Synthesis, crystal structures, magnetic properties and catecholase activity of double phenoxido-bridged penta-coordinated dinuclear nickel(II) complexes derived from reduced Schiff-base ligands: mechanistic inference of catecholase activity

Three double phenoxido-bridged dinuclear nickel(II) complexes, namely [Ni-2(L-1)(2)(NCS)(2)] (1), [Ni-2(L-2)(2)(NCS)(2)] (2), and [Ni-2(L-3)(2)(NCS)(2)] (3) have been synthesized using the reduced tridentate Schiff-base ligands 2-[1-(3-methylamino-propylamino)-ethyl]-phenol (HL1), 2-[1-(2-dimethylamino-ethylamino)-ethyl]-phenol (HL2), and 2-[1-(3-dimethylarnino-propylamino)-ethyl]-phenol (HL3), respectively. The coordination compounds have been characterized by X-ray structural analyses, magnetic-susceptibility measurements, and various spectroscopic methods. In all complexes, the nickel(II) ions are penta-coordinated in a square-pyramidal environment, which is severely distorted in the case of 1 (Addison parameter tau = 0.47) and 3 (tau = 0.29), while it is almost perfect for 2 (tau = 0.03). This arrangement leads to relatively strong antiferromagnetic interactions between the Ni(II) (S = 1) metal centers as mediated by double phenoxido bridges (with J values of -23.32 (1), -35.45 (2), and -34.02 (3) cm(3) K mol(-1), in the convention H = -2JS(1)S(2)). The catalytic activity of these Ni compounds has been investigated for the aerial oxidation of 3,5-di-tert-butylcatechol. Kinetic data analysis following Michaelis-Menten treatment reveals that the catecholase activity of the complexes is influenced by the flexibility of the ligand and also by the geometry around the metal ion. Electrospray ionization mass spectroscopy (ESI-MS) studies (in the positive mode) have been performed for all the coordination compounds in the presence of 3,5-DTBC to characterize potential complex-substrate intermediates. The mass-spectrometry data, corroborated by electron paramagnetic resonance (EPR) measurements, suggest that the metal centers are involved in the catecholase activity exhibited by the complexes.

Effect of an ancillary ligand on single helix-double helix interconversion in copper complexes. Copper(I)-water bond

Reaction of Cu(ClO(4))(2)center dot 6H(2)O with the 1:2 condensate of benzildihydrazone and 2-acetylpyridine, in methanol in equimolar ratio yields a green compound which upon recrystallisation from 1:1 CH(2)Cl(2)-C(6)H(6) mixture affords [CuL(H(2)O)](ClO(4))(2)center dot 1/2C(6)H(6). The complex crystallises in the space group P-1 with a = 8.028(11) angstrom, b = 12.316(17) angstrom, c = 18.14(3) angstrom, alpha = 97.191(10)degrees, beta = 94.657(10)degrees and gamma = 108.039(10)degrees. It is single helical with the metal having a distorted trigonal bipyramidal N(4)O coordination sphere. The acid dissociation constant of the Cu(I) complex in CH(3)CN is 3.34 +/- 0.19. The X band EPR spectrum of the compound is rhombic with g(1) = 2.43, g(2) = 2.10 g(3) = 2.02 and A(1) = 79.3 x 10(-4) cm(-1). The Cu(II/I) potential of the complex in CH(2)Cl(2) at a glassy carbon electrode is 0.43 V vs SCE. It is argued that the copper-water bond persists in the corresponding copper(I) species. Its implications on the single helix-double helix interconversion in copper helicates are discussed. DFT calculations at the B3LYP/6-311G** level shows that the binding energy of water in the single helicol live-coordinate copper(I) species [CuL(H(2)O)](+) is similar to 40 kJ mol(-1).

Preferred orientation in an angled intercalation site of a chloro-substituted lambda- [Ru(TAP)2(dppz)]2+ complex bound to d(TCGGCGCCGA)2

The crystal structure of the ruthenium DNA ‘light-switch’ complex -[Ru(TAP)2(11-Cl-dppz)]2+ (TAP = tetraazaphenanthrene, dppz = dipyrido[3,2-a':2',3'-c]phenazine)) bound to the oligonucleotide duplex d(TCGGCGCCGA)2 is reported. The synthesis of the racemic ruthenium complex is described for the first time, and the racemate was used in this study. The crystal structure, at atomic resolution (1.0 Å), shows one ligand as a wedge in the minor groove, resulting in the 51 kinking of the double helix, as with the parent lambda-[Ru(TAP)2(dppz)]2+. Each complex binds to one duplex by intercalation of the dppz ligand and also by semi-intercalation of one of the orthogonal TAP ligands into a second symmetrically equivalent duplex. The 11-Cl substituent binds with the major component (66%) oriented with the 11-chloro substituent on the purine side of the terminal step of the duplex.

Study of picosecond processes of an intercalated dipyridophenazine Cr(iii) complex bound to defined sequence DNAs using transient absorption and time-resolved infrared methods

Picosecond transient absorption (TA) and time-resolved infrared (TRIR) measurements of rac-[Cr(phen)2(dppz)]3+ (1) intercalated into double-stranded guanine-containing DNA reveal that the excited state is very rapidly quenched. As no evidence was found for the transient electron transfer products, it is proposed that the back electron transfer reaction must be even faster (<3 ps).

Optimizing the nipple-areola sparing mastectomy with double concentric periareolar incision and biodimensional expander-implant reconstruction: Aesthetic and technical refinements

Although the biodimensional anatomical expander-implant system (BEIS) is a reliable technique, little information has been available regarding outcome following nipple-areola sparing mastectomy (NSM). To perform the resection of glandular tissue, while improving the surgical access and maintaining the nipple-areola vascularization we have developed a new approach for NSM based on the double concentric periareolar incision (DCPI). The purpose of this study is to analyze the feasibility, surgical planning and its outcome following NSM. 18 patients underwent NSM reconstructions. Mean time of follow-up was 29 months. The technique was indicated in patients with small/moderate volume breasts. Flap complications were evaluated and information on aesthetic results and patient satisfaction were collected. 83.3% had tumors measuring 2 cm or less (T1) and 72.1% were stage 0 and 1. All patients presented peripherally tumors located (at least 5 cm from the nipple). Skin complications occurred in 11.1%. One patient (5.5%) presented small skin necrosis and a wound dehiscence was observed in one patient (5.5%). The aesthetic result was good/very good in 94.4 percent and the majority of patients were very satisfied/satisfied. No local recurrences were observed. All complications except one were treated by a conservative approach. DCPI-BEIS is a simple and reliable technique for NSM reconstruction. The success depends on patient selection, coordinated planning with the oncologic surgeon and careful intra-operative and post-operative management. (C) 2009 Elsevier Ltd. All rights reserved.

Organization of ventral tegmental area projections to the ventral tegmental area-nigral complex in the rat

The ventral tegmental area (VTA) is a nodal link in reward circuitry. Based on its striatal output, it has been subdivided in a caudomedial part which targets the ventromedial striatum, and a lateral part which targets the ventrolateral striatum [Ikemoto S (2007) Dopamine reward circuitry: two projection systems from the ventral midbrain to the nucleus accumbens-olfactory tubercle complex. Brain Res Rev 56:27-78]. Whether these two VTA parts are interconnected and to what extent the VTA innervates the substantia nigra compacta (SNc) and retrorubral nucleus (RR) are critical issues for understanding information processing in the basal ganglia. Here, VTA projections to the VTA-nigral complex were examined in rats, using Phaseolus vulgaris leucoagglutinin (PHA-L) as anterograde tracer. The results show that the dorsolateral VTA projects to itself, as well as to the dorsal tier of the SNc and RR, largely avoiding the caudomedial VTA. The ventrolateral VTA innervates mainly the interfascicular nucleus. The components of the caudomedial VTA (the interfascicular, paranigral and caudal linear nuclei) are connected with each other. In addition, the caudomedial VTA (especially the paranigral and caudal linear nuclei) innervates the lateral VTA, and, to a lesser degree, the SNc and RR. The caudal pole of the VTA sends robust, bilateral projections to virtually all the VTA-nigral complex, which terminate in the dorsal and ventral tiers. Modest inputs from the medial supramammillary nucleus to ventromedial parts of the VTA-nigral complex were also identified. In double-immunostained sections, PHA-L-labeled varicosities were sometimes found apposed to tyrosine hydroxylase-positive neurons in the ventral mesencephalon. Overall, the results underscore that VTA projections to the VTA-nigral complex are substantial and topically organized. In general, these projections, like the spiralated striato-nigro-striatal loops, display a medial-to-lateral organization. This anatomical arrangement conceivably permits the ventromedial striatum to influence the activity of the lateral striatum. The caudal pole of the VTA appears to be a critical site for a global recruitment of the mesotelencephalic system. (C) 2008 IBRO. Published by Elsevier Ltd. All rights reserved.

Interaction of polysaccharide-protein complex from Agaricus blazei with Langmuir and Langmuir-Blodgett films of phospholipids

The use of natural substances in health applications may be hampered by the difficulties in establishing the mechanisms of action, especially at molecular-level. The protein-polysaccharide complex extracted from the mushroom Agaricus blazei Murill, referred to as CAb, has been considered for treating various diseases with probable interaction with cell membranes. In this study, we investigate the interaction between CAb and a cell membrane model represented by a Langmuir monolayer of dimyristoyl phosphatidic acid (DMPA). CAb affects the structural properties of DMPA monolayers causing expansion and increasing compressibility. In addition, interaction with DMPA polar heads led to neutralization of the electrical double layer, yielding a zero surface potential at large areas per molecule. CAb remained at the interface even at high surface pressures, which allowed transfer of Langmuir-Blodgett (LB) films onto solid supports with the CAb-DMPA mixture. The mass transferred, according to quartz crystal microbalance (QCM) measurements, increased linearly with the number of deposited layers. With UV-vis absorption, fluorescence and FTIR spectroscopies, we confirmed that the LB films contain polysaccharides, proteins and DMPA. Therefore, the CAb biological action must be attributed not only to polysaccharides but also to proteins in the complex. (C) 2008 Elsevier Inc. All rights reserved.

Spectroscopic Investigation on the Formation of a Dinuclear Me(2)SO-Ru(2)-Mercaptopyridine Bridged Complex: [Ru(2)Cl(3)(mu-pyS)(mu-dmso)(dmso)(4)]center dot 2H(2)O

A dinuclear ruthenium(II) complex double-bridged by an N-aromatic ligand 2-mercaptopyridine (2-pyridinethiol or 2-pyridyl mercaptan) and a methyl sulfoxide (dmso) have been characterized by X-ray crystallography. The reported compound with formula [Ru(2)Cl(3) (mu-pyS)(mu-dmso)(dmso)(4)] center dot 2H(2)O, [C(15)H(36)Cl(3)NO(7)S(6)Ru(2)] (P2/c, a = 13.8175(2) angstrom, b = 10.5608(2) angstrom, c = 21.3544 (3) angstrom, beta = 106.090(1)degrees, V = 2,994.05(8) angstrom(3), Z = 4) represents a seven-membered ring system with both rutheniums in an octahedral geometry. All the hydrogen bonds (C-H-Cl) and the van der Waals contacts give rise to three-dimensional network in the structure and add stability to the dinuclear compound. To our knowledge, this is the first time that the formation of a dinuclear ruthenium(II) complex double-bridged by an N-aromatic ligand 2-mercaptopyridine and dmso have been reported. The study also provided valuable insight into bioinorganic chemistry as continuing efforts are being made to develop metal-based cancer chemotherapeutics. A major feature of this paper is the resolution of a double bridged ruthenium structure which contributes to a better understanding of ruthenium reactivity.

Deciphering the role of the electrostatic interactions in the alpha-tropomyosin head-to-tail complex

Skeletal alpha-tropomyosin (Tm) is a dimeric coiled-coil protein that forms linear assemblies under low ionic strength conditions in vitro through head-to-tail interactions. A previously published NMR structure of the Tin head-to-tail complex revealed that it is formed by the insertion of the N-terminal coiled-coil of one molecule into a cleft formed by the separation of the helices at the C-terminus of a second molecule. To evaluate the contribution of charged residues to complex stability, we employed single and double-mutant Tm fragments in which specific charged residues were changed to alanine in head-to-tail binding assays, and the effects of the mutations were analyzed by thermodynamic double-mutant cycles and protein-protein docking. The results show that residues K5, K7, and D280 are essential to the stability of the complex. Though D2, K6, D275, and H276 are exposed to the solvent and do not participate in intermolecular contacts in the NMR structure, they may contribute to head-to-tail complex stability by modulating the stability of the helices at the Tm termini.

Double-strand DNA cleavage induced by oxindole-Schiff base copper(II) complexes with potential antitumor activity

Some oxindole-Schiff base copper(II) complexes have already shown potential antitumor activity towards different cells, inducing apoptosis in a process modulated by the ligand, and having nuclei and mitochondria as main targets. Here, three novel copper(II) complexes with analogous ligands were isolated and characterized by spectroscopic techniques, having their reactivity compared to the so far most active complex in this class. Cytotoxicity experiments carried out toward human neuroblastoma SH-SY5Y cells confirmed its proapoptosis property. DNA cleavage studies were then performed in the presence of these complexes, in order to verify the influence of ligand structural features in its nuclease activity. All of them were able to cause double-strand DNA scissions, giving rise to nicked circular Form II and linear Form III species, in the presence of hydrogen peroxide. Additionally, DNA Form II was also detected in the absence of peroxide when the most active complex, [Cu(isaepy)(2)](2+) 1, was used. In an effort to better elucidate their interactions with DNA, solutions of the different complexes titrated with DNA had their absorption spectra monitored. An absorbance hyperchromism observed at 260 nm pointed to the intercalation of these complexes into the DNA structure. Further, investigations of 2-deoxy-D-ribose (DR) oxidation catalyzed by each of those complexes, using 2-thiobarbituric acid reactive species (TBARS) method, and detection of reactive oxygen species (ROS) formation by spin-trapping EPR, suggested that their mechanism of action in performing efficiently DNA cleavage occurs preferentially, but not only by oxidative pathways. (C) 2007 Elsevier Inc. All rights reserved.

Double stranded DNA-binding studies of potential Rhodium(ll) antitumor complexes

In 1952, Dwyer and coworkers began testing a series of metal complexes for potential inhibition of cancer cell proliferation in animals.[l] The complexes tested were unsuitable for such studies due to their high toxicity. Therefore, no further work was done on the project. However, in 1965, Rosenberg and coworkers revisited the possibility of potential metal-based drugs. Serendipitously, they discovered that cis-diamminedichloroplatinum(lI) (cisplatin) inhibits cell division in E. coli.[2] Further studies of this and other platinum compounds revealed inhibition of tumor cell lines sarcoma 180 and leukemia LI2l0 in mice.[l] Cisplatin was approved by the Food and Drug Administration in 1970 as a chemical chemotherapeutic agent in the treatment of cancer. The drug has primarily been used in the treatment of testicular and ovarian cancers, although the powerful chemotherapeutic properties of the compound indicate use against a variety of other cancers.[3] The toxicity of this compound, however, warrants the development of other metal-based potential antitumor agents. The success of cisplatin, a transition-metal-based chemotherapeutic, opened the doors to a host of research on the antitumor effects of other transition-metal complexes. Beginning in the 1970s, researchers looked to rhodium for potential use in antitumor complexes. Dirhodium complexes with bridging equatorial ligands (Figure I) were the primary focus for this research. The overwhelming majority of these complexes were dirhodium(II) carboxylate complexes, containing two rhodium(II) centers, four equatorial ligands in a lantero formation around the metal center, and an axial ligand on either end. The family of complexes in Figure 1 will be referred to as dirhodium(II) carboxylate complexes. The dirhodium centers are each d? with a metal-metal bond between them. Although d? atoms are paramagnetic, the two unpaired electrons pair to make the complex diamagnetic. The basic formula of the dirhodium(lI) carboxylate complexes is Rh?(RCOO)?(L)? with R being methyl, ethyl, propyl, or butyl groups and L being water or the solvent in which the complex was crystalized. Of these dirbodium(II) carboxylate complexes, our research focuses on Rb la and two other similar complexes Rh2 and Rh3 (Figure 2). Rh2 is an activated form of Rhla, with four acetonitrile groups in place of two of the bidentate acetate ligands. Rh3 is similar to Rhla, with trifluoromethyl groups in place of the methyl groups on the acetate ligands.

Scattering and bound states of spin-0 particles in a nonminimal vector double-step potential

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Variable parameter and double sampling (X)over-bar charts in the presence of correlation: The Markov chain approach

The general assumption under which the (X) over bar chart is designed is that the process mean has a constant in-control value. However, there are situations in which the process mean wanders. When it wanders according to a first-order autoregressive (AR (1)) model, a complex approach involving Markov chains and integral equation methods is used to evaluate the properties of the (X) over bar chart. In this paper, we propose the use of a pure Markov chain approach to study the performance of the (X) over bar chart. The performance of the chat (X) over bar with variable parameters and the (X) over bar with double sampling are compared. (C) 2011 Elsevier B.V. All rights reserved.

Electroluminescence of a device based on europium beta-diketonate with phosphine oxide complex

Rare earth (RE) ions have spectroscopic characteristics to emit light in narrow lines, which makes RE complexes with organic ligands candidates for full color OLED (Organic Light Emitting Diode) applications. In particular, beta-diketone rare earth (RE(3+)) complexes show high fluorescence emission efficiency due to the high absorption coefficient of the beta-diketone and energy transfer to the central ion. In this work, the fabrication and the electroluminescent properties of devices containing a double and triple-layer OLED using a new beta-diketone complex, [Eu(bmdm)(3)(tppo)(2)], as transporting and emitting layers are compared and discussed. The double and triple-layer devices based on this complex present the following configurations respectively: device 1: ITO/TPD (40 nm)/[Eu(bmdm)(3)(tppo)(2)] (40 nm)/Al (150 nm); device 2: ITO/TPD (40 nm)/[Eu(bmdm)(3) (tppo)(2)] (40 nm)/Alq(3) (20 nm)/Al (150 nm) and device 3: ITO/TPD (40 nm)/bmdm-ligand (40 nm)/Al (150 nm), were TPD is (N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1-biphenil-4,4-diamine) and bmdm is butyl methoxy-dibenzoyl-methane. All the films were deposited by thermal evaporation carried out in a high vacuum system. These devices exhibit high intensity photo- (PL) and electro-luminescent (EL) emission. Electroluminescence spectra show emission from Eu(3+) ions attributed to the (5)D(0) to (7)F(J) (J = 0, 1, 2, 3 and 4) transitions with the hypersensitive (5)D(o) -> (7)F(2) transition (around 612 nm) as the most prominent one. Moreover, a transition from (5)D(1) to (7)F(1) is also observed around 538 nm. The OLED light emission was almost linear with the current density. The EL CIE chromaticity coordinates (X = 0.66 and Y = 0.33) show the dominant wavelength, lambda(d) = 609 nm, and the color gamut achieved by this device is 0.99 in the CIE color space. (c) 2006 Elsevier B.V. All rights reserved.

Clinical study of a multivitamin and polymineral complex associated with Panax ginseng extract (Natus Gerin®)

This study aimed to stablish the efficacy of a multivitamin and polyminerals supplemented with Panax ginseng extract (Natus Gerin ®) on patients subjected to common physical or mental stress. Patients were randomly divided in two groups and underwent a thorough clinical examination. Group A received Natus Gerin ® capsules and B placebo capsules. Two capsules were taken daily during meals during four weeks. Mood and physical activity were evaluated through a questionnaire assessing quality of life. From the 176 patients enrolled, 17 were excluded due to voluntary withdrawal, 81 completed the study in group A and 78 in group B. The treatment with Natus Gerin ® increased the quality of life when compared to placebo. After 15 and 30 days, group A showed a significant increase in average scoring score from 1.78 to 3.78, and finally 5.32 points. The study has shown that the daily use of Natus Gerin ® can be effective in improving quality of life in patients suffering from physical and mental stress.