Crystal Structure, Ultraviolet Spectrum, and Electronic Structure of a Strongly Twisted Push-Pull Ethylene, approaching an Amidinium-Vinylogous Dithioate Zwitterion

The crystal structure of 1,3-di benzyl -2 - (4,4-dimet hyl- 2,5- bist hioxocyclo hexylidene) imidazolidine (2) shows a twist of 80.8(5)' about the inter-ring bond, which has a length of 1.482(6) A. The near orthogonality of the donor and acceptor parts of this formal push-pull ethylene makes the structure approach that of a zwitterion, as evidenced by bond lengths indicating strong electron delocalization. The acceptor part approaches a vinylogous dithioate structure, the donor part an amidinium system. The U.V. spectrum shows an n + R and a R + R transition, at 51 1 and 41 7.5 nm, respectively; according to CNDO/S calculations these are located entirely in the [S-C-C-C-SI- part. Two bands at shorter wavelength are ascribed to transitions from combinations of the lone-pair orbitals on the sulphur atoms to a n* orbital in the [N-C-N] + part; this is facilitated by the near perpendicularity of the two parts of the molecule.

2-Thioacetamido thiazole as an ambidentate ligand. Complexes of Zn(II), Cd(II), Hg(II) and Cu(I)

Metal complexes of thiazoles have been studied in recent years[I-3] because of their biochemical importance[4,5]. However, data on metal complexes of thiazole derivatives containing another coordinating function are limited[2]. We have synthesized and examined the donor characteristics of a new ligand, 2-thioacetamide thiazole (TATZ)(I) towards chlorides and bromides of Zn(II), Cd(II), Hg(II) and Cu(I). The presence of four potential donor atoms and extensive charge delocalization should render TATZ a versatile ligand.

Comparison of promoter-specific events during transcription initiation in mycobacteria

DNA protein interactions that occur during transcription initiation play an important role in regulating gene expression. To initiate transcription, RNA polymerase (RNAP) binds to promoters in a sequence-specific fashion. This is followed by a series of steps governed by the equilibrium binding and kinetic rate constants, which in turn determine the overall efficiency of the transcription process. We present here the first detailed kinetic analysis of promoter RNAP interactions during transcription initiation in the sigma(A)-dependent promoters P-rrnAPCL1, P-rrnB and P-gyr of Mycobacterium smegmatis. The promoters show comparable equilibrium binding affinity but differ significantly in open complex formation, kinetics of isomerization and promoter clearance. Furthermore, the two rrn promoters exhibit varied kinetic properties during transcription initiation and appear to be subjected to different modes of regulation. In addition to distinct kinetic patterns, each one of the housekeeping promoters studied has its own rate-limiting step in the initiation pathway, indicating the differences in their regulation.

Synthesis of Diversified Thioethers,1-Aroylalkylisoquinolin-1-yl Thioethers, by Electrophilic S-Alkylation of 3-Phenyl Isoquinoline-1(2H)-thione

A mild and efficient method for the synthesis of thioethers has been developed. The 3-phenylisoquinoline-1(2H)-thione underwent S-alkylation to afford structurally diverse sulfides in high yield.

Vertical Uplift Resistance of a Group of Two Coaxial Anchors in Clay

The vertical uplift resistance for a group of two horizontal coaxial rigid strip anchors embedded in clay under undrained condition has been determined by using the upper bound theorem of limit analysis in combination with finite elements. An increase of undrained shear strength of soil mass with depth has been incorporated. The uplift factor F-c gamma has been computed. As compared to a single isolated anchor, a group of two anchors provides greater magnitude of the uplift resistance. For a given embedment ratio, the group of two anchors generates almost the maximum uplift resistance when the upper anchor is located midway between ground surface and the lower anchor. For a given embedment ratio, F-c gamma increases linearly with an increase in the normalized unit weight of soil mass up to a certain value before attaining a certain maximum magnitude; the maximum value of F-c gamma increases with an increase in embedment ratio. DOI: 10.1061/(ASCE)GT.19435606.0000599. (C) 2012 American Society of Civil Engineers.

On the solution of bivariate population balance equations for aggregation: Pivotwise expansion of solution domain

The solution of a bivariate population balance equation (PBE) for aggregation of particles necessitates a large 2-d domain to be covered. A correspondingly large number of discretized equations for particle populations on pivots (representative sizes for bins) are solved, although at the end only a relatively small number of pivots are found to participate in the evolution process. In the present work, we initiate solution of the governing PBE on a small set of pivots that can represent the initial size distribution. New pivots are added to expand the computational domain in directions in which the evolving size distribution advances. A self-sufficient set of rules is developed to automate the addition of pivots, taken from an underlying X-grid formed by intersection of the lines of constant composition and constant particle mass. In order to test the robustness of the rule-set, simulations carried out with pivotwise expansion of X-grid are compared with those obtained using sufficiently large fixed X-grids for a number of composition independent and composition dependent aggregation kernels and initial conditions. The two techniques lead to identical predictions, with the former requiring only a fraction of the computational effort. The rule-set automatically reduces aggregation of particles of same composition to a 1-d problem. A midway change in the direction of expansion of domain, effected by the addition of particles of different mean composition, is captured correctly by the rule-set. The evolving shape of a computational domain carries with it the signature of the aggregation process, which can be insightful in complex and time dependent aggregation conditions. (c) 2012 Elsevier Ltd. All rights reserved.

Vertical uplift resistance of two horizontal strip anchors with common vertical axis

With an application of the upper bound finite element limit analysis, the vertical pullout capacity of a group of two horizontal strip plate anchors, with the common vertical axis and placed in a cohesive-frictional soil, has been computed. The variation of the uplift factors Fc, Fq and Fy, due to the contributions of soil cohesion, surcharge pressure and unit weight, respectively, has been evaluated for different combinations of S/B and H/B. As compared to single isolated anchor, the group of two anchors generates significantly greater magnitude of Fc for Φ ≤ 20° especially with greater values of H/B and under fully bonded anchor-soil interface condition. The factor Fc attains almost the maximum value when the upper anchor plate is placed midway between ground surface and the lower anchor plate. The factors Fq and Fy, on the other hand, for a group of two anchors are found to remain almost equal to that of a single isolated anchor as long as the levels of the lower plate in the group and the single isolated anchor are kept the same.

The 2014 M-w 6.1 Bay of Bengal, Indian Ocean, Earthquake: A Possible Association with the 85 degrees E Ridge

Oceanic intraplate earthquakes are known to occur either on active ridge-transform structures or by reactivation of their inactive counterparts, generally referred to as fossil ridges or transforms. The Indian Ocean, one of the most active oceanic intraplate regions, has generated large earthquakes associated with both these types of structures. The moderate earthquake that occurred on 21 May 2014 (M-w 6.1) in the northern Bay of Bengal followed an alternate mechanism, as it showed no clear association either with active or extinct ridge-transform structures. Its focal depth of >50 km is uncommon but not improbable, given the similar to 90 Ma age of the ocean floor with 12-km-thick overlying sediments. No tectonic features have been mapped in the near vicinity of its epicenter, the closest being the 85 degrees E ridge, located similar to 100 km to its west, hitherto regarded as seismically inactive. The few earthquakes that have occurred here in the past are clustered around its southern or northern limits, and a few are located midway, at around 10 degrees N. The 2014 earthquake, sourced close to the northern cluster, seems to be associated with a northwest-southeast-oriented fracture, located on the eastern flanks of the 85 degrees E ridge. If this causal association is possible, we believe that reactivation of fossil hotspot trails could be considered as another mechanism for oceanic intraplate seismicity.