the gas molecules is small compared to the characteristic dimension of the sphere or cylinder. The usual hydrodynamic results are recovered in this kinetic theory calculation.Work supported in part by the National Science Foundation Grant No. CHE 77-16308.     

Lewis acid induced reactions of propargyl trimethyl silane with ω-ethoxy lactams synthesis of γ-allenyl-GABA

Reactions of propargyl trimethyl silane with ω-ethoxy lactams 1a-c under the influence of boron trifluoride etherate afford ω-allenyl lactams 3a-c; 5-allenyl-2-pyrrolidinone is hydrolysed to γ-allenyl-GABA.     

Transpose-free formulations of Lanczos-type methods for nonsymmetric linear systems

We present a transpose-free version of the nonsymmetric scaled Lanczos procedure. It generates the same tridiagonal matrix as the classical algorithm, using two matrix–vector products per iteration without accessing A^T. We apply this algorithm to obtain a transpose-free version of the Quasi-minimal residual method of Freund and Nachtigal [15] (without look-ahead), which requires three matrix–vector products per iteration. We also present a related transpose-free version of the bi-conjugate gradients algorithm. This revised version was published online in June 2006 with corrections to the Cover Date.     

INDO calculations on the sigmatropic [1, 5] H-Shift in 1,3-cyclohexadiene and 1,3,5-cycloheptatriene A homo-cyclopentadienyl transition state model

INDO calculations have been performed for the activated complex of the [1, 5] H.-shift in 1,3-cyclohexadiene and 1,3,5-cycloheptatriene. During the migration in the cyclohexadiene system a homoconjugation was calculated between the carbon atoms C₁ and C₅. For cycloheptatriene it could be demonstrated that one double bond does not participate in the reaction. Activation enthalpies are related to (homo)conjugation in the transition state of the reaction for cyclic conjugated dienes and trienes. The electron density on the migrating hydrogen can be related to the electron affinity of the ring system in the transition state.[/p]     

Novel approach to trans-fused carbobicycles

The combination of a silicon directed N-acyliminium ion cyclization reaction and a subsequent S_N2′ substitution of an imide nitrogen with lithium dimethyl cuprate constitutes a novel approach to functionalized transfused carbobicycles.     

Intramolecular reactions of acyclic n-acyliminium ions II allyl silanes as nucleophiles

Intramolecular reactions of acyclic N-acyliminium ions with allyl silanes, induced by protic or Lewis acid, lead to 3-vinylpyrrolidines or 3-vinylpiperidines.     

Hierarchical self-assembly of columnar aggregates

Biology often uses hierarchical self-assembly to produce complex functional structures from smaller components. At each level of this stepwise process, non-covalent interactions bring together the subunits of a lower level of complexity, using the information encoded in their structures. Applying this approach to synthetic systems represents a formidable challenge, because it requires a high degree of command of non-covalent interactions. In this tutorial review, recent developments in the hierarchical self-assembly of discrete columnar aggregates are discussed.