Theory of adiabatic Hexaamminecobalt-Self-Exchange

We have reexamined the thermally induced Co(NH_3)_6^{2+/3+} [Co(II/III)] redox reaction using the first principles density-functional-theory method, semiclassical Marcus theory, and known charge transfer parameters. We confirm a previously suggested mechanism involving excited state (^2E_g) of Co(II) which becomes lower than the ground state (^4T_1g) in the transition state region. This lowers the transition state barrier considerably by about 6.9 kcal/mol and leads to a spin-allowed and adiabatic electron exchange process. Our calculations are consistent with previous experimental results regarding the spin-excitation energy (^3T_1g) of Co(III), and the fact that an optical absorption peak (^2E_g) of the Co(II) species could not be found experimentally. Our rate is of order 6 10^{-3} 1/Ms and hence 2 orders of magnitude faster than determined previously by experiments.Comment: 10 pages, 5 figures, 4 tables; submitted to J.Chem.Phy

preclinical evidence from C57BL/6 mice

Chemotherapy-induced central nervous system (CNS) neurotoxicity presents an unmet medical need. Patients often report a cognitive decline in temporal correlation to chemotherapy, particularly for hippocampus-dependent verbal and visuo-spatial abilities. We treated adult C57Bl/6 mice with 12 × 20 mg kg−1 paclitaxel (PTX), mimicking clinical conditions of dose-dense chemotherapy, followed by a pulse of bromodesoxyuridine (BrdU) to label dividing cells. In this model, mice developed visuo-spatial memory impairments, and we measured peak PTX concentrations in the hippocampus of 230 nm l−1, which was sevenfold higher compared with the neocortex. Histologic analysis revealed a reduced hippocampal cell proliferation. In vitro, we observed severe toxicity in slowly proliferating neural stem cells (NSC) as well as human neuronal progenitor cells after 2 h exposure to low nanomolar concentrations of PTX. In comparison, mature post-mitotic hippocampal neurons and cell lines of malignant cells were less vulnerable. In PTX-treated NSC, we observed an increase of intracellular calcium levels, as well as an increased activity of calpain- and caspase 3/7, suggesting a calcium-dependent mechanism. This cell death pathway could be specifically inhibited with lithium, but not glycogen synthase kinase 3 inhibitors, which protected NSC in vitro. In vivo, preemptive treatment of mice with lithium prevented PTX-induced memory deficits and abnormal adult hippocampal neurogenesis. In summary, we identified a molecular pathomechanism, which invokes PTX-induced cytotoxicity in NSC independent of cell cycle status. This pathway could be pharmacologically inhibited with lithium without impairing paclitaxel’s tubulin-dependent cytostatic mode of action, enabling a potential translational clinical approach

Aviram-Ratner rectifying mechanism for DNA base pair sequencing through graphene nanogaps

We demonstrate that biological molecules such as Watson-Crick DNA base pairs can behave as biological Aviram-Ratner electrical rectifiers because of the spatial separation and weak hydrogen bonding between the nucleobases. We have performed a parallel computational implementation of the ab-initio non-equilibrium Green's function (NEGF) theory to determine the electrical response of graphene---base-pair---graphene junctions. The results show an asymmetric (rectifying) current-voltage response for the Cytosine-Guanine base pair adsorbed on a graphene nanogap. In sharp contrast we find a symmetric response for the Thymine-Adenine case. We propose applying the asymmetry of the current-voltage response as a sensing criterion to the technological challenge of rapid DNA sequencing via graphene nanogaps

Fragmentation and systematics of the Pygmy Dipole Resonance in the stable N=82 isotones

The low-lying electric dipole (E1) strength in the semi-magic nucleus 136Xe has been measured which finalizes the systematic survey to investigate the so-called pygmy dipole resonance (PDR) in all stable even N=82 isotones with the method of nuclear resonance fluorescence using real photons in the entrance channel. In all cases, a fragmented resonance-like structure of E1 strength is observed in the energy region 5 MeV to 8 MeV. An analysis of the fragmentation of the strength reveals that the degree of fragmentation decreases towards the proton-deficient isotones while the total integrated strength increases indicating a dependence of the total strength on the neutron-to-proton ratio. The experimental results are compared to microscopic calculations within the quasi-particle phonon model (QPM). The calculation includes complex configurations of up to three phonons and is able to reproduce also the fragmentation of the E1 strength which allows to draw conclusions on the damping of the PDR. Calculations and experimental data are in good agreement in the degree of fragmentation and also in the integrated strength if the sensitivity limit of the experiments is taken into account

Optical conductivity of wet DNA

Motivated by recent experiments we have studied the optical conductivity of DNA in its natural environment containing water molecules and counter ions. Our density functional theory calculations (using SIESTA) for four base pair B-DNA with order 250 surrounding water molecules suggest a thermally activated doping of the DNA by water states which generically leads to an electronic contribution to low-frequency absorption. The main contributions to the doping result from water near DNA ends, breaks, or nicks and are thus potentially associated with temporal or structural defects in the DNA.Comment: 4 pages, 4 figures included, final version, accepted for publication in Phys. Rev. Let

The decay of quadrupole-octupole 1−1^- states in 40^{40}Ca and 140^{140}Ce

Background: Two-phonon excitations originating from the coupling of two collective one-phonon states are of great interest in nuclear structure physics. One possibility to generate low-lying $E1$ excitations is the coupling of quadrupole and octupole phonons. Purpose: In this work, the $\gamma$-decay behavior of candidates for the $(2_1^+\otimes 3_1^-)_{1^-}$ state in the doubly-magic nucleus $^{40}$Ca and in the heavier and semi-magic nucleus $^{140}$Ce is investigated. Methods: $(\vec{\gamma},\gamma')$ experiments have been carried out at the High Intensity $\gamma$-ray Source (HI${\gamma}$S) facility in combination with the high-efficiency $\gamma$-ray spectroscopy setup $\gamma^3$ consisting of HPGe and LaBr$_3$ detectors. The setup enables the acquisition of $\gamma$-$\gamma$ coincidence data and, hence, the detection of direct decay paths. Results: In addition to the known ground-state decays, for $^{40}$Ca the decay into the $3^-_1$ state was observed, while for $^{140}$Ce the direct decays into the $2^+_1$ and the $0^+_2$ state were detected. The experimentally deduced transition strengths and excitation energies are compared to theoretical calculations in the framework of EDF theory plus QPM approach and systematically analyzed for $N=82$ isotones. In addition, negative parities for two $J=1$ states in $^{44}$Ca were deduced simultaneously. Conclusions: The experimental findings together with the theoretical calculations support the two-phonon character of the $1^-_1$ excitation in the light-to-medium-mass nucleus $^{40}$Ca as well as in the stable even-even $N=82$ nuclei.Comment: 11 pages, 6 figures, as accepted in Phys. Rev.

One particle interchain hopping in coupled Hubbard chains

Interchain hopping in systems of coupled chains of correlated electrons is investigated by exact diagonalizations and Quantum-Monte-Carlo methods. For two weakly coupled Hubbard chains at commensurate densities (e.g. n=1/3) the splitting at the Fermi level between bonding and antibonding bands is strongly reduced (but not suppressed) by repulsive interactions extending to a few lattice spacings. The magnitude of this reduction is directly connected to the exponent $\alpha$ of the 1D Luttinger liquid. However, we show that the incoherent part of the single particle spectral function is much less affected by the interchain coupling. This suggests that incoherent interchain hopping could occur for intermediate $\alpha$ values.Comment: 4 pages, LaTeX 3.0, 7 PostScript figures in uuencoded for

Strong electron correlations in cobalt valence tautomers

We have examined cobalt based valence tautomer molecules such as Co(SQ)$_2$(phen) using density functional theory (DFT) and variational configuration interaction (VCI) approaches based upon a model Hamiltonian. Our DFT results extend earlier work by finding a reduced total energy gap (order 0.6 eV) between high temperature and low temperature states when we fully relax the coordinates (relative to experimental ones). Futhermore we demonstrate that the charge transfer picture based upon formal valence arguments succeeds qualitatively while failing quantitatively due to strong covalency between the Co 3$d$ orbitals and ligand $p$ orbitals. With the VCI approach, we argue that the high temperature, high spin phase is strongly mixed valent, with about 30 % admixture of Co(III) into the predominantly Co(II) ground state. We confirm this mixed valence through a fit to the XANES spectra. Moreover, the strong electron correlations of the mixed valent phase provide an energy lowering of about 0.2-0.3 eV of the high temperature phase relative to the low temperature one. Finally, we use the domain model to account for the extraordinarily large entropy and enthalpy values associated with the transition.Comment: 10 pages, 4 figures, submitted to J. Chem. Phy

Isospin Character of the Pygmy Dipole Resonance in 124Sn

The pygmy dipole resonance has been studied in the proton-magic nucleus 124Sn with the (a,a'g) coincidence method at E=136 MeV. The comparison with results of photon-scattering experiments reveals a splitting into two components with different structure: one group of states which is excited in (a,a'g) as well as in (g,g') reactions and a group of states at higher energies which is only excited in (g,g') reactions. Calculations with the self-consistent relativistic quasiparticle time-blocking approximation and the quasiparticle phonon model are in qualitative agreement with the experimental results and predict a low-lying isoscalar component dominated by neutron-skin oscillations and a higher-lying more isovector component on the tail of the giant dipole resonance