Modified (22pi) smaragdyrins with large two-photon absorption cross section: a structure function correlation

[structure: see text] Two-photon absorption (TPA) cross-section values for a series of 22pi smaragdyrins bearing phenylacetylenylphenyl and [(phenylacetylenyl)phenylacetylenyl]phenyl meso links and their Rh(I) derivatives are reported.     

X-ray studies of the structure of thermotropic copolyesters

This paper describes x-ray analysis of the structure of a group of wholly aromatic thermotropic liquid crystalline copolyesters, focusing on two systems: condensation copolymers of 4-hydroxy-benzoic acid (HBA) and 2-hydroxy–6-naphthoic acid; and of HBA, 2,6-dihydroxy-naphthalene, and terephthalic acid. The fiber diagrams of these copolymers contain a series of aperiodic meridional maxima that shift in position with the monomer ratio. We have shown that these characteristics are predicted by a structure consisting of an array of chains of completely random monomer sequence. The positions of the maxima are predicted by a simple model in which the monomers are represented by points, separated from their neighbors by the appropriate monomer lengths. Use of atomic models for the monomers leads to prediction of both the positions and the intensities of the maxima. Calculations for nonrandom sequence distribution show that all but minimal blockiness can be ruled out. From the breath of the meridional maximum at d = 2.1 Å it is possible to estimate the correlation or persistence length for the stiff chain conformation in the solid state.     

Effect of pit formation and surface roughness on size-dependent thermal conductivity of nanometer-thick semiconducting films

In this work, the thermal conductivity variation due to pit formation and surface roughness in nanometer-thick semiconducting films has been studied. It is shown that the thermal conductivity of thin films is reduced due to the presence of these effects in the films. This reduction in thermal conductivity is dependent on film thickness. The present analysis has been done on GaAs nanometer-thick films using the available experimental data.     

On a monotone iterative method for a class of three point nonlinear nonsingular BVPs with upper and lower solutions in reverse order

In this article we consider the following class of three point boundary value problem and use monotone iterative technique to derive some sufficient conditions of existence. Examples are included to illustrate the effectiveness of the proposed results. We consider both well ordered and reverse ordered upper and lower solutions.     

Effect of initial orientation on twinning in commercially pure titanium

Abstract

The effect of initial orientation on twinning micro-mechanisms during tensile deformation of commercially pure titanium has been studied using micro focus X-ray diffraction and electron back scatter diffraction (EBSD) in a scanning electron microscope. Three orientations A, B and C obtained from a rolled and annealed block of commercially pure titanium were deformed in uniaxial tension till failure and the tested specimens were characterised with regard to bulk texture, microstructure and crystal orientation mapping using EBSD. Orientation B along the transverse direction in ND-TD plane exhibits higher strength and lower strain hardening compared to orientations A and C along the rolling direction in TD-RD and ND-RD plane, respectively. This is attributed to different texture of sample B compared to samples A and C leading to dissimilar twinning micro-mechanisms and characteristic variation in nature of twinning. It is observed that limited twin nucleation and prominent lateral growth plays a dominant role in orientation B while multiple twin nucleation with significant non-Schmid behaviour is dominant for the other two orientations. It is proposed from this study that conventional factors associated with twin formation like Schmid factor play a main role in twin nucleation and propagation, however, growth or lateral thickening of the twins is explained by elastic stiffness variation across twins and their parent grains.     

Quench dynamics of edge states in 2-D topological insulator ribbons

We study the dynamics of edge states of the two dimensional BHZ Hamiltonian in a ribbon geometry following a sudden quench to the quantum critical point separating the topological insulator phase from the trivial insulator phase. The effective edge state Hamiltonian is a collection of decoupled qubit-like two-level systems which get coupled to bulk states following the quench. We notice a pronounced collapse and revival of the Lochschmidt echo for low-energy edge states illustrating the oscillation of the state between the two edges. We also observe a similar collapse and revival in the spin Hall current carried by these edge states, leading to a persistence of its time-averaged value.     

Microwave‐Assisted Synthesis and Antituberculosis Screening of Some 4‐((3‐(Trifluoromethyl)‐5,6‐dihydro‐[1,2,4]triazolo[4,3‐a]pyrazin‐7(8H)‐l)methyl)benzenamine Hybrids

In the present investigation, a series of 4‐((3‐(trifluoromethyl)‐5,6‐dihydro‐[1,2,4]triazolo[4,3‐a]pyrazin‐7(8H)‐yl)methyl)benzenamine analogs 6a–o were synthesized and characterized by IR, NMR (¹H and ¹³C), and mass spectra. All newly synthesized compounds 6a–o were prepared under conventional and microwave irradiation methods. These compounds obtained in higher yields and in shorter reaction times in the microwave irradiation method when compared with the conventional method. Synthesized compounds 6a–o were inspected for their in vitro antitubercular activity against Mycobacterium tuberculosis H₃₇Ra using an established XTT reduction menadione assay. Among the screened compounds, 6i (IC₅₀: 1.82 μg/mL), 6j (IC₅₀: 1.02 μg/mL), and 6k (IC₅₀: 1.59 μg/mL) showed excellent activity. Furthermore, compound 6i showed MIC₉₀ value of 16.02 μg/mL. In summary, the results indicate the identification of some novel, selective, and specific inhibitors against M. tuberculosis that can be explored further for the potential antitubercular drug.     

A Garratt-Braverman cyclization route towards the synthesis of phenanthridine derivatives and their DNA-binding studies

Garratt-Braverman cyclization has been employed to synthesize a series of dihydroisofuran fused phenanthridine derivatives. The established protocol proposes a simpler synthetic alternative to have access to these therapeutically relevant cytotoxic scaffolds. Single crystal X-ray data unambiguously confirmed the structures of the synthesized phenanthridine derivatives. UV–Vis absorption titration with calf-thymus DNA followed by fluorescence-based competitive ethidium bromide displacement assay established the synthesized target compounds as potent DNA-intercalating agents with intrinsic binding constant of the range 10³-10⁵. Results obtained from the molecular docking further justified the spectroscopically obtained results.     

A Singular System with Precise Dosing and Spatiotemporal Control of CRISPR‐Cas9

Several genome engineering applications of CRISPR‐Cas9, an RNA‐guided DNA endonuclease, require precision control of Cas9 activity over dosage, timing, and targeted site in an organism. While some control of Cas9 activity over dose and time have been achieved using small molecules, and spatial control using light, no singular system with control over all the three attributes exists. Furthermore, the reported small‐molecule systems lack wide dynamic range, have background activity in the absence of the small‐molecule controller, and are not biologically inert, while the optogenetic systems require prolonged exposure to high‐intensity light. We previously reported a small‐molecule‐controlled Cas9 system with some dosage and temporal control. By photocaging this Cas9 activator to render it biologically inert and photoactivatable, and employing next‐generation protein engineering approaches, we have built a system with a wide dynamic range, low background, and fast photoactivation using a low‐intensity light while rendering the small‐molecule activator biologically inert. We anticipate these precision controls will propel the development of practical applications of Cas9.     

Scaling behavior in on‐chip field‐amplified sample stacking

Field amplified sample stacking (FASS) uses differential electrophoretic velocity of analyte ions in the high‐conductivity background electrolyte zone and low conductivity sample zone for increasing the analyte concentration. The stacking rate of analyte ions in FASS is limited by molecular diffusion and convective dispersion due to nonuniform electroosmotic flow (EOF). We present a theoretical scaling analysis of stacking dynamics in FASS and its validation with a large set of on‐chip sample stacking experiments and numerical simulations. Through scaling analysis, we have identified two stacking regimes that are relevant for on‐chip FASS, depending upon whether the broadening of the stacked peak is dominated by axial diffusion or convective dispersion. We show that these two regimes are characterized by distinct length and time scales, based on which we obtain simplified nondimensional relations for the temporal growth of peak concentration and width in FASS. We first verify the theoretical scaling behavior in diffusion‐ and convection‐dominated regimes using numerical simulations. Thereafter, we show that the experimental data of temporal growth of peak concentration and width at varying electric fields, conductivity gradients, and EOF exhibit the theoretically predicted scaling behavior. The scaling behavior described in this work provides insights into the effect of varying experimental parameters, such as electric field, conductivity gradient, electroosmotic mobility, and electrophoretic mobility of the analyte on the dynamics of on‐chip FASS.