Synthesis of 2-substituted benzofurans and indoles using functionalized titanium benzylidene reagents on solid phase

Titanium(IV) benzylidenes bearing a masked oxygen or nitrogen nucleophile in the ortho position were generated from thioacetals, using low-valent titanocene complex, Cp2Ti[P(OEt)3]2. Methylene acetal, alkyl ether, silyl ether, fluoro, tertiary amino, and N-alkyl, N-benzyl, N-prenyl, and N-silyl tert-butyl carbamate groups were tolerated in the titanium alkylidene reagents (Schrock carbenes). Aryl-chlorine bonds were stable to the titanium benzylidene functionality, but there was poor chemoselectivity for the reduction of the thioacetal in the presence of an aryl chloride. The titanium benzylidenes converted Merrifield and Wang resin-bound esters into enol ethers. The oxygen nucleophile was masked as a TMS ether, and when the resin-bound enol ethers bearing this ortho substituent were treated with 1% TFA in dichloromethane, benzofurans were released from resin in high yields. The chameleon catch strategy ensured excellent purity. In a similar way, N-alkylated and N-silylated tert-butyl carbamates were used for the synthesis of N-alkyl and N-Boc indoles, respectively. These traceless solid-phase syntheses of heterocycles are believed to involve postcleavage modification rather than cyclative termination.     

ELECTRON TRANSFER REACTIONS OCCURRING UPON LASER FLASH PHOTOLYSIS OF PHOSPHOLIPID BILAYER SYSTEMS CONTAINING CHLOROPHYLL,BENZOQUINONE AND CYTOCHROME c-II. ELECTRICALLY NEUTRAL AND POSITIVELY-CHARGED VESICLES*

Abstract— The primary and secondary electron transfer reactions which occurred upon laser flash photolysis of electrically neutral and positively-charged lipid bilayer vesicles containing chlorophyll, benzoquinone and cytochrome c were determined by time-resolved difference spectral and kinetic measurements, and compared with previous results obtained with negatively-charged vesicles (Y. Fang and G. Tollin, Photochem. Photobiol. 1988). The extent to which oxidized cytochrome c could function as an electron acceptor from triplet state chlorophyll, and reduced cytochrome c could act as an electron donor to chlorophyll cation radical, decreased from negatively-charged to electrically neutral to positively-charged vesicles, in agreement with expectations based on changes in the ability of cytochrome c to bind to the bilayer. In all three types of vesicles, cytochrome c reduction by benzoquinone anion radical occurred in the aqueous phase.     

Spectral properties of random Schrödinger operators with unbounded potentials

We investigate spectral properties of random Schrödinger operators H = - + _n()(1 + |n|) acting onl ²(Z ^d), where _n are independent random variables uniformly distributed on [0, 1].Research partially supported by a Sloan Doctoral Dissertation Fellowship and NSERC under grant OGP-0007901Research partially supported by NSF grant DMS-9101716     

Limit on the electron electric dipole moment in gadolinium-iron garnet

A new method for the detection of the electron electric dipole moment (EDM) using a solid is described. The method involves the measurement of a voltage induced across the solid by the alignment of the sample's magnetic dipoles in an applied magnetic field, H. A first application of the method to GdIG has resulted in a limit on the electron EDM of 5 x 10(-24)e cm, which is a factor of 40 below the limit obtained from the only previous solid-state EDM experiment. The result is limited by the imperfect discrimination of an unexpectedly large voltage that is even upon the reversal of the sample magnetization.     

Construction of the Incipient Infinite Cluster for Spread-out Oriented Percolation Above 4 + 1 Dimensions

 We construct the incipient infinite cluster measure (IIC) for sufficiently spread-out oriented percolation on ℤ ^d × ℤ₊, for d +1 > 4+1. We consider two different constructions. For the first construction, we define ℙ ⁿ (E) by taking the probability of the intersection of an event E with the event that the origin is connected to (x,n)  ℤ ^d × ℤ₊, summing this probability over x  ℤ ^d , and normalising the sum to get a probability measure. We let n → ∞ and prove existence of a limiting measure ℙ_∞, the IIC. For the second construction, we condition the connected cluster of the origin in critical oriented percolation to survive to time n, and let n → ∞. Under the assumption that the critical survival probability is asymptotic to a multiple of n ⁻¹, we prove existence of a limiting measure ℚ_∞, with ℚ_∞ = ℙ_∞. In addition, we study the asymptotic behaviour of the size of the level set of the cluster of the origin, and the dimension of the cluster of the origin, under ℙ_∞. Our methods involve minor extensions of the lace expansion methods used in a previous paper to relate critical oriented percolation to super-Brownian motion, for d+1 > 4+1. Received: 13 December 2001 / Accepted: 11 July 2002 Published online: 29 October 2002 RID="*" ID="*" Present address: Department of Mathematics and Computer Science, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven, The Netherlands. E-mail: rhofstad@win.tue.nl     

Observation of D+(s)K- and evidence for D+(s)pi- final states in neutral B decays

We report the first observation of a B meson decay that is not accessible by a direct spectator process. The channel B(0)-->D(+)(s)K- is found in a sample of 85 x 10(6) BB; events, collected with the Belle detector at KEKB, with a branching fraction B(B(0)-->D(+)(s)K-)=(4.6(+1.2)(-1.1)+/-1.3) x 10(-5). We also obtain evidence for the B0-->D(+)(s)pi(-) decay with branching fraction B(B0-->D(+)(s)pi(-))=(2.4(+1.0)(-0.8)+/-0.7) x 10(-5). This value may be used to extract a model-dependent value of |V(ub)|.     

Electronic properties of iron arsenic high temperature superconductors revealed by angle resolved photoemission spectroscopy (ARPES)

We present an overview of the electronic properties of iron arsenic high temperature superconductors with emphasis on low energy band dispersion, Fermi surface and superconducting gap. ARPES data is compared with full-potential linearized plane wave (FLAPW) calculations. We focus on single layer NdFeAsO_0.9F_0.1 (R1111) and two layer Ba_1?xK_xFe₂As₂ (B122) compounds. We find general similarities between experimental data and calculations in terms of character of Fermi surface pockets, and overall band dispersion. We also find a number of differences in details of the shape and size of the Fermi surfaces as well as the exact energy location of the bands, which indicate that magnetic interaction and ordering significantly affects the electronic properties of these materials. The Fermi surface consists of several hole pockets centered at Γ and electron pockets located in zone corners. The size and shape of the Fermi surface changes significantly with doping. Emergence of a coherent peak below the critical temperature T_c and diminished spectral weight at the chemical potential above T_c closely resembles the spectral characteristics of the cuprates, however the nodeless superconducting gap clearly excludes the possibility of d-wave order parameter. Instead it points to s-wave or extended s-wave symmetry of the order parameter.     

Predicting XAFS scattering path cumulants and XAFS spectra for metals (Cu,Ni, Fe,Ti, Au) using molecular dynamics simulations

The ability of molecular dynamics (MD) simulations to support the analysis of X‐ray absorption fine‐structure (XAFS) data for metals is evaluated. The low‐order cumulants (ΔR, σ², C₃) for XAFS scattering paths are calculated for the metals Cu, Ni, Fe, Ti and Au at 300 K using 28 interatomic potentials of the embedded‐atom method type. The MD cumulant predictions were evaluated within a cumulant expansion XAFS fitting model, using global (path‐independent) scaling factors. Direct simulations of the corresponding XAFS spectra, χ(R), are also performed using MD configurational data in combination with the FEFFab initio code. The cumulant scaling parameters compensate for differences between the real and effective scattering path distributions, and for any errors that might exist in the MD predictions and in the experimental data. The fitted value of ΔR is susceptible to experimental errors and inadvertent lattice thermal expansion in the simulation crystallites. The unadjusted predictions of σ² vary in accuracy, but do not show a consistent bias for any metal except Au, for which all potentials overestimate σ². The unadjusted C₃ predictions produced by different potentials display only order‐of‐magnitude consistency. The accuracy of direct simulations of χ(R) for a given metal varies among the different potentials. For each of the metals Cu, Ni, Fe and Ti, one or more of the tested potentials was found to provide a reasonable simulation of χ(R). However, none of the potentials tested for Au was sufficiently accurate for this purpose.