Iron(III) Catecholates for Cellular Imaging and Photocytotoxicity in Red Light

Iron(III) complexes Fe(L)(L') (NO3)]-in which L is phenyl-N, N-bis(pyridin-2-yl) methyl]methanamine (1), (anthracen-9-yl)N, N-bis(pyridin-2-yl) methyl] methanamine (2), (pyreny-1-yl)-N, N-bis(pyridin- 2-yl) methyl] methanamine (3-5), and L' is catecholate (1-3), 4-tert-butyl catecholate (4), and 4-(2-aminoethyl)benzene- 1,2-diolate (5)-were synthesized and their photocytotoxic proper-ties examined. The five electron-paramagnetic complexes displayed a FeIII/ Fe-II redox couple near similar to 0.4 V versus a saturated calomel electrode (SCE) in DMF/0.1m tetrabutylammonium perchlorate (TBAP). They showed unpre-cedented photocytotoxicity in red light (600-720 nm) to give IC50-15 mm in various cell lines by means of apoptosis to generate reactive oxygen species. They were ingested in the nucleus of HeLa and HaCaT cells in 4 h, thereby interacting favorably with calf thymus (ct)-DNA and photocleaving pUC19 DNA in red light of 785 nm to form hydroxyl radicals.

Self-Assembled, Aligned ZnO Nanorod Buffer Layers for High-Current-Density, Inverted Organic Photovoltaics

Two different soft-chemical, self-assembly-based solution approaches are employed to grow zinc oxide (ZnO) nanorods with controlled texture. The methods used involve seeding and growth on a substrate. Nanorods with various aspect ratios (1-5) and diameters (15-65 nm) are grown. Obtaining highly oriented rods is determined by the way the substrate is mounted within the chemical bath. Furthermore, a preheat and centrifugation step is essential for the optimization of the growth solution. In the best samples, we obtain ZnO nanorods that are almost entirely oriented in the (002) direction; this is desirable since electron mobility of ZnO is highest along this crystallographic axis. When used as the buffer layer of inverted organic photovoltaics (I-OPVs), these one-dimensional (1D) nanostructures offer: (a) direct paths for charge transport and (b) high interfacial area for electron collection. The morphological, structural, and optical properties of ZnO nanorods are studied using scanning electron microscopy, X-ray diffraction, and ultraviolet-visible light (UV-vis) absorption spectroscopy. Furthermore, the surface chemical features of ZnO films are studied using X-ray photoelectron spectroscopy and contact angle measurements. Using as-grown ZnO, inverted OPVs are fabricated and characterized. For improving device performance, the ZnO nanorods are subjected to UV-ozone irradiation. UV-ozone treated ZnO nanorods show: (i) improvement in optical transmission, (ii) increased wetting of active organic components, and (iii) increased concentration of Zn-O surface bonds. These observations correlate well with improved device performance. The devices fabricated using these optimized buffer layers have an efficiency of similar to 3.2% and a fill factor of 0.50; this is comparable to the best I-OPVs reported that use a P3HT-PCBM active layer.

Generalized Model Predictive Static Programming and Angle-Constrained Guidance of Air-to-Ground Missiles

A new generalized model predictive static programming technique is presented for rapidly solving a class of finite-horizon nonlinear optimal control problems with hard terminal constraints. Two key features for its high computational efficiency include one-time backward integration of a small-dimensional weighting matrix dynamics, followed bya static optimization formulation that requires only a static Lagrange multiplier to update the control history. It turns out that under Euler integration and rectangular approximation of finite integrals it is equivalent to the existing model predictive static programming technique. In addition to the benchmark double integrator problem, usefulness of the proposed technique is demonstrated by solving a three-dimensional angle-constrained guidance problem for an air-to-ground missile, which demands that the missile must meet constraints on both azimuth and elevation angles at the impact point in addition to achieving near-zero miss distance, while minimizing the lateral acceleration demand throughout its flight path. Simulation studies include maneuvering ground targets along with a first-order autopilot lag. Comparison studies with classical augmented proportional navigation guidance and modern general explicit guidance lead to the conclusion that the proposed guidance is superior to both and has a larger capture region as well.

Remarkable visible light-triggered cytotoxicity of mitochondria targeting mixed-ligand cobalt(III) complexes of curcumin and phenanthroline bases binding to human serum albumin

Six new mixed-ligand cobalt(III) complexes of formulation Co(N-N)(2)(O-O)](ClO4)(2) (1-6), where N-N is a N,N-donor phenanthroline base, namely, 1,10-phenanthroline (phen in 1, 2), dipyrido3,2-d:2',3'-f] quinoxaline (dpq in 3, 4), and dipyrido3,2-a:2',3'-c]phenazine (dppz in 5, 6), O-O is acetylacetonate (acac in 1, 3, 5) or curcumin (bis(4-hydroxy-3-methoxyphenyl)-1,6-diene-3,5-dione, cur in 2, 4, 6), have been synthesized and characterized. The X-ray crystal structures of complex 1 (as PF6- salt, 1a) and 3 show distorted octahedral geometries formed by the CoN4O2 core. The complexes 1, 3 and 5 having the simple acac ligand are prepared as control species to understand the role of curcumin. The optimized geometries and the frontier orbitals of the curcumin complexes 2, 4, and 6 are obtained from the DFT calculations. The complexes 2, 4, and 6 having the photoactive curcumin moiety display an absorption band in the visible region near 420 nm and show remarkable photocytotoxicity in HeLa cancer cells with respective IC50 values of 7.4 mu M, 5.1 mu M and 1.6 mu M while being much less toxic in dark. MTT assay using complex 6 shows that it is not significantly photocytotoxic to MCF-10A normal cells. The control complexes having the acac ligand are non-toxic both in the presence and absence of light. The cell death is apoptotic in nature and triggered by the photogeneration of reactive oxygen species. Fluorescence imaging experiments on HeLa cells reveals that complex 6 accumulated primarily inside the mitochondria. Human serum albumin (HSA) binding experiments show that the complexes bind HSA with good affinity, but 6 binds with the highest affinity, with a K-b value of 9.8 x 10(5) M-1. Thus, complex 6 with its negligible toxicity in the dark and in normal cells but remarkable toxicity in visible light holds significant photochemotherapeutic potential.

Three Dimensional Impact Angle Constrained Guidance Law using Sliding Mode Control

In this paper, three dimensional impact angle control guidance laws are proposed for stationary targets. Unlike the usual approach of decoupling the engagement dynamics into two mutually orthogonal 2-dimensional planes, the guidance laws are derived using the coupled dynamics. These guidance laws are designed using principles of conventional as well as nonsingular terminal sliding mode control theory. The guidance law based on nonsingular terminal sliding mode guarantees finite time convergence of interceptor to the desired impact angle. In order to derive the guidance laws, multi-dimension switching surfaces are used. The stability of the system, with selected switching surfaces, is demonstrated using Lyapunov stability theory. Numerical simulation results are presented to validate the proposed guidance law.

Significant photocytotoxic effect of an iron(III) complex of a Schiff base ligand derived from vitamin B-6 and thiosemicarbazide in visible light

Iron(III)-Schiff base complexes, namely, Fe(tsc-py)(2)](NO3) (1), Fe(tsc-acpy)(2)](NO3) (2) and Fe(tsc-VB6)(2)](NO3) (3), where tsc-py, tsc-acpy and tsc-VB6 are the respective Schiff bases derived from thiosemicarbazide (tsc) and pyridine-2-aldehyde (tsc-py), 2-acetyl pyridine (tsc-acpy) and vitamin B-6 (pyridoxal, tsc-VB6), have been prepared, structurally characterized and their photocytotoxicity studied in cancer HeLa cells. The single crystal X-ray structures of the complexes 1 and 2 show a distorted octahedral geometry formed by the FeN4S2 core. The low-spin and 1 : 1 electrolytic complexes display a broad absorption band in the visible region. Complexes 1 and 2, without any VB6 moiety are not cytotoxic under light or dark conditions. Complex 3 is significantly photocytotoxic under visible light of 400-700 nm giving an IC50 value of 22.5 mu M in HeLa cells with no dark toxicity (IC50 > 100 mu M). The photo-induced cell death is attributable to apoptotic pathways involving photo-assisted generation of intracellular ROS. The observed photocytotoxicity of complex 3 could be the result of its better photosensitizing property combined with its enhanced uptake into cancer cells via a VB6 transporting membrane carrier (VTC) mediated diffusion pathway due to the presence of the VB6 moiety compared to the two non-vitamin B-6 analogues, complexes 1 and 2.

Iron(III) Complexes of a Pyridoxal Schiff Base for Enhanced Cellular Uptake with Selectivity and Remarkable Photocytotoxicity

Iron(III) complexes of pyridoxal (vitamin B6, VB6) or salicylaldehyde Schiff bases and modified dipicolylamines, namely, Fe(B)(L)](NO3) (15), where B is phenyl-N,N-bis((pyridin-2-yl)methyl)methanamine (phbpa in 1), (anthracen-9-yl)-N,N-bis((pyridin-2-yl)methyl)methanamine (anbpa in 2, 4) and (pyren-1-yl)-N,N-bis((pyridin-2-yl)methyl)methanamine (pybpa in 3, 5) (H2L1 is 3-hydroxy-5-(hydroxymethyl)-4-(((2-hydroxyphenyl)imino)methyl)-2-methylp yridine (13) and H2L2 is 2-(2-hydroxyphenyl-imino)methyl]phenol), were prepared and their uptake in cancer cells and photocytotoxicity were studied. Complexes 4 and 5, having a non-pyridoxal Schiff base, were prepared to probe the role of the pyridoxal group in tumor targeting and cellular uptake. The PF6 salt (1a) of complex 1 is structurally characterized. The complexes have a distorted six-coordinate FeN4O2 core where the metal is in the +3 oxidation state with five unpaired electrons. The complexes display a ligand to metal charge transfer band near 520 and 420 nm from phenolate to the iron(III) center. The photophysical properties of the complexes are explained from the time dependent density functional theory calculations. The redox active complexes show a quasi-reversible Fe(III)/Fe(II) response near -0.3 V vs saturated calomel electrode. Complexes 2 and 3 exhibit remarkable photocytotoxicity in various cancer cells with IC50 values ranging from 0.4 to 5 mu M with 10-fold lower dark toxicity. The cell death proceeded by the apoptotic pathway due to generation of reactive oxygen species upon light exposure. The nonvitamin complexes 4 and 5 display 3-fold lower photocytotoxicity compared to their VB6 analogues, possibly due to preferential and faster uptake of the vitamin complexes in the cancer cells. Complexes 2 and 3 show significant uptake in the endoplasmic reticulum, while complexes 4 and 5 are distributed throughout the cells without any specific localization pattern.

Nonlinear Differential Games-Based Impact-Angle-Constrained Guidance Law

The problem of intercepting a maneuvering target at a prespecified impact angle is posed in nonlinear zero-sum differential games framework. A feedback form solution is proposed by extending state-dependent Riccati equation method to nonlinear zero-sum differential games. An analytic solution is obtained for the state-dependent Riccati equation corresponding to the impact-angle-constrained guidance problem. The impact-angle-constrained guidance law is derived using the states line-of-sight rate and projected terminal impact angle error. Local asymptotic stability conditions for the closed-loop system corresponding to these states are studied. Time-to-go estimation is not explicitly required to derive and implement the proposed guidance law. Performance of the proposed guidance law is validated using two-dimensional simulation of the relative nonlinear kinematics as well as a thrust-driven realistic interceptor model.

Simulations of impinging droplets with surfactant-dependent dynamic contact angle

An arbitrary Lagrangian-Eulerian (ALE) finite element scheme for computations of soluble surfactant droplet impingement on a horizontal surface is presented. The numerical scheme solves the time-dependent Navier-Stokes equations for the fluid flow, scalar convection-diffusion equation for the surfactant transport in the bulk phase, and simultaneously, surface evolution equations for the surfactants on the free surface and on the liquid-solid interface. The effects of surfactants on the flow dynamics are included into the model through the surface tension and surfactant-dependent dynamic contact angle. In particular, the dynamic contact angle (theta(d)) of the droplet is defined as a function of the surfactant concentration at the contact line and the equilibrium contact angle (theta(0)(e)) of the clean surface using the nonlinear equation of state for surface tension. Further, the surface forces are included into the model as surface divergence of the surface stress tensor that allows to incorporate the Marangoni effects without calculating the surface gradient of the surfactant concentration on the free surface. In addition to a mesh convergence study and validation of the numerical results with experiments, the effects of adsorption and desorption surfactant coefficients on the flow dynamics in wetting, partially wetting and non-wetting droplets are studied in detail. It is observed that the effects of surfactants are more in wetting droplets than in the non-wetting droplets. Further, the presence of surfactants at the contact line reduces the equilibrium contact angle further when theta(0)(e) is less than 90 degrees, and increases it further when theta(0)(e) is greater than 90 degrees. Nevertheless, the presence of surfactants has no effect on the contact angle when theta(0)(e) = 90 degrees. The numerical study clearly demonstrates that the surfactant-dependent contact angle has to be considered, in addition to the Marangoni effect, in order to study the flow dynamics and the equilibrium states of surfactant droplet impingement accurately. The proposed numerical scheme guarantees the conservation of fluid mass and of the surfactant mass accurately. (C) 2015 Elsevier Inc. All rights reserved.

Visible light-induced cytotoxicity of a dinuclear iron(III) complex of curcumin with low-micromolar IC50 value in cancer cells

Photoactive metal complexes have emerged as potential candidates in the photodynamic therapy (PDT) of cancer. We present here the synthesis, characterization and visible light-triggered anticancer activity of two novel mixed-ligand oxo-bridged iron(III) complexes, viz., {Fe(L)(acac)}(2)(mu-O)](ClO4)(2) (1) and {Fe (L)(cur)}(2)(mu-O)](ClO4)(2) (2) where L is bis-(2-pyridylmethyl)-benzylamine, acac is acetylacetonate and cur is the monoanion of curcumin (bis(4-hydroxy-3-methoxyphenyl)-1,6-diene-3,5-dione). The crystal structure of complex 1 (as PF6 salt, 1a) shows distorted octahedral geometry of each iron(III) centre formed by the FeN3O3 core. The 1: 2 electrolytic complexes are stable in solution and retain their oxo-bridged identity in aqueous medium. Complex 2 has a strong absorption band in the visible region and shows promising photocytotoxicity in HeLa and MCF-7 cancer cells in visible light giving respective IC50 values of 3.1 +/- 0.4 lM and 4.9 +/- 0.5 lM while remains non-toxic in the dark (IC50 > 50 lM). The control complex 1 is inactive both in the light and dark. Complex 2 accumulates in cytoplasm of HeLa and MCF-7 cells as evidenced from fluorescence microscopy and triggers apoptotic cell death via light-assisted generation of reactive oxygen species (ROS). Taken together, complex 2 with its promising photocytotoxicity but negligible dark toxicity in cancer cells has significant photochemotherapeutic potential for applications in PDT. (C) 2015 Elsevier B.V. All rights reserved.

Binary group III-nitride based heterostructures: band offsets and transport properties

In the last few years, there has been remarkable progress in the development of group III-nitride based materials because of their potential application in fabricating various optoelectronic devices such as light emitting diodes, laser diodes, tandem solar cells and field effect transistors. In order to realize these devices, growth of device quality heterostructures are required. One of the most interesting properties of a semiconductor heterostructure interface is its Schottky barrier height, which is a measure of the mismatch of the energy levels for the majority carriers across the heterojunction interface. Recently, the growth of non-polar III-nitrides has been an important subject due to its potential improvement on the efficiency of III-nitride-based opto-electronic devices. It is well known that the c-axis oriented optoelectronic devices are strongly affected by the intrinsic spontaneous and piezoelectric polarization fields, which results in the low electron-hole recombination efficiency. One of the useful approaches for eliminating the piezoelectric polarization effects is to fabricate nitride-based devices along non-polar and semi-polar directions. Heterostructures grown on these orientations are receiving a lot of focus due to enhanced behaviour. In the present review article discussion has been carried out on the growth of III-nitride binary alloys and properties of GaN/Si, InN/Si, polar InN/GaN, and nonpolar InN/GaN heterostructures followed by studies on band offsets of III-nitride semiconductor heterostructures using the x-ray photoelectron spectroscopy technique. Current transport mechanisms of these heterostructures are also discussed.

Gauge invariance in the theoretical description of time-resolved angle-resolved pump/probe photoemission spectroscopy

Nonequilibrium calculations in the presence of an electric field are usually performed in a gauge, and need to be transformed to reveal the gauge-invariant observables. In this work, we discuss the issue of gauge invariance in the context of time-resolved angle-resolved pump/probe photoemission. If the probe is applied while the pump is still on, one must ensure that the calculations of the observed photocurrent are gauge invariant. We also discuss the requirement of the photoemission signal to be positive and the relationship of this constraint to gauge invariance. We end by discussing some technical details related to the perturbative derivation of the photoemission spectra, which involve processes where the pump pulse photoemits electrons due to nonequilibrium effects.

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.

Composite Guidance for Impact Angle Control Against Higher Speed Targets

In the literature, the impact angle control problem has been addressed mostly against lower speed or stationary targets. However, in the current defense scenario, targets of much higher speeds than interceptors are a reality. Moreover, approaching a higher speed target from a specified angle is important for effective seeker acquisition and enhanced warhead effectiveness. This paper proposes a composite proportional navigation guidance law using a combination of the standard proportional navigation and the recently proposed retroproportional navigation guidance laws for intercepting higher speed nonmaneuvering targets at specified impact angles in three-dimensional engagements. An analysis of the set of achievable impact angles by the composite proportional navigation guidance law is presented. It is shown that there exists an impulse bias that, when added to the composite proportional navigation guidance command, expands this set further by reversing the direction of the line-of-sight angular rotation vector. A bound on the magnitude of the bias is also derived. Finally, an implementation of this impulse bias, in the form of a series of pulses, is proposed and analyzed. Simulation results are also presented to support the analysis.