Impact of metal on the DNA photocleavage activity and cytotoxicity of ferrocenyl terpyridine 3d metal complexes

Ferrocenyl terpyridine 3d metal complexes and their analogues, viz. [M(Fc-tpy)(2)](ClO(4))(2) (1-4), [Zn(Ph-tpy)(2)](ClO(4))(2) (5) and [Zn(Fc-dpa)(2)]X(2) (X = ClO(4), 6; PF6, 6a), where M = Fe(II) in 1, Co(II) in 2, Cu(II) in 3 and Zn(II) in 4, Fc-tpy is 4'-ferrocenyl-2,2': 6', 2 `'-terpyridine, Ph-tpy is 4'-phenyl-2,2': 6', 2 `'-terpyridine and Fc-dpa is ferrocenyl-N,N-dipicolylmethanamine, are prepared and their DNA binding and photocleavage activity in visible light studied. Complexes 2, 4, 5 and 6a that are structurally characterized by X-ray crystallography show distorted octahedral geometry with the terpyridyl ligands binding to the metal in a meridional fashion, with Fc-dpa in 6a showing a facial binding mode. The Fc-tpy complexes display a charge transfer band in the visible region. The ferrocenyl (Fc) complexes show a quasi-reversible Fc(+)-Fc redox couple within 0.48 to 0.66 V vs. SCE in DMF-0.1 M TBAP. The DNA binding constants of the complexes are similar to 10(4) M(-1). Thermal denaturation and viscometric data suggest DNA surface binding through electrostatic interaction by the positively charged complexes. Barring the Cu(II) complex 3, the complexes do not show any chemical nuclease activity in the presence of glutathione. Complexes 1-4 exhibit significant plasmid DNA photocleavage activity in visible light via a photoredox pathway. Complex 5, without the Fc moiety, does not show any DNA photocleavage activity. The Zn(II) complex 4 shows a significant PDT effect in HeLa cancer cells giving an IC(50) value of 7.5 mu M in visible light, while being less toxic in the dark (IC(50) = 49 mu M).

Spatial filter based 3D resolution improvement and polarization properties of multiphoton multiple-excitation-spot-optical microscopy

Three-dimensional (3D) resolution improvement in multi-photon multiple-excitation-spot-optical microscopy is proposed. Specially designed spatial filter is employed for improving the overall 3D resolution of the imaging system. An improvement up to a factor of 14.5 and sub-femto liter volume excitation is achieved. The system shows substantial sidelobe reduction (<4%) due to the non-linear intensity dependence of multiphoton process. Polarization effect on x-oriented and freely rotating dipoles shows dramatic change in the field distribution at the focal-plane. The resulting point-spread function has the ability to produce several strongly localized polarization dependent field patterns which may find applications in optical engineering and bioimaging.

3D Acoustic Analysis Of Spherical Chamber Having Single Inlet And Multiple Outlet: An Impedance Matrix Approach

The transmission loss (TL) performance of spherical chambers having single inlet and multiple outlet is obtained analytically through modal expansion of acoustic field inside the spherical cavity in terms of the spherical Bessel functions and Legendre polynomials. The uniform piston driven model based upon the impedance [Z] matrix is used to characterize the multi-port spherical chamber. It is shown analytically that the [Z] parameters are independent of the azimuthal angle (phi) due to the axisymmetric shape of the sphere; rather, they depend only upon the polar angle (theta) and radius of the chamber R(0). Thus, the effects of relative polar angular location of the ports and number of outlet ports are investigated. The analytical results are shown to be in good agreement with the 3D FEA results, thereby validating the procedure suggested in this work.

3D finite element modelling of a composite patch repair

Composite-patching on cracked/weak metallic aircraft structures improves structural integrity. A Boron Epoxy patch employed to repair a cracked Aluminum sheet is modeled employing 3D Finite Element Method (FEM). SIFs extracted using ''displacement extrapolation'' are used to measure the repair effectiveness. Two issues viz., patch taper and symmetry have been looked into.

Efficient sequential assignments in proteins with reduced dimensionality 3D HN(CA)NH

We present reduced dimensionality (RD) 3D HN(CA)NH for efficient sequential assignment in proteins. The experiment correlates the N-15 and H-1 chemical shift of a residue ('i') with those of its immediate N-terminal (i - 1) and C-terminal (i + 1) neighbors and provides four-dimensional chemical shift correlations rapidly with high resolution. An assignment strategy is presented which combines the correlations observed in this experiment with amino acid type information obtained from 3D CBCA(CO)NH. By classifying the 20 amino acid types into seven distinct categories based on C-13(beta) chemical shifts, it is observed that a stretch of five sequentially connected residues is sufficient to map uniquely on to the polypeptide for sequence specific resonance assignments. This method is exemplified by application to three different systems: maltose binding protein (42 kDa), intrinsically disordered domain of insulin-like growth factor binding protein-2 and Ubiquitin. Fast data acquisition is demonstrated using longitudinal H-1 relaxation optimization. Overall, 3D HN(CA)NH is a powerful tool for high throughput resonance assignment, in particular for unfolded or intrinsically disordered polypeptides.

Reduced dimensionality 3D HNCAN for unambiguous HN, CA and N assignment in proteins

We present here an improvisation of HNN (Panchal, Bhavesh et al., 2001) called RD 3D HNCAN for backbone (HN, CA and N-15) assignment in both folded and unfolded proteins. This is a reduced dimensionality experiment which employs CA chemical shifts to improve dispersion. Distinct positive and negative peak patterns of various triplet segments along the polypeptide chain observed in HNN are retained and these provide start and check points for the sequential walk. Because of co-incrementing of CA and N-15, peaks along one of the dimensions appear at sums and differences of the CA and N-15 chemical shifts. This changes the backbone assignment protocol slightly and we present this in explicit detail. The performance of the experiment has been demonstrated using Ubiquitin and Plasmodium falciparum P2 proteins. The experiment is particularly valuable when two neighboring amino acid residues have nearly identical backbone N-15 chemical shifts. (C) 2012 Elsevier Inc. All rights reserved.

Wrinkled and slack membranes: nonlinear 3D elasticity solutions via smooth DMS-FEM and experiment

The smooth DMS-FEM, recently proposed by the authors, is extended and applied to the geometrically nonlinear and ill-posed problem of a deformed and wrinkled/slack membrane. A key feature of this work is that three-dimensional nonlinear elasticity equations corresponding to linear momentum balance, without any dimensional reduction and the associated approximations, directly serve as the membrane governing equations. Domain discretization is performed with triangular prism elements and the higher order (C1 or more) interelement continuity of the shape functions ensures that the errors arising from possible jumps in the first derivatives of the conventional C0 shape functions do not propagate because the ill-conditioned tangent stiffness matrices are iteratively inverted. The present scheme employs no regularization and exhibits little sensitivity to h-refinement. Although the numerically computed deformed membrane profiles do show some sensitivity to initial imperfections (nonplanarity) in the membrane profile needed to initiate transverse deformations, the overall patterns of the wrinkles and the deformed shapes appear to be less so. Finally, the deformed profiles, computed through the DMS FEM-based weak formulation, are compared with those obtained through an experiment on an ultrathin Kapton membrane, wherein wrinkles form because of the applied boundary displacement conditions. Comparisons with a reported experiment on a rectangular membrane are also provided. These exercises lend credence to the feasibility of the DMS FEM-based numerical route to computing post-wrinkled membrane shapes. Copyright (c) 2012 John Wiley & Sons, Ltd.

Guided Wave based Damage Detection in a Composite T-joint using 3D Scanning Laser Doppler Vibrometer

Composite T-joints are commonly used in modern composite airframe, pressure vessels and piping structures, mainly to increase the bending strength of the joint and prevents buckling of plates and shells, and in multi-cell thin-walled structures. Here we report a detailed study on the propagation of guided ultrasonic wave modes in a composite T-joint and their interactions with delamination in the co-cured co-bonded flange. A well designed guiding path is employed wherein the waves undergo a two step mode conversion process, one is due to the web and joint filler on the back face of the flange and the other is due to the delamination edges close to underneath the accessible surface of the flange. A 3D Laser Doppler Vibrometer is used to obtain the three components of surface displacements/velocities of the accessible face of the flange of the T-joint. The waves are launched by a piezo ceramic wafer bonded on to the back surface of the flange. What is novel in the proposed method is that the location of any change in material/geometric properties can be traced by computing a frequency domain power flow along a scan line. The scan line can be chosen over a grid either during scan or during post-processing of the scan data off-line. The proposed technique eliminates the necessity of baseline data and disassembly of structure for structural interrogation.

Parallel Computation of 3D Morse-Smale Complexes

The Morse-Smale complex is a topological structure that captures the behavior of the gradient of a scalar function on a manifold. This paper discusses scalable techniques to compute the Morse-Smale complex of scalar functions defined on large three-dimensional structured grids. Computing the Morse-Smale complex of three-dimensional domains is challenging as compared to two-dimensional domains because of the non-trivial structure introduced by the two types of saddle criticalities. We present a parallel shared-memory algorithm to compute the Morse-Smale complex based on Forman's discrete Morse theory. The algorithm achieves scalability via synergistic use of the CPU and the GPU. We first prove that the discrete gradient on the domain can be computed independently for each cell and hence can be implemented on the GPU. Second, we describe a two-step graph traversal algorithm to compute the 1-saddle-2-saddle connections efficiently and in parallel on the CPU. Simultaneously, the extremasaddle connections are computed using a tree traversal algorithm on the GPU.

Thermodynamics of higher spin black holes in 3D

We examine the thermodynamic properties of recently constructed black hole solutions in SL(3, R) x SL(3, R) Chern-Simons theory in the presence of a chemical potential for spin-3 charge, which acts as an irrelevant deformation of the dual CFT with W-3 X W-3 symmetry. The smoothness or holonomy conditions admit four branches of solutions describing a flow between two AdS(3) backgrounds corresponding to two different CFTs. The dominant branch at low temperatures, connected to the BTZ black hole, merges smoothly with a thermodynamically unstable branch and disappears at higher temperatures. We confirm that the UV region of the flow satisfies the Ward identities of a CFT with W-3((2)) x W-3((2)) symmetry deformed by a spin-3/2 current. This allows to identify the precise map between UV and HI thermodynamic variables. We find that the high temperature regime is dominated by a black hole branch whose thermodynamics can only be consistently inferred with reference to this W-3((2)) x W-3((2)) CFT.

Fracture studies on 3D geometrically similar beams

In the present work, a discrete numerical approach is adopted to understand size effect and fracture behavior in concrete. First, a comparison is performed between 2D and 3D geometrically similar structures to analyze thickness effect. The study is supplemented with element failure pattern to analyze crack propagation. Further, changing influence of notch to depth ratio is analyzed by comparing 3D geometrically similar structures with different values of notch depth ratio. Finally, a statistical analysis is performed to understand the influence of structure size and heterogeneity on regression parameters namely Bf(t)' and D-0. (C) 2012 Elsevier Ltd. All rights reserved.

A new 3D cadmium(II) coordination polymer having mu(4)-oxalato, mu-aquo and mu-chlorido bridges: crystal structure, solid state fluorescence and thermal behavior

A new 3D cadmium(II) coordination polymer, Cd(C2O4)(0.5)Cl(H2O)](n) (1) has been synthesized from a mixture of CdCl2. H2O and (NH4)(2)C2O4 in a slightly acidic pH. Its molecular structure was determined by single crystal X-ray diffraction which reveals that the new polymeric structure consists of simultaneous mu(4)-oxalato, mu-aquo, and mu-chlorido bridges between the metal centers, embedded in distorted pentagonal bipyramidal geometries. On thermal analysis compound exhibits high thermal stability up to 330 degrees C. Compound 1 also exhibits strong fluorescent emission. (c) 2013 Elsevier B.V. All rights reserved.

Vorticity moments in four numerical simulations of the 3D Navier-Stokes equations

The issue of intermittency in numerical solutions of the 3D Navier-Stokes equations on a periodic box 0, L](3) is addressed through four sets of numerical simulations that calculate a new set of variables defined by D-m(t) = (pi(-1)(0) Omega(m))(alpha m) for 1 <= m <= infinity where alpha(m) = 2m/(4m - 3) and Omega(m)(t)](2m) = L-3 integral(v) vertical bar omega vertical bar(2m) dV with pi(0) = vL(-2). All four simulations unexpectedly show that the D-m are ordered for m = 1,..., 9 such that Dm+1 < D-m. Moreover, the D-m squeeze together such that Dm+1/D-m NE arrow 1 as m increases. The values of D-1 lie far above the values of the rest of the D-m, giving rise to a suggestion that a depletion of nonlinearity is occurring which could be the cause of Navier-Stokes regularity. The first simulation is of very anisotropic decaying turbulence; the second and third are of decaying isotropic turbulence from random initial conditions and forced isotropic turbulence at fixed Grashof number respectively; the fourth is of very-high-Reynolds-number forced, stationary, isotropic turbulence at up to resolutions of 4096(3).

High-resolution restoration of 3D structures from widefield images with extreme low signal-to-noise-ratio

Four-dimensional fluorescence microscopy-which records 3D image information as a function of time-provides an unbiased way of tracking dynamic behavior of subcellular components in living samples and capturing key events in complex macromolecular processes. Unfortunately, the combination of phototoxicity and photobleaching can severely limit the density or duration of sampling, thereby limiting the biological information that can be obtained. Although widefield microscopy provides a very light-efficient way of imaging, obtaining high-quality reconstructions requires deconvolution to remove optical aberrations. Unfortunately, most deconvolution methods perform very poorly at low signal-to-noise ratios, thereby requiring moderate photon doses to obtain acceptable resolution. We present a unique deconvolution method that combines an entropy-based regularization function with kernels that can exploit general spatial characteristics of the fluorescence image to push the required dose to extreme low levels, resulting in an enabling technology for high-resolution in vivo biological imaging.