517 research outputs found
Electronic Control of Spin Alignment in pi-Conjugated Molecular Magnets
Intramolecular spin alignment in pi-conjugated molecules is studied
theoretically in a model of a Peierls-Hubbard chain coupled with two localized
spins. By means of the exact diagonalization technique, we demonstrate that a
spin singlet (S=0) to quartet (S=3/2) transition can be induced by electronic
doping, depending on the chain length, the positions of the localized spins,
and the sign of the electron-spin coupling. The calculated results provides a
theoretical basis for understanding the mechanism of spin alignment recently
observed in a diradical donor molecule.Comment: 4 pages, 4 figures, Physical Review Letters (in press
Dynamic ductile to brittle transition in a one-dimensional model of viscoplasticity
We study two closely related, nonlinear models of a viscoplastic solid. These
models capture essential features of plasticity over a wide range of strain
rates and applied stresses. They exhibit inelastic strain relaxation and steady
flow above a well defined yield stress. In this paper, we describe a first step
in exploring the implications of these models for theories of fracture and
related phenomena. We consider a one dimensional problem of decohesion from a
substrate of a membrane that obeys the viscoplastic constitutive equations that
we have constructed. We find that, quite generally, when the yield stress
becomes smaller than some threshold value, the energy required for steady
decohesion becomes a non-monotonic function of the decohesion speed. As a
consequence, steady state decohesion at certain speeds becomes unstable. We
believe that these results are relevant to understanding the ductile to brittle
transition as well as fracture stability.Comment: 10 pages, REVTeX, 12 postscript figure
Second-order electronic correlation effects in a one-dimensional metal
The Pariser-Parr-Pople (PPP) model of a single-band one-dimensional (1D)
metal is studied at the Hartree-Fock level, and by using the second-order
perturbation theory of the electronic correlation. The PPP model provides an
extension of the Hubbard model by properly accounting for the long-range
character of the electron-electron repulsion. Both finite and infinite version
of the 1D-metal model are considered within the PPP and Hubbard approximations.
Calculated are the second-order electronic-correlation corrections to the total
energy, and to the electronic-energy bands. Our results for the PPP model of 1D
metal show qualitative similarity to the coupled-cluster results for the 3D
electron-gas model. The picture of the 1D-metal model that emerges from the
present study provides a support for the hypothesis that the normal metallic
state of the 1D metal is different from the ground state.Comment: 21 pages, 16 figures; v2: small correction in title, added 3
references, extended and reformulated a few paragraphs (detailed information
at the end of .tex file); added color to figure
Hydrogen Bonding Controls Excited-State Decay of the Photoactive Yellow Protein Chromophore
International audienceWe have performed excited-state dynamics simulations of a Photoactive Yellow Protein chromophore analogue in water. The results of the simulations demonstrate that in water the chromophore predominantly undergoes single-bond photoisomerization, rather than double-bond photoisomerization. Despite opposite charge distributions in the chromophore, excited-state decay takes place very efficiently from both single- and double-bond twisted minima in water. Radiationless decay is facilitated by ultrafast solvent reorganization, which stabilizes both minima by specific hydrogen bond interactions. Changing the solvent to the slightly more viscous D(2)O leads to an increase of the excited-state lifetime. Together with previous simulations, the present results provide a complete picture of the effect of the protein on the photoisomerization of the chromophore in PYP: the positive guanidinium group of Arg52 favors double-bond isomerization over single-bond isomerization by lowering the barrier for double-bond isomerization, while the hydrogen bonds with Tyr42 and Glu46 enhance deactivation from the double-bond twisted minimum
Flat-Band Ferromagnetism in Organic Polymers Designed by a Computer Simulation
By coupling a first-principles, spin-density functional calculation with an
exact diagonalization study of the Hubbard model, we have searched over various
functional groups for the best case for the flat-band ferromagnetism proposed
by R. Arita et al. [Phys. Rev. Lett. {\bf 88}, 127202 (2002)] in organic
polymers of five-membered rings. The original proposal (poly-aminotriazole) has
turned out to be the best case among the materials examined, where the reason
why this is so is identified here. We have also found that the ferromagnetism,
originally proposed for the half-filled flat band, is stable even when the band
filling is varied away from the half-filling. All these make the ferromagnetism
proposed here more experimentally inviting.Comment: 11 pages, 13figure
Fluorescence studies on new potential antitumoral benzothienopyran-1-ones in solution and in liposomes
Fluorescence properties of four new potential
antitumoral compounds, 3-arylbenzothieno[2,3-c]pyran-1-ones, were studied in solution and in lipid membranes of dipalmitoyl phosphatidylcholine (DPPC), egg yolk phosphatidylcholine (Egg-PC) and dioctadecyldimethylammonium bromide (DODAB). The 3-(4-methoxyphenyl)benzothieno[2,3-c]pyran-1-one (1c) exhibits the higher fluorescence quantum yields in all solvents studied. All compounds present a solvent sensitive emission, with significant red shifts in polar solvents for the methoxylated compounds. The results point to an ICT character of the excited state, more pronounced for compound 1c. Fluorescence (steady-state) anisotropy measurements of the compounds incorporated in liposomes of DPPC, DODAB and Egg-PC indicate that all compounds have two different locations, one due to a deep penetration in the lipid membrane and another corresponding to a more hydrated environment. In general, the methoxylated compounds prefer hydrated environments inside the liposomes. The 3-(4-
fluorophenyl)benzothieno[2,3-c]pyran-1-one (1a) clearly prefers a hydrated environment, with some molecules located at the outer part of the liposome interface. On the contrary, the preferential location of 3-(2-fluorophenyl)benzothieno[2,3-c]pyran-1-one (1b) is in the region of lipid hydrophobic tails. Compounds with a planar geometry (1a and 1c) have higher mobility in the lipid membranes when phase transition occurs.Portugal and FEDER (Fundo Europeu de Desenvolvimento Regional), for financial support through Centro de FΓsica (CFUM) and Centro de QuΓmica (CQ-UM) of University of Minho and through the Project PTDC/QUI/81238/2006. M.S.D. Carvalho and R.C. Calhelha acknowledge FCT for their PhD grants SFRH/BD/47052/2008 and SFRH/BD/29274/2006, respectively.Fundação para a CiΓͺncia e a Tecnologia (FCT
Microglial Interactions with Synapses Are Modulated by Visual Experience
Microglia, the brain's immune cells, show unique interactions with nearby synaptic elements under non-pathological conditions that are sensitive to changes in sensory experience
Analysis of Area-Specific Expression Patterns of RORbeta, ER81 and Nurr1 mRNAs in Rat Neocortex by Double In Situ Hybridization and Cortical Box Method
BACKGROUND: The mammalian neocortex is subdivided into many areas, each of which exhibits distinctive lamina architecture. To investigate such area differences in detail, we chose three genes for comparative analyses, namely, RORbeta, ER81 and Nurr1, mRNAs of which have been reported to be mainly expressed in layers 4, 5 and 6, respectively. To analyze their qualitative and quantitative coexpression profiles in the rat neocortex, we used double in situ hybridization (ISH) histochemistry and cortical box method which we previously developed to integrate the data of different staining and individuals in a standard three-dimensional space. PRINCIPAL FINDINGS: Our new approach resulted in three main observations. First, the three genes showed unique area distribution patterns that are mostly complementary to one another. The patterns revealed by cortical box method matched well with the cytoarchitectonic areas defined by Nissl staining. Second, at single cell level, RORbeta and ER81 mRNAs were coexpressed in a subpopulation of layer 5 neurons, whereas Nurr1 and ER81 mRNAs were not colocalized. Third, principal component analysis showed that the order of hierarchical processing in the cortex correlates well with the expression profiles of these three genes. Based on this analysis, the dysgranular zone (DZ) in the somatosensory area was considered to exhibit a profile of a higher order area, which is consistent with previous proposal. CONCLUSIONS/SIGNIFICANCE: The tight relationship between the expression of the three layer specific genes and functional areas were revealed, demonstrating the usefulness of cortical box method in the study on the cerebral cortex. In particular, it allowed us to perform statistical evaluation and pattern matching, which would become important in interpreting the ever-increasing data of gene expression in the cortex
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