Three Bis‐BODIPY Analogous Diruthenium Redox Series: Characterization and Electronic Structure Analysis

The dianion derived from (2Z,6Z)‐3,7‐diphenyl‐N2,N6‐di(pyridin‐2‐yl)pyrrolo[2,3‐f]indole‐2,6(1H,5H)‐diimine (H₂BL), a modified BODIPY ligand precursor, is shown to be capable of bridging two metal complex fragments RuL₂, L=2,4‐pentanedionato (acac^?), 2,2’‐bipyridine (bpy) or 2‐phenylazopyridine (pap) in [Ru(acac)₂Ru(μ‐BL)Ru(acac)₂] ( 1 / 2 ), [Ru(bpy)₂Ru(μ‐BL)Ru(bpy)₂](ClO₄)₂ ([ 3 ](ClO₄)₂) and [Ru(pap)₂Ru(μ‐BL)Ru(pap)₂](ClO₄)₂ ([ 4 ](ClO₄)₂). The compounds, including a diastereoisomeric pair 1 (meso) and 2 (rac) were spectroscopically and structurally characterized. Reversible electron transfers as revealed by cyclic and differential pulse voltammetry allowed for an EPR and UV‐vis‐NIR spectroelectrochemical investigation of several neighboring charge states. Together with susceptibility measurements and TD‐DFT calculations the assignment of oxidation states reveals that 1 , 2 are diruthenium(III) species which can be oxidized or reduced by one electron whereas 3 ²⁺ and 4 ²⁺ contain ruthenium(II) and get reduced or oxidized mainly at the dianionic bridge ( 3 ²⁺) or are reduced at the ancillary ligands pap ( 4 ²⁺).     

Unusual Surface Latent Heat Flux Variations and Their Critical Dynamics Revealed before Strong Earthquakes

We focus on the possible thermal channel of the well-known Lithosphere–Atmosphere–Ionosphere Coupling (LAIC) mechanism to identify the behavior of thermal anomalies during and prior to strong seismic events. For this, we investigate the variation of Surface Latent Heat Flux (SLHF) as resulting from satellite observables. We demonstrate a spatio-temporal variation in the SLHF before and after a set of strong seismic events occurred in Kathmandu, Nepal, and Kumamoto, Japan, having magnitudes of 7.8, 7.3, and 7.0, respectively. Before the studied earthquake cases, significant enhancements in the SLHF were identified near the epicenters. Additionally, in order to check whether critical dynamics, as the signature of a complex phenomenon such as earthquake preparation, are reflected in the SLHF data, we performed a criticality analysis using the natural time analysis method. The approach to criticality was detected within one week before each mainshock.     

Effect of Controlled Deposition of ZnS Shell on the Photostability of CdTe Quantum Dots as Studied by Conventional Fluorescence and FCS Techniques

The effect of one and two monolayers of ZnS shells on the photostability of CdTe quantum dots (QDs) in aqueous and nonaqueous media has been studied by monitoring the fluorescence behavior of the QDs under ensemble and single‐molecule conditions. ZnS capping of the CdTe QDs leads to significant enhancement of the fluorescence brightness of these QDs. Considerable enhancement of the photostability of the shell‐protected QDs, including the suppression of photoactivation, is also observed. Fluorescence correlation spectroscopy measurements reveal an increase in the number of particles undergoing reversible fluorescent on–off transitions in the volume under observation with increasing excitation power; this effect is found to be more pronounced in the case of core‐only QDs than for core–shell QDs.     

Oxygen-sensitive 19F NMR imaging of the vascular system in vivo

The fluorine nuclear magnetic resonance spin-lattice relaxation rate (1/T1) of the perfluorochemical blood substitute perfluorotripropylamine (FTPA) is very sensitive to oxygen tension. This presents the possibility of measuring blood oxygen tension by 19F MR imaging. We obtained oxygen-sensitive 19F NMR images of the circulatory system of rats infused with emulsified FTPA. Blood oxygenation was assessed under conditions of both air- and 100% O2-breathing. T1 relaxation times were derived from MR images using a partial saturation pulse sequence. The T1 times were compared with a phantom calibration curve to calculate average blood pO2 values in the lung, liver, and spleen. The results showed marked, organ-specific increases in blood oxygen tension when the rat breathed 100% O2 instead of air.     

A self-consistent variation-perturbation theory for open shell atomic systems: Calculation of polarizabilities and shielding factors

In this paper a fully coupled variation-perturbation theory has been introduced for handling open-shell atomic systems in the presence of static perturbations. The static dipolar and quadrupolar polarizabilities and shielding factors for Li, Be⁺, B²⁺, B, C⁺, Na and Al have been calculated and compared with available results. Important sources of discrepancies in previous calculations of shielding factors have been noticed and critically examined. The dipolar shielding factors calculated in this paper show satisfactory agreement with the theoretical N/Z ratio. In the absence of any theoretical test for the quadrupolar shielding factor, the accuracy of the calculations of γ_∞, should be judged in the light of the accuracy of the corresponding β∞ values.     

Acceleration of the universe with a simple trigonometric potential

In this paper, we investigate the quintessence model with a minimally coupled scalar field in the context of recent supernovae observations. By choosing a particular form of the deceleration parameter q, which gives an early deceleration and late time acceleration for the dust dominated model, we show that this sign flip in q can be obtained by a simple trigonometric potential. The early matter dominated model expands with q = 1/2 as desired and enters a negative q phase quite late during the evolution.     

Characterization of core-shell nanoparticles by small angle neutron scattering

The Ni₃Si-type nanoparticles dispersed in a mixture of H₂O/D₂O were characterised by SANS using the contrast variation method. The existence of a core-shell structure in the nanoparticles with a Ni₃Si(Al) core and amorphous SiO_x shell is confirmed by the SANS measurements. The nanoparticles were produced by extracting precipitates from a bulk Ni-13.3Si-2Al ( at. %) alloy using electrochemical phase separation technique and were pre-characterised by X-ray diffraction and transmission electron microscopy. By comparing the precipitate morphology in the Ni-Si-Al alloy with the extracted nanoparticles in the SANS measurements, it is clearly established that the precipitates shape and size are unaffected by the extraction process and that the amorphous shell forms on top of the particle core. However, the present measurement could not confirm or exclude the presence of H atoms in the shell structure. PACS 61.12.Ex; 61.12.-q; 61.46.Df; 61.82.Rx     

Contrasting Response of Two Dipolar Fluorescence Probes in a Leucine‐Based Organogel and Its Implications

The microenvironments of a leucine‐based organogel are probed by monitoring the fluorescence behavior of coumarin 153 (C153) and 4‐aminophthalimide (AP). The steady‐state data reveals distinctly different locations of the two molecules in the gel. Whereas AP resides close to the hydroxyl moieties of the gelator and engages in hydrogen‐bonding interactions, C153 is found in bulk‐toluene‐like regions. In contrast to C153, AP exhibits excitation‐wavelength‐dependent emission, indicating that the environments of the hydrogen‐bonded AP molecules are not all identical. A two‐component fluorescence decay of AP in gel, unlike C153, supports this model. A time‐resolved fluorescence anisotropy study of the rotational motion of the molecules also reveals the strong association of only AP with the gelator. That AP influences the critical gelation concentration implies its direct involvement in the gel‐formation process. The results highlight the importance of guest–gelator interactions in gels containing guest molecules.     

Co-operative intra-protein structural response due to protein–protein complexation revealed through thermodynamic quantification: study of MDM2-p53 binding

The p53 protein activation protects the organism from propagation of cells with damaged DNA having oncogenic mutations. In normal cells, activity of p53 is controlled by interaction with MDM2. The well understood p53-MDM2 interaction facilitates design of ligands that could potentially disrupt or prevent the complexation owing to its emergence as an important objective for cancer therapy. However, thermodynamic quantification of the p53-peptide induced structural changes of the MDM2-protein remains an area to be explored. This study attempts to understand the conformational free energy and entropy costs due to this complex formation from the histograms of dihedral angles generated from molecular dynamics simulations. Residue-specific quantification illustrates that, hydrophobic residues of the protein contribute maximum to the conformational thermodynamic changes. Thermodynamic quantification of structural changes of the protein unfold the fact that, p53 binding provides a source of inter-element cooperativity among the protein secondary structural elements, where the highest affected structural elements (α2 and α4) found at the binding site of the protein affects faraway structural elements (β1 and Loop1) of the protein. The communication perhaps involves water mediated hydrogen bonded network formation. Further, we infer that in inhibitory F19A mutation of P53, though Phe19 is important in the recognition process, it has less prominent contribution in the stability of the complex. Collectively, this study provides vivid microscopic understanding of the interaction within the protein complex along with exploring mutation sites, which will contribute further to engineer the protein function and binding affinity.