π1-classification of real arrangements with up to eight lines

One of the open questions in the geometry of line arrangements is to what extent does the incidence lattice of an arrangement determine its fundamental group. Line arrangements of up to 6 lines were recently classified by K.M. Fan (Michigan Math. J. 44(2) (1997) 283), and it turns out that the incidence lattice of such arrangements determines the projective fundamental group. We use actions on the set of wiring diagrams, introduced in (Garber et al. (J. Knot Theory Ramf.), to classify real arrangements of up to 8 lines. In particular, we show that the incidence lattice of such arrangements determines both the affine and the projective fundamental groups.     

Dihedral crossed products of exponent 2 are abelian

We prove that assuming enough roots of unity in the base field, a central simple algebra of exponent 2 which is split by a dihedral group, is also split by certain abelian groups.     

Stereocontrolled synthesis of cis-dibenzoquinolizine chlorofumarates: curare-like agents of ultrashort duration

The quaternizations of dibenzoquinolizines 9 and 14 with 3-halo-1-propanols are highly cis-selective (94-100% cis), results consistent with the N-methylation of O-methylcapaurine (7b), but in contrast to the proposed trans-stereochemistry of dibenzo[a,h]quinolizine methiodide 10 and the analogous quaternizations of 1-benzyl- and 1-phenylisoquinoline congeners 5b and 5c. In this report, we describe stereoselective preparation of the unique cis-dibenzoquinolizinium propanols 15 and 16and their transformation into bis- and mixed-onium chlorofumarates 19, 20ab, and 26. Dibenzo[a,g]quinolizinium propanol 15 was prepared enantioselectively in three steps from dihydroisoquinoline 11. Asymmetric transfer hydrogenation of 11 in the presence of triethylamine/formic acid and Noyori's chiral ruthenium catalyst 12 produced R-(-)-5',8-dimethoxynorlaudanosine (13) in 98% yield and 87% ee. Pictet-Spengler cyclization of 13 in formalin/formic acid afforded the dibenzo[a,g]quinolizine 14 in 65% yield. Quaternization of 14 with 3-chloro-1-propanol under Finkelstein conditions generated cis-dibenzoquinolizinium propanol 15 in 85% yield with >94% cis-selectivity. The cis-dibenzo[a,h]quinolizinium propanol 16 was obtained as a single stereoisomer by reaction of the known tetramethoxyquinolizine 9 with neat 3-iodo-1-propanol. Bis-onium chlorofumarates 18 and 19 and the mixed-onium derivative 20ab were prepared by a pool synthesis procedure from (1R)-trans-6a, 16, and chlorofumaryl chloride (17). Mixed-onium alpha-chlorofumarate 26 was synthesized from (1S)-trans-6d, 15 and (+/-)-trans-2,3-dichlorosuccinic anhydride (22), employing a recently disclosed chlorofumarate mixed-diester synthesis. The title compounds (19, 20ab, and 26) displayed curare-like effects of ultrashort duration in rhesus monkeys.     

Lithium and potassium isotope separation using radiofrequency spectroscopy

Separation of lithium and potassium isotopes has been achieved using the isotopic differences in the radiofrequency spectrum. The isotope separation was studied in a supersonic molecular beam magnetic resonance spectrometer, and enrichment factors up to 30 obtained.     

Applying ZEKE-spectroscopy to clusters

In this paper we describe the application of a special form of electron photodetachment spectroscopy, zero electron kinetic energy (ZEKE) spectroscopy, to the study of cold metal cluster anions. From this study we have obtained vibrational and thus structural information of several neutral and charged clusters, e.g. Au ₂ ^?/0 , Ag ₃ ^?/0 , Sn ₂ ^?/0 and Al ₃ ^?/0 . In addition, in separate measurements of the relative photodetachment cross section of Au ₂ ^? , we have discovered sharp resonances which are due to electronic autodetachment from a short lived excited state.     

Intercalation of trioxatriangulenium ion in DNA: binding,electron transfer,x-ray crystallography,and electronic structure

Trioxatriangulenium ion (TOTA(+)) is a flat, somewhat hydrophobic compound that has a low-energy unoccupied molecular orbital. It binds to duplex DNA by intercalation with a preference for G-C base pairs. Irradiation of intercalated TOTA(+) causes charge (radical cation) injection that results in strand cleavage (after piperidine treatment) primarily at GG steps. The X-ray crystal structure of TOTA(+) intercalated in the hexameric duplex d[CGATCG](2) described here reveals that intercalation of TOTA(+) results in an unusually large extension of the helical rise of the DNA and that the orientation of TOTA(+) is sensitive to hydrogen-bonding interactions with backbone atoms of the DNA. Electronic structure calculations reveal no meaningful charge transfer from DNA to TOTA(+) because the lowest unoccupied molecular orbital of TOTA(+), (LUMO)(T), falls in the gap between the highest occupied molecular orbital, (HOMO)(D), and the (LUMO)(D) of the DNA bases. These calculations reveal the importance of backbone, water, and counterion interactions, which shift the energy levels of the bases and the intercalated TOTA(+) orbitals significantly. The calculations also show that the inserted TOTA(+) strongly polarizes the intercalation cavity where a sheet of excess electron density surrounds the TOTA(+).     

Determination of the population,depopulation and the anisotropic spin lattice relaxation rates in the photoexcited triplet state of phenazine. A light modulation-EPR study

The photoexcited triplet state of phenazine in toluene glasses at 35 K is investigated by light modulation-EPR spectroscopy. From the transient EPR spectra and the kinetics in the three canonical orientations (p = x, y, z) the rate parameters are determined. Thus, the depopulation rate constants k_p, the anisotropic spin lattice relaxation rate constants W_p, and the ratios between the population constants A_p are calculated: k_x = (2.2 ± 0.3) × 10² s^?1, k_y = (0.21 ± 0.04) × 10² s^?1, k_z = (0.06 ± 0.03) × 10² s^?1, W_x = (8.6 ± 0.9) × 10³ s^?1, W_y = (11.0 ± 1.0) × 10³ s^?1, W_z = (14.0 ± 1.4) × 10³ s^?1, and A_x: _Ay:A_z ≈ 1:0.04:0.02. It is concluded therefore that the in-plane spin state |τ_x > is the active one.     

Bonding in Cu,Ag, and Au clusters: relativistic effects,trends, and surprises

Electronic structure and bonding in anionic coinage metal clusters are investigated via density-functional calculations, focusing on an extensive set of isomers of Cu(-)(7), Ag(-)(7), and Au(-)(7). While the ground states of Cu(-)(7) and Ag(-)(7) are three dimensional (3D), that of Au(-)(7) is planar, separated from the optimal 3D isomer by 0.5 eV. The simulated thermally weighted photoabsorption spectrum of Au(-)(7) is dominated by planar structures, and it agrees well with the measured one. The propensity of Au(-)(N) clusters to favor planar structures (with N as large as 13) is correlated with strong hybridization of the atomic 5d and 6s orbitals due to relativistic effects.