Photochemistry of Far Red Responsive Tetrahydroquinoxaline-Based Squaraine Dyes

The photochemical and redox properties of two newly synthesized tetrahydroquinoxaline-based squaraine dyes (SQ) are investigated Using femto- and nanosecond laser flash photolysis, pulse radiolysis, and cyclic voltammetry. In acetonitrile and dichloromethane, these squaraines exist its monomers in the zwitterionic form (lambda(max) approximate to 715 nm, epsilon(max) approximate to 1.66 x 10(5) M-1 cm(-1) in acetonitrile). Their excited sin-let states ((1)SQ*) exhibit a broad absorption hand at 480 nm, with singlet lifetimes of 44 and 123 ps for the two dyes. Both squaraines exhibit poor intersystem crossing efficiency (Phi(ISC) < 0.001). Their excited triplet states ((3)SQ*), however, Ire efficiently generated by triplet-triplet energy transfer Using triplet excited 9,10-dibromoanthracene. The excited triplet states of the squaraines dyes exhibit it broad absorption hand at ca. 560 nm (epsilon(triplet) approximate to 4.2 x 10(4) M-1 cm(-1)) and undergo deactivation via triplet-triplet annihilation and ground-state quenching processes. The oxidized forms of the investigated squaraines (SQ(center dot+)) exhibit absorption maxima at 510 and 610 nm.

Photocytotoxicity and near-IR light DNA cleavage activity of oxovanadium(IV) Schiff base complexes having phenanthroline bases

Oxovanadium(IV) complexes VO(L)(B)] (1-3), where H2L is a Schiff base ligand 2-(2-hydroxybenzylideneamino) phenol and B is 1,10-phenanthroline (phen for 1), dipyrido3,2-d:2',3'-f]quinoxaline (dpq for 2) or dipyrido3,2-a:2',3'-c]phenazine (dppz for 3), have been prepared, characterized and their DNA binding property and photo-induced DNA cleavage activity studied. Complex 3 which is structurally characterized by X-ray crystallography shows the presence of an oxovanadium(IV) moiety in a six coordinate VO3N3 coordination geometry. The complexes show a d-d band within 800-850 nm in DMF. The complexes display an oxidative response near 0.7 V versus SCE for V(V)-V(IV) and a reductive response within -1.1 to -1.3 V due to V(IV)-V(III) couple in DMF-0.1 M TBAP. The complexes are avid binders to calf thymus DNA giving binding constant values of 4.2 x 10(4) to 1.2 x 10(5) M (1). The complexes do not show any ``chemical nuclease'' activity in dark. The dpq and dppz complexes are photocleavers of plasmid DNA in UV-A light of 365 nm via O-1(2) pathway and in near-IR light (752.5 to 799.3 nm IR optics) by HO* pathway. Complex 3 exhibits significant photocytotoxicity in visible light in HeLa cells giving IC50 value of 13 mu M, while it is less toxic in dark (IC50 = 97 mu M). (C) 2010 Elsevier B.V. All rights reserved.

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).

Phase relations and Gibbs energies of spinel phases and solid solutions in the system Mg-Rh-O

Pure stoichiometric MgRh(2)O(4) could not be prepared by solid state reaction from an equimolar mixture of MgO and Rh(2)O(3) in air. The spinel phase formed always contained excess of Mg and traces of Rh or Rh(2)O(3). The spinel phase can be considered as a solid solution of Mg(2)RhO(4) in MgRh(2)O(4). The compositions of the spinel solid solution in equilibrium with different phases in the ternary system Mg-Rh-O were determined by electron probe microanalysis. The oxygen potential established by the equilibrium between Rh + MgO + Mg(1+x)Rh(2-x)O(4) was measured as a function of temperature using a solid-state cell incorporating yttria-stabilized zirconia as an electrolyte and pure oxygen at 0.1 MPa as the reference electrode. To avoid polarization of the working electrode during the measurements, an improved design of the cell with a buffer electrode was used. The standard Gibbs energies of formation of MgRh(2)O(4) and Mg(2)RhO(4) were deduced from the measured electromotive force (e.m.f.) by invoking a model for the spinel solid solution. The parameters of the model were optimized using the measured composition of the spinel solid solution in different phase fields and imposed oxygen partial pressures. The results can be summarized by the equations: MgO + beta -Rh(2)O(3) -> MgRh(2)O(4); Delta G degrees (+ 1010)/J mol(-1) = -32239 + 7.534T; 2MgO + RhO(2) -> Mg(2)RhO(4); Delta G degrees(+/- 1270)/J mol(-1) = 36427 -4.163T; Delta G(M)/J mol(-1) = 2RT(xInx + (1-x)In(1-x)) + 4650x(1-x), where Delta G degrees is the standard Gibbs free energy change for the reaction and G(M) is the free energy of mixing of the spinel solid solution Mg(1+x)Rh(2-x)O(4). (C) 2011 Elsevier B. V. All rights reserved.

Synthesis, antimicrobial, DNA-binding and photonuclease studies of Cobalt(III) and Nickel(II) Schiff base complexes

New metal complexes of the type M(nih)(L)](PF6)(n)center dot xAH(2)O and M(nih)(2)](PF6)center dot xH(2)O (where M = Co(III) or Ni(II), L = 1,10-phenanthroline (phen)/or 2,2' bipyridine (bpy), nih = 2-hydroxy-1-naphthaldehyde isonicotinoyl hydrazone, n = 2 or 1 and x = 3 or 2) have been synthesized and characterized by elemental analysis, magnetic, IR and H-1 NMR spectral data. The electronic and magnetic moment 2.97-3.07 B.M. data infers octahedral geometry for all the complexes. The IR data reveals that Schiff base (nih) form coordination bond with the metal ion through azomethine-nitrogen, phenolic-oxygen and carbonyl-oxygen in a tridentate fashion. In addition, DNA-binding properties of these six metal complexes were investigated using absorption spectroscopy, viscosity measurements and thermal denaturation methods. The results indicated that the nickel(II) complex strongly bind with calf-thymus DNA with intrinsic DNA binding constant K-b value of 4.9 x 10(4) M-1 for (3), 4.2 x 10(4) M-1 for (4), presumably via an intercalation mechanism compared to cobalt(III) complex with K-b value of 4.6 x 10(4) M-1 (1) and 4.1 x 10(4) M-1 (2). The DNA Photoclevage experiment shows that, the complexes act as effective DNA cleavage agent. (C) 2012 Elsevier B.V. All rights reserved.

Tailoring the band gap and transport properties of Cu3BiS3 nanopowders for photodetector applications

We report a facile route to synthesize high quality earth abundant absorber Cu3BiS3, tailoring the band gap with the morphology manipulation and thereby analyzed the secondary phases and their role in the transport property. The sample at 48 hours reaction profile showed good semiconducting behavior, whereas other samples showed mostly a metallic behavior. Band gap was varied from 1.86 eV to 1.42 eV upon controling the reaction profile from 8 hours to 48 hours. The activation energy was calculated to be 0.102 eV. The temperature coefficient of resistance (TCR) was found to be 0.03432 K-1 at 185 K. The IR photodectection properties in terms of photoresponse have been demonstrated. The high internal gain (G = 3.7 x 10(4)), responsivity (R = 3.2 x 10(4) A W-1) for 50 mW cm(-2) at 5 V make Cu3BiS3, an alternative potential absorber in meliorating the technological applications as near IR photodetectors.

Metal based photosensitizers of tetradentate Schiff base: Promising role in anti-tumor activity through singlet oxygen generation mechanism

In the present investigation, a Schiff base N'(1),N'(3)-bis(Z)-(2-hydroxynapthyl)methylidene]benzene-1,3-dicarbod ihydrazide (L-1) and its Co(II), Ni(II) and Cu(II) complexes have been synthesized and characterized as novel photosensitizing agents for photodynamic therapy (PDT). The interaction of these complexes with calf thymus DNA (CT DNA) has been explored using absorption, thermal denaturation and viscometric studies. The experimental results revealed that Co(II) and Ni(II) complexes on binding to CT DNA imply a covalent mode, most possibly involving guanine N7 nitrogen of DNA, with an intrinsic binding constant K-b of 4.5 x 10(4) M-1 and 4.2 x 10(4) M-1, respectively. However, interestingly, the Cu(II) complex is involved in the surface binding to minor groove via phosphate backbone of DNA double helix with an intrinsic binding constant K-b of 5.7 x 10(4) M-1. The Co(II), Ni(II) and Cu(II) complexes are active in cleaving supercoiled (SC) pUC19 DNA on photoexposure to UV-visible light of 365 nm, through O-1(2) generation with quantum yields of 0.28, 0.25 and 0.30, respectively. Further, these complexes are cytotoxic in A549 lung cancer cells, showing an enhancement of cytotoxicity upon light irradiation. (C) 2013 Elsevier B.V. All rights reserved.

Phase Inversion of Agitated Liquid-Liquid Dispersions in the Presence of Micrometer-Sized Particles

We have investigated the impact of partially wetting particles of tens of micrometers on inversion instability of agitated liquid liquid dispersions. Particles of this size can be easily separated from the exit streams to avoid downstream processing-related issues. The results show that the presence of hydrophilic particles in small quantities (volume fraction range of 2 X 10(-4) to 1.25 x 10(-2)) significantly decreases the dispersed phase fraction at which water-in-oil (w/o) dispersions invert but leaves the inversion of oil-in-water (o/w) dispersions nearly unaffected. The addition of the same particles after they are hydrophobized decreases the dispersed phase fraction at which o/w dispersions invert but leaves the inversion of w/o dispersions unaffected. These findings suggest an increased rate of coalescence of drops when particles wet drops preferentially and a marginal decrease when they wet the continuous phase preferentially. High-speed conductivity measurements on w/o dispersion show transient conduction of a few hundred milliseconds duration through voltage pulses. Close to the inversion point, voltage pulses appear at high frequency for even 7 cm separation between the electrodes. The presence of hydrophilic particles produces a nearly identical signal at a significantly lower dispersed phase fraction itself, close to the new lowered inversion point in the presence of particles. We propose formation of elongated domains of the conducting dispersed phase through a rapid coalescence-deformation-breakup process to explain the new observations. The voltage signal appears as a forerunner of inversion instability.

Population dynamics of the skipjack tuna (Katsuwonus pelamis) of the Eastern Pacific Ocean

ENGLISH: Catches of skipjack tuna supporting major fisheries in parts of the western, central and eastern Pacific Ocean have increased in recent years; thus, it is important to examine the dynamics of the fishery to determine man's effect on the abundance of the stocks. A general linear hypothesis model was developed to standardize fishing effort to a single vessel size and gear type. Standardized effort was then used to compute an index of abundance which accounts for seasonal variability in the fishing area. The indices of abundance were highly variable from year to year in both the northern and southern areas of the fishery but indicated a generally higher abundance in the south. Data from 438 fish tagged and recovered in the eastern Pacific Ocean were used to compute growth curves. A least-squares technique was used to estimate the parameters of the von Bertalanffy growth function. Two estimates of the parameters were made by analyzing the same data in different ways. For the first set of estimates, K= 0.819 on an annual instantaneous basis and L= 729 mm; for the second, K = 0.431 and L=881. These compared well with estimates derived using the Chapman-Richards growth function, which includes the von Bertalanffy function as a special case. It was concluded that the latter function provided an adequate empirical fit to the skipjack data since the more complicated function did not significantly improve the fit. Tagging data from three cruises involving 8852 releases and 1777 returns were used to compute mortality rates during the time the fish were in the fishery. Two models were used in the analyses. The best estimates of the catchability coefficient (q) in the north and south were 8.4 X 10- 4 and 5.0 X 10- 5 respectively. The other loss rate (X), which included losses due to emigration, natural mortality and mortality due to carrying a tag, was 0.14 on an annual instantaneous basis for both areas. To detect the possible effect of fishing on abundance and total yield, the relation between abundance and effort and between total catch and effort was examined. It was found that at levels of intensity observed in the fishery, fishing does not appear to have had any measurable effect on the stocks. It was concluded therefore that the total catch could probably be increased by substantially increasing total effort beyond the present level, and that the fluctuations in abundance are fishery-independent. The estimates of growth, mortality and fishing effort were used to compute yield-per-recruitment isopleths for skipjack in both the northern and southern areas. For a size at first entry of about 425 mm, the yield per recruitment was calculated at 3 pounds in the north and 1.5 pounds in the south. In both areas it would be possible to increase the yield per recruitment by increasing fishing effort. It was not possible to assess potential production of the skipjack stocks fished in the eastern Pacific, except to note that the fishery had not affected their abundance and that they were certainly under-exploited. It was concluded that the northern and southern stocks could support increased harvests, especially the latter. SPANISH: Las capturas de atún barrilete que sostienen las pesquerías principales de la parte occidental, central y oriental del Océano Pacífico han aumentado en los últimos años; así que es importante examinar la dinámica de la pesquería para determinar el efecto que pueda tener sobre la abundancia de los stocks. Se desarrolló un modelo hipotético, lineal para standardizar el esfuerzo de pesca a un solo tamaño de barco y tipo de arte. Luego se usó el esfuerzo standardizado para computar un índice de la abundancia que pueda dar razón de la variabilidad estacional en el área de pesca. Los índices de la abundancia variaron mucho de un año a otro tanto en el área septentrional como en el área meridional de la pesquería, pero indicaron una abundancia generalmente superior en el sur. Se emplearon los datos de 438 peces marcados y recuperados en el Océano Pacífico oriental para computar las curvas de crecimiento. Una técnica de mínimos cuadrados fue usada para estimar los parámetros de la función de crecimiento de van Bertalanffy. Se hicieron dos estimativos de los parámetros mediante el análisis de los mismos datos, de diferente manera. Para el primer juego de estimativos, K=0.819 sobre una base anual instantánea y L∞=729 mm; para el segundo, K=0.431 y L∞=881. Estos se correlacionaron bien con los estimativos obtenidos usando la función de crecimiento de Chapman-Richards, que incluye la de von Bertalanffy como un caso especial. Se decidió que la última función proveía un ajuste empírico, adecuado a los datos del barrilete, ya que la función más complicada no mejoró significativamente el ajuste. Los datos de marcación de tres cruceros incluyendo 8852 liberaciones y 1777 retornos, fueron usados para computar las tasas de mortalidad durante el tiempo en que los peces estuvieron en la pesquería. Se usaron dos modelos en los análisis. Los mejores estimativos del coeficiente de capturabilidad (q) en el norte y en el sur fueron 8.4 X 10-4 y 5.0 X 10-5 , respectivamente. La otra tasa de pérdida (X), la cual incluyó pérdidas debidas a la emigración, mortalidad natural y mortalidad debida a llevar una marca, fue 0.14 sobre una base anual instantánea para las dos áreas. Con el fin de descubrir el efecto que posiblemente pueda tener la pesca sobre la abundancia y el rendimiento total, se examinó la relación entre la abundancia y el esfuerzo y entre la captura total y el esfuerzo. Se encontró que a los niveles de la intensidad observada en la pesquería, la pesca no parece haber tenido ningún efecto perceptible en los stocks. Por lo tanto se decidió que mediante un aumento substancial del esfuerzo total, más allá del nivel actual, la captura total probablemente podría aumentarse, y que las fluctuaciones de la abundancia son independientes de la pesquería. Los estimativos del crecimiento, mortalidad y esfuerzo de pesca fueron usados para computar las isopletas del rendimiento por recluta del barrilete, tanto en las áreas del norte como del sur. Para una talla de primera entrada de unos 425 mm, el rendimiento por recluta fue calculado en 3 libras en el norte y 1.5 libras en el sur. En ambas áreas sería posible aumentar el rendimiento por recluta mediante un aumento del esfuerzo de pesca. No fue posible determinar la producción potencial de los stocks del barrilete pescado en el Pacífico oriental, excepto para observar que la pesquería no ha afectado su abundancia y que ciertamente se encuentran subexplotados. Se concluyó que los stocks norte y sur pueden soportar un aumento en el rendimiento, especialmente este último. (PDF contains 274 pages.)

Characterisation of impact response of metallic foam/ceramic laminates

The impact response of laminated composites consisting of alternate layers of AI ahoy foam and Al2O3 was studied experimentally in low and intermediate velocity regimes. Low velocity impacts (1.2-2.8 m s(-1)) were conducted using an instrumented falling weight apparatus and were compared with static indentation tests (0.2 x 10(-4) m s(-1)). Intermediate velocity impacts were carried out by means of both Hopkinson bar (60 m s(-1)) and gas gun (200 m s(-1)) tests, Post-impact damage was assessed using X-ray radiography and microscopy, It was found that there is good correlation between low velocity impact and quasi-static responses. In both cases, penetration of the layered targets resulted in the formation of a distinctive plug. Increasing impact velocity (intermediate velocity range) snitched the penetration mode from plugging to fragmentation, giving rise to an increase in the absorbed energy. In this range, impacts led to localisation of damage in the region under the projectile, Furthermore, a comparison has been made between the penetration response of foam laminates and dense metal laminates of equivalent areal density. Preliminary results suggest that the dense metal laminates are superseded by the foam laminates on an energy absorption basis.

ABO_3, A_2BO_4型复合氧化物的固体化学性质与催化性能

本论文系统地研究了La_(1-x)Sr_xNiO_3, La_(1-1.333x)Th_xNiO_3，La_(2-x)Sr_xNiO_4, La_(2-x)Sr_xCuO_4 (0 ≤ x ≤ 1)四系列催化剂的固体化学性质和用于氨氧化制硝酸的催化活性之间的关系。为了更深入地探讨多元复合氧化物的固体化学性质与催化行为之间的关系，本论文还开展了对稀土A_2BO_4型复合氧化物：La_(2-x)Sr_xNiO_4和La_(2-x)Sr_xCuO_4 (0 ≤ x ≤ 1)两系列催化剂的固化性质与催化性能的研究。ABO_3, A_2BO_4两类复合氧化物用于氨氧化，都可能遵循氧化－还原(Redox)机理，高价B离子为主要活性离子，高温区脱出的氧可能为主要活性氧种。比较ABO_3和A_2BO_4两类复合氧化物，ABO_3能稳定较高含量的高价B离子，但结构不如A_2BO_4稳定。A_2BO_4结构稳定，能在较宽掺杂范围内保持结构不变，但高价B离子含量不如ABO_3中高。

Synthesis, photophysical and electrophosphorescent properties of mononuclear Pt(II) complexes with arylamine functionalized cyclometalating ligands

Four cyclometalated Pt(II) complexes, i.e., [(L-2)PtCl] (1b), [(L-3)PtCl] (1c), [(L-2)PtC CC6H5] (2b) and [(L-3)PtC CC6H5] (2c) (HL2 = 4-[p-(N-butyl-N-phenyl)anilino]-6-phenyl-2,2'-bipyridine and HL3 = 4-[p(-N,N'-dibutyl-N'-phenyl)phenylene-diamino]-phenyl-6-phenyl-2,2'-bipyridine), have been synthesized and verified by H-1 NMR, C-13 NMR and X-ray crystallography. Unlike previously reported complexes [(L-1)PtCl] (1a) and [(L-1)PtC CC6H5] (2a) (HL1 = 4,6-diphenyl-2,2'-bipyridine), intense and continuous absorption bands in the region of 300-500 nm with strong metal-to-ligand charge transfer ((MLCT)-M-1) (d pi(Pt) -> pi*(L)) transitions (epsilon similar to 2 x 10(4) dm(3) mol (1) cm (1)) at 449-467 nm were observed in the UV-Vis absorption spectra of complexes 1b, 1c, 2b and 2c.

Oxidation of ascorbic acid by rutin at a glassy carbon electrode modified with lipid films

A stable film was prepared by casting dipalmitoylphosphatidylcholine (DPPC) and rutin onto the surface of a glassy carbon (GC) electrode. The electrochemistry behavior of rutin in the DPPC film was investigated. The modified electrode coated with rutin shows a quasi-reversible reduction-oxidation peak on the cyclic voltammogram in phosphate buffer (pH 7.4). This model of biological membrane was not only used to provide biological environment but also to investigate the oxidation of ascorbic acid by rutin. The DPPC-rutin modified electrode behaves as electrocatalytic oxidation to ascorbic acid. The oxidation peak current of ascorbic acid increases drastically and the peak potential of 4 x 10(-4) mol L-1 ascorbic acid shifts negatively about 100 mV compared with that obtained at a bare glassy carbon electrode. The catalytic current increased linearly with the ascorbic acid concentration in the range of 2 x 10(-4) mol L-1 and 1.4 x 10(-3) mol L-1 at a scan rate of 50 mV s(-1).

In-situ circular dichroism spectroelectrochemical study on the redox process of norepinephrine

The redox process of norepinephrine in pH = 7.0 phosphate buffer solution at glassy carbon electrode was studied by circular dichroism spectroelectrochemistry with a long optical path thin layer cell. The spectroelectrochemical data were analyzed with the double logarithm method. According to the double logarithsmic plot results, the mechanism of electrochemical oxidation of norepinephrine is an irreversible process with a subsequent chemical reaction (EC) to form a norepinephrinechrome. Both of norepinephrinequinone and norepinephrinechrome are followed E mechanisms. Some kinetic parameters about the electrochemical process, i.e. the electron transfer coefficient and number of electron transfered, alpha n = 0.38, the formal potential, E-1(0)' = 0.20 V, the standard heterogenous electron transfer rate constant, k(1)(0) = 1.2 x 10(-4) cm s(-1) for the oxidation of norepinephrine, alpha n = 0.37, E-2(0)' = 0.25 V and k(2)(0) = 4.4 x 10(-5) cm . s(-1) for the reduction of norepinephrinequnone and alpha n = 0.33, E-3(0)' = -0.25V and k(3)(0) = 1.1 x 10(-4) cm . s(-1) for the reduction of norpinephrinechrome, were also estimated.

ELECTROCHEMICAL AND INSITU SPECTROELECTROCHEMICAL STUDY OF (TETRAPHENYLPORPHINATO)MANGANESE (III) PERCHLORATE IN THE PRESENCE OF CHLORIDE ANIONS .1. REDUCTION PROCESSES

The mechanism of electrochemical redox reactions of (tetra-phenylporphinato) managanese(III) perchlorate, (TPP)Mn(III)ClO4, was studied In the presence of chloride anions in dichloroethane solution. It was demonstrated that Mn(II) or Mn (III) centre can be coordinated with only one chloride anion, this result makes an about 100 mV negative shift of half-wave potential of Mn (III)/Mn (II) reduction. An equilibrium constant of 2.2 x 10(4) was determined for the complexation reaction of Cl- and Mn(III) centre.