A new route to 2-styrylbenzimidazoles

An attempt was made to prepare 2-benzylquinoxalin-3-one by hydrolyzing the azlactone, 2-phenyl-4-benzylidene-5-oxazolone to β-phenylpyruvic acid and then treating this in situ with o-phenylenediamine (OPDA). The initial hydrolysis apparantly proceeded only as far as opening the azlactone ring forming 2-benzamidocinnamic acid which condensed with OPDA to form a substituted styrylbenzimidazole.     

Direct Electrochemical Investigations of 17-Electron Complexes of CpM(CO)(3)(*) (M = Mo, W, and Cr)

Photolysis of complexes of the type M(2)(CO)(6)(RC(5)H(4))(2) (where M = W, Mo, Cr and R = H (Cp) or CH(3) (Cp')) leads to the production of short lived 17-electron radicals. Direct electrochemical characterization of these intermediates has been achieved using a technique known as photomodulated voltammetry (PMV). The results from PMV analysis are in excellent agreement with literature estimates for CpMo(CO)(3)(*) and CpCr(CO)(3)(*). However, CpW(CO)(3)(*) is found to be shifted oxidatively 115 mV relative to previous literature estimates. The change in the value for the tungsten complex changes previous estimates to the bond dissociation energy for tungsten metal hydrides by 3.0 +/- 0.9 kcal/mol. Lifetime information on the radicals is also reported based on the phase shift of the electrochemical signal observed by PMV under limiting current conditions.     

Concerted cycloaddition of chlorosulfonyl isocyanate to α-pinene stepwise rearrangement of the β-lactam cycloadduct to a γ-lactam

Chlorosulfonyl isocyanate adds to α-pinene in concerted fashion to give the unrearranged N-chlorosulfonyl-β-lactam 2 (75%). Thermolysis of cycloadduct 2 affords the rearranged N-chlorosulfonyl-γ-lactam 6 (60%) via a sequence of transient carbonium ions (45). Reductive hydrolysis of 2 and 6 gave, respectively, the NH-β-lactam 3 (70%) and the NH-γ-lactam 7 (70%). Proof of structure of the rearranged γ-lactams 6 and 7 are provided, respectively, by X-ray crystallographic analysis and the application of the Eu(dpm)₃ NMR shift reagent.     

Verification of the optimal probabilistic basis of aural processing in pitch of complex tones

Periodicity pitch for complex tones has been quantitatively accounted for by a two-stage process of Fourier-frequency analysis subject to random errors and significant nonlinearities, followed by an harmonic pattern recognizer that makes an optimum probabilistic estimate of the fundamental period of musical and speech sounds. The theory predicts that periodicity pitch is a multimodal probabilistic function of a given stimulus. A clear and empirically supported distinction is made between limitations on the pitch mechanism caused by the stochastic nature of aural frequency representation and by the deterministic resolution bandwidths of aural frequency analysis. This model was developed earlier [J. L. Goldstein, J. Acoust. Soc. Am 54, 1496-1516 (1973)] to account for probabilistic data on pitch errors [A. J. M. Houtsma and J. L. Goldstein, J. Acoust. Soc. Am. 51, 520 (1972)] measured with periodic stimuli comprising two successive harmonics. This paper presents new predictions by the theory that were calculated, with computer simulation where needed, for known probabilistic pitch data from stimuli comprising three to six successive harmonics. Predicted pitch errors increase with increasing errors in estimating the frequencies of stimulus harmonics and decrease as more harmonics are added to the stimulus. Optimum processor theory fully accounts for the multicomponent pitch data on the basis of similar errors in estimating component stimulus frequencies as reported earlier, thus providing further evidence for the optimum probabilistic basis of aural signal processing in pitch of complex tones.     

Elasticity and critical bending moment of model colloidal aggregates

The bending mechanics of singly bonded colloidal aggregates are measured using laser tweezers. We find that the colloidal bonds are capable of supporting significant torques, providing a direct measurement of the tangential interactions between particles. A critical bending moment marks the limit of linear bending elasticity, past which small-scale rearrangements occur. These mechanical properties underlie the rheology and dynamics of colloidal gels formed by diffusion-limited cluster aggregation, and give critical insight into the contact interactions between Brownian particles.     

Influence of Cyclodextrins on the Kinetics of Oxidation of Amino Acids and BSA by Hydrazyl Radicals

The kinetics of oxidation of amino acids (Arg, His, Lys, Phe, Thr and Tyr), a dipeptide (Gly-His), and BSA (bovine serum albumin) by two persistent water soluble free radicals of the hydrazyl type has been studied.The rate decreases in the order Arg>Lys>Tyr>Thr>HisBSAPheGly-His with bothfree radicals. Addition to the reaction mixture of - and -cyclodextrin decreases the oxidation rate, probably due to amino acidencapsulation in the cyclodextrin cavity. -Cyclodextrin protects more efficiently against oxidation than -cyclodextrin.     

The microscopic investigation of structures of moving flux lines by neutron and muon techniques

We have used a variety of microscopic techniques to reveal the structure and motion of flux line arrangements, when the flux lines in low T _c type II superconductors are caused to move by a transport current. Using small-angle neutron scattering by the flux line lattice (FLL), we are able to demonstrate directly the alignment by motion of the nearest-neighbor FLL direction. This tends to be parallel to the direction of flux line motion, as had been suspected from two-dimensional simulations. We also see the destruction of the ordered FLL by plastic flow and the bending of flux lines. Another technique that our collaboration has employed is the direct measurement of flux line motion, using the ultra-high-resolution spectroscopy of the neutron spin-echo technique to observe the energy change of neutrons diffracted by moving flux lines. The muon spin rotation (μSR) technique gives the distribution of values of magnetic field within the FLL. We have recently succeeded in performing μSR measurements while the FLL is moving. Such measurements give complementary information about the local speed and orientation of the FLL motion. We conclude by discussing the possible application of this technique to thin film superconductors.     

Nitrogen-15 nuclear magnetic resonance spectroscopy. Chemical shifts of methyl substituted cis-decahydroquinolines

¹⁵N Chemical shifts of cis-decahydroquinoline, N-methyl-cis-decahydroquinoline, and of 19 methyl substituted NH- and NCH₃-cis-decahydroquinolines are reported. Shift values of conformationally homogeneous compounds can be used to determine the chemical shifts of the possible conformations of the mobile compounds. Equilibrium constants derived from the shifts of the contributing conformations agree with results of low temperature ¹³C NMR spectroscopy.