Gold‐Catalyzed Cycloisomerization of 1,6,8‐Dienyne Carbonates and Esters to cis‐Cyclohepta‐4,8‐diene‐Fused Pyrrolidines

A synthetic approach that provides access to cis‐cyclohepta‐4,8‐diene‐fused pyrrolidines efficiently through Au^I‐catalyzed cycloisomerization of 1,6,8‐dienyne carbonates and esters at a low catalyst loading of 2 mol % is reported. Starting carbonates and esters with a pendant alkyl group on the terminal alkenyl carbon center were found to favor tandem 1,2‐acyloxy migration/cyclopropanation followed by Cope rearrangement of the resulting cis‐3‐azabicyclo[3.1.0]hexane intermediate. On the other hand, substrates containing a terminal diene or starting materials in which the distal alkene moiety bears a phenyl substituent were observed to undergo competitive but reversible 1,3‐acyloxy migration prior to the nitrogen‐containing bicyclic ring formation. The delineated reaction mechanism also provides experimental evidence for the reversible interconversion between the oft‐proposed organogold intermediates obtained in this step of the tandem process.     

Inner hair cell loss and steady-state potentials from the inferior colliculus and auditory cortex of the chinchilla

Steady-state evoked potentials were measured from unanesthetized chinchillas both before and after carboplatin-induced selective inner hair cell loss. Recordings were made from both the inferior colliculus (IC) and the auditory cortex (AC). The steady-state potential was measured in the form of the envelope following response (EFR), obtained by presenting a two-tone stimulus (f1 = 2000 Hz; f2 = 2020, 2040, 2080, 2160, or 2320 Hz), and measuring the magnitude of the Fourier coefficient at the f2-f1 difference frequency. From the IC, precarboplatin, EFR amplitude vs difference tone frequency showed a bandpass pattern, with maximum amplitude at either 160 or 80 Hz, depending upon stimulus level. Postcarboplatin, the preferred difference frequency was 80 Hz for all stimulus levels. From the AC, EFR amplitude versus difference tone frequency also showed a bandpass pattern, with the maximum amplitude at 80 Hz both pre- and postcarboplatin. EFR amplitude from the IC was decreased for some conditions postcarboplatin, while the amplitude from the AC showed no significant change.     

Achievable accuracy of parameter estimation for multidimensional NMR experiments

A fundamental issue in NMR spectroscopy is the estimation of parameters such as the Larmor frequencies of nuclei, J coupling constants, and relaxation rates. The Cramer-Rao lower bound provides a method to assess the best achievable accuracy of parameter estimates resulting from an unbiased estimation procedure. We show how the Cramer-Rao lower bound can be calculated for data obtained from multidimensional NMR experiments. The Cramer-Rao lower bound is compared to the variance of parameter estimates for simulated data using a least-squares estimation procedure. It is also shown how our results on the Cramer-Rao lower bound can be used to analyze whether an experimental design can be improved to provide experimental data which can result in parameter estimates with higher accuracy. The concept of nonuniform averaging in the indirect dimension is introduced and studied in connection with nonuniform sampling of the data.     

Do light colored scalars exist?

The general question of the properties of light, neutral colored spin-zero particles in QCD is examined. Models with spontaneous breaking of QCD at very large distances, such as that of DeRújula, Giles, and Jaffe and the SO(3) scheme of Slansky, Goldman, and Shaw, require such light colored Higgs scalars. These scalars will form color-singlet hadronic bound states at short distances and estimates are given of bound state masses, decay widths, and production rates in processes such as ψ → γ + X within the MIT bag model. The resulting states are expected in the mass neighborhood ～1.5 GeV and should resemble glueballs.     

The reaction π−p → K0Σ0 up to 2375 MeV/c

Differential cross-section and polarization measurements for the reaction π^?p → K⁰Σ⁰ are presented from 1395 to 2375 MeV/c incident beam momentum. The polarization data from an earlier experiment, from thershold to 1334 MeV/c, have been re-analysed by an improved method leading to a substantial reduction in the errors.     

ππ scattering in the I = 2 channel

I=2π⁺π⁺ scattering is studied in π⁺p reactions at 5.45 GeV/c. The π⁺π⁺ cross sections and phase shifts have been determined from the reaction π⁺p → π⁺π⁺n using first a pure and then a modified Chew-Low extrapolation to the pion pole.     

Dimetallic complexes of acyclic pyridine-armed ligands derived from 3,6-diformylpyridazine

A bis(pyridine-armed) acyclic Schiff base ligand L1 has been synthesised from 3,6-diformylpyridazine and two equivalents of 2-(2-aminoethyl)pyridine. Reduction of this ligand using NaBH(4) resulted in the formation of the amine analogue L2. Complexes of the form [M(2)L1(mu-X)]Y(2)ClO(4)[where: M = Cu(II), X = OH(-) and Y = ClO(4)(-) 1, Cl(-) 2, Br(-) 3 or I(-) 4; M = Co(II), X = OH(-) and Y = ClO(4)(-) 5; M = Ni(II), X = SCN(-) 6 or X = N(3)(-) 7 and Y = ClO(4)(-)], and [Cu(2)L2(mu-OH)](ClO(4))(3) 8 were prepared and characterised. The complexes 1 and 5-7 have been characterised by single-crystal X-ray diffraction. The acyclic L1 ligand provides three nitrogen donor atoms per metal centre, including a pyridazine bridge between the metal centres, and the anion X also bridges the two metal centres. As required, coordinating solvent molecules or additional anions make up the remainder of the coordination sphere. The two copper centres of 1 are very strongly antiferromagnetically coupled (2J=-1146 cm(-1))via the pyridazine and hydroxide ion bridges, whereas the competing antiferromagnetic pyridazine bridging pathway and ferromagnetic 1,1-bridging azide pathway resulted in the observation of weak antiferromagnetic exchange in the dinickel(II) complex 7 (2J=-14 cm(-1)). Electrochemical examination of L1, L2 and complexes 1 and 5-8 revealed multiple redox processes. These have been tentatively assigned to a mixture of metal centred and ligand centred redox processes on the basis of cyclic voltammetry and coulometry results and comparisons with literature examples.     

Control of molecular architecture by the degree of deprotonation: self-assembled di- and tetranuclear copper(II) complexes of N,N'-bis(2-pyridylmethyl)pyrazine-2,3-dicarboxamide

In the absence of added base, a deep navy-blue dimeric copper complex [CuII(H2L)(MeCN)]2(BF4)4 (1) of the non-deprotonated bis-terdentate diamide ligand H2L self-assembles whereas in the presence of base a grass-green [2 x 2] grid complex [CuII(HL)]4(BF4)4 (2) of the monodeprotonated ligand HL-, a rare example of a discrete grid of pyrazine-bridged metal ions, is formed.     

NMR analysis of lignins in CAD-deficient plants. Part 1. Incorporation of hydroxycinnamaldehydes and hydroxybenzaldehydes into lignins

Peroxidase/H2O2-mediated radical coupling of 4-hydroxycinnamaldehydes produces 8-O-4-, 8-5-, and 8-8-coupled dehydrodimers as has been documented earlier, as well as the 5-5-coupled dehydrodimer. The 8-5-dehydrodimer is however produced kinetically in its cyclic phenylcoumaran form at neutral pH. Synthetic polymers produced from mixtures of hydroxycinnamaldehydes and normal monolignols provide the next level of complexity. Spectral data from dimers, oligomers, and synthetic polymers have allowed a more substantive assignment of aldehyde components in lignins isolated from a CAD-deficient pine mutant and an antisense-CAD-downregulated transgenic tobacco. CAD-deficient pine lignin shows enhanced levels of the typical benzaldehyde and cinnamaldehyde end-groups, along with evidence for two types of 8-O-4-coupled coniferaldehyde units. The CAD-downregulated tobacco also has higher levels of hydroxycinnamaldehyde and hydroxybenzaldehyde (mainly syringaldehyde) incorporation, but the analogous two types of 8-O-4-coupled products are the dominant features. 8-8-Coupled units are also clearly evident. There is clear evidence for coupling of hydroxycinnamaldehydes to each other and then incorporation into the lignin, as well as for the incorporation of hydroxycinnamaldehyde monomers into the growing lignin polymer. Coniferaldehyde and sinapaldehyde (as well as vanillin and syringaldehyde) co-polymerize with the traditional monolignols into lignins and do so at enhanced levels when CAD-deficiency has an impact on the normal monolignol production. The implication is that, particularly in angiosperms, the aldehydes behave like the traditional monolignols and should probably be regarded as authentic lignin monomers in normal and CAD-deficient plants.