Iron(III) salicylates of dipicolylamine bases showing photo-induced anticancer activity and cytosolic localization

An iron(III) salicylate having a dipicolylamine base (andpa) with a photoactive anthracenyl moiety is prepared, characterized, and studied for its photo-induced anticancer activity and cellular localization in HeLa and MCF-7 cells. Its phenyl analogue is structurally characterized by X-ray crystallography. The complex has a ternary structure in which the dipicolylamine ligand and salicylic acid in dianionic form (sal) display respective tridentate and bidentate mode of coordination in Fe(sal)(phdpa)Cl] (1). Complex Fe(sal)(andpa)Cl] (2) having a pendant anthracenyl moiety shows significant photocytotoxicity in visible light (400-700 nm) giving IC50 values of 8.6 +/- 0.7 and 3.4 +/- 0.9 mu M in HeLa and MCF-7 cells, while being essentially nontoxic in the dark (IC50 > 100 mu M). The complex shows cytosolic localization in the cancer cells. Formation of hydroxyl radicals ((OH)-O-center dot) as the reactive oxygen species is evidenced from the pUC19 DNA photocleavage studies. (C) 2015 Elsevier Ltd. All rights reserved.

The Effect of Periodic Segmentation Cracks on the Interfacial Debonding: Study on Interfacial Stresses

Hard coatings on relatively soft substrate always face the danger of debonding along the interface. Interfacial stresses are considered to be the initial driving force for the interfacial debonding of the relatively strong bonded coatings. Interfacial stresses due to the mismatch of strain between the coating and substrate are simulated with FEM firstly. The distribution of the interfacial stresses is achieved, which confirms an excessive stresses concentration near the interface end. Subsequently, the redistribution of interfacial stresses is calculated for a coating with periodic segmentation cracks. Results indicate that the distribution of interfacial stresses is altered greatly with the periodic segmentation cracks. To reveal the effect of the spacing of the periodic segmentation cracks on the distribution of interfacial stresses, different crack density is modeled within the coating. It is found that that the peak values of the interfacial stresses decrease with the increase of crack density, i.e. with reduction of spacing of segmentation cracks.

Interfacial microstructure and mechanical behaviour in laser clad TiCp/Ni alloy coatings

Coatings of TiCp reinforced composite have been produced by laser cladding. Two kinds of coating with different TiCp origins were investigated, i.e. undissolved TiCp and in situ TiCp. For undissolved TiCp, epitaxial growth of TiC, precipitation of CrB, and a chemical reaction occur at phase interfaces, and nanoindentation loading curves show pop in marks caused by the plastic deformation associated with crack formation or debonding of TiCp from the matrix. As for in situ TiCp, no pop in mark appears. Meanwhile, in situ TiCp produces hardness and elastic modulus values that are higher than those produced by the coating that contains undissolved TiCp.

Dislocations emission and crack extension at the atomistic crack tip in body-centered-cubic metal Mo

The behaviors of a crack in body-centered-cubic metal Mo under different loading modes were studied using the molecular dynamics method. Dislocation emission was observed near the crack tip in response to mode II loading with theta = 0 degrees in which theta is the inclination angle of the slip plane with respect to the crack plane, and two full dislocations were observed at the stress level of K-II = 1.17 MPa m(1/2) without any evidence of crack extension. Within the range of 0 degrees less than or equal to theta less than or equal to 45 degrees, crack extension was observed in response to mode I loading, and the effect of crystal orientation on the crack propagation was studied, The crack propagated along the [111] slip direction without any evidence of dislocations emission.

Crack Tip Field and J-Integral with Strain Gradient Effect

The mode I plane strain crack tip field with strain gradient effects is presented in this paper based on a simplified strain gradient theory within the framework proposed by Acharya and Bassani. The theory retains the essential structure of the incremental version of the conventional J_2 deformation theory No higher-order stress is introduced and no extra boundary value conditions beyond the conventional ones are required. The strain gradient effects are considered in the constitutive relation only through the instantaneous tangent modulus. The strain gradient measures are included into the tangent modulus as internal parameters. Therefore the boundary value problem is the same as that in the conventional theory Two typical crack Problems are studied: (a) the crack tip field under the small scale yielding condition induced by a linear elastic mode-I K-field and (b) the complete field for a compact tension specimen. The calculated results clearly show that the stress level near the crack tip with strain gradient effects is considerable higher than that in the classical theory The singularity of the strain field near the crack tip is nearly equal to the square-root singularity and the singularity of the stress field is slightly greater than it. Consequently, the J-integral is no longer path independent and increases monotonically as the radius of the calculated circular contour decreases.

Steady-state crack growth and fracture work based on the theory of mechanism-based strain gradient plasticity

Mode I steady-state crack growth is analyzed under plane strain conditions in small scale yielding. The elastic-plastic solid is characterized by the mechanism-based strain gradient (MSG) plasticity theory [J. Mech. Phys. Solids 47 (1999) 1239, J. Mech. Phys. Solids 48 (2000) 99]. The distributions of the normal separation stress and the effective stress along the plane ahead of the crack tip are computed using a special finite element method based on the steady-state fundamental relations and the MSG flow theory. The results show that during the steady-state crack growth, the normal separation stress on the plane ahead of the crack tip can achieve considerably high value within the MSG strain gradient sensitive zone. The results also show that the crack tip fields are insensitive to the cell size parameter in the MSG theory. Moreover, in the present research, the steady-state fracture toughness is computed by adopting the embedded process zone (EPZ) model. The results display that the steady-state fracture toughness strongly depends on the separation strength parameter of the EPZ model and the length scale parameter in the MSG theory. Furthermore, in order for the results of steady crack growth to be comparable, an approximate relation between the length scale parameters in the MSG theory and in the Fleck-Hutchinson strain gradient plasticity theory is obtained.

On The Thermally Induced Interfacial Delamination Of A Segmented Coating

The thermally induced interfacial delamination problem of a segmented coating is investigated using finite element method (FEM). The coating-substrate system, modeled as a coated semi-infinite medium with periodic segmentation cracks within coating, is assumed to be exposed to convective cooling from surface. The failure criterion based on the interfacial fracture toughness is adopted, in which the energy release rate for an interface crack is considered to be the driving force for interfacial delamination extension. The results confirm that a segmented coating has higher delamination resistance than an intact one under the same thermal transients, as the segmentation crack spacing is smaller than a critical value. Based on dimensional analysis, sensitivity analyses of the crack driving force are also obtained as a function of various dimensionless parameters such as time, convection severity and material constants. These results may provide some helpful references for the integrity of coating-substrate systems under thermal loading. (C) 2007 Elsevier B.V. All rights reserved.

Crack propagation in the power-law nonlinear viscoelastic material

An analysis on crack creep propagation problem of power-law nonlinear viscoelastic materials is presented. The creep incompressilility assumption is used. To simulate fracture behavior of craze region, it is assumed that in the fracture process zone near the crack tip, the cohesive stress sigma(f) acts upon the crack surfaces and resists crack opening. Through a perturbation method, i. e., by superposing the Mode-I applied force onto a referential uniform stress state, which has a trivial solution and gives no effect on the solution of the original problem, the nonlinear viscoelastic problem is reduced to linear problem. For weak nonlinear materials, for which the power-law index n similar or equal to 1, the expressions of stress and crack surface displacement are derived. Then, the fracture process zone local energy criterion is proposed and based on which the formulas of cracking incubation time t

Crack propagation in structures subjected to periodic excitation

In the present paper, a simple mechanical model is developed to predict the dynamic response of a cracked structure subjected to periodic excitation, which has been used to identify the physical mechanisms in leading the growth or arrest of cracking. The structure under consideration consists of a beam with a crack along the axis, and thus, the crack may open in Mode I and in the axial direction propagate when the beam vibrates. In this paper, the system is modeled as a cantilever beam lying on a partial elastic foundation, where the portion of the beam on the foundation represents the intact portion of the beam. Modal analysis is employed to obtain a closed form solution for the structural response. Crack propagation is studied by allowing the elastic foundation to shorten (mimicking crack growth) if a displacement criterion, based on the material toughness, is met. As the crack propagates, the structural model is updated using the new foundation length and the response continues. From this work, two mechanisms for crack arrest are identified. It is also shown that the crack propagation is strongly influenced by the transient response of the structure.

On crack path stability in a layered material

Crack paths in an elastic layer on top of a substrate are considered. Crack growth is initiated from an edge crack in the layer. The plane of the initially straight crack forms an angle to the free surface. The load consists of a pair of forces applied at the crack mouth and parallel to the interface. Crack paths are calculated using a boundary element method. Crack growth is assumed to proceed along a path for which the mode II stress intensity factor vanishes. The inclination and the length of the initial crack are varied. The effect of two different substrates on the crack path evolution is demonstrated. A crack path initially leading perpendicularly to the interface is shown to be directionally unstable for a rigid substrate. Irrespective of its initial angle, the crack does not reach the interface, but reaches the free surface if the layer is infinitely long. At finite layer length the crack reaches the upper free surface if the initial crack inclination to the surface is small enough. For an inextendable flexible substrate, on the other hand, the crack reaches the interface if its initial inclination is large enough. For the flexible substrate an unstable path parallel with the sides of an infinitely long layer is identified. The results are compared with experimental results and discussed in view of characterisation of directionally unstable crack paths. The energy release rate for an inclined edge crack is determined analytically.

Molecular dynamics simulation of interaction of a dislocation array from a crack tip with grain boundaries

The interaction of a dislocation array emitted from a crack tip under mode II loading with asymmetric tilt grain boundaries (GBs) is analysed by the molecular dynamics method. The GBs can generally be described by planar and linear matching zones and unmatching zones. All GBs are observed to emit dislocations. The GBs migrated easily due to their planar and linear matching structure and asymmetrical type. The diffusion induced by stress concentration is found to promote the GB migration. The transmissions of dislocations are either along the matched plane or along another plane depending on tilt angle theta. Alternate processes of stress concentration and stress relaxation take place ahead of the pileup. The stress concentration can be released either by transmission of dislocations, by atom diffusion along GBs, or by migration of GBs by formation of twinning bands. The simulated results also unequivocally demonstrate two processes, i.e. asymmetrical GBs evolving into symmetrical ones and unmatching zones evolving into matching ones during the loading process.

Transient effect on ideally plastic stationary crack-tip fields

This paper analyses the transient effect on ideally plastic stationary crack-tip fields under mode I plane strain conditions, when the inertial forces are not negligible. It is shown that the governing equation for such a problem can be expressed in formal simplicity when referred to a system of moving curvilinear coordinates, which is a generalization of the system defined by the slip-line field in quasi-static plasticity. A perturbation method of solving the equations is described and illustrated by application to problems of ideally plastic stationary crack-tip fields when the inertia forces are not negligible.

Transient effect on ideally plastic stationary crack-tip fields

This paper analyses the transient effect on ideally plastic stationary crack tip fields under mode I plane strain conditions, when the inertial forces are not negligible. It is shown that the governing equation for such a problem can be expressed in formal simplicity when referred to a system of moving curvilinear coordinates, which is a generalization of the system defined by the slip-line field in quasi-static plasticity. A perturbation method of solving the equations is described and illustrated by application to problems of ideally plastic stationary crack tip fields when the inertial forces are not negligible.

Molecular dynamics simulation of crack-tip processes in copper

The crack tip processes in copper under mode II loading have been simulated by a molecular dynamics method. The nucleation, emission, dislocation free zone (DFZ) and pile-up of the dislocations are analyzed by using a suitable atom lattice configuration and Finnis & Sinclair potential. The simulated results show that the dislocation emitted always exhibits a dissociated fashion. The stress intensity factor for dislocation nucleation, DFZ and dissociated width of partial dislocations are strongly dependent on the loading rate. The stress distributions are in agreement with the elasticity solution before the dislocation emission, but are not in agreement after the emission. The dislocation can move at subsonic wave speed (less than the shear wave speed) or at transonic speed (greater than the shear wave speed but less than the longitudinal wave speed), but at the longitudinal wave speed the atom lattice breaks down.

Elastodynamic stress intensity factor history for a semi-infinite crack under three-dimensional transient loading

The dynamic stress intensity factor history for a semi-infinite crack in an otherwise unbounded elastic body is analyzed. The crack is subjected to a pair of suddenly-applied point loadings on its faces at a distance L away from the crack tip. The exact expression for the mode I stress intensity factor as a function of time is obtained. The method of solution is based on the direct application of integral transforms, the Wiener-Hopf technique and the Cagniard-de Hoop method. Due to the existence of the characteristic length in loading this problem was long believed a knotty problem. Some features of the solutions are discussed and graphical result for numerical computation is presented.