Ferromagnetically coupled cobalt-benzene-cobalt: the smallest molecular spin filter with unprecedented spin injection coefficient

Here, we predict that the ferromagnetically coupled cobalt-benzene-cobalt system will act as the smallest molecular spin filter with unprecedented spin injection coefficient. To validate our in-silico observation, we have performed state-of-the-art nonequilibrium Green's function calculations and analyzed the density of states of cobalt at the relativistic and nonrelativistic level of theory. Remarkably, we found that unpaired 3d electrons of cobalt are not participating in the spin transport process like other transition metal containing multidecker complexes. Instead, an admixture of the outer-sphere 4s and 4p orbitals of cobalt along with the 2p orbital of carbon of the benzene moiety is contributing to the singly occupied highest molecular orbital in the majority spin channel that creates a path for coherent spin transport leading to the extremely high spin injection coefficient of the system. The absence of the 3d electrons of cobalt in the spin transport process has been carefully examined, and it was found that the nodal structure of the 3d orbital of cobalt is not at all suitable for bonding in the cobalt-benzene-cobalt system. The whole study indicates that the underlying mechanism of the spin filter action in cobalt-benzene-cobalt is completely distinctive from the other known materials.     

Measurement of the Diffusivity of Cesium Ion in Aqueous Rubidium Chloride Solution

For the first time cesium diffusivity in aqueous solutions of rubidium chloride is being reported here in the concentration range from 0.001 to 4.00 mol⋅dm⁻³. The measurement use a radioactive tracer technique employing a sliding cell mechanism. These diffusivity values were utilized to understand the transport mechanism of Cs ion in the RbCl–H₂O system using the Onsager-Gosting-Harned equation and the extended Debye-Hückel equation. The observed deviation between the theoretical and experimental diffusivities are explained by introducing the concept of Field-Dielectric-Gradient forces and energies that exist around an ion, which takes care of the finite size of the ion, ion-water interaction and the ion-ion interaction in a continuum basis.     

Simultaneous occurrence of energy transfer and photoinduced electron transfer in interactions of hen egg white lysozyme with 4-nitroquinoline-1-oxide

The carcinogenic drug 4-nitroquinoline-1-oxide (4NQO) has been found to bind with the protein hen egg white lysozyme as evident from fluorescence quenching experiments. The binding constant and stoichiometry have been determined. The values of the thermodynamic parameters indicate that the interaction is an enthalpy-driven spontaneous phenomenon. The experimental value of change in free energy is similar to that obtained from the docking study. The far UV circular dichroism spectra show some changes in the secondary structure of protein. The high value of bimolecular quenching constant leads to the possibility of Förster resonance energy transfer (FRET). Along with FRET, the photoinduced electron transfer (PET) from tryptophan residue of protein to 4NQO has also been evident from the transient absorption spectra obtained in laser flash photolysis experiments. The simultaneous occurrence of FRET and PET is the key factor for quenching of intrinsic fluorescence of the protein as it binds with the drug.     

Structure, interactions, and antibacterial activities of MSI-594 derived mutant peptide MSI-594F5A in lipopolysaccharide micelles: role of the helical hairpin conformation in outer-membrane permeabilization

Lipopolysaccharide (LPS) provides a well-organized permeability barrier at the outer membrane of Gram-negative bacteria. Host defense cationic antimicrobial peptides (AMPs) need to disrupt the outer membrane before gaining access to the inner cytoplasmic membrane or intracellular targets. Several AMPs are largely inactive against Gram-negative pathogens due to the restricted permeation through the LPS layer of the outer membrane. MSI-594 (GIGKFLKKAKKGIGAVLKVLTTG) is a highly active AMP with a broad-spectrum of activities against bacteria, fungi, and virus. In the context of LPS, MSI-594 assumes a hairpin helical structure dictated by packing interactions between two helical segments. Residue Phe5 of MSI-594 has been found to be engaged in important interhelical interactions. In order to understand plausible structural and functional inter-relationship of the helical hairpin structure of MSI-594 with outer membrane permeabilization, a mutant peptide, termed MSI-594F5A, containing a replacement of Phe5 with Ala has been prepared. We have compared antibacterial activities, outer and inner membrane permeabilizations, LPS binding affinity, perturbation of LPS micelles structures by MSI-594 and MSI-594F5A peptides. Our results demonstrated that the MSI-594F5A has lower activities against Gram-negative bacteria, due to limited permeabilization through the LPS layer, however, retains Gram-positive activity, akin to MSI-594. The atomic-resolution structure of MSI-594F5A has been determined in LPS micelles by NMR spectroscopy showing an amphipathic curved helix without any packing interactions. The 3D structures, interactions, and activities of MSI-594 and its mutant MSI-594F5A in LPS provide important mechanistic insights toward the requirements of LPS specific conformations and outer membrane permeabilization by broad-spectrum antimicrobial peptides.     

Correspondence Between Ricci and Other Dark Energies

Purpose of the present paper is to view the correspondence between Ricci and other dark energies. We have considered the Ricci dark energy in presence of dark matter in non-interacting situation. Subsequently, we have derived the pressure and energy density for Ricci dark energy. The equation of state parameter has been generated from these pressure and energy density. Next, we have considered the correspondence between Ricci and other dark energy models, namely tachyonic field, DBI-essence and new agegraphic dark energy without any interaction and investigated possible cosmological consequences.     

Floating and sinking: the imprint of massive scalars around rotating black holes

We study the coupling of massive scalar fields to matter in orbit around rotating black holes. It is generally expected that orbiting bodies will lose energy in gravitational waves, slowly inspiraling into the black hole. Instead, we show that the coupling of the field to matter leads to a surprising effect: because of superradiance, matter can hover into "floating orbits" for which the net gravitational energy loss at infinity is entirely provided by the black hole's rotational energy. Orbiting bodies remain floating until they extract sufficient angular momentum from the black hole, or until perturbations or nonlinear effects disrupt the orbit. For slowly rotating and nonrotating black holes floating orbits are unlikely to exist, but resonances at orbital frequencies corresponding to quasibound states of the scalar field can speed up the inspiral, so that the orbiting body sinks. These effects could be a smoking gun of deviations from general relativity.     

On the extendedness of eigenstates in a hierarchical lattice: A critical view

We take a critical view at the basic definition of extended single particle states in a non-translationally invariant system. For this, we present the case of a hierarchical lattice and incorporate long range interactions that are also distributed in a hierarchical fashion. We show that it is possible to explicitly construct eigenstates with constant amplitudes (normalized to unity) at every lattice point for special values of the electron-energy. However, the end-to-end transmission, corresponding to the above energy of the electron in such a hierarchical system depends strongly on a special correlation between the numerical values of the parameters of the Hamiltonian. Keeping the energy and the distribution of the amplitudes invariant, one can transform the lattice from conducting to insulating simply by tuning the numerical values of the long range interaction. The values of these interactions themselves display a fractal character.     

A study of diquark and meson condensation in the Nambu–Jona-Lasinio model and Fermi momentum

Using a three- and four-dimensional Pauli–Villars regularization scheme, we investigate quark–antiquark and diquark condensation in the framework of the Nambu–Jona-Lasinio model. Using the particle Fermi momentum as a cutoff parameter, we study the energy gap width and coherence length for the meson condensate 〈\(q\bar q\)〉. We also study the energy gap width and critical coherence length (the distance over which there would be no diquark condensation) for the diquark 〈qq〉 and the dependence on the Fermi momentum. We obtain an estimate of the Fermi momentum value for meson and diquark condensates with an energy gap width of the order of 100 MeV.     

New design strategy for the two-photon active material based on push-pull substituted bisanthene molecule

In the present work, we have critically examined the origin of strong two-photon transition probability of a donor-acceptor substituted bisanthene molecule that imitates a small piece of edge passivated (4, 4) graphene nanoribbon. In our calculations, we have considered -OMe, and -NH(2) as donors and -NO(2) as an acceptor. The one- and two-photon absorption parameters are evaluated using state-of-the-art linear and quadratic response theory, respectively, and all these calculations are carried out within the framework of time dependent density functional theory. To give a proper judgment on our findings, we have used the long-range corrected CAMB3LYP functional for all of the time dependent calculations. The present investigation reveals that the bisanthene molecule with three pairs of donor/acceptor moiety has a lower two-photon transition probability than that of a suitably designed bisanthene with only a single pair of donor/acceptor moiety. This in silico observation is consistent for all of the donor/acceptor moieties chosen in the present work. A comprehensive analysis at the two state model level of theory clearly offers us a verdict that by placing the donor/acceptor moiety in a suitable position of bisanthene, we can create a significant asymmetry in the electron density in the first excited state, which eventually leads to a significant difference in the ground and excited state dipole moment and is attributed to the higher two-photon transition probability of a particular bisanthene with a single pair of donor/acceptor moiety than bisanthene with three pairs of donor/acceptor.     

MRDCI study of the low-lying electronic states of PbSi

Electronic states of the PbSi molecule up to 4 eV have been studied by carrying out ab initio based MRDCI calculations which include relativistic effective core potentials (RECPs) of both the atoms. The use of semicore RECPs of Pb produces better dissociation limits than the full-core one. However, the (3)P(0)-(3)P(1) splitting due to Pb is underestimated by about 4000 cm(-1). At least 25 bound electronic states of the Λ-S symmetry are predicted for PbSi. The computed zero-field-splitting in the ground state is about 544 cm(-1). A strong spin-orbit mixing changes the nature of the potential energy curves of many Ω states. The overall splitting among the spin components of A(3)Π is computed to be 4067 cm(-1). However, the largest spin-orbit splitting is reported for the (3)Δ state. A number of spin-allowed and spin-forbidden transitions are predicted. The partial radiative lifetime for the A(3)Π-X(3)Σ(-) transition is of the order of milliseconds. The computed bond energy in the ground state is 1.68 eV, considering the spin-orbit coupling. The vertical ionization energy for the ionization to the X(4)Σ(-) ground state of PbSi(+) is about 6.93 eV computed at the same level of calculations.