Conformation-selective coordination-driven self-assembly of a ditopic donor with Pd-II acceptors

Coordination-driven self-assembly of 3-(5-(pyridin-3-yl)-1H-1,2,4-triazol-3-yl)pyridine (L) was investigated with 90 degrees cis-blocked Pd(II) acceptors and tetratopic Pd(NO3)(2). Although the ligand is capable of binding in several different conformations (acting as a ditopic donor through the pyridyl nitrogens), the experimental results (including X-ray structures) showed that it adopts a particular conformation when it binds with 90 degrees cis-blocked Pd(II) acceptors (two available sites) to yield 2 + 2] self-assembled macrocycles. On the other hand, with Pd(NO3)(2) (where four available sites are present) a different conformer of the same donor was selectively bound to form a molecular cubic cage. The experimental findings were corroborated well with the density functional theory (B3LYP) calculations. The tetratopic Pd(NO3)(2) yielded a 6 + 12] self-assembled Pd6L12 molecular cube, which contains a potential void occupied by nitrate and perchlorate ions. Being a triazole based ligand, the free space inside the cage is enriched with several sp(2) hybridised nitrogen atoms with lone pairs of electrons to act as Lewis basic sites. Knoevenagel condensation reactions of several aromatic aldehydes with active methylene compounds were successfully performed in reasonably high yields in the presence of the cage.

Intertwined vorticity and elastodynamics in flapping wing propulsion

We performed numerical experiments on a one-dimensional elastic solid oscillating in a two-dimensional viscous incompressible fluid with the intent of discerning the interplay of vorticity and elastodynamics in flapping wing propulsion. Perhaps for the first time, we have established the role of foil deflection topology and its influence on vorticity generation, through spatially and temporally evolving foil slope and curvature. Though the frequency of oscillation of the foil has a definite role, it is the phase relation between foil slope and pressure that determines thrust or drag. Similarly, the phase difference between flapping velocity, and pressure and inertial forces, determine the power input to the foil, and in turn drives propulsive efficiency. At low frequencies of oscillation, the sympathetic slope and curvature of deformation of the foil allow generation of leading-edge vortices that do not separate; they cause substantial rise in pressure between the leading edge and mid-chord. The circulatory component of pressure is determined primarily by the leading-edge vortex and therefore thrust too is predominantly circulatory in origin at low frequencies. In the intermediate and high-frequency range, thrust and drag on the foil spatially alternate and non-circulatory forces dominate over circulatory and viscous forces. For the mass ratios we simulated, thrust due to flapping varies quadratically as a function of Strouhal number or trailing-edge flapping velocity; further, the trailing edge flapping velocities peak at the same set of frequencies where the thrust is also a maximum. Propulsive efficiency, on the other hand, is roughly a mirror image of the thrust variation with respect to Strouhal number. Given that most instances of flapping propulsion in nature are primarily through distributed muscular actuation that enables precise control of deformation shape, leading to high thrust and efficiency, the results presented here are pointers towards understanding some of the mechanisms that drive thrust and propulsive efficiency.

Lifshitz transition and modulation of electronic and transport properties of bilayer graphene by sliding and applied normal compressive strain

Using density functional theory (DFT) we investigate the changes in electronic and transport properties of graphene bilayer caused by sliding one of the layers. Change in stacking pattern breaks the lattice symmetry, which results in Lifshitz transition together with the modulation of the electronic structure. Going from AA to AB stacking by sliding along armchair direction leads to a drastic transition in electronic structure from linear to parabolic dispersion. Our transport calculations show a significant change in the overall transmission value for large sliding distances along zigzag direction. The increase in interlayer coupling with normal compressive strain increases the overlapping of conduction and valence band, which leads to further shift in the Dirac points and an enhancement in the Lifshitz transition. The ability to tune the topology of band structure by sliding and/or applying normal compressive strain will open doors for controlled tuning of many physical phenomenon such as Landau levels and quantum Hall effect in graphene. (C) 2015 Elsevier Ltd. All rights reserved.

Transitions and blowoff of unconfined non-premixed swirling flame

The present experimental work reports the first observations of primary and secondary transitions in the time-averaged flame topology in a non-premixed swirling flame as the geometric swirl number S-G (a non dimensional number used to quantify the intensity of imparted swirl) is varied from a magnitude of zero till flame blowout. First observations of two transition types viz. primary and secondary transitions are reported. The primary transition represents a transformation from yellow straight jet flame (at S-G = 0) to lifted flame with blue base and finally to swirling seated (burner attached) yellow flame. Time-averaged streamline plot obtained from 2D PIV in mid-longitudinal plane shows a recirculation zone (RZ) at the immediate vicinity of burner exit. The lifted flame is stabilized along the vortex core of this RZ. Further, when S-G similar to 1.4-3, the first occurrence of vortex breakdown (VB) induced internal recirculation zone (IRZ) is witnessed. The flame now stabilizes at the upstream stagnation point of the VB-IRZ, which is attached to the burner lip. The secondary transition represents a transformation from a swirling seated flame to swirling flame with a conical tailpiece and finally to a highly-swirled near blowout oxidizer-rich flame. This transition is understood to be the result of transition in vortex breakdown modes of the swirling flow field from dual-ring VB bubble to central toroidal recirculation zone (CTRZ). The physics of transition is described on the basis of modified Rossby number (Ro(m)). Finally, when the swirl intensity is very high i.e. SG similar to 10, the flame blows out due to excessive straining and due to entrainment of large amount of oxidizer due to partial premixing. The present investigation involving changes in flame topology is immensely important because any change in global flame structure causes oscillatory heat release that can couple with dynamic pressure and velocity fluctuations leading to unsteady combustion. In this light, understanding mechanisms of flame stabilization is essential to tackle the problem of thermo-acoustic instability. (C) 2015 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

Pressure-induced phase transition in Bi2Se3 at 3 GPa: electronic topological transition or not?

In recent years, a low pressure transition around P similar to 3 GPa exhibited by the A(2)B(3)-type 3D topological insulators is attributed to an electronic topological transition (ETT) for which there is no direct evidence either from theory or experiments. We address this phase transition and other transitions at higher pressure in bismuth selenide (Bi2Se3) using Raman spectroscopy at pressure up to 26.2 GPa. We see clear Raman signatures of an isostructural phase transition at P similar to 2.4 GPa followed by structural transitions at similar to 10 GPa and 16 GPa. First-principles calculations reveal anomalously sharp changes in the structural parameters like the internal angle of the rhombohedral unit cell with a minimum in the c/a ratio near P similar to 3 GPa. While our calculations reveal the associated anomalies in vibrational frequencies and electronic bandgap, the calculated Z(2) invariant and Dirac conical surface electronic structure remain unchanged, showing that there is no change in the electronic topology at the lowest pressure transition.

Folding of Protein L with Implications for Collapse in the Denatured State Ensemble

A fundamental question in protein folding is whether the coil to globule collapse transition occurs during the initial stages of folding (burst phase) or simultaneously with the protein folding transition. Single molecule fluorescence resonance energy transfer (FRET) and small-angle X-ray scattering (SAXS) experiments disagree on whether Protein L collapse transition occurs during the burst phase of folding. We study Protein L folding using a coarse-grained model and molecular dynamics simulations. The collapse transition in Protein L is found to be concomitant with the folding transition. In the burst phase of folding, we find that FRET experiments overestimate radius of gyration, R-g, of the protein due to the application of Gaussian polymer chain end-to-end distribution to extract R-g from the FRET efficiency. FRET experiments estimate approximate to 6 angstrom decrease in R-g when the actual decrease is approximate to 3 angstrom on guanidinium chloride denaturant dilution from 7.5 to 1 M, thereby suggesting pronounced compaction in the protein dimensions in the burst phase. The approximate to 3 angstrom decrease is close to the statistical uncertainties of the R-g data measured from SAXS experiments, which suggest no compaction, leading to a disagreement with the FRET experiments. The transition-state ensemble (TSE) structures in Protein L folding are globular and extensive in agreement with the Psi-analysis experiments. The results support the hypothesis that the TSE of single domain proteins depends on protein topology and is not stabilized by local interactions alone.

Autoregulation of topoisomerase I expression by supercoiling sensitive transcription

The opposing catalytic activities of topoisomerase I (TopoI/relaxase) and DNA gyrase (supercoiling enzyme) ensure homeostatic maintenance of bacterial chromosome supercoiling. Earlier studies in Es-cherichia coli suggested that the alteration in DNA supercoiling affects the DNA gyrase and TopoI expression. Although, the role of DNA elements around the promoters were proposed in regulation of gyrase, the molecular mechanism of supercoiling mediated control of TopoI expression is not yet understood. Here, we describe the regulation of TopoI expression from Mycobacterium tuberculosis and Mycobac-terium smegmatis by a mechanism termed Supercoiling Sensitive Transcription (SST). In both the organisms, topoI promoter(s) exhibited reduced activity in response to chromosome relaxation suggesting that SST is intrinsic to topoI promoter(s). We elucidate the role of promoter architecture and high transcriptional activity of upstream genes in topoI regulation. Analysis of the promoter(s) revealed the presence of suboptimal spacing between the -35 and -10 elements, rendering them supercoiling sensitive. Accordingly, upon chromosome relaxation, RNA polymerase occupancy was decreased on the topoI promoter region implicating the role of DNA topology in SST of topoI. We propose that negative supercoiling induced DNA twisting/writhing align the -35 and -10 elements to facilitate the optimal transcription of topoI.