Chemically Initiated Electron Exchange Luminescence of Silyloxyaryl-Substituted Spiroadamantyl Dioxetanes: Kinetics and Excited State Yields

Abstract— The kinetics of the fluoride-induced decomposition of the thermally stable silyloxyaryl-substituted spiroadamantyl dioxetanes 1a,b and the excited state formation of this chemically initiated electron exchange luminescence (CIEEL) have been investigated. Two limiting kinetic regimes flash and glow have been identified, which depend on the fluoride concentration, the first at high, the second at low [F^-] triggering, whose detailed kinetic analysis affords the rate constants for the deprotected dioxetanes 2a,b cleavage in acetonitrile and dimethyl sulfoxide and chemiluminescence measurements the CIEEL and phen-olate 4 (CIEEL emitter) excitation yields. Chloro-substi-tution in the spiroadamantyl dioxetane does not affect the deprotection step k ₂ but leads to a ca five-fold faster cleavage of the deprotected dioxetane 2, while the chemiexcitation yield is the same for both dioxetanes. The energies of the first excited singlet and triplet states of the emitting phenolate 4 were estimated by AM1 configuration interaction calculations with explicit consideration of acetonitrile as solvent (self-consistent reaction field approach). The first excited singlet and triplet state of the CIEEL emitter phenolate 4 possess π,π* character, as suggested by the π-type molecular orbitals and the large singlet-triplet energy gap. The chemiexcitation of both singlet and triplet states of the excited phenolate 4 is feasible during the dioxetanes 1a,b cleavage, but the experimentally determined high singlet excitation yields suggest that preferentially the phenolate 4 singlet state is populated in the fluoride ion-triggered CIEEL process.     

Photochemical and Photobiotogical Studies with Acridine and Phenanthridine Hydroperoxides in Cell-free DNA

Abstract— The acridine and phenanthridine hydroperoxides 3 and 7 were synthesized as photochemical hydroxyl radical sources for oxidative DNA damage studies. The generation of hydroxyl radicals upon UVA irradiation (Λ. = 350 nm) was verified by trapping experiments with 5,5-di-methyl-1-pyrroline N -oxide and benzene. The enzymatic assays of the damage in cell-free DNA from bacteriophage PM2 caused by the acridine and phenanthridine hydroperoxides 3 and 7 under near-UVA irradiation revealed a wide range of DNA modifications. Particularly, extensive single-strand break formation and DNA base modifications sensitive to formamidopyrimidine DNA glycosylase (Fpg protein) were observed. In the photooxida-tion of calf thymus DNA, up to 0.69±0.03% 8-oxo-7,8-dihydroguanine was formed by the hydroperoxides 3 and 7 on irradiation, whose yield was reduced up to 40% in the presence of the hydroxyl radical scavengers mannitol and fert-butanol. The acridine and phenanthridine hydroperoxides 3 and 7 also induce DNA damage through the type I photooxidation process, for which photoinduced electron transfer from 2'-deoxyguanosine to the singlet states of 3 and 7 was estimated by the Rehm-Weller equation to possess a negative Gibb's free energy of cα -5 kcal/ mol. Control experiments with the sensitizers acridine 1 and the acridine alcohol 4 in calf thymus and PM2 DNA confirmed the photosensitizing propensity of the UVA-ab-sorbing chromophores. The present study emphasizes that for the development of selective and efficient photochemical hydroxyl radical sources, chromophores with low photosensitizing ability must be chosen to avoid type I and type II photooxidation processes.     

Conformal changes of metrics and the initial-value problem of general relativity

Conformal techniques are reviewed with respect to applications to the initial-value problem of general relativity. Invariant transverse traceless decompositions of tensors, one of its main tools, are related to representations of the group of conformeomorphisms acting on the space of all Riemannian metrics onM. Conformal vector fields, a kernel in the decomposition, are analyzed on compact manifolds with constant scalar curvature. The realization of arbitrary functions as scalar curvature of conformally equivalent metrics, a generalization of Yamabe's conjecture, is applied to the Hamiltonian constraint and to the issue of positive energy of gravitational fields. Various approaches to the solution of the initial-value equations produced by altering the scaling behavior of the second fundamental form are compared.     

The eightfold way to color geometrodynamics

Color models of strong interactions are generalized to aGL(8,) ^f GL(8,) ^c gauge theory incorporating space-time curvature and Cartan's torsion. Following Salam, the dynamics is determined by an Einstein-Dirac-type Lagrangian. The resulting field equations are anonlinear (due to the torsion) Heisenberg-Pauli-Weyl equation for the fundamental spinor fields and a generalized Einstein equation for the background metric of hadronic dimensions. According to this model baryonic quarks are confined ingeon (black soliton)-type objects by the tensor gluons ofstrong gravity. This approach also leads to a black soliton mass formula which is in qualitative agreement with part of the baryon spectrum. Hadronic mesons are interpreted as gluon strings trapped in a multiconnected space-time. Interrelations of color geometrodynamics with other bag models are pointed out. Finally, the conceptual origin of this space-time foundation of quark confinement is presented.     

Two dimensional interacting electrons on a torus in a strong magnetic field: Symmetry properties and the effect of disorder

We discuss the symmetry properties of two dimensional interacting electrons on a torus in a strong magnetic field. Invariance under magnetic translations of the center of mass leads to a decomposition of the Hilbert space into a direct sum of subspaces. The degenerate ground states are out of one of these subspaces. This is used to calculate the energy splitting of the ground state energy due to a disordered background potential. The energy splitting is small and vanishes in thermodynamic limit if the denominator of the filling factor is odd and small. Numerical calculations confirm our results.     

Progress in metric-affine gauge theories of gravity with local scale invariance

Einstein's general relativity theory describes very well the gravitational phenomena in themacroscopic world. In themicroscopic domain of elementary particles, however, it does not exhibit gauge invariance or approximate Bjorken type scaling, properties which are believed to be indispensible for arenormalizable field theory. We argue that thelocal extension of space-time symmetries, such as of Lorentz and scale invariance, provides the clue for improvement. Eventually, this leads to aGL(4, R)-gauge approach to gravity in which the metric and the affine connection acquire the status ofindependent fields. The Yang-Mills type field equations, the Noether identities, and conformal models of gravity are discussed within this framework. After symmetry breaking, Einstein's GR surfaces as an effective low-energy theory.Based on a plenary talk given by one of us (EWM) at the 53rd annual meeting of the Deutsche Physikalische Gesellschaft in Bonn on March 14, 1989.Supported by the German-Israeli Foundation for Scientific Research and Development (GIF), Jerusalem and Munich.Supported by the Deutsche Forschungsgemeinschaft (DFG), Bonn, project He 528/12-1.Supported in part by DOE Grant DE-FG05-85-ER40200.     

Homogenization for rate-independent systems

This paper is devoted to the homogenization for a class of rate-independent systems described by the energetic formulation. The associated nonlinear partial differential system has periodically oscillating coefficients, but has the form of a standard evolutionary variational inequality. Thus, the model applies to standard linearized elastoplasticity with hardening. Using the recently developed methods of two-scale convergence, periodic unfolding and the new introduced one, periodic folding, we show that the homogenized problem can be represented as a two-scale limit which is again an energetic formulation, but now involving the macroscopic variable in the physical domain as well as the microscopic variable in the periodicity cell. (© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Molecules with multiple switching units on a Au(111) surface: self-organization and single-molecule manipulation

Three different molecules, each containing two azobenzene switching units, were synthesized, successfully deposited onto a Au(111) surface by sublimation and studied by scanning tunneling microscopy at low temperatures. To investigate the influence of electronic coupling between the switching units as well as to the surface, the two azo moieties were connected either via π-conjugated para-phenylene or decoupling meta-phenylene bridges, and the number of tert-butyl groups was varied in the meta-phenylene-linked derivatives. Single molecules were found to be intact after deposition as identified by their characteristic appearance in STM images. Due to their mobility on the Au(111) surface at room temperature, the molecules spontaneously formed self-organized molecular arrangements that reflected their chemical structure. While lateral displacement of the molecules was accomplished by manipulation, trans-cis isomerization processes, typical for azobenzene switches, could not be induced.