Metabolic profiling of rodent biological fluids via 1H NMR spectroscopy using a 1 mm microlitre probe

The application of a 1 mm TXI (1H/13C/15N) microlitre NMR probe with z-gradient for metabolic profiling of biofluids is described. The probe was used to provide spectral profiles for rat blood plasma using only approximately 2 microl of fluid with a range of solvent suppression techniques. Using a similar amount of fluid, spectra were obtained from rat and mouse cerebrospinal fluid, demonstrating that the probe could be used to profile rodents metabolically via biofluids previously inaccessible to NMR analysis without the need for termination.     

Amplification of a cyclic mixed-metalloporphyrin tetramer from a dynamic combinatorial library through orthogonal metal coordination

A cyclic porphyrin tetramer, consisting of two bis-phosphine substituted zinc(II) porphyrin units and two Rh(III)TPP units, is selected and amplified virtually quantitatively from a dynamic combinatorial library using 4,4'-bipy as a scaffold and using orthogonal binding modes.     

Controlling chemoselectivity in vinyl and allylic C-X bond activation with palladium catalysis: a pK(a)-based electronic switch

It has been demonstrated that the same Pd catalyst can be used to effect allylic substitution or vinylic cross-coupling reactions selectively and interchangeably on polyfunctionalized olefin building blocks despite the differences in reaction mechanism. This was achieved by altering the pK(a) of the conjugate acid of the allylic leaving group while keeping the vinyl coupling partner constant. In the case of 2,3-dibromo-1-propene, Pd-catalyzed allylic ionization with malonate nucleophile proceeded selectively and quantitatively in the presence of the Suzuki reaction components necessary for cross-coupling. Conversely, the bromide of 2-bromo-1-(4-ethylphenoxy)-2-propene could be cross-coupled selectively without activation of the allylic phenoxy substituent. In both reactions, the same catalyst could then be used to complete the sequence, which typically involved heating as the trigger to promote the second, more reluctant reaction. Mechanistic considerations as well as synthetic applications demonstrating the value of this interchangeable catalyzed sequence are presented.     

Measurement of orientation distributions using chemical shift amplification

A new three-dimensional magic angle spinning (MAS) experiment is proposed, based on a combination of the two-dimensional rotor-synchronized MAS experiment of Spiess and co-workers and a new chemical shift anisotropy amplification method. The new experiment is demonstrated on a macroscopically ordered sample of ultra-high molecular weight poly(ethylene).     

Double-quantum dipolar recoupling at high magic-angle spinning rates

A full investigation of the possible homonuclear double-quantum recoupling sequences, based on the RN family of sequences with N < or = 20, is given. Several new RN sequences, R16(6)(5), R18(8)(5), and R18(10)(5), were applied at high magic-angle spinning rates and compared with theory. The R18(10)(5) technique can be used to recouple dipolar couplings at spinning rates up to 39 kHz, and the application of the sequence in an INADEQUATE experiment is shown for a spinning rate of 30 kHz.     

A Geometric Invariant for Metabelian Pro-p Groups

In [2] Bieri and Strebel introduced a geometric invariant forfinitely generated abstract metabelian groups that determineswhich groups are finitely presented. For a valuable survey oftheir results, see [6]; we recall the definition briefly inSection 4. We shall introduce a similar invariant for pro-pgroups. Let F be the algebraic closure of F_p and U be the formal powerseries algebra F[T], with group of units U^x. Let Q be a finitelygenerated abelian pro-p group. We write Z_p[Q] for the completedgroup algebra of Q over Z_p. Let T(Q) be the abelian group Hom(Q,U^x) of continuous homomorphisms from Q to U^x. We write 1 forthe trivial homomorphism. Each vT(Q) extends to a unique continuousalgebra homomorphism from Z_p[Q]to U.     

13C NMR spectra of diazastilbenes. I—trans-styryldiazines

The ¹³C NMR spectra of all trans-styryldiazines, methyldiazines and trans-styrylpyridines have been fully assigned. Empirical shift increments were obtained for the chemical shifts of the carbon atoms; these are discussed in the light of theoretical considerations.