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  1. FORMULA ESTABLISHMENT OF COLORLESS Pb(II COMPLEX WITH N-BENZOYL-N-PHENYL HYDROXYLAMINE (BPA USING ATOMIC ABSORPTION SPECTROSCOPY

    Directory of Open Access Journals (Sweden)

    Dhananjay B Sarode

    2012-02-01

    Full Text Available A new method for determination of stoichiometry of colorless complexes by using atomic absorption spectrophotometric technique in continuous variation method and slope ratio method was described here. This method can be used in same manner as that of mole ratio method and slope ratio method. In this method atomic absorption spectroscopy was used instead of UV-Vis spectrophotometry. Atomic absorption spectrophotometric technique is superior to UV-Vis spectrophotometry as it can be applied to colorless soluble complexes. Pb(II and n-benzoyl-n-phenyl hydroxylamine react to form colorless complex at pH 6.5, which can be easily determined by this method. It was found that Pb(II forms 1:2 complex with n-benzoyl-n-phenyl hydroxylamine and is quantitatively extracted back to aqueous solution for AAS analysis.

  2. Absorption and fluorescence spectroscopy of 3-hydroxy-3-phenyl-1-o-carboxyphenyltriazene and its copper (II), nickel (II) and zinc (II) complexes: a novel fluorescence sensor

    International Nuclear Information System (INIS)

    Ressalan, S.; Iyer, C.S.P.

    2005-01-01

    Absorption and fluorescence spectroscopic properties of 3-hydroxy-3-phenyl-1-o-carboxyphenyltriazene (HT) are studied. The mechanism of photo-induced electron transfer (PET) followed by energy transfer process of the ligand and the Cu (II), Ni (II) and Zn (II) metal complexes have been investigated. The excited state photo induced intramolecular hydrogen transfer from N-OH to triazene 1-nitrogen atom is explained. The effect of pH, solvent and concentration on the absorption and fluorescence of the ligand is studied and it has been found that the absorption and fluorescence of HT is highly pH, solvent and concentration dependent. Participation of the N-OH proton of HT in the solvent assisted O to N-proton transfer has also been proposed. The fluorescence band shift and changes in intensity is modulated by protonation and complexation with metal ions. This fluorophore can thus be used as a pH dependent and M (n+1)+ /M n+ redox on/off switchable molecular sensor

  3. Two photon absorption energy transfer in the light-harvesting complex of photosystem II (LHC-II) modified with organic boron dye

    Science.gov (United States)

    Chen, Li; Liu, Cheng; Hu, Rui; Feng, Jiao; Wang, Shuangqing; Li, Shayu; Yang, Chunhong; Yang, Guoqiang

    2014-07-01

    The plant light-harvesting complexes of photosystem II (LHC-II) play important roles in collecting solar energy and transferring the energy to the reaction centers of photosystems I and II. A two photon absorption compound, 4-(bromomethyl)-N-(4-(dimesitylboryl)phenyl)-N-phenylaniline (DMDP-CH2Br), was synthesized and covalently linked to the LHC-II in formation of a LHC-II-dye complex, which still maintained the biological activity of LHC-II system. Under irradiation with femtosecond laser pulses at 754 nm, the LHC-II-dye complex can absorb two photons of the laser light effectively compared with the wild type LHC-II. The absorbed excitation energy is then transferred to chlorophyll a with an obvious fluorescence enhancement. The results may be interesting and give potentials for developing hybrid photosystems.

  4. Effects of excited state mixing on transient absorption spectra in dimers Application to photosynthetic light-harvesting complex II

    CERN Document Server

    Valkunas, L; Trinkunas, G; Müller, M G; Holzwarth, A R

    1999-01-01

    The excited state mixing effect is taken into account considering the difference spectra of dimers. Both the degenerate (homo) dimer as well as the nondegenerate (hetero) dimer are considered. Due to the higher excited state mixing with the two-exciton states in the homodimer, the excited state absorption (or the difference spectrum) can be strongly affected in comparison with the results obtained in the Heitler-London approximation. The difference spectrum of the heterodimer is influenced by two resonance effects (i) mixing of the ground state optical transitions of both monomers in the dimer and (ii) mixing of the excited state absorption of the excited monomer with the ground state optical transition in the nonexcited monomer. These effects have been tested by simulating the difference absorption spectra of the light-harvesting complex of photosystem II (LHC II) experimentally obtained with the 60 fs excitation pulses at zero delay times and various excitation wavelengths. The pairs of coupled chlorophylls...

  5. (II) complexes

    African Journals Online (AJOL)

    activities of Schiff base tin (II) complexes. Neelofar1 ... Conclusion: All synthesized Schiff bases and their Tin (II) complexes showed high antimicrobial and ...... Singh HL. Synthesis and characterization of tin (II) complexes of fluorinated Schiff bases derived from amino acids. Spectrochim Acta Part A: Molec Biomolec.

  6. A Femtosecond Visible/Visible and Visible/Mid-Infrared Transient Absorption Study of the Light Harvesting Complex II

    NARCIS (Netherlands)

    Stahl, A.D.; Di Donato, M.; van Stokkum, I.H.M.; van Grondelle, R.; Groot, M.L.

    2009-01-01

    Light harvesting complex II (LHCII) is the most abundant protein in the thylakoid membrane of higher plants and green algae. LHCII acts to collect solar radiation, transferring this energy mainly toward photosystem II, with a smaller amount going to photosystem I; it is then converted into a

  7. Ruthenium(II) chloro-bis(bipyridyl) complexes with substituted pyridine ligands: interpretation of their electronic absorption spectra

    International Nuclear Information System (INIS)

    Sizova, O.V.; Ershov, A.Yu.; Ivanova, N.V.; Shashko, A.D.; Kutejkina-Teplyakova, A.V.

    2003-01-01

    A number of complexes cis-[Ru(Bipy) 2 (L)(Cl)](BF 4 ), where Bipy-2,2'-bipyridine, L-pyridine, 4-aminopyridine, 4-picoline, nicotinamide, isonicotinamide, 3- and 4-cyanopyridine, 4,4'-bipyridine, trans-1,2-bis(4-pyridyl)ethylene, 4,4'-azopyridine, pyrazine, imidazole and NH 3 , were prepared. Using the CINDO-CI semiempirical method the energies and intensities of transition in electronic absorption spectra (EAS) of the complexes were calculated. It is shown that major differences in EAS of the compounds stem from position of transitions with charge transfer d π (Ru)→π*(L) [ru

  8. Transdermic absorption of Melagenina II

    International Nuclear Information System (INIS)

    Hernandez Gonzalez, I.; Martinez Lopez, B.; Ruiz Pena, M.; Caso Pena, R.

    1997-01-01

    The transdermic absorption of Melagenina II (MII) was evaluated. MII was a labelled with 125I by the yodogen method and purified by column chromatography with Sephadex LH-20 in ethanol: water (7:3). In vitro absorption of ( 125I ) - MII thought human skin was carried out in Keshary-Chien modified diffusion cells. Tape stripping method was applied after 24 hours to evaluate the accumulated activity in dermis and epidermis. In vivo assays were performed in Sprague Dawley rats to analyze absorption of MII until 24 hours after a single application and for five days a low penetrability of the drug while in vivo there were not found blood levels significantly greater than zero , nevertheless and important amount of radioactivity was found in feces and urine. The activity was concentrated mainly in the application site in both models

  9. X-ray diffraction and X-ray K absorption near edge studies of copper (II) complexes with amino acids

    Science.gov (United States)

    Sharma, P. K.; Mishra, Ashutosh; Malviya, Varsha; Kame, Rashmi; Malviya, P. K.

    2017-05-01

    Synthesis of copper (II) complexes [CuL1L2X].nH2O, where n=1, 2,3 (X=Cl,Br,NO3) (L1is 2,2’-bipyridine and L2 is L-tyrosine) by the chemical root method. The XRD data for the samples have been recorded. EXAFS spectra have also been recorded at the K-edge of Cu using the dispersive beam line BL-8 at 2.5 Gev Indus-2 Synchrotron radiation source at RRCAT, Indore, India. XRD and EXAFS data have been analysed using the computer software. X-ray diffraction studies of all complexes indicate their crystalline nature. Lattice parameter, bond length, particle size have been determined from XRD data.

  10. Polarized X-ray absorption spectroscopy of single-crystal Mn(V) complexes relevant to the oxygen-evolving complex of photosystem II

    DEFF Research Database (Denmark)

    Yano, Junko; Robblee, John; Pushkar, Yulia

    2007-01-01

    High-valent Mn-oxo species have been suggested to have a catalytically important role in the water splitting reaction which occurs in the Photosystem II membrane protein. In this study, five- and six-coordinate mononuclear Mn(V) compounds were investigated by polarized X-ray absorption spectroscopy...... structure of the metal site was then studied by measuring the polarization dependence of X-ray absorption near-edge spectroscopy (XANES) pre-edge spectra (1s to 3d transition) and comparing with the results of density functional theory (DFT) calculations. The Mn(V)-nitrido compound, in which the manganese......-edge peak. This component was interpreted as a 1s to 3d(xz,yz) transition with 4px,y mixing, due to the displacement of the Mn atom out of the equatorial plane. The XANES results have been correlated to DFT calculations, and the spectra have been simulated using a TD (time-dependent)-DFT approach...

  11. (II) COMPLEX COMPOUND

    African Journals Online (AJOL)

    user

    electrochemical sensors, as well as in various chromatographic ... were carried out using Jenway pH meter Model 3320 and a conductivity ... Figure 1: the proposed molecular structure of the copper (II) Schiff base complex. M = Cu (II) or Mn (II).

  12. A new Kaempferol-based Ru(II) coordination complex, Ru(kaem)Cl(DMSO){sub 3}: Structure and absorption-emission spectroscopy study

    Energy Technology Data Exchange (ETDEWEB)

    Shao, Ming Wei; Gang, Jong Back; Kim, Sang Ho; Yoon, Min Young [Gachon University, Sungnam (Korea, Republic of)

    2016-10-15

    Recent interest in developing a new anticancer drug with low side effects has led to the study of the combination of two new anticancer drugs. Although both kaempferol (kaem) and Ru-based metal complexes have not been proven as effective drugs, their unique anticancer activities with reduced side effects have drawn our attention to the need for further studies on their potential in anticancer application. Herein, we report the synthesis, characterization, structure, and spectroscopic properties of a kaem-based Ru (II) complex, RuCl(kaem)(DMSO){sub 3} (1). Because of the presence of a catechol-like functional group in its dihydropyran ring, kaem can strongly bind to the Ru(II) metal center in a basic medium. The molecular structure of the complex was characterized by spectroscopic studies and X-ray crystal structure analysis. In addition, the complex forms a molecular dimer as a result of the cooperative effect of H-bonding and π–π stacking interactions. Moreover, the molecular dimer forms a ladder-like one-dimensional network structure by water mediated H-bonding that further extended into a three-dimensional packing structure. UV–Vis spectroscopy studies of the complex demonstrated the appearance of a strong metal to ligand charge transfer (MLCT) band in the visible region with strong fluorescence emission derived from the MLCT. Further studies are now in progress to demonstrate synergetic anticancer activity.

  13. A new Kaempferol-based Ru(II) coordination complex, Ru(kaem)Cl(DMSO)3: Structure and absorption-emission spectroscopy study

    International Nuclear Information System (INIS)

    Shao, Ming Wei; Gang, Jong Back; Kim, Sang Ho; Yoon, Min Young

    2016-01-01

    Recent interest in developing a new anticancer drug with low side effects has led to the study of the combination of two new anticancer drugs. Although both kaempferol (kaem) and Ru-based metal complexes have not been proven as effective drugs, their unique anticancer activities with reduced side effects have drawn our attention to the need for further studies on their potential in anticancer application. Herein, we report the synthesis, characterization, structure, and spectroscopic properties of a kaem-based Ru (II) complex, RuCl(kaem)(DMSO) 3 (1). Because of the presence of a catechol-like functional group in its dihydropyran ring, kaem can strongly bind to the Ru(II) metal center in a basic medium. The molecular structure of the complex was characterized by spectroscopic studies and X-ray crystal structure analysis. In addition, the complex forms a molecular dimer as a result of the cooperative effect of H-bonding and π–π stacking interactions. Moreover, the molecular dimer forms a ladder-like one-dimensional network structure by water mediated H-bonding that further extended into a three-dimensional packing structure. UV–Vis spectroscopy studies of the complex demonstrated the appearance of a strong metal to ligand charge transfer (MLCT) band in the visible region with strong fluorescence emission derived from the MLCT. Further studies are now in progress to demonstrate synergetic anticancer activity

  14. Determination of Tetracycline in Pharmaceutical Preparation by Molecular and Atomic Absorption Spectrophotometry and High Performance Liquid Chromatography via Complex Formation with Au(III) and Hg(II) Ions in Solutions

    Science.gov (United States)

    Abdulghani, Ahlam Jameel; Jasim, Hadi Hassan; Hassan, Abbas Shebeeb

    2013-01-01

    UV-visible and atomic spectrophotometry and HPLC techniques were applied for the determination of tetracycline (TC) in pharmaceutical preparations via complexation of the drug with Au(III) and Hg(II) ions in solutions. The mole ratio of TC to metal ions was 1 : 1. Maximum peak absorption at λ 425 and 320 nm for the two ions, respectively, was optimized at heating temperature 75°C for 15 minutes at pH = 4 followed by the extraction with ethyl acetate. The percentage of extraction and stability constants for the two complexes was 95.247, 95.335% and 2.518 × 104, 1.162 × 105 M−1, respectively. HPLC method was applied without extraction process. The analytical data obtained from direct calibration curves of UV-visible absorption, FAAS, and HPLC for Au(III) complexes were recovery (100.78, 104.85, and 101.777%, resp.); detection limits (0.7403, 0.0997, and 2.647 μg/ml, resp.); linearity (5–70, 5–30, and 10–150 μg/ml, resp.), and correlation coefficient (0.9991, 0.9967, and 0.9986, resp.). The analytical data obtained from direct calibration curves for Hg(II) complexes by UV-visible spectrophotometry and HPLC were recovery (100.95 and 102.000%, resp.); detection limits (0.5867 and 2.532 μg/ml, resp.); linearity (5–70 and 10–150 μg/ml, resp.); and correlation coefficients (0.9989 and 0.9997, resp.). PMID:23853607

  15. Thermodynamic Modeling of Poorly Complexing Metals in Concentrated Electrolyte Solutions: An X-Ray Absorption and UV-Vis Spectroscopic Study of Ni(II) in the NiCl2-MgCl2-H2O System

    Science.gov (United States)

    Zhang, Ning; Brugger, Joël; Etschmann, Barbara; Ngothai, Yung; Zeng, Dewen

    2015-01-01

    Knowledge of the structure and speciation of aqueous Ni(II)-chloride complexes is important for understanding Ni behavior in hydrometallurgical extraction. The effect of concentration on the first-shell structure of Ni(II) in aqueous NiCl2 and NiCl2-MgCl2 solutions was investigated by Ni K edge X-ray absorption (XAS) and UV-Vis spectroscopy at ambient conditions. Both techniques show that no large structural change (e.g., transition from octahedral to tetrahedral-like configuration) occurs. Both methods confirm that the Ni(II) aqua ion (with six coordinated water molecules at R Ni-O = 2.07(2) Å) is the dominant species over the whole NiCl2 concentration range. However, XANES, EXAFS and UV-Vis data show subtle changes at high salinity (> 2 mol∙kg-1 NiCl2), which are consistent with the formation of small amounts of the NiCl+ complex (up to 0.44(23) Cl at a Ni-Cl distance of 2.35(2) Å in 5.05 mol∙kg-1 NiCl2) in the pure NiCl2 solutions. At high Cl:Ni ratio in the NiCl2-MgCl2-H2O solutions, small amounts of [NiCl2]0 are also present. We developed a speciation-based mixed-solvent electrolyte (MSE) model to describe activity-composition relationships in NiCl2-MgCl2-H2O solutions, and at the same time predict Ni(II) speciation that is consistent with our XAS and UV-Vis data and with existing literature data up to the solubility limit, resolving a long-standing uncertainty about the role of chloride complexing in this system. PMID:25885410

  16. Measurements of Narrow Mg II Associated Absorption Doublets with ...

    Indian Academy of Sciences (India)

    2016-01-27

    Jan 27, 2016 ... The measurement of the variations of absorption lines over time is a good method to study the physical conditions of absorbers. In this paper, we measure the variations of the line strength of 36 narrow Mg II2796, 2803 associated absorption doublets, which are imprinted on 31 quasar spectra with two ...

  17. Average [O II] nebular emission associated with Mg II absorbers: dependence on Fe II absorption

    Science.gov (United States)

    Joshi, Ravi; Srianand, Raghunathan; Petitjean, Patrick; Noterdaeme, Pasquier

    2018-05-01

    We investigate the effect of Fe II equivalent width (W2600) and fibre size on the average luminosity of [O II] λλ3727, 3729 nebular emission associated with Mg II absorbers (at 0.55 ≤ z ≤ 1.3) in the composite spectra of quasars obtained with 3 and 2 arcsec fibres in the Sloan Digital Sky Survey. We confirm the presence of strong correlations between [O II] luminosity (L_{[O II]}) and equivalent width (W2796) and redshift of Mg II absorbers. However, we show L_{[O II]} and average luminosity surface density suffer from fibre size effects. More importantly, for a given fibre size, the average L_{[O II]} strongly depends on the equivalent width of Fe II absorption lines and found to be higher for Mg II absorbers with R ≡W2600/W2796 ≥ 0.5. In fact, we show the observed strong correlations of L_{[O II]} with W2796 and z of Mg II absorbers are mainly driven by such systems. Direct [O II] detections also confirm the link between L_{[O II]} and R. Therefore, one has to pay attention to the fibre losses and dependence of redshift evolution of Mg II absorbers on W2600 before using them as a luminosity unbiased probe of global star formation rate density. We show that the [O II] nebular emission detected in the stacked spectrum is not dominated by few direct detections (i.e. detections ≥3σ significant level). On an average, the systems with R ≥ 0.5 and W2796 ≥ 2 Å are more reddened, showing colour excess E(B - V) ˜ 0.02, with respect to the systems with R < 0.5 and most likely trace the high H I column density systems.

  18. Mechanism of pion absorption in complex nuclei

    International Nuclear Information System (INIS)

    Doss, K.G.N.; Wharton, W.R.

    Basic geometrical arguments are used to analyze the A dependence of the total pion absorption cross section, the effective number of nucleons sharing the pion momentum and energy, and the proton yields from π + - and π - -induced reactions. The results are consistent with the pions penetrating some distance through the nuclear volume and annihilating on a pair of nucleons. 3 figures

  19. Photocleavage of DNA by copper (II) complexes

    Indian Academy of Sciences (India)

    The chemistry of ternary and binary copper(II) complexes showing efficient visible lightinduced DNA cleavage activity is summarized in this article. The role of the metal in photo-induced DNA cleavage reactions is explored by designing complex molecules having a variety of ligands. Ternary copper(II) complexes with amino ...

  20. Complexes cobalt(II, zinc(II and copper(II with some newly synthesized benzimidazole derivatives and their antibacterial activity

    Directory of Open Access Journals (Sweden)

    S. O. PODUNAVAC-KUZMANOVIC

    1999-05-01

    Full Text Available The preparation and properties of some complexes of cobalt(II, zinc(II and copper(II with several newly synthesized benzimidazole derivatives (L are reported. The complexes, of the general formula [MCl2L2] (M=Co(II, Zn(II and [CuCl2L(H2O], have a tetrahedral structure. The complexes were characterized by elemental analysis, molar conductivity, magnetic susceptibility measurements, IR and absorption electronic spectra. The antibacterial activitiy of the benzimidazoles and their complexes was evaluated against Erwinia carotovora subsp. carotovora and Erwinia amylovora. The complexes were found to be more toxic than the ligands.

  1. Ni (II) and Cu(II) complexes of

    African Journals Online (AJOL)

    ADOWIE PERE

    ABSTRACT: The objective of this study is to investigate the antimicrobial activity of novel. Schiff base metal complexes. The resistance of micro-organisms to classical antimicrobial compounds poses a challenge to effective management and treatment of some diseases. In line with this, copper (II), nickel (II) and cobalt (II) ...

  2. The O2-Evolving Complex of Photosystem II: Recent Insights from Quantum Mechanics/Molecular Mechanics (QM/MM), Extended X-ray Absorption Fine Structure (EXAFS), and Femtosecond X-ray Crystallography Data.

    Science.gov (United States)

    Askerka, Mikhail; Brudvig, Gary W; Batista, Victor S

    2017-01-17

    Efficient photoelectrochemical water oxidation may open a way to produce energy from renewable solar power. In biology, generation of fuel due to water oxidation happens efficiently on an immense scale during the light reactions of photosynthesis. To oxidize water, photosynthetic organisms have evolved a highly conserved protein complex, Photosystem II. Within that complex, water oxidation happens at the CaMn 4 O 5 inorganic catalytic cluster, the so-called oxygen-evolving complex (OEC), which cycles through storage "S" states as it accumulates oxidizing equivalents and produces molecular oxygen. In recent years, there has been significant progress in understanding the OEC as it evolves through the catalytic cycle. Studies have combined conventional and femtosecond X-ray crystallography with extended X-ray absorption fine structure (EXAFS) and quantum mechanics/molecular mechanics (QM/MM) methods and have addressed changes in protonation states of μ-oxo bridges and the coordination of substrate water through the analysis of ammonia binding as a chemical analog of water. These advances are thought to be critical to understanding the catalytic cycle since protonation states regulate the relative stability of different redox states and the geometry of the OEC. Therefore, establishing the mechanism for substrate water binding and the nature of protonation/redox state transitions in the OEC is essential for understanding the catalytic cycle of O 2 evolution. The structure of the dark-stable S 1 state has been a target for X-ray crystallography for the past 15 years. However, traditional X-ray crystallography has been hampered by radiation-induced reduction of the OEC. Very recently, a revolutionary X-ray free electron laser (XFEL) technique was applied to PSII to reveal atomic positions at 1.95 Å without radiation damage, which brought us closer than ever to establishing the ultimate structure of the OEC in the S 1 state. However, the atom positions in this crystal

  3. Beryllium(II), manganese(II) and uranyl(VI)-salicylamide complexes

    Energy Technology Data Exchange (ETDEWEB)

    Maurya, P L; Agarwala, B V; Dey, A K [Allahabad Univ. (India)

    1977-01-01

    The preparation, composition, general properties and i.r. absorption spectra of the solid chelates formed by salicylamide with beryllium(II), manganese(II) and uranyl(VI) are described. The complexes have been synthesized by refluxing a mixture of ethanolic solutions of the reactants (metal:ligand :: 1:2) for several hours in the presence of alkali. Attempts to isolate the complexes by the interaction of ethanolic solutions of the metal salts and the ligand in the absence of alkali did not succeed.

  4. Absorption dynamics and delay time in complex potentials

    Science.gov (United States)

    Villavicencio, Jorge; Romo, Roberto; Hernández-Maldonado, Alberto

    2018-05-01

    The dynamics of absorption is analyzed by using an exactly solvable model that deals with an analytical solution to Schrödinger’s equation for cutoff initial plane waves incident on a complex absorbing potential. A dynamical absorption coefficient which allows us to explore the dynamical loss of particles from the transient to the stationary regime is derived. We find that the absorption process is characterized by the emission of a series of damped periodic pulses in time domain, associated with damped Rabi-type oscillations with a characteristic frequency, ω = (E + ε)/ℏ, where E is the energy of the incident waves and ‑ε is energy of the quasidiscrete state of the system induced by the absorptive part of the Hamiltonian; the width γ of this resonance governs the amplitude of the pulses. The resemblance of the time-dependent absorption coefficient with a real decay process is discussed, in particular the transition from exponential to nonexponential regimes, a well-known feature of quantum decay. We have also analyzed the effect of the absorptive part of the potential on the dynamical delay time, which behaves differently from the one observed in attractive real delta potentials, exhibiting two regimes: time advance and time delay.

  5. TETRACYANONICKELATE(II) PYRIDAZINE COMPLEXES

    African Journals Online (AJOL)

    B. S. Chandravanshi

    and therefore they have been attracting increasing attention from scientists [1]. .... in the spectra of the complexes studied are listed in Table 1, together with free ..... Raman spectra were recorded at Anadolu University, Department of Physics.

  6. Synthesis, Characterization, and Biological Activity of Nickel (II and Palladium (II Complex with Pyrrolidine Dithiocarbamate (PDTC

    Directory of Open Access Journals (Sweden)

    Sk Imadul Islam

    2016-01-01

    Full Text Available The synthesis of square planar Ni(II and Pd(II complexes with pyrrolidine dithiocarbamate (PDTC was characterized by elemental, physiochemical, and spectroscopic methods. Two complexes were prepared by the reaction of nickel acetate and palladium acetate with pyrrolidine dithiocarbamate (PDTC in 1 : 2 molar ratio. The bovine serum albumin (BSA interaction with complexes was examined by absorption and fluorescence spectroscopic techniques at pH 7.4. All the spectral data suggest that coordination of the pyrrolidine dithiocarbamate (PDTC takes place through the two sulphur atoms in a symmetrical bidentate fashion. All the synthesized compounds were screened for their antimicrobial activity against some species of pathogenic bacteria (Escherichia coli, Vibrio cholerae, Streptococcus pneumonia, and Bacillus cereus. It has been observed that complexes have higher activity than the free ligand.

  7. Complexes of cobalt(II), nickel(II), copper(II), zinc(II), cadmium(II) and dioxouranium(II) with thiophene-2-aldehydethiosemicarbazone

    International Nuclear Information System (INIS)

    Singh, Balwan; Misra, Harihar

    1986-01-01

    Metal complexes of thiosemicarbazides have been known for their pharmacological applications. Significant antitubercular, fungicidal and antiviral activities have been reported for thiosemicarbazides and their derivatives. The present study describes the systhesis and characterisation of complexes of Co II , Cu II , Zn II ,Cd II and UO II with thiosemicarbazone obtained by condensing thiophene-2-aldehyde with thiosemicarbazide. 17 refs., 2 tables. (author)

  8. The redshift number density evolution of Mg II absorption systems

    International Nuclear Information System (INIS)

    Chen Zhi-Fu

    2013-01-01

    We make use of the recent large sample of 17 042 Mg II absorption systems from Quider et al. to analyze the evolution of the redshift number density. Regardless of the strength of the absorption line, we find that the evolution of the redshift number density can be clearly distinguished into three different phases. In the intermediate redshift epoch (0.6 ≲ z ≲ 1.6), the evolution of the redshift number density is consistent with the non-evolution curve, however, the non-evolution curve over-predicts the values of the redshift number density in the early (z ≲ 0.6) and late (z ≳ 1.6) epochs. Based on the invariant cross-section of the absorber, the lack of evolution in the redshift number density compared to the non-evolution curve implies the galaxy number density does not evolve during the middle epoch. The flat evolution of the redshift number density tends to correspond to a shallow evolution in the galaxy merger rate during the late epoch, and the steep decrease of the redshift number density might be ascribed to the small mass of halos during the early epoch.

  9. Solid-phase extraction of Mn(II), Co(II), Ni(II), Cu(II), Cd(II) and Pb(II) ions from environmental samples by flame atomic absorption spectrometry (FAAS)

    Energy Technology Data Exchange (ETDEWEB)

    Duran, Celal [Department of Chemistry, Faculty of Art and Science, Karadeniz Technical University, 61080 Trabzon (Turkey); Gundogdu, Ali [Department of Chemistry, Faculty of Art and Science, Karadeniz Technical University, 61080 Trabzon (Turkey); Bulut, Volkan Numan [Department of Chemistry, Giresun Faculty of Art and Science, Karadeniz Technical University, 28049 Giresun (Turkey); Soylak, Mustafa [Department of Chemistry, Faculty of Art and Science, Erciyes University, 38039 Kayseri (Turkey)]. E-mail: soylak@erciyes.edu.tr; Elci, Latif [Department of Chemistry, Faculty of Art and Science, Pamukkale University, 20020 Denizli (Turkey); Sentuerk, Hasan Basri [Department of Chemistry, Faculty of Art and Science, Karadeniz Technical University, 61080 Trabzon (Turkey); Tuefekci, Mehmet [Department of Chemistry, Faculty of Art and Science, Karadeniz Technical University, 61080 Trabzon (Turkey)

    2007-07-19

    A new method using a column packed with Amberlite XAD-2010 resin as a solid-phase extractant has been developed for the multi-element preconcentration of Mn(II), Co(II), Ni(II), Cu(II), Cd(II), and Pb(II) ions based on their complex formation with the sodium diethyldithiocarbamate (Na-DDTC) prior to flame atomic absorption spectrometric (FAAS) determinations. Metal complexes sorbed on the resin were eluted by 1 mol L{sup -1} HNO{sub 3} in acetone. Effects of the analytical conditions over the preconcentration yields of the metal ions, such as pH, quantity of Na-DDTC, eluent type, sample volume and flow rate, foreign ions etc. have been investigated. The limits of detection (LOD) of the analytes were found in the range 0.08-0.26 {mu}g L{sup -1}. The method was validated by analyzing three certified reference materials. The method has been applied for the determination of trace elements in some environmental samples.

  10. Transdermic absorption of Melagenina II; Evaluacion de la absorcion transdermica de la Melagenina II

    Energy Technology Data Exchange (ETDEWEB)

    Hernandez Gonzalez, I; Martinez Lopez, B; Ruiz Pena, M; Caso Pena, R [Centro de Isotopos, La Habana (Cuba)

    1998-12-31

    The transdermic absorption of Melagenina II (MII) was evaluated. MII was a labelled with {sup 125I} by the yodogen method and purified by column chromatography with Sephadex LH-20 in ethanol: water (7:3). In vitro absorption of ({sup 125I}) - MII thought human skin was carried out in Keshary-Chien modified diffusion cells. Tape stripping method was applied after 24 hours to evaluate the accumulated activity in dermis and epidermis. In vivo assays were performed in Sprague Dawley rats to analyze absorption of MII until 24 hours after a single application and for five days a low penetrability of the drug while in vivo there were not found blood levels significantly greater than zero , nevertheless and important amount of radioactivity was found in feces and urine. The activity was concentrated mainly in the application site in both models

  11. Ni(II) complexes of dithiophosphonic acids

    Indian Academy of Sciences (India)

    aDepartment of Chemistry, Science and Research Branch, Islamic Azad ... The compounds were characterized by 1H, 13C and 31P NMR, IR spectroscopy and elemental analysis. The ... design and synthesize Ni(II) complexes with new ..... Yield: 86%. ..... 28 65. 18. Greenwood D 1989 Antimicrobial chemotherapy (New.

  12. DNA binding and biological activity of mixed ligand complexes of Cu(II, Ni(II and Co(II with quinolones and N donor ligand

    Directory of Open Access Journals (Sweden)

    S.M M Akram

    2015-10-01

    Full Text Available  AbstractMixed ligand complexes of  Cu(II, Ni(II and Co(II have been synthesized by using levofloxacin and bipyridyl and characterized using spectral and analytical techniques. The binding behavior of the Ni(II and Cu(II complexes with herring sperm DNA(Hs-DNA were determined using electronic absorption titration, viscometric measurements and cyclic voltammetry measurements. The binding constant calculated  for Cu(II and Ni(II complexes are 2.0 x 104 and 4.0 x 104 M-1 respectively. Detailed analysis reveals that these metal complexes interact with DNA through intercalative binding mode. The nuclease activity of  Cu(II and Ni(II complexes with ct-DNA was carried out using agarose gel electrophoresis technique. The antioxidant activities for the synthesized complexes have been tested and the antibacterial activity for Ni(II complex was also checked.Key words: Intercalation, hypochromism, red shift and  peak potential.

  13. Biologically active new Fe(II, Co(II, Ni(II, Cu(II, Zn(II and Cd(II complexes of N-(2-thienylmethylenemethanamine

    Directory of Open Access Journals (Sweden)

    C. SPÎNU

    2008-04-01

    Full Text Available Iron(II, cobalt(II, nickel (II, copper (II, zinc(II and cadmium(II complexes of the type ML2Cl2, where M is a metal and L is the Schiff base N-(2-thienylmethylenemethanamine (TNAM formed by the condensation of 2-thiophenecarboxaldehyde and methylamine, were prepared and characterized by elemental analysis as well as magnetic and spectroscopic measurements. The elemental analyses suggest the stoichiometry to be 1:2 (metal:ligand. Magnetic susceptibility data coupled with electronic, ESR and Mössbauer spectra suggest a distorted octahedral structure for the Fe(II, Co(II and Ni(II complexes, a square-planar geometry for the Cu(II compound and a tetrahedral geometry for the Zn(II and Cd(II complexes. The infrared and NMR spectra of the complexes agree with co-ordination to the central metal atom through nitrogen and sulphur atoms. Conductance measurements suggest the non-electrolytic nature of the complexes, except for the Cu(II, Zn(II and Cd(II complexes, which are 1:2 electrolytes. The Schiff base and its metal chelates were screened for their biological activity against Escherichia coli, Staphylococcus aureus and Pseudomonas aeruginosa and the metal chelates were found to possess better antibacterial activity than that of the uncomplexed Schiff base.

  14. Narrow absorption lines complex I: one form of broad absorption line

    Science.gov (United States)

    Lu, Wei-Jian; Lin, Ying-Ru

    2018-03-01

    We discover that some of the broad absorption lines (BALs) are actually a complex of narrow absorption lines (NALs). As a pilot study of this type of BAL, we show this discovery through a typical example in this paper. Utilizing the two-epoch observations of J002710.06-094435.3 (hereafter J0027-0944) from the Sloan Digital Sky Survey (SDSS), we find that each of the C IV and Si IV BAL troughs contains at least four NAL doublets. By resolving the Si IV BAL into multiple NALs, we present the following main results and conclusions. First, all these NALs show coordinated variations between the two-epoch SDSS observations, suggesting that they all originate in the quasar outflow, and that their variations are due to global changes in the ionization condition of the absorbing gas. Secondly, a BAL consisting of a number of NAL components indicates that this type of BAL is basically the same as the intrinsic NAL, which tends to support the inclination model rather than the evolution model. Thirdly, although both the C IV and Si IV BALs originate from the same clumpy substructures of the outflow, they show different profile shapes: multiple absorption troughs for the Si IV BAL in a wider velocity range, while P-Cygni for the C IV BAL in a narrower velocity range. This can be interpreted by the substantial differences in fine structure and oscillator strength between the Si IVλλ1393, 1402 and C IVλλ1548, 1551 doublets. Based on the above conclusions, we consider that the decomposition of a BAL into NALs can serve as a way to resolve the clumpy structure for outflows, and it can be used to learn more about characteristics of the clumpy structure and to test the outflow model, when utilizing high-resolution spectra and photoionization model.

  15. Absorption of acoustic waves by sunspots. II - Resonance absorption in axisymmetric fibril models

    Science.gov (United States)

    Rosenthal, C. S.

    1992-01-01

    Analytical calculations of acoustic waves scattered by sunspots which concentrate on the absorption at the magnetohydrodynamic Alfven resonance are extended to the case of a flux-tube embedded in a uniform atmosphere. The model is based on a flux-tubes of varying radius that are highly structured, translationally invariant, and axisymmetric. The absorbed fractional energy is determined for different flux-densities and subphotospheric locations with attention given to the effects of twist. When the flux is highly concentrated into annuli efficient absorption is possible even when the mean magnetic flux density is low. The model demonstrates low absorption at low azimuthal orders even in the presence of twist which generally increases the range of wave numbers over which efficient absorption can occur. Resonance absorption is concluded to be an efficient mechanism in monolithic sunspots, fibril sunspots, and plage fields.

  16. 3-color DPAS Aerosol Absorption Monitor, Phase II

    Data.gov (United States)

    National Aeronautics and Space Administration — We propose to develop a highly sensitive and compact RGB DPAS aerosol absorption monitor for NASA's Airborne Measurement Program. It will measure aerosol light...

  17. Cyclometallated ruthenium(II) carbonyl complexes with 1 ...

    Indian Academy of Sciences (India)

    The characterization of the complexes having the ... Electronic spectra of the complexes display multiple strong absorptions in the ... Microanalyses (CHN) were performed by using a ..... proton.47,49 Absence of this signal in the spectra of.

  18. Deactivation of the EBR-II complex

    International Nuclear Information System (INIS)

    Michelbacher, J.A.; Earle, O.K.; Henslee, S.P.; Wells, P.B.; Zahn, T.P.

    1996-01-01

    In January of 1994, the Department of Energy mandated the termination of the Integral Fast Reactor (IFR) Program, effective October 1, 1994. To comply with this decision, Argonne National Laboratory-West (ANL-W) prepared a plan providing detailed requirements to place the Experimental Breeder Reactor-II (EBR-II) in a radiologically and industrially safe condition, including removal of all irradiated fuel assemblies from the reactor plant, and removal and stabilization of the primary and secondary sodium, a liquid metal used to transfer heat within the reactor plant. The ultimate goal of the deactivation process is to place the EBR-II complex in a stable condition until a decontamination and decommissioning (D and D) plan can be prepared, thereby minimizing requirements for maintenance and surveillance and maximizing the amount of time for radioactive decay. The final closure state will be achieved in full compliance with federal, state and local environmental, safety, and health regulations and requirements. The decision to delay the development of a detailed D and D plan has necessitated this current action

  19. Deactivation of the EBR-II complex

    Energy Technology Data Exchange (ETDEWEB)

    Michelbacher, J A; Earle, O K; Henslee, S P; Wells, P B; Zahn, T P

    1996-01-01

    In January of 1994, the Department of Energy mandated the termination of the Integral Fast Reactor (IFR) Program, effective October 1, 1994. To comply with this decision, Argonne National Laboratory-West (ANL-W) prepared a plan providing detailed requirements to place the Experimental Breeder Reactor-II (EBR-II) in a radiologically and industrially safe condition, including removal of all irradiated fuel assemblies from the reactor plant, and removal and stabilization of the primary and secondary sodium, a liquid metal used to transfer heat within the reactor plant. The ultimate goal of the deactivation process is to place the EBR-II complex in a stable condition until a decontamination and decommissioning (D and D) plan can be prepared, thereby minimizing requirements for maintenance and surveillance and maximizing the amount of time for radioactive decay. The final closure state will be achieved in full compliance with federal, state and local environmental, safety, and health regulations and requirements. The decision to delay the development of a detailed D and D plan has necessitated this current action.

  20. Absorption spectra analysis of hydrated uranium(III) complex chlorides

    Science.gov (United States)

    Karbowiak, M.; Gajek, Z.; Drożdżyński, J.

    2000-11-01

    Absorption spectra of powdered samples of hydrated uranium(III) complex chlorides of the formulas NH 4UCl 4 · 4H 2O and CsUCl 4 · 3H 2O have been recorded at 4.2 K in the 4000-26 000 cm -1 range. The analysis of the spectra enabled the determination of crystal-field parameters and assignment of 83 and 77 crystal-field levels for the tetrahydrate and trihydrate, respectively. The energies of the levels were computed by applying a simplified angular overlap model as well as a semiempirical Hamiltonian representing the combined atomic and crystal-field interactions. Ab initio calculations have enabled the application of a simplified parameterization and the determination of the starting values of the AOM parameters. The received results have proved that the AOM approach can quite well predict both the structure of the ground multiplet and the positions of the crystal-field levels in the 17 000-25 000 cm -1 range, usually obscured by strong f-d bands.

  1. Deactivation of the EBR-II complex

    Energy Technology Data Exchange (ETDEWEB)

    Michelbacher, J.A.; Earle, O.K.; Henslee, S.P. [and others

    1997-12-31

    In January of 1994, the Department of Energy mandated the termination of the Integral Fast Reactor (IFR) Program, effective October 1, 1994. To comply with this decision, Argonne National Laboratory-West (ANL-W) prepared a plan providing detailed requirements to place the Experimental Breeder Reactor-II (EBR-II) in a radiologically and industrially safe condition, including removal of all irradiated fuel assemblies from the reactor plant, and removal and stabilization of the primary and secondary sodium, a liquid metal used to transfer heat within the reactor plant. The ultimate goal of the deactivation process is to place the EBR-II complex in a stable condition until a decontamination and decommissioning (D&D) plan can be prepared, thereby minimizing requirements for maintenance and surveillance and maximizing the amount of time for radioactive decay. The final closure state will be achieved in full compliance with federal, state and local environmental, safety, and health regulations and requirements. The decision to delay the development of a detailed D&D plan has necessitated this current action. The EBR-II is a pool-type reactor. The primary system contains approximately 87,000 gallons of sodium, while the secondary system has 13,000 gallons. In order to properly dispose of the sodium in compliance with the Resource Conservation and Recovery Act (RCRA), a facility has been built to react the sodium to a dry carbonate powder in a two stage process. Deactivation of a liquid metal fast breeder reactor (LMFBR) presents unique concerns. Residual amounts of sodium remaining in the primary and secondary systems must be either reacted or inerted to preclude future concerns with sodium-air reactions that generate explosive mixtures of hydrogen and leave corrosive compounds. Residual amounts of sodium on components will effectively {open_quotes}solder{close_quotes} components in place, making future operation or removal unfeasible.

  2. Deactivation of the EBR-II complex

    International Nuclear Information System (INIS)

    Michelbacher, J.A.; Earle, O.K.; Henslee, S.P.

    1997-01-01

    In January of 1994, the Department of Energy mandated the termination of the Integral Fast Reactor (IFR) Program, effective October 1, 1994. To comply with this decision, Argonne National Laboratory-West (ANL-W) prepared a plan providing detailed requirements to place the Experimental Breeder Reactor-II (EBR-II) in a radiologically and industrially safe condition, including removal of all irradiated fuel assemblies from the reactor plant, and removal and stabilization of the primary and secondary sodium, a liquid metal used to transfer heat within the reactor plant. The ultimate goal of the deactivation process is to place the EBR-II complex in a stable condition until a decontamination and decommissioning (D ampersand D) plan can be prepared, thereby minimizing requirements for maintenance and surveillance and maximizing the amount of time for radioactive decay. The final closure state will be achieved in full compliance with federal, state and local environmental, safety, and health regulations and requirements. The decision to delay the development of a detailed D ampersand D plan has necessitated this current action. The EBR-II is a pool-type reactor. The primary system contains approximately 87,000 gallons of sodium, while the secondary system has 13,000 gallons. In order to properly dispose of the sodium in compliance with the Resource Conservation and Recovery Act (RCRA), a facility has been built to react the sodium to a dry carbonate powder in a two stage process. Deactivation of a liquid metal fast breeder reactor (LMFBR) presents unique concerns. Residual amounts of sodium remaining in the primary and secondary systems must be either reacted or inerted to preclude future concerns with sodium-air reactions that generate explosive mixtures of hydrogen and leave corrosive compounds. Residual amounts of sodium on components will effectively open-quotes solderclose quotes components in place, making future operation or removal unfeasible

  3. Stark effect measurements on monomers and trimers of reconstituted light-harvesting complex II of plants

    NARCIS (Netherlands)

    Palacios, M.A.; Caffarri, S.; Bassi, R.; Grondelle, van R.; Amerongen, van H.

    2004-01-01

    The electric-field induced absorption changes (Stark effect) of reconstituted light-harvesting complex II (LHCII) in different oligomerisation states - monomers and trimers - with different xanthophyll content have been probed at 77 K. The Stark spectra of the reconstituted control samples,

  4. The xanthophylls in light-harvesting complex II of higher plants: light harvesting and triplet quenching.

    NARCIS (Netherlands)

    Peterman, E.J.G.; Gradinaru, C.C.; Calkoen, F.; Borst, J.C.; van Grondelle, R.; van Amerongen, H.

    1997-01-01

    A spectral and functional assignment of the xanthophylls in monomeric and trimeric light-harvesting complex II of green plants has been obtained using HPLC analysis of the pigment composition, laser-flash induced triplet- minus-singlet, fluorescence excitation, and absorption spectra. It is shown

  5. Measurements of Narrow Mg II Associated Absorption Doublets with ...

    Indian Academy of Sciences (India)

    time is a good method to study the physical conditions of absorbers. In this paper ... The intervening absorption systems are often believed to be associated with the galaxies ... that about 30% intrinsic NALs are variable to some unspecified level. Although ..... This model is supported by some recent studies on the BAL vari-.

  6. Experimental broadband absorption enhancement in silicon nanohole structures with optimized complex unit cells.

    Science.gov (United States)

    Lin, Chenxi; Martínez, Luis Javier; Povinelli, Michelle L

    2013-09-09

    We design silicon membranes with nanohole structures with optimized complex unit cells that maximize broadband absorption. We fabricate the optimized design and measure the optical absorption. We demonstrate an experimental broadband absorption about 3.5 times higher than an equally-thick thin film.

  7. Synthesis, characterization and thermal studies of nickel (II), copper (II), zinc (II) and cadmium (II) complexes with some mixed ligands

    International Nuclear Information System (INIS)

    Mitra, Samiran; Kundu, Parimal; Singh, Rajkumar Bhubon

    1998-01-01

    Dichloro-(DCA) and trichloroacetate(TCA) -cyclic ligand morpholine (Morph)/thiomorpholine (Tmorph)/methylmorpholine (Mmorph)/dimethyl-piperazine (DMP) complexes of nickel (II), copper (II), zinc (II) and cadmium (II) with the compositions [Ni(tmorph) 2 (DCA) 2 ], [Ni(tmorph) 2 (TCA) 2 ].2H 2 O, [Cu(DMP) 2 (TCA) 2 ],[ML 2 X 2 ].nH 2 O where M=Zn II or Cd II , L=Morph, DMP or tmorph and X=DCA or TCA and n=O except in case of [Cd (Morph) 2 (TCA) 2 ] where n=1 have been synthesised. Some intermediate complexes have been isolated by temperature arrest technique (pyrolysis) and characterised. Configurational and conformational changes have been studied by elemental analyses, IR and electronic spectra, magnetic moment data (in the case of Ni(II) and Cu(II) complexes) and thermal analysis. E a * , ΔH, and ΔS for the decomposition reaction of these complexes are evaluated and the stability of the complexes with respect to activation energy has also been compared. The linear correlation has been found between E a * and ΔS for the decomposition of the complexes. (author)

  8. DNA damage by the cobalt (II) and zinc (II) complexes of ...

    African Journals Online (AJOL)

    STORAGESEVER

    2008-09-03

    Sep 3, 2008 ... distributed in grade 3. The results indicated that Co(II)-L induced a relatively high level of DNA damage in comparison with the level of damage induced by Zn(II)-L. Key words: Tetraazamacrocycle Zn(II) complex, tetraazamacrocycle Co(II) complex, Tetrahymena thermophila, DNA damage, the comet assay.

  9. Effects of angiotensin II and ionomycin on fluid and bicarbonate absorption in the rat proximal tubule

    International Nuclear Information System (INIS)

    Chatsudthipong, V.; Chan, Y.L.

    1986-01-01

    Microperfusion of proximal convoluted tubule(PCT) and peritubular capillaries was performed to examine the effects of angiotensin II(Ang II) and ionomycin on fluid and bicarbonate absorption. Bicarbonate was determined by microcalorimetry and C-14 inulin was used as a volume marker. The rates of bicarbonate absorption (JHCO 3 ) was 143 peq/min x mm and fluid absorption(Jv) was 2.70 nl/min x mm, when PCT and capillary perfusate contained normal Ringer solution. Addition of Ang II (10 -6 M) to the capillary perfusate caused reductions of JHCO 3 and Jv by 35%. A similar effect was observed when ionomycin was added to the capillary perfusate. Ang II antagonist, (Sar 1 , Ile 8 )-Angiotensin II(10 -6 M), completely blocked the inhibitory effect of Ang II on Jv and JHCO 3 . Removal of calcium from both luminal and capillary perfusate did not change the effect of Ang II on Jv and JHCO 3 . Our results indicate that Ang II inhibits the sodium-hydrogen exchanger in the proximal tubule via interacting with angiotensin receptor. The mechanism of Ang II action may involve mobilization of intracellular calcium

  10. Density of phonon states in the light-harvesting complex II of green plants

    CERN Document Server

    Pieper, J K; Irrgang, K D; Renger, G

    2002-01-01

    In photosynthetic antenna complexes, the coupling of electronic transitions to low-frequency vibrations of the protein matrix (phonons) plays an essential role in light absorption and ultra-fast excitation energy transfer (EET). The model calculations presented here indicate that inelastic neutron scattering experiments provide invaluable information on the phonon density of states for light-harvesting complex II, which may permit a consistent interpretation of contradictory results from high-resolution optical spectroscopy. (orig.)

  11. Cloud point extraction and flame atomic absorption spectrometric determination of cadmium(II), lead(II), palladium(II) and silver(I) in environmental samples

    Energy Technology Data Exchange (ETDEWEB)

    Ghaedi, Mehrorang, E-mail: m_ghaedi@mail.yu.ac.ir [Chemistry Department, Yasouj University, Yasouj 75914-353 (Iran, Islamic Republic of); Shokrollahi, Ardeshir [Chemistry Department, Yasouj University, Yasouj 75914-353 (Iran, Islamic Republic of); Niknam, Khodabakhsh [Chemistry Department, Persian Gulf University, Bushehr (Iran, Islamic Republic of); Niknam, Ebrahim; Najibi, Asma [Chemistry Department, Yasouj University, Yasouj 75914-353 (Iran, Islamic Republic of); Soylak, Mustafa [Chemistry Department, University of Erciyes, 38039 Kayseri (Turkey)

    2009-09-15

    The phase-separation phenomenon of non-ionic surfactants occurring in aqueous solution was used for the extraction of cadmium(II), lead(II), palladium(II) and silver(I). The analytical procedure involved the formation of understudy metals complex with bis((1H-benzo [d] imidazol-2yl)ethyl) sulfane (BIES), and quantitatively extracted to the phase rich in octylphenoxypolyethoxyethanol (Triton X-114) after centrifugation. Methanol acidified with 1 mol L{sup -1} HNO{sub 3} was added to the surfactant-rich phase prior to its analysis by flame atomic absorption spectrometry (FAAS). The concentration of BIES, pH and amount of surfactant (Triton X-114) was optimized. At optimum conditions, the detection limits of (3 sdb/m) of 1.4, 2.8, 1.6 and 1.4 ng mL{sup -1} for Cd{sup 2+}, Pb{sup 2+}, Pd{sup 2+} and Ag{sup +} along with preconcentration factors of 30 and enrichment factors of 48, 39, 32 and 42 for Cd{sup 2+}, Pb{sup 2+}, Pd{sup 2+} and Ag{sup +}, respectively, were obtained. The proposed cloud point extraction has been successfully applied for the determination of metal ions in real samples with complicated matrix such as radiology waste, vegetable, blood and urine samples.

  12. Cloud point extraction and flame atomic absorption spectrometric determination of cadmium(II), lead(II), palladium(II) and silver(I) in environmental samples

    International Nuclear Information System (INIS)

    Ghaedi, Mehrorang; Shokrollahi, Ardeshir; Niknam, Khodabakhsh; Niknam, Ebrahim; Najibi, Asma; Soylak, Mustafa

    2009-01-01

    The phase-separation phenomenon of non-ionic surfactants occurring in aqueous solution was used for the extraction of cadmium(II), lead(II), palladium(II) and silver(I). The analytical procedure involved the formation of understudy metals complex with bis((1H-benzo [d] imidazol-2yl)ethyl) sulfane (BIES), and quantitatively extracted to the phase rich in octylphenoxypolyethoxyethanol (Triton X-114) after centrifugation. Methanol acidified with 1 mol L -1 HNO 3 was added to the surfactant-rich phase prior to its analysis by flame atomic absorption spectrometry (FAAS). The concentration of BIES, pH and amount of surfactant (Triton X-114) was optimized. At optimum conditions, the detection limits of (3 sdb/m) of 1.4, 2.8, 1.6 and 1.4 ng mL -1 for Cd 2+ , Pb 2+ , Pd 2+ and Ag + along with preconcentration factors of 30 and enrichment factors of 48, 39, 32 and 42 for Cd 2+ , Pb 2+ , Pd 2+ and Ag + , respectively, were obtained. The proposed cloud point extraction has been successfully applied for the determination of metal ions in real samples with complicated matrix such as radiology waste, vegetable, blood and urine samples.

  13. Synthesis and spectroscopic studies of biologically active tetraazamacrocyclic complexes of Mn(II, Co(II, Ni(II, Pd(II and Pt(II

    Directory of Open Access Journals (Sweden)

    Monika Tyagi

    2014-01-01

    Full Text Available Complexes of Mn(II, Co(II, Ni(II, Pd(II and Pt(II were synthesized with the macrocyclic ligand, i.e., 2,3,9,10-tetraketo-1,4,8,11-tetraazacycoletradecane. The ligand was prepared by the [2 + 2] condensation of diethyloxalate and 1,3-diamino propane and characterized by elemental analysis, mass, IR and 1H NMR spectral studies. All the complexes were characterized by elemental analysis, molar conductance, magnetic susceptibility measurements, IR, electronic and electron paramagnetic resonance spectral studies. The molar conductance measurements of Mn(II, Co(II and Ni(II complexes in DMF correspond to non electrolyte nature, whereas Pd(II and Pt(II complexes are 1:2 electrolyte. On the basis of spectral studies an octahedral geometry has been assigned for Mn(II, Co(II and Ni(II complexes, whereas square planar geometry assigned for Pd(II and Pt(II. In vitro the ligand and its metal complexes were evaluated against plant pathogenic fungi (Fusarium odum, Aspergillus niger and Rhizoctonia bataticola and some compounds found to be more active as commercially available fungicide like Chlorothalonil.

  14. Photocleavage of DNA by copper(II) complexes

    Indian Academy of Sciences (India)

    The chemistry of ternary and binary copper(II) complexes showing efficient visible lightinduced DNA cleavage activity is summarized in this article. The role of the metal in photo-induced DNA cleavage reactions is explored by designing complex molecules having a variety of ligands. Ternary copper(II) complexes with amino ...

  15. Unsymmetrical Mesoporphyrinic Complexes of Copper (II and Zinc (II. Microwave-Assisted Synthesis, Spectral Characterization and Cytotoxicity Evaluation

    Directory of Open Access Journals (Sweden)

    Rica Boscencu

    2011-06-01

    Full Text Available New unsymmetrical mesoporphyrinic complexes, namely 5-(4-hydroxyphenyl-10,15,20–tris-(4-carboxymethylphenyl–21,23-Zn(II-porphine and 5-(4-hydroxyphenyl-10,15,20–tris-(4-carboxymethylphenyl–21,23-Cu(II-porphine, were synthesized using a microwave irradiation method. The structures of the porphyrinic complexes were confirmed using FT-IR, UV–Vis, EPR and NMR spectral data. The spectral absorption and emission properties of the porphyrinic complexes were studied in organic solvents of different polarities and the influence of solvent polarity on the wavelengths of the absorbance and fluorescence band maxima is described. The cytotoxicity evaluation of the porphyrinic complexes was performed on human colon adenocarcinoma cell line HT29 for different doses and incubation times. The obtained result indicates a lack of or low toxicity for both compounds, thus recommending them for further testing in light activation protocols.

  16. Determination of cobalt(II) and nickel(II) with isoamylxanthate as a complexing reagent in micellar media

    International Nuclear Information System (INIS)

    Shar, G.A.; Soomro, G.A.

    2008-01-01

    Cobalt(II) and nickel(II) were determined spectrophotometrically using sodium isoamyl xanthate as a complexing reagent in aqueous phase in the presence of anionic surfactant sodium dodecylsulphate (SDS). Beer's law was obeyed for Co(ll) and Ni(ll) over the concentration range 3.0-35 and 2.0-37 micro gmL/sup -1/ respectively. The lambda/sub max/ molar absorptivity and Sandell's sensitivity of Co(ll) and Ni(ll) were 360 nm and 416 nm; is 0.19 and 0.2 (x 10/sup 4/ mol/sup -1/ cm/sup -1/) 31.1 and 29.3 ng cm/sup -2/ respectively. Maximum absorbance at 1:2 (M: L) molar ratio suggested the formation of M(C/sub 6/H/sub 11/ OS/sub 2/)/sub 2/ where M = Co(II) and Ni(II). The complex remained stable for more than 2 h. The optimized reagent concentration 0.5% was used throughout the study. Surfactant concentration of 1.0% SDS caused significant enhancement in absorbance. Maximum absorption was observed at 360 nm and 416 nm for Co and Ni complexes, respectively. The absorption maxima were obtained at optimized pH of 7.0. Validation of method has been made by comparing the results with Atomic Absorption Spectrometry, no significant difference was obtained between the two methods at 95% confidence interval. The method is simple, accurate, economical and has been applied to the determination of cobalt(ll) and nickel(ll) in industrial wastewater, pharmaceutical and edible oil samples. (author)

  17. Laser absorption spectroscopy - Method for monitoring complex trace gas mixtures

    Science.gov (United States)

    Green, B. D.; Steinfeld, J. I.

    1976-01-01

    A frequency stabilized CO2 laser was used for accurate determinations of the absorption coefficients of various gases in the wavelength region from 9 to 11 microns. The gases investigated were representative of the types of contaminants expected to build up in recycled atmospheres. These absorption coefficients were then used in determining the presence and amount of the gases in prepared mixtures. The effect of interferences on the minimum detectable concentration of the gases was measured. The accuracies of various methods of solution were also evaluated.

  18. DNA damage by the cobalt (II) and zinc (II) complexes of ...

    African Journals Online (AJOL)

    Using the single cell gel electrophoresis method, the tetraazamacrocycle Zn(II) complex (Zn(II)-L) and the tetraazamacrocycle Co(II) complex (Co(II)-L) were investigated focusing on their DNA damage to Tetrahymena thermophila. When the cells were treated with the 0.05, 0.25 and 0.50 mg/ml Zn(II)-L, the tail length ...

  19. Optical absorption of copper met-myoglobin complexes

    International Nuclear Information System (INIS)

    Lamy, M.T.; Ribeiro, P.C.; Nascimento, O.R.; Bemski, G.

    1976-01-01

    It is reported on the use of a known denaturing agent, namely Cu 2+ ions, to induce a gradual change in the optical spectrum of Mb solutions, in order to identify the absorption bands that undergo similar changes which may be attributed to the transitions between correlated energy levels [pt

  20. The Associated Absorption Features in Quasar Spectra of the Sloan Digital Sky Survey. I. Mg II Absorption Doublets

    Science.gov (United States)

    Chen, Zhi-Fu; Huang, Wei-Rong; Pang, Ting-Ting; Huang, Hong-Yan; Pan, Da-Sheng; Yao, Min; Nong, Wei-Jing; Lu, Mei-Mei

    2018-03-01

    Using the SDSS spectra of quasars included in the DR7Q or DR12Q catalogs, we search for Mg II λλ2796, 2803 narrow absorption doublets in the spectra data around Mg II λ2798 emission lines. We obtain 17,316 Mg II doublets, within the redshift range of 0.3299 ≤ z abs ≤ 2.5663. We find that a velocity offset of υ r 6000 km s‑1. If associated Mg II absorbers are defined by υ r present at least one associated Mg II system with {W}{{r}}λ 2796≥slant 0.2 \\mathringA . The fraction of associated Mg II systems with high-velocity outflows correlates with the average luminosities of their central quasars, indicating a relationship between outflows and the quasar feedback power. The υ r distribution of the outflow Mg II absorbers is peaked at 1023 km s‑1, which is smaller than the corresponding value of the outflow C IV absorbers. The redshift number density evolution of absorbers (dn/dz) limited by υ r > ‑3000 km s‑1 differs from that of absorbers constrained by υ r > 2000 km s‑1. Absorbers limited by υ r > 2000 km s‑1 and higher values exhibit profiles similar to dn/dz. In addition, the dn/dz is smaller when absorbers are constrained with larger υ r . The distributions of equivalent widths, and the ratio of {W}rλ 2796/{W}rλ 2803, are the same for associated and intervening systems, and independent of quasar luminosity.

  1. Preparation and Spectral Properties of Mixed-Ligand Complexes of VO(IV, Ni(II, Zn(II, Pd(II, Cd(II and Pb(II with Dimethylglyoxime and N-acetylglycine

    Directory of Open Access Journals (Sweden)

    Shayma A. Shaker

    2010-01-01

    Full Text Available A number of mixed-ligand complexes of the general formula [M(D(G] where D=dimethylglyoximato monoanion, G=N-acetylglycinato and M=VO(IV, Ni(II, Zn(II, Pd(II, Cd(II and Pb(II were prepared. Each complex was characterized by elemental analysis, determination of metal, infrared spectra, electronic spectra, (1H and 13C NMR spectra, conductivity and magnetic moments. All these complexes were not soluble in some of the organic solvent but highly soluble in dimethylformamide. The conductivity data showed the non-electrolytic nature of the complexes. The electronic spectra exhibited absorption bands in the visible region caused by the d-d electronic transition such as VO(IV, Ni(II and Pd(II. The IR and (1H, 13C NMR spectra which have indicate that the dimethylglyoxime was coordinated with the metal ions through the N and O atoms of the oxime group and N-acetylglycine was coordinated with metal ions through the N atom and terminal carboxyl oxygen atom.

  2. EXAFS Studies of Some Copper(II) Mixed-Ligand Complexes

    International Nuclear Information System (INIS)

    Joshi, S. K.; Katare, R. K.; Shrivastava, B. D.

    2007-01-01

    X-ray K-absorption spectroscopic studies have been carried out on copper (II) mixed-ligand complexes with glutamic acid and aspartic acid as the primary ligands, where as water, pyridine, imidazole and benz-imidazole have been used as secondary ligands. Chemical shifts obtained from the X-ray absorption data have indicated that the glutamic acid complexes are more ionic as compared to their corresponding aspartic acid complexes having similar secondary ligands. Further, we have estimated the average metal-ligand bond distances from the from structure data. For the different complexes studied under the present investigation, the studies reveal that the bonding parameter α1 decreases with the increase in the percentage covalency of the metal-ligand bond. Thus, the bonding parameter α1 may be used for the estimation of percentage covalency of the metal-ligand bond in other similar complexes

  3. Redox reactions of Cu(II)-amine complexes in aqueous solutions

    International Nuclear Information System (INIS)

    Kumbhar, A.G.; Kishore, Kamal

    2003-01-01

    A number of amines can be employed for all volatile treatment (AVT) of steam generator (SG) systems of nuclear power reactors. These amines form complexes with Cu 2+ and Ni 2+ ions which come into water due to corrosion. The redox reactions of a number of Cu(II)-AVT amine complexes and the stability of the transient species formed have been studied by pulse radiolysis technique. Rate constants for the reaction of e aq - with a number of Cu(II)-amine complexes have been determined by following the decay of e aq - absorption. Stability of Cu(I)-amine complexes was studied by following the kinetics of the bleaching signal formed at the λ max of the Cu(II) amine complex. Except for Cu(I)-triethanolamine complex all other Cu(I)-amine complexes were found to be stable. One-electron oxidation of Cu(II) amine complexes was studied using azidyl radicals for the oxidation reaction as OH radicals react with the alcohol groups present in the amines used in this study. Cu(III)-amine complexes were found to be unstable and decayed by second-order kinetics

  4. Transition metal M(II complexes with isonicotinoylhydrazone-9-anthraldehyde

    Directory of Open Access Journals (Sweden)

    Dianu M.L.

    2010-01-01

    Full Text Available New complexes of isonicotinoylhydrazone-9-anthraldehyde with Cu(II, Co(II and Ni(II have been prepared and characterized by analytical and physico-chemical techniques, such as elemental and thermal analyses, magnetic susceptibility and conductivity measurements, and electronic, EPR and IR spectral studies. The infrared spectral studies revealed the bidentate or monodentate nature of the Schiff base in the complexes; the pyridine nitrogen does not participate in the coordination. A tetrahedral geometry is suggested for the nitrate-complexes and an octahedral geometry for the others. Thermal studies support the chemical formulation of these complexes.

  5. Antibacterial, antimalarial and leishmanicidal activities of Cu (II) and nickel (II) complexes of diclofenac sodium

    International Nuclear Information System (INIS)

    Rehman, F.U.; Khan, M.F.; Khan, G.M.; Khan, H.; Khan, I.U.

    2010-01-01

    Metal complexes are famous for a wide array of chemotherapeutic effects. The current study was designed to synthesize and evaluate unexplored chemotherapeutic effects of Cu (II) and Nickel (II) complexes of the non-steroidal anti-inflammatory drug diclofenac. Nickel complex exhibited significant leishmanicidal activity against Lieshmania major, while the copper complex was found to possess low activity against the same pathogen. Both of the complexes revealed low antibacterial activities and were interestingly failed to produce any considerable antimalarial activity against Plasmodium falciparum 3D7. Selective leishmanicidal activities of Nickel (II) complex of diclofenac needs further improvement to be developed as potential new metal-based leishmanicidal agent.(author)

  6. Antibacterial, antimalarial and leishmanicidal activities of Cu (II) and nickel (II) complexes of diclofenac sodium

    Energy Technology Data Exchange (ETDEWEB)

    Rehman, F U; Khan, M F; Khan, G M; Khan, H [Gomal University, D.I. Khan (Pakistan). Dept. of Faculty of Pharmacy; Khan, I U [University of Peshawar (Pakistan). Dept. of Faculty of Pharmacy

    2010-08-15

    Metal complexes are famous for a wide array of chemotherapeutic effects. The current study was designed to synthesize and evaluate unexplored chemotherapeutic effects of Cu (II) and Nickel (II) complexes of the non-steroidal anti-inflammatory drug diclofenac. Nickel complex exhibited significant leishmanicidal activity against Lieshmania major, while the copper complex was found to possess low activity against the same pathogen. Both of the complexes revealed low antibacterial activities and were interestingly failed to produce any considerable antimalarial activity against Plasmodium falciparum 3D7. Selective leishmanicidal activities of Nickel (II) complex of diclofenac needs further improvement to be developed as potential new metal-based leishmanicidal agent.(author)

  7. DNA-Binding Studies of Some Potential Antitumor 2,2'-bipyridine Pt(II)/Pd(II) Complexes of piperidinedithiocarbamate. Their Synthesis, Spectroscopy and Cytotoxicity.

    Science.gov (United States)

    Mansouri-Torshizi, Hassan; Eslami-Moghadam, Mahboube; Divsalar, Adeleh; Saboury, Ali-Akbar

    2011-12-01

    In this study two platinum(II) and palladium(II) complexes of the type [M(bpy)(pip-dtc)]NO3 (where M=Pt(II) or Pd(II), bpy=2,2'-bipyridine, pip-dtc=piperidinedithiocarbamate) were synthesized by reaction between diaquo-2,2'-bipyridine Pt(II)/Pd(II) nitrate and sodium salt of dithiocarbamate. These cationic water soluble complexes were characterized by elemental analysis, molar conductance, IR, electronic and 1H NMR spectroscopic studies. The cyclic dithiocarbamate was found to coordinate as bidentate fasion with Pt(II) or Pd(II) center. Their biological activities were tested against chronic myelogenous leukemia cell line, K562, at micromolar concentration. The obtained cytotoxic concentration (IC50) values were much lower than cisplatin. The interaction of these complexes with highly polymerized calf thymus DNA (ct-DNA) was extensively studied by means of electronic absorption, fluorescence, circular dichroism and other measurements. The experimental results, thermodynamic and binding parameters, suggested that these complexes cooperatively bind to DNA presumably via intercalation. Moreover, the tendency of the Pt(II) complex to interact with DNA was more than that of Pd(II) complex.

  8. A rapidly-reversible absorptive and emissive vapochromic Pt(II) pincer-based chemical sensor.

    Science.gov (United States)

    Bryant, M J; Skelton, J M; Hatcher, L E; Stubbs, C; Madrid, E; Pallipurath, A R; Thomas, L H; Woodall, C H; Christensen, J; Fuertes, S; Robinson, T P; Beavers, C M; Teat, S J; Warren, M R; Pradaux-Caggiano, F; Walsh, A; Marken, F; Carbery, D R; Parker, S C; McKeown, N B; Malpass-Evans, R; Carta, M; Raithby, P R

    2017-11-27

    Selective, robust and cost-effective chemical sensors for detecting small volatile-organic compounds (VOCs) have widespread applications in industry, healthcare and environmental monitoring. Here we design a Pt(II) pincer-type material with selective absorptive and emissive responses to methanol and water. The yellow anhydrous form converts reversibly on a subsecond timescale to a red hydrate in the presence of parts-per-thousand levels of atmospheric water vapour. Exposure to methanol induces a similarly-rapid and reversible colour change to a blue methanol solvate. Stable smart coatings on glass demonstrate robust switching over 10 4 cycles, and flexible microporous polymer membranes incorporating microcrystals of the complex show identical vapochromic behaviour. The rapid vapochromic response can be rationalised from the crystal structure, and in combination with quantum-chemical modelling, we provide a complete microscopic picture of the switching mechanism. We discuss how this multiscale design approach can be used to obtain new compounds with tailored VOC selectivity and spectral responses.

  9. Electron transfer reactions of ruthenium(II) complexes with polyphenolic acids in micelles

    Energy Technology Data Exchange (ETDEWEB)

    Rajeswari, Angusamy [School of Chemistry, Madurai Kamaraj University, Madurai 625 021 (India); Department of Chemistry, Fatima College, Madurai 625 018 (India); Ramdass, Arumugam [School of Chemistry, Madurai Kamaraj University, Madurai 625 021 (India); Research Department of Chemistry, Aditanar College of Arts and Science, Tiruchendur 628 216 (India); Muthu Mareeswaran, Paulpandian [School of Chemistry, Madurai Kamaraj University, Madurai 625 021 (India); Department of Industrial Chemistry, Alagappa University, Karaikudi 630 003 (India); Rajagopal, Seenivasan, E-mail: rajagopalseenivasan@yahoo.com [School of Chemistry, Madurai Kamaraj University, Madurai 625 021 (India)

    2016-02-15

    The electron transfer in a microhetrogeneous system is a perfect mimic of biological electron transfer. The electron transfer between biologically important phenolic acids and ruthenium (II) complexes is systematically studied in the presence of anionic and cationic micelles. The photophysical properties of these ruthenium (II) complexes with anionic and cationic micelles and their binding abilities with these two type of micelles are also studies using absorption, emission and excited state lifetime spectral techniques. Pseudophase Ion Exchange (PIE) Model is applied to derive mechanism of electron transfer in two types of micelles. - Highlights: • Effect of microhetrogeneous system is studied using ruthenium (II) complexes and gallic acid is studied. • Pseudophase Ion exchange model is applied to derive the mechanism. • Binding constants are in the range of 10{sup 2}–10{sup 4} M{sup −1}.

  10. Metalloantibiotic Mn(II)-bacitracin complex mimicking manganese superoxide dismutase

    International Nuclear Information System (INIS)

    Piacham, Theeraphon; Isarankura-Na-Ayudhya, Chartchalerm; Nantasenamat, Chanin; Yainoy, Sakda; Ye Lei; Buelow, Leif; Prachayasittikul, Virapong

    2006-01-01

    Superoxide dismutase (SOD) activities of various metallobacitracin complexes were evaluated using the riboflavin-methionine-nitro blue tetrazolium assay. The radical scavenging activity of various metallobacitracin complexes was shown to be higher than those of the negative controls, e.g., free transition metal ions and metal-free bacitracin. The SOD activity of the complex was found to be in the order of Mn(II) > Cu(II) > Co(II) > Ni(II). Furthermore, the effect of bacitracin and their complexation to metals on various microorganisms was assessed by antibiotic susceptibility testing. Moreover, molecular modeling and quantum chemical calculation of the metallobacitracin complex was performed to evaluate the correlation of electrostatic charge of transition metal ions on the SOD activity

  11. Solid Phase Extraction of Trace Al(III), Fe(II), Co(II), Cu(II), Cd(II) and Pb(II) Ions in Beverages on Functionalized Polymer Microspheres Prior to Flame Atomic Absorption Spectrometric Determinations.

    Science.gov (United States)

    Berber, Hale; Alpdogan, Güzin

    2017-01-01

    In this study, poly(glycidyl methacrylate-methyl methacrylate-divinylbenzene) was synthesized in the form of microspheres, and then functionalized by 2-aminobenzothiazole ligand. The sorption properties of these functionalized microspheres were investigated for separation, preconcentration and determination of Al(III), Fe(II), Co(II), Cu(II), Cd(II) and Pb(II) ions using flame atomic absorption spectrometry. The optimum pH values for quantitative sorption were 2 - 4, 5 - 8, 6 - 8, 4 - 6, 2 - 6 and 2 - 3 for Al(III), Fe(II), Co(II), Cu(II), Cd(II) and Pb(II), respectively, and also the highest sorption capacity of the functionalized microspheres was found to be for Cu(II) with the value of 1.87 mmol g -1 . The detection limits (3σ; N = 6) obtained for the studied metals in the optimal conditions were observed in the range of 0.26 - 2.20 μg L -1 . The proposed method was successfully applied to different beverage samples for the determination of Al(III), Fe(II), Co(II), Cu(II), Cd(II) and Pb(II) ions, with the relative standard deviation of <3.7%.

  12. A comparative investigation on absorption performances of three expanded graphite-based complex materials for toluene

    International Nuclear Information System (INIS)

    Li Shande; Tian Shuanghong; Feng Yunfeng; Lei Jiajia; Wang, Piaopiao; Xiong Ya

    2010-01-01

    Three kinds of expanded graphite-based complex materials were prepared to absorb toluene by dispersing plant oil, animal oil and mineral oil on the surface of expanded graphite, respectively. These complex materials were characterized by scanning electronic micrograph, contact angle meter and Brunauer-Emmett-Teller surface area. And their absorption capacities for toluene were comparatively investigated. The results showed that the surfaces of the three types of sorbents were very hydrophobic and nonporous, but they all had excellent absorption capacities for toluene. And their absorption capacities were proportional to the toluene concentration in streams and decreased differently with increasing the absorption temperature. It was noteworthy that the absorption capacities varied with the unsaturated degree of the complex materials and kept unchanged under different relative humidities of streams. Moreover, the regeneration experiments showed that after 15-run regeneration the absorption capacities of expanded graphite modified by mineral oil almost kept unchanged, while that of expanded graphite loaded plant oil and animal oil dropped by 157 and 93.6 mg g -1 , respectively. The losses of their absorption capacities were ascribed to the destruction of their unsaturated carbon bounds.

  13. Interaction of Cr (III), Ni (II), Pb (II) with DTPA complexes of essential metal ions

    International Nuclear Information System (INIS)

    Gulzar, S.; Zahida; Maqsood, T.; Naqvi, R.R.

    2002-01-01

    With the increase of anthropogenic activities in the environment, heavy metal toxicity (Chromium, Nickel and Lead) is more common now. DTPA (diethylene triamine pentaacetic acid) a polyamino carboxylic acid is widely used to form hydrophilic and stable complexes with most of the metal ions. In this spectrophotometric study, concentration of Cr(III), Ni(II) and Pb(II) (toxic metal ions) exchanged with Fe(III), Zn(II) and Ca(II) from their DTPA complexes were estimated at pH 4,7 and 9. Concentration of added metal was varied from 1-4 times to that of complexed metal. (author)

  14. Photocleavage of DNA by copper(II) complexes

    Indian Academy of Sciences (India)

    Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore 560 012 e-mail: ... induced DNA cleavage activity is summarized in this article. ... per(II) complexes play important roles in DNA cleavage reactions.

  15. Ultrafast relaxation dynamics of amine-substituted bipyridyl ruthenium(II) complexes

    Science.gov (United States)

    Song, Hongwei; Wang, Xian; Yang, WenWen; He, Guiying; Kuang, Zhuoran; Li, Yang; Xia, Andong; Zhong, Yu-Wu; Kong, Fan'ao

    2017-09-01

    The excited state properties of a series of ruthenium(II) amine-substituted bipyridyl complexes, [Ru(bpy)n(NNbpy)3-n]2+, were investigated by steady-state and transient absorption spectroscopy, as well as quantum chemical calculations. The steady-state absorption spectra of these complexes in CH3CN show a distinct red-shift of the 1MLCT absorption with increasing numbers of amine substituent, whereas the emission spectra indicate an energy gap order of [Ru(bpy)3]2+ > [Ru(bpy)2(NNbpy)]2+ > [Ru(NNbpy)3]2+ > [Ru(bpy)(NNbpy)2]2+. Nanosecond, femtosecond transient absorption and electrochemical measurements suggest that NNbpy ligand has a strong influence on the electronic and emission properties of these complexes, due to electron-rich amine substituent. We illustrate how the numbers of amine substituent modulate the spectroscopic properties of transition metal complexes, which is related to the design of new electro-active systems with novel photoelectrochemical properties.

  16. Synthesis, structural characterization and cytotoxic activity of two new organoruthenium(II complexes

    Directory of Open Access Journals (Sweden)

    SANJA GRGURIC-SIPKA

    2008-06-01

    Full Text Available Two new p-cymene ruthenium(II complexes containing as additional ligands N-methylpiperazine ([(η6-p-cymeneRuCl2(CH3NH(CH24NH]PF6, complex 1 or vitamin K3-thiosemicarbazone ([(η6-p-cymeneRuCl2(K3tsc], complex 2 were synthesized starting from [(η6-p-cymene2RuCl2]2 and the corresponding ligand. The complexes were characterized by elemental analysis, IR, electronic absorption and NMR spectroscopy. The X-ray crystal structure determination of complex 1 revealed “piano-stool” geometry. The differences in the cytotoxic activity of the two complexes are discussed in terms of the ligand present.

  17. Antimalarial, antimicrobial, cytotoxic, DNA interaction and SOD like activities of tetrahedral copper(II) complexes

    Science.gov (United States)

    Mehta, Jugal V.; Gajera, Sanjay B.; Patel, Mohan N.

    2015-02-01

    The mononuclear copper(II) complexes with P, O-donor ligand and different fluoroquinolones have been synthesized and characterized by elemental analysis, electronic spectra, TGA, EPR, FT-IR and LC-MS spectroscopy. An antimicrobial efficiency of the complexes has been tested against five different microorganisms in terms of minimum inhibitory concentration (MIC) and displays very good antimicrobial activity. The binding strength and binding mode of the complexes with Herring Sperm DNA (HS DNA) have been investigated by absorption titration and viscosity measurement studies. The studies suggest the classical intercalative mode of DNA binding. Gel electrophoresis assay determines the ability of the complexes to cleave the supercoiled form of pUC19 DNA. Synthesized complexes have been tested for their SOD mimic activity using nonenzymatic NBT/NADH/PMS system and found to have good antioxidant activity. All the complexes show good cytotoxic and in vitro antimalarial activities.

  18. Biophysical study on the interaction between two palladium(II) complexes and human serum albumin by Multispectroscopic methods

    Energy Technology Data Exchange (ETDEWEB)

    Saeidifar, Maryam, E-mail: saeidifar@merc.ac.ir [Department of Nanotechnology and Advanced Materials, Materials and Energy Research Center, Karaj (Iran, Islamic Republic of); Mansouri-Torshizi, Hassan [Department of Chemistry, University of Sistan and Baluchestan, Zahedan (Iran, Islamic Republic of); Akbar Saboury, Ali [Institute of Biochemistry and Biophysics, University of Tehran, Tehran (Iran, Islamic Republic of)

    2015-11-15

    The interaction of [Pd(bpy)(n-pr-dtc)]Br (I) and ([Pd(phen)(n-pr-dtc)]Br (II) (bpy=2,2′-bipyridine, phen=1,10-phenanthroline and n-pr-dtc=n-propyldithiocarbamate) with human serum albumin (HSA) was investigated using fluorescence, UV–vis absorption and circular dichroism (CD) spectroscopy techniques under simulative physiological conditions (pH=7.4). It was observed that the two complexes interact with HSA via static fluorescence quenching. The thermodynamic parameters indicate that the binding process was spontaneous and that hydrogen bonds and van der Waals forces play a major role in the association of the HSA–Pd(II) complexes. The activation energy (E{sub a}), binding constant (K{sub b}) and number of binding sites (n) of the HSA–Pd(II) complexes were calculated from fluorescence data at 293 K, 303 K and 311 K. The conformational alternations of protein secondary structure in the presence of Pd(II) complexes were demonstrated using synchronous fluorescence, three-dimensional fluorescence spectra, UV–vis absorption and circular dichroism techniques. Furthermore, the apparent distance between donor (HSA) and acceptor (Pd(II) complexes) was determined using fluorescence resonance energy transfer (FRET). The binding studies between these complexes and HSA give us key insights into the transportation, distribution and toxicity of newly design antitumor Pd(II) complexes in human blood. - Highlights: • The HSA binding properties of two Palladium (II) complexes were studied. • Static quenching mechanism is effective in the interaction of HSA with Pd(II) complexes. • Hydrogen bonds and van der Waals forces were involved in the Pd(II) complexes–HSA interaction. • 3D fluorescence was used to study the interaction between two complexes and HSA.

  19. TRACING OUTFLOWS AND ACCRETION: A BIMODAL AZIMUTHAL DEPENDENCE OF Mg II ABSORPTION

    Energy Technology Data Exchange (ETDEWEB)

    Kacprzak, Glenn G. [Swinburne University of Technology, Victoria 3122 (Australia); Churchill, Christopher W.; Nielsen, Nikole M., E-mail: gkacprzak@astro.swin.edu.au [New Mexico State University, Las Cruces, NM 88003 (United States)

    2012-11-20

    We report a bimodality in the azimuthal angle distribution of gas around galaxies as traced by Mg II absorption: halo gas prefers to exist near the projected galaxy major and minor axes. The bimodality is demonstrated by computing the mean azimuthal angle probability distribution function using 88 spectroscopically confirmed Mg II-absorption-selected galaxies [W{sub r} (2796) {>=} 0.1 A] and 35 spectroscopically confirmed non-absorbing galaxies [W{sub r} (2796) < 0.1 A] imaged with Hubble Space Telescope and Sloan Digital Sky Survey. The azimuthal angle distribution for non-absorbers is flat, indicating no azimuthal preference for gas characterized by W{sub r} (2796) < 0.1 A. We find that blue star-forming galaxies clearly drive the bimodality while red passive galaxies may exhibit an excess along their major axis. These results are consistent with galaxy evolution scenarios where star-forming galaxies accrete new gas, forming new stars and producing winds, while red galaxies exist passively due to reduced gas reservoirs. We further compute an azimuthal angle dependent Mg II absorption covering fraction, which is enhanced by as much as 20%-30% along the major and minor axes. The W{sub r} (2796) distribution for gas along the major axis is likely skewed toward weaker Mg II absorption than for gas along the projected minor axis. These combined results are highly suggestive that the bimodality is driven by gas accreted along the galaxy major axis and outflowing along the galaxy minor axis. Adopting these assumptions, we find that the opening angle of outflows and inflows to be 100 Degree-Sign and 40 Degree-Sign , respectively. We find that the probability of detecting outflows is {approx}60%, implying that winds are more commonly observed.

  20. TRACING OUTFLOWS AND ACCRETION: A BIMODAL AZIMUTHAL DEPENDENCE OF Mg II ABSORPTION

    International Nuclear Information System (INIS)

    Kacprzak, Glenn G.; Churchill, Christopher W.; Nielsen, Nikole M.

    2012-01-01

    We report a bimodality in the azimuthal angle distribution of gas around galaxies as traced by Mg II absorption: halo gas prefers to exist near the projected galaxy major and minor axes. The bimodality is demonstrated by computing the mean azimuthal angle probability distribution function using 88 spectroscopically confirmed Mg II-absorption-selected galaxies [W r (2796) ≥ 0.1 Å] and 35 spectroscopically confirmed non-absorbing galaxies [W r (2796) r (2796) r (2796) distribution for gas along the major axis is likely skewed toward weaker Mg II absorption than for gas along the projected minor axis. These combined results are highly suggestive that the bimodality is driven by gas accreted along the galaxy major axis and outflowing along the galaxy minor axis. Adopting these assumptions, we find that the opening angle of outflows and inflows to be 100° and 40°, respectively. We find that the probability of detecting outflows is ∼60%, implying that winds are more commonly observed.

  1. Bis(bipyridine)ruthenium(II) complexes with an aliphatic sulfinato donor: synthesis, characterization, and properties.

    Science.gov (United States)

    Tamura, Motoshi; Tsuge, Kiyoshi; Igashira-Kamiyama, Asako; Konno, Takumi

    2011-06-06

    Treatment of a thiolato-bridged Ru(II)Ag(I)Ru(II) trinuclear complex, [Ag{Ru(aet)(bpy)(2)}(2)](3+) (aet = 2-aminoethanthiolate; bpy = 2,2'-bipyridine), with NaI in aqueous ethanol under an aerobic condition afforded a mononuclear ruthenium(II) complex having an S-bonded sulfinato group, [1](+) ([Ru(aesi-N, S)(bpy)(2)](+) (aesi = 2-aminoethanesulfinate)). Similar treatment of optically active isomers of an analogous Ru(II)Ag(I)Ru(II) trinuclear complex, Δ(D)Δ(D)- and Λ(D)Λ(D)-[Ag{Ru(d-Hpen-O,S)(bpy)(2)}(2)](3+) (d-pen = d-penicillaminate), with NaI also produced mononuclear ruthenium(II) isomers with an S-bonded sulfinato group, Δ(D)- and Λ(D)-[2](+) ([Ru(d-Hpsi-O,S)(bpy)(2)](+) (d-psi = d-penicillaminesulfinate)), respectively, retaining the bidentate-O,S coordination mode of a d-Hpen ligand and the absolute configuration (Δ or Λ) about a Ru(II) center. On refluxing in water, the Δ(D) isomer of [2](+) underwent a linkage isomerization to form Δ(D)-[3] (+) ([Ru(d-Hpsi-N,S)(bpy)(2)](+)), in which a d-Hpsi ligand coordinates to a Ru(II) center in a bidentate-N,S mode. Complexes [1](+), Δ(D)- and Λ(D)-[2](+), and Δ(D)-[3](+) were fully characterized by electronic absorption, CD, NMR, and IR spectroscopies, together with single-crystal X-ray crystallography. The electrochemical properties of these complexes, which are highly dependent on the coordination mode of sulfinate ligands, are also described. © 2011 American Chemical Society

  2. Azobenzene Pd(II) complexes with N^N- and N^O-type ligands

    Science.gov (United States)

    Nikolaeva, M. V.; Puzyk, An. M.; Puzyk, M. V.

    2017-05-01

    Methods of synthesis of cyclometalated azobenzene palladium(II) complexes of [Pd(N^N)Azb]ClO4 and [Pd(N^O)Azb]ClO4 types (where Azb- is the deprotonated form of azobenzene; N^N is 2NH3, ethylenediamine, or 2,2'-bipyridine; and (N^O)- is the deprotonated form of amino acid (glycine, α-alanine, β-alanine, tyrosine, or tryptophan)) are developed. The electronic absorption and the electrochemical properties of these complexes are studied.

  3. Synthesis, molecular structure, biological properties and molecular docking studies on Mn(II), Co(II) and Zn(II) complexes containing bipyridine-azide ligands.

    Science.gov (United States)

    Thamilarasan, Vijayan; Jayamani, Arumugam; Sengottuvelan, Nallathambi

    2015-01-07

    Metal complexes of the type Mn(bpy)2(N3)2 (1), Co(bpy)2(N3)2·3H2O (2) and Zn2(bpy)2(N3)4 (3) (Where bpy = 2,2-bipyridine) have been synthesized and characterized by elemental analysis and spectral (FT-IR, UV-vis) studies. The structure of complexes (1-3) have been determined by single crystal X-ray diffraction studies and the configuration of ligand-coordinated metal(II) ion was well described as distorted octahedral coordination geometry for Mn(II), Co(II) and distorted square pyramidal geometry for Zn(II) complexes. DNA binding interaction of these complexes (1-3) were investigated by UV-vis absorption, fluorescence circular dichroism spectral and molecular docking studies. The intrinsic binding constants Kb of complexes 1, 2 and 3 with CT-DNA obtained from UV-vis absorption studies were 8.37 × 10(4), 2.23 × 10(5) and 5.52 × 10(4) M(-1) respectively. The results indicated that the three complexes are able to bind to DNA with different binding affinity, in the order 2 > 1 > 3. Complexes (1-3) exhibit a good binding propensity to bovine serum albumin (BSA) proteins having relatively high binding constant values. Gel electrophoresis assay demonstrated the ability of the complexes 1-3 promote the cleavage ability of the pBR322 plasmid DNA in the presence of the reducing agent 3-mercaptopropionic acid (MPA) but with different cleavage mechanisms: the complex 3 cleaves DNA via hydrolytic pathway (T4 DNA ligase assay), while the DNA cleavage by complexes 1 and 2 follows oxidative pathway. The chemical nuclease activity follows the order: 2 > 1 > 3. The effects of various activators were also investigated and the nuclease activity efficacy followed the order MPA > GSH > H2O2 > Asc. The cytotoxicity studies of complexes 1-3 were tested in vitro on breast cancer cell line (MCF-7) and they found to be active. Copyright © 2014. Published by Elsevier Masson SAS.

  4. DNA incision evaluation, binding investigation and biocidal screening of Cu(II), Ni(II) and Co(II) complexes with isoxazole Schiff bases.

    Science.gov (United States)

    Ganji, Nirmala; Chityala, Vijay Kumar; Marri, Pradeep Kumar; Aveli, Rambabu; Narendrula, Vamsikrishna; Daravath, Sreenu; Shivaraj

    2017-10-01

    Two new series of binary metal complexes [M(L 1 ) 2 ] and [M(L 2 ) 2 ] where, M=Cu(II), Ni(II) & Co(II) and L 1 =4-((3,4-dimethylisoxazol-5-ylimino)methyl)benzene-1,3-diol; L 2 =2-((3,4-dimethylisoxazol-5-ylimino)methyl)-5-methoxyphenol were synthesized and characterized by elemental analysis, 1 H NMR, 13 C NMR, FT-IR, ESI mass, UV-Visible, magnetic moment, ESR, SEM and powder XRD studies. Based on these results, a square planar geometry is assigned for all the metal complexes where the Schiff base acts as uninegatively charged bidentate chelating agent via the hydroxyl oxygen and azomethine nitrogen atoms. DNA binding studies of all the complexes with calf thymus DNA have been comprehensively investigated using electronic absorption spectroscopy, fluorescence quenching and viscosity studies. The oxidative and photo cleavage affinity of metal complexes towards supercoiled pBR322 DNA has been ascertained by agarose gel electrophoresis assay. From the results, it is observed that all the metal complexes bind effectively to CT-DNA via an intercalative mode of binding and also cleave pBR322 DNA in a promising manner. Further the Cu(II) complexes have shown better binding and cleavage properties towards DNA. The antimicrobial activities of the Schiff bases and their metal complexes were studied on bacterial and fungal strains and the results denoted that the complexes are more potent than their Schiff base ligands. Copyright © 2017 Elsevier B.V. All rights reserved.

  5. I. Redox chemistry of bimetallic fulvalene complexes II. Oligocyclopentadienyl complexes

    Energy Technology Data Exchange (ETDEWEB)

    Brown, David Stephen [Univ. of California, Berkeley, CA (United States). Dept. of Chemistry; Lawrence Berkeley Lab., CA (United States). Chemical Sciences Div.

    1993-11-01

    The electrochemistry of the heterobimetallic complexes (fulvalene)WFe(CO)5 (30) and (fulvalene)WRu(CO)5 (31) has been investigated. Compound 30 is reduced in two one-electron processes, and this behavior was exploited synthetically to prepare a tetranuclear dimer by selective metal reduction. Complex 31 displayed a distinction between the metals upon reoxidation of the dianion, allowing the formation of a dimer by selective metal anion oxidation. The redox behavior of 30 led to an investigation of the use of electrocatalysis to effect metal-specific ligand substitution. It was found that reduction of 30 with a catalytic amount of CpFe(C6Me6) (97) in the presence of excess P(OMe)3 or PMe5 led to the formation of the zwitterions (fulvalene)[W(CO)3-][Fe(CO)PR3+] (107, R = P(OMe)3; 108, R = PMe3). Compound 31 also displayed unique behavior with different reducing agents, as the monosubstituted zwitterion (fulvalene)[W(CO)3-][Ru(CO)2(PMe3+] was obtained when 97 was used while the disubstituted complex (fulvalene) [W(CO)3-] [Ru(CO)(PMe3)2+] was produced when Cp*Fe(C6Me6) was the catalyst. Potential synthetic routes to quatercyclopentadienyl complexes were also explored. Various attempts to couple heterobimetallic fulvalene compounds proved to be unsuccessful. 138 refs.

  6. X-ray absorption near edge structure (XANES) study of some hydroxamic mixed ligand copper complexes

    International Nuclear Information System (INIS)

    Mishra, A; Parsai, N; Shrivastava, B D; Soni, N

    2012-01-01

    With the advent of modern bright synchrotron radiation sources, X-ray absorption spectra has emerged as a powerful technique for local structure determination, which can be applied to any type of material. The X-ray absorption measurements of four hydroxamic mixed ligand copper complexes have been performed at the recently developed BL-8 Dispersive EXAFS beamline at 2.5 GeV Indus-2 synchrotron at RRCAT, Indore, India. The X-ray absorption near edge structure (XANES) data obtained has been processed using data analysis program Athena. The energies of the K absorption edge, chemical shifts, edge-widths, shifts of the principal absorption maximum in the complexes have been determined. The values of the chemical shift suggest that copper is in oxidation state +2 in all of the complexes. The chemical shift data has been utilized to estimate effective nuclear charge on copper atom. The order of the chemical shifts has been correlated to the relative ionic character of the bonding in these complexes.

  7. Nickel(II) complexes containing ONS donor ligands: Synthesis ...

    Indian Academy of Sciences (India)

    MS received 23 July 2014; revised 28 November 2014; accepted 28 November 2014 ... Nickel(II) complexes; X-ray structure; Kumada-Corriu reaction; Suzuki reaction; ...... 29 75. 37. Kovala-Demertzi D, Demertzis M A, Miller J R,. Papadopoulou C ... Biochem. 86 555. 38. Bellamy L J 1985 In The Infrared Spectra of Complex.

  8. Mixed-Ligand Complexes Of Nickel (II) With 2-Acetylpyridine ...

    African Journals Online (AJOL)

    The preparation and spectral properties of five nickel (II) mixed-ligands complexes (Ni [2-Actsc.Y]CI2), derived from 2-acetylpyridinethiosermicarbazones and some nitrogen/sulphur monodentate ligands such as thiophene, ammonia, picoline, pyridine and aniline are described. The complexes have been characterized on ...

  9. Polypyridyl iron(II) complexes showing remarkable photocytotoxicity ...

    Indian Academy of Sciences (India)

    reported a high spin (S=5/2) ternary iron(III) complex. [Fe(BHA)(L)Cl] of a ... designed low-spin iron(II) complexes as a new class of ..... They were moderately soluble in methanol, ethanol and .... Cell permeable DCFDA on oxidation by cel-.

  10. Inversion of In Situ Light Absorption and Attenuation Measurements to Estimate Constituent Concentrations in Optically Complex Shelf Seas

    Science.gov (United States)

    Ramírez-Pérez, M.; Twardowski, M.; Trees, C.; Piera, J.; McKee, D.

    2018-01-01

    A deconvolution approach is presented to use spectral light absorption and attenuation data to estimate the concentration of the major nonwater compounds in complex shelf sea waters. The inversion procedure requires knowledge of local material-specific inherent optical properties (SIOPs) which are determined from natural samples using a bio-optical model that differentiates between Case I and Case II waters and uses least squares linear regression analysis to provide optimal SIOP values. A synthetic data set is used to demonstrate that the approach is fundamentally consistent and to test the sensitivity to injection of controlled levels of artificial noise into the input data. Self-consistency of the approach is further demonstrated by application to field data collected in the Ligurian Sea, with chlorophyll (Chl), the nonbiogenic component of total suspended solids (TSSnd), and colored dissolved organic material (CDOM) retrieved with RMSE of 0.61 mg m-3, 0.35 g m-3, and 0.02 m-1, respectively. The utility of the approach is finally demonstrated by application to depth profiles of in situ absorption and attenuation data resulting in profiles of optically significant constituents with associated error bar estimates. The advantages of this procedure lie in the simple input requirements, the avoidance of error amplification, full exploitation of the available spectral information from both absorption and attenuation channels, and the reasonably successful retrieval of constituent concentrations in an optically complex shelf sea.

  11. Copper(II) Thiosemicarbazone Complexes and Their Proligands upon UVA Irradiation: An EPR and Spectrophotometric Steady-State Study.

    Science.gov (United States)

    Hricovíni, Michal; Mazúr, Milan; Sîrbu, Angela; Palamarciuc, Oleg; Arion, Vladimir B; Brezová, Vlasta

    2018-03-21

    X- and Q-band electron paramagnetic resonance (EPR) spectroscopy was used to characterize polycrystalline Cu(II) complexes that contained sodium 5-sulfonate salicylaldehyde thiosemicarbazones possessing a hydrogen, methyl, ethyl, or phenyl substituent at the terminal nitrogen. The ability of thiosemicarbazone proligands to generate superoxide radical anions and hydroxyl radicals upon their exposure to UVA irradiation in aerated aqueous solutions was evidenced by the EPR spin trapping technique. The UVA irradiation of proligands in neutral or alkaline solutions and dimethylsulfoxide (DMSO) caused a significant decrease in the absorption bands of aldimine and phenolic chromophores. Mixing of proligand solutions with the equimolar amount of copper(II) ions resulted in the formation of 1:1 Cu(II)-to-ligand complex, with the EPR and UV-Vis spectra fully compatible with those obtained for the dissolved Cu(II) thiosemicarbazone complexes. The formation of the complexes fully inhibited the photoinduced generation of reactive oxygen species, and only subtle changes were found in the electronic absorption spectra of the complexes in aqueous and DMSO solutions upon UVA steady-state irradiation. The dark redox activity of copper(II) complexes and proligand/Cu(II) aqueous solutions towards hydrogen peroxide which resulted in the generation of hydroxyl radicals, was confirmed by spin trapping experiments.

  12. Studies of mn (ii) and ni (ii) complexes with schiff base derived from ...

    African Journals Online (AJOL)

    However, manganese(II) complex is insoluble in most organic solvents but soluble in dimethylsulphoxide (DMSO). The molar conductance of the complexes measured are, indicating their non-electrolytic nature. The potentiometric and spectrophotometric studies of the complex compounds revealed 1:1 metal to ligand ratio.

  13. Studies of Mn (II) and Ni (II) complexes with Schiff base derived from ...

    African Journals Online (AJOL)

    However, manganese(II) complex is insoluble in most organic solvents but soluble in dimethylsulphoxide (DMSO). The molar conductance of the complexes measured are low, indicating their non-electrolytic nature. The potentiometric and spectrophotometric studies of the complex compounds revealed 1:1 metal to ligand ...

  14. Synthesis, spectral, thermal and antimicrobial studies on cobalt(II), nickel(II), copper(II), zinc(II) and palladium(II) complexes containing thiosemicarbazone ligand

    Science.gov (United States)

    El-Sawaf, Ayman K.; El-Essawy, Farag; Nassar, Amal A.; El-Samanody, El-Sayed A.

    2018-04-01

    The coordination characteristic of new N4-morpholinyl isatin-3-thiosemicarbazone (HL) towards Co(II), Ni(II), Cu(II), Zn(II) and Pd(II) has been studies. The structures of the complexes were described by elemental analyses, molar conductivity, magnetic, thermal and spectral (IR, UV-Vis, 1H and 13C NMR and ESR) studies. On the basis of analytical and spectral studies the ligand behaves as monobasic tridentate ONS donor forming two five membered rings towards cobalt, copper and palladium and afforded complexes of the kind [M(L)X], (Mdbnd Co, Cu or Pd; Xdbnd Cl, Br or OAc). Whereas the ligand bound to NiCl2 as neutral tridentate ONS donor and with ZnCl2 as neutral bidentate NS donor. The newly synthesized thiosemicarbazone ligand and some of its complexes were examined for antimicrobial activity against 2 gram negative bacterial strains (Escherichia coli Pseudomonas and aeruginosa), 2 gram positive bacterial strains (Streptococcus pneumoniae and Staphylococcus aureus)} and two Pathogenic fungi (Aspergillus fumigatus and Candida albicans). All metal complexes possess higher antimicrobial activity comparing with the free thiosemicarbazone ligand. The high potent activities of the complexes may arise from the coordination and chelation, which tends to make metal complexes act as more controlling and potent antimicrobial agents, thus hindering the growing of the microorganisms. The antimicrobial results also show that copper bromide complex is better antimicrobial agent as compared to the Schiff base and its metal complexes.

  15. Synthesis, characterization, DNA interaction and antimicrobial screening of isatin-based polypyridyl mixed-ligand Cu(II and Zn(II complexes

    Directory of Open Access Journals (Sweden)

    NATARAJAN RAMAN

    2010-06-01

    Full Text Available Several mixed ligand Cu(II/Zn(II complexes using 3-(phenyl-imino-1,3-dihydro-2H-indol-2-one (obtained by the condensation of isatin and aniline as the primary ligand and 1,10-phenanthroline (phen/2,2’-bipyridine (bpy as an additional ligand were synthesized and characterized analytically and spectroscopically by elemental analyses, magnetic susceptibility and molar conductance measurements, as well as by UV–Vis, IR, NMR and FAB mass spectroscopy. The interaction of the complexes with calf thymus (CT DNA was studied using absorption spectra, cyclic voltammetric and viscosity measurements. They exhibit absorption hypochromicity, and the specific viscosity increased during the binding of the complexes to calf thymus DNA. The shifts in the oxidation–reduction potential and changes in peak current on addition of DNA were shown by CV measurements. The Cu(II/Zn(II complexes were found to promote cleavage of pUC19 DNA from the supercoiled form I to the open circular form II and linear form III. The complexes show enhanced antifungal and antibacterial activities compared with the free ligand.

  16. Synthesis and characterization of iron(III), manganese(II), cobalt(II), nickel(II), copper(II) and zinc(II) complexes of salicylidene-N-anilinoacetohydrazone (H2L1) and 2-hydroxy-1-naphthylidene-N-anilinoacetohydrazone (H2L2).

    Science.gov (United States)

    AbouEl-Enein, S A; El-Saied, F A; Kasher, T I; El-Wardany, A H

    2007-07-01

    Salicylidene-N-anilinoacetohydrazone (H(2)L(1)) and 2-hydroxy-1-naphthylidene-N-anilinoacetohydrazone (H(2)L(2)) and their iron(III), manganese(II), cobalt(II), nickel(II), copper(II) and zinc(II) complexes have been synthesized and characterized by IR, electronic spectra, molar conductivities, magnetic susceptibilities and ESR. Mononuclear complexes are formed with molar ratios of 1:1, 1:2 and 1:3 (M:L). The IR studies reveal various modes of chelation. The electronic absorption spectra and magnetic susceptibility measurements show that the iron(III), nickel(II) and cobalt(II) complexes of H(2)L(1) have octahedral geometry. While the cobalt(II) complexes of H(2)L(2) were separated as tetrahedral structure. The copper(II) complexes have square planar stereochemistry. The ESR parameters of the copper(II) complexes at room temperature were calculated. The g values for copper(II) complexes proved that the Cu-O and Cu-N bonds are of high covalency.

  17. Gamma radiolysis of Cu(II) complex of metronidazole

    International Nuclear Information System (INIS)

    Mandal, P.C.; Bardhan, D.K.; Bhattacharyya, S.N.

    1990-01-01

    Aqueous solutions of Cu(II)Metronidazole (Cu(II)M) at neutral pH were irradiated with 60 Co γ-rays under different conditions of radiolysis. The radiolytic formation of HNO 2 and Cu(I) was followed. The radiolytic yields of chromophore loss of Cu(II)M were also determined under different conditions. The OH radicals attack the metal complex to give the OH adducts of the ligand at C 2 , C 4 , and C 5 either directly or through the formation of Cu(III) species. The C 5 -OH adduct, however, undergoes oxidative denitration and as a result the metal complex is decomposed. The OH adducts also undergo electron transfer to Cu(II) ion to give reduced complex. No denitration was observed due to the reaction of e eq - with the metal complex. On the other hand, the nitro group of the ligand in the complex undergoes successive 4-electron reduction to give hydroxylamino derivative. From the competition kinetics using t-butyl alcohol as the scavenger of OH in N 2 O saturated solution of the metal complex, the rate constant for the reaction of OH with complex was evaluated to be ca. 2.1x10 9 dm 3 mol -1 s -1 which is of the same order as that observed in the case of free metronidazole. (author)

  18. Computation of Collision-Induced Absorption by Simple Molecular Complexes, for Astrophysical Applications

    Science.gov (United States)

    Abel, Martin; Frommhold, Lothar; Li, Xiaoping; Hunt, Katharine L. C.

    2012-06-01

    The interaction-induced absorption by collisional pairs of H{_2} molecules is an important opacity source in the atmospheres of various types of planets and cool stars, such as late stars, low-mass stars, brown dwarfs, cool white dwarf stars, the ambers of the smaller, burnt out main sequence stars, exoplanets, etc., and therefore of special astronomical interest The emission spectra of cool white dwarf stars differ significantly in the infrared from the expected blackbody spectra of their cores, which is largely due to absorption by collisional H{_2}-H{_2}, H{_2}-He, and H{_2}-H complexes in the stellar atmospheres. Using quantum-chemical methods we compute the atmospheric absorption from hundreds to thousands of kelvin. Laboratory measurements of interaction-induced absorption spectra by H{_2} pairs exist only at room temperature and below. We show that our results reproduce these measurements closely, so that our computational data permit reliable modeling of stellar atmosphere opacities even for the higher temperatures. First results for H_2-He complexes have already been applied to astrophysical models have shown great improvements in these models. L. Frommhold, Collision-Induced Absorption in Gases, Cambridge University Press, Cambridge, New York, 1993 and 2006 X. Li, K. L. C. Hunt, F. Wang, M. Abel, and L. Frommhold, Collision-Induced Infrared Absorption by Molecular Hydrogen Pairs at Thousands of Kelvin, Int. J. of Spect., vol. 2010, Article ID 371201, 11 pages, 2010. doi: 10.1155/2010/371201 M. Abel, L. Frommhold, X. Li, and K. L. C. Hunt, Collision-induced absorption by H{_2} pairs: From hundreds to thousands of Kelvin, J. Phys. Chem. A, 115, 6805-6812, 2011} L. Frommhold, M. Abel, F. Wang, M. Gustafsson, X. Li, and K. L. C. Hunt, "Infrared atmospheric emission and absorption by simple molecular complexes, from first principles", Mol. Phys. 108, 2265, 2010 M. Abel, L. Frommhold, X. Li, and K. L. C. Hunt, Infrared absorption by collisional H_2-He complexes

  19. Synthesis and Spectroscopic Studies of Mixed Ligand Complexes of Pt(II and Pd(II with Ethyl-α-Isonitrosoacetoacetate and Dienes

    Directory of Open Access Journals (Sweden)

    Anita Krishankant Taksande

    2015-12-01

    Full Text Available The mixed ligand complexes of the kind [M(L1 (L2] where M= Pt(II, Pd(II.L1 = primary ligand ethyl-α-isonitrosoacetoacetate derived from reaction between ethyl acetoacetate, acetic acid and sodium nitrite and L2=secondary ligand para-phenyldiamine (PPD are synthesized. All the prepared complexes were identified and confirmed by elemental analysis, molar conductance measurements, and infrared electronic absorption. Their complexes has been made based on elemental analysis, molar conductivity, UV-Vis, FT-IR and 1HNMR spectroscopy and magnetic moment measurements as well as thermal analysis (TGA and DTA. The elemental analysis information recommends that the stoichiometry of the complexes to be 1:2:1. The molar conductance measurements of the complexes indicate their non-electrolytic nature. The infrared spectral information showed the coordination sites of the free ligand with the central metal particle. The electronic absorption spectral information disclosed the existence of an octahedral geometry for Pt(II and Pd(II complexes. DOI: http://dx.doi.org/10.17807/orbital.v7i4.633 

  20. Spectroscopic and thermal degradation behavior of Mg(II, Ca(II, Ba(II and Sr(II complexes with paracetamol drug

    Directory of Open Access Journals (Sweden)

    Moamen S. Refat

    2017-05-01

    Full Text Available Complexes of Mg(II, Ca(II, Ba(II and Sr(II with paracetamol drug were synthesized and characterized by elemental analysis, conductivity, UV–Vis, IR, and 1H NMR spectroscopy and thermal analysis, as well as screened for antimicrobial activity. The IR spectral data suggested that the ligand behaves as paracetamol behaves as a neutral bidentate ligand coordinated to the metal ions via the lone pair of electrons of nitrogen and carbonyl-O atoms of the amide group. From the microanalytical data, the stoichiometry of the complexes reacts with Mg(II, Ca(II, Ba(II and Sr(II by molar ratios (2:1 (paracetamol:metal ion. The thermal behavior (TG/DTG of the complexes was studied. The ligand and their metal complexes were screened against both of antibacterial and fungicidal activities.

  1. Cobalt(III), nickel(II) and ruthenium(II) complexes of 1,10 ...

    Indian Academy of Sciences (India)

    Co(II) and Ru(II) complexes investigated in this study effect photocleavage of the supercoiled ... DNA is related to their utility in the design and development of synthetic restriction ..... ∗Quasi-reversible/irreversible (electrochemical behaviour of ...

  2. Synthesis and spectral studies of manganese(II), cobalt(II), nickel(II), copper(II), zinc(II), cadmium(II) and mercury(II) complexes of 4-oxo-4H-1-benzopyran-3-carboxaldehyde hydrazone derivatives

    International Nuclear Information System (INIS)

    Nawar, N.; Khattab, M.A.; Bekheit, M.M.; El-Kaddah, A.H.

    1996-01-01

    A few complexes of Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II) with 4-oxo-4H-1-benzopyran-3-(carboxaldehyde-4-chlorobenzylhydrazone) (BCBH) and 4-oxo-4H-1-benzopyran-3-(carboxaldehyde-4-methylbenzylhydrazone) (BMBH) have been synthesised and characterized by elemental analysis, molar conductivities, magnetic measurements and infrared (IR) and visible spectral studies. The IR spectra show that BCBH and BMBH behave as bidentate ligands either in the keto or enol form. (author). 24 refs., 2 tabs

  3. Optical Absorption, Stability and Structure of NpO2+ Complexes with Dicarboxylic Acids

    International Nuclear Information System (INIS)

    Guoxin Tian; Linfeng Rao

    2006-01-01

    Complexation of NpO2+ with oxalic acid (OX),2,2'-oxydiacetic acid (ODA), 2,2'-iminodiacetic acid (IDA) and 2,2'-thiodiacetic acid (TDA), has been studied using spectrophotometry in1 M NaClO4. Both the position and the intensity of the absorption band of NpO2+ at 980 nm are affected by the formation of NpO2+/dicarboxylate complexes, providing useful information on the complexation strength, the coordination mode and the structure of the complexes

  4. Synthesis and studies on Cu(II), Co(II), Ni(II) complexes of Knoevenagel β-diketone ligands

    Science.gov (United States)

    Sumathi, S.; Tharmaraj, P.; Sheela, C. D.; Anitha, C.

    2012-11-01

    Transition metal complexes of various acetylacetone based ligands of the type ML [where M = Cu(II), Ni(II), Co(II); L = 3-(aryl)-pentane-2,4-dione] have been synthesized. The structural features have been derived from their elemental analysis, magnetic susceptibility, molar conductance, IR, UV-Vis, 1H NMR, Mass and ESR spectral studies. Conductivity measurements reveal that all the complexes are non-electrolytic in nature. Spectroscopic and other analytical data of the complexes suggest octahedral geometry for other metal(II) complexes. The redox behavior of the copper(II) complexes have been studied by cyclic voltammetry. The free ligands and their metal complexes have been screened for their in vitro biological activities against the bacteria Pseudomonas aeruginosa, Escherichia coli and Staphylococcus aureus as well as the fungus Candida albicans by well diffusion method. The zone of inhibition value indicates that the most of the metal(II) complexes are found to possess increased activities compared to those of the free ligands. All synthesized compounds may serve as potential photoactive materials as indicated from their characteristic fluorescence properties. The second harmonic generation (SHG) efficiency of the ligands (L1-L3) was found to be considerable effect than that of urea and KDP (potassium dihydrogen phosphate).

  5. Mixed-ligand complexes of copper (II with ditiolfenols and heterocyclic diamines

    Directory of Open Access Journals (Sweden)

    K. A. Kuliev

    2017-01-01

    Full Text Available By the methods spectrophotometric methods was investigated complex formation of copper with 2,6-ditiolphenol and its derivatives (2,6-ditiol-4-methylphenol, 2,6-ditiol-4-ethylphenol and 2,6-ditiol-4-tert-buthylphenol in the presence of heterocyclic diamines. As heterocyclic diamines phenantroline (Fen, batophenantroline and dipyridile were used. It was established, that mixedligand complex were formed in weak acidic medium (pHop=6,0-8,5. Maximum of light absorption observed at (=522–550 nm. Molar coefficient of light absorption was ( = (3.08–4.92?104. The stoichiometry of complexes had been discovered using shift the equilibrium and relative yield methods. During the extraction of copper(II complexes with ditiol-phenols with the presence of heterocyclic diamines there was discovered that there is no chlorophorm molecules in the composition of the extracted complexes. IR spectra shows that hydroxyl group is involved to the formation of a bond with the metal and that phenantroline is included in the composition of the copper complex. In the organic phase mixed-ligand complexes have the monomeric form and can’t polymerize; that fact can be proved by calculations. By dint of spectrophotometric, IR-spectroscopic, thermogravimetric experiments and some published data we were able to determine the structural formula of complexes. Also had been determined main spectrophotometric characteristics of copper(II mixed-ligand complexes: pH of the beginning of the deposition, optimal pH, detection limit and sensivity. For separation and finding copper, we studied the effect of interfering foreign ions: alkali, alkaline earth and rare earth elements, as well as acid anions selected masking reagents. On the base of the results was offered photometric method for determination of copper in steel different trade-marks and in food. This method characterized by good reproduction (relatively standard deviation no more 0.05 and low limit of discovery.

  6. Synthesis, spectral, thermal studies and electrical conductivity of Co (II) and Ni (II) complexes 3-[4-dimethylaminophenyl]-1-(2-pyridyl) prop-2-en-1-one (DMAPP)

    Energy Technology Data Exchange (ETDEWEB)

    Gaber, Mohamed, E-mail: abuelazm@yahoo.com [Chemistry Department, Faculty of Science, Tanta University, 31527 Tanta (Egypt); Al-Daly, Samy; Fayed, Tarek [Chemistry Department, Faculty of Science, Tanta University, 31527 Tanta (Egypt); El-Sayed, Yousif [Department of Chemistry, Faculty of Science, Tanta University, Tanta (Egypt)

    2015-01-15

    Co(II) and Ni(II) complexes of 3-[4-dimethylaminophenyl]-1-(2-pyridyl)prop-2-en-1-one have been prepared and characterized on the basis of elemental analyses, molar conductance, magnetic susceptibility measurements, IR, electronic spectra as well as thermal studies. The magnetic and spectral studies suggested the octahedral geometry for Co(II) and Ni(II) complexes. The kinetic parameters of the thermal decomposition stages have been evaluated using Coats–Redfern method. The electrical conductivity of the titled ligand and its Co(II) complexes was studied. The effects of different alcoholic solvents, pH and temperature on the complexation formation were considered. Also, the effect of Co(II) and Ni(II) ions on the emission spectrum of the free DMAPP was assigned. The stoichiometry of the metal complexes, the conditional formation constant, free energy, Beer{sup '}s law, molar extinction coefficient as well as specific absorptivity were evaluated. The ability of using the titled ligand as metalochromic indicator in complexometric titration was studied.

  7. Structure and reactivity of a mononuclear gold(II) complex

    Science.gov (United States)

    Preiß, Sebastian; Förster, Christoph; Otto, Sven; Bauer, Matthias; Müller, Patrick; Hinderberger, Dariush; Hashemi Haeri, Haleh; Carella, Luca; Heinze, Katja

    2017-12-01

    Mononuclear gold(II) complexes are very rare labile species. Transient gold(II) species have been suggested in homogeneous catalysis and in medical applications, but their geometric and electronic structures have remained essentially unexplored: even fundamental data, such as the ionic radius of gold(II), are unknown. Now, an unprecedentedly stable neutral gold(II) complex of a porphyrin derivative has been isolated, and its structural and spectroscopic features determined. The gold atom adopts a 2+2 coordination mode in between those of gold(III) (four-coordinate square planar) and gold(I) (two-coordinate linear), owing to a second-order Jahn-Teller distortion enabled by the relativistically lowered 6s orbital of gold. The reactivity of this gold(II) complex towards dioxygen, nitrosobenzene and acids is discussed. This study provides insight on the ionic radius of gold(II), and allows it to be placed within the homologous series of nd9 Cu/Ag/Au divalent ions and the 5d8/9/10 Pt/Au/Hg 'relativistic' triad in the periodic table.

  8. Photochemical redox reactions of copper(II)-alanine complexes in aqueous solutions.

    Science.gov (United States)

    Lin, Chen-Jui; Hsu, Chao-Sheng; Wang, Po-Yen; Lin, Yi-Liang; Lo, Yu-Shiu; Wu, Chien-Hou

    2014-05-19

    The photochemical redox reactions of Cu(II)/alanine complexes have been studied in deaerated solutions over an extensive range of pH, Cu(II) concentration, and alanine concentration. Under irradiation, the ligand-to-metal charge transfer results in the reduction of Cu(II) to Cu(I) and the concomitant oxidation of alanine, which produces ammonia and acetaldehyde. Molar absorptivities and quantum yields of photoproducts for Cu(II)/alanine complexes at 313 nm are characterized mainly with the equilibrium Cu(II) speciation where the presence of simultaneously existing Cu(II) species is taken into account. By applying regression analysis, individual Cu(I) quantum yields are determined to be 0.094 ± 0.014 for the 1:1 complex (CuL) and 0.064 ± 0.012 for the 1:2 complex (CuL2). Individual quantum yields of ammonia are 0.055 ± 0.007 for CuL and 0.036 ± 0.005 for CuL2. Individual quantum yields of acetaldehyde are 0.030 ± 0.007 for CuL and 0.024 ± 0.007 for CuL2. CuL always has larger quantum yields than CuL2, which can be attributed to the Cu(II) stabilizing effect of the second ligand. For both CuL and CuL2, the individual quantum yields of Cu(I), ammonia, and acetaldehyde are in the ratio of 1.8:1:0.7. A reaction mechanism for the formation of the observed photoproducts is proposed.

  9. THE PITTSBURGH SLOAN DIGITAL SKY SURVEY Mg II QUASAR ABSORPTION-LINE SURVEY CATALOG

    International Nuclear Information System (INIS)

    Quider, Anna M.; Nestor, Daniel B.; Turnshek, David A.; Rao, Sandhya M.; Weyant, Anja N.; Monier, Eric M.; Busche, Joseph R.

    2011-01-01

    We present a catalog of intervening Mg II quasar absorption-line systems in the redshift interval 0.36 ≤ z ≤ 2.28. The catalog was built from Sloan Digital Sky Survey Data Release Four (SDSS DR4) quasar spectra. Currently, the catalog contains ∼17, 000 measured Mg II doublets. We also present data on the ∼44, 600 quasar spectra which were searched to construct the catalog, including redshift and magnitude information, continuum-normalized spectra, and corresponding arrays of redshift-dependent minimum rest equivalent widths detectable at our confidence threshold. The catalog is available online. A careful second search of 500 random spectra indicated that, for every 100 spectra searched, approximately one significant Mg II system was accidentally rejected. Current plans to expand the catalog beyond DR4 quasars are discussed. Many Mg II absorbers are known to be associated with galaxies. Therefore, the combination of large size and well understood statistics makes this catalog ideal for precision studies of the low-ionization and neutral gas regions associated with galaxies at low to moderate redshift. An analysis of the statistics of Mg II absorbers using this catalog will be presented in a subsequent paper.

  10. Formation of Hg(II) Tetrathiolate Complexes with Cysteine at Neutral pH.

    Science.gov (United States)

    Warner, Thomas; Jalilehvand, Farideh

    2016-04-01

    Mercury(II) ions precipitate from aqueous cysteine (H 2 Cys) solutions containing H 2 Cys/Hg(II) mole ratio ≥ 2.0 as Hg( S -HCys) 2 . In absence of additional cysteine, the precipitate dissolves at pH ~12 with the [Hg( S,N -Cys) 2 ] 2- complex dominating. With excess cysteine (H 2 Cys/Hg(II) mole ratio ≥ 4.0), higher complexes form and the precipitate dissolves at lower pH values. Previously, we found that tetrathiolate [Hg( S -Cys) 4 ] 6- complexes form at pH = 11.0; in this work we extend the investigation to pH values of physiological interest. We examined two series of Hg(II)-cysteine solutions in which C Hg(II) varied between 8 - 9 mM and 80 - 100 mM, respectively, with H 2 Cys/Hg(II) mole ratios from 4 to ~20. The solutions were prepared in the pH range 7.1 - 8.8, at the pH at which the initial Hg( S -HCys) 2 precipitate dissolved. The variations in the Hg(II) speciation were followed by 199 Hg NMR, X-ray absorption and Raman spectroscopic techniques. Our results show that in the dilute solutions ( C Hg(II) = 8 - 9 mM), mixtures of di-, tri- (major) and tetrathiolate complexes exist at moderate cysteine excess ( C H2Cys ~ 0.16 M) at pH 7.1. In the more concentrated solutions ( C Hg(II) = 80 - 100 mM) with high cysteine excess ( C H2Cys > 0.9 M), tetrathiolate [Hg( S -cysteinate) 4 ] m -6 ( m = 0 - 4) complexes dominate in the pH range 7.3 - 7.8, with lower charge than for the [Hg( S -Cys) 4 ] 6- complex due to protonation of some ( m ) of the amino groups of the coordinated cysteine ligands. The results of this investigation could provide a key to the mechanism of biosorption and accumulation of Hg(II) ions in biological / environmental systems.

  11. Isolation and Purification of Complex II from Proteus Mirabilis Strain ATCC 29245

    Science.gov (United States)

    Shabbiri, Khadija; Ahmad, Waqar; Syed, Quratulain; Adnan, Ahmad

    2010-01-01

    A respiratory complex was isolated from plasma membrane of pathogenic Proteus mirabilis strain ATCC 29245. It was identified as complex II consisting of succinate:quinone oxidoreductase (EC 1.3.5.1) containing single heme b. The complex II was purified by ion-exchange chromatography and gel filtration. The molecular weight of purified complex was 116.5 kDa and it was composed of three subunits with molecular weights of 19 kDa, 29 kDa and 68.5 kDa. The complex II contained 9.5 nmoles of cytochrome b per mg protein. Heme staining indicated that the 19 kDa subunit was cytochrome b. Its reduced form showed absorptions peaks at 557.0, 524.8 and 424.4 nm. The α-band was shifted from 557.0 nm to 556.8 nm in pyridine ferrohemochrome spectrum. The succinate: quinone oxidoreductase activity was found to be high in this microorganism. PMID:24031557

  12. XAFS study of copper(II) complexes with square planar and square pyramidal coordination geometries

    Science.gov (United States)

    Gaur, A.; Klysubun, W.; Nitin Nair, N.; Shrivastava, B. D.; Prasad, J.; Srivastava, K.

    2016-08-01

    X-ray absorption fine structure of six Cu(II) complexes, Cu2(Clna)4 2H2O (1), Cu2(ac)4 2H2O (2), Cu2(phac)4 (pyz) (3), Cu2(bpy)2(na)2 H2O (ClO4) (4), Cu2(teen)4(OH)2(ClO4)2 (5) and Cu2(tmen)4(OH)2(ClO4)2 (6) (where ac, phac, pyz, bpy, na, teen, tmen = acetate, phenyl acetate, pyrazole, bipyridine, nicotinic acid, tetraethyethylenediamine, tetramethylethylenediamine, respectively), which were supposed to have square pyramidal and square planar coordination geometries have been investigated. The differences observed in the X-ray absorption near edge structure (XANES) features of the standard compounds having four, five and six coordination geometry points towards presence of square planar and square pyramidal geometry around Cu centre in the studied complexes. The presence of intense pre-edge feature in the spectra of four complexes, 1-4, indicates square pyramidal coordination. Another important XANES feature, present in complexes 5 and 6, is prominent shoulder in the rising part of edge whose intensity decreases in the presence of axial ligands and thus indicates four coordination in these complexes. Ab initio calculations were carried out for square planar and square pyramidal Cu centres to observe the variation of 4p density of states in the presence and absence of axial ligands. To determine the number and distance of scattering atoms around Cu centre in the complexes, EXAFS analysis has been done using the paths obtained from Cu(II) oxide model and an axial Cu-O path from model of a square pyramidal complex. The results obtained from EXAFS analysis have been reported which confirmed the inference drawn from XANES features. Thus, it has been shown that these paths from model of a standard compound can be used to determine the structural parameters for complexes having unknown structure.

  13. Spectroscopic evaluation of Co(II), Ni(II) and Cu(II) complexes derived from thiosemicarbazone and semicarbazone

    Science.gov (United States)

    Chandra, Sulekh; Kumar, Anil

    2007-12-01

    Co(II), Ni(II) and Cu(II) complexes were synthesized with thiosemicarbazone (L 1) and semicarbazone (L 2) derived from 2-acetyl furan. These complexes were characterized by elemental analysis, molar conductance, magnetic moment, mass, IR, electronic and EPR spectral studies. The molar conductance measurement of the complexes in DMSO corresponds to non-electrolytic nature. All the complexes are of high-spin type. On the basis of different spectral studies six coordinated geometry may be assigned for all the complexes except Co(L) 2(SO 4) and Cu(L) 2(SO 4) [where L = L 1 and L 2] which are of five coordinated square pyramidal geometry.

  14. Manganese L-edge X-ray absorption spectroscopy of manganese catalase from Lactobacillus plantarum and mixed valence manganese complexes

    Energy Technology Data Exchange (ETDEWEB)

    Grush, M.M.; Chen, J.; George, S.J. [Univ. of California, Davis, CA (United States)] [and others

    1996-01-10

    The first Mn L-edge absorption spectra of a Mn metalloprotein are presented in this paper. Both reduced and superoxidized Mn catalase have been examined by fluorescence-detected soft X-ray absorption spectroscopy, and their Mn L-edge spectra are dramatically different. The spectrum of reduced Mn(II)Mn(II) catalase has been interpreted by ligand field atomic multiplet calculations and by comparison to model compound spectra. The analysis finds a 10 Dq value of nearly 1.1 eV, consistent with coordination by predominately nitrogen and oxygen donor ligands. For interpretation of mixed valence Mn spectra, an empirical simulation procedure based on the addition of homovalent model compound spectra has been developed and was tested on a variety of Mn complexes and superoxidized Mn catalase. This routine was also used to determine the oxidation state composition of the Mn in [Ba{sub 8}Na{sub 2}ClMn{sub 16}(OH){sub 8}(CO{sub 3}){sub 4}L{sub 8}] .53 H{sub 2}O (L=1,3-diamino-2-hydroxypropane-N,N,N`N`-tetraacetic acid). 27 refs., 6 figs.

  15. Photoreactions of ruthenium(II) and osmium(II) complexes with deoxyribonucleic acid (DNA).

    Science.gov (United States)

    Moucheron, C; Kirsch-De Mesmaeker, A; Kelly, J M

    1997-09-01

    The design of Ru(II) and Os(II) complexes which are photoreactive with deoxyribonucleic acid (DNA) represents one of the main targets for the development of novel molecular tools for the study of DNA and, in the future, for the production of new, metal-based, anti-tumor drugs. In this review, we explain how it is possible to make a complex photoreactive with nucleobases and nucleic acids. According to the photophysical behaviour of the Ru(II) compounds, two types of photochemistry are expected: (1) photosubstitution of a ligand by a nucleobase and another monodentate ligand, which takes place from the triplet, metal-centred (3MC) state; this state is populated thermally from the lowest lying triplet metal to ligand charge transfer (3MLCT) state; (2) photoreaction from the 3MLCT state, corresponding to photoredox processes with DNA bases. The two photoreactivities are in competition. By modulating appropriately the redox properties of the 3MLCT state, an electron transfer process from the base to the excited complex takes place, and is directly correlated with DNA cleavage or the formation of an adduct of the complex to DNA. In this adduct, guanine is linked by N2 to the alpha-position of a non-chelating nitrogen of the polyazaaromatic ligand without destruction of the complex. Different strategies are explained which increase the affinity of the complexes for DNA and direct the complex photoreactivity to sites of special DNA topology or targeted sequences of bases. Moreover, the replacement of the Ru(II) ion by the Os(II) ion in the photoreactive complexes leads to an increased specificity of photoreaction. Indeed, only one type of photoreactivity (from the 3MLCT state) is present for the Os(II) complexes because the 3MC state is too high in energy to be populated at room temperature.

  16. Fe(II) and Co (II) complexes of (4-(4-bromophenyl)-[2,2'-bipyridine]-6-carboxylic acid) synthesis, characterization and electrochromic studies

    International Nuclear Information System (INIS)

    Saba, A.; Maqsood, Z.T.; Wasim, A.A.; Basha, F.Z.

    2017-01-01

    In this study novel complexes of substituted bipyridine (4-(4-bromophenyl)-[2,2'-bipyridine]-6-carboxylic acid) with Fe/sup +2/ and Co/sup +2/ were synthesized and characterized by different physical, analytical and spectral techniques which includes /sup 1/ H-NMR, MALDI-MS, FTIR, UV-VIS Spectrophotometry, CHN analysis and conductometry. Mole ratio method revealed that both complexes satisfied ML2 stoichiometry. Other characterization studies showed that substituted bipyridine acted as a tridentate ligand, with two pyridine N and one carboxylic O atom as binding sites per ligand molecule. The complexes were found octahedral, neutral and possessed fairly high molar absorptivities in visible region. Electrochromic studies revealed that Fe (II) complex had relatively good electrochromic properties with a reversible color change from blue to pale yellow. Co (II) complex, however, did not show significant electrochromic properties in the visible region. (author)

  17. Synthesis, crystallographic and spectral studies of homochiral cobalt(II) and nickel(II) complexes of a new terpyridylaminoacid ligand

    Science.gov (United States)

    Wang, Xing; Gao, Chang-Qing; Gao, Zhi-Yang; Wu, Ben-Lai; Niu, Yun-Yin

    2018-04-01

    Based on a chiral terpyridylaminoacid ligand, a series of homochiral Co(II) and Ni(II) complexes, namely, [Co(H2L)(HL)]·Cl·(PF6)2·2H2O (1), [Ni(H2L)(HL)]·Cl·(PF6)2 (2), [Co2(L)2(CH3OH)(H2O)]·(PF6)2·CH3OH (3), [Ni2(L)2(CH3OH)2]·(PF6)2·2CH3OH (4), [Co2(L)2(N3)2]·3H2O (5), and [Ni2(L)2(SCN)2]·4H2O (6) have been successfully synthesized and characterized by elemental analysis, TGA, spectroscopic methods (IR, CD and electronic absorption spectra) and single-crystal X-ray diffraction structural analysis (HL = (S)-2-((4-([2,2':6‧,2″-terpyridin]-4‧-yl)benzyl)amino)-4-methylpentanoic acid). In the acidic reaction conditions, one protonated (H2L)+ and one zwitterionic HL only used their terpyridyl groups to chelate one metal ion Co(II) or Ni(II), forming chiral mononuclear cationic complexes 1 or 2. But in the basic and hydro(solvo)thermal reaction conditions, deprotonated ligands (L)‒ acting as bridges used their terpyridyl and amino acid groups to link with two Co(II) or Ni(II) ions, fabricating chiral dinuclear metallocyclic complexes 3-6. Those chiral mononuclear and dinuclear complexes whose chirality originates in the homochiral ligand HL further self-assemble into higher-dimensional homochiral supramolecular frameworks through intermolecular hydrogen-bonding and π···π interactions. Notably, the coordination mode, hydrogen-bonding site, and existence form of HL ligand can be controlled by the protonation of its amino group, and the architectural diversity of those supramolecular frameworks is adjusted by pH and counter anions. Very interestingly, the 3D porous supramolecular frameworks built up from the huge chiral mononuclear cationic complexes 1 and 2 have novel helical layers only formed through every right-handed helical chain intertwining with two adjacent same helical chains, and the 2D supramolecular helicate 5 consists of two types of left-handed helical chains.

  18. Synthesis, spectroscopic and DNA binding ability of CoII, NiII, CuII and ZnII complexes of Schiff base ligand (E)-1-(((1H-benzo[d]imidazol-2-yl)methylimino)methyl)naphthalen-2-ol. X-ray crystal structure determination of cobalt (II) complex.

    Science.gov (United States)

    Yarkandi, Naeema H; El-Ghamry, Hoda A; Gaber, Mohamed

    2017-06-01

    A novel Schiff base ligand, (E)-1-(((1H-benzo[d]imidazol-2-yl)methylimino)methyl)naphthalen-2-ol (HL), has been designed and synthesized in addition to its metal chelates [Co(L) 2 ]·l2H 2 O, [Ni(L)Cl·(H 2 O) 2 ].5H 2 O, [Cu(L)Cl] and [Zn(L)(CH 3 COO)]. The structures of the isolated compounds have been confirmed and identified by means of different spectral and physicochemical techniques including CHN analysis, 1 H & 13 C NMR, mass spectral analysis, molar conductivity measurement, UV-Vis, infrared, magnetic moment in addition to TGA technique. The infrared spectral results ascertained that the ligand acts as monobasic tridentate binding to the metal centers via deprotonated hydroxyl oxygen, azomethine and imidazole nitrogen atoms. The UV-Vis, magnetic susceptibility and molar conductivity data implied octahedral geometry for Co(II) & Ni(II) complexes, tetrahedral for Zn(II) complex and square planar for Cu(II) complex. X-ray structural analysis of Co(II) complex 1 has been reported and discussed. Moreover, the type of interaction between the ligand & its complexes towards salmon sperm DNA (SS-DNA) has been examined by the measurement of absorption spectra and viscosity which confirmed that the ligand and its complexes interact with DNA via intercalation interaction as concluded from the values of binding constants (K b ). Copyright © 2017 Elsevier B.V. All rights reserved.

  19. Curcumin-Zn(II) complex for enhanced solubility and stability: an approach for improved delivery and pharmacodynamic effects.

    Science.gov (United States)

    Sareen, Rashmi; Jain, Nitin; Dhar, K L

    2016-08-01

    The aim of present investigation was to prepare Curcumin-Zn(II) complex in a view to enhance solubility, stability and pharmacodynamic effect in experimentally induced ulcerative colitis. Curcumin-Zn(II) complex was prepared by stirring curcumin with anhydrous zinc chloride at a molar ratio of 1:1. The prepared curcumin metallocomplex was characterized by TLC, FTIR, UV spectroscopy and (1)H NMR. In vitro kinetic degradation and solubility of Curcumin and Curcumin-Zn(II) complex was analyzed spectrophotometrically. Pharmacodynamic evaluation of curcumin and its metal complex was assessed in ulcerative colitis in mice. Curcumin showed chelation with zinc ion as confirmed by the TLC, FTIR, UV spectroscopy and (1)H NMR. The results of TLC [Rf value], IR Spectroscopy [shifting of stretching vibrations of υ(C=C) and υ(C=O)], UV spectra [deconvoluted with absorption band at 432-466.4 nm] of Curcumin-Zn(II) complex compared to curcumin confirmed the formation of metallocomplex. (1)HNMR spectra of Curcumin-Zn(II) showed the upfield shift of Ha and Hb. Kinetic stability studies showed metallocomplex with zinc exhibited good stability. In vivo study revealed significant reduction in severity and extent of colonic damage with Curcumin-Zn(II) which were further confirmed by histopathological study. This study recognizes higher solubility and stability of Curcumin-Zn(II) complex and suggested better pharmacodynamic effects.

  20. 1 SUPPLEMENTARY INFORMATION A novel zinc(II) complex ...

    Indian Academy of Sciences (India)

    BİLGİSAYAR

    1. SUPPLEMENTARY INFORMATION. A novel zinc(II) complex containing square pyramidal, octahedral and tetrahedral geometries on the same polymeric chain constructed from pyrazine-2,3-dicarboxylic acid and 1-vinylimidazole. HAKAN YILMAZ* and OMER ANDAC. Department of Chemistry, Ondokuz Mayis University, ...

  1. Polystyrene with pendant mixed functional ruthenium(II)-terpyridine complexes

    NARCIS (Netherlands)

    Heller, M.; Schubert, U.S.

    2002-01-01

    A vinyl substituted 2,2:6,2-terpyridine and a mixed, bifunctional ruthenium(II)-terpyridine complex bearing a vinyl and a hydroxymethyl group are utilized as comonomers for radical copolymerization with styrene. The resulting polymers are characterized by means of UV-vis spectroscopy and gel

  2. Polypyridyl iron(II) complexes showing remarkable photocytotoxicity ...

    Indian Academy of Sciences (India)

    aditya

    Polypyridyl iron(II) complexes showing remarkable photocytotoxicity in visible light. ADITYA GARAI a. , UTTARA BASU a. , ILA PANT b. , PATURU KONDAIAH*. ,b. AND. AKHIL R. CHAKRAVARTY*. ,a a. Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore. 560012, India. E-mail: ...

  3. (II) complexes containing isocyanide and labile nitrile ligands

    African Journals Online (AJOL)

    A new ruthenium(II) complex containing both acetonitrile and propionitrile moieties as coordinating ligands has been prepared. The treatment of the polymer [{RuCl2(COD)}x], (COD = cycloocta-1,5-diene) (1) with a mixture of acetonitrile and propionitrile under reflux produced a new precursor ...

  4. AND Ca(II) COMPLEXES WITH AN ANTIRETROVIRAL DRUG

    African Journals Online (AJOL)

    Metal ions perform range of functions such as iron containing protein; the haemoglobin binds with the oxygen to carry ... into an AZT-resistant form [12, 13]. ..... Das, R.; Pitre, K.S. Bioinorganic studies on nickel(II)-zidovudine complex. J. Indian ...

  5. Powerhouse down: Complex II dissociation in the respiratory chain

    Czech Academy of Sciences Publication Activity Database

    Hwang, M.-S.; Rohlena, Jakub; Dong, L.-F.; Neužil, Jiří; Grimm, S.

    2014-01-01

    Roč. 19, Part A SI (2014), 20-28 ISSN 1567-7249 R&D Projects: GA MŠk(CZ) ED1.1.00/02.0109; GA ČR GAP301/12/1851 Institutional support: RVO:86652036 Keywords : Mitochondria * Apoptosis * Complex II Subject RIV: EB - Genetics ; Molecular Biology Impact factor: 3.249, year: 2014

  6. Cd(II and Pb(II complexes of the polyether ionophorous antibiotic salinomycin

    Directory of Open Access Journals (Sweden)

    Tanabe Makoto

    2011-09-01

    Full Text Available Abstract Background The natural polyether ionophorous antibiotics are used for the treatment of coccidiosis in poultry and ruminants. They are effective agents against infections caused by Gram-positive microorganisms. On the other hand, it was found that some of these compounds selectively bind lead(II ions in in vivo experiments, despite so far no Pb(II-containing compounds of defined composition have been isolated and characterized. To assess the potential of polyether ionophores as possible antidotes in the agriculture, a detailed study on their in vitro complexation with toxic metal ions is required. In the present paper we report for the first time the preparation and the structure elucidation of salinomycin complexes with ions of cadmium(II and lead(II. Results New metal(II complexes of the polyether ionophorous antibiotic salinomycin with Cd(II and Pb(II ions were prepared and structurally characterized by IR, FAB-MS and NMR techniques. The spectroscopic information and elemental analysis data reveal that sodium salinomycin (SalNa undergoes a reaction with heavy metal(II ions to form [Cd(Sal2(H2O2] (1 and [Pb(Sal(NO3] (2, respectively. Abstraction of sodium ions from the cavity of the antibiotic is occurring during the complexation reaction. Salinomycin coordinates with cadmium(II ions as a bidentate monoanionic ligand through the deprotonated carboxylic moiety and one of the hydroxyl groups to yield 1. Two salinomycin anions occupy the equatorial plane of the Cd(II center, while two water molecules take the axial positions of the inner coordination sphere of the metal(II cation. Complex 2 consists of monoanionic salinomycin acting in polydentate coordination mode in a molar ratio of 1: 1 to the metal ion with one nitrate ion for charge compensation. Conclusion The formation of the salinomycin heavy metal(II complexes indicates a possible antidote activity of the ligand in case of chronic/acute intoxications likely to occur in the stock

  7. Cd(II) and Pb(II) complexes of the polyether ionophorous antibiotic salinomycin

    Science.gov (United States)

    2011-01-01

    Background The natural polyether ionophorous antibiotics are used for the treatment of coccidiosis in poultry and ruminants. They are effective agents against infections caused by Gram-positive microorganisms. On the other hand, it was found that some of these compounds selectively bind lead(II) ions in in vivo experiments, despite so far no Pb(II)-containing compounds of defined composition have been isolated and characterized. To assess the potential of polyether ionophores as possible antidotes in the agriculture, a detailed study on their in vitro complexation with toxic metal ions is required. In the present paper we report for the first time the preparation and the structure elucidation of salinomycin complexes with ions of cadmium(II) and lead(II). Results New metal(II) complexes of the polyether ionophorous antibiotic salinomycin with Cd(II) and Pb(II) ions were prepared and structurally characterized by IR, FAB-MS and NMR techniques. The spectroscopic information and elemental analysis data reveal that sodium salinomycin (SalNa) undergoes a reaction with heavy metal(II) ions to form [Cd(Sal)2(H2O)2] (1) and [Pb(Sal)(NO3)] (2), respectively. Abstraction of sodium ions from the cavity of the antibiotic is occurring during the complexation reaction. Salinomycin coordinates with cadmium(II) ions as a bidentate monoanionic ligand through the deprotonated carboxylic moiety and one of the hydroxyl groups to yield 1. Two salinomycin anions occupy the equatorial plane of the Cd(II) center, while two water molecules take the axial positions of the inner coordination sphere of the metal(II) cation. Complex 2 consists of monoanionic salinomycin acting in polydentate coordination mode in a molar ratio of 1: 1 to the metal ion with one nitrate ion for charge compensation. Conclusion The formation of the salinomycin heavy metal(II) complexes indicates a possible antidote activity of the ligand in case of chronic/acute intoxications likely to occur in the stock farming

  8. Synthesis, spectral and theoretical studies of Ni(II), Pd(II) and Pt(II) complexes of 5-mercapto-1,2,4-triazole-3-imine-2‧-hydroxynaphyhaline

    Science.gov (United States)

    Gaber, Mohamed; El-Ghamry, Hoda; Atlam, Faten; Fathalla, Shaimaa

    2015-02-01

    Ni(II), Pd(II) and Pt(II) complexes of 5-mercapto-1,2,4-triazole-3-imine-2‧-hydroxynaphthaline have been isolated and characterized by elemental analysis, IR, 1H NMR, EI-mass, UV-vis, molar conductance, magnetic moment measurements and thermogravimetric analysis. The molar conductance values indicated that the complexes are non-electrolytes. The magnetic moment values of the complexes displayed diamagnetic behavior for Pd(II) and Pt(II) complexes and tetrahedral geometrical structure for Ni(II) complex. From the bioinorganic applications point of view, the interaction of the ligand and its metal complexes with CT-DNA was investigated using absorption and viscosity titration techniques. The Schiff-base ligand and its metal complexes have also been screened for their antimicrobial and antitumor activities. Also, theoretical investigation of molecular and electronic structures of the studied ligand and its metal complexes has been carried out. Molecular orbital calculations were performed using DFT (density functional theory) at B3LYP level with standard 6-31G(d,p) and LANL2DZ basis sets to access reliable results to the experimental values. The calculations were performed to obtain the optimized molecular geometry, charge density distribution, extent of distortion from regular geometry, the highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO), Mulliken atomic charges, reactivity index (ΔE), dipole moment (D), global hardness (η), softness (σ), electrophilicity index (ω), chemical potential and Mulliken electronegativity (χ).

  9. Spectral, thermal, electrochemical and analytical studies on Cd(II) and Hg(II) thiosemicarbazone complexes

    Science.gov (United States)

    El-Asmy, A. A.; El-Gammal, O. A.; Saleh, H. S.

    2008-11-01

    The coordination characteristic of the investigated thiosemicarbazones towards hazard pollutants, Cd(II) and Hg(II), becomes the first goal. Their complexes have been studied by microanalysis, thermal, electrochemical and spectral (electronic, IR and MS) studies. The substitutent (salicylaldehyde, acetophenone, benzophenone, o-hydroxy- p-methoxybenzophenone or diacetylmonoxime) plays an important role in the complex formation. The coordination sites were the S for thiosemicarbazide (HTS); NN for benzophenone thiosemicarbazone (HBTS); NS for acetophenone thiosemicarbazone (HATS) and salicylaldehyde thiosemicarbazone (H 2STS); NNS or NSO for diacetylmonoxime thiosemicarbazone (H 2DMTS). The stability constants of Hg(II) complexes were higher than Cd(II). The kinetic and thermodynamic parameters for the different thermal decomposition steps in the complexes have been evaluated. The activation energy values of the first step ordered the complexes as: [Cd(H 2STS)Cl 2]H 2O > [Cd(H 2DAMTS)Cl 2] > [Cd(HBTS) 2Cl 2]2H 2O > [Cd(HATS) 2Cl 2]. The CV of [Cd(H 2STS)Cl 2]H 2O and [Hg(HBTS)Cl 2] were recorded. The use of H 2DMTS as a new reagent for the separation and determination of Cd(II) ions from water and some synthetic samples using flotation technique is aimed to be discussed.

  10. Synthesis, characterization and behavior to gamma radiation of copper (II) complex and l-asparagine

    International Nuclear Information System (INIS)

    Rodrigues, E.R.

    1982-01-01

    Synthesis and caracterization of coordination compound formed by interation between l-asparagina (HL) and copper (II) ion are discussed. Elemental analysis, Visible and Ultraviolet electronic Spectroscopy, Infrared Vibrational Spectroscopy, Proton Nuclear Magnetic Resonance and melting and/or decomposition point are made; it is also possible to: a) Synthesize the complex with high degree of purity; b)determine the #betta# sub(max) for absorption in the Visible and Ultraviolet, as well as the molar absorption coefficient; c) determine the probable structure of the complex; d) calculate the kinetic parameters and the break factor by means of radiolysis in ammoniacal aqueous solution of sample submitted by a 60 Co source of #betta#-radiation (Gamma Cell); e) separate the complex from the ionic fractions formed by radiolysis, by means of cromatography in their layers; f) determine the porcentage of Cu in this complex by neutron activation; g) justify the complex resistence in solid phase, to gamma radiation. (A.R.H.) [pt

  11. Investigation of the effects of different carotenoids on the absorption and CD signals of light harvesting 1 complexes

    NARCIS (Netherlands)

    Georgakopoulou, S.; van der Zwan, G.; Olsen, J.D.; Hunter, C.N.; Niederman, R.A.; van Grondelle, R.

    2006-01-01

    Absorption and circular dichroism (CD) spectra of light-harvesting (LH)1 complexes from the purple bacteria Rhodobacter (Rba.) sphaeroides and Rhodospirillum (Rsp.) rubrum are presented. The complexes exhibit very low intensity, highly nonconservative, near-infrared (NIR) CD spectra. Absorption and

  12. The intestinal absorption of dietary cholesterol by hypercholesterolemic (type II) and normocholesterolemic humans.

    Science.gov (United States)

    Connor, W E; Lin, D S

    1974-04-01

    The incomplete absorption of dietary cholesterol may represent an adaptive intestinal barrier that prevents hypercholesterolemia. To explore this mechanism, we compared cholesterol absorption in 15 normocholesterolemic and 6 hypercholesterolemic (type II) subjects fed background cholesterol-free formula diets with 40% of calories as fat. Each test meal consisted of a breakfast into which was incorporated scrambled egg yolk containing 300-500 mg of cholesterol and [4-(14)C]cholesterol (3-22 muCi), either naturally incorporated into the yolk cholesterol by previous isotope injection into the laying hen or added in peanut oil to the yolk of the test breakfast. In some instances [1alpha-(3)H]cholesterol was the radioactive marker. The radioactivity of the fecal neutral sterol fraction was determined in daily stool samples for the next 7 days to provide an estimate of unabsorbed dietary cholesterol. The amount of absorbed and reexcreted labeled cholesterol proved negligible. Most unabsorbed dietary cholesterol appeared in the stool on the second or third day after the meal, and 95% or more was recovered in the stool by 6 days. Plasma specific activity curves were usually maximal at 48 h. Normal subjects absorbed 44.5+/-9.3 (SD) of the administered cholesterol (range 25.9-60.3). Hypercholesterolemics absorbed the same percentage of cholesterol as normals: 47.6+/-12.6% (range 29.3-67.3). Absorption was similar whether the radiolabeled cholesterol was added to egg yolk or naturally incorporated in it (42.1+/-9.3 vs. 48.9+/-9.8%). Six normal subjects were fed a cholesterol-free formula for 4 wk, and then different amounts of cholesterol (110-610 mg/day) were added for another 4 wk. At the end of each period, single test meals containing either 110, 310, or 610 mg of cholesterol and [1alpha-(3)H]cholesterol were administered. Cholesterol absorption was 42.3+/-6.0% and 45.4+/-8.3% for the two dietary periods, respectively. The absolute cholesterol absorption was linearly

  13. Chemical speciation of Pb(II, Cd(II, Hg(II, Co(II, Ni(II, Cu(II and Zn(II binary complexes of l-methionine in 1,2-propanediol-water mixtures

    Directory of Open Access Journals (Sweden)

    M. Padma Latha

    2007-04-01

    Full Text Available Chemical speciation of Pb(II, Cd(II, Hg(II, Co(II, Ni(II, Cu(II and Zn(II complexes of L-methionine in 0.0-60 % v/v 1,2-propanediol-water mixtures maintaining an ionic strength of 0.16 M at 303 K has been studied pH metrically. The active forms of ligand are LH2+, LH and L-. The predominant species detected are ML, MLH, ML2, ML2H, ML2H2 and MLOH. Models containing different numbers of species were refined by using the computer program MINIQUAD 75. The best-fit chemical models were arrived at based on statistical parameters. The trend in variation of complex stability constants with change in the dielectric constant of the medium is explained on the basis of electrostatic and non-electrostatic forces.

  14. Photosynthetic complex LH2 – Absorption and steady state fluorescence spectra

    International Nuclear Information System (INIS)

    Zapletal, David; Heřman, Pavel

    2014-01-01

    Nowadays, much effort is devoted to the study of photosynthesis which could be the basis for an ideal energy source in the future. To be able to create such an energy source – an artificial photosynthetic complex, the first step is a detailed understanding of the function of photosynthetic complexes in living organisms. Photosynthesis starts with the absorption of a solar photon by one of the LH (light-harvesting) pigment–protein complexes and transferring the excitation energy to the reaction center where a charge separation is initiated. The geometric structure of some LH complexes is known in great detail, e.g. for the LH2 complexes of purple bacteria. For understanding of photosynthesis first stage efficiency, it is necessary to study especially optical properties of LH complexes. In this paper we present simulated absorption and steady-state fluorescence spectra for ring molecular system within full Hamiltonian model. Such system can model bacteriochlorophyll ring of peripheral light-harvesting complex LH2 from purple bacterium Rhodopseudomonas acidophila (Rhodoblastus acidophilus). Dynamic disorder (coupling with phonon bath) simultaneously with uncorrelated static disorder (transfer integral fluctuations) is used in our present simulations. We compare and discuss our new results with our previously published ones and of course with experimental data. - Highlights: • We model absorption and steady state fluorescence spectra for B850 ring from LH2. • Fluctuations of environment is modelled by static and dynamic disorder. • Full Hamiltonian model is compared with the nearest neighbour approximation one. • Simulated fluorescence spectrum is compared with experimental data

  15. Quasar 2175 Å dust absorbers - II. Correlation analysis and relationship with other absorption line systems

    Science.gov (United States)

    Ma, Jingzhe; Ge, Jian; Prochaska, J. Xavier; Zhang, Shaohua; Ji, Tuo; Zhao, Yinan; Zhou, Hongyan; Lu, Honglin; Schneider, Donald P.

    2018-03-01

    We present the cold neutral content (H I and C I gas) of 13 quasar 2175 Å dust absorbers (2DAs) at z = 1.6-2.5 to investigate the correlation between the presence of the UV extinction bump with other physical characteristics. These 2DAs were initially selected from the Sloan Digital Sky Surveys I-III and followed up with the Keck-II telescope and the Multiple Mirror Telescope as detailed in our Paper I. We perform a correlation analysis between metallicity, redshift, depletion level, velocity width, and explore relationships between 2DAs and other absorption line systems. The 2DAs on average have higher metallicity, higher depletion levels, and larger velocity widths than Damped Lyman α absorbers (DLAs) or subDLAs. The correlation between [Zn/H] and [Fe/Zn] or [Zn/H] and logΔV90 can be used as alternative stellar mass estimators based on the well-established mass-metallicity relation. The estimated stellar masses of the 2DAs in this sample are in the range of ˜109 to ˜2 × 1011 M⊙ with a median value of ˜2 × 1010 M⊙. The relationship with other quasar absorption line systems can be described as (1) 2DAs are a subset of Mg II and Fe II absorbers, (2) 2DAs are preferentially metal-strong DLAs/subDLAs, (3) More importantly, all of the 2DAs show C I detections with logN(C I) > 14.0 cm-2, and (4) 2DAs can be used as molecular gas tracers. Their host galaxies are likely to be chemically enriched, evolved, massive (more massive than typical DLA/subDLA galaxies), and presumably star-forming galaxies.

  16. Fluorescent copper(II complexes: The electron transfer mechanism, interaction with bovine serum albumin (BSA and antibacterial activity

    Directory of Open Access Journals (Sweden)

    Madhumita Hazra

    2017-01-01

    Full Text Available Dinuclear copper(II complexes with formula [Cu2(L2(N32] (1 and [Cu2(L2(NCS2] (2 HL = (1-[(3-methyl-pyridine-2-ylimino-methyl]-naphthalen-2-ol were synthesized by controlling the molar ratio of Cu(OAC2·6H2O, HL, sodium azide (1 and ammonium thiocyanate (2. The end on bridges appear exclusively in azide and thiocyanate to copper complexes. The electron transfer mechanism of copper(II complexes is examined by cyclic voltammetry indicating copper(II complexes are Cu(II/Cu(I couple. The interactions of copper(II complexes towards bovine serum albumin (BSA were examined with the help of absorption and fluorescence spectroscopic tools. We report a superficial solution-based route for the synthesis of micro crystals of copper complexes with BSA. The antibacterial activity of the Schiff base and its copper complexes were investigated by the agar disc diffusion method against some species of pathogenic bacteria (Escherichia coli, Vibrio cholerae, Streptococcus pneumonia and Bacillus cereus. It has been observed that the antibacterial activity of all complexes is higher than the ligand.

  17. SPECIATION OF BINARY COMPLEXES OF Pb(II) AND Cd(II) WITH ...

    African Journals Online (AJOL)

    ABSTRACT. Chemical speciation of L-Asparagine complexes of Pb(II) and Cd(II) in presence of (0-50% v/v) dimethyl sulfoxide(DMSO)-water mixtures has been studied potentiometrically at 303.0 K and at an ionic strength of 0.16 mol L-1. The models containing different number of species were refined by using the ...

  18. Optical characterization and blu-ray recording properties of metal(II) azo barbituric acid complex films

    Energy Technology Data Exchange (ETDEWEB)

    Li, X.Y. [Shanghai Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Shanghai 201800 (China)], E-mail: xyli@siom.ac.cn; Wu, Y.Q. [Shanghai Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Shanghai 201800 (China); Key Lab of Functional Inorganic Material Chemistry (Heilongjiang University), Ministry of Education, Haerbin 150080 (China)], E-mail: yqwu@siom.ac.cn; Gu, D.D.; Gan, F.X. [Shanghai Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Shanghai 201800 (China)

    2009-02-25

    Smooth thin films of nickel(II), cobalt(II) and zinc(II) complexes with azo barbituric acid were prepared by the spin-coating method. Absorption spectra of the thin films on K9 glass substrates in 300-700 nm wavelength region were measured. Optical constants (complex refractive index N = n + ik) of the thin films prepared on single-crystal silicon substrates in 275-695 nm wavelength region were investigated on rotating analyzer-polarizer type of scanning ellipsometer, and dielectric constant {epsilon} ({epsilon} = {epsilon}{sub 1} + i{epsilon}{sub 2}) as well as absorption coefficient {alpha} of thin films were calculated at 405 nm. In addition, static optical recording properties of the cobalt(II) complex thin film with an Ag reflective layer was carried out using a 406.7 nm blue-violet laser and a high numerical aperture (NA) of 0.90. Clear recording marks with high reflectivity contrast (>60%) at proper laser power and pulse width were obtained, and the size of recording mark was as small as 250 nm. The results indicate that these metal(II) complexes are promising organic recording medium for the blu-ray optical storage system.

  19. A treatise on benzimidazole based Schiff base metal(II) complexes accentuating their biological efficacy: Spectroscopic evaluation of DNA interactions, DNA cleavage and antimicrobial screening

    Energy Technology Data Exchange (ETDEWEB)

    Kumaravel, Ganesan; Raman, Natarajan, E-mail: ramchem1964@gmail.com

    2017-01-01

    Two novel imidazole derived Schiff bases, (Z)-1-(1H-benzo[d]imidazol-2-yl)-N-benzylidenemethanamine (L{sup 1}) and 1-(1H-benzo[d]imidazol-2-yl)-N-(4-nitrobenzylidene) methanamine, and a series of their transition metal complexes of the types [M(L{sup 1}){sub 2}]Cl{sub 2} and [M(L{sup 2}){sub 2}]Cl{sub 2} where, M = Cu(II), Ni(II), Co(II) and Zn(II) have been designed and synthesized. These compounds were characterized by various spectral and physicochemical data. UV–Vis, magnetic susceptibility and molar conductivity data indicate that all the complexes adopt square planar geometry. The EPR spectral data of the Cu(II) complexes have provided supportive evidence to the conclusion derived on the basis of electronic absorption and magnetic moment values. Moreover, the interaction of complexes with DNA via intercalation has been explored by absorption, fluorescence spectroscopy, cyclic voltammetry, viscosity and circular dichroism. Agarose gel electrophoresis technique reveals that the complexes are good metallonucleases. All the compounds have relatively high antibacterial and antifungal potencies. Among the metal complexes, Cu(II) complexes exhibit higher efficacy against all the pathogens. - Highlights: • Synthesis of new and efficient benzimidazole based DNA targeting complexes • Synthesis of efficient metallointercalators • Excellent DNA exploiting ability of Cu(II) complexes • Efficient antimicrobial agents against various pathogens.

  20. Band shape of IR-absorption of complex molecules and restricted rotational diffusion

    International Nuclear Information System (INIS)

    Ivanov, E.N.; Umidulaev, Sh.U.

    1989-01-01

    The development of the theory of band shape (and Breadth) IR-absorption of complex molecules (regarding the molecules inside motions) is considered. It is supposed that a molecule fragment being responsible for IR-absorption takes part in the restricted rotational diffusion (RRD) with respect to the frame, and the molecule itself in general makes rotational motion (RM). Both kinds of motions are discussed in accordance with the theory of group motions representations. On the basis of correlative functions calculations of dipole moment a simple expression for the IR-absorption band shape have been obtained, which in itself uses to be the super position of two Lorencians with the semibreadths 2D 1 and 2D 1 +ν 2 0 (ν 2 0 +1D R accordingly (here D 1 is the coefficient of RM, D 2 is the coefficient of RRD, ν 2 0 is the well known function of RRD-cone divergence angle) in case of symmetric rotary abrasive disc. Analysis of experimental band shape of IR-absorption on the basis of the expression obtained allows to get information of MR-molecule parameters in general and RRD. It is really possible to determine the RRD-cone divergency angle from experimental weights of Lorencians. In accordance with experimental semibreadths the coefficient of RM D 1 and the coefficient of RRD D 2 are obtained. In conclusion it is noted that D 1 →0 (in the expression for the band shape of IR-absorption obtained), one of the Lorencians turns to the δ-function and finally there is an expression which describes IR-absorption band shape of molecules in polymer-mats. (author)

  1. Unsaturated b-ketoesters and their Ni(II, Cu(II and Zn(II complexes

    Directory of Open Access Journals (Sweden)

    MUHAMMED BASHEER UMMATHUR

    2009-03-01

    Full Text Available A new series of b-ketoesters in which the keto group is attached to the olefinic linkage were synthesized by the reaction of methyl acetoacetate and aromatic aldehydes under specified conditions. The existence of these compounds predominantly in the intramolecularly hydrogen bonded enol form was well demonstrated from their IR, 1H-NMR and mass spectral data. Details on the formation of their [ML2] complexes with Ni(II, Cu(II and Zn(II and the nature of the bonding are discussed on the basis of analytical and spectral data.

  2. Synthesis, spectroscopic and DNA binding ability of Co{sup II}, Ni{sup II}, Cu{sup II} and Zn{sup II} complexes of Schiff base ligand (E)-1-(((1H-benzo[d]imidazol-2-yl)methylimino)methyl)naphthalen-2-ol. X-ray crystal structure determination of cobalt (II) complex

    Energy Technology Data Exchange (ETDEWEB)

    Yarkandi, Naeema H. [Chemistry Department, Faculty of Applied Science, Umm Al–Qura University, Makkah (Saudi Arabia); El-Ghamry, Hoda A., E-mail: helghamrymo@yahoo.com [Chemistry Department, Faculty of Applied Science, Umm Al–Qura University, Makkah (Saudi Arabia); Chemistry Department, Faculty of Science, Tanta University, Tanta (Egypt); Gaber, Mohamed [Chemistry Department, Faculty of Science, Tanta University, Tanta (Egypt)

    2017-06-01

    A novel Schiff base ligand, (E)-1-(((1H-benzo[d]imidazol-2-yl)methylimino)methyl)naphthalen-2-ol (HL), has been designed and synthesized in addition to its metal chelates [Co(L){sub 2}]·l2H{sub 2}O, [Ni(L)Cl·(H{sub 2}O){sub 2}].5H{sub 2}O, [Cu(L)Cl] and [Zn(L)(CH{sub 3}COO)]. The structures of the isolated compounds have been confirmed and identified by means of different spectral and physicochemical techniques including CHN analysis, {sup 1}H &{sup 13}C NMR, mass spectral analysis, molar conductivity measurement, UV–Vis, infrared, magnetic moment in addition to TGA technique. The infrared spectral results ascertained that the ligand acts as monobasic tridentate binding to the metal centers via deprotonated hydroxyl oxygen, azomethine and imidazole nitrogen atoms. The UV–Vis, magnetic susceptibility and molar conductivity data implied octahedral geometry for Co(II) & Ni(II) complexes, tetrahedral for Zn(II) complex and square planar for Cu(II) complex. X-ray structural analysis of Co(II) complex 1 has been reported and discussed. Moreover, the type of interaction between the ligand & its complexes towards salmon sperm DNA (SS-DNA) has been examined by the measurement of absorption spectra and viscosity which confirmed that the ligand and its complexes interact with DNA via intercalation interaction as concluded from the values of binding constants (K{sub b}). - Highlights: • Synthesis of Co{sup II}, Ni{sup II}, Cu{sup II} and Zn{sup II} complexes of the Schiff base ligand based on 2-(aminomethyl)benzimidazole moiety. • The constitutions and structures of the ligand and complexes were elucidated. • Molecular structure of Co{sup II} complex was confirmed by single crystal X-ray diffraction method. • The ligand and its complexes interact with SS-DNA via intercalation mods.

  3. Anionic Palladium(0) and Palladium(II) Ate Complexes.

    Science.gov (United States)

    Kolter, Marlene; Böck, Katharina; Karaghiosoff, Konstantin; Koszinowski, Konrad

    2017-10-16

    Palladium ate complexes are frequently invoked as important intermediates in Heck and cross-coupling reactions, but so far have largely eluded characterization at the molecular level. Here, we use electrospray-ionization mass spectrometry, electrical conductivity measurements, and NMR spectroscopy to show that the electron-poor catalyst [L 3 Pd] (L=tris[3,5-bis(trifluoromethyl)phenyl]phosphine) readily reacts with Br - ions to afford the anionic, zero-valent ate complex [L 3 PdBr] - . In contrast, more-electron-rich Pd catalysts display lower tendencies toward the formation of ate complexes. Combining [L 3 Pd] with LiI and an aryl iodide substrate (ArI) results in the observation of the Pd II ate complex [L 2 Pd(Ar)I 2 ] - . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. The Chameleonic Nature of Platinum(II) Imidazopyridine Complexes.

    Science.gov (United States)

    Pinter, Piermaria; Pittkowski, Rebecca; Soellner, Johannes; Strassner, Thomas

    2017-10-12

    The synthesis and characterization of cyclometalated C^C* platinum(II) complexes with unique photophysical properties, aggregation induced enhancement of the quantum yields with a simultaneous decrease of phosphorescence lifetimes, is reported. Additionally, a change of emission color is induced by variation of the excitation wavelength. The aggregation behavior of these complexes is controlled by the steric demand of the substituents. The photophysical properties of these complexes are investigated through emission-excitation matrix analysis (EEM). The monomeric complexes are excellent room temperature phosphorescent blue emitters with emission maxima below 470 nm and quantum yields of up to 93 %. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Spectroscopic characterization of some Cu(II) complexes

    International Nuclear Information System (INIS)

    Singh, Puja; Sharma, S.

    2014-01-01

    3-hydroxy-4-methoxy benzaldehyde semicarbazone (HMBS) is a biologically active compound which has several potential donor sites. This compound has been used for complexation with Cu(II) ions to synthesize complexes of general formula [Cu(HMBS) 2 X 2 ] where X is Cl − , NO 3 − and CH 3 COO − . Cu(II) is a d 9 system for which 2 D term is generated. Under O h symmetry, this term splits into 2 E g and 2 T 2g . the ground term 2 Eg is doubly degenerate and hence suffers strong Jahn-Teller effect and accordingly the further splitting of terms occur to lower the symmetry from perfect O h . Here, the ligand occupies four planar positions while the two axial positions have been varied by using different ions like Cl − , NO 3 − and CH 3 COO − . These variations on the axial positions also add to the distortion in O h symmetry. Under strong distortion, the electronic spectral band splits into multiplets exhibiting tetragonal distortion in complexes. The extent of distortion has been derived by the derivation of the two radial parameters D s and D t from electronic spectral bands. The ESR spectra of complexes reveal the real position of the only unpaired electron of the d 9 system in complexes

  6. Inhibition of intestinal radiocaesium absorption from Chernobyl contaminated whey by hexacyanoferrates(II) in pigs

    International Nuclear Information System (INIS)

    Dresow, B.; Asmus, J.; Fischer, R.; Nielsen, P.; Heinrich, H.C.

    1993-01-01

    The inhibition of radiocaesium transfer from Chernobyl contaminated whey powder to the pork and liver of fattening pigs using various dosages of different hexacyanoferrate (II) compounds (HCF) was studied under normal feeding conditions. Increasing amounts of all three hexacyanoferates tested resulted in a dose-dependent reduction in the 134+137 Cs activity concentration in all of the tissues sampled. KFe[Fe(CN) 6 ] and NE 4 Fe(CN) 6 ] were effective to the same extent while Fe 4 [Fe(CN) 6 ] 3 was less effective at dosages of 1-3 g d -1 HCF. Administration of 10 g d -1 HCF resulted in an almost complete inhibition (>99%) of intestinal radiocaesium absorption for all three compounds. (Author)

  7. COPPER(II) COMPLEXES OF o -VANILLIN ACETYLHYDRAZONE ...

    African Journals Online (AJOL)

    A hydrazonic ligand, o-vanillin acetylhydrazone (H2L) has been prepared and used as chelating agent towards copper(II) ion. The ligand acts like a tridentate ligand in the monodeprotonated (HL-) and dideprotonated (L2-) states. Monoanionic complexes [{Cu(HL)(H2O)}2]•2BF4 and [{Cu(HL)(Hpz)(H2O)}]•NO3 have been ...

  8. Biphenolate Iron (II) Complexes with Intramolecularly Coordinating Nitrogen Lewis Bases

    NARCIS (Netherlands)

    Koten, G. van; Brandts, J.A.M.; Janssen, M.D.; Hogerheide, M.P.; Boersma, J.; Spek, A.L.

    1999-01-01

    The synthesis and characterisation of a novel Fe(II) bisphenolate complex [Fe(OC{6}H{4}CH{2}NMe{2}-2){2}]{2} (1) from [Na(OC{6}H{4}CH{2}NMe{2}-2)] and anhydrous FeCl{2} is reported. The solid state structure has been elucidated by single crystal X-ray analysis and shows a dimeric structure with two

  9. Studies on nickel (II and palladium (II complexes with some tetraazamacrocycles containing tellurium

    Directory of Open Access Journals (Sweden)

    Rathee Nitu

    2012-01-01

    Full Text Available The synthesis of 10-membered and 12-membered tellurium containing tetraazamacrocyclic complexes of divalent nickel and palladium by template condensation of diaryltellurium dichlorides, (aryl = p-hydroxyphenyl, 3-methyl-4-hydroxyphenyl, p-methoxyphenyl with 1,2-diaminoethane and 1,3-diaminopropane in the presence of metal dichloride is reported. The resulting complexes have been subjected to elemental analyses, magnetic measurements, electronic absorption, infra-red, and proton magnetic resonance spectral studies. The formation of proposed macrocyclic skeletons and their donor sites have been identified on the basis of spectral studies. Distorted octahedral structure for the nickel complexes in the solid state and squareplanar structure for the palladium complexes have been suggested.

  10. Simultaneous absorption of NO and SO{sub 2} into hexamminecobalt(II)/iodide solution

    Energy Technology Data Exchange (ETDEWEB)

    Long, X.L.; Xiao, W.D.; Yuan, W.K. [East China University of Science & Technology, Shanghai (China)

    2005-05-01

    An innovative catalyst system has been developed to simultaneously remove NO and SO{sub 2} from combustion flue gas. Such catalyst system may be introduced to the scrubbing solution using ammonia solution to accomplish sequential absorption and catalytic oxidation of both NO and SO{sub 2} in the same reactor. When the catalyst system is utilized for removing NO and SO{sub 2} from the flue gas, Co(NH{sub 3}){sub 6}{sup 2+} ions act as the catalyst and I{sup -} as the co-catalyst. Dissolved oxygen, in equilibrium with the residual oxygen in the flue gas, is the oxidant. The overall removal process is further enhanced by UV irradiation at 365 nm. More than 95% of NO is removed at a feed concentration of 250-900 ppm, and nearly 100% of SO{sub 2} is removed at a feed concentration of 800-2500 ppm. The sulfur dioxide co-existing in the flue gas is beneficial to NO absorption into hexamminecobalt(II)/iodide solution. NO and SO{sub 2} can be converted to ammonium sulfate and ammonium nitrate that can be used as fertilizer materials. The process described here demonstrates the feasibility of removing SO{sub 2} and NO simultaneously only by retrofitting the existing wet ammonia flue-gas-desulfurization (FGD) scrubbers.

  11. Simultaneous absorption of NO and SO2 into hexamminecobalt(II)/iodide solution.

    Science.gov (United States)

    Long, Xiang-Li; Xiao, Wen-De; Yuan, Wei-kang

    2005-05-01

    An innovative catalyst system has been developed to simultaneously remove NO and SO2 from combustion flue gas. Such catalyst system may be introduced to the scrubbing solution using ammonia solution to accomplish sequential absorption and catalytic oxidation of both NO and SO2 in the same reactor. When the catalyst system is utilized for removing NO and SO2 from the flue gas, Co(NH3)(6)2+ ions act as the catalyst and I- as the co-catalyst. Dissolved oxygen, in equilibrium with the residual oxygen in the flue gas, is the oxidant. The overall removal process is further enhanced by UV irradiation at 365 nm. More than 95% of NO is removed at a feed concentration of 250-900 ppm, and nearly 100% of SO2 is removed at a feed concentration of 800-2500 ppm. The sulfur dioxide co-existing in the flue gas is beneficial to NO absorption into hexamminecobalt(II)/iodide solution. NO and SO2 can be converted to ammonium sulfate and ammonium nitrate that can be used as fertilizer materials. The process described here demonstrates the feasibility of removing SO2 and NO simultaneously only by retrofitting the existing wet ammonia flue-gas-desulfurization (FGD) scrubbers.

  12. Synthesis, Characterization, and Biological Activity of Mn(II, Fe(II, Co(II, Ni(II, Cu(II, Zn(II, and Cd(II Complexes of N-Thiophenoyl-N′-Phenylthiocarbohydrazide

    Directory of Open Access Journals (Sweden)

    M. Yadav

    2013-01-01

    Full Text Available Mn(II, Fe(II, Co(II, Ni(II, Cu(II, Zn(II, and Cd(II complex of N-thiophenoyl -N′-phenylthiocarbohydrazide (H2 TPTH have been synthesized and characterized by elemental analysis, magnetic susceptibility measurements, infrared, NMR, electronic, and ESR spectral studies. The complexes were found to have compositions [Mn(H TPTH2], [Co(TPTH (H2O2], [Ni(TPTH (H2O2], [Cu(TPTH], [Zn(H TPTH], [Cd(H TPTH2], and [Fe(H TPTH2(EtOH]. The magnetic and electronic spectral studies suggest square planar geometry for [Cu(TPTH], tetrahedral geometry for [Zn(TPTH] and [Cd(H TPTH2], and octahedral geometry for rest of the complexes. The infrared spectral studies of the 1 : 1 deprotonated complexes suggest bonding through enolic oxygen, thiolato sulfur, and both the hydrazinic nitrogens. Thus, H2TPTH acts as a binegative tetradentate ligand. H2 TPTH and its metal complexes have been screened against several bacteria and fungi.

  13. Pressure and solvent shifts of charge transfer absorption band of iodine complexes

    International Nuclear Information System (INIS)

    Sawamura, Seiji; Taniguchi, Yoshihiro; Suzuki, Keizo

    1979-01-01

    Absorption spectra of the CT band of I 2 complexes were observed in several nonpolar solvents at 1 bar, and in heptane up to 4400 bar. All solvent shifts were red with an increase in (n 2 - 1)/(2n 2 + 1), the refractive index (n) function of solvents, consistent with the solvent shift theory. On the other hand pressure caused a variety of shifts, that is, red shifts in benzene-, toluene-, and mesitylene-I 2 complexes, an inversion shift from red to blue in HMB-I 2 complex, and blue shifts in Et 3 N-, n-Pr 3 N-, and n-Bu 3 N-I 2 complexes, though increase in pressure invariably raises the (n 2 - 1)/(2n 2 + 1) value of solvent. The pressure shifts of I 2 complexes seem to be interpreted by a sum of two effects. One is the increased polarity of the solvent, which causes a red shift. The other is the decrease in the bond distance between a donor and an acceptor, which contributes to a blue shift in a strong CT complex and to a red shift in a week one. The pressure and solvent shifts of I 2 complexes were compared with those of π-donor-TCNE complexes. (author)

  14. Preparation of Schiff s base complexes of Mn(II), Co(II), Ni(II), Cu(II), Zn(II), and Cd(II) and their spectroscopic, magnetic, thermal, and antifungal studies

    International Nuclear Information System (INIS)

    Parekh, H.M.; Patel, M.N.

    2006-01-01

    The potassium salt of salicylidene-DL-alanine (KHL), bis(benzylidene)ethylenediamine (A 1 ), thiophene-o-carboxaldene-p-toluidine (A 2 ), and its metal complexes of the formula [(M II (L)(A)(H 2 O)] (M=Mn(II), Co(II), Ni(II), Cu(II), Zn(II), and Cd(II); A = A 1 or A 2 ) are prepared. They are characterized by elemental analysis, magnetic susceptibility measurements, thermogravimetric analysis, and infrared and electronic spectral studies. The electronic spectral and magnetic moment data suggest an octahedral geometry for the complexes. All of these complexes, metal nitrates, fungicides (bavistin and emcarb), and ligands are screened for their antifungal activity against Aspergillus niger, Fusarium oxysporum, and Aspergillus flavus using a plate poison technique. The complexes show higher activity than those of the free ligands, metal nitrate, and the control (DMSO) and moderate activity against bavistin and emcarb [ru

  15. One-dimensional Co(II)/Ni(II) complexes of 2-hydroxyisophthalate: Structures and magnetic properties

    International Nuclear Information System (INIS)

    Wang, Kai; Zou, Hua-Hong; Chen, Zi-Lu; Zhang, Zhong; Sun, Wei-Yin; Liang, Fu-Pei

    2015-01-01

    The solvothermal reactions of 2-hydroxyisophthalic acid (H 3 ipO) with M(NO 3 ) 2 ∙6H 2 O (M=Co, Ni) afforded two complexes [Co 2 (HipO) 2 (Py) 2 (H 2 O) 2 ] (1) and [Ni(HipO)(Py)H 2 O] (2) (Py=pyridine). They exhibit similar zig-zag chain structures with the adjacent two metal centers connected by a anti-syn bridging carboxylate group from the HipO 2− ligand. The magnetic measurements reveal the dominant antiferromagnetic interactions and spin-canting in 1 while ferromagnetic interactions in 2. Both of them exhibit magnetocaloric effect (MCE) with the resulting entropy changes (−ΔS m ) of 12.51 J kg −1 K −1 when ΔH=50 kOe at 3 K for 1 and 11.01 J kg −1 K −1 when ΔH=50 kOe at 3 K for 2, representing the rare examples of one-dimensional complexes with MCE. - Graphical abstract: Synopsis: Two Co(II)/Ni(II) complexes with zig-zag chain structures have been reported. 1-Co shows cant-antiferromagnetism while 2-Ni shows ferromagnetism. Magnetocaloric effect is also found in both of them. - Highlights: • Two one-dimensional Co(II)/Ni(II) complexes were solvothermally synthesized. • The Co-complex exhibits canted antiferromagnetism. • The Ni-complex exhibits ferromagnetism. • Both of the complexes display magnetocaloric effect

  16. Preconcentration, Separation and Determination of lead(II) with Methyl Thymol Blue Adsorbed on Activated Carbon Using Flame Atomic Absorption Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Ensafi, Ali A.; Ghaderi, Ali R. [Isfahan University of Technology, Isfahan (Iran, Islamic Republic of)

    2008-02-15

    An on-line system for preconcentration and separation of lead(II) is presented. The method is based on the complex formation of Pb(II) with adsorbed Methyl thymol blue on activated carbon. The conditions of preparing the solid phase reagent and of quantitative recovery of Pb(II) from diluted solutions, such as acidity of aqueous phase, solid phase capacity, and flow variables were studied as well as effect of potential interfering ions. After preconcentration step, the metal ions are eluted automatically by 5 ml of 0.5 M HNO{sub 3} solution and the lead ions content was determined by flame atomic absorption spectrometry. Under the optimum conditions, the lead ions in aqueous samples were separated and preconcentrated about 1000-fold by the column. The detection limit was 0.001 μg mL{sup -1}. Lead has been determined in river and tap water samples, with recovery of 98 to 102%.

  17. Synthesis and structural characterization of nickel(II), cobalt(II), Zinc(II), manganese(II), cadmium(II) and uranium(VI) complexes of α-oximinoacetoacet-o/p-anisidide thiosemicarbazone

    International Nuclear Information System (INIS)

    Patel, P.S.; Patel, M.M.; Ray, R.M.

    1993-01-01

    A few metal complexes of α-oximinoacetoacet-o/p-anisidide thiosemicarbazones (OAOATS)/(OAPATS) with Ni(II), Co(II), Zn(II), Mn(II), Hg(II), Cd(II) and UO 2 (II) have been prepared and characterized by elemental analyses, conductivity, differential scanning calorimetry study, thermogravimetric analyses and infrared and electronic spectral measurements in conjunction with magnetic susceptibility measurements at room temperature. They have also been tested for their antimicrobial activities. (author). 24 refs., 2 tabs

  18. Absorption enhancement in type-II coupled quantum rings due to existence of quasi-bound states

    Science.gov (United States)

    Hsieh, Chi-Ti; Lin, Shih-Yen; Chang, Shu-Wei

    2018-02-01

    The absorption of type-II nanostructures is often weaker than type-I counterpart due to spatially separated electrons and holes. We model the bound-to-continuum absorption of type-II quantum rings (QRs) using a multiband source-radiation approach using the retarded Green function in the cylindrical coordinate system. The selection rules due to the circular symmetry for allowed transitions of absorption are utilized. The bound-tocontinuum absorptions of type-II GaSb coupled and uncoupled QRs embedded in GaAs matrix are compared here. The GaSb QRs act as energy barriers for electrons but potential wells for holes. For the coupled QR structure, the region sandwiched between two QRs forms a potential reservoir of quasi-bound electrons. Electrons in these states, though look like bound ones, would ultimately tunnel out of the reservoir through barriers. Multiband perfectly-matched layers are introduced to model the tunneling of quasi-bound states into open space. Resonance peaks are observed on the absorption spectra of type-II coupled QRs due to the formation of quasi-bound states in conduction bands, but no resonance exist in the uncoupled QR. The tunneling time of these metastable states can be extracted from the resonance and is in the order of ten femtoseconds. Absorption of coupled QRs is significantly enhanced as compared to that of uncoupled ones in certain spectral windows of interest. These features may improve the performance of photon detectors and photovoltaic devices based on type-II semiconductor nanostructures.

  19. Excited state electron and energy relays in supramolecular dinuclear complexes revealed by ultrafast optical and X-ray transient absorption spectroscopy.

    Science.gov (United States)

    Hayes, Dugan; Kohler, Lars; Hadt, Ryan G; Zhang, Xiaoyi; Liu, Cunming; Mulfort, Karen L; Chen, Lin X

    2018-01-28

    The kinetics of photoinduced electron and energy transfer in a family of tetrapyridophenazine-bridged heteroleptic homo- and heterodinuclear copper(i) bis(phenanthroline)/ruthenium(ii) polypyridyl complexes were studied using ultrafast optical and multi-edge X-ray transient absorption spectroscopies. This work combines the synthesis of heterodinuclear Cu(i)-Ru(ii) analogs of the homodinuclear Cu(i)-Cu(i) targets with spectroscopic analysis and electronic structure calculations to first disentangle the dynamics at individual metal sites by taking advantage of the element and site specificity of X-ray absorption and theoretical methods. The excited state dynamical models developed for the heterodinuclear complexes are then applied to model the more challenging homodinuclear complexes. These results suggest that both intermetallic charge and energy transfer can be observed in an asymmetric dinuclear copper complex in which the ground state redox potentials of the copper sites are offset by only 310 meV. We also demonstrate the ability of several of these complexes to effectively and unidirectionally shuttle energy between different metal centers, a property that could be of great use in the design of broadly absorbing and multifunctional multimetallic photocatalysts. This work provides an important step toward developing both a fundamental conceptual picture and a practical experimental handle with which synthetic chemists, spectroscopists, and theoreticians may collaborate to engineer cheap and efficient photocatalytic materials capable of performing coulombically demanding chemical transformations.

  20. Synthesis, molecular docking and DNA binding studies of phthalimide-based copper(II) complex: In vitro antibacterial, hemolytic and antioxidant assessment

    Science.gov (United States)

    Arif, Rizwan; Nayab, Pattan Sirajuddin; Ansari, Istikhar A.; Shahid, M.; Irfan, Mohammad; Alam, Shadab; Abid, Mohammad; Rahisuddin

    2018-05-01

    In the present research work, we prepared N-substituted phthalimide, 2-(-(2-(2-(2-(1,3-dioxoisoindoline-2-yl-ethylamino)ethylamino)ethyl)isoindoline-1,3-dione (DEEI) and its copper(II) complex. The ligand (DEEI) and its Cu(II) complex were structurally identified using absorption, FTIR, NMR, electron spin resonance, X-ray diffraction spectral studies, thermogravimetric and elemental analyses. The electronic spectrum and magnetic moment value proposed that Cu(II) complex has square planar geometry. The DNA interaction ability of the ligand (DEEI) and Cu(II) complex was studied by means of absorption and fluorescence spectrophotometer, viscosity measurements, cyclic voltammetery, and circular dichroism methods. The extent of DNA binding (Kb) with Calf thymus (Ct-DNA) follows the order of Cu(II) complex (1.11 × 106 M-1) > DEEI (1.0 × 105 M-1), indicating that Cu(II) complex interact with Ct-DNA through groove binding mode and more sturdily than ligand (DEEI). Interestingly, in silico predictions were corroborated with in vitro DNA binding studies. The antibacterial evaluation of these compounds was screened against a panel of bacterial strains Pseudomonas aeruginosa (MTCC 2453), Salmonella enterica (MTCC 3224), Streptococcus pneumoniae (MTCC 655), Enterococcus faecalis (MTCC 439), Klebsiella pneumonia and Escherichia coli (ATCC 25922). The results showed that the copper(II) complex has significant antibacterial potential (IC50 = 0.0019 μg/mL) against Salmonella enteric comparable with ligand (DEEI) and standard drug ciprofloxacin. Growth curve study of Cu(II) complex against only three bacterial strains S. enterica, E. faecalis and S. pneumoniae showed its bactericidal nature. Cu(II) complex showed less than 2% hemolysis on human RBCs indicating its non toxic nature. The results of antioxidant assay demonstrated that scavenging activity of Cu(II) complex is higher as compared to ligand and ascorbic acid as standard.

  1. Studies on femtosecond fluorescence dynamics of photosystem II Particle complex at low temperature

    CERN Document Server

    Liu Xiao; He, Jun Fang; Cai, Xia; Peng Jun Fang; Kuang Ting Yun

    2004-01-01

    In order to understanding the diversity of energy transfer in PS II at different temperatures, PS II particle complex purified from spinach was investigated with femtosecond time-resolved fluorescence spectroscopy in the case of excitation 507 nm at 83 K, 160 K, 273 K. The data were analyzed by Gauss analysis and fluorescence decay time- fitting. Some results were achieved. (1) Increase of the temperature results in a broadening of the fluorescence emission spectra due to the temperature-dependent expressions for nonradiative transitions between two electronic states. (2) There are at least several characteristic Chl molecules exist in PS II particle complex, i.e. Chl b/sub 639//sup 640/, Chl b/sub 640//sup 645/, Chl a/sub 660//sup 663/, Chl a/sub 667//sup 668/, Chl a/sub 673//sup 676/, Chl a/sub 680 //sup 681/, Chl a/sub 680/681//sup 682/, Chl a/sub 684,685//sup 668 /689/, Chl a/sub 688//sup 698/, (Chl a/b/sub a//sup e/: a represents the peak of absorption, e represents the peak of emission). (3) Though the ...

  2. A High Molar Extinction Coefficient Mono-Anthracenyl Bipyridyl Heteroleptic Ruthenium(II Complex: Synthesis, Photophysical and Electrochemical Properties

    Directory of Open Access Journals (Sweden)

    Peter A. Ajibade

    2011-06-01

    Full Text Available In our quest to develop good materials as photosensitizers for photovoltaic dye-sensitized solar cells (DSSCs, cis-dithiocyanato-4-(2,3-dimethylacrylic acid-2,2'-bipyridyl-4-(9-anthracenyl-(2,3-dimethylacrylic-2,2'-bipyridyl ruthenium(II complex, a high molar extinction coefficient charge transfer sensitizer, was designed, synthesized and characterized by spectroscopy and electrochemical techniques. Earlier studies on heteroleptic ruthenium(II complex analogues containing functionalized oligo-anthracenyl phenanthroline ligands have been reported and documented. Based on a general linear correlation between increase in the length of π-conjugation bond and the molar extinction coefficients, herein, we report the photophysical and electrochemical properties of a Ru(II bipyridyl complex analogue with a single functionalized anthracenyl unit. Interestingly, the complex shows better broad and intense metal-to ligand charge transfer (MLCT band absorption with higher molar extinction coefficient (λmax = 518 nm, e = 44900 M−1cm−1, and appreciable photoluminescence spanning the visible region than those containing higher anthracenyl units. It was shown that molar absorption coefficient of the complexes may not be solely depended on the extended π-conjugation but are reduced by molecular aggregation in the molecules.

  3. Synthesis and Crystal Structures of Luminescent Mononuclear Ni(ii and Cd(ii Complexes with 1,10-phenanthroline

    Directory of Open Access Journals (Sweden)

    Ecaterina Tocana

    2017-12-01

    Full Text Available New supramolecular systems of Ni(II and Cd(II with 1,10-phenanthroline constructed by non-covalent interactions have been synthesized and characterized by single-crystal X-ray diffractometry. The smaller nickel(II ion forms a cis complex with outer-sphere perchlorates, while the cadmium(II ion forms a trans complex involving inner-sphere perchlorates. Both compoundsrevealintraligand-basedluminescentproperties.

  4. Matrix modifiers application during microimpurities determination in complex samples by electrothermal atomic-absorption spectrometry

    International Nuclear Information System (INIS)

    Bejzel', N.F.; Daaman, F.I.; Fuks-Pol', G.R.; Yudelevich, I.G.

    1993-01-01

    The review covers publications of primarily last 5 years and is devoted to the use of matrix modifiers (MM) for the determinations of trace impurities in complex samples by electrothermal atomic-absorption analysis. The role of MM in analytical process has been discussed as well as MM influence on all the elements of analytical system; factors, determining the effectiveness of MM action, the basis types of MM have been described. A great body of information is tabulated on the use of different MM for the determination of particular analysis in geological, medicobiological, technological, ecological samples and in pure materials and chemicals

  5. Matrix modification for determination of microimpurities in complex samples by electrothermal atomic-absorption spectrometry

    International Nuclear Information System (INIS)

    Bejzel', N.F.; Daaman, F.I.; Fuks-Pol', G.R.; Yudelevich, I.G.

    1993-01-01

    The review covers publications of primarily last 5 years and is devoted to the use of matrix modifiers (MM) for the determinations of trace impurities in complex samples by electrothermal atomic-absorption analysis. The role of MM in analytical process has been discussed as well as MM influence on all the elements of analytical system; factors, determining the effectiveness of MM action, the basis types of MM have been described. A great body of information is tabulated on the use of different MM for the determination of particular analysis in geological, medicobiological, technological, ecological samples and in pure materials and chemicals

  6. High capacity hydrogen absorption in transition-metal ethylene complexes: consequences of nanoclustering

    International Nuclear Information System (INIS)

    Phillips, A B; Shivaram, B S

    2009-01-01

    We have recently shown that organo-metallic complexes formed by laser ablating transition metals in ethylene are high hydrogen absorbers at room temperature (Phillips and Shivaram 2008 Phys. Rev. Lett. 100 105505). Here we show that the absorption percentage depends strongly on the ethylene pressure. High ethylene pressures (>100 mTorr) result in a lowered hydrogen uptake. Transmission electron microscopy measurements reveal that while low pressure ablations result in metal atoms dispersed uniformly on a near atomic scale, high pressure ones yield distinct nanoparticles with electron energy-loss spectroscopy demonstrating that the metal atoms are confined solely to the nanoparticles.

  7. Electronic absorption bands of HoCl3 and SmCl3 complexes in alcohols

    International Nuclear Information System (INIS)

    Ramesh Babu, V.; Buddhudu, S.; Rangarajan, V.N.

    1987-01-01

    The normal absorption and second derivative spectra of ten alcoholic complexes of HoCl 3 and SmCl 3 were recorded. From the observed bands, energies and intensity values were measured. To fit in these measured values with the theoretical values, a set of spectroscopic parameters namely, Judd-Ofelt (T 2 , T 4 , T 6 ), intensity (Ω 2 , Ω 4 , Ω 6 ) had been computed. A good fit of intensities was obtained between the experimental and theoretical data. The environmental influences on the intensities of the hypersensitive transitions of Sm(III) and Ho(III) ions were found to be noteworthy. (author). 7 tables, 20 refs

  8. Cationic dyes as extraction and spectrophotometric reagents: extraction of thiocyanate complex of mercury (II) in association with malachite green

    Energy Technology Data Exchange (ETDEWEB)

    Iyer, N V; Murthy, T K.S.

    1975-01-01

    An extraction spectrophotometric method for the determination of Hg(II) is described. This is based on the extraction of Hg(CNS)/sub 3//sup -/ complex in association with the cation of malachite green into benzene. The benzene extract has lambda max at 640 mm. Maximal extraction takes place from an aqueous solution of pH 4.5. Although four extractions are needed for quantitative recovery of Hg(II), a single extraction with aqueous organic = 2.5 : 1 is recommended for analysis and the apparent molar absorptivity is 65,000. The interference from a number of anions and cations has also been studied. (auth)

  9. Mg II ABSORPTION CHARACTERISTICS OF A VOLUME-LIMITED SAMPLE OF GALAXIES AT z ∼ 0.1

    International Nuclear Information System (INIS)

    Barton, Elizabeth J.; Cooke, Jeff

    2009-01-01

    We present an initial survey of Mg II absorption characteristics in the halos of a carefully constructed, volume-limited subsample of galaxies embedded in the spectroscopic part of the Sloan Digital Sky Survey (SDSS). We observed quasars near sightlines to 20 low-redshift (z ∼ 0.1), luminous (M r + 5log h ≤-20.5) galaxies in SDSS DR4 and DR6 with the LRIS-B spectrograph on the Keck I telescope. The primary systematic criteria for the targeted galaxies are a redshift z ∼> 0.1 and the presence of an appropriate bright background quasar within a projected 75 h -1 kpc of its center, although we preferentially sample galaxies with lower impact parameters and slightly more star formation within this range. Of the observed systems, six exhibit strong (W eq (2796) ≥ 0.3 A) Mg II absorption at the galaxy's redshift, six systems have upper limits which preclude strong Mg II absorption, while the remaining observations rule out very strong (W eq (2796) ≥ 1-2 A) absorption. The absorbers fall at higher impact parameters than many non-absorber sightlines, indicating a covering fraction f c ∼ -1 kpc (f c ∼ 0.25). The data are consistent with a possible dependence of covering fraction and/or absorption halo size on the environment or star-forming properties of the central galaxy.

  10. Structural characterization and antioxidant properties of Cu(II) and Ni(II) complexes derived from dicyandiamide

    Science.gov (United States)

    Kertmen, Seda Nur; Gonul, Ilyas; Kose, Muhammet

    2018-01-01

    New Cu(II) and Ni(II) complexes derived from dicyandiamide were synthesized and characterised by spectroscopic and analytical methods. Molecular structures of the complexes were determined by single crystal X-ray diffraction studies. In the complexes, the Cu(II) or Ni(II) ions are four-coordinate with a slight distorted square planar geometry. The ligands (L-nPen and L-iPen) derived from dicyandiamide formed via nucleophilic addition of alcohol solvent molecule in the presence Cu(II) or Ni(II) ions. Complexes were stabilised by intricate array of hydrogen bonding interactions. Antioxidant activity of the complexes was evaluated by DPPH radical scavenging and CUPRAC methods. The complexes exhibit antioxidant activity, however, their activities were much lower than standard antioxidants (Vitamin C and trolox).

  11. Platinum(II) complexes as spectroscopic probes for biomolecules

    Energy Technology Data Exchange (ETDEWEB)

    Ratilla, E.

    1990-09-21

    The use of platinum(II) complexes as tags and probes for biomolecules is indeed advantageous for their reactivities can be selective for certain purposes through an interplay of mild reaction conditions and of the ligands bound to the platinum. The use of {sup 195}Pt NMR as a method of detecting platinum and its interactions with biomolecules was carried out with the simplest model of platinum(II) tagging to proteins. Variable-temperature {sup 195}Pt NMR spectroscopy proved useful in studying the stereodynamics of complex thioethers like methionine. The complex, Pt(trpy)Cl{sup +}, with its chromophore has a greater potential for probing proteins. It is a noninvasive and selective tag for histidine and cysteine residues on the surface of cytochrome c at pH 5. The protein derivatives obtained are separable, and the tags are easily quantitated and differentiated through the metal-to-ligand charge transfer bands which are sensitive to the environment of the tag. Increasing the pH to 7.0 led to the modification by Pt(trpy)Cl{sup +}of Arg 91 in cytochrome c. Further studies with guanidine-containing ligands as models for arginine modification by Pt(trpy)Cl{sup +} showed that guanidine can act as a terminal ligand and as a bridging ligand. Owing to the potential utility of Pt(trpy)L{sup n+} as electron dense probes of nucleic acid structure, interactions of this bis-Pt(trpy){sup 2+} complex with nucleic acids was evaluated. Indeed, the complex interacts non-covalently with nucleic acids. Its interactions with DNA are not exactly the same as those of its precedents. Most striking is its ability to form highly immobile bands of DNA upon gel electrophoresis. 232 refs.

  12. X-ray Absorption Spectroscopy Identifies Calcium-Uranyl-Carbonate Complexes at Environmental Concentrations

    International Nuclear Information System (INIS)

    Kelly, Shelly D.; Kemner, Kenneth M.; Brooks, Scott C.

    2007-01-01

    Current research on bioremediation of uranium-contaminated groundwater focuses on supplying indigenous metal-reducing bacteria with the appropriate metabolic requirements to induce microbiological reduction of soluble uranium(VI) to poorly soluble uranium(IV). Recent studies of uranium(VI) bioreduction in the presence of environmentally relevant levels of calcium revealed limited and slowed uranium(VI) reduction and the formation of a Ca-UO2-CO3 complex. However, the stoichiometry of the complex is poorly defined and may be complicated by the presence of a Na-UO2-CO3 complex. Such a complex might exist even at high calcium concentrations, as some UO2-CO3 complexes will still be present. The number of calcium and/or sodium atoms coordinated to a uranyl carbonate complex will determine the net charge of the complex. Such a change in aqueous speciation of uranium(VI) in calcareous groundwater may affect the fate and transport properties of uranium. In this paper, we present the results from X-ray absorption fine structure (XAFS) measurements of a series of solutions containing 50 lM uranium(VI) and 30 mM sodium bicarbonate, with various calcium concentrations of 0-5 mM. Use of the data series reduces the uncertainty in the number of calcium atoms bound to the UO2-CO3 complex to approximately 0.6 and enables spectroscopic identification of the Na-UO2-CO3 complex. At nearly neutral pH values, the numbers of sodium and calcium atoms bound to the uranyl triscarbonate species are found to depend on the calcium concentration, as predicted by speciation calculations

  13. Spectroscopic evidence for ternary surface complexes in the lead(II)-malonic acid-hematite system

    Science.gov (United States)

    Lenhart, J.J.; Bargar, J.R.; Davis, J.A.

    2001-01-01

    Using extended X-ray absorption fine structure (EXAFS) and attenuated total reflectance Fourier-transform infrared (ATR-FTIR) measurements, we examined the sorption of Pb(II) to hematite in the presence of malonic acid. Pb LIII-edge EXAFS measurements performed in the presence of malonate indicate the presence of both Fe and C neighbors, suggesting that a major fraction of surface-bound malonate is bonded to adsorbed Pb(II). In the absence of Pb(II), ATR-FTIR measurements of sorbed malonate suggest the formation of more than one malonate surface complex. The dissimilarity of the IR spectrum of malonate sorbed on hematite to those for aqueous malonate suggest at least one of the sorbed malonate species is directly coordinated to surface Fe atoms in an inner-sphere mode. In the presence of Pb, little change is seen in the IR spectrum for sorbed malonate, indicating that geometry of malonate as it coordinates to sorbed Pb(II) adions is similar to the geometry of malonate as it coordinates to Fe in the hematite surface. Fits of the raw EXAFS spectra collected from pH 4 to pH 8 result in average Pb-C distances of 2.98 to 3.14 A??, suggesting the presence of both four- and six-membered Pb-malonate rings. The IR results are consistent with this interpretation. Thus, our results suggest that malonate binds to sorbed Pb(II) adions, forming ternary metal-bridging surface complexes. ?? 2001 Academic Press.

  14. High Molecular Weight Forms of Mammalian Respiratory Chain Complex II

    Czech Academy of Sciences Publication Activity Database

    Kovářová, Nikola; Mráček, Tomáš; Nůsková, Hana; Holzerová, Eliška; Vrbacký, Marek; Pecina, Petr; Hejzlarová, Kateřina; Klučková, Katarína; Rohlena, Jakub; Neužil, Jiří; Houštěk, Josef

    2013-01-01

    Roč. 8, č. 8 (2013), e71869 E-ISSN 1932-6203 R&D Projects: GA ČR(CZ) GPP303/10/P227; GA MŠk(CZ) LL1204; GA MZd(CZ) NT12370; GA ČR(CZ) GAP301/10/1937 Institutional research plan: CEZ:AV0Z50520701 Institutional support: RVO:67985823 Keywords : supercomplexes * high molecular weihgt forms of complex II * native electrophoretic systems Subject RIV: EB - Genetics ; Molecular Biology Impact factor: 3.534, year: 2013

  15. Studies on Manganese (II), Cobalt (II) and Cadmium (II) complexes with L-Cystine

    International Nuclear Information System (INIS)

    Hossain, M. Alamgir; Ahmed, A.H. Moinuddin; Iqbal, M. Monocheher

    1995-01-01

    A study has been carried out to prepare the manganese, cobalt and cadmium complexes of L-cystine using the metal salts and lithium cystinate. The crystalline 1:1 stoichiometric complexes with the empirical formulae of [Mn(SCH 2 CHNH 2 COO) 2 ], [Co(SCH 2 CHNH 2 COO) 2 ] and [Cd(SCH 2 CHNH 2 COO) 2 ] are obtained from the reaction of equimolar amount of the corresponding metal ions and ligand in aqueous solution. The complexes have been characterized by chemical analyses, infrared and ultraviolet spectra, magnetic measurements, optical and thermal decomposition methods. Studies show that L-cystine behaves as tetradentate ligand forming chelates with metal ions where the bonding sites of the ligand are the carboxylate O and the amino N atoms. 15 refs., 2 tables, 3 figs (author)

  16. Complexes of Cu(II), Ni(II), Co(II), oxovanadium(IV) and dioxouranium(VI) with N,N'-ethylenebis (2-hydroxy-4-methylpropiophenoneimine)

    International Nuclear Information System (INIS)

    Patel, M.M.; Patel, M.R.; Patel, M.N.; Patel, R.P.

    1982-01-01

    Complexes of Cu(II), Ni(II), Co(II), oxovanadium(IV) and dioxouranium(VI) with the schiff base, N,N'-ethylenebis(2-hydroxy-4-methylpropiophenoneimine)(4-MeOHPEN), have been synthesised and characterised on the basis of elemental analyses, conductivity, magnetic moment, electronic and infrared spectral data. Square-planar structures are suggested for Cu(II), Ni(II) and Co(II) complexes while a distorted square-pyramidal structure is suggested for the oxovanadium(IV) complex. (author)

  17. A curcumin-based TPA four-branched copper(II) complex probe for in vivo early tumor detection

    Energy Technology Data Exchange (ETDEWEB)

    Pi, Zongxin [Department of Chemical and Chemical Engineering, Hefei Normal University, Hefei 230001 (China); Wang, Jiafeng; Jiang, Bo [Department of Pharmacy, Anhui University of Chinese Medicine, Hefei 230038 (China); Cheng, Gang [Department of Chemical and Chemical Engineering, Hefei Normal University, Hefei 230001 (China); Zhou, Shuangsheng, E-mail: zshuangsheng@126.com [Department of Pharmacy, Anhui University of Chinese Medicine, Hefei 230038 (China); Center of Modern Experimental Technology, Anhui University, Hefei 230038 (China)

    2015-01-01

    A multibranched Cu(II) complex CuL{sub 2} curcumin-based was synthesized and characterized by single-crystal X-ray diffraction analysis. The photophysical properties of the complex have been investigated both experimentally and theoretically. The results show that the target complex exhibits higher quantum yield and larger two-photon absorption (TPA) cross-section in the near infrared (NIR) region compared with its free ligand. The cell imaging studies in vitro and in vivo reveal that the complex shows good photostability and excellent tumor targeting capability to tested cancerous cells, which can be potentially used for early tumor detection. - Graphical abstract: A multibranched Cu(II) complex was prepared from curcumin. The photophysical properties of the obtained complex have been investigated. The results exhibit that the complex has high capability to test cancerous cells and can distinguish between the cancerous and noncancerous cells, which should be potentially used for early tumor detection. - Highlights: • A novel multi-branched copper complex was synthesized. • The obtained compounds exhibited obvious TPA in high polar solvents. • The complex is a low toxicity at low-micromolar concentrations. • The complex exhibits larger TPA cross-section and brighter TPF imaging. • The complex has excellent targeting capability to tested cancerous cells.

  18. Spectroscopic and thermal degradation behavior of Mg(II), Ca(II), Ba(II) and Sr(II) complexes with paracetamol drug

    OpenAIRE

    Moamen S. Refat; Gehad G. Mohamed; Mohamed Y. El-Sayed; Hamada M.A. Killa; Hammad Fetooh

    2017-01-01

    Complexes of Mg(II), Ca(II), Ba(II) and Sr(II) with paracetamol drug were synthesized and characterized by elemental analysis, conductivity, UV–Vis, IR, and 1H NMR spectroscopy and thermal analysis, as well as screened for antimicrobial activity. The IR spectral data suggested that the ligand behaves as paracetamol behaves as a neutral bidentate ligand coordinated to the metal ions via the lone pair of electrons of nitrogen and carbonyl-O atoms of the amide group. From the microanalytical dat...

  19. Synthesis, photophysical and electrochemical characterization of terpyridine-functionalized dendritic oligothiophenes and their Ru(II complexes

    Directory of Open Access Journals (Sweden)

    Amaresh Mishra

    2013-05-01

    Full Text Available Pd-catalyzed Sonogashira cross-coupling reactions were used to synthesize novel π-conjugated oligothienylene-ethynylene dendrons and their corresponding terpyridine-based ligands. Their complexation with Ru(II led to interesting novel metallodendrimers with rich spectroscopic properties. All new compounds were fully characterized by 1H and 13C NMR, as well as MALDI–TOF mass spectra. Density functional theory (DFT calculations performed on these complexes gave more insight into the molecular orbital distributions. Photophysical and electrochemical studies were carried out in order to elucidate structure–property relationships and the effect of the dendritic structure on the metal complexes. Photophysical studies of the complexes revealed broad absorption spectra covering from 250 to 600 nm and high molar extinction coefficients. The MLCT emission of these complexes were significantly red-shifted (up to 115 nm compared to the parent [Ru(tpy2]2+ complex.

  20. Tracking the complex absorption in NGC 2110 with two Suzaku observations

    Energy Technology Data Exchange (ETDEWEB)

    Rivers, Elizabeth; Markowitz, Alex; Rothschild, Richard [Center for Astrophysics and Space Sciences, University of California, San Diego, 9500 Gilman Dr., La Jolla, CA 92093-0424 (United States); Bamba, Aya [Department of Physics and Mathematics, Aoyama Gakuin University, 5-10-1 Fuchinobe, Chuo-ku, Sagamihara, Kanagawa 252-5258 (Japan); Fukazawa, Yasushi [Department of Physical Science, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8526 (Japan); Okajima, Takashi [NASA/Goddard Space Flight Center, Greenbelt, MD 20771 (United States); Reeves, James [Astrophysics Group, School of Physical and Geographical Sciences, Keele University, Keele, Staffordshire, ST5 5BG (United Kingdom); Terashima, Yuichi [Department of Physics, Ehime University 2-5 Bunkyo-cho, Matsuyama, Ehime 790-8577 (Japan); Ueda, Yoshihiro, E-mail: erivers@caltech.edu [Department of Astronomy, Kyoto University, Kyoto 606-8502 (Japan)

    2014-05-10

    We present spectral analysis of two Suzaku observations of the Seyfert 2 galaxy, NGC 2110. This source has been known to show complex, variable absorption which we study in depth by analyzing these two observations set 7 yr apart and by comparing them to previously analyzed observations with the XMM-Newton and Chandra observatories. We find that there is a relatively stable, full-covering absorber with a column density of ∼3× 10{sup 22} cm{sup –2}, with an additional patchy absorber that is likely variable in both column density and covering fraction over timescales of years, consistent with clouds in a patchy torus or in the broad line region. We model a soft emission line complex, likely arising from ionized plasma and consistent with previous studies. We find no evidence for reflection from an accretion disk in this source with contribution from neither relativistically broadened Fe Kα line emission, nor from a Compton reflection hump.

  1. Tracking the complex absorption in NGC 2110 with two Suzaku observations

    International Nuclear Information System (INIS)

    Rivers, Elizabeth; Markowitz, Alex; Rothschild, Richard; Bamba, Aya; Fukazawa, Yasushi; Okajima, Takashi; Reeves, James; Terashima, Yuichi; Ueda, Yoshihiro

    2014-01-01

    We present spectral analysis of two Suzaku observations of the Seyfert 2 galaxy, NGC 2110. This source has been known to show complex, variable absorption which we study in depth by analyzing these two observations set 7 yr apart and by comparing them to previously analyzed observations with the XMM-Newton and Chandra observatories. We find that there is a relatively stable, full-covering absorber with a column density of ∼3× 10 22 cm –2 , with an additional patchy absorber that is likely variable in both column density and covering fraction over timescales of years, consistent with clouds in a patchy torus or in the broad line region. We model a soft emission line complex, likely arising from ionized plasma and consistent with previous studies. We find no evidence for reflection from an accretion disk in this source with contribution from neither relativistically broadened Fe Kα line emission, nor from a Compton reflection hump.

  2. Ligand-field symmetry effects in Fe(ii) polypyridyl compounds probed by transient X-ray absorption spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Cho, Hana; Strader, Matthew L.; Hong, Kiryong; Jamula, Lindsey; Gullikson, Eric M.; Kim, Tae Kyu; de Groot, Frank M. F.; McCusker, James K.; Schoenlein, Robert W.; Huse, Nils

    2012-01-01

    Ultrafast excited-state evolution in polypyridyl FeII complexes are of fundamental interest for understanding the origins of the sub-ps spin-state changes that occur upon photoexcitation of this class of compounds as well as for the potential impact such ultrafast dynamics have on incorporation of these compounds in solar energy conversion schemes or switchable optical storage technologies. We have demonstrated that ground-state and, more importantly, ultrafast time-resolved x-ray absorption methods can offer unique insights into the interplay between electronic and geometric structure that underpin the photo-induced dynamics of this class of compounds. The present contribution examines in greater detail how the symmetry of the ligand field surrounding the metal ion can be probed using these x-ray techniques. In particular, we show that steady-state K-edge spectroscopy of the nearest-neighbour nitrogen atoms reveals the characteristic chemical environment of the respective ligands and suggests an interesting target for future charge-transfer femtosecond and attosecond spectroscopy in the x-ray water window.

  3. potentiometric studies of the complexes formed by copper (ii)

    African Journals Online (AJOL)

    MBI

    The overall stability constants of copper (II) and zinc (II) ions with some polar ... The average number of coordinated amino acids to the copper (II) and zinc (II) ions .... of chelated rings (Yamuchi and Odani, 1996). ... Synthesis and techniques in.

  4. Photodynamic killing of cancer cells by a Platinum(II) complex with cyclometallating ligand

    Science.gov (United States)

    Doherty, Rachel E.; Sazanovich, Igor V.; McKenzie, Luke K.; Stasheuski, Alexander S.; Coyle, Rachel; Baggaley, Elizabeth; Bottomley, Sarah; Weinstein, Julia A.; Bryant, Helen E.

    2016-03-01

    Photodynamic therapy that uses photosensitizers which only become toxic upon light-irradiation provides a strong alternative to conventional cancer treatment due to its ability to selectively target tumour material without affecting healthy tissue. Transition metal complexes are highly promising PDT agents due to intense visible light absorption, yet the majority are toxic even without light. This study introduces a small, photostable, charge-neutral platinum-based compound, Pt(II) 2,6-dipyrido-4-methyl-benzenechloride, complex 1, as a photosensitizer, which works under visible light. Activation of the new photosensitizer at low concentrations (0.1-1 μM) by comparatively low dose of 405 nm light (3.6 J cm-2) causes significant cell death of cervical, colorectal and bladder cancer cell lines, and, importantly, a cisplatin resistant cell line EJ-R. The photo-index of the complex is 8. We demonstrate that complex 1 induces irreversible DNA single strand breaks following irradiation, and that oxygen is essential for the photoinduced action. Neither light, nor compound alone led to cell death. The key advantages of the new drug include a remarkably fast accumulation time (diffusion-controlled, minutes), and photostability. This study demonstrates a highly promising new agent for photodynamic therapy, and attracts attention to photostable metal complexes as viable alternatives to conventional chemotherapeutics, such as cisplatin.

  5. Identification of different coordination geometries by XAFS in copper(II) complexes with trimesic acid

    Science.gov (United States)

    Gaur, A.; Klysubun, W.; Soni, Balram; Shrivastava, B. D.; Prasad, J.; Srivastava, K.

    2016-10-01

    X-ray absorption spectroscopy (XAS) is very useful in revealing the information about geometric and electronic structure of a transition-metal absorber and thus commonly used for determination of metal-ligand coordination. But XAFS analysis becomes difficult if differently coordinated metal centers are present in a system. In the present investigation, existence of distinct coordination geometries around metal centres have been studied by XAFS in a series of trimesic acid Cu(II) complexes. The complexes studied are: Cu3(tma)2(im)6 8H2O (1), Cu3(tma)2(mim)6 17H2O (2), Cu3(tma)2(tmen)3 8.5H2O (3), Cu3(tma) (pmd)3 6H2O (ClO4)3 (4) and Cu3(tma)2 3H2O (5). These complexes have not only Cu metal centres with different coordination but in complexes 1-3, there are multiple coordination geometries present around Cu centres. Using XANES spectra, different coordination geometries present in these complexes have been identified. The variation observed in the pre-edge features and edge features have been correlated with the distortion of the specific coordination environment around Cu centres in the complexes. XANES spectra have been calculated for the distinct metal centres present in the complexes by employing ab-initio calculations. These individual spectra have been used to resolve the spectral contribution of the Cu centres to the particular XANES features exhibited by the experimental spectra of the multinuclear complexes. Also, the variation in the 4p density of states have been calculated for the different Cu centres and then correlated with the features originated from corresponding coordination of Cu. Thus, these spectral features have been successfully utilized to detect the presence of the discrete metal centres in a system. The inferences about the coordination geometry have been supported by EXAFS analysis which has been used to determine the structural parameters for these complexes.

  6. Speciation of iron (II) and (III) by using solvent extraction and flame atomic absorption spectrometry

    International Nuclear Information System (INIS)

    Yaman, Mehmet; Kaya, Gokce

    2005-01-01

    A method for speciation, preconcentration and separation of Fe 2+ and Fe 3+ in different matrices was developed using solvent extraction and flame atomic absorption spectrometry. PAN as complexing reagent for Fe 2+ and chloroform as organic solvent were used. The complex of Fe 2+ -PAN was extracted into chloroform phase in the pH range of 0.75-4.0 and Fe 3+ remains in water phase in the pH range 0.75-1.25. The optimum conditions for maximum recovery of Fe 2+ and minimum recovery of Fe 3+ were determined as pH = 1, the stirring time of 20 min, the PAN amount of 0.5 mg and chloroform volume of 8 mL. The developed method was applied to the determination of Fe 2+ and Fe 3+ in tea infusion, fruit juice, cola and pekmez. It is seen that there is high bioavailable iron (Fe 2+ ) in pekmez. The developed method is sensitive, simple and need the shorter time in comparison with other similar studies

  7. Identification of MgII Absorption Line Systems from SDSS Quasar ...

    Indian Academy of Sciences (India)

    Motivation. The quasar absorption lines are crucial to our understanding of the Universe since the absorption lines provide a wealth of information on the gaseous Universe from high redshift to present day. The absorption lines can also allow us to probe the metallicity and ionization state of the gas (Wild et al. 2008).

  8. A colorimetric and luminescent dual-modal assay for Cu(II ion detection using an iridium(III complex.

    Directory of Open Access Journals (Sweden)

    Dik-Lung Ma

    Full Text Available A novel iridium(III complex-based chemosensor bearing the 5,6-bis(salicylideneimino-1,10-phenanthroline ligand receptor was developed, which exhibited a highly sensitive and selective color change from colorless to yellow and a visible turn-off luminescence response upon the addition of Cu(II ions. The interactions of this iridium(III complex with Cu2+ ions and thirteen other cations have been investigated by UV-Vis absorption titration, emission titration, and 1H NMR titration.

  9. Infrared multiple photon dissociation spectroscopy of group I and group II metal complexes with Boc-hydroxylamine.

    Science.gov (United States)

    Dain, Ryan P; Gresham, Gary; Groenewold, Gary S; Steill, Jeffrey D; Oomens, Jos; Van Stipdonk, Michael J

    2013-08-30

    Hydroxamates are essential growth factors for some microbes, acting primarily as siderophores that solubilize iron for transport into a cell. Here we determined the intrinsic structure of 1:1 complexes between Boc-protected hydroxylamine and group I ([M(L)](+)) and group II ([M(L-H)](+)) cations, where M and L are the cation and ligand, respectively, which are convenient models for the functional unit of hydroxamate siderphores. The relevant complex ions were generated by electrospray ionization (ESI) and isolated and stored in a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. Infrared spectra of the isolated complexes were collected by monitoring (infrared) photodissociation yield as a function of photon energy. Experimental spectra were then compared to those predicted by density functional theory (DFT) calculations. The infrared multiple photon dissociation (IRMPD) spectra collected are in good agreement with those predicted to be lowest-energy by DFT. The spectra for the group I complexes contain six resolved absorptions that can be attributed to amide I and II type and hydroxylamine N-OH vibrations. Similar absorptions are observed for the group II cation complexes, with shifts of the amide I and amide II vibrations due to the change in structure with deprotonation of the hydroxylamine group. IRMPD spectroscopy unequivocally shows that the intrinsic binding mode for the group I cations involves the O atoms of the amide carbonyl and hydroxylamine groups of Boc-hydroxylamine. A similar binding mode is preferred for the group II cations, except that in this case the metal ion is coordinated by the O atom of the deprotonated hydroxylamine group. Copyright © 2013 John Wiley & Sons, Ltd.

  10. Synthesis and coordination behavior of a bipyridine platinum(II) complex with thioglucose.

    Science.gov (United States)

    Tsuji, Takaaki; Kuwamura, Naoto; Yoshinari, Nobuto; Konno, Takumi

    2013-05-06

    A mononuclear platinum(II) complex with two monodentate-S H4tg(-) ligands, [Pt(H4tg-κS)2(bpy)] (1), was newly synthesized by the reaction of [PtCl2(bpy)] (bpy = 2,2'-bipyridyl) with NaH4tg (NaH4tg =1-thio-β-d-glucose sodium salt) in water. Complex 1 reacted with additional [PtCl2(bpy)] in water to give an S-bridged dinuclear complex, [Pt2(μ2-H4tg-κ(1)S:κ(1)S)2(bpy)2](2+) ([2](2+)), in which a square-planar [Pt(H4tg)2(bpy)] unit binds to a [Pt(bpy)](2+) moiety through two thiolato groups. Treatments of 1 with Cu(2+) and Ni(2+) in water in the presence of bpy produced S-bridged dinuclear complexes [PtCu(μ2-H4tg-κ(1)S:κ(2)O,S)2(bpy)2](2+) ([3](2+)) and [PtNi(μ2-H4tg-κ(1)S:κ(2)O,S)2(bpy)2](2+) ([4](2+)), respectively, in which a square-planar [Pt(H4tg)2(bpy)] unit binds to a [M(bpy)](2+) (M = Cu(II), Ni(II)) moiety through two thiolato and two hydroxyl groups to form a chiral [M(N)2(O)2(S)2] octahedron with the Δ configuration. On the other hand, similar treatment with Cd(2+) in the presence of bpy resulted in the formation of an S-bridged trinuclear complex, [Cd{Pt(μ2-H4tg-κ(1)S:κ(2)O,S)(μ2-H4tg-κ(1)S:κ(1)S)(bpy)}2](2+) ([5](2+)), in which each of two square-planar [Pt(H4tg)2(bpy)] units binds to a Cd(II) ion through two thiolato groups and one hydroxyl group to form a chiral [Cd(O)2(S)4] octahedron with the Λ configuration. Of two geometrical configurations, syn and anti, which arise from the relative arrangement of two β-D-pyranose moieties, [2](2+) adopts the syn configuration with symmetric bridging sulfur atoms, while [3](2+), [4](2+), and [5](2+) all have the anti configuration with R configurational bridging sulfur atoms. All of the complexes were fully characterized by electronic absorption, CD, and NMR spectroscopies, along with single-crystal X-ray crystallography.

  11. Synthesis and Characterization of a Heteroleptic Ru(II Complex of Phenanthroline Containing Oligo-Anthracenyl Carboxylic Acid Moieties

    Directory of Open Access Journals (Sweden)

    Peter A. Ajibade

    2010-09-01

    Full Text Available In an effort to develop new ruthenium(II complexes, this work describes the design, synthesis and characterization of a ruthenium(II functionalized phenanthroline complex with extended π-conjugation. The ligand were L1 (4,7-bis(2,3-dimethylacrylic acid-1,10-phenanthroline, synthesized by a direct aromatic substitution reaction, and L2 (4,7-bis(trianthracenyl-2,3-dimethylacrylic acid-1,10-phenanthroline, which was synthesized by the dehalogenation of halogenated aromatic compounds using a zero-valent palladium cross-catalyzed reaction in the absence of magnesium-diene complexes and/or cyclooctadienyl nickel (0 catalysts to generate a new carbon-carbon bond (C-C bond polymerized hydrocarbon units. The ruthenium complex [RuL1L2(NCS2] showed improved photophysical properties (red-shifted metal-to-ligand charge-transfer transition absorptions and enhanced molar extinction coefficients, luminescence and interesting electrochemical properties. Cyclic and square wave voltammetry revealed five major redox processes. The number of electron(s transferred by the ruthenium complex was determined by chronocoulometry in each case. The results show that processes I, II and III are multi-electron transfer reactions while processes IV and V involved one-electron transfer reaction. The photophysical property of the complex makes it a promising candidate in the design of chemosensors and photosensitizers, while its redox-active nature makes the complex a potential mediator of electron transfer in photochemical processes.

  12. Synthesis, spectral and theoretical studies of Ni(II), Pd(II) and Pt(II) complexes of 5-mercapto-1,2,4-triazole-3-imine-2'-hydroxynaphthaline.

    Science.gov (United States)

    Gaber, Mohamed; El-Ghamry, Hoda; Atlam, Faten; Fathalla, Shaimaa

    2015-02-25

    Ni(II), Pd(II) and Pt(II) complexes of 5-mercapto-1,2,4-triazole-3-imine-2'-hydroxynaphthaline have been isolated and characterized by elemental analysis, IR, (1)H NMR, EI-mass, UV-vis, molar conductance, magnetic moment measurements and thermogravimetric analysis. The molar conductance values indicated that the complexes are non-electrolytes. The magnetic moment values of the complexes displayed diamagnetic behavior for Pd(II) and Pt(II) complexes and tetrahedral geometrical structure for Ni(II) complex. From the bioinorganic applications point of view, the interaction of the ligand and its metal complexes with CT-DNA was investigated using absorption and viscosity titration techniques. The Schiff-base ligand and its metal complexes have also been screened for their antimicrobial and antitumor activities. Also, theoretical investigation of molecular and electronic structures of the studied ligand and its metal complexes has been carried out. Molecular orbital calculations were performed using DFT (density functional theory) at B3LYP level with standard 6-31G(d,p) and LANL2DZ basis sets to access reliable results to the experimental values. The calculations were performed to obtain the optimized molecular geometry, charge density distribution, extent of distortion from regular geometry, the highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO), Mulliken atomic charges, reactivity index (ΔE), dipole moment (D), global hardness (η), softness (σ), electrophilicity index (ω), chemical potential and Mulliken electronegativity (χ). Copyright © 2014 Elsevier B.V. All rights reserved.

  13. Influence of the absorptive part of the complex potential on the S-Matrix poles

    International Nuclear Information System (INIS)

    Grama, C.; Grama, N.; Zamfirescu, I

    2001-01-01

    Although the polology of the S-matrix has been extensively studied, it occurred that some aspects remained disputable in the case of complex central potential V(r)=gV(r), g in C . These aspects are related to the origin of the observed narrow Σ-hypernuclear states that have been interpreted by Gal, Toker and Alexander as states which correspond to S-matrix poles situated in the second k-plane quadrant. From the analytical properties of the S-matrix for a real potential it results that there is no pole in the first and second k-plane quadrants, except for the imaginary k-axis. By switching on the absorption the S-matrix poles for real potential can evolve into the second quadrant of the k-plane. A critical study of the Σ-hypernuclear states needs the analysis of the motion of the S-matrix poles in the k-plane for variable complex coupling strength g. Recently contradictory opinions relative to the S-matrix poles trajectories in the complex k-plane for a complex square potential occurred. According to some authors the poles in the second quadrant can occur either from bound state poles moving anticlockwise, or from virtual state poles and capture resonant state poles moving clockwise as the absorption is switched on. Dabrowski argues that the statement made by Gal et al, Bonetti et al and Oset et al concerning the movement of the virtual poles with increasing absorptive potential is in general not correct. Dabrowski relates the direction in which the pole moves when the potential absorption increases to the direction in which the pole moves with increasing the real part of the potential, without clarifying this last question. For example, two poles moving in opposite directions along the imaginary k-axis are associated by Dabrowski to the same state. This is a wrong result, because one should associate a single pole to each quantum state. The aim of our work is to study the influence of the absorptive part of the potential on the S-matrix poles for the non

  14. Synthesis and properties of complexes of copper(II), nickel(II), cobalt(II) and uranyl ions with 3-(p-tolylsulphonamido)rhodamine

    International Nuclear Information System (INIS)

    El-Bindary, A.A.; El-Sonbati, A.Z.

    2000-01-01

    Metal complexes of copper(II), nickel(II), cobalt(II) and uranyl ions with 3-(p-tolylsulphonamido)rhodamine (HL) have been prepared and characterized by chemical and thermal analyses, molar conductivity , magnetic susceptibility measurements, and infrared, electronic and EPR spectra. The visible and EPR spectra indicated that the Cu(II) complex has a tetragonal geometry. From EPR spectrum of the Cu(II) complex,various parameters were calculated. The crystal field parameters of Ni(II) complex were calculated and were found to agree fairly well with the values reported for known square pyramidal complexes. The infrared spectral studies showed a monobasic bidentate behaviour with the oxygen and nitrogen donor system. Thermal stabilities of the complexes are also reported. (author)

  15. Excitation energy transfer between Light-harvesting complex II and Photosystem I in reconstituted membranes.

    Science.gov (United States)

    Akhtar, Parveen; Lingvay, Mónika; Kiss, Teréz; Deák, Róbert; Bóta, Attila; Ughy, Bettina; Garab, Győző; Lambrev, Petar H

    2016-04-01

    Light-harvesting complex II (LHCII), the major peripheral antenna of Photosystem II in plants, participates in several concerted mechanisms for regulation of the excitation energy and electron fluxes in thylakoid membranes. In part, these include interaction of LHCII with Photosystem I (PSI) enhancing the latter's absorption cross-section - for example in the well-known state 1 - state 2 transitions or as a long-term acclimation to high light. In this work we examined the capability of LHCII to deliver excitations to PSI in reconstituted membranes in vitro. Proteoliposomes with native plant thylakoid membrane lipids and different stoichiometric ratios of LHCII:PSI were reconstituted and studied by steady-state and time-resolved fluorescence spectroscopy. Fluorescence emission from LHCII was strongly decreased in PSI-LHCII membranes due to trapping of excitations by PSI. Kinetic modelling of the time-resolved fluorescence data revealed the existence of separate pools of LHCII distinguished by the time scale of energy transfer. A strongly coupled pool, equivalent to one LHCII trimer per PSI, transferred excitations to PSI with near-unity efficiency on a time scale of less than 10ps but extra LHCIIs also contributed significantly to the effective antenna size of PSI, which could be increased by up to 47% in membranes containing 3 LHCII trimers per PSI. The results demonstrate a remarkable competence of LHCII to increase the absorption cross-section of PSI, given the opportunity that the two types of complexes interact in the membrane. Copyright © 2016 Elsevier B.V. All rights reserved.

  16. Synthesis, spectroscopic studies and reactivity of triphenylphosphine ruthenium (II) complexes with N-heterocyclic ligands

    International Nuclear Information System (INIS)

    Rivera, A.B.

    1989-01-01

    Reported is the chemistry of triphenylphosphine ruthenium (II) complexes of general formula RuCl 2 (PPh 3 ) 2 L 2 and RuCl 2 (PPh 3 ) 2 A, obtained from the reaction of RuCl 2 (PPh 3 ) 3 with N-heterocyclic ligands L, or A (of ambidentate nature). The electronic spectra exhibit two strong metal-to-ligand charge-transfer bands, ascribed to the b 1 (dxz)->b 1 (pi) and a 2 (dxy)->a 2 (pi) transitions, and a third, weak band ascribed to the b 2 (dyz)->a 2 (pi) transition. The electronic states and the vibrational modes of the complexes were characterized by means of their resonance Raman and infrared absorption spectra. Thermogravimetric and thermodifferential analysis indicated that the melting process is succeeded by an exothermic reaction, and that the weigh loss starts to occur only after this step. The complexes dissociated in CHCl 3 solution, showing preferential labilization of the phosphine ligands, as in the case of the hydrogenation catalyst Ru(PPh 3 ) 3 Cl 2 . In the presence of CO, RuCl 2 (CO) 2 L 2 complexes were gennerated. Several derivatives were isolated and characterized. (author) [pt

  17. Neuroprotective Effects and Mechanisms of Curcumin–Cu(II and –Zn(II Complexes Systems and Their Pharmacological Implications

    Directory of Open Access Journals (Sweden)

    Fa-Shun Yan

    2017-12-01

    Full Text Available Alzheimer’s disease (AD is the main form of dementia and has a steadily increasing prevalence. As both oxidative stress and metal homeostasis are involved in the pathogenesis of AD, it would be interesting to develop a dual function agent, targeting the two factors. Curcumin, a natural compound isolated from the rhizome of Curcuma longa, is an antioxidant and can also chelate metal ions. Whether the complexes of curcumin with metal ions possess neuroprotective effects has not been evaluated. Therefore, the present study was designed to investigate the protective effects of the complexes of curcumin with Cu(II or Zn(II on hydrogen peroxide (H2O2-induced injury and the underlying molecular mechanisms. The use of rat pheochromocytoma (PC12 cells, a widely used neuronal cell model system, was adopted. It was revealed that curcumin–Cu(II complexes systems possessed enhanced O2·–-scavenging activities compared to unchelated curcumin. In comparison with unchelated curcumin, the protective effects of curcumin–Cu(II complexes systems were stronger than curcumin–Zn(II system. Curcumin–Cu(II or –Zn(II complexes systems significantly enhanced the superoxide dismutase, catalase, and glutathione peroxidase activities and attenuated the increase of malondialdehyde levels and caspase-3 and caspase-9 activities, in a dose-dependent manner. The curcumin–Cu(II complex system with a 2:1 ratio exhibited the most significant effect. Further mechanistic study demonstrated that curcumin–Cu(II or –Zn(II complexes systems inhibited cell apoptosis via downregulating the nuclear factor κB (NF-κB pathway and upregulating Bcl-2/Bax pathway. In summary, the present study found that curcumin–Cu(II or –Zn(II complexes systems, especially the former, possess significant neuroprotective effects, which indicates the potential advantage of curcumin as a promising agent against AD and deserves further study.

  18. Neuroprotective Effects and Mechanisms of Curcumin-Cu(II) and -Zn(II) Complexes Systems and Their Pharmacological Implications.

    Science.gov (United States)

    Yan, Fa-Shun; Sun, Jian-Long; Xie, Wen-Hai; Shen, Liang; Ji, Hong-Fang

    2017-12-28

    Alzheimer's disease (AD) is the main form of dementia and has a steadily increasing prevalence. As both oxidative stress and metal homeostasis are involved in the pathogenesis of AD, it would be interesting to develop a dual function agent, targeting the two factors. Curcumin, a natural compound isolated from the rhizome of Curcuma longa , is an antioxidant and can also chelate metal ions. Whether the complexes of curcumin with metal ions possess neuroprotective effects has not been evaluated. Therefore, the present study was designed to investigate the protective effects of the complexes of curcumin with Cu(II) or Zn(II) on hydrogen peroxide (H₂O₂)-induced injury and the underlying molecular mechanisms. The use of rat pheochromocytoma (PC12) cells, a widely used neuronal cell model system, was adopted. It was revealed that curcumin-Cu(II) complexes systems possessed enhanced O₂ ·- -scavenging activities compared to unchelated curcumin. In comparison with unchelated curcumin, the protective effects of curcumin-Cu(II) complexes systems were stronger than curcumin-Zn(II) system. Curcumin-Cu(II) or -Zn(II) complexes systems significantly enhanced the superoxide dismutase, catalase, and glutathione peroxidase activities and attenuated the increase of malondialdehyde levels and caspase-3 and caspase-9 activities, in a dose-dependent manner. The curcumin-Cu(II) complex system with a 2:1 ratio exhibited the most significant effect. Further mechanistic study demonstrated that curcumin-Cu(II) or -Zn(II) complexes systems inhibited cell apoptosis via downregulating the nuclear factor κB (NF-κB) pathway and upregulating Bcl-2/Bax pathway. In summary, the present study found that curcumin-Cu(II) or -Zn(II) complexes systems, especially the former, possess significant neuroprotective effects, which indicates the potential advantage of curcumin as a promising agent against AD and deserves further study.

  19. Synthesis, characterization and biological studies of metal complexes of Co (II), Ni (II), Cu (II), Zn (II) with sulphadimidine-benzylidene

    International Nuclear Information System (INIS)

    Tahira, F.; Imran, M.; Iqbal, J.

    2009-01-01

    Some novel complexes of Co (II), Ni (II), Cu (II), and Zn (II) have been synthesized with a Schiff base ligand derived from sulphadimidine and benzaldehyde. The structural features of the complexes have been determined by elemental analysis, magnetic susceptibility, conductance measurement, UV/ Vis. and infrared spectroscopy. IR studies revealed that the Schiff base ligand Sulphadimidine-benzylidene has monoanionic bidendate nature and coordinate with metal ions through nitrogen atom of azomethine (>C = N) and deprotonated -NH group. All the complexes were assigned octahedral geometry on the basis of magnetic moment and electronic spectroscopic data. Low value of conductance supports their non-electrolytic nature. The ligand, as well as its complexes were checked for their in vitro antimicrobial activities against two gram positive bacterial strains, Bacillus subtillus. Staphylococcus aureus and one gram negative Salmonella typhae and five fungal strains, Nigrospora oryzae, Curvularia lunata, Drechslera rostrata, Aspergillus niger and Candida olbicans by disc diffusion method and agar plate technique, respectively. Both the antibacterial and antitungal activities of the synthesized metal complexes were found to be more as compared to parent drug and uncomplexed ligand. All the complexes contain coordinated water, which is lost at 141-160 degree C. (author)

  20. Synthesis, spectral characterization thermal stability, antimicrobial studies and biodegradation of starch–thiourea based biodegradable polymeric ligand and its coordination complexes with [Mn(II), Co(II), Ni(II), Cu(II), and Zn(II)] metals

    OpenAIRE

    Nahid Nishat; Ashraf Malik

    2016-01-01

    A biodegradable polymer was synthesized by the modification reaction of polymeric starch with thiourea which is further modified by transition metals, Mn(II), Co(II), Ni(II), Cu(II) and Zn(II). All the polymeric compounds were characterized by (FT-IR) spectroscopy, 1H NMR spectroscopy, 13C NMR spectroscopy, UV–visible spectra, magnetic moment measurements, thermogravimetric analysis (TGA) and antibacterial activities. Polymer complexes of Mn(II), Co(II) and Ni(II) show octahedral geometry, wh...

  1. Ultrafast Transient Absorption Spectroscopy of Polymer-Based Organophotoredox Catalysts Mimicking Transition-Metal Complexes

    Science.gov (United States)

    Jamhawi, Abdelqader; Paul, Anam C.; Smith, Justin D.; Handa, Sachin; Liu, Jinjun

    2017-06-01

    Transition-metal complexes of rare earth metals including ruthenium and iridium are most commonly employed as visible-light photocatalysts. Despite their highly important and broad applications, they have many disadvantages including high cost associated with low abundance in earth crust, potential toxicity, requirement of specialized ligands for desired activity, and difficulty in recycling of metal contents as well as associated ligands. Polymer-based organophotoredox catalysts are promising alternatives and possess unique advantages such as easier synthesis from inexpensive starting material, longer excited state life time, broad range of activity, sustainability, and recyclability. In this research talk, time-resolved photoluminescence and femtosecond transient absorption (TA) spectroscopy measurements of three novel polymer-based organophotoredox catalysts will be presented. By our synthetic team, their catalytic activity has been proven in some highly valuable chemical transformations, that otherwise require transition metal complexes. Time-resolved spectroscopic investigations have demonstrated that photoinduced processes in these catalysts are similar to the transition metal complexes. Especially, intramolecular vibrational relaxation, internal conversion, and intersystem crossing from the S1 state to the T1 state all occur on a sub-picosecond timescale. The long lifetime of the T1 state ( 2-3 microsecond) renders these polymers potent oxidizing and reducing agents. A spectroscopic and kinetic model has been developed for global fitting of TA spectra in both the frequency and time domains. Implication of the current ultrafast spectroscopy studies of these novel molecules to their roles in photocatalysis will be discussed.

  2. Separation/preconcentration of trace Pb(II and Cd(II with 2-mercaptobenzothiazole impregnated Amberlite XAD-1180 resin and their determination by flame atomic absorption spectrometry

    Directory of Open Access Journals (Sweden)

    Şerife Tokalıoğlu

    2017-01-01

    Full Text Available A new chelating resin, 2-mercaptobenzothiazole loaded Amberlite XAD-1180 was prepared and used for separation and preconcentration of Cd(II and Pb(II ions prior to their determinations by flame atomic absorption spectrometry. The optimum pH for simultaneous retention of the elements and the best elution means for their simultaneous elution were 9.5 and 2 mol L−1 HNO3, respectively. The detection limits for Cd(II and Pb(II were 0.35 and 5.0 μg L−1, respectively. The accuracy of the method was confırmed both by analyzing the certified reference material (RM 8704 Buffalo river sediment and performing recovery studies.

  3. Nickel complexes of o-amidochalcogenophenolate(2-)/o-iminochalcogenobenzosemiquinonate(1-) pi-radical: synthesis, structures, electron spin resonance, and x-ray absorption spectroscopic evidence.

    Science.gov (United States)

    Hsieh, Chung-Hung; Hsu, I-Jui; Lee, Chien-Ming; Ke, Shyue-Chu; Wang, Tze-Yuan; Lee, Gene-Hsiang; Wang, Yu; Chen, Jin-Ming; Lee, Jyh-Fu; Liaw, Wen-Feng

    2003-06-16

    The preparation of complexes trans-[Ni(-SeC(6)H(4)-o-NH-)(2)](-) (1), cis-[Ni(-TeC(6)H(4)-o-NH-)(2)](-) (2), trans-[Ni(-SC(6)H(4)-o-NH-)(2)](-) (3), and [Ni(-SC(6)H(4)-o-S-)(2)](-) (4) by oxidative addition of 2-aminophenyl dichalcogenides to anionic [Ni(CO)(SePh)(3)](-) proves to be a successful approach in this direction. The cis arrangement of the two tellurium atoms in complex 2 is attributed to the intramolecular Te.Te contact interaction (Te.Te contact distance of 3.455 A). The UV-vis electronic spectra of complexes 1 and 2 exhibit an intense absorption at 936 and 942 nm, respectively, with extinction coefficient epsilon > 10000 L mol(-)(1) cm(-)(1). The observed small g anisotropy, the principal g values at g(1) = 2.036, g(2) = 2.062, and g(3) = 2.120 for 1 and g(1) = 2.021, g(2) = 2.119, and g(3) = 2.250 for 2, respectively, indicates the ligand radical character accompanied by the contribution of the singly occupied d orbital of Ni(III). The X-ray absorption spectra of all four complexes show L(III) peaks at approximately 854.5 and approximately 853.5 eV. This may indicate a variation of contribution of the Ni(II)-Ni(III) valence state. According to the DFT calculation, the unpaired electron of complex 1 and 2 is mainly distributed on the 3d(xz)() orbital of the nickel ion and on the 4p(z)() orbital of selenium (tellurium, 5p(z)()) as well as the 2p(z)() orbital of nitrogen of the ligand. On the basis of X-ray structural data, UV-vis absorption, electron spin resonance, magnetic properties, DFT computation, and X-ray absorption (K- and L-edge) spectroscopy, the monoanionic trans-[Ni(-SeC(6)H(4)-o-NH-)(2)](-) and cis-[Ni(-TeC(6)H(4)-o-NH-)(2)](-) complexes are appositely described as a resonance hybrid form of Ni(III)-bis(o-amidochalcogenophenolato(2-)) and Ni(II)-(o-amidochalcogenophenolato(2-))-(o-iminochalcogenobenzosemiquinonato(1-) pi-radical; i.e., complexes 1 and 2 contain delocalized oxidation levels of the nickel ion and ligands.

  4. Interaction and Binding Modes of bis-Ruthenium(II Complex to Synthetic DNAs

    Directory of Open Access Journals (Sweden)

    Hasi Rani Barai

    2016-06-01

    Full Text Available [μ-(linkerL2(dipyrido[3,2-a:2′,3′-c]phenazine2(phenanthroline2Ru(II2]2+ with linker: 1,3-bis-(4-pyridyl-propane, L: PF6 (bis-Ru-bpp was synthesized and their binding properties to a various polynucleotides were investigated by spectroscopy, including normal absorption, circular dichroism(CD, linear dichroism(LD, and luminescence techniques in this study. On binding to polynucleotides, the bis-Ru-bpp complex with poly[d(A-T2], and poly[d(I-C2] exhibited a negative LDr signal whose intensity was as large as that in the DNA absorption region, followed by a complicated LDr signal in the metal-to-ligand charge transfer region. Also, the emission intensity and equilibrium constant of the bis-Ru-bpp complex with poly[d(A-T2], and poly[d(I-C2] were enhanced. It was reported that both of dppz ligand of the bis-Ru-bpp complex intercalated between DNA base-pairs when bound to native, mixed sequence DNA. Observed spectral properties resemble to those observed for poly[d(A-T2] and poly[d(I-C2], led us to be concluded that both dppz ligands intercalate between alternated AT and IC bases-pairs In contrast when bis-Ru-bpp complex was bound to poly[d(G-C2], the magnitude of the LDr in the dppz absorption region, as well as the emission intensity, was half in comparison to that of bound to poly[d(A-T2], and poly[d(I-C2]. Therefore the spectral properties of the bis-Ru-bpp-poly[d(G-C2] complex suggested deviation from bis-intercalation model in the poly[d(G-C2] case. These results can be explained by a model whereby one of the dppz ligands is intercalated while the other is exposed to solvent or may exist near to phosphate. Also it is indicative that the amine group of guanine in the minor groove provides the steric hindrance for incoming intercalation binder and it also takes an important role in a difference in binding of bis-Ru-bpp bound to poly[d(A-T2] and poly[d(I-C2].

  5. A Heteroleptic Ferrous Complex with Mesoionic Bis(1,2,3-triazol-5-ylidene) Ligands: Taming the MLCT Excited State of Iron(II)

    DEFF Research Database (Denmark)

    Liu, Yizhu; Kjær, Kasper Skov; Fredin, Lisa A.

    2015-01-01

    based on sequentially furnishing the Fe-II center with the benchmark 2,2-bipyridine (bpy) ligand and the more strongly sigma-donating mesoionic ligand, 4,4-bis(1,2,3-triazol-5-ylidene) (btz). Complex1 was comprehensively characterized by electrochemistry, static and ultrafast spectroscopy, and quantum...... chemical calculations and compared to [Fe(bpy)(3)](PF6)(2) and (TBA)(2)[Fe(bpy)(CN)(4)]. Heteroleptic complex1 extends the absorption spectrum towards longer wavelengths compared to a previously synthesized homoleptic Fe-II NHC complex. The combination of the mesoionic nature of btz and the heteroleptic...

  6. Cu(II AND Zn(II COMPLEX COMPOUNDS WITH BIGUANIDES AROMATIC DERIVATIVES. SYNTHESIS, CHARACTERIZATION, BIOLOGICAL ACTIVITY

    Directory of Open Access Journals (Sweden)

    Ticuţa Negreanu-Pîrjol

    2011-05-01

    Full Text Available In this paper we report the synthesis, physical-chemical characterization and antimicrobial activity of some new complex compounds of hetero-aromatic biguanides ligands, chlorhexidine base (CHX and chlorhexidine diacetate (CHXac2 with metallic ions Cu(II and Zn(II, in different molar ratio. The synthesized complexes were characterized by elemental chemical analysis and differential thermal analysis. The stereochemistry of the metallic ions was determined by infrared spectra, UV-Vis, EPR spectroscopy and magnetic susceptibility in the aim to establish the complexes structures. The biological activity of the new complex compounds was identified in solid technique by measuring minimum inhibition diameter of bacterial and fungal culture, against three standard pathogen strains, Escherichia coli ATCC 25922, Staphilococcus aureus ATCC 25923 and Candida albicans ATCC 10231. The results show an increased specific antimicrobial activity for the complexes chlorhexidine:Cu(II 1:1 and 1:2 compared with the one of the Zn(II complexes.

  7. Synthesis, Characterization and Antimicrobial Activity of Cu(II, Co(II and Ni(II Complexes with O, N, and S Donor Ligands

    Directory of Open Access Journals (Sweden)

    Vidyavati Reddy

    2008-01-01

    Full Text Available The complexes of the type ML2 [where M = Cu(II, Co(II, and Ni(II] L = 1-phenyl-1-ene-3-(2-hydroxyphenyl-prop-2-ene with 3- substituted-5-mercapto-4-amino-1,2,4-triazoles. Schiff base ligands have been prepared by reacting 3-(2-hydroxyphenyl-1-phenylprop-2-en-1-one and 3-phenyl/pyridyl-4-amino-5-mercapto-1,2,4-triazoles in an alcoholic medium. The complexes are non-electrolytes in DMF. The resulting complexes were characterized by elemental analysis, magnetic measurements, conductivity measurements and spectral studies. The Schiff base acts as a tridentate dibasic and coordinating through the deprotonated oxygen, thioenolic sulphur and azomethine nitrogen atoms. It is found that Cu(II, Co(II, and Ni(II complexes exhibited octahedral geometry. The antimicrobial activities of ligands and its complexes were screened by cup plate method.

  8. Mixed ligand complexes of alkaline earth metals: Part XII. Mg(II, Ca(II, Sr(II and Ba(II complexes with 5-chlorosalicylaldehyde and salicylaldehyde or hydroxyaromatic ketones

    Directory of Open Access Journals (Sweden)

    MITHLESH AGRAWAL

    2002-04-01

    Full Text Available The reactions of alkaline earth metal chlorides with 5-chlorosalicylaldehyde and salicylaldehyde, 2-hydroxyacetophenone or 2-hydroxypropiophenone have been carried out in 1 : 1 : 1 mole ratio and the mixed ligand complexes of the type MLL’(H2O2 (where M = Mg(II, Ca(II, Sr(II and Ba(II, HL = 5-chlorosalicylaldehyde and HL’ = salicylaldehyde, 2-hydroxyacetophenone or 2-hydroxypropiophenone have been isolated. These complexes were characterized by TLC, conductance measurements, IR and 1H-NMR spectra.

  9. Calculation of Vibrational and Electronic Excited-State Absorption Spectra of Arsenic-Water Complexes Using Density Functional Theory

    Science.gov (United States)

    2016-06-03

    Naval Research Laboratory Washington, DC 20375-5320 NRL/MR/6390--16-9681 Calculation of Vibrational and Electronic Excited -State Absorption Spectra...NUMBER OF PAGES 17. LIMITATION OF ABSTRACT Calculation of Vibrational and Electronic Excited -State Absorption Spectra of Arsenic-Water Complexes Using...Unclassified Unlimited Unclassified Unlimited 59 Samuel G. Lambrakos (202) 767-2601 Calculations are presented of vibrational and electronic excited -state

  10. 454 sequencing reveals extreme complexity of the class II Major Histocompatibility Complex in the collared flycatcher

    Directory of Open Access Journals (Sweden)

    Gustafsson Lars

    2010-12-01

    Full Text Available Abstract Background Because of their functional significance, the Major Histocompatibility Complex (MHC class I and II genes have been the subject of continuous interest in the fields of ecology, evolution and conservation. In some vertebrate groups MHC consists of multiple loci with similar alleles; therefore, the multiple loci must be genotyped simultaneously. In such complex systems, understanding of the evolutionary patterns and their causes has been limited due to challenges posed by genotyping. Results Here we used 454 amplicon sequencing to characterize MHC class IIB exon 2 variation in the collared flycatcher, an important organism in evolutionary and immuno-ecological studies. On the basis of over 152,000 sequencing reads we identified 194 putative alleles in 237 individuals. We found an extreme complexity of the MHC class IIB in the collared flycatchers, with our estimates pointing to the presence of at least nine expressed loci and a large, though difficult to estimate precisely, number of pseudogene loci. Many similar alleles occurred in the pseudogenes indicating either a series of recent duplications or extensive concerted evolution. The expressed alleles showed unambiguous signals of historical selection and the occurrence of apparent interlocus exchange of alleles. Placing the collared flycatcher's MHC sequences in the context of passerine diversity revealed transspecific MHC class II evolution within the Muscicapidae family. Conclusions 454 amplicon sequencing is an effective tool for advancing our understanding of the MHC class II structure and evolutionary patterns in Passeriformes. We found a highly dynamic pattern of evolution of MHC class IIB genes with strong signals of selection and pronounced sequence divergence in expressed genes, in contrast to the apparent sequence homogenization in pseudogenes. We show that next generation sequencing offers a universal, affordable method for the characterization and, in perspective

  11. Parameterization of light absorption by components of seawater in optically complex coastal waters of the Crimea Peninsula (Black Sea).

    Science.gov (United States)

    Dmitriev, Egor V; Khomenko, Georges; Chami, Malik; Sokolov, Anton A; Churilova, Tatyana Y; Korotaev, Gennady K

    2009-03-01

    The absorption of sunlight by oceanic constituents significantly contributes to the spectral distribution of the water-leaving radiance. Here it is shown that current parameterizations of absorption coefficients do not apply to the optically complex waters of the Crimea Peninsula. Based on in situ measurements, parameterizations of phytoplankton, nonalgal, and total particulate absorption coefficients are proposed. Their performance is evaluated using a log-log regression combined with a low-pass filter and the nonlinear least-square method. Statistical significance of the estimated parameters is verified using the bootstrap method. The parameterizations are relevant for chlorophyll a concentrations ranging from 0.45 up to 2 mg/m(3).

  12. Synthesis and characterization of heterobimetallic complexes of the type [Cu(pn2][MCl4] where M = Co(II, Ni(II, Cu(II, Zn(II, Cd(II, and Hg(II

    Directory of Open Access Journals (Sweden)

    Seema Yadav

    2016-11-01

    Full Text Available A series of new bimetallic transition metal complexes of the type [Cu(pn2] [MCl4] have been synthesized (where M = Co(II, Ni(II, Cu(II, Zn(II, Cd(II and Hg(II, pn = 1,3-diaminopropane and characterized by elemental analysis, molar conductance, TGA, IR and electronic spectra. All the compounds are 1:1 electrolyte in DMF. The Cu(II ion is square-planar while metal ions in the anionic moiety acquire their usual tetrahedral arrangement. On the basis of these studies it is concluded that anionic moiety is electrically stabilized by its cationic counterpart.

  13. ynthesis, theoretical study on Zinc (II and Ni(II complexes of 5-methoxyisatin 3-[N-(4-chlorophenyl thiosemicarbazone

    Directory of Open Access Journals (Sweden)

    Fatma Kandemirli

    2012-03-01

    Full Text Available Zinc(II and nickel(II-complexes of 5-methoxyisatin 3-[N-(4-chlorophenyl thiosemicarbazone] (H2MICP were synthesized and characterized by infrared, ultraviolet and 1H-NMR spectroscopies as well as elemental analysis. Model of H2MICP and its zinc(II and nickel(II-complexes were optimized with B3LYP method using 6-31G(d,p, 6-311G(d,p, 6-311++G(d,p, 6-311++G(2d,2p basis sets. The calculated 1H-NMR, UV and IR spectra data were compared with experimental results. In addition to the Natural Bond Orbital (NBO analysis of H2MICP and its Zinc(II and Nickel(II complexes, Fukui functions of H2MICP were also reported.

  14. HELIUM IN NATAL H II REGIONS: THE ORIGIN OF THE X-RAY ABSORPTION IN GAMMA-RAY BURST AFTERGLOWS

    International Nuclear Information System (INIS)

    Watson, Darach; Andersen, Anja C.; Fynbo, Johan P. U.; Hjorth, Jens; Krühler, Thomas; Laursen, Peter; Leloudas, Giorgos; Malesani, Daniele; Zafar, Tayyaba; Gorosabel, Javier; Jakobsson, Páll

    2013-01-01

    Soft X-ray absorption in excess of Galactic is observed in the afterglows of most gamma-ray bursts (GRBs), but the correct solution to its origin has not been arrived at after more than a decade of work, preventing its use as a powerful diagnostic tool. We resolve this long-standing problem and find that absorption by He in the GRB's host H II region is responsible for most of the absorption. We show that the X-ray absorbing column density (N H X ) is correlated with both the neutral gas column density and with the optical afterglow's dust extinction (A V ). This correlation explains the connection between dark bursts and bursts with high N H X values. From these correlations, we exclude an origin of the X-ray absorption which is not related to the host galaxy, i.e., the intergalactic medium or intervening absorbers are not responsible. We find that the correlation with the dust column has a strong redshift evolution, whereas the correlation with the neutral gas does not. From this, we conclude that the column density of the X-ray absorption is correlated with the total gas column density in the host galaxy rather than the metal column density, in spite of the fact that X-ray absorption is typically dominated by metals. The strong redshift evolution of N H X /A V is thus a reflection of the cosmic metallicity evolution of star-forming galaxies and we find it to be consistent with measurements of the redshift evolution of metallicities for GRB host galaxies. We conclude that the absorption of X-rays in GRB afterglows is caused by He in the H II region hosting the GRB. While dust is destroyed and metals are stripped of all of their electrons by the GRB to great distances, the abundance of He saturates the He-ionizing UV continuum much closer to the GRB, allowing it to remain in the neutral or singly-ionized state. Helium X-ray absorption explains the correlation with total gas, the lack of strong evolution with redshift, as well as the absence of dust, metal or

  15. Interaction of a copper (II) complex containing an artificial sweetener (aspartame) with calf thymus DNA.

    Science.gov (United States)

    Shahabadi, Nahid; Khodaei, Mohammad Mehdi; Kashanian, Soheila; Kheirdoosh, Fahimeh

    2014-01-01

    A copper (II) complex containing aspartame (APM) as ligand, Cu(APM)2Cl2⋅2H2O, was synthesized and characterized. In vitro binding interaction of this complex with native calf thymus DNA (CT-DNA) was studied at physiological pH. The interaction was studied using different methods: spectrophotometric, spectrofluorometric, competition experiment, circular dichroism (CD) and viscosimetric techniques. Hyperchromicity was observed in UV absorption band of Cu(APM)2Cl2⋅2H2O. A strong fluorescence quenching reaction of DNA to Cu(APM)2Cl2⋅2H2O was observed and the binding constants (Kf) and corresponding numbers of binding sites (n) were calculated at different temperatures. Thermodynamic parameters, enthalpy change (ΔH) and entropy change (ΔS) were calculated to be+89.3 kJ mol(-1) and+379.3 J mol(-1) K(-1) according to Van't Hoff equation which indicated that reaction is predominantly entropically driven. Experimental results from spectroscopic methods were comparable and further supported by viscosity measurements. We suggest that Cu(APM)2Cl2⋅2H2O interacts with calf thymus DNA via a groove interaction mode with an intrinsic binding constant of 8×10+4 M(-1). Binding of this copper complex to DNA was found to be stronger compared to aspartame which was studied recently. Copyright © 2013 Elsevier B.V. All rights reserved.

  16. Synthesis of Tb_4O_7 complexed with reduced graphene oxide for Rhodamine-B absorption

    International Nuclear Information System (INIS)

    Gao, Hui; Zhou, Yang; Chen, Keqin; Li, Xiaolong

    2016-01-01

    Highlights: • Tb–rGO composite was fabricated via a facile thermally reduction process. • The green and blue emissions were both observed in the composite. • The composite exhibited efficient absorption capability for Rhodamine-B. - Abstract: Tb_4O_7 complexed with reduced graphene oxide composite (Tb–rGO) had been designed and fabricated by a facile thermal reduction method. The formation of Tb_4O_7 particles and reduction of graphene oxide (GO) occurred simultaneously, and partial terbium ions would be complexed with rGO via oxygen-containing function groups on rGO sheets. Introducing of terbium ions could effectively tune the photoluminescence properties of rGO, and the composite exhibited the typical green emission of terbium ions as well as the blue self-luminescence of graphene entered at 440 nm. Moreover, Tb–rGO had demonstrated its high capability as an organic dye (Rhodamine-B) scavenger with high speed and efficiency. The findings showed the promising applications for large-scale removal of organic dye contaminants, especially in the field of waste water treatment.

  17. Deciphering complex, functional structures with synchrotron-based absorption and phase contrast tomographic microscopy

    Science.gov (United States)

    Stampanoni, M.; Reichold, J.; Weber, B.; Haberthür, D.; Schittny, J.; Eller, J.; Büchi, F. N.; Marone, F.

    2010-09-01

    Nowadays, thanks to the high brilliance available at modern, third generation synchrotron facilities and recent developments in detector technology, it is possible to record volumetric information at the micrometer scale within few minutes. High signal-to-noise ratio, quantitative information on very complex structures like the brain micro vessel architecture, lung airways or fuel cells can be obtained thanks to the combination of dedicated sample preparation protocols, in-situ acquisition schemes and cutting-edge imaging analysis instruments. In this work we report on recent experiments carried out at the TOMCAT beamline of the Swiss Light Source [1] where synchrotron-based tomographic microscopy has been successfully used to obtain fundamental information on preliminary models for cerebral fluid flow [2], to provide an accurate mesh for 3D finite-element simulation of the alveolar structure of the pulmonary acinus [3] and to investigate the complex functional mechanism of fuel cells [4]. Further, we introduce preliminary results on the combination of absorption and phase contrast microscopy for the visualization of high-Z nanoparticles in soft tissues, a fundamental information when designing modern drug delivery systems [5]. As an outlook we briefly discuss the new possibilities offered by high sensitivity, high resolution grating interferomtery as well as Zernike Phase contrast nanotomography [6].

  18. Spectral simplicity of apparent complexity. II. Exact complexities and complexity spectra

    Science.gov (United States)

    Riechers, Paul M.; Crutchfield, James P.

    2018-03-01

    The meromorphic functional calculus developed in Part I overcomes the nondiagonalizability of linear operators that arises often in the temporal evolution of complex systems and is generic to the metadynamics of predicting their behavior. Using the resulting spectral decomposition, we derive closed-form expressions for correlation functions, finite-length Shannon entropy-rate approximates, asymptotic entropy rate, excess entropy, transient information, transient and asymptotic state uncertainties, and synchronization information of stochastic processes generated by finite-state hidden Markov models. This introduces analytical tractability to investigating information processing in discrete-event stochastic processes, symbolic dynamics, and chaotic dynamical systems. Comparisons reveal mathematical similarities between complexity measures originally thought to capture distinct informational and computational properties. We also introduce a new kind of spectral analysis via coronal spectrograms and the frequency-dependent spectra of past-future mutual information. We analyze a number of examples to illustrate the methods, emphasizing processes with multivariate dependencies beyond pairwise correlation. This includes spectral decomposition calculations for one representative example in full detail.

  19. Mass transfer with complex reversible chemical reactions—II. parallel reversible chemical reactions

    OpenAIRE

    Versteeg, G.F.; Kuipers, J.A.M.; Beckum, F.P.H. van; Swaaij, W.P.M. van

    1990-01-01

    An absorption model has been developed which can be used to calculate rapidly absorption rates for the phenomenon mass transfer accompanied by multiple complex parallel reversible chemical reactions. This model can be applied for the calculation of the mass transfer rates, enhancement factors and concentration profiles for a wide range of processes and conditions, for both film and penetration model. With the aid of this mass transfer model it is demonstrated that the absorption rates in syst...

  20. Absorption spectroscopy of complex rare earth ion doped hybrid materials over a broad wavelength range

    NARCIS (Netherlands)

    Dekker, R.; Worhoff, Kerstin; Stouwdam, J.W.; van Veggel, F.C.J.M.; Driessen, A.

    2005-01-01

    In the present work we applied a measurement setup to determine several relevant properties of rare-earth doped nanoparticles dispersed in polymer slab waveguides in a single absorption measurement: background absorption of the polymer host material, water absorption, polymer composition

  1. Absorption spectroscopy of complex rare earth ion doped hybrid materials over a broad wavelength range

    NARCIS (Netherlands)

    Dekker, R.; Worhoff, Kerstin; Stouwdam, J.W.; van Veggel, F.C.J.M.; Driessen, A.

    In the present work we applied a measurement setup to determine several relevant properties of rare-earth doped nanoparticles dispersed in polymer slab waveguides in a single absorption measurement: background absorption of the polymer host material, water absorption, polymer composition

  2. Airborne Laser Infrared Absorption Spectrometer (ALIAS-II) for in situ Atmospheric Measurements of N(sub 2)0, CH(sub 4), CO, HCl, and NO(sub 2) from Balloon or RPA Platforms

    Science.gov (United States)

    Scott, D.; Herman, R.; Webster, C.; May, R.; Flesch, G.; Moyer, E.

    1998-01-01

    The Airborne Laser Infrared Absorption Spectrometer II (ALIAS-II) is a lightweight, high-resolution (0.0003 cm-1), scanning, mid-infrared absorption spectrometer based on cooled (80 K) lead-salt tunable diode laser sources.

  3. A dispersive liquid--liquid microextraction methodology for copper (II) in environmental samples prior to determination using microsample injection flame atomic absorption spectrometry.

    Science.gov (United States)

    Alothman, Zeid A; Habila, Mohamed; Yilmaz, Erkan; Soylak, Mustafa

    2013-01-01

    A simple, environmentally friendly, and efficient dispersive liquid-liquid microextraction method combined with microsample injection flame atomic absorption spectrometry was developed for the separation and preconcentration of Cu(II). 2-(5-Bromo-2-pyridylazo)-5-(diethylamino)phenol (5-Br-PADAP) was used to form a hydrophobic complex of Cu(II) ions in the aqueous phase before extraction. To extract the Cu(II)-5-Br-PADAP complex from the aqueous phase to the organic phase, 2.0 mL of acetone as a disperser solvent and 200 microL of chloroform as an extraction solvent were used. The influences of important analytical parameters, such as the pH, types and volumes of the extraction and disperser solvents, amount of chelating agent, sample volume, and matrix effects, on the microextraction procedure were evaluated and optimized. Using the optimal conditions, the LOD, LOQ, preconcentration factor, and RSD were determined to be 1.4 microg/L, 4.7 microg/L, 120, and 6.5%, respectively. The accuracy of the proposed method was investigated using standard addition/recovery tests. The analysis of certified reference materials produced satisfactory analytical results. The developed method was applied for the determination of Cu in real samples.

  4. Structure of the Hydrated Platinum(II) Ion And the Cis-Diammine-Platinum(II) Complex in Acidic Aqueous Solution: An EXAFS Study

    Energy Technology Data Exchange (ETDEWEB)

    Jalilehvand, F.; Laffin, L.J.

    2009-05-18

    Careful analysis of Pt L{sub 3}-edge extended X-ray absorption fine structure (EXAFS) spectra shows that the hydrated platinum(II) ion in acidic (HClO{sub 4}) aqueous solution binds four water molecules with the Pt-O bond distance 2.01(2) {angstrom} and one (or two) in the axial position at 2.39(2) {angstrom}. The weak axial water coordination is in accordance with the unexpectedly small activation volume previously reported for water exchange in an interchange mechanism with associative character. The hydrated cis-diammineplatinum(II) complex has a similar coordination environment with two ammine and two aqua ligands strongly bound with Pt-O/N bond distances of 2.01(2) {angstrom} and, in addition, one (or two) axial water molecule at 2.37(2) {angstrom}. This result provides a new basis for theoretical computational studies aiming to connect the function of the anticancer drug cis-platin to its ligand exchange reactions, where usually four-coordinated square planar platinum(II) species are considered as the reactant and product. {sup 195}Pt NMR spectroscopy has been used to characterize the Pt(II) complexes.

  5. New 3D gas density maps of NaI and CaII interstellar absorption within 300 pc

    Science.gov (United States)

    Welsh, B. Y.; Lallement, R.; Vergely, J.-L.; Raimond, S.

    2010-02-01

    Aims: We present new high resolution (R > 50 000) absorption measurements of the NaI doublet (5889-5895 Å) along 482 nearby sight-lines, in addition to 807 new measurements of the CaII K (3933 Å) absorption line. We have combined these new data with previously reported measurements to produce a catalog of absorptions towards a total of 1857 early-type stars located within 800 pc of the Sun. Using these data we have determined the approximate 3-dimensional spatial distribution of neutral and partly ionized interstellar gas density within a distance-cube of 300 pc from the Sun. Methods: All newly recorded spectra were analyzed by means of a multi-component line profile-fitting program, in most cases using simultaneous fits to the line doublets. Normalized absorption profiles were fitted by varying the velocity, doppler width and column density for all intervening interstellar clouds. The resulting total column densities were then used in conjunction with the Hipparcos distances of the target stars to construct inversion maps of the 3D spatial density distribution of the NaI and CaII bearing gas. Results: A plot of the equivalent width of NaI versus distance reveals a wall of neutral gas at ~80 pc that can be associated with the boundary wall to the central rarefied Local Cavity region. In contrast, a similar plot for the equivalent width of CaII shows no sharply increasing absorption at 80 pc, but instead we observe a slowly increasing value of CaII equivalent width with increasing sight-line distance sampled. Low values for the volume density of NaI (nNaI values in the range 10-8 >nNaI > 10-10 cm-3 are found for sight-lines with distance >300 pc. Both high and low values of the volume density of CaII (nCaII) are found for sight-lines 100 pc a value of nCaII ~ 10-9 cm-3 is typical for most sight-lines, indicating that the distribution of CaII bearing gas is fairly uniform throughout the general ISM. Our three maps of the 3D spatial distribution of local neutral Na

  6. Stability constants of glutarate complexes of copper(II), zinc(II), cobalt(II) and uranyl(II) by paper electrophoresis

    International Nuclear Information System (INIS)

    Singh, R.K.P.; Yadava, J.R.; Yadava, K.L.

    1981-01-01

    Stability constants of Copper(II), Zinc(II), Cobalt(II) and Uranyl(II) glutarates have been determined by paper electrophoresis. Glutaric acid (0.005 mol dmsup(-3)) was added to the background electrolyte : 0.1 mol dmsup(-3) HClO 4 . The proportions of (CH 2 ) 3 COOH COO - and (CH 2 ) 3 C 2 O 4 2- were varied by changing the pH of the electrolyte. These anions yielded the complexes Cu(CH 2 ) 3 C 2 O 4 , [Zn(CH 2 ) 3 COOH COO] + [Co(CH 2 ) 3 COOH COO] + and UO 2 (CH 2 ) 3 C 2 O 4 whose stability constants are found to be 10sup(3.9), 10sup(2.9), 10sup(2.7) and 10sup(13.5) respectively. (author)

  7. Thermodynamics of the CO2–Absorption/Desorption Section in the Integrated Gasifying Combined cycle — II. Analysis

    Directory of Open Access Journals (Sweden)

    Jaroslav KOZACZKA

    2012-06-01

    Full Text Available The thermodynamic analysis of the absorption/desorption section of the ICGC–cycle has been presented using the Second Law with special emphasis on the thermodynamic effectivity concept and usability for complex systems investigations. Essential problems have been discussed based on the classical bibliographical items on the subject. Numerical calculations have been accomplished using results obtained in the first part, which contained absorption and desorption modeling approach oriented onto thermodynamic analyzes. Additionally the special properties of dilute solutions, especially the CO2/water system, have been presented and the problem of the solute chemical concentration exergy change suggested.

  8. Kinetics and equilibria for the formation of a new DNA metal-intercalator: the cyclic polyamine Neotrien/copper(II) complex.

    Science.gov (United States)

    Biver, Tarita; Secco, Fernando; Tinè, Maria Rosaria; Venturini, Marcella

    2004-01-01

    A study has been performed of the kinetics and equilibria involved in complex formation between the macrocyclic polyamine 2,5,8,11-tetraaza[12]-[12](2,9)[1,10]-phenanthrolinophane (Neotrien) and Cu(II) in acidic aqueous solution and ionic strength 0.5 M (NaCl), by means of the stopped-flow method and UV spectrophotometry. Spectrophotometric titrations and kinetic experiments revealed that the binding of Cu(II) to Neotrien gives rise to several 1:1 complexes differing in their degree of protonation. Under the experimental hydrogen ion concentration range investigated, complexation occurs by two parallel paths: (a) M2+ + (H4L)4+ (MH4L)6+ and (b) M2+ + (H3L)3+ (MH3L)5+. The rate constants values found for complex formation, by paths (a) and (b), are much lower than the values expected from water exchange at copper(II) and other amine/Cu(II) complexation kinetic constants. Kinetic experiments at different NaCl concentrations indicated that this finding was not due to chloride ion competition in complex formation with Neotrien, but it was related to a ring rigidity effect. As the phenanthroline moiety could, in principle, interact with nucleic acids by intercalation or external binding, some preliminary measurements concerned with the possible interactions occurring between the Cu(II)/Neotrien complex and calf thymus DNA (CT-DNA) have also been carried out. The absorption spectra of the Cu(II)/Neotrien complex change upon addition of CT-DNA at pH 7.0, revealing the occurrence of complex-nucleic acid interactions. Moreover, fluorescence titrations, carried out by adding the Cu(II)/Neotrien complex to CT-DNA, previously saturated with ethidium bromide (EB), show that the Cu(II)/Neotrien complex is able to displace EB from DNA, suggesting the complex is able to intercalate into the polynucleotide and then to cleave the phosphodiester bond of DNA.

  9. Mass transfer with complex reversible chemical reactions—II. parallel reversible chemical reactions

    NARCIS (Netherlands)

    Versteeg, G.F.; Kuipers, J.A.M.; Beckum, F.P.H. van; Swaaij, W.P.M. van

    1990-01-01

    An absorption model has been developed which can be used to calculate rapidly absorption rates for the phenomenon mass transfer accompanied by multiple complex parallel reversible chemical reactions. This model can be applied for the calculation of the mass transfer rates, enhancement factors and

  10. Mass transfer with complex reversible chemical reactions. II: Parallel reversible chemical reactions

    NARCIS (Netherlands)

    Versteeg, Geert; van Beckum, F.P.H.; Kuipers, J.A.M.; van Swaaij, Willibrordus Petrus Maria

    1990-01-01

    An absorption model has been developed which can be used to calculate rapidly absorption rates for the phenomenon mass transfer accompanied by multiple complex parallel reversible chemical reactions. This model can be applied for the calculation of the mass transfer rates, enhancement factors and

  11. Mass transfer with complex reversible chemical reactions. II: parallel reversible chemical reactions

    NARCIS (Netherlands)

    Versteeg, G.F.; Kuipers, J.A.M.; Beckum, van F.P.H.; van Swaaij, W.P.M.

    1990-01-01

    An absorption model has been developed which can be used to calculate rapidly absorption rates for the phenomenon mass transfer accompanied by multiple complex parallel reversible chemical reactions. This model can be applied for the calculation of the mass transfer rates, enhancement factors and

  12. Synthesis and characterization of zinc(II), cadmium(II) and mercury(II) complexes with bis(bidentate) Schiff bases

    International Nuclear Information System (INIS)

    Das, Mrinal Kanti; Ghosh, Shyamali

    1998-01-01

    A few Zn(II), Cd(II) and Hg(II) complexes of the bis(bidentate) Schiff bases derived from p-phenylenediamine and salicylaldehyde (H 2 Salpphen), and o-phenylenediamine and o-vanillin (H 2 Vanophen), of the type MCl 2 .H 2 L(H 2 L = H 2 Salpphen or H 2 Vanophen) have been synthesised. The complexes have been characterized by elemental analysis, infrared, 1 H and 13 C NMR and mass spectra. (author)

  13. Synthesis, spectral characterization thermal stability, antimicrobial studies and biodegradation of starch–thiourea based biodegradable polymeric ligand and its coordination complexes with [Mn(II, Co(II, Ni(II, Cu(II, and Zn(II] metals

    Directory of Open Access Journals (Sweden)

    Nahid Nishat

    2016-09-01

    Full Text Available A biodegradable polymer was synthesized by the modification reaction of polymeric starch with thiourea which is further modified by transition metals, Mn(II, Co(II, Ni(II, Cu(II and Zn(II. All the polymeric compounds were characterized by (FT-IR spectroscopy, 1H NMR spectroscopy, 13C NMR spectroscopy, UV–visible spectra, magnetic moment measurements, thermogravimetric analysis (TGA and antibacterial activities. Polymer complexes of Mn(II, Co(II and Ni(II show octahedral geometry, while polymer complexes of Cu(II and Zn(II show square planar and tetrahedral geometry, respectively. The TGA revealed that all the polymer metal complexes are more thermally stable than their parental ligand. In addition, biodegradable studies of all the polymeric compounds were also carried out through ASTM-D-5338-93 standards of biodegradable polymers by CO2 evolution method which says that coordination decreases biodegradability. The antibacterial activity was screened with the agar well diffusion method against some selected microorganisms. Among all the complexes, the antibacterial activity of the Cu(II polymer–metal complex showed the highest zone of inhibition because of its higher stability constant.

  14. Topoisomerase II poisoning by indazole and imidazole complexes ...

    Indian Academy of Sciences (India)

    Unknown

    These molecules constitute two of the few most effective anticancer ruthenium compounds. ... however was hindered due to toxic side effects on the human body. Our ... cells. The catalytic cycle of topoisomerase II (topo II) typically involves ...

  15. OBSERVATIONS OF Mg II ABSORPTION NEAR z ∼ 1 GALAXIES SELECTED FROM THE DEEP2 REDSHIFT SURVEY

    International Nuclear Information System (INIS)

    Lovegrove, Elizabeth; Simcoe, Robert A.

    2011-01-01

    We study the frequency of Mg II absorption in the outer halos of galaxies at z = 0.6-1.4 (with median z = 0.87), using new spectra obtained of 10 background quasars with galaxy impact parameters of b r = 0.15-1.0 A, though not all absorbers correlate with DEEP galaxies. We find five unique absorbers within Δv = 500 km s -1 and b r > 1.0 A, consistent with other samples of galaxy-selected Mg II systems. We speculate that Mg II systems with 0.3 r r are more likely to reflect the more recent star-forming history of their associated galaxies.

  16. Membrane filtration of nickel(II) on cellulose acetate filters for its preconcentration, separation, and flame atomic absorption spectrometric determination

    Energy Technology Data Exchange (ETDEWEB)

    Soylak, Mustafa [Chemistry Dept., Faculty of Science Arts, University of Erciyes, Kayseri (Turkey); Unsal, Yunus Emre; Aydin, Ayse [Fen Bilimleri Enstitusu, University of Erciyes, Kayseri (Turkey); Kizil, Nebiye [Saglik Bilimleri Enstitusu, University of Erciyes, Kayseri (Turkey)

    2010-01-15

    An enrichment method for trace amounts of Ni(II), as 8-hydroxyquinoline chelates, has been established on a cellulose acetate membrane filter. Ni(II)-8-hydroxyquinoline chelates adsorbed on a membrane filter were eluted using 5 mL of 1 M HNO{sub 3}. The eluent nickel concentration was determined by a flame atomic absorption spectrometer. The influence of some analytical parameters, including pH, amount of reagent, sample volume, etc., on recovery was investigated. The interference of co-existent ions was studied. The nickel detection limit was 4.87 {mu}g/L. The method was applied to real samples for the determination of nickel(II) ions. (Abstract Copyright [2010], Wiley Periodicals, Inc.)

  17. Synthesis and Characterization of 4-Benzyloxybenzaldehyde-4-methyl-3-thiosemicarbazone (Containing Sulphur and Nitrogen Donor Atoms and Its Cd(II Complex

    Directory of Open Access Journals (Sweden)

    Lakshmi Narayana Suvarapu

    2015-12-01

    Full Text Available A chelating agent, 4-benzyloxybenzaldehyde-4-methyl-3-thiosemicarbazone (BBMTSC, containing sulphur and nitrogen donor atoms was synthesized and applied as a ligand for the chelation of Cd(II. Both the BBMTSC and its Cd(II complex were characterized by elemental analysis, UV-Vis absorption spectra, Fourier transform infrared spectroscopy (FT-IR, mass spectra, nuclear magnetic resonance spectroscopy (NMR, X-ray powder diffraction (XRD, and field emission scanning electron microscopy (FESEM. The FTIR spectra confirmed the formation of both BBMTSC and its Cd(II complex. XRD revealed the polycrystalline nature of the synthesized compounds. BBMTSC exhibited a flake-like micro-rod morphology, whereas the Cd(II complex had a flower-like nanorod structure.

  18. Collision-Induced Infrared Absorption by Collisional Complexes in Dense Hydrogen-Helium Gas Mixtures at Thousands of Kelvin

    Science.gov (United States)

    Abel, Martin; Frommhold, Lothar; Li, Xiaoping; Hunt, Katharine L. C.

    2011-06-01

    The interaction-induced absorption by collisional pairs of H{_2} molecules is an important opacity source in the atmospheres of the outer planets and cool stars. The emission spectra of cool white dwarf stars differ significantly in the infrared from the expected blackbody spectra of their cores, which is largely due to absorption by collisional H{_2}-H{_2}, H{_2}-He, and H{_2}-H complexes in the stellar atmospheres. Using quantum-chemical methods we compute the atmospheric absorption from hundreds to thousands of kelvin. Laboratory measurements of interaction-induced absorption spectra by H{_2} pairs exist only at room temperature and below. We show that our results reproduce these measurements closely, so that our computational data permit reliable modeling of stellar atmosphere opacities even for the higher temperatures. L. Frommhold, Collision-Induced Absorption in Gases, Cambridge University Press, Cambridge, New York, 1993 and 2006 Xiaoping Li, Katharine L. C. Hunt, Fei Wang, Martin Abel, and Lothar Frommhold, "Collision-Induced Infrared Absorption by Molecular Hydrogen Pairs at Thousands of Kelvin", International Journal of Spectroscopy, vol. 2010, Article ID 371201, 11 pages, 2010. doi: 10.1155/2010/371201 M. Abel, L. Frommhold, X. Li, and K. L. C. Hunt, "Collision-induced absorption by H{_2} pairs: From hundreds to thousands of Kelvin," J. Phys. Chem. A, published online, DOI: 10.1021/jp109441f L. Frommhold, M. Abel, F. Wang, M. Gustafsson, X. Li, and K. L. C. Hunt, "Infrared atmospheric emission and absorption by simple molecular complexes, from first principles", Mol. Phys. 108, 2265, 2010

  19. The relative absorption cross-sections of photosystem I and photosystem II in chloroplasts from three types of Nicotiana tabacum.

    Science.gov (United States)

    Melis, A; Thielen, A P

    1980-02-08

    In the present study we used three types of Nicotiana tabacum, cv John William's Broad Leaf (the wild type and two mutants, the yellow-green Su/su and the yellow Su/su var. Aurea) in order to correlat functional properties of Photosystem II and Photosystem I with the structural organization of their chloroplasts. The effective absorption cross-section of Photosystem II and Photosystem I centers was measured by means of the rate constant of their photoconversion under light-limiting conditions. In agreement with earlier results (Okabe, K., Schmid, G.H. and Straub, J. (1977) Plant Physiol. 60, 150--156) the photosynthetic unit size for both System II and System I in the two mutants was considerably smaller as compared to the wild type. We observed biphasic kinetics in the photoconversion of System II in all three types of N. tabacum. However, the photoconversion of System I occurred with monophasic and exponential kinetics. Under our experimental conditions, the effective cross-section of Photosystem I was comparable to that of the fast System II component (alpha centers). The relative amplitude of the slow System II component (beta centers) varied between 30% in the wild type to 70% in the Su/su var. Aurea mutant. The increased fraction of beta centers is correlated with the decreased fraction of appressed photosynthetic membranes in the chloroplasts of the two mutants. As a working hypothesis, it is suggested that beta centers are located on photosynthetic membranes directly exposed to the stroma medium.

  20. Antibacterial Co(II, Ni(II, Cu(II and Zn(II complexes with biacetyl-derived Schiff bases

    Directory of Open Access Journals (Sweden)

    MUHAMMAD IMRAN

    2010-08-01

    Full Text Available The condensation reactions of biacetyl with ortho-hydroxyaniline and 2-aminobenzoic acid to form bidendate NO donor Schiff bases were studied. The prepared Schiff base ligands were further utilized for the formation of metal chelates having the general formula [ML2(H2O2] where M = Co(II, Ni(II, Cu(II and Zn(II and L = HL1 and HL2. These new compounds were characterized by conductance measurements, magnetic susceptibility measurements, elemental analysis, and IR, 1H-NMR, 13C-NMR and electronic spectroscopy. Both Schiff base ligands were found to have a mono-anionic bidentate nature and octahedral geometry was assigned to all metal complexes. All the complexes contained coordinated water which was lost at 141–160 °C. These compounds were also screened for their in vitro antibacterial activity against four bacterial species, namely: Escherichia coli, Staphylococcus aureus, Salmonella typhi and Bacillus subtilis. The metal complexes were found to have greater antibacterial activity than the uncomplexed Schiff base ligands.

  1. Template synthesis of poly aza macrocyclic copper(II) and nickel(II) complexes: Spectral characterization and antimicrobial studies

    Energy Technology Data Exchange (ETDEWEB)

    Gurumoorthy, P.; Ravichandran, J.; Kaliur Rahiman, A. [The New College, Chennai (India); Karthikeyan, N.; Palani, P. [Univ. of Madras, Chennai (India)

    2012-07-15

    The template synthesis of copper(II) and nickel(II) complexes derived from 2,6-diformyl-4-methylphenol with diethylenetriamine or 1,2-bis(3-amino propylamino)ethane produce the 12-membered N{sub 3}O and 17-membered N{sub 4}O macrocyclic complexes, respectively. The geometry of the complexes has been determined with the help of electronic and EPR spectroscopic values and found to be five coordinated square pyramidal and, six coordinated distorted tetragonal for 12-membered and 17-membered macrocyclic complexes, respectively. Electrochemical studies of the mononuclear N{sub 3}O and N{sub 4}O copper(II) complexes show one irreversible one electron reduction wave at E{sup pc} = .1.35 and .1.15 V respectively, and the corresponding nickel(II) complexes show irreversible one-electron reduction wave at E{sup pc} = .1.25 and .1.22 V, respectively. The nickel(II) complexes show irreversible one-electron oxidation wave at Epa = +0.84 and +0.82 V, respectively. All the complexes were evaluated for in vitro antimicrobial activity against the human pathogenic bacteria and fungi.

  2. Transient absorption study of two-photon excitation mechanism in the LH2 complex from purple bacterium Rhodobacter sphaeroides.

    Science.gov (United States)

    Stepanenko, Ilya; Kompanetz, Viktor; Makhneva, Zoya; Chekalin, Sergey; Moskalenko, Andrei; Razjivin, Andrei

    2012-03-08

    The mechanism of two-photon excitation of a peripheral light-harvesting complex LH2 (B800-850) from purple bacterium Rhodobacter sphaeroides was explained on the basis of femtosecond transient absorption data. Fast bleaching of the B850 absorption band was measured under two-photon excitation by 1350 nm femtosecond pulses, showing fast subpicosecond arrival of excitation energy to B850 circular aggregates. Any spectral changes connected with the B800 absorption band of B800-BChl molecules were absent. A similar picture was observed under one-photon excitation of the LH2 complex by 675 nm femtosecond pulses. We believe these effects may be attributed to direct excitation of high-energy excitonic states of a B850 circular aggregate or its vibrational manifold in accordance with the model of Abe [Chem. Phys. 2001, 264, 355-363].

  3. Nonuniform Effect of Carrier Separation Efficiency and Light Absorption in Type-II Perovskite Nanowire Solar Cells

    Science.gov (United States)

    Wang, Weiping; He, Jialun; Cao, Yiyan; Kong, Lijing; Zheng, Xuanli; Wu, Yaping; Chen, Xiaohong; Li, Shuping; Wu, Zhiming; Kang, Junyong

    2017-03-01

    Coaxial structures exhibit great potential for the application of high-efficiency solar cells due to the novel mechanism of radial charge separation. Here, we intensively investigate the nonuniform effect of carrier separation efficiency (CSE) and light absorption in perovskite-based type-II coaxial nanowire solar cells (ZnO/CH3NH3PbI3). Results show that the CSE rapidly decreases along the radial direction in the shell, and the value at the outer side becomes extremely low for the thick shell. Besides, the position of the main light absorption gradually moves to the outer side with the increase of the shell thickness. As a result, the external quantum efficiency shows a positional dependence with a maximal value close to the border of the nanowire. Eventually, in our case, it is found that the maximal power conversion efficiency of the solar cells reduces from 19.5 to 17.9% under the effect of the nonuniformity of CSE and light absorption. This work provides a basis for the design of high-efficiency solar cells, especially type-II nanowire solar cells.

  4. Surface reaction of SnII on goethite (α-FeOOH): surface complexation, redox reaction, reductive dissolution, and phase transformation.

    Science.gov (United States)

    Dulnee, Siriwan; Scheinost, Andreas C

    2014-08-19

    To elucidate the potential risk of (126)Sn migration from nuclear waste repositories, we investigated the surface reactions of Sn(II) on goethite as a function of pH and Sn(II) loading under anoxic condition with O2 level redox state and surface structure were investigated by Sn K edge X-ray absorption spectroscopy (XAS), goethite phase transformations were investigated by high-resolution transmission electron microscopy and selected area electron diffraction. The results demonstrate the rapid and complete oxidation of Sn(II) by goethite and formation of Sn(IV) (1)E and (2)C surface complexes. The contribution of (2)C complexes increases with Sn loading. The Sn(II) oxidation leads to a quantitative release of Fe(II) from goethite at low pH, and to the precipitation of magnetite at higher pH. To predict Sn sorption, we applied surface complexation modeling using the charge distribution multisite complexation approach and the XAS-derived surface complexes. Log K values of 15.5 ± 1.4 for the (1)E complex and 19.2 ± 0.6 for the (2)C complex consistently predict Sn sorption across pH 2-12 and for two different Sn loadings and confirm the strong retention of Sn(II) even under anoxic conditions.

  5. Evaluation of Intestinal Absorption and Bioavailability of a Bergenin-Phospholipid Complex Solid Dispersion in Rats.

    Science.gov (United States)

    Gao, Haoshi; Wei, Yue; Xi, Long; Sun, Yuanyuan; Zhang, Tianhong

    2018-05-01

    Bergenin (BN) is a Biopharmaceutics Classification System class IV (BCS IV) drug with poor hydrophilicity and lipophilicity and is potentially eliminated by the efflux function of P-glycoprotein (P-gp). These factors may explain its low oral bioavailability. In the present study, a BN-phospholipid complex solid dispersion (BNPC-SD) was prepared by solvent evaporation and characterized based on differential scanning calorimetry, powder X-ray diffraction, scanning electron microscopy, infrared diffraction, solubility, octanol-water partition coefficient, and in vitro dissolution. To investigate how P-gp can inhibit BN absorption in vivo, the P-gp inhibitor verapamil was co-administered with BNPC-SD to Sprague Dawley rats. By in situ single-pass intestinal perfusion, the membrane permeability of BN from BNPC-SD was higher than that of BN given alone and was improved further by co-administered verapamil. A pharmacokinetics study was done in Sprague Dawley rats, with plasma BN levels estimated by high-performance liquid chromatography. C max and AUC 0 → t values for BN were significantly higher for BNPC-SD than for BN given alone and were increased further by verapamil. Thus, the relative oral bioavailability of BNPC-SD as well as BNPC-SD co-administered with verapamil was 156.33 and 202.46%, respectively, compared with the value for BN given alone. These results showed that BNPC-SD can increase the oral bioavailability of BCS IV drugs.

  6. Absorption spectroscopy of complex rare earth ion doped hybrid materials over a broad wavelength range

    OpenAIRE

    Dekker, R.; Worhoff, Kerstin; Stouwdam, J.W.; van Veggel, F.C.J.M.; Driessen, A.

    2005-01-01

    In the present work we applied a measurement setup to determine several relevant properties of rare-earth doped nanoparticles dispersed in polymer slab waveguides in a single absorption measurement: background absorption of the polymer host material, water absorption, polymer composition (overtones), rare earth concentration, and ligand contribution (increase of exponential loss trend in the UV). Furthermore, nanoparticle size and concentration in case of a refractive index mismatch (1//spl l...

  7. Physicochemical impact studies of gamma rays on "aspirin" analgesics drug and its metal complexes in solid form: Synthesis, spectroscopic and biological assessment of Ca(II), Mg(II), Sr(II) and Ba(II) aspirinate complexes

    Science.gov (United States)

    Refat, Moamen S.; Sharshar, T.; Elsabawy, Khaled M.; Heiba, Zein K.

    2013-09-01

    Metal aspirinate complexes, M2(Asp)4, where M is Mg(II), Ca(II), Sr(II) or Ba(II) are formed by refluxed of aspirin (Asp) with divalent non-transition metal ions of group (II) and characterized by elemental analysis and spectroscopic measurements (infrared, electronic, 1H NMR, Raman, X-ray powder diffraction and scanning electron microscopy). Elemental analysis of the chelates suggests the stoichiometry is 1:2 (metal:ligand). Infrared spectra of the complexes agree with the coordination to the central metal atom through three donation sites of two oxygen atoms of bridge bidentate carboxylate group and oxygen atom of sbnd Cdbnd O of acetyl group. Infrared spectra coupled with the results of elemental analyzes suggested a distorted octahedral structure for the M(II) aspirinate complexes. Gamma irradiation was tested as a method for stabilization of aspirin as well as their complexes. The effect of gamma irradiation, with dose of 80 Gy, on the properties of aspirinate complexes was studied. The aspirinate chelates have been screened for their in vitro antibacterial activity against four bacteria, gram-positive (Bacillus subtilis and Staphylococcus aureus) and gram-negative (Escherichia coli and Pseudomonas aeruginosa) and two strains of fungus (Aspergillus flavus and Candida albicans). The metal chelates were shown to possess more antibacterial activity than the free aspirin chelate.

  8. Overcoming Matrix Effects in a Complex Sample: Analysis of Multiple Elements in Multivitamins by Atomic Absorption Spectroscopy

    Science.gov (United States)

    Arnold, Randy J.; Arndt, Brett; Blaser, Emilia; Blosser, Chris; Caulton, Dana; Chung, Won Sog; Fiorenza, Garrett; Heath, Wyatt; Jacobs, Alex; Kahng, Eunice; Koh, Eun; Le, Thao; Mandla, Kyle; McCory, Chelsey; Newman, Laura; Pithadia, Amit; Reckelhoff, Anna; Rheinhardt, Joseph; Skljarevski, Sonja; Stuart, Jordyn; Taylor, Cassie; Thomas, Scott; Tse, Kyle; Wall, Rachel; Warkentien, Chad

    2011-01-01

    A multivitamin tablet and liquid are analyzed for the elements calcium, magnesium, iron, zinc, copper, and manganese using atomic absorption spectrometry. Linear calibration and standard addition are used for all elements except calcium, allowing for an estimate of the matrix effects encountered for this complex sample. Sample preparation using…

  9. Mononuclear Pd(II) complex as a new therapeutic agent: Synthesis, characterization, biological activity, spectral and DNA binding approaches

    Science.gov (United States)

    Saeidifar, Maryam; Mirzaei, Hamidreza; Ahmadi Nasab, Navid; Mansouri-Torshizi, Hassan

    2017-11-01

    The binding ability between a new water-soluble palladium(II) complex [Pd(bpy)(bez-dtc)]Cl (where bpy is 2,2‧-bipyridine and bez-dtc is benzyl dithiocarbamate), as an antitumor agent, and calf thymus DNA was evaluated using various physicochemical methods, such as UV-Vis absorption, Competitive fluorescence studies, viscosity measurement, zeta potential and circular dichroism (CD) spectroscopy. The Pd(II) complex was synthesized and characterized using elemental analysis, molar conductivity measurements, FT-IR, 1H NMR, 13C NMR and electronic spectra studies. The anticancer activity against HeLa cell lines demonstrated lower cytotoxicity than cisplatin. The binding constants and the thermodynamic parameters were determined at different temperatures (300 K, 310 K and 320 K) and shown that the complex can bind to DNA via electrostatic forces. Furthermore, this result was confirmed by the viscosity and zeta potential measurements. The CD spectral results demonstrated that the binding of Pd(II) complex to DNA induced conformational changes in DNA. We hope that these results will provide a basis for further studies and practical clinical use of anticancer drugs.

  10. Copper(II) and palladium(II) complexes with tridentate NSO donor Schiff base ligand: Synthesis, characterization and structures

    Science.gov (United States)

    Kumar, Sujit Baran; Solanki, Ankita; Kundu, Suman

    2017-09-01

    Mononuclear copper(II) complex [CuL2] and palladium(II) complexes [Pd(X)L] where X = benzoate(bz) or salicylate(sal) and HL = 2-(methylthio)phenylimino)methyl)phenol, a Schiff base ligand with NSO coordination sites have been synthesized and characterized by microanalyses, IR, UV-Visible spectra, conductivity measurement and magnetic studies. Crystal structures of all the complexes have been solved by single crystal X-ray diffraction studies and showed that there are two molecules in a unit cell in the [CuL2] complex - one molecule has square planar geometry whereas second molecule has distorted square pyramidal geometry and palladium(II) complexes have distorted square planar geometry.

  11. DETECTION OF CA II ABSORPTION BY A HIGH-VELOCITY CLOUD IN THE DIRECTION OF THE QUASAR PKS 0837-120

    NARCIS (Netherlands)

    ROBERTSON, JG; SCHWARZ, UJ; VANWOERDEN, H; MURRAY, JD; MORTON, DC; HULSBOSCH, ANM

    1991-01-01

    We present optical absorption spectroscopy of the Ca II K and H lines along the sight line to the quasar PKS 0837-120, which lies in the direction of a high-velocity cloud (HVC) detected in H I 21-cm emission at V(LSR) = + 105 km s-1. Our data show Ca II absorption due to the HVC as well as a lower

  12. Synthesis, Spectral and Antimicrobial Studies of Some Co(II, Ni(II and Cu(II Complexes Containing 2-Thiophenecarboxaldehyde Moiety

    Directory of Open Access Journals (Sweden)

    A. P. Mishra

    2012-01-01

    Full Text Available Some new Schiff base metal complexes of Co(II, Ni(II and Cu(II derived from 3-chloro-4-fluoroaniline (HL1 and 4-fluoroaniline (HL2 with 2-thiophenecarboxaldehyde have been synthesized and characterized by elemental analysis, FT-IR, FAB-mass, molar conductance, electronic spectra, ESR and magnetic susceptibility. The complexes exhibit coordination number 4 or 6. The complexes are colored and stable in air. Analytical data revealed that all the complexes exhibited 1:2 (metal: ligand ratio. FAB-mass data show degradation pattern of the complexes. The Schiff base and metal complexes show a good activity against the bacteria; B. subtilis, E. coli and S. aureus and fungi A. niger, A. flavus and C. albicans. The antimicrobial results also indicate that the metal complexes are better antimicrobial agents as compared to the Schiff bases.

  13. Synthesis, structure, DNA binding and anticancer activity of mixed ligand ruthenium(II) complex

    Science.gov (United States)

    Gilewska, Agnieszka; Masternak, Joanna; Kazimierczuk, Katarzyna; Trynda, Justyna; Wietrzyk, Joanna; Barszcz, Barbara

    2018-03-01

    In order to obtain a potential chemotherapeutic which is not affected on the normal BALB/3T3 cell line, a new arene ruthenium(II) complex {[RuCl(L1)(η6-p-cymene)]PF6}2 · H2O has been synthesized by a direct reaction of precursor, [{(η6-p-cymene)Ru(μ-Cl)}2Cl2], with N,N-chelating ligand (L1 - 2,2‧-bis(4,5-dimethylimidazole). The compound has been fully characterized by elemental analysis, X-ray diffraction, IR, UV-Vis and 1H, 13C NMR spectroscopies. X-ray analysis have confirmed that the compound crystallized in the monoclinic group Cc as an inversion twin. The asymmetric unit contains two symmetrically independent cationic complexes [RuCl(L1)(η6-p-cymene)]+ whose charge is balanced by two PF6- counterions. The shape of each cationic coordination polyhedral can be described as a distorted dodecahedron and shows a typical piano-stool geometry. In addition, an analysis of the crystal structure and the Hirshfeld surface analysis were used to detect and visualize important hydrogen bonds and intermolecular interaction. Moreover, the antiproliferative behavior of the obtained complex was assayed against three human cells: MV-4-11, LoVo, MCF-7 and BALB/3T3 - normal mice fibroblast cells. To predict a binding mode, a potential interaction of ruthenium complex with calf thymus DNA (CT-DNA) has been explored using UV absorption and circular dichroism (CD).

  14. Effects of PEGylated lipid nanoparticles on the oral absorption of one BCS II drug: a mechanistic investigation

    Directory of Open Access Journals (Sweden)

    Zhang XW

    2014-11-01

    Full Text Available Xingwang Zhang,* Guijiang Chen,* Tianpeng Zhang, Zhiguo Ma, Baojian WuDivision of Pharmaceutics, College of Pharmacy, Jinan University, Guangzhou, People’s Republic of China*These authors contributed equally to this workAbstract: Lipid nanocarriers are becoming a versatile platform for oral delivery of lipophilic drugs. In this article, we aimed to explore the gastrointestinal behaviors of lipid nanoparticles and the effect of PEGylation on oral absorption of fenofibrate (FN, a Biopharmaceutics Classification System (BCS II model drug. FN-loaded PEGylated lipid nanoparticles (FN-PLNs were prepared by the solvent-diffusion method and characterized by particle size distribution, morphology, Fourier transform infrared spectroscopy, and drug release. Lipolytic experiments were performed to assess the resistance of lipid nanoparticles against pancreatic lipase. Pharmacokinetics was evaluated in rats after oral administration of FN preparations. The obtained FN-PLNs were 186.7 nm in size with an entrapment efficiency of >95%. Compared to conventional lipid nanoparticles, PLNs exhibited slower drug release in the lipase-containing medium, strikingly reduced mucin binding, and suppressed lipolysis in vitro. Further, oral absorption of FN was significantly enhanced using PLNs with relative bioavailability of 123.9% and 157.0% to conventional lipid nanoparticles and a commercial formulation (Lipanthyl®, respectively. It was demonstrated that reduced mucin trapping, suppressed lipolysis, and/or improved mucosal permeability were responsible for increased oral absorption. These results facilitated a better understanding of the in vivo fate of lipid nanoparticles, and suggested the potential of PLNs as oral carriers of BCS II drugs.Keywords: fenofibrate, lipid nanoparticles, PEGylation, oral bioavailability, absorption mechanism

  15. Simulating Ru L3-edge X-ray absorption spectroscopy with time-dependent density functional theory: model complexes and electron localization in mixed-valence metal dimers.

    Science.gov (United States)

    Van Kuiken, Benjamin E; Valiev, Marat; Daifuku, Stephanie L; Bannan, Caitlin; Strader, Matthew L; Cho, Hana; Huse, Nils; Schoenlein, Robert W; Govind, Niranjan; Khalil, Munira

    2013-05-30

    Ruthenium L3-edge X-ray absorption (XA) spectroscopy probes unoccupied 4d orbitals of the metal atom and is increasingly being used to investigate the local electronic structure in ground and excited electronic states of Ru complexes. The simultaneous development of computational tools for simulating Ru L3-edge spectra is crucial for interpreting the spectral features at a molecular level. This study demonstrates that time-dependent density functional theory (TDDFT) is a viable and predictive tool for simulating ruthenium L3-edge XA spectroscopy. We systematically investigate the effects of exchange correlation functional and implicit and explicit solvent interactions on a series of Ru(II) and Ru(III) complexes in their ground and electronic excited states. The TDDFT simulations reproduce all of the experimentally observed features in Ru L3-edge XA spectra within the experimental resolution (0.4 eV). Our simulations identify ligand-specific charge transfer features in complicated Ru L3-edge spectra of [Ru(CN)6](4-) and Ru(II) polypyridyl complexes illustrating the advantage of using TDDFT in complex systems. We conclude that the B3LYP functional most accurately predicts the transition energies of charge transfer features in these systems. We use our TDDFT approach to simulate experimental Ru L3-edge XA spectra of transition metal mixed-valence dimers of the form [(NC)5M(II)-CN-Ru(III)(NH3)5](-) (where M = Fe or Ru) dissolved in water. Our study determines the spectral signatures of electron delocalization in Ru L3-edge XA spectra. We find that the inclusion of explicit solvent molecules is necessary for reproducing the spectral features and the experimentally determined valencies in these mixed-valence complexes. This study validates the use of TDDFT for simulating Ru 2p excitations using popular quantum chemistry codes and providing a powerful interpretive tool for equilibrium and ultrafast Ru L3-edge XA spectroscopy.

  16. Visible Light Absorption of Binuclear TiOCoII Charge-Transfer UnitAssembled in Mesoporous Silica

    Energy Technology Data Exchange (ETDEWEB)

    Han, Hongxian; Frei, Heinz

    2007-01-30

    Grafting of CoII(NCCH3)2Cl2 onto mesoporous Ti-MCM-41 silicain acetonitrile solution affords binuclear Ti-O-CoII sites on the poresurface under complete replacement of the precursor ligands byinteractions with anchored Ti centers and the silica surface. The CoIIligand field spectrum signals that the Co centers are anchored on thepore surface in tetrahedral coordination. FT-infrared action spectroscopyusing ammonia gas adsorption reveals Co-O-Si bond modes at 831 and 762cm-1. No Co oxide clusters are observed in the as-synthesized material.The bimetallic moieties feature an absorption extending from the UV intothe visible to about 600 nm which is attributed to the TiIV-O-CoII?3TiIII-O-CoIII metal-to-metal charge-transfer (MMCT) transition. Thechromophore is absent in MCM-41 containing Ti and Co centers isolatedfrom each other; this material was synthesized by grafting CoII onto aTi-MCM-41 sample with the Ti centers protected by a cyclopentadienylligand. The result indicates that the appearance of the charge-transferabsorption requires that the metal centers are linked by an oxo bridge,which is additionally supported by XANES spectroscopy. The MMCTchromophore of Ti-O-CoII units has sufficient oxidation power to serve asvisible light electron pump for driving multi-electron transfer catalystsof demanding uphill reactions such as water oxidation.

  17. Zeolite-encapsulated Co(II), Mn(II), Cu(II) and Cr(III) salen complexes as catalysts for efficient selective oxidation of benzyl alcohol

    Science.gov (United States)

    Li, F. H.; Bi, H.; Huang, D. X.; Zhang, M.; Song, Y. B.

    2018-01-01

    Co(II), Mn(II), Cu(II) and Cr(III) salen type complexes were synthesized in situ in Y zeolite by the reaction of ion-exchanged metal ions with the flexible ligand molecules that had diffused into the cavities. Data of characterization indicates the formation of metal salen complexes in the pores without affecting the zeolite framework structure, the absence of any extraneous species and the geometry of encapsulated complexes. The catalytic activity results show that Cosalcyen Y exhibited higher catalytic activity in the water phase selective oxidation of benzyl alcohol, which could be attributed to their geometry and the steric environment of the metal actives sites.

  18. Coordination behavior of tetraaza [N4] ligand towards Co(II), Ni(II), Cu(II), Cu(I) and Pd(II) complexes: Synthesis, spectroscopic characterization and anticancer activity

    Science.gov (United States)

    El-Boraey, Hanaa A.

    2012-11-01

    Novel eight Co(II), Ni(II), Cu(II), Cu(I) and Pd(II) complexes with [N4] ligand (L) i.e. 2-amino-N-{2-[(2-aminobenzoyl)amino]ethyl}benzamide have been synthesized and structurally characterized by elemental analysis, spectral, thermal (TG/DTG), magnetic, and molar conductivity measurements. On the basis of IR, mass, electronic and EPR spectral studies an octahedral geometry has been proposed for Co(II), Ni(II) complexes and Cu(II) chloride complex, square-pyramidal for Cu(I) bromide complex. For Cu(II) nitrate complex (6), Pd(II) complex (8) square planar geometry was proposed. The EPR data of Cu(II) complexes in powdered form indicate dx2-y2 ground state of Cu(II) ion. The antitumor activity of the synthesized ligand and some selected metal complexes has been studied. The palladium(II) complex (8) was found to display cytotoxicity (IC50 = 25.6 and 41 μM) against human breast cancer cell line MCF-7 and human hepatocarcinoma HEPG2 cell line.

  19. Excited-state dynamics of a ruthenium(II) catalyst studied by transient photofragmentation in gas phase and transient absorption in solution

    Energy Technology Data Exchange (ETDEWEB)

    Imanbaew, D.; Nosenko, Y. [Fachbereich Chemie, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 52–54, 67663 Kaiserslautern (Germany); Forschungszentrum OPTIMAS, Erwin-Schrödinger-Str. 46, 67663 Kaiserslautern (Germany); Kerner, C. [Fachbereich Chemie, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 52–54, 67663 Kaiserslautern (Germany); Chevalier, K.; Rupp, F. [Fachbereich Physik, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 46, 67663 Kaiserslautern (Germany); Riehn, C., E-mail: riehn@chemie.uni-kl.de [Fachbereich Chemie, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 52–54, 67663 Kaiserslautern (Germany); Forschungszentrum OPTIMAS, Erwin-Schrödinger-Str. 46, 67663 Kaiserslautern (Germany); Thiel, W.R. [Fachbereich Chemie, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 52–54, 67663 Kaiserslautern (Germany); Diller, R. [Fachbereich Physik, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 46, 67663 Kaiserslautern (Germany)

    2014-10-17

    Graphical abstract: - Highlights: • Ultrafast dynamics of new Ru(II) catalysts investigated in gas phase and solution. • Catalyst activation (HCl loss) achieved in ion trap by UV photoexcitation. • Electronic relaxation proceeds by IVR and IC followed by ground state dissociation. • No triplet formation in contrast to other Ru-polypyridine complexes. • Solvent prohibits catalyst activation in solution by fast vibrational cooling. - Abstract: We report studies on the excited state dynamics of new ruthenium(II) complexes [(η{sup 6}-cymene)RuCl(apypm)]PF{sub 6} (apypm=2-NR{sub 2}-4-(pyridine-2-yl)-pyrimidine, R=CH{sub 3} (1)/H (2)) which, in their active form [1{sup +}-HCl] and [2{sup +}-HCl], catalyze the transfer hydrogenation of arylalkyl ketones in the absence of a base. The investigations encompass femtosecond pump–probe transient mass spectrometry under isolated conditions and transient absorption spectroscopy in acetonitrile solution, both on the cations [(η{sup 6}-cymene)RuCl(apypm)]{sup +} (1{sup +}, 2{sup +}). Gas phase studies on mass selected ions were performed in an ESI ion trap mass spectrometer by transient photofragmentation, unambiguously proving the formation of the activated catalyst species [1{sup +}-HCl] or [2{sup +}-HCl] after photoexcitation being the only fragmentation channel. The primary excited state dynamics in the gas phase could be fitted to a biexponential decay, yielding time constants of <100 fs and 1–3 ps. Transient absorption spectroscopy performed in acetonitrile solution using femtosecond UV/Vis and IR probe laser pulses revealed additional deactivation processes on longer time scales (∼7–12 ps). However, the formation of the active catalyst species after photoexcitation could not be observed in solution. The results from both studies are compared to former CID investigations and DFT calculations concerning the activation mechanism.

  20. Evanescent wave sensing and absorption analysis of herbal tea floral extracts in the presence of silver metal complexes

    Science.gov (United States)

    Priyamvada, V. C.; Radhakrishnan, P.

    2017-06-01

    Fiber optic evanescent wave sensors are used for studying the absorption properties of biochemical samples. The studies give precise information regarding the actual ingredients of the samples. Recent studies report the corrosion of silver in the presence glucose dissolved in water and heated to a temperature of 70°C. Based on this report evanescent absorption studies are carried out in hibiscus herbal tea floral extracts in the presence of silver metal complexes. These studies can also lead to the evaluation of the purity of the herbal tea extract.

  1. One-Photon Absorption Properties from a Hybrid Polarizable Density Embedding/Complex Polarization Propagator Approach for Polarizable Solutions

    DEFF Research Database (Denmark)

    Hršak, Dalibor; Nørby, Morten Steen; Coriani, Sonia

    2018-01-01

    We present a formulation of the polarizable density embedding (PDE) method in combination with the complex polarization propagator (CPP) method for the calculation of absorption spectra of molecules in solutions. The method is particularly useful for the calculation of near-edge X-ray absorption...... fine structure (NEXAFS) spectra. We compare the performance of PDE-CPP with the previously formulated polarizable embedding (PE)-CPP model for the calculation of the NEXAFS spectra of adenine, formamide, glycine, and adenosine triphosphate (ATP) in water at the carbon and nitrogen K-edges, as well...

  2. Synthesis and characterization of the Rhodium (II) citrate complex

    International Nuclear Information System (INIS)

    Najjar, R.; Santos, F.S. dos; Seidel, W.

    1987-01-01

    The preparation and characterization of the rhodium (II) citrate is described. Rhodium citrate was prepared by reacting citric acid trihydrated (3,4 g, 16 mmols) with anhydrous rhodium acetate (0,44 g, 1 mmol). Th electronic instruments, thermogravimetric curve and spectrum of rhodium (II) citrate are analysed. (M.J.C.) [pt

  3. Synthesis, spectral and third-order nonlinear optical properties of terpyridine Zn(II) complexes based on carbazole derivative with polyether group

    Science.gov (United States)

    Kong, Ming; Liu, Yanqiu; Wang, Hui; Luo, Junshan; Li, Dandan; Zhang, Shengyi; Li, Shengli; Wu, Jieying; Tian, Yupeng

    2015-01-01

    Four novel Zn(II) terpyridine complexes (ZnLCl2, ZnLBr2, ZnLI2, ZnL(SCN)2) based on carbazole derivative group were designed, synthesized and fully characterized. Their photophysical properties including absorption and one-photon excited fluorescence, two-photon absorption (TPA) and optical power limiting (OPL) were further investigated systematically and interpreted on the basis of theoretical calculations (TD-DFT). The influences of different solvents on the absorption and One-Photon Excited Fluorescence (OPEF) spectral behavior, quantum yields and the lifetime of the chromophores have been investigated in detail. The third-order nonlinear optical (NLO) properties were investigated by open/closed aperture Z-scan measurements using femtosecond pulse laser in the range from 680 to 1080 nm. These results revealed that ZnLCl2 and ZnLBr2 exhibited strong two-photon absorption and ZnLCl2 showed superior optical power limiting property.

  4. Coordination chemistry of sugar-phosphate complexes with palladium(II), rhenium(V) and zinc(II)

    Energy Technology Data Exchange (ETDEWEB)

    Steinborn, Christian Martin

    2013-05-21

    As described before, some studies dealing with coordination chemistry of sugar phosphates are available but no analogous complexes of Zn{sup II} have been investigated yet. The primary goal of this work is, therefore, to fill this gap. In order to stay close to the active sites of enzymes such as class-II-aldolase, the simple metal fragment Zn{sup II}(dien) is used. NMR spectroscopy is used primarily as analytical method since it enables the investigation of both complex equilibria in solution and pH dependence of metal-binding sites. Since this approach is challenging due to the fast metal-ligand exchange and the absence of CIS values, it is necessary to improve the significance of NMR data collected from sugar-phosphate complexes with Zn{sup II}. Hence, further experiments are performed with molecules similar to sugar phosphates such as reducing and methylated sugars or polyols. Beside NMR spectroscopy, crystal-structure analysis will be used to get more detailed information about the binding pattern of the complexes. Additionally, sugar-phosphate complexes of Pd{sup II} are investigated. Further experiments are conducted, on the one hand, to synthesise more sugarphosphate complexes with ReVON2 fragments, and, on the other hand, to grow crystals confirming the theory about mixed sugar-core-phosphate chelation.

  5. Functional and structural analysis of photosystem II core complexes from spinach with high oxygen evolution capacity

    NARCIS (Netherlands)

    Haag, Elisabeth; Irrgang, Klaus-D.; Boekema, Egbert J.; Renger, Gernot

    1990-01-01

    Oxygen-evolving photo system II core complexes were prepared from spinach by solubilizing photosystem II membrane fragments with dodecyl-β-D-maltoside. The core complexes consist of the intrinsic 47-kDa, 43-kDa, D1 and D2 polypeptides, the two subunits of cytochrome b559 and the extrinsic 33-kDa

  6. Organoruthenium (II) complexes produced by insertion reactions of substituted olefins into a hydrido-ruthenium bond

    Energy Technology Data Exchange (ETDEWEB)

    Hiraki, Katsuma; Sasada, Yoko; Kitamura, Tsuneyuki [Nagasaki Univ. (Japan)

    1980-04-01

    Dimethyl fumarate, 2-vinylpyridine, and acrylonitrile insert into a H-Ru bond of (RuClH(CO)(PPh/sub 3/)/sub 3/) (1) to yield new substituted alkylruthenium(II) complexes. Methyl sorbate also reacted with 1 to give a new substituted eta/sup 3/-allylruthenium(II) complex.

  7. Synthesis and Spectral Studies of Ni(II Dithiocarbamate Complexes and Their Use as Precursors for Nickel Sulphides Nanocrystals

    Directory of Open Access Journals (Sweden)

    Azile Nqombolo

    2016-01-01

    Full Text Available Ni(II dithiocarbamate complexes have been synthesized and characterized by UV-Vis, FTIR, and NMR spectroscopic techniques. Electronic spectra measurements indicate that the complexes are four-coordinate square planar geometry while the FTIR confirmed that the dithiocarbamates act as bidentate chelating ligands. The compounds were used as single source precursors and thermolysed at 220°C to prepare HDA-capped NiS nanocrystals which were characterized by absorption and photoluminescence (PL spectra measurements, powder X-ray diffraction (PXRD, transmission electron microscopy (TEM, scanning electron microscopy (SEM, and energy dispersive spectroscopy (EDS. Absorption spectra studies showed that the synthesized NiS nanoparticles are blue-shifted relative to the bulk material and PL studies showed emission maxima that are red-shifted compared to the absorption band edges. The XRD patterns of the as-prepared NiS nanoparticles revealed cubic crystalline phases. TEM images showed spherical and close-to-spherical nanocrystals with the size in the range 12–38 nm for NiS1, 8–11 nm for NiS2, and 9–16 nm for NiS3. SEM images showed homogeneous surface morphology and EDS confirmed the presence of Ni and S and the formation of NiS nanoparticles.

  8. Syntheses, Crystal Structures and Thermal Behaviors of Two Supramolecular Salamo-Type Cobalt(II and Zinc(II Complexes

    Directory of Open Access Journals (Sweden)

    Gang Li

    2017-07-01

    Full Text Available This paper reports the syntheses of two new complexes, [Co(L1(H2O2] (1 and [{Zn(L2(μ-OAcZn(n-PrOH}2] (2, from asymmetric halogen-substituted Salamo-type ligands H2L1 and H3L2, respectively. Investigation of the crystal structure of complex 1 reveals that the complex includes one Co(II ion, one (L12− unit and two coordinated water molecules. Complex 1 shows slightly distorted octahedral coordination geometry, forming an infinite 2D supramolecular structure by intermolecular hydrogen bond and π–π stacking interactions. Complex 2 contains four Zn(IIions, two completely deprotonated (L23− moieties, two coordinated μ-OAc− ions and n-propanol molecules. The Zn(II ions in complex 2 display slightly distorted trigonal bipyramidal or square pyramidal geometries.

  9. Polymerization of Methyl Methacrylate Catalyzed by Co(II), Cu(II), and Zn(II) Complexes Bearing N-Methyl-N-((pyridin-2-yl)methyl) cyclohexanamine

    Energy Technology Data Exchange (ETDEWEB)

    Ahn, Seoung Hyun; Lee, Hyosun [Kyungpook National University, Daegu (Korea, Republic of); Shin, Jongwon [POSTECH, Pohang (Korea, Republic of); Nayab, Saira [Shaheed Benazir Bhutto University, Sheringal (Pakistan)

    2016-05-15

    We demonstrated the synthesis and characterization of Co(II), Cu(II), and Zn(II) complexes ligated to N-methyl-N-((pyridin-2-yl)methyl)cyclohexanamine. The complex [Co(nmpc)Cl{sub 2}] in the presence of MMAO showed the highest catalytic activity for MMA polymerization at 60 °C compared with its Zn(II) and Cu(II) analogs. The metal center showed an obvious influence on the catalytic activity, although this appeared to have no effect on the stereo-regularity of the resultant PMMA. X-ray diffraction analysis revealed that [Co(nmpc)Cl{sub 2}] and [Zn(nmpc)Cl{sub 2}] crystallized in the monoclinic system with space group P2{sub 1}/c and existed as monomeric and solvent-free complexes.

  10. Recognition of thymine in DNA bulges by a Zn(II) macrocyclic complex.

    Science.gov (United States)

    del Mundo, Imee Marie A; Fountain, Matthew A; Morrow, Janet R

    2011-08-14

    A Zn(II) macrocyclic complex with appended quinoline is a bifunctional recognition agent that uses both the Zn(II) center and the pendent aromatic group to bind to thymine in bulges with good selectivity over DNA containing G, C or A bulges. Spectroscopic studies show that the stem containing the bulge stays largely intact in a DNA hairpin with the Zn(II) complex bound to the thymine bulge. This journal is © The Royal Society of Chemistry 2011

  11. MAGIICAT III. Interpreting self-similarity of the circumgalactic medium with virial mass using Mg II absorption

    International Nuclear Information System (INIS)

    Churchill, Christopher W.; Trujillo-Gomez, Sebastian; Nielsen, Nikole M.; Kacprzak, Glenn G.

    2013-01-01

    In Churchill et al., we used halo abundance matching applied to 182 galaxies in the Mg II Absorber-Galaxy Catalog (MAGIICAT) and showed that the mean Mg II λ2796 equivalent width follows a tight inverse-square power law, W r (2796)∝(D/R vir ) –2 , with projected location relative to the galaxy virial radius and that the Mg II absorption covering fraction is effectively invariant with galaxy virial mass, M h , over the range 10.7 ≤ log M h /M ☉ ≤ 13.9. In this work, we explore multivariate relationships between W r (2796), virial mass, impact parameter, virial radius, and the theoretical cooling radius that further elucidate self-similarity in the cool/warm (T = 10 4 -10 4.5 K) circumgalactic medium (CGM) with virial mass. We show that virial mass determines the extent and strength of the Mg II absorbing gas such that the mean W r (2796) increases with virial mass at fixed distance while decreasing with galactocentric distance for fixed virial mass. The majority of the absorbing gas resides within D ≅ 0.3 R vir , independent of both virial mass and minimum absorption threshold; inside this region, and perhaps also in the region 0.3 < D/R vir ≤ 1, the mean W r (2796) is independent of virial mass. Contrary to absorber-galaxy cross-correlation studies, we show there is no anti-correlation between W r (2796) and virial mass. We discuss how simulations and theory constrained by observations support self-similarity of the cool/warm CGM via the physics governing star formation, gas-phase metal enrichment, recycling efficiency of galactic scale winds, filament and merger accretion, and overdensity of local environment as a function of virial mass.

  12. MAGIICAT III. Interpreting self-similarity of the circumgalactic medium with virial mass using Mg II absorption

    Energy Technology Data Exchange (ETDEWEB)

    Churchill, Christopher W.; Trujillo-Gomez, Sebastian; Nielsen, Nikole M. [New Mexico State University, Las Cruces, NM 88003 (United States); Kacprzak, Glenn G. [Swinburne University of Technology, Victoria 3122 (Australia)

    2013-12-10

    In Churchill et al., we used halo abundance matching applied to 182 galaxies in the Mg II Absorber-Galaxy Catalog (MAGIICAT) and showed that the mean Mg II λ2796 equivalent width follows a tight inverse-square power law, W{sub r} (2796)∝(D/R {sub vir}){sup –2}, with projected location relative to the galaxy virial radius and that the Mg II absorption covering fraction is effectively invariant with galaxy virial mass, M {sub h}, over the range 10.7 ≤ log M {sub h}/M {sub ☉} ≤ 13.9. In this work, we explore multivariate relationships between W{sub r} (2796), virial mass, impact parameter, virial radius, and the theoretical cooling radius that further elucidate self-similarity in the cool/warm (T = 10{sup 4}-10{sup 4.5} K) circumgalactic medium (CGM) with virial mass. We show that virial mass determines the extent and strength of the Mg II absorbing gas such that the mean W{sub r} (2796) increases with virial mass at fixed distance while decreasing with galactocentric distance for fixed virial mass. The majority of the absorbing gas resides within D ≅ 0.3 R {sub vir}, independent of both virial mass and minimum absorption threshold; inside this region, and perhaps also in the region 0.3 < D/R {sub vir} ≤ 1, the mean W{sub r} (2796) is independent of virial mass. Contrary to absorber-galaxy cross-correlation studies, we show there is no anti-correlation between W{sub r} (2796) and virial mass. We discuss how simulations and theory constrained by observations support self-similarity of the cool/warm CGM via the physics governing star formation, gas-phase metal enrichment, recycling efficiency of galactic scale winds, filament and merger accretion, and overdensity of local environment as a function of virial mass.

  13. New Mn(II, Ni(II, Cd(II, Pb(II complexes with 2-methylbenzimidazole and other ligands. Synthesis, spectroscopic characterization, crystal structure, magnetic susceptibility and biological activity studies

    Directory of Open Access Journals (Sweden)

    Shayma A. Shaker

    2016-11-01

    Full Text Available Synthesis and characterization of Mn(II, Ni(II, Cd(II and Pb(II mixed ligand complexes of 2-methylbenzimidazole with other ligands have been reported. The structure of the ligands and their complexes was investigated using elemental analysis, IR, UV–Vis, (1H, 13C NMR spectroscopy, molar conductivity and magnetic susceptibility measurements. In all the studies of complexes, the 2-methylbenzimidazole behaves as a neutral monodentate ligand which is coordinated with the metal ions through the N atom. While benzotriazole behaves as a neutral bidentate ligand which is coordinated with the Ni(II ion through the two N atoms. Moreover, the N-acetylglycine behaves as a bidentate ligand which is coordinated with the Mn(II, Ni(II and Pb(II ions through the N atom and the terminal carboxyl oxygen atom. The magnetic and spectral data indicate the tetrahedral geometry for Mn(II complex, irregular tetrahedral geometry for Pb(II complex and octahedral geometry for Ni(II complex. The X-ray single crystal diffraction method was used to confirm a centrosymmetric dinuclear Cd(II complex as each two metal ions are linked by a pair of thiocyanate N = S bridge. Two 2-methylbenzimidazole N-atom donors and one terminal thiocyanate N atom complete a highly distorted square pyramid geometry around the Cd atom. Besides, different cell types were used to determine the inhibitory effect of Mn(II, Ni(II, Cd(II and Pb(II complexes on cell growth using MTT assay. Cd(II complex showed cytotoxic effect on various types of cancer cell lines with different EC50 values.

  14. Diethylenetriamine/diamines/copper (II complexes [Cu(dien(NN]Br2: Synthesis, solvatochromism, thermal, electrochemistry, single crystal, Hirshfeld surface analysis and antibacterial activity

    Directory of Open Access Journals (Sweden)

    Fatima Abu Saleemh

    2017-09-01

    Full Text Available Two dicationic water soluble mixed triamine/diamine copper (II complexes, of general formula [Cu(dienNN]Br2 (1–2 [dien = diethelenetriamine and NN is en = ethylenediamine or Me4en = N,N′,N,N′-tetramethylethylenediamine] were prepared under ultrasonic mode with a relatively high yield. These complexes were characterized by elemental microanalysis, UV visible IR spectroscopy, and thermal and electrochemical techniques. In addition, complex 2 structure was solved by X-ray single crystal and Hirshfeld surface analysis. The complex exhibits a distorted square pyramidal coordination environment around Cu(II centre. The solvatochromism of the desired complexes was investigated in water and other suitable organic solvents. The results show that the Guttmann’s DN parameter values of the solvents have mainly contributed to the shift of the d–d absorption band towards the linear increase in the wavelength of the absorption maxima of the complexes. The complex 1 showed higher antibacterial activity against the studied microorganisms compared to complex 2. Both complexes revealed promising antibacterial activities.

  15. Preparation, infrared, raman and nmr spectra of N,N'-diethylthiourea complexes with zinc(II), cadmium(II) and mercury(II) halides

    Energy Technology Data Exchange (ETDEWEB)

    Marcotrigiano, G [Bari Univ. (Italy). Cattedra di Chimica, Facolta di Medicina-Veterinaria

    1976-05-01

    Several complexes of N,N'-diethylthiourea (Dietu) with zinc(II), cadmium(II) and mercury(II) halides were prepared and characterized by i.r. (4000-60 cm/sup -1/), raman (400-60 cm/sup -1/), in the solid state and n.m.r. and conductometric methods in solution. The complexes Zn(Dietu)/sub 2/X/sub 2/, Cd(Dietu)/sub 2/X/sub 2/ (X=Cl, Br, I) and Hg(Dietu)/sub 2/X/sub 2/ (X=Br, I) are tetrahedral species in which intramolecular -NH...X interactions have been observed. The 1:1 mercury(II) complexes, Hg(Dietu)X/sub 2/ (X=Cl, Br), appear to have a dimeric tetrahedral halide-bridged structure in the solid state. In all these complexes N,N'-diethylthiourea is sulphur-bonded to the metal.

  16. Incorporation of amphiphilic ruthenium(II) ammine complexes into Langmuir-Blodgett thin films with switchable quadratic nonlinear optical behavior.

    Science.gov (United States)

    Boubekeur-Lecaque, Leïla; Coe, Benjamin J; Harris, James A; Helliwell, Madeleine; Asselberghs, Inge; Clays, Koen; Foerier, Stijn; Verbiest, Thierry

    2011-12-19

    Nine nonlinear optical (NLO) chromophores with pyridinium electron acceptors have been synthesized by complexing new proligands with {Ru(II)(NH(3))(5)}(2+) electron-donor centers. The presence of long alkyl/fluoroalkyl chain substituents imparts amphiphilic properties, and these cationic complexes have been characterized as their PF(6)(-) salts by using various techniques including electronic absorption spectroscopy and cyclic voltammetry. Each complex shows three reversible/quasireversible redox processes; a Ru(III/II) oxidation and two ligand-based reductions. The energies of the intense visible d → π* metal-to-ligand charge-transfer (MLCT) absorptions correlate to some extent with the ligand reduction potentials. (1)H NMR spectroscopy also provides insights into the relative electron-withdrawing strengths of the new ligands. Single crystal X-ray structures have been determined for two of the proligand salts and one complex salt, [Ru(II)(NH(3))(5)(4-C(16)H(33)PhQ(+))]Cl(3)·3.25H(2)O (PhQ(+) = N-phenyl-4,4'-bipyridinium), showing centrosymmetric packing structures in each case. The PF(6)(-) analogue of the latter complex has been used to deposit reproducibly high-quality, multilayered Langmuir-Blodgett (LB) thin films. These films show a strong second harmonic generation (SHG) response from a 1064 nm laser; their MLCT absorbance increases linearly with the number of layers (N) and I(2ω)/I(ω)(2) (I(2ω) = intensity at 532 nm; I(ω) = intensity at 1064 nm) scales quadratically with N, consistent with homogeneous deposition. LB films on indium tin oxide (ITO)-coated glass show electrochemically induced switching of the SHG response, with a decrease in activity of about 50% on Ru(II) → Ru(III) oxidation. This effect is reversible, but reproducible over only a few cycles before the signal from the Ru(II) species diminishes. This work extrapolates our original solution studies (Coe, B. J. et al. Angew. Chem., Int. Ed.1999, 38, 366) to the first demonstration of

  17. Syntheses, crystal structures and spectroscopic properties of copper(II)-tetracyanometallate(II) complexes with nicotinamide and isonicotinamide ligands

    Science.gov (United States)

    Sayın, Elvan; Kürkçüoğlu, Güneş Süheyla; Yeşilel, Okan Zafer; Hökelek, Tuncer

    2015-09-01

    Four new one dimensional (1D) cyanide complexes, namely {[Cu(NH3)4(μ-na)][M‧(CN)4]}n and {[Cu(NH3)2(ina)2M‧(μ-CN)2(CN)2]}n (M‧(II) = Pd (1 and 3) or Pt (2 and 4), na:nicotinamide and ina:isonicotinamide) have been synthesized and characterized by elemental, spectral (FT-IR and Raman), and thermal (TG, DTG and DTA) analyses. The crystal structures of complexes 1-3 have been determined by single crystal X-ray diffraction technique. In complexes 1 and 2, na ligand is coordinated to the adjacent Cu(II) ions as a bridging ligand, giving rise to 1D linear cationic chain and the [M‧(CN)4]2- anionic complex acts as a counter ion. Complexes 3 and 4 are also 1D linear chain in which two cyanide ligands bridged neighboring M‧(II) and Cu(II) ions, while ina ligand is coordinated Cu(II) ion through nitrogen atom of pyridine ring. In the complexes, the Cu(II) ions adopt distorted octahedral geometries, while M‧(II) ions are four coordinated with four carbon atoms from cyanide ligands in square-planar geometries. The adjacent chains are further stacked through intermolecular hydrogen bond, Nsbnd Hṡṡṡπ, Csbnd H⋯M‧ and M‧⋯π interactions to form 3D supramolecular networks. Vibration assignments are given for all the observed bands. In addition, thermal stabilities of the compounds are also discussed.

  18. Solvation structure determination of nickel(II) ion in six nitriles using extended X-ray absorption fine structure spectroscopy

    International Nuclear Information System (INIS)

    Inada, Yasuhiro; Funahashi, Shigenobu

    1997-01-01

    The solvation structures of the nickel(II) ion in six nitriles have been determined using X-ray absorption fine structure spectroscopy. The coordination number and the Ni-N bond length are 6 and 206.9 ± 0.6 pm in acetonitrile, 5.9 ± 0.2 and 206.9 ± 0.6 pm in propionitrile, 6.0 ± 0.2 and 206.8 ± 0.6 pm in butyronitrile, 6.0 ± 0.2 and 206.8 ± 0.6 pm in isobutyronitrile, 6.0 ± 0.2 and 206.8 ± 0.6 pm in valeronitrile, and 6.0 ± 0.2 and 206.5 ± 0.7 pm in benzonitrile, respectively. The structure parameters around the nickel(II) ion in all the nitriles are not affected by the bulkiness of the nitrile molecules. On the basis of the obtained structure parameters, we have discussed the structural characteristics around the nickel(II) ion with nitrogen and oxygen donor solvents and the reaction mechanisms for nitrile exchange on the nickel(II) ion. (author)

  19. Influence of absorption on the time of flight of the light going through a complex medium

    Directory of Open Access Journals (Sweden)

    M. Kervella

    2011-09-01

    Full Text Available The aim of this work is to evaluate the influence of absorption processes on the time of flight of light going through an absorbing and scattering thick medium (clouds, paints, gas cell, etc. In order to study statistical scattering and absorbing processes, we use a Monte-Carlo simulation code with temporal phase function and Debye modes. The main result is that absorption inside particles induces a decrease of the global time delay.

  20. Low-energy absorption and luminescence of higher plant photosystem II core samples

    International Nuclear Information System (INIS)

    Hughes, Joseph L.; Smith, Paul J.; Pace, Ron J.; Krausz, Elmars

    2007-01-01

    The charge-separating state of PSII has been recently assigned as a homogeneously broadened band peaking at 705 nm. The possibility of observing emission due to luminescence from the charge-separating state was investigated. Emission from the charge-separating state is predicted to be both broad and substantially Stokes shifted. Our PSII cores show an easily observable and broad emission peaking near 735 nm when excited at 707 nm and beyond for temperatures below 100 K as well as the well-known F685 and F695 nm emission when excited at 633 nm. However, the 735 nm emission bears a close correspondence to that previously reported for the light harvesting pigment of photosystem I (PSI), LHCI-730, and we attribute our observed emission to a minor contamination of our sample with this protein. High sensitivity circular dichroism (CD) spectra establish that LHCI and/or PSI contamination of our samples does not contribute significantly to the absorption seen in the 700-730 nm region. Furthermore, systematic illumination-induced absorption changes seen in this region are shown to quantitatively track with charge separation and the subsequent secondary acceptor plastoquinone (Q A ) acceptor anion formation. These results confirm that absorption in the 700-730 nm region is associated with the reaction centre of active PSII

  1. Synthesis and characterization of poly(phenylacetylene)s with Ru(II) bis-terpyridine complexes in the side-chain.

    Science.gov (United States)

    Breul, Alexander M; Kübel, Joachim; Häupler, Bernhard; Friebe, Christian; Hager, Martin D; Winter, Andreas; Dietzek, Benjamin; Schubert, Ulrich S

    2014-04-01

    An alkyne-functionalized ruthenium(II) bis-terpyridine complex is directly copolymerized with phenylacetylene by alkyne polymerization. The polymer is characterized by size-exclusion chromatography (SEC), (1) H NMR spectroscopy, cyclic voltammetry (CV) measurements, and thermal analysis. The photophysical properties of the polymer are studied by UV-vis absorption spectroscopy. In addition, spectro-electrochemical measurements are carried out. Time-resolved luminescence lifetime decay curves show an enhanced lifetime of the metal complex attached to the conjugated polymer backbone compared with the Ru(tpy)2 (2+) model complex. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Micellar effect on metal-ligand complexes of Co(II, Ni(II, Cu(II and Zn(II with citric acid

    Directory of Open Access Journals (Sweden)

    Nageswara Rao Gollapalli

    2009-12-01

    Full Text Available Chemical speciation of citric acid complexes of Co(II, Ni(II, Cu(II and Zn(II was investigated pH-metrically in 0.0-2.5% anionic, cationic and neutral micellar media. The primary alkalimetric data were pruned with SCPHD program. The existence of different binary species was established from modeling studies using the computer program MINIQUAD75. Alkalimetric titrations were carried out in different relative concentrations (M:L:X = 1:2:5, 1:3:5, 1:5:3 of metal (M to citric acid. The selection of best chemical models was based on statistical parameters and residual analysis. The species detected were MLH, ML2, ML2H and ML2H2. The trend in variation of stability constants with change in mole fraction of the medium is explained on the basis of electrostatic and non-electrostatic forces. Distributions of the species with pH at different compositions of micellar media are also presented.

  3. Synthesis, singlet-oxygen photogeneration, two-photon absorption, photo-induced DNA cleavage and cytotoxic properties of an amphiphilic β-Schiff-base linked Ru(II) polypyridyl–porphyrin conjugate

    International Nuclear Information System (INIS)

    Ke, Hanzhong; Ma, Wanpeng; Wang, Hongda; Cheng, Guoe; Yuan, Han; Wong, Wai-Kwok; Kwong, Daniel W.J.; Tam, Hoi-Lam; Cheah, Kok-Wai; Chan, Chi-Fai; Wong, Ka-Leung

    2014-01-01

    A novel porphyrin–polypyridyl ruthenium(II) conjugate (TPP–Ru), in which the ruthenium(II) polypyridyl moiety is linked to the β-position of the tetraphenylporphyrin via a Schiff base linkage, has been synthesized and characterized by 1 H NMR, HRMS and UV–visible spectroscopy. The relative singlet oxygen quantum yield and two-photon absorption cross-section of this conjugate, together with its photo-induced DNA cleavage and cytotoxic activities were measured. The results show that the amphiphilic ruthenium(II) polypyridyl–porphyrin conjugate is an effective DNA photocleavage agent, with potential application in one- and two-photon absorption anti-cancer photodynamic therapy. - Highlights: • New porphyrin–ruthenium(II) polypyridyl complexes (TTP–Ru) have been synthesized. • The TTP–Ru shows substantial two-photon absorption cross-section (σ 2 =391 GM). • The TTP–Ru exhibits a substantial 1 O 2 quantum yield (0.64±0.13). • The TTP–Ru exhibits a strong DNA cleavage activity upon photo-excitation. • The TTP–Ru is available for in vitro imaging and as a photodynamic therapy agent

  4. Synthesis, singlet-oxygen photogeneration, two-photon absorption, photo-induced DNA cleavage and cytotoxic properties of an amphiphilic β-Schiff-base linked Ru(II) polypyridyl–porphyrin conjugate

    Energy Technology Data Exchange (ETDEWEB)

    Ke, Hanzhong, E-mail: kehanz@163.com [Faculty of Material Science and Chemistry, China University of Geosciences, Wuhan, Hubei 430074 (China); Ma, Wanpeng; Wang, Hongda; Cheng, Guoe [Faculty of Material Science and Chemistry, China University of Geosciences, Wuhan, Hubei 430074 (China); Yuan, Han [Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong SAR (China); Wong, Wai-Kwok, E-mail: wkwong@hkbu.edu.hk [Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong SAR (China); Institute of Advanced Materials, Hong Kong Baptist University, Kowloon Tong, Hong Kong SAR (China); Kwong, Daniel W.J. [Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong SAR (China); Tam, Hoi-Lam; Cheah, Kok-Wai [Department of Physics, Hong Kong Baptist University, Kowloon Tong, Hong Kong SAR (China); Institute of Advanced Materials, Hong Kong Baptist University, Kowloon Tong, Hong Kong SAR (China); Chan, Chi-Fai; Wong, Ka-Leung [Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong SAR (China)

    2014-10-15

    A novel porphyrin–polypyridyl ruthenium(II) conjugate (TPP–Ru), in which the ruthenium(II) polypyridyl moiety is linked to the β-position of the tetraphenylporphyrin via a Schiff base linkage, has been synthesized and characterized by {sup 1}H NMR, HRMS and UV–visible spectroscopy. The relative singlet oxygen quantum yield and two-photon absorption cross-section of this conjugate, together with its photo-induced DNA cleavage and cytotoxic activities were measured. The results show that the amphiphilic ruthenium(II) polypyridyl–porphyrin conjugate is an effective DNA photocleavage agent, with potential application in one- and two-photon absorption anti-cancer photodynamic therapy. - Highlights: • New porphyrin–ruthenium(II) polypyridyl complexes (TTP–Ru) have been synthesized. • The TTP–Ru shows substantial two-photon absorption cross-section (σ{sub 2}=391 GM). • The TTP–Ru exhibits a substantial {sup 1}O{sub 2} quantum yield (0.64±0.13). • The TTP–Ru exhibits a strong DNA cleavage activity upon photo-excitation. • The TTP–Ru is available for in vitro imaging and as a photodynamic therapy agent.

  5. Thermal, spectral, magnetic and biological studies of thiosemicarbazones complexes with metal ions: Cu(II), Co(II), Ni(II), Fe(III), Zn(II), Mn(II) and UO2(VI)

    International Nuclear Information System (INIS)

    Mashaly, M.M.; Seleem, H.S.; El-Behairy, M.A.; Habib, H.A.

    2004-01-01

    Thiosemicarbazones ligands, isatin-3-thiosemicarbazone(HIT) and N-acetylisatin-3-thiosemicarbazone (HAIT), which have tridentate ONN coordinating sites were prepared. The complexes of both ligands with Cu(II), Co(II), Ni(II), Fe(III), Zn(II), Mn(II) and UO 2 (VI) ions were isolated. The ligands and their metal complexes were characterized by elemental analysis, IR, UV-Vis and mass spectra, also by conductance, magnetic moment and TG-DSC measurements. All the transition metal complexes have octahedral configurations, except Cu-complexes which have planar geometry and the UO 2 (VI) complexes which have coordination number 8 and may acquire the distorted dodecahedral geometry. Thermal studies explored the possibility of obtaining new complexes. Inversion from octahedral to square-planar configuration occurred upon heating the parent Ni-HIAT complex to form the corresponding pyrolytic product. The antifungal activity against the tested organisms showed that some metal complexes enhanced the activity with respect to the parent ligands. (author)

  6. Iron(II) tris(3-bromo-1,10-phenanthroline) complex:synthesis, crystal structure and electropolymerization

    CERN Document Server

    Lee, K J; Lee, S S; Lee, B Y

    2002-01-01

    The complex of iron(II) tris(3-Br-phen)(3-Br-phen; 3-bromo-1,10-phenanthroline) was prepared as a precursor of electropolymerization and the crystal structure of [Fe(3-Br-phen) sub 3](PF sub 6) sub 2 centre dot CH sub 3 CN with a distorted octahedral geometry has been investigated. The reductive electropolymerization of [Fe(3-Br-phen) sub 3] sup 2 sup + complex onto the surface of a glassy carbon electrode and indium tin oxide (ITO) optically transparent electrode were performed in acetonitrile at room temperature. Thin film of poly-[Fe(3-Br-phen) sub 3] sup 2 sup + formed was adherent, electroactive and stably deposited on a glassy carbon disk electrode. The thin metallopolymeric film formed was also confirmed by absorption spectroscopy.

  7. Interpretation of the Electron Paramagnetic Resonance Spectra of Copper(II)-Tyrosine Complex

    Science.gov (United States)

    Xu, Xiao-Hui; Kuang, Min-Quan

    2017-12-01

    The electron paramagnetic resonance (EPR) spectra of [Cu(l-tyrosine)2]n (CuA) were interpreted based on the fourth-order perturbation treatments where the contributions due to the local distortion, ligand orbit and spin-orbit coupling were included. The calculated band transitions d_{x^2} - y^2 to dxy (≈16412 cm-1) and d_{z^2} (≈14845 cm-1) agree well with the band analysis results (d_{x^2} - y^2 \\to d_{xy} ≈16410 and d_{x^2} - y^2 \\to d_{z^2} ≈14850 cm-1). The unresolved separations d_{x^2} - y^2 \\to d_{xz} and d_{x^2} - y^2 \\to d_{yz} in the absorption spectra were evaluated as 26283 and 26262 cm-1, respectively. For CuA, copper chromophores in 1,3-diaminorpropane isophtalate copper(II) complex (CuB) and N-methyl-1,2-diaminoetaane-bis copper(II) polymer (CuC), the transition d_{x^2} - y^2 \\to d_{xy} (=E1≈10Dq) suffered an increase with a decrease in R̅L which was evaluated as the mean value of the copper-ligand bond lengths. The correlations between the tetragonal elongation ratio ρ (=(Rz-R̅L)/R̅L) (or the ratio G=(gz-ge)/((gx+gy)/2-ge)) and the g isotropy gav (=(gx+gy+gz)/3) (or the covalency factor N) for CuA, CuB and CuC were acquired and all the results were discussed.

  8. Study on the interaction of a copper(II) complex containing the artificial sweetener aspartame with human serum albumin.

    Science.gov (United States)

    Shahabadi, Nahid; Khodaei, Mohammad Mehdi; Kashanian, Soheila; Kheirdoosh, Fahimeh; Filli, Soraya Moradi

    2014-05-01

    A copper(II) complex containing aspartame (APM) as ligand, Cu(APM)2Cl2·2H2O, was synthesized and characterized. In vitro binding interaction of this complex with human serum albumin (HSA) was studied at physiological pH. Binding studies of this complex with HSA are useful for understanding the Cu(APM)2Cl2·2H2O-HSA interaction mechanism and providing guidance for the application and design of new and more efficient artificial sweeteners drive. The interaction was investigated by spectrophotometric, spectrofluorometric, competition experiment and circular dichroism. Hyperchromicity observed in UV absorption band of Cu(APM)2Cl2·2H2O. A strong fluorescence quenching reaction of HSA to Cu(APM)2Cl2·2H2O was observed and the binding constant (Kf) and corresponding numbers of binding sites (n) were calculated at different temperatures. Thermodynamic parameters, enthalpy change (∆H) and entropy change (∆S) were calculated to be -458.67 kJ mol(-1) and -1,339 J mol(-1 )K(-1) respectively. According to the van't Hoff equation, the reaction is predominantly enthalpically driven. In conformity with experimental results, we suggest that Cu(APM)2Cl2·2H2O interacts with HSA. In comparison with previous study, it is found that the Cu(II) complex binds stronger than aspartame.

  9. Cr(III,Mn(II,Fe(III,Co(II,Ni(II,Cu(II and Zn(II Complexes with Diisobutyldithiocarbamato Ligand

    Directory of Open Access Journals (Sweden)

    Mohammad Tarique

    2011-01-01

    Full Text Available The synthesis of sulphur and nitrogen containing dithiocarbamato ligand derived from diisobutylamine as well as its coordination compounds with 3d series transition metals is presented. These synthesized compounds were characterized on the basis of elemental analysis, conductometric measurements and IR spectral studies. The analytical data showed the stoichiometry 1:2 and 1:3 for the compounds of the types ML2 {M=Mn(II, Co(II, Ni(II, Cu(II and Zn(II} and M'L3{M'=Cr(III and Fe(III} respectively. The conductometric measurements proved the non-electrolytic behaviour of all the compounds. The bidentate nature of dithiocarbamato moiety was confirmed on the basis of IR spectral data.

  10. Band gaps and photocurrent responses of two novel alkaline earth metal(II) complexes based on 4,5-di(4′-carboxylphenyl)benzene

    Energy Technology Data Exchange (ETDEWEB)

    Meng, Jiang Ping; Yan, Zhi Shuo; Long, Ji Ying [Department of Applied Chemistry, College of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400030 (China); Gong, Yun, E-mail: gongyun7211@cqu.edu.cn [Department of Applied Chemistry, College of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400030 (China); Lin, Jian Hua, E-mail: jhlin@pku.edu.cn [Department of Applied Chemistry, College of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400030 (China); State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 (China)

    2017-01-15

    By using a rigid dicarboxylate ligand, 4,5-di(4′-carboxylphenyl)benzene (H{sub 2}L), two complexes formulated as SrL(DMF)(H{sub 2}O)·(CH{sub 3}CN) (DMF=N,N′-dimethylformamide) (1) and BaL(H{sub 2}O){sub 2} (2) were solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction. Complexes 1 and 2 display two-dimensional (2D) layer structures. The two complexes exhibit different electrochemical and photoelectrochemical properties. Their thermal stabilities, cyclic voltammograms, UV–vis absorption and diffuse reflectance spectra and photoluminescence properties have been investigated. The band structures, the total density of states (TDOS) and partial density of states (PDOS) of the two complexes were calculated by CASTEP program. Complex 2 exhibits much higher photocurrent density than complex 1. The Mott–Schottky plots reveal that complexes 1 and 2 both are p-type semiconductors, which are in agreement with their band structure calculations. - Graphical abstract: Two alkaline earth metal(II) complexes with 2D layer structures are p-type semiconductors, they possess different band structures and density of states. And the Ba(II) complex 2 exhibits much higher photocurrent density than the Sr(II) complex 1.

  11. Comparison of two methods for blood lead analysis in cattle: graphite-furnace atomic absorption spectrometry and LeadCare(R) II system.

    Science.gov (United States)

    Bischoff, Karyn; Gaskill, Cynthia; Erb, Hollis N; Ebel, Joseph G; Hillebrandt, Joseph

    2010-09-01

    The current study compared the LeadCare(R) II test kit system with graphite-furnace atomic absorption spectrometry for blood lead (Pb) analysis in 56 cattle accidentally exposed to Pb in the field. Blood Pb concentrations were determined by LeadCare II within 4 hr of collection and after 72 hr of refrigeration. Blood Pb concentrations were determined by atomic absorption spectrometry, and samples that were coagulated (n = 12) were homogenized before analysis. There was strong rank correlation (R(2) = 0.96) between atomic absorption and LeadCare II (within 4 hr of collection), and a conversion formula was determined for values within the observed range (3-91 mcg/dl, although few had values >40 mcg/dl). Median and mean blood pb concentrations for atomic absorption were 7.7 and 15.9 mcg/dl, respectively; for LeadCare II, medians were 5.2 mcg/dl at 4 hr and 4.9 mcg/dl at 72 hr, and means were 12.4 and 11.7, respectively. LeadCare II results at 4 hr strongly correlated with 72 hr results (R(2) = 0.96), but results at 72 hr were lower (P atomic absorption. Although there have been several articles that compared LeadCare with other analytical techniques, all were for the original system, not LeadCare II. The present study indicated that LeadCare II results correlated well with atomic absorption over a wide range of blood Pb concentrations and that refrigerating samples for up to 72 hr before LeadCare II analysis was acceptable for clinical purposes.

  12. Cu(II) salen complex with propylene linkage: An efficient catalyst in the formation of Csbnd X bonds (X = N, O, S) and biological investigations

    Science.gov (United States)

    Azam, Mohammad; Dwivedi, Sourabh; Al-Resayes, Saud I.; Adil, S. F.; Islam, Mohammad Shahidul; Trzesowska-Kruszynska, Agata; Kruszynski, Rafal; Lee, Dong-Ung

    2017-02-01

    The catalytic property of a mononuclear Cu(II) salen complex in Chan-Lam coupling reaction with phenyl boronic acid at room temperature is reported. The studied complex is found to be potential catalyst in the preparation of carbon-heteroatom bonds with excellent yields. The studied Cu(II) salen complex is monoclinic with cell parameters, a = 9.6807(5) (α 90°), (b = 17.2504(8) (β 112.429 (2), c = 11.1403 (6) (γ = 90°), and has distorted square planar environment around Cu(II) ion. Furthermore, there is no π⋯π interactions in the reported complex due to large distance between the centroid of aromatic rings. In addition, DNA binding study of Cu(II) salen complex by fluorescence and absorption spectroscopy is also reported. Moreover, the reported Cu(II) salen complex exhibits significant anticancer activity against MCF-7 cancer cell lines, and displays potential antimicrobial biofilm activity against P. aeruginosa, suggesting antimicrobial biofilm an important tool for suppression of resistant infections caused by P. aeruginosa.

  13. The Formation of Metal (M=Co(II), Ni(II), and Cu(II)) Complexes by Aminosilanes Immobilized within Mesoporous Molecular Sieves

    International Nuclear Information System (INIS)

    Park, Dong Ho; Park, Sung Soo; Choe, Sang Joon

    1999-01-01

    The immobilization of APTMS(3-(2-aminoethylamino)propyltrimethoxysilane) and AAPTMS(3-(2-(2-aminoethyl) aminoethylamino)propyltrimethoxysilane) on the surface of high quality mesoporous molecular sieves MCM-41 and MCM-48 have been confirmed by F.T.-IR spectroscopy, Raman spectroscopy, 29 Si solid state NMR, and a surface polarity measurement using Reichardt's dye. The formation of metal (Co(II), Ni(II), and Cu(II)) complexes by immobilized aminosilanes have been investigated by photoacoustic spectroscopy(PAS). The assignment of UV-Vis. PAS bands makes it possible to identify the structure of metal complexes within mesoporous molecular sieves. Co(II) ion may be coordinated mainly in a tetrahedral symmetry by two APTMS onto MCM-41, and in an octahedral one by two AAPTMS. Both Ni(II) and Cu(II) coordinated by aminosilanes within MCM-41 form possibly the octahedral complexes such as [Ni(APTMS) 2 (H 2 O) 2 ] 2+ , [Ni(AAPTMS) 2 ] 2+ , [Cu(APTMS) 2 (H 2 O) 2 ] 2+ , and [Cu(AAPTMS)(H 2 O) 3 ] 2+ , respectively. The PAS band shapes of complexes onto MCM-48 are similar to those of corresponding MCM-41 with the variation of PAS intensity. Most of metal ion(II) within MCM-41 and MCM-48 are coordinated by aminosilanes without the impregnation on the surface

  14. Ni(II, Pd(II and Pt(II complexes with ligand containing thiosemicarbazone and semicarbazone moiety: synthesis, characterization and biological investigation

    Directory of Open Access Journals (Sweden)

    SULEKH CHANDRA

    2008-07-01

    Full Text Available The synthesis of nickel(II, palladium(II and platinum(II complexes with thiosemicarbazone and semicarbazone of p-tolualdehyde are reported. All the new compounds were characterized by elemental analysis, molar conductance measurements, magnetic susceptibility measurements, mass, 1H-NMR, IR and electronic spectral studies. Based on the molar conductance measurements in DMSO, the complexes may be formulated as [Ni(L2Cl2] and [M(L2]Cl2 (where M = Pd(II and Pt(II due to their non-electrolytic and 1:2 electrolytic nature, respectively. The spectral data are consistent with an octahedral geometry around Ni(II and a square planar geometry for Pd(II and Pt(II, in which the ligands act as bidentate chelating agents, coordinated through the nitrogen and sulphur/oxygen atoms. The ligands and their metal complexes were screened in vitro against fungal species Alternaria alternata, Aspergillus niger and Fusarium odum, using the food poison technique.

  15. Theoretical study of the magnetic behavior of hexanuclear Cu(II) and Ni(II) polysiloxanolato complexes.

    Science.gov (United States)

    Ruiz, Eliseo; Cano, Joan; Alvarez, Santiago; Caneschi, Andrea; Gatteschi, Dante

    2003-06-04

    A theoretical density functional study of the exchange coupling in hexanuclear polysiloxanolato-bridged complexes of Cu(II) and Ni(II) is presented. By calculating the energies of three different spin configurations, we can obtain estimates of the first-, second-, and third-neighbor exchange coupling constants. The study has been carried out for the complete structures of the Cu pristine cluster and of the chloroenclathrated Ni complex as well as for the hypotethical pristine Ni compound and for magnetically dinuclear analogues M(2)Zn(4) (M = Cu, Ni).

  16. Fe (III), Co(II), Ni(II), Cu(II) and Zn(II) complexes of schiff bases based-on glycine and phenylalanine: Synthesis, magnetic/thermal properties and antimicrobial activity

    Science.gov (United States)

    Sevgi, Fatih; Bagkesici, Ugur; Kursunlu, Ahmed Nuri; Guler, Ersin

    2018-02-01

    Zinc (II), copper (II), nickel (II), cobalt (II) and iron (III) complexes of Schiff bases (LG, LP) derived from 2-hydroxynaphthaldehyde with glycine and phenylalanine were reported and characterized by 1H NMR, 13C NMR, elemental analyses, melting point, FT-IR, magnetic susceptibility and thermal analyses (TGA). TGA data show that iron and cobalt include to the coordinated water and metal:ligand ratio is 1:2 while the complex stoichiometry for Ni (II), Cu (II) and Zn (II) complexes is 1:1. As expected, Ni (II) and Zn (II) complexes are diamagnetic; Cu (II), Co (II) and Fe (III) complexes are paramagnetic character due to a strong ligand of LG and LP. The LG, LP and their metal complexes were screened for their antimicrobial activities against five Gram-positive (Staphylococcus aureus, Methicillin resistant Staphylococcus aureus (MRSA), Bacillus cereus, Streptococcus mutans and Enterococcus faecalis) and three Gram-negative (Escherichia coli, Klebsiella pneumoniae and Pseudomonas aeruginosa) and one fungi (Candida albicans) by using broth microdilution techniques. The activity data show that ligands and their metal complexes exhibited moderate to good activity against Gram-positive bacteria and fungi.

  17. Spectroscopic and DFT studies of flurbiprofen as dimer and its Cu(II) and Hg(II) complexes

    Science.gov (United States)

    Sagdinc, Seda; Pir, Hacer

    2009-07-01

    The vibrational study in the solid state of flurbiprofen and its Cu(II) and Hg(II) complexes was performed by IR and Raman spectroscopy. The changes observed between the IR and Raman spectra of the ligand and of the complexes allowed us to establish the coordination mode of the metal in both complexes. The comparative vibrational analysis of the free ligand and its complexes gave evidence that flurbiprofen binds metal (II) through the carboxylate oxygen. The fully optimized equilibrium structure of flurbiprofen and its metal complexes was obtained by density functional B3LYP method by using LanL2DZ and 6-31 G(d,p) basis sets. The harmonic vibrational frequencies, infrared intensities and Raman scattering activities of flurbiprofen were calculated by density functional B3LYP methods by using 6-31G(d,p) basis set. The scaled theoretical wavenumbers showed very good agreement with the experimental values. The electronic properties of the free molecule and its complexes were also performed at B3LYP/6-31G(d,p) level of theory. Detailed interpretations of the infrared and Raman spectra of flurbiprofen are reported. The UV-vis spectra of flurbiprofen and its metal complexes were also investigated in organic solvents.

  18. New heteroleptic Zn(II) complexes of thiosemicarbazone and diimine Co-Ligands: Structural analysis and their biological impacts

    Science.gov (United States)

    Mathan Kumar, Shanmugaiah; Kesavan, Mookkandi Palsamy; Vinoth Kumar, Gujuluva Gangatharan; Sankarganesh, Murugesan; Chakkaravarthi, Ganesan; Rajagopal, Gurusamy; Rajesh, Jegathalaprathaban

    2018-02-01

    A thiosemicarbazone ligand HL appended new Zn(II) complexes [Zn(L)(bpy)] (1) and [Zn(L)(phen)] (2) (where, HL = {2-(3-bromo-5-chloro-2-hydroxybenzylidene)-N-phenylhydrazinecarbothioamide}, bpy = 2, 2‧-bipyridine and phen = 1, 10-phenanthroline) have been synthesized and well characterized using conventional spectroscopic techniques viz.,1H NMR, FTIR and UV-Vis spectra. The crystal structures of complexes 1 and 2 have been determined by single crystal X-ray diffraction studies. Both the complex 1 (τ = 0.5) and 2 (τ = 0.37) possesses square based pyramidally distorted trigonal bipyramidal geometry. The ground state electronic structures of complexes 1 and 2 were investigated by DFT/B3LYP theoretical analysis using 6-311G (d,p) and LANL2DZ basis set level. The superior DNA binding ability of complex 2 has been evaluated using absorption and fluorescence spectral titration studies. Antimicrobial evaluation reveals that complex 2 endowed better screening than HL and complex 1 against both bacterial as well as fungal species. Consequently, complex 2 possesses highest antibacterial screening against Staphylococcus aureus (MIC = 3.0 ± 0.23 mM) and antifungal screening against Candida albicans (MIC = 6.0 ± 0.11 mM). Furthermore, the anticancer activity of the ligand HL, complexes 1 and 2 have been examined against the MCF-7 cell line (Human breast cancer cell line) using MTT assay. It is remarkable that complex 2 (12 ± 0.67 μM) show highest anticancer activity than HL (25.0 ± 0.91 μM) and complex 1 (15 ± 0.88 μM) due to the presence of phen ligand moiety.

  19. Complexation Effect on Redox Potential of Iron(III)-Iron(II) Couple: A Simple Potentiometric Experiment

    Science.gov (United States)

    Rizvi, Masood Ahmad; Syed, Raashid Maqsood; Khan, Badruddin

    2011-01-01

    A titration curve with multiple inflection points results when a mixture of two or more reducing agents with sufficiently different reduction potentials are titrated. In this experiment iron(II) complexes are combined into a mixture of reducing agents and are oxidized to the corresponding iron(III) complexes. As all of the complexes involve the…

  20. Vacuum ultraviolet photochemistry of CH4 and isotopomers. II. Product channel fields and absorption spectra

    International Nuclear Information System (INIS)

    Wang, Jen-Han; Liu, Kopin; Min, Zhiyuan; Su, Hongmei; Bersohn, Richard; Preses, Jack; Larese, John Z.

    2000-01-01

    In part I of this work the relative velocities and anisotropies of the atomic H and D fragments from methane photolysis at 10.2 eV were measured. In this paper the relative abundance of the methyl and methylene fragments are reported. A complete set of quantum yields for the different photodissociation channels of each isotopomer is obtained by combining the two sets of data. Previously it was found that H atoms are almost four times more likely than D atoms to be ejected; now it is found that hydrogen molecule photofragments are much richer in H atoms than in D. Overall, the heavier D atoms are more likely than the H atoms to remain attached to the carbon atom. An implication for astrophysics is discussed. The VUV absorption spectra of CH 4 and CH 3 D are almost identical both at room temperature and 75 K. There is, as expected, no variation in the absorption spectrum with temperature. Evidence is given that all or almost all of the methylene is produced in the a 1 A 1 and not in the ground 3 B 1 state. (c) 2000 American Institute of Physics

  1. Zinc(II) complexes of carboxamide derivatives: Crystal structures ...

    Indian Academy of Sciences (India)

    can form complexes with a variety of metal ions. Recently, bi- ... tural analyses of both ligands and complex 1 by single crystal X-ray ..... software over a Red Hat Linux IBM cluster using den- .... Change in the relative viscosity (η/ηo)1/3 of CT-.

  2. Unprecedented hetero-geometric discrete copper(II) complexes ...

    Indian Academy of Sciences (India)

    Copper; X-ray structure; radical activity; catechol oxidase activity. 1. Introduction ... dylamine and thiocyanate ions but none of these groups .... Independent reflections. 7978 ... was added to it to achieve the ultimate concentration of .... as exchange couples so as to form a single species with ... cantly on central Cu(II) ion.

  3. Alternative basis for the theory of complex spectra II

    International Nuclear Information System (INIS)

    Harter, W.G.; Patterson, C.W.

    1975-01-01

    The atomic angular factor calculation methods are simplified and extended to include a treatment of spin-orbit operators and multiple shell configurations (II'...) sup(n). A tableau formula is given for the matrix between slater states and states of definite total spin

  4. Copper(II) complex of 3-cinnamalideneacetylacetone: Synthesis and ...

    Indian Academy of Sciences (India)

    Unknown

    measurements, ESR and electronic spectral data indicate the presence of six coordinated Cu(II) ion. The ligand ... the test solution was diffused into the plate and affected the growth of the inoculated. Pseudomonas aeroginosa. .... bacteria Pseudomonas aerogenosa using the diffusion method 4. The antibacterial activity.

  5. (II) complexes as sensitizers for dye sensitized solar cells

    Indian Academy of Sciences (India)

    dimethyl-3-propyl-1 H-imidazol-3-ium iodide (DMPII),. 4-tert-butyl-pyridine (TBP) and ... cymene) ruthenium(II) dimer was synthesized according to the reported ... saturated ammonium chloride (200 ml) solution was added to decompose the ...

  6. Synthesis and structure of copper(II) complexes: Potential cyanide ...

    Indian Academy of Sciences (India)

    easy accessibility to Cu(I), Cu(II) and Cu(III) oxidation states.3,20–38 ... erty to oxidize primary alcohol to aldehyde since they are potential N,O ... Electronic spectra were recorded on a. Shimadzu .... the appropriate temperature 37. ◦. C for 24h.

  7. Mononuclear zinc(II) complexes of 2-((2-(piperazin-1-yl)ethylimino)methyl)-4-substituted phenols: Synthesis, structural characterization, DNA binding and cheminuclease activities

    Science.gov (United States)

    Ravichandran, J.; Gurumoorthy, P.; Karthick, C.; Kalilur Rahiman, A.

    2014-03-01

    Four new zinc(II) complexes [Zn(HL1-4)Cl2] (1-4), where HL1-4 = 2-((2-(piperazin-1-yl)ethylimino)methyl)-4-substituted phenols, have been isolated and fully characterized using various spectro-analytical techniques. The X-ray crystal structure of complex 4 shows the distorted trigonal-bipyramidal coordination geometry around zinc(II) ion. The crystal packing is stabilized by intermolecular NH⋯O hydrogen bonding interaction. The complexes display no d-d electronic band in the visible region due to d10 electronic configuration of zinc(II) ion. The electrochemical properties of the synthesized ligands and their complexes exhibit similar voltammogram at reduction potential due to electrochemically innocent Zn(II) ion, which evidenced that the electron transfer is due to the nature of the ligand. Binding interaction of complexes with calf thymus DNA was studied by UV-Vis absorption titration, viscometric titration and cyclic voltammetry. All complexes bind with CT DNA by intercalation, giving the binding affinity in the order of 2 > 1 ≫ 3 > 4. The prominent cheminuclease activity of complexes on plasmid DNA (pBR322 DNA) was observed in the absence and presence of H2O2. Oxidative pathway reveals that the underlying mechanism involves hydroxyl radical.

  8. Complexes of uranyl with N-oxides of heterocyclic amines. Electron-vibrational absorption spectra

    International Nuclear Information System (INIS)

    Jezowska-Trzebiatowska, B.; Wieczorek, M.

    1977-01-01

    A number of coordination compounds formed by uranyl chloride and nitrate with N-oxides of heterocyclic amines have been prepared and characterized by spectral measurements in the absorption region 20000-50000 cm -1 . The electrons and vibronic transitions have been determined and discussed. (author)

  9. Comparative study of copper(II)-curcumin complexes as superoxide dismutase mimics and free radical scavengers.

    Science.gov (United States)

    Barik, Atanu; Mishra, Beena; Kunwar, Amit; Kadam, Ramakant M; Shen, Liang; Dutta, Sabari; Padhye, Subhash; Satpati, Ashis K; Zhang, Hong-Yu; Indira Priyadarsini, K

    2007-04-01

    Two stoichiometrically different copper(II) complexes of curcumin (stoichiometry, 1:1 and 1:2 for copper:curcumin), were examined for their superoxide dismutase (SOD) activity, free radical-scavenging ability and antioxidant potential. Both the complexes are soluble in lipids and DMSO. The formation constants of the complexes were determined by voltammetry. EPR spectra of the complexes in DMSO at 77K showed that the 1:2 Cu(II)-curcumin complex is square planar and the 1:1 Cu(II)-curcumin complex is distorted orthorhombic. Cu(II)-curcumin complex (1:1) with larger distortion from square planar structure shows higher SOD activity. These complexes inhibit gamma-radiation induced lipid peroxidation in liposomes and react with DPPH acting as free radical scavengers. One-electron oxidation of the two complexes by radiolytically generated azide radicals in Tx-100 micellar solutions produced phenoxyl radicals, indicating that the phenolic moiety of curcumin in the complexes participates in free radical reactions. Depending on the structure, these two complexes possess different SOD activities, free radical neutralizing abilities and antioxidant potentials. In addition, quantum chemical calculations with density functional theory have been performed to support the experimental observations.

  10. UNIFORM INFALL TOWARD THE COMETARY H II REGION IN THE G34.26+0.15 COMPLEX?

    International Nuclear Information System (INIS)

    Liu, Tie; Wu, Yuefang; Zhang, Huawei

    2013-01-01

    Gas accretion is a key process in star formation. However, gas infall detections in high-mass, star-forming regions with high spatial resolution observations are rare. Here, we report the detection of gas infall toward a cometary ultracompact H II region ( C) in the G34.26+0.15 complex. The observations were made with the IRAM 30 m, the James Clerk Maxwell Telescope 15 m telescope, and the Submillimeter Array (SMA). The hot core associated with 'C' has a mass of ∼76 ± 11 M ☉ and a volume density of (1.1 ± 0.2) × 10 8 cm –3 . The HCN (3-2) and HCO + (1-0) lines observed by single dishes and the CN (2-1) lines observed by the SMA show redshifted absorption features, indicating gas infall. We found a linear relationship between the line width and optical depth of the CN (2-1) lines. Those transitions with larger optical depths and line widths have larger absorption areas. However, the infall velocities measured from different lines seem to be constant, indicating that the gas infall is uniform. We also investigated the evolution of gas infall in high-mass, star-forming regions. A tight relationship was found between the infall velocity and the total dust/gas mass. At stages prior to the hot core phase, the typical infall velocity and mass infall rate are ∼1 km s –1 and ∼10 –4 M ☉ yr –1 , respectively. While in more evolved regions, the infall velocity and mass infall rates can reach as high as several km s –1 and ∼10 –3 -10 –2 M ☉ yr –1 , respectively. Accelerated infall has been detected toward some hypercompact H II and ultracompact H II regions. However, the acceleration phenomenon is not seen in more evolved ultracompact H II regions (e.g., G34.26+0.15)

  11. A Nanostructured Lipid System as a Strategy to Improve the in Vitro Antibacterial Activity of Copper(II Complexes

    Directory of Open Access Journals (Sweden)

    Patricia B. da Silva

    2015-12-01

    Full Text Available The aim of this study was to construct a nanostructured lipid system as a strategy to improve the in vitro antibacterial activity of copper(II complexes. New compounds with the general formulae [CuX2(INH2]·nH2O (X = Cl− and n = 1 (1; X = NCS− and n = 5 (2; X = NCO− and n = 4 (3; INH = isoniazid, a drug widely used to treat tuberculosis derived from the reaction between the copper(II chloride and isoniazid in the presence or absence of pseudohalide ions (NCS− or NCO− were synthesized and characterized by infrared spectrometry, electronic absorption spectroscopy, electron paramagnetic resonance (EPR spectroscopy, elemental analysis, melting points and complexometry with 2,2′,2′′,2′′′-(Ethane-1,2-diyldinitrilotetraacetic acid (EDTA. The characterization techniques allowed us to confirm the formation of the copper(II complexes. The Cu(II complexes were loaded into microemulsion (MEs composed of 10% phase oil (cholesterol, 10% surfactant [soy oleate and Brij® 58 (1:2] and 80% aqueous phase (phosphate buffer pH = 7.4 prepared by sonication. The Cu(II complex-loaded MEs displayed sizes ranging from 158.0 ± 1.060 to 212.6 ± 1.539 nm, whereas the polydispersity index (PDI ranged from 0.218 ± 0.007 to 0.284 ± 0.034. The antibacterial activity of the free compounds and those that were loaded into the MEs against Staphylococcus aureus ATCC® 25923 and Escherichia coli ATCC® 25922, as evaluated by a microdilution technique, and the cytotoxicity index (IC50 against the Vero cell line (ATCC® CCL-81TM were used to calculate the selectivity index (SI. Among the free compounds, only compound 2 (MIC 500 μg/mL showed activity for S. aureus. After loading the compounds into the MEs, the antibacterial activity of compounds 1, 2 and 3 was significantly increased against E. coli (MIC’s 125, 125 and 500 μg/mL, respectively and S. aureus (MICs 250, 500 and 125 μg/mL, respectively. The loaded compounds were less toxic against the Vero

  12. Mn(II) complexes with bipyridine, phenanthroline and benzoic acid ...

    Indian Academy of Sciences (India)

    MS received 20 October 2015; revised 19 January 2016; accepted 28 January 2016 ... Manganese complex; catalase; biological activity; hydrogen peroxide; bipyridine; phenanthroline. 1. .... and control drugs were recorded as MIC values, in.

  13. Photocytotoxic ternary copper(II) complexes of histamine Schiff base ...

    Indian Academy of Sciences (India)

    ARC

    complexes 1 and 2 (7.5 μM) using SC pUC19 DNA (0.2 μg, 30 μM b.p.) in the presence of. 1 mM glutathione (GSH) as a reducing agent: lane-1, DNA control; lane-2, DNA + GSH; lane-3, DNA + 1 + GSH; lane-4, DNA + 2 + GSH. Figure S10. Cell viability plot showing the photocytotoxicity of complex 1 in HeLa cells on.

  14. Nuclease-like activity of some Cu(II) complexes

    International Nuclear Information System (INIS)

    Durackova, Z.; Fenikova, L.; Svorenova, L.; Labudova, O.; Kollarova, M.; Labuda, J.

    1995-01-01

    The nuclease reaction of a copper complex with the macrocyclic Schiff base ligand tetrabenzo[b,f,j,n][a,3,9,13]tetraaza cyclohexadecine (TAAB) at the cleavage of DNA in aerobic conditions and the presence of ascorbic acid has been investigated and compared with that of the copper phenanthroline complex. The AT specifity of the Cu(TAAB) 2+ for both single-stranded and double-stranded DNA templates was observed. (authors), 4 figs., 6 refs

  15. Acceptors in II-IV Semiconductors - Incorporation and Complex Formation

    CERN Multimedia

    2002-01-01

    A strong effort is currently devoted to the investigation of defects and the electrical activation of dopant atoms in II-VI semiconductors. In particular, the knowledge about the behaviour of acceptors, prerequisite for the fabrication of p-type semiconductors, is rather limited. The perturbed $\\,{\\gamma\\gamma}$ -angular correlation technique (PAC) and the photoluminescence spectroscopy (PL) using the radioactive isotopes $^{77}\\!$Br and $^{111}\\!$Ag will be applied for investigating the behaviour of acceptor dopant atoms and their interactions with defects in II-VI semiconductors. The main topic will be the identification of the technical conditions for the incorporation of electrically active acceptors in the II-VI semiconductors ~ZnS, ZnSe, ZnTe, CdS, CdSe, and CdTe with particular emphasis on the compounds~ CdTe, ZnSe, and ZnTe. The investigations will be supplemented by first exploratory PL experiments with the group V acceptors $^{71}\\!$As and $^{121}\\!$Sb. With help of the probe $^{111}\\!$Ag, the pos...

  16. Determination of lead in water by electrothermal atomic absorption spectrometry with a nickel(II)-ammonium tartrate modifier

    International Nuclear Information System (INIS)

    Sekerka, I.; Lechner, J.F.

    1991-01-01

    A method is described for the determination of low concentrations of lead in water samples. Atomic absorption spectrometry is used with a tungsten ribbon furnace and Zeeman background correction. Interferences are eliminated by the addition of ammonium tartrate and nickel(II) nitrate to the samples to act as a matrix modifier and adjust the pH. The results show the superior performance of this modifier over other types used conventionally. The detection limit is 1 μg l -1 relative standard deviation of -1 can be obtained. The instrumentation is simple and the method is efficient for the determination of lead in various water samples. 25 refs.; 7 figs.; 6 tabs

  17. THE H I MASS DENSITY IN GALACTIC HALOS, WINDS, AND COLD ACCRETION AS TRACED BY Mg II ABSORPTION

    Energy Technology Data Exchange (ETDEWEB)

    Kacprzak, Glenn G. [Swinburne University of Technology, Victoria 3122 (Australia); Churchill, Christopher W., E-mail: gkacprzak@astro.swin.edu.au, E-mail: cwc@nmsu.edu [New Mexico State University, Las Cruces, NM 88003 (United States)

    2011-12-20

    It is well established that Mg II absorption lines detected in background quasar spectra arise from gas structures associated with foreground galaxies. The degree to which galaxy evolution is driven by the gas cycling through halos is highly uncertain because their gas mass density is poorly constrained. Fitting the Mg II equivalent width (W) distribution with a Schechter function and applying the N(H I)-W correlation of Menard and Chelouche, we computed {Omega}(H I){sub MgII} {identical_to} {Omega}(H I){sub halo} = 1.41{sup +0.75}{sub -0.44} Multiplication-Sign 10{sup -4} for 0.4 {<=} z {<=} 1.4. We exclude damped Ly{alpha}'s (DLAs) from our calculations so that {Omega}(H I){sub halo} comprises accreting and/or outflowing halo gas not locked up in cold neutral clouds. We deduce that the cosmic H I gas mass density fraction in galactic halos traced by Mg II absorption is {Omega}(H I){sub halo}/{Omega}(H I){sub DLA} {approx_equal} 15% and {Omega}(H I){sub halo}/{Omega}{sub b} {approx_equal} 0.3%. Citing several lines of evidence, we propose that infall/accretion material is sampled by small W whereas outflow/winds are sampled by large W, and find that {Omega}(H I){sub infall} is consistent with {Omega}(H I){sub outflow} for bifurcation at W = 1.23{sup +0.15}{sub -0.28} Angstrom-Sign ; cold accretion would then comprise no more than {approx}7% of the total H I mass density. We discuss evidence that (1) the total H I mass cycling through halos remains fairly constant with cosmic time and that the accretion of H I gas sustains galaxy winds, and (2) evolution in the cosmic star formation rate depends primarily on the rate at which cool H I gas cycles through halos.

  18. The dust, nebular emission, and dependence on QSO radio properties of the associated Mg II absorption line systems

    International Nuclear Information System (INIS)

    Khare, Pushpa; Daniel, Vanden Berk; Rahmani, Hadi; York, Donald G.

    2014-01-01

    We studied dust reddening and [O II] emission in 1730 Mg II associated absorption systems (AAS; relative velocity with respect to QSOs, ≤3000 km s –1 ; in units of velocity of light, β, ≤0.01) with 0.4 ≤z abs ≤ 2 in the Sloan Digital Sky Survey DR7, focusing on their dependence on the radio and other QSO properties. We used control samples, several with matching radio properties, to show that (1) AAS in radio-detected (RD) QSOs cause 2.6 ± 0.2 times higher dust extinction than those in radio-undetected (RUD) ones, which in turn cause 2.9 ± 0.7 times the dust extinction in the intervening systems; (2) AAS in core-dominated QSOs cause 2.0 ± 0.1 times higher dust extinction than those in lobe-dominated QSOs; (3) the occurrence of AAS is 2.1 ± 0.2 times more likely in RD QSOs than in RUD QSOs and 1.8 ± 0.1 time more likely in QSOs having black holes with masses larger than 1.23 × 10 9 M ☉ than in those with lower-mass black holes; and (4) there is excess flux in [O II]λ3727 emission in the composite spectra of the AAS samples compared with those of the control samples, which is at the emission redshift. The presence of AAS enhances the O II emission from the active galactic nucleus and/or the host galaxy. This excess is similar for both RD and RUD samples and is 2.5 ± 0.4 times higher in lobe-dominated samples than in core-dominated samples. The excess depends on the black hole mass and Eddington ratio. All these point to the intrinsic nature of the AAS except for the systems with z abs > z em , which could be infalling galaxies.

  19. Synthesis, crystal structure, spectroscopic characterization and nonlinear optical properties of Co(II)- picolinate complex

    Energy Technology Data Exchange (ETDEWEB)

    Tamer, Ömer, E-mail: omertamer@sakarya.edu.tr; Avcı, Davut; Atalay, Yusuf

    2015-11-15

    A cobalt(II) complex of picolinate was synthesized, and its structure was fully characterized by the applying of X-ray diffraction method as well as FT-IR, FT-Raman and UV–vis spectroscopies. In order to both support the experimental results and convert study to more advanced level, density functional theory calculations were performed by using B3LYP level. Single crystal X-ray structural analysis shows that cobalt(II) ion was located to the center of distorted octahedral geometry. The C=O, C=C and C=N stretching vibrations were found as highly active and strong peaks, inducing the molecular charge transfer within Co(II) complex. The small energy gap between frontier molecular orbital energies was another indicator of molecular charge transfer interactions within Co(II) complex. The nonlinear optical properties of Co(II) complex were investigated at DFT/B3LYP level, and the hypepolarizability parameter was found to be decreased due to the presence of inversion symmetry. The natural bond orbital (NBO) analysis was performed to investigate molecular stability, hyperconjugative interactions, intramolecular charge transfer (ICT) and bond strength for Co(II) complex. Finally, molecular electrostatic potential (MEP) and spin density distributions for Co(II) complex were evaluated. - Highlights: • Co(II) complex of picolinate was prepared. • Its FT-IR, FT-Raman and UV–vis spectra were measured. • DFT calculations were performed to support experimental results. • Small HOMO-LUMO energy gap is an indicator of molecular charge transfer. • Spin density localized on Co(II) as well as O and N atoms.

  20. Synthesis, EPR, Electronic and Magnetic Studies on Cobalt (II) Complexes of Semicarbazone and Thiosemicarbazone

    International Nuclear Information System (INIS)

    Chandra, S.; Gupta, L.K.; Sharma, K.K.

    2005-01-01

    Cobalt (II) complexes having the general composition Co(L2) X2 [where Lisopropyl methyl ketone semicarbazone (LLA), isopropyl methyl ketone thiosemicarbazone (LLB), 4-aminoacetophenone semicarbazone (LLC) and4-aminoacetophenone thiosemicarbazone (LLD) and X=Cl] have been synthesized. All the Co(II) complexes reported here have been characterized by elemental analyses, magnetic moments, IR, electronic and EPR spectral studies. All the complexes were found to have magnetic moments corresponding to three unpaired electrons. The possible geometries of the complexes were assigned on the basis of electronic infrared and EPR spectral studies. (author) = = = = = = = = = = = = = = =

  1. A solid phase extraction procedure for the determination of Cd(II) and Pb(II) ions in food and water samples by flame atomic absorption spectrometry.

    Science.gov (United States)

    Daşbaşı, Teslima; Saçmacı, Şerife; Ülgen, Ahmet; Kartal, Şenol

    2015-05-01

    A relatively rapid, accurate and precise solid phase extraction method is presented for the determination of cadmium(II) and lead(II) in various food and water samples. Quantitation is carried out by flame atomic absorption spectrometry (FAAS). The method is based on the retention of the trace metal ions on Dowex Marathon C, a strong acid cation exchange resin. Some important parameters affecting the analytical performance of the method such as pH, flow rate and volume of the sample solution; type, concentration, volume, flow rate of the eluent; and matrix effects on the retention of the metal ions were investigated. Common coexisting ions did not interfere on the separation and determination of the analytes. The detection limits (3 σb) for Cd(II) and Pb(II) were found as 0.13 and 0.18 μg L(-1), respectively, while the limit of quantification values (10 σb) were computed as 0.43 and 0.60 μg L(-1) for the same sequence of the analytes. The precision (as relative standard deviation was lower than 4% at 5 μg L(-1) Cd(II) and 10 μg L(-1) Pb(II) levels, and the preconcentration factor was found to be 250. The accuracy of the proposed procedure was verified by analysing the certified reference materials, SPS-WW2 Batch 108 wastewater level 2 and INCT-TL-1 tea leaves, with the satisfactory results. In addition, for the accuracy of the method the recovery studies (⩾ 95%) were carried out. The method was applied to the determination of the analytes in the various natural waters (lake water, tap water, waste water with boric acid, waste water with H2SO4) and food samples (pomegranate flower, organic pear, radish leaf, lamb meat, etc.), and good results were obtained. While the food samples almost do not contain cadmium, they have included lead at low levels of 0.13-1.12 μg g(-1). Copyright © 2014 Elsevier Ltd. All rights reserved.

  2. Computational complexity of the landscape II-Cosmological considerations

    Science.gov (United States)

    Denef, Frederik; Douglas, Michael R.; Greene, Brian; Zukowski, Claire

    2018-05-01

    We propose a new approach for multiverse analysis based on computational complexity, which leads to a new family of "computational" measure factors. By defining a cosmology as a space-time containing a vacuum with specified properties (for example small cosmological constant) together with rules for how time evolution will produce the vacuum, we can associate global time in a multiverse with clock time on a supercomputer which simulates it. We argue for a principle of "limited computational complexity" governing early universe dynamics as simulated by this supercomputer, which translates to a global measure for regulating the infinities of eternal inflation. The rules for time evolution can be thought of as a search algorithm, whose details should be constrained by a stronger principle of "minimal computational complexity". Unlike previously studied global measures, ours avoids standard equilibrium considerations and the well-known problems of Boltzmann Brains and the youngness paradox. We also give various definitions of the computational complexity of a cosmology, and argue that there are only a few natural complexity classes.

  3. Lead complexation in wines with the dimers of the grape pectic polysaccharide rhamnogalacturonan II

    Directory of Open Access Journals (Sweden)

    Patrice Pellerin

    1997-03-01

    Our study is the first to show that in wine most of the lead is complexed with a pectic polysaccharide that is not degraded during vinification. dRG-II-B is also known to form complexes with other cations, including strontium and barium. However, it is not known what role dRG-II-B has in determining the metabolic fate in humans of toxic cations present in wine.

  4. Complex exercise rehabilitation program for women of the II period of age with metabolic syndrome

    OpenAIRE

    Lee, Eun-Ok; Olga, Kozyreva

    2013-01-01

    The purpose of this study was to develop a complex exercise program integrating Eastern and Western complex exercise rehabilitation programs in order to examine the effects of it on the human body with the subjects for women of the II period of mature age with metabolic syndrome. The subjects of this study are 60 II period of mature aged women with metabolic syndrome living in G City, and the experimental group conducted Taekwon-aerobic exercise, European rehabilitation gymnastics, gym ball e...

  5. Liquid-crystalline dendrimer Cu(II) complexes and Cu(0) nanoclusters based on the Cu(II) complexes: An electron paramagnetic resonance investigation

    Science.gov (United States)

    Domracheva, N. E.; Mirea, A.; Schwoerer, M.; Torre-Lorente, L.; Lattermann, G.

    2007-07-01

    New nanostructured materials, namely, the liquid-crystalline copper(II) complexes that contain poly(propylene imine) dendrimer ligands of the first (ligand 1) and second (ligand 2) generations and which have a columnar mesophase and different copper contents (x = Cu/L), are investigated by EPR spectroscopy. The influence of water molecules and nitrate counterions on the magnetic properties of complex 2 (x = 7.3) is studied. It is demonstrated that water molecules can extract some of the copper ions from dendrimer complexes and form hexaaqua copper complexes with free ions. The dimer spectra of fully hydrated complex 2 (x = 7.3) are observed at temperatures T dendrimer copper(II) complex. The temperature-induced valence tautomerism attended by electron transport is revealed for the first time in blue dendrimer complexes 1 (x = 1.9) with a dimer structure. The activation energy for electron transport is estimated to be 0.35 meV. The coordination of the copper ion site (NO4) and the structural arrangement of green complexes 1 (x = 1.9) in the columnar mesophase are determined. Complexes of this type form linear chains in which nitrate counterions serve as bridges between copper centers. It is revealed that green complexes 1 (x = 1.9) dissolved in isotropic inert solvents can be oriented in the magnetic field (B 0 = 8000 G). The degree of orientation of these complexes is rather high (S z = 0.76) and close to that of systems with a complete ordering (S z = 1) in the magnetic field. Copper(0) nanoclusters prepared by reduction of complex 2 (x = 7.3) in two reducing agents (NaBH4, N2H4 · H2O) are examined. A model is proposed for a possible location of Cu(0) nanoclusters in a dendrimer matrix.

  6. New Ru(II) complexes for dual photoreactivity: ligand exchange and (1)O2 generation.

    Science.gov (United States)

    Knoll, Jessica D; Albani, Bryan A; Turro, Claudia

    2015-08-18

    Uncovering the factors that govern the electronic structure of Ru(II)-polypyridyl complexes is critical in designing new compounds for desired photochemical reactions, and strategies to tune excited states for ligand dissociation and (1)O2 production are discussed herein. The generally accepted mechanism for photoinduced ligand dissociation proposes that population of the dissociative triplet ligand field ((3)LF) state proceeds through thermal population from the vibrationally cooled triplet metal-to-ligand charge transfer ((3)MLCT) state; however, temperature-dependent emission spectroscopy provides varied activation energies using the emission and ligand exchange quantum yields for [Ru(bpy)2(L)2](2+) (bpy = 2,2'-bipyridine; L = CH3CN or py). This suggests that population of the (3)LF state proceeds from the vibrationally excited (3)MLCT state. Because the quantum yield of ligand dissociation for nitriles is much more efficient than that for py, steric bulk was introduced into the ligand set to distort the pseudo-octahedral geometry and lower the energy of the (3)LF state. The py dissociation quantum yield with 500 nm irradiation in a series of [Ru(tpy)(NN)(py)](2+) complexes (tpy = 2,2':6',2″-terpyridine; NN = bpy, 6,6'-dimethyl-2,2'-bipyridine (Me2bpy), 2,2'-biquinoline (biq)) increases by 2-3 orders of magnitude with the sterically bulky Me2bpy and biq ligands relative to bpy. Ultrafast transient absorption spectroscopy reveals population of the (3)LF state within 3-7 ps when NN is bulky, and density functional theory calculations support stabilized (3)LF states. Dual activity via ligand dissociation and (1)O2 production can be achieved by careful selection of the ligand set to tune the excited-state dynamics. Incorporation of an extended π system in Ru(II) complexes such as [Ru(bpy)(dppn)(CH3CN)2](2+) (dppn = benzo[i]dipyrido[3,2-a:2',3'-c]phenazine) and [Ru(tpy)(Me2dppn)(py)](2+) (Me2dppn = 3,6-dimethylbenzo[i]dipyrido[3,2-a:2',3'-c]phenazine) introduces

  7. New Ru(II) Complexes for Dual Photoreactivity: Ligand Exchange and 1O2 Generation

    Science.gov (United States)

    Knoll, Jessica D.; Albani, Bryan A.; Turro, Claudia

    2016-01-01

    CONSPECTUS Uncovering the factors that govern the electronic structure of Ru(II)–polypyridyl complexes is critical in designing new compounds for desired photochemical reactions, and strategies to tune excited states for ligand dissociation and 1O2 production are discussed herein. The generally accepted mechanism for photoinduced ligand dissociation proposes that population of the dissociative triplet ligand field (3LF) state proceeds through thermal population from the vibrationally cooled triplet metal-to-ligand charge transfer (3MLCT) state; however, temperature-dependent emission spectroscopy provides varied activation energies using the emission and ligand exchange quantum yields for [Ru(bpy)2(L)2]2+ (bpy = 2,2′-bipyridine; L = CH3CN or py). This suggests that population of the 3LF state proceeds from the vibrationally excited 3MLCT state. Because the quantum yield of ligand dissociation for nitriles is much more efficient than that for py, steric bulk was introduced into the ligand set to distort the pseudo-octahedral geometry and lower the energy of the 3LF state. The py dissociation quantum yield with 500 nm irradiation in a series of [Ru(tpy)(NN)(py)]2+ complexes (tpy = 2,2′:6′,2″-terpyridine; NN = bpy, 6,6′-dimethyl-2,2′-bipyridine (Me2bpy), 2,2′-biquinoline (biq)) increases by 2–3 orders of magnitude with the sterically bulky Me2bpy and biq ligands relative to bpy. Ultrafast transient absorption spectroscopy reveals population of the 3LF state within 3–7 ps when NN is bulky, and density functional theory calculations support stabilized 3LF states. Dual activity via ligand dissociation and 1O2 production can be achieved by careful selection of the ligand set to tune the excited-state dynamics. Incorporation of an extended π system in Ru(II) complexes such as [Ru(bpy)(dppn)(CH3CN)2]2+ (dppn = benzo[i]dipyrido[3,2-a:2′,3′-c]phenazine) and [Ru(tpy)(Me2dppn)(py)]2+ (Me2dppn = 3,6-dimethylbenzo[i]dipyrido[3,2-a:2′,3

  8. Coordination and structure of Ca(II)-acetate complexes in aqueous solution studied by a combination of Raman and XAFS spectroscopies

    Science.gov (United States)

    Muñoz Noval, Álvaro; Nishio, Daisuke; Kuruma, Takuya; Hayakawa, Shinjiro

    2018-06-01

    The determination of the structure of Ca(II)-acetate in aqueous solution has been addressed by combining Raman and X-ray absorption fine structure spectroscopies. The pH-dependent speciation of the acetate/Ca(II) system has been studied observing modifications in specific Raman bands of the carboxyl group. The current results evidence the Ca(II)-acetate above acetate pKa forms a bidentate complex and presents a coordination 6, in which the Ca-O shell radius decrease of about 0.1 Å with respect the hydrated Ca2+ with coordination 8. The experimental results show the OCO angle of the carboxyl in the complex is close to 124°, being the OCaO angle about 60°.

  9. Crystal structures of copper(II) chloride, copper(II) bromide, and copper(II) nitrate complexes with pyridine-2-carbaldehyde thiosemicarbazone

    Science.gov (United States)

    Chumakov, Yu. M.; Tsapkov, V. I.; Jeanneau, E.; Bairac, N. N.; Bocelli, G.; Poirier, D.; Roy, J.; Gulea, A. P.

    2008-09-01

    The crystal structures of chloro-(2-formylpyridinethiosemicarbazono)copper dimethyl sulfoxide solvate ( I), bromo-(2-formylpyridinethiosemicarbazono)copper ( II), and (2-formylpyridinethiosemicarbazono)copper(II) nitrate dimethyl sulfoxide solvate ( III) are determined using X-ray diffraction. In the crystals, complexes I and II form centrosymmetric dimers in which the thiosemicarbazone sulfur atom serves as a bridge and occupies the fifth coordination site of the copper atom of the neighboring complex related to the initial complex through the center of symmetry. In both cases, the coordination polyhedron of the complexing ion is a distorted tetragonal bipyramid. Complex III in the crystal structure forms polymer chains in which the copper atom of one complex forms the coordination bond with the thicarbamide nitrogen atom of the neighboring complex. In this structure, the coordination polyhedron of the central atom is an elongated tetragonal bipyramid. It is established that complexes I III at a concentration of 10-5 mol/l selectively inhibit the growth of 60 to 90 percent of the cancer tumor cells of the human myeloid leukemia (HL-60).

  10. Crystal structures of copper(II) chloride, copper(II) bromide, and copper(II) nitrate complexes with pyridine-2-carbaldehyde thiosemicarbazone

    International Nuclear Information System (INIS)

    Chumakov, Yu. M.; Tsapkov, V. I.; Jeanneau, E.; Bairac, N. N.; Bocelli, G.; Poirier, D.; Roy, J.; Gulea, A. P.

    2008-01-01

    The crystal structures of chloro-(2-formylpyridinethiosemicarbazono)copper dimethyl sulfoxide solvate (I), bromo-(2-formylpyridinethiosemicarbazono)copper (II), and (2-formylpyridinethiosemicarbazono)copper(II) nitrate dimethyl sulfoxide solvate (III) are determined using X-ray diffraction. In the crystals, complexes I and II form centrosymmetric dimers in which the thiosemicarbazone sulfur atom serves as a bridge and occupies the fifth coordination site of the copper atom of the neighboring complex related to the initial complex through the center of symmetry. In both cases, the coordination polyhedron of the complexing ion is a distorted tetragonal bipyramid. Complex III in the crystal structure forms polymer chains in which the copper atom of one complex forms the coordination bond with the thicarbamide nitrogen atom of the neighboring complex. In this structure, the coordination polyhedron of the central atom is an elongated tetragonal bipyramid. It is established that complexes I-III at a concentration of 10 -5 mol/l selectively inhibit the growth of 60 to 90 percent of the cancer tumor cells of the human myeloid leukemia (HL-60).

  11. Crystal structures of copper(II) chloride, copper(II) bromide, and copper(II) nitrate complexes with pyridine-2-carbaldehyde thiosemicarbazone

    Energy Technology Data Exchange (ETDEWEB)

    Chumakov, Yu. M., E-mail: chumakov.xray@phys.asm.md [Academy of Sciences of Moldova, Institute of Applied Physics (Moldova, Republic of); Tsapkov, V. I. [State University of Moldova (Moldova, Republic of); Jeanneau, E. [Universite Claude Bernard, Laboratoire des Multimateriaux et Interfaces (France); Bairac, N. N. [State University of Moldova (Moldova, Republic of); Bocelli, G. [National Research Council (IMEM-CNR), Institute of Materials for Electronics and Magnetism (Italy); Poirier, D.; Roy, J. [Centre Hospitalier Universitaire de Quebec (CHUQ) (Canada); Gulea, A. P. [State University of Moldova (Moldova, Republic of)

    2008-09-15

    The crystal structures of chloro-(2-formylpyridinethiosemicarbazono)copper dimethyl sulfoxide solvate (I), bromo-(2-formylpyridinethiosemicarbazono)copper (II), and (2-formylpyridinethiosemicarbazono)copper(II) nitrate dimethyl sulfoxide solvate (III) are determined using X-ray diffraction. In the crystals, complexes I and II form centrosymmetric dimers in which the thiosemicarbazone sulfur atom serves as a bridge and occupies the fifth coordination site of the copper atom of the neighboring complex related to the initial complex through the center of symmetry. In both cases, the coordination polyhedron of the complexing ion is a distorted tetragonal bipyramid. Complex III in the crystal structure forms polymer chains in which the copper atom of one complex forms the coordination bond with the thicarbamide nitrogen atom of the neighboring complex. In this structure, the coordination polyhedron of the central atom is an elongated tetragonal bipyramid. It is established that complexes I-III at a concentration of 10{sup -5} mol/l selectively inhibit the growth of 60 to 90 percent of the cancer tumor cells of the human myeloid leukemia (HL-60).

  12. Synthesis of thin film containing 4-amino-1,2,4-triazole iron(II) complexes

    Energy Technology Data Exchange (ETDEWEB)

    Onggo, Djulia, E-mail: djulia@Chem.itb.ac.id [Inorganic and Physical Chemistry Research Group, Faculty of Mathematics and Natural Sciences, Institut Teknologi Bandung, Jl. Ganesha 10 Bandung 40132 (Indonesia)

    2014-03-24

    The Iron(II) complex with 4-amino-1,2,4 triazole (NH{sub 2}-trz) ligand has potential applications as smart material since the compounds show a distinct color change from lilac at low temperature to colorless at high temperature. The lilac color of the complex represent the diamagnetic low spin state while the colorless correspond to the paramagnetic high spin state of iron(II). The transition between the two states could be tuned by changing the anionic group. Generally, the complex was synthesized directly from aqueous solution of iron(II) salt with considerable amounts of NH{sub 2}-trz solution produced solid powder compound. For application as an electronic molecular device, the complex should be obtained as a thin film. The transparent [Fe(NH{sub 2}trz){sub 3}]-Nafion film has been successfully obtained, however, no anion variation can be produced since the nafion is an anionic resin. In this work, the [Fe(NH{sub 2}trz){sub 3}]-complexes with several anions have been synthesized inside nata de coco membrane that commonly used as a medium for deposition metal nano-particles. After drying the membrane containing the complex became a thin film. At room temperature, the film containing iron(II) complexes of sulphate and nitrate salts show lilac color, similar to that of the original complexes in the powder form. On heating, the color of the complex film changed to colorless and this color change was observed reversibly. In contrast, the films containing perchlorate and tetrafluoroborate iron(II) complexes are colorless at room temperature and changed to lilac on cooling. The significant color changing of the iron(II)complexes in the nata de coco film can be used for demonstration thermo chromic effect of smart materials with relatively small amount of the compounds.

  13. Preparation of phenacylchloride, morpholinophenacyl and N-Piperidinophenacyl oximes and study of their complexation with Copper (II) and Cobalt (II) ions

    International Nuclear Information System (INIS)

    Ali, Kamal Eldin Ahmed

    1999-01-01

    The aim of the present work is to prepare phenacyl chloride oxime and phenacyl of N-Piperidine and morpholine derivatives, and mainly to study their complexes with Cu(II) and Co(II) ions with objective ascertaining that one of these ligands can be used in quantitative extraction of these metal ions from the aqueous solution. Copper (II) salts form 1:1 complexes with the phenyacyl oximes of N-piperidine and morpholine and 1:2 complex with phenacyl chloride oxime. However, cobalt(II) salts form 1:2 complexes with phenacyl oxime of N-piperidine and morpholine but does not complex with phenacyl chloride oxime. The stoichiometry of these complexes were determined by UV/VIS spectrophotometry using the mole ratio, continuous variation and slope ratio methods.The stability constants of the five complexes were calculated from aberrances using Job's method. They showed that the copper (II) and cobalt (II) complexes with N-piperidinophenacy oxime are more stable than those with morpholinophenacyl oxime. Copper (II) complexes with any of these two ligands are more stable than those of cobalt (II). IR spectra of the complexes of copper (II) and cobalt (II) with phenacyl oxime of N-piperidine and morpholine show diminished peaks of hydrogen bonds between N and O atoms of the ligand. Specific extractabilities using amylalcohol of copper (II) complexes with the three ligands increase from PH4 to reach its maximum at PH8. The high value for N-piperidinophenacyl oxime ligand (96%-97%) indicates that, this ligand can be used as analytical reagent for the quantitative spectrophotometric determination of copper (II) salts in aqueous media. Cobalt (II) complexes were formed and extracted from solution only at PH6 (specific PH). The extractabilities ranging from 81.6-87.2% warrants the use of these ligands in quantitative spectrophotometric determination of cobalt (II).(Author)

  14. Spectroscopic study of cadmium (II) complexes with heterocyclic dithiocarbamate ligands

    International Nuclear Information System (INIS)

    Garcia-Fontan, S.; Rodriguez-Seoane, P.; Casas, J.S.; Sordo, J.; Jones, M.M.

    1993-01-01

    Cadmium(II) dithiocarbamates [Cd(dtc) 2 ] (dtc=4-carboxamidopiperidine-1-carbodithioate, morpholine-1-carbodithioate or 4-(2-hydroxyethyl)piperazine-1-carbodithioate) and [Cd(dtc) 2 ].H 2 O (dtc=4-hydroxypiperidine-1-carbodithioate} have been prepared and characterized by thermal analysis and IR and NMR ( 13 C, 113 Cd) spectrometry. Two of these ligands have previously been shown capable of removing cadmium from its aged in vivo storage sites. The use of solid state 13 C NMR measurements to establish the coordination mode of the dithiocarbomate ligands is also examined and the difficulties which arise are discussed. (orig.)

  15. Chemical speciation of L-glutamine complexes with Co(II), Ni(II) and ...

    African Journals Online (AJOL)

    The trend in the variation of stability constants of the complexes with mole fraction of the surfactant is attributed to the compartmentalization of complexation equilibria. Distribution of species and effect of influential parameters on chemical speciation have also been presented. KEY WORDS: Chemical speciation, complex ...

  16. Intercalation of a Zn(II) complex containing ciprofloxacin drug between DNA base pairs.

    Science.gov (United States)

    Shahabadi, Nahid; Asadian, Ali Ashraf; Mahdavi, Mryam

    2017-11-02

    In this study, an attempt has been made to study the interaction of a Zn(II) complex containing an antibiotic drug, ciprofloxacin, with calf thymus DNA using spectroscopic methods. It was found that Zn(II) complex could bind with DNA via intercalation mode as evidenced by: hyperchromism in UV-Vis spectrum; these spectral characteristics suggest that the Zn(II) complex interacts with DNA most likely through a mode that involves a stacking interaction between the aromatic chromophore and the base pairs of DNA. DNA binding constant (K b = 1.4 × 10 4 M -1 ) from spectrophotometric studies of the interaction of Zn(II) complex with DNA is comparable to those of some DNA intercalative polypyridyl Ru(II) complexes 1.0 -4.8 × 10 4 M -1 . CD study showed stabilization of the right-handed B form of DNA in the presence of Zn(II) complex as observed for the classical intercalator methylene blue. Thermodynamic parameters (ΔH DNA-MB, indicating that it binds to DNA in strong competition with MB for the intercalation.

  17. Investigation of detergent effects on the solution structure of spinach Light Harvesting Complex II

    Energy Technology Data Exchange (ETDEWEB)

    Cardoso, Mateus B; Smolensky, Dmitriy; Heller, William T; O' Neill, Hugh, E-mail: hellerwt@ornl.gov, E-mail: oneillhm@ornl.gov [Center for Structural Molecular Biology, Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831 (United States)

    2010-11-01

    The properties of spinach light harvesting complex II (LHC II), stabilized in the detergents Triton X-100 (TX100) and n-Octyl-{beta}-D-Glucoside (BOG), were investigated by small-angle neutron scattering (SANS). The LHC II-BOG scattering curve overlaid well with the theoretical scattering curve generated from the crystal structure of LHC II indicating that the protein preparation was in its native functional state. On the other hand, the simulated LHC II curve deviated significantly from the LHC II-TX100 experimental data. Analysis by circular dichroism spectroscopy supported the SANS analysis and showed that LHC II-TX100 is inactivated. This investigation has implications for extracting and stabilizing photosynthetic membrane proteins for the development of biohybrid photoconversion devices.

  18. Thermal Studies of Zn(II, Cd(II and Hg(II Complexes of Some N-Alkyl-N-Phenyl-Dithiocarbamates

    Directory of Open Access Journals (Sweden)

    Peter A. Ajibade

    2012-07-01

    Full Text Available The thermal decomposition of Zn(II, Cd(II and Hg(II complexes of N-ethyl-N-phenyl and N-butyl-N-phenyl dithiocarbamates have been studied using thermogravimetric analysis (TGA and differential scanning calorimetry (DSC. The products of the decomposition, at two different temperatures, were further characterized by scanning electron microscopy (SEM and energy-dispersive X-ray spectroscopy (EDX. The results show that while the zinc and cadmium complexes undergo decomposition to form metal sulphides, and further undergo oxidation forming metal oxides as final products, the mercury complexes gave unstable volatiles as the final product.

  19. Synthesis and Characterization of Some New Cu(II, Ni(II and Zn(II Complexes with Salicylidene Thiosemicarbazones: Antibacterial, Antifungal and in Vitro Antileukemia Activity

    Directory of Open Access Journals (Sweden)

    Tudor Rosu

    2013-07-01

    Full Text Available Thirty two new Cu(II, Ni(II and Zn(II complexes (1–32 with salicylidene thiosemicarbazones (H2L1–H2L10 were synthesized. Salicylidene thiosemicarbazones, of general formula (XN-NH-C(S-NH(Y, were prepared through the condensation reaction of 2-hydroxybenzaldehyde and its derivatives (X with thiosemicarbazide or 4-phenylthiosemicarbazide (Y = H, C6H5. The characterization of the new formed compounds was done by 1H-NMR, 13C-NMR, IR spectroscopy, elemental analysis, magnetochemical, thermoanalytical and molar conductance measurements. In addition, the structure of the complex 5 has been determined by X-ray diffraction method. All ligands and metal complexes were tested as inhibitors of human leukemia (HL-60 cells growth and antibacterial and antifungal activities.

  20. Determination of mixed stability constants of lead(II/uranyl(II-NTA-cysteine complexes by paper electrophoresis

    Directory of Open Access Journals (Sweden)

    Brij Bhushan Tewari

    2005-12-01

    Full Text Available A method involving the use of paper ionophoresis is described for the study of equilibria in mixed – ligand complex systems in solution. The technique is based on the movement of a spot of metal ion under an electric field with the complexants added to the background electrolyte at pH 8.5. The stability constants of the complexes Pb(II – nitrilotriacetate – cysteine and UO2(II – nitrilotriacetate – cysteine are found to be 5.35 plus or minus 0.02 and 6.27 plus or minus 0.07 (logarithm of stability constant values at ionic strength 0.1 M and a temperature of 35 0C.

  1. Shedding light on the photophysical properties of newly designed platinum(II) complexes by adding substituents on functionalized ligands as highly efficient OLED emitters from a theoretical viewpoint

    Energy Technology Data Exchange (ETDEWEB)

    Li, Jieqiong [Institute of Environmental and Analytical Sciences, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475004 (China); Wang, Li, E-mail: chemwangl@henu.edu.cn [Institute of Environmental and Analytical Sciences, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475004 (China); Wang, Xin [Institute of Environmental and Analytical Sciences, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475004 (China); He, Chaozheng, E-mail: hecz2013@nynu.edu.cn [College of Physics and Electronic Engineering, Nanyang Normal University, Nanyang 473061 (China); Zhang, Jinglai, E-mail: zhangjinglai@henu.edu.cn [Institute of Environmental and Analytical Sciences, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475004 (China)

    2015-08-01

    The phosphorescent properties of three synthesized and three new designed platinum(II) complexes are focused on in this work. To reveal their structure–property relationships, a density functional theory/time-dependent density functional theory (DFT/TDDFT) investigation is performed on the geometric and electronic structures, absorption and emission spectra. The electroluminescent (EL) properties are evaluated by the ionization potential (IP), electron affinity (EA), and reorganization energy (λ). Furthermore, the radiative rate constant (k{sub r}) is qualitatively elucidated by various factors including the strength of the SOC interaction between the higher-lying singlet excited states (S{sub n}) and the T{sub 1} state, the oscillator strength (f) of the S{sub n} states that can couple with the T{sub 1} state, and the energy separation between the coupled states. A combined analysis of various elements that could affect the phosphorescent efficiency is beneficial to exploring efficient triplet phosphors in OLEDs. Consequently, complexes Pt-1 and 1 would be more suitable blue-emitting phosphorescent materials with balance of EL properties and acceptable quantum yields. - Graphical abstract: Display Omitted - Highlights: • The absorption and phosphorescence spectra of Pt(II) complexes are investigated. • Their Φ{sub em}, IP, EA, and reorganization energy are compared. • Three new Pt(II) complexes are designed.

  2. Synthesis, characterization and thermal behaviour of cadmium (II) complexes of photosubstituted octacyano-molybdate(IV) and -tungstate(IV) with ethylenediamine

    International Nuclear Information System (INIS)

    Ali, S.I.; Majid, Kowsar

    1998-01-01

    Photosubstituted ethylenediamine complexes of M(CN) 8 4- [where M =Mo(IV) or W(IV)] with cadmium (II) chloride have been synthesized and characterized by infrared (IR), thermogravimetric (TG) and differential scanning calorimetry (DSC). Both Mo(IV) and W(IV) show similar stoichiometric as well as thermal decomposition behaviour. The assigned general formula is Cd[M(CN) 3 (OH)(C 2 H 8 N 2 ) 2 ](C 2 H 8 N 2 ) Cl 2 XH 2 O [where M = Mo(IV) for which X = 1(I) and M = W(IV) for which X = 2 (II)]. The presence of CN - , OH - and C 2 H 8 N 2 has been shown by observed characteristic IR peaks. The extra absorption bands appearing in complex (II) are due to librational modes of water which show the formation of hydrogen bonding, which is also supported by TG analysis. The loss of these absorption bands rules out this type of bonding in (I). Both the complexes decompose in three steps up to 650 degC after which there is no change. DSC of the complexes also shows three transitions, two exothermic and one endothermic. On the basis of TG and DSC thermograms, mechanism for the decomposition of each step has been shown. Kinetic parameters like activation energy (E a ), frequency factor (A) and entropy of activation (ΔS) have been calculated using different integral methods. (author)

  3. Thermal behaviour of zinc(II) 5-chlorosalicylate complex compounds

    Czech Academy of Sciences Publication Activity Database

    Györyová, K.; Chomič, J.; Kovářová, Jana

    2005-01-01

    Roč. 80, č. 2 (2005), s. 375-380 ISSN 1388-6150 Grant - others:Slovak Ministry of Education(SK) VEGA 1/2474/05 Institutional research plan: CEZ:AV0Z40500505 Keywords : caffeine * chlorosalicylate complexes * nicotinamide Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.425, year: 2005

  4. Antimicrobial and mutagenic activity of some carbono- and thiocarbonohydrazone ligands and their copper(II), iron(II) and zinc(II) complexes.

    Science.gov (United States)

    Bacchi, A; Carcelli, M; Pelagatti, P; Pelizzi, C; Pelizzi, G; Zani, F

    1999-06-15

    Several mono- and bis- carbono- and thiocarbonohydrazone ligands have been synthesised and characterised; the X-ray diffraction analysis of bis(phenyl 2-pyridyl ketone) thiocarbonohydrazone is reported. The coordinating properties of the ligands have been studied towards Cu(II), Fe(II), and Zn(II) salts. The ligands and the metal complexes were tested in vitro against Gram positive and Gram negative bacteria, yeasts and moulds. In general, the bisthiocarbonohydrazones possess the best antimicrobial properties and Gram positive bacteria are the most sensitive microorganisms. Bis(ethyl 2-pyridyl ketone) thiocarbonohydrazone, bis(butyl 2-pyridyl ketone)thiocarbonohydrazone and Cu(H2nft)Cl2 (H2nft, bis(5-nitrofuraldehyde)thiocarbonohydrazone) reveal a strong activity with minimum inhibitory concentrations of 0.7 microgram ml-1 against Bacillus subtilis and of 3 micrograms ml-1 against Staphylococcus aureus. Cu(II) complexes are more effective than Fe(II) and Zn(II) ones. All bisthiocarbono- and carbonohydrazones are devoid of mutagenic properties, with the exception of the compounds derived from 5-nitrofuraldehyde. On the contrary a weak mutagenicity, that disappears in the copper complexes, is exhibited by monosubstituted thiocarbonohydrazones.

  5. Incremental binding free energies of aluminum (III) vs. magnesium (II) complexes

    International Nuclear Information System (INIS)

    Mercero, Jose M.; Mujika, Jon I.; Matxain, Jon M.; Lopez, Xabier; Ugalde, Jesus M.

    2003-01-01

    A sequential ligand addition to the aluminum (III) cation has been studied using the B3LYP functional and a combined all-electron/pseudopotentials basis set. The aluminum complexes are compared with analogous magnesium (II) complexes. Different thermodynamical data, such as incremental binding energies, enthalpies, entropies and free energies, are presented for these addition reactions. While the magnesium (II) cation can only accommodate three negatively charged ligands, aluminum (III) accommodates four even after including bulk solvent effects. The main differences between both cations complexing with the neutral ligands, is that aluminum (III) is not able to form complexes with methanol until the number of methanol ligands is equal to 3. Magnesium (II) prefers to bind methanol and formamide when the number of ligands is small, while aluminum prefers formamide. For the largest complexes both cations prefer to bind water

  6. A study on complex formation of cadmium (II) ions, 9

    International Nuclear Information System (INIS)

    Matsui, Haruo

    1984-01-01

    Formation constants of cadmium (11) complexes with dicarboxylic acids such as oxalic, malonic, methylmalonic, succinic, and glutaric acids were determined in aqueous solutions containing 3 mol.dm -3 LiClO 4 as a constan ionic medium at 25 0 C by potentiometric titrations. It was reported in the previous works that cadmium (11)- aspartic acid complexes contained two chelate rings. However, a problem remained whether the second chelate ring could be formed by six membered-ring containing -O-Cd-N- bond or by seven membered-ring containing -O-Cd-O- bond. The results of the present work suggested that it would be formed by a six membered ring. Cadmium (11) ions were coordinated with a carboxylic group of the dicarboxylic acids studied, and formed no chelate ring within the complexes. The white precipitate appeared in the solution containing cadmium (11) ion and oxalic acid, in the pH range below 3.0, therefore, the chelate formation was not ascertained in this case. The formation constants, log βsub(pr)= log([Cdsub(p)Lsub(r)sup((2p-2r)+)]/([Cd 2+ ]sup(p)[L 2- ]sup(r))), of the complexes were: log β 11 = 1.98, log β 12 = 3.05 for cadmium (11)-malonic acid; log β 11 = 2.28, log β 12 = 3.06 for cadmium (11)-methylmalonic acid; log β 11 = 1.78, log β 12 = 3.08 for cadmium (11)-succinic acid; log β 11 = 1.85, log β 12 = 3.28 for cadmium (11)-glutaric acid complexes. (author)

  7. Novel C-2 epimerization of aldoses promoted by nickel(II) diamine complexes, involving a stereospecific pinacol-type 1,2-carbon shift

    International Nuclear Information System (INIS)

    Tanase, Tomoaki; Shimizu, Fumihiko; Kuse, Manabu; Yano, Shigenobu; Hidai, Masanobu; Yoshikawa, Sadao

    1988-01-01

    The newly discovered C-2 epimerization of aldoses promoted by nickel(II) diamine complexes has been investigated in detail by using 13 C-enriched D-glucose, 13 C NMR spectroscopy, and EXAFS (extended x-ray absorption fine structure) analysis. Aldoses treated with nickel(II) diamine complexes (diamine = N,N,N'-trimethylethylenediamine (N,N,N'-Me 3 en), N,N,N',N'-tetramethylethylenediamine (N,N,N',N'-Me 4 en), etc.) in methanolic solutions were rapidly (60 degree C, 3-5 min) epimerized at C-2 to give equilibrium mixtures where the ratio of C-2 epimers shifts to the side of the naturally rare mannose-type aldoses (having the cis arrangement of C-2 and C-3 hydroxyl groups) compared with those in the thermodynamic equilibrium states. The epimerization product of D-[1- 13 C]glucose was exclusively D-[2- 13 C]mannose, demonstrating that the reaction involves a stereospecific 1,2-shift of the carbon skeleton resulting in inversion of configuration at C-2. Furthermore, the absorption and circular dichroism spectra of the reaction solutions indicated the presence of an intermediate nickel(II) complex containing both diamine and sugar components, which was directly revealed by EXAFS analysis to be a mononuclear nickel(II) complex having octahedral coordination geometry. All these observations strongly suggest that the C-2 epimerization proceeds through an intermediate mononuclear nickel(II) complex, where the carbinolamine-like adduct of aldose with diamine in an open-chain form is epimerized at C-2 by a stereospecific rearrangement of the carbon skeleton or a pinacol-type rearrangement involving a cyclic transition state. 44 refs., 5 figs., 4 tabs

  8. Structural oxidation state studies of the manganese cluster in the oxygen evolving complex of photosystem II

    Energy Technology Data Exchange (ETDEWEB)

    Liang, Wenchuan [Univ. of California, Berkeley, CA (United States)

    1994-11-01

    X-ray absorption spectroscopy (XAS) was performed on Photosystem II (PSII)-enriched membranes prepared from spinach to explore: (1) the correlation between structure and magnetic spin state of the Mn cluster in the oxygen evolving complex (OEC) in the S2 state; and (2) the oxidation state changes of the Mn cluster in the flash-induced S-states. The structure of the Mn cluster in the S2 state with the g~4 electron paramagnetic resonance (EPR) signal (S2-g4 state) was compared with that in the S2 state with multiline signal (S2-MLS state) and the S1 state. The S2-g4 state has a higher XAS inflection point energy than that of the S1 state, indicating the oxidation of Mn in the advance from the S1 to the S2-g4 state. Differences in the edge shape and in the extended X-ray absorption fine structure (EXAFS) show that the structure of the Mn cluster in the S2-g4 state is different from that in the S2-MLS or the S1 state. In the S2-g4 state, the second shell of backscatterers from the Mn absorber contains two Mn-Mn distances of 2.73 Å and 2.85 Å. Very little distance disorder exists in the second shell of the S1 or S2-MLS states. The third shell of the S2-g4 state at about 3.3 Å also contains increased heterogeneity relative to that of the S2-MLS or the S1 state. Various S-states were prepared at room-temperature by saturating, single-turnover flashes. The flash-dependent oscillation in the amplitude of the MLS was used to characterize the S-state composition and to construct "pure" S-state Mn K-edge spectra. The edge position shifts to higher energy by 1.8 eV upon the S1 → S2 transition.

  9. XANES, EXAFS and Kbeta spectroscopic studies of the oxygen-evolving complex in Photosystem II

    Energy Technology Data Exchange (ETDEWEB)

    Robblee, John Henry [Univ. of California, Berkeley, CA (United States)

    2000-12-01

    A key question for the understanding of photosynthetic water oxidation is whether the four oxidizing equivalents necessary to oxidize water to dioxygen are accumulated on the four Mn ions of the oxygen evolving complex (OEC), or whether some ligand-centered oxidations take place before the formation and release of dioxygen during the S3 → [S4] → S0 transition. Progress in instrumentation and flash sample preparation allowed us to apply Mn Kβ X-ray emission spectroscopy (Kb XES) to this problem for the first time. The Kβ XES results, in combination with Mn X-ray absorption near-edge structure (XANES) and electron paramagnetic resonance (EPR) data obtained from the same set of samples, show that the S2 → S3 transition, in contrast to the S0 → S1 and S1 → S2 transitions, does not involve a Mn-centered oxidation. This is rationalized by manganese μ-oxo bridge radical formation during the S2 → S3 transition. Using extended X-ray absorption fine structure (EXAFS) spectroscopy, the local environment of the Mn atoms in the S0 state has been structurally characterized. These results show that the Mn-Mn distance in one of the di-μ-oxo-bridged Mn-Mn moieties increases from 2.7 Å in the S1} state to 2.85 Å in the S0 state. Furthermore, evidence is presented that shows three di-μ-oxo binuclear Mn2 clusters may be present in the OEC, which is contrary to the widely held theory that two such clusters are present in the OEC. The EPR properties of the S0 state have been investigated and a characteristic ''multiline'' signal in the S0 state has been discovered in the presence of methanol. This provides the first direct confirmation that the native S0 state is paramagnetic. In addition, this signal was simulated using parameters derived from three

  10. New Cu (II), Co(II) and Ni(II) complexes of chalcone derivatives: Synthesis, X-ray crystal structure, electrochemical properties and DFT computational studies

    Science.gov (United States)

    Tabti, Salima; Djedouani, Amel; Aggoun, Djouhra; Warad, Ismail; Rahmouni, Samra; Romdhane, Samir; Fouzi, Hosni

    2018-03-01

    The reaction of nickel(II), copper(II) and cobalt(II) with 4-hydroxy-3-[(2E)-3-(1H-indol-3-yl)prop-2-enoyl]-6-methyl-2H-pyran-2-one (HL) leads to a series of new complexes: Ni(L)2(NH3), Cu(L)2(DMF)2 and Co(L)2(H2O). The crystal structure of the Cu(L)2(DMF)2 complex have been determined by X-ray diffraction methods. The Cu(II) lying on an inversion centre is coordinated to six oxygen atoms forming an octahedral elongated. Additionally, the electrochemical behavior of the metal complexes were investigated by cyclic voltammetry at a glassy carbon electrode (GC) in CH3CN solutions, showing the quasi-reversible redox process ascribed to the reduction of the MII/MI couples. The X-ray single crystal structure data of the complex was matched excellently with the optimized monomer structure of the desired compound; Hirschfeld surface analysis supported the packed crystal lattice 3D network intermolecular forces. HOMO/LUMO energy level and the global reactivity descriptors quantum parameters are also calculated. The electrophilic and nucleophilic potions in the complex surface are theoretically evaluated by molecular electrostatic potential and Mulliken atomic charges analysis.

  11. Separation and preconcentration of ultratrace levels of cadmium(II) in a sequential injection (SI) system with a PTFE packed column as a mimic sequential injection lab-on-valve (SI-LOV) system with renewable column employing detection by electrothermal atomic absorption spectrometry (ETAAS)

    DEFF Research Database (Denmark)

    Long, Xiangbao; Chomchoei, Roongrat; Gała, Piotr

    of cadmium(II) by detection with electrothermal atomic absorption spectrometry (ETAAS). The non-charged complex formed between the analyste and the chelating reagent diethyldithiophosphate (DDPA) was selectively adsorbed on the surface of the PTFE beads and eluted by ethanol before being directed...

  12. Evaluation of a novel PTFE material for use as a means for separation and preconcentration of trace levels of metal ions in sequential injection (SI) and sequential injection lab-on-valve (SI-LOV) systems. Determination of cadmium (II) with detection by electrothermal atomic absorption spectrometry

    DEFF Research Database (Denmark)

    Long, Xiangbao; Chomchoei, Roongrat; Hansen, Elo Harald

    2004-01-01

    with an external packed column and in a sequential injection lab-on-valve (SI-LOV) system. Employed for the determination of cadmium(II), complexed with diethyldithiophosphate (DDPA), and detection by electrothermal atomic absorption spectrometry (ETAAS), its performance was compared to that of a previously used...

  13. Ubiquitination regulates MHC class II-peptide complex retention and degradation in dendritic cells

    OpenAIRE

    Walseng, Even; Furuta, Kazuyuki; Bosch, Berta; Weih, Karis A.; Matsuki, Yohei; Bakke, Oddmund; Ishido, Satoshi; Roche, Paul A.

    2010-01-01

    The expression and turnover of MHC class II-peptide complexes (pMHC-II) on the surface of dendritic cells (DCs) is essential for their ability to activate CD4 T cells efficiently. The half-life of surface pMHC-II is significantly greater in activated (mature) DCs than in resting (immature) DCs, but the molecular mechanism leading to this difference remains unknown. We now show that ubiquitination of pMHC-II by the E3 ubiquitin ligase membrane-associated RING-CH 1 (March-I) regulates surface e...

  14. Ultrafast pump-probe spectroscopy of Zinc Phthalocynine (ZnPc) and light harvesting complex II (LHC II)

    CSIR Research Space (South Africa)

    Ombinda-Lemboumba, Saturnin

    2009-07-01

    Full Text Available pump-probe spectroscopy of Zinc Phthalocynine (ZnPc) and light harvesting complex II (LHC II) SAIP 7-10 July 2009, University of Kwazulu Natal. S. Ombinda-Lemboumba1, 2 A. du Plessis1, L. Botha1, D.E. Roberts1, P. Molukanele1, 3, R.W. Sparrow3, E... and phtobiology (2008) Page 12 Conclusion SAIP 7-10 July 2009, University of Kwazulu natal Femto group © CSIR 2008 www.csir.co.za • Presented our method of correcting chirp induced by white light generation. • Pump...

  15. Calcium EXAFS establishes the Mn-Ca cluster in the oxygen-evolving complex of Photosystem II

    Energy Technology Data Exchange (ETDEWEB)

    Cinco, Roehl M.; McFarlane Holman, Karen L.; Robblee, John H.; Yano, Junko; Pizarro, Shelly A.; Bellacchio, Emanuele; Sauer, Kenneth; Yachandra, Vittal K.

    2002-08-02

    The proximity of Ca to the Mn cluster of the photosynthetic water-oxidation complex is demonstrated by X-ray absorption spectroscopy. We have collected EXAFS data at the Ca K-edge using active PS II membrane samples that contain approximately 2 Ca per 4 Mn. These samples are much less perturbed than previously investigated Sr-substituted samples, which were prepared subsequent to Ca depletion. The new Ca EXAFS clearly shows backscattering from Mn at 3.4 angstroms, a distance that agrees with that surmised from previously recorded Mn EXAFS. This result is also consistent with earlier related experiments at the Sr K-edge, using samples that contained functional Sr, that show Mn is {approx}; 3.5 angstroms distant from Sr. The totality of the evidence clearly advances the notion that the catalytic center of oxygen evolution is a Mn-Ca heteronuclear cluster.

  16. Computational Investigation of the Influence of Halogen Atoms on the Photophysical Properties of Tetraphenylporphyrin and Its Zinc(II) Complexes.

    Science.gov (United States)

    De Simone, Bruna C; Mazzone, Gloria; Russo, Nino; Sicilia, Emilia; Toscano, Marirosa

    2018-03-15

    How the tetraphenylporphyrin (TPP) and its zinc(II) complexes (ZnTPP) photophysical properties (absorption energies, singlet-triplet energy gap and spin-orbit coupling contributions) can change due to the presence of an increasing number of heavy atoms in their molecular structures has been investigated by means of density functional theory and its time-dependent formulation. Results show that the increase of the atomic mass of the substituted halogen strongly enhances the spin-orbit coupling values, allowing a more efficient singlet-triplet intersystem crossing. Different deactivation channels have been considered and rationalized on the basis of El-Sayed and Kasha rules. Most of the studied compounds possess the appropriate properties to generate cytotoxic singlet molecular oxygen ( 1 Δ g ) and, consequently, they can be proposed as photosensitizers in photodynamic therapy.

  17. Heterometallic Pd(II)-Ni(II) complexes with meso-substituted dibenzotetraaza[14]annulene: double C-H bond activation and formation of a rectangular tetradibenzotetraaza[14]annulene.

    Science.gov (United States)

    Khaledi, Hamid; Olmstead, Marilyn M; Fukuda, Takamitsu; Ali, Hapipah Mohd

    2014-11-03

    Three isomeric 2[Pd(II)-Ni(II)] metal complexes, derived from indoleninyl meso-substituted dibenzotetraaza[14]annulene, were synthesized. The resulting dimers feature Ni···Ni or, alternatively, Ni···π interactions in staggered or slipped cofacial structures. A remarkable insertion of palladium into two different C-H bonds yielded a 4[Pd(II)-Ni(II)] rectangular complex with dimensions of 8.73 × 10.38 Å.

  18. Synthesis and Spectral Investigations of Manganese(II, Cobalt(II, Nickel(II, Copper(II and Zinc(II Complexes of New Polydentate Ligands Containing a 1,8-Naphthyridine Moiety

    Directory of Open Access Journals (Sweden)

    Sunkari Jyothi

    2006-12-01

    Full Text Available 2-(o-Hydroxyphenyl-1,8-naphthyridine (HN, 2-(4-hydroxy-6-methylpyran-2-one-3-yl-1,8-naphthyridine (HMPN and 2-(benzimidazol-2-yl-1,8-naphthyridine(BN react with acetates of Mn(II, Co(II, Ni(II, Cu(II and Zn(II to yield metal ioncomplexes of definite composition. These compounds were characterized by elementalanalyses, molar conductivity, magnetic susceptibility measurements, thermal studies, IR,UV-visible, NMR and mass spectral investigations. The complexes are found to have theformulae [M(HN2(H2O2], [M(HMPN2(H2O2] and [M(BN2(OAc2], respectively.

  19. Nickel(II) and palladium(II) triphenylphosphine complexes incorporating tridentate Schiff base ligands: Synthesis, characterization and biocidal activities

    Science.gov (United States)

    Shabbir, Muhammad; Akhter, Zareen; Ashraf, Ahmad Raza; Ismail, Hammad; Habib, Anum; Mirza, Bushra

    2017-12-01

    Nickel(II) and palladium(II) triphenylphosphine complexes incorporating tridentate Schiff bases have been prepared and characterized by elemental analysis as well as by spectroscopic techniques (FTIR & NMR). The synthesized compounds were assessed to check their potential biocidal activity by using different biological assays (brine shrimp cytotoxicity, antimicrobial, antioxidant, antitumor and drug-DNA interaction). Results of brine shrimp cytotoxicity assay showed that ligand molecules are more bioactive than metal complexes with LD50 as low as 12.4 μg/mL. The prominent antitumor activity was shown by nickel complexes while the palladium complexes exhibited moderate activity. The synthesized compounds have shown high propensity for DNA binding either through intercalation or groove binding which represents the mechanism of antitumor effect of these compounds. Additionally, ligand molecules and nickel metal complexes showed significant antioxidant activity with IC50 values as low as 3.1 μg/mL and 18.9 μg/mL respectively while palladium complexes exhibited moderate activity. Moreover, in antimicrobial assays H2L1, Ni(L1)PPh3 and H2L3 showed dual inhibition against bacterial and fungal strains while for the rest of the compounds varying degree of activity was recorded against different strains. Overall comparison of results suggests that the synthesized compounds can be promising candidate for drug formulation and development.

  20. Co(II) and Cd(II) Complexes Derived from Heterocyclic Schiff-Bases: Synthesis, Structural Characterisation, and Biological Activity

    Science.gov (United States)

    Ahmed, Riyadh M.; Yousif, Enaam I.; Al-Jeboori, Mohamad J.

    2013-01-01

    New monomeric cobalt and cadmium complexes with Schiff-bases, namely, N′-[(E)-(3-hydroxy-4-methoxyphenyl)methylidene]furan-2-carbohydrazide (L1) and N′-[(E)-(3-hydroxy-4-methoxyphenyl)methylidene]thiophene-2-carbohydrazide (L2) are reported. Schiff-base ligands L1 and L2 were derived from condensation of 3-hydroxy-4-methoxybenzaldehyde (iso-vanillin) with furan-2-carboxylic acid hydrazide and thiophene-2-carboxylic acid hydrazide, respectively. Complexes of the general formula [M(L)2]Cl2 (where M = Co(II) or Cd(II), L = L1 or L2) have been obtained from the reaction of the corresponding metal chloride with the ligands. The ligands and their metal complexes were characterised by spectroscopic methods (FTIR, UV-Vis, 1H, and 13C NMR spectra), elemental analysis, metal content, magnetic measurement, and conductance. These studies revealed the formation of four-coordinate complexes in which the geometry about metal ion is tetrahedral. Biological activity of the ligands and their metal complexes against gram positive bacterial strain Bacillus (G+) and gram negative bacteria Pseudomonas (G−) revealed that the metal complexes become less resistive to the microbial activities as compared to the free ligands. PMID:24027449

  1. Geometry and Framework Interactions of Zeolite-Encapsulated Copper(II)-Histidine Complexes

    NARCIS (Netherlands)

    Weckhuysen, B.M.; Grommen, R.; Manikandan, P.; Gao, Y.; Shane, T.; Shane, J.J.; Schoonheydt, R.A.; Goldfarb, D.

    2000-01-01

    The coordination geometry of zeolite-encapsulated copper(II)-histidine (CuHis) complexes, prepared by ion exchange of the complexes from aqueous solutions into zeolite NaY, was determined by a combination of UV-vis-NIR diffuse reflectance spectroscopy (DRS), X-band EPR, electron-spin-echo envelope

  2. BIOASSAY STUDIES OF METAL(II) COMPLEXES OF 2,2'-(ETHANE ...

    African Journals Online (AJOL)

    Preferred Customer

    diyldiimino)diacetic acid (EDDA) were prepared and characterized. Coordination complexes of the EDDA ... corresponding amines with alkyl halide to bear diammines of the same class with different substituents. ... Bioassay studies of metal(II) complexes of 2,2'-(ethane-1,2-diyldiimino)diacetic acid. Bull. Chem. Soc. Ethiop.

  3. Mixed-ligand copper(II) complexes of dipicolylamine and 1,10 ...

    Indian Academy of Sciences (India)

    Unknown

    DNA repair mechanism.13,14 Copper(II) complexes containing heterocyclic bases have received consid- erable current interest in nucleic acid chemistry due to their diverse applications following the discovery of the “chemical nuclease” activity of the [Cu. (phen)2]+ (phen = 1,10-phenanthroline) complex in the presence of ...

  4. AN STIS ATLAS OF Ca II TRIPLET ABSORPTION LINE KINEMATICS IN GALACTIC NUCLEI

    International Nuclear Information System (INIS)

    Batcheldor, D.; Mandalou, J.; Axon, D.; Valluri, M.; Merritt, D.

    2013-01-01

    The relations observed between supermassive black holes and their host galaxies suggest a fundamental link in the processes that cause these two objects to evolve. A more comprehensive understanding of these relations could be gained by increasing the number of supermassive black hole mass (M . ) measurements. This can be achieved, in part, by continuing to model the stellar dynamics at the centers of galactic bulges using data of the highest possible spatial resolution. Consequently, we present here an atlas of galaxies in the Space Telescope Imaging Spectrograph (STIS) data archive that may have spectra suitable for new M . estimates. Archived STIS G750M data for all non-barred galactic bulges are co-aligned and combined, where appropriate, and the radial signal-to-noise ratios calculated. The line-of-sight velocity distributions from the Ca II triplet are then determined using a maximum penalized likelihood method. We find 19 out of 42 galaxies may provide useful new M . estimates since they are found to have data that is comparable in quality with data that has been used in the past to estimate M . . However, we find no relation between the signal-to-noise ratio in the previously analyzed spectra and the uncertainties of the black hole masses derived from the spectra. We also find that there is a very limited number of appropriately observed stellar templates in the archive from which to estimate the effects of template mismatching

  5. Synthesis, CMC Determination, Antimicrobial Activity and Nucleic Acid Binding of A Surfactant Copper(II) Complex Containing Phenanthroline and Alanine Schiff-Base.

    Science.gov (United States)

    Nagaraj, Karuppiah; Sakthinathan, Subramanian; Arunachalam, Sankaralingam

    2014-03-01

    A new water-soluble surfactant copper(II) complex [Cu(sal-ala)(phen)(DA)] (sal-ala = salicylalanine, phen = 1,10-phenanthroline, DA = dodecylamine), has been synthesized and characterized by physico-chemical and spectroscopic methods. The critical micelle concentration (CMC) values of this surfactant-copper(II) complex in aqueous solution were obtained from conductance measurements. Specific conductivity data (at 303, 308, 313. 318 and 323 K) served for the evaluation of the temperature-dependent CMC and the thermodynamics of micellization (ΔG(0)m, ΔH(0)m and ΔS(0)m). The interaction of this complex with nucleic acids (DNA and RNA) has been explored by using electronic absorption spectral titration, competitive binding experiment, cyclic voltammetry, circular dichroism (CD) spectra, and viscosity measurements. Electronic absorption studies have revealed that the complex can bind to nucleic acids by the intercalative binding mode which has been verified by viscosity measurements. The DNA binding constants have also been calculated (Kb = 1.2 × 10(5) M(-1) for DNA and Kb = 1.6 × 10(5) M(-1) for RNA). Competitive binding study with ethidium bromide (EB) showed that the complex exhibits the ability to displace the DNA-bound-EB indicating that the complex binds to DNA in strong competition with EB for the intercalative binding site. The presence of hydrophobic ligands, alanine Schiff-base, phenanthroline and long aliphatic chain amine in the complex were responsible for this strong intercalative binding. The surfactant-copper (II) complex was screened for its antibacterial and antifungal activities against various microorganisms. The results were compared with the standard drugs, amikacin(antibacterial) and ketokonazole(antifungal).

  6. The origin of the split B800 absorption peak in the LH2 complexes from Allochromatium vinosum.

    Science.gov (United States)

    Löhner, Alexander; Carey, Anne-Marie; Hacking, Kirsty; Picken, Nichola; Kelly, Sharon; Cogdell, Richard; Köhler, Jürgen

    2015-01-01

    The absorption spectrum of the high-light peripheral light-harvesting (LH) complex from the photosynthetic purple bacterium Allochromatium vinosum features two strong absorptions around 800 and 850 nm. For the LH2 complexes from the species Rhodopseudomonas acidophila and Rhodospirillum molischianum, where high-resolution X-ray structures are available, similar bands have been observed and were assigned to two pigment pools of BChl a molecules that are arranged in two concentric rings (B800 and B850) with nine (acidophila) or eight (molischianum) repeat units, respectively. However, for the high-light peripheral LH complex from Alc. vinosum, the intruiging feature is that the B800 band is split into two components. We have studied this pigment-protein complex by ensemble CD spectroscopy and polarisation-resolved single-molecule spectroscopy. Assuming that the high-light peripheral LH complex in Alc. vinosum is constructed on the same modular principle as described for LH2 from Rps. acidophila and Rsp. molischianum, we used those repeat units as a starting point for simulating the spectra. We find the best agreement between simulation and experiment for a ring-like oligomer of 12 repeat units, where the mutual arrangement of the B800 and B850 rings resembles those from Rsp. molischianum. The splitting of the B800 band can be reproduced if both an excitonic coupling between dimers of B800 molecules and their interaction with the B850 manifold are taken into account. Such dimers predict an interesting apoprotein organisation as discussed below.

  7. Synthesis, Spectral Characterization and Antioxidant Activity of Tin(II-Morin Complex

    Directory of Open Access Journals (Sweden)

    Shahabuddin Memon

    2012-12-01

    Full Text Available The study focuses on the interaction between morin and Tin(II and the resulting complex was characterized through various analytical techniques by comparing it with morin. The complexation was confirmed at first by UV-Vis study, which shows that addition of Tin(II to morin may produce bathochromic shifts indicative of complex formation. IR spectral studies indicated that carbonyl has involved in coordination with Tin(II. Moreover, 1H-NMR studies validated that in conjunction with carbonyl, 3-OH of morin is more appropriate to be involved in complexation by replacement of its proton. Scavenging activities of morin and its Tin(II complex on DPPH• radical showed the inhibitory rates of 65% and 49%, respectively. In addition, the reducing capacity of morin was outstanding at 0.5 and 2.0 mg/ml concentrations relative to Tin(II complex. Overall, the study potentially shows the strong impact in order to design the anticancer drugs jointly from its cytotoxic potential and antioxidant activities, thereby selectively targeting the cancerous cells in result increasing their therapeutic index as well as extra advantages over other anticancer drugs.

  8. The three isoforms of the light-harvesting complex II Spectroscopic features, trimer formation, and functional roles

    CERN Document Server

    Standfuss, Jorg

    2004-01-01

    The major light-harvesting complex (LHC-II) of higher plants plays a crucial role in capturing light energy for photosynthesis and in regulating the flow of energy within the photosynthetic apparatus. Native LHC-II isolated from plant tissue consists of three isoforms, Lhcb1, Lhcb2, and Lhcb3, which form homo- and heterotrimers. All three isoforms are highly conserved among different species, suggesting distinct functional roles. We produced the three LHC-II isoforms by heterologous expression of the polypeptide in Escherichia coli and in vitro refolding with purified pigments. Although Lhcb1 and Lhcb2 are very similar in polypeptide sequence and pigment content, Lhcb3 is clearly different because it lacks an N-terminal phosphorylation site and has a higher chlorophyll a/b ratio, suggesting the absence of one chlorophyll b. Low temperature absorption and fluorescence emission spectra of the pure isoforms revealed small but significant differences in pigment organization. The oligomeric state of the pure isofo...

  9. Alcohol-catalyzed photoreduction of iron-porphyrin complexes revealed by resonance raman and absorption spectroscopies

    Science.gov (United States)

    Ogura, T.; Fidler, V.; Ozaki, Y.; Kitagawa, T.

    1990-06-01

    Photoreduction of Fe III(OEP) (2-MeIm) (OEP is octaethylporphyrin; 2-MeIm is 2-methylimidazole) was found to be catalyzed by a trace amount of MeOH present in Ch 2Cl 2 as a stabilizer. The absence of either 2-MeIm or MeOH in the CH 2Cl 2 solution of Fe III(OEP) X (X is Cl -, Br - or I -) leads to no photoreduction. The presence of MeOH in the Fe III(OEP) (2-MeIm) solution results in the appearance of a new absorption band at 585 nm, and when Raman scattering was excited at 590 nm, a new Raman band appeared at 524 cm -. This band exhibited an upshift by 4 cm - with 54Fe(OEP) (2-MeIm)(CH 3OH) and a downshift by 12 cm -1 with 56Fe(OEP)(2-MeIm) (CD 3OD) and was therefore assigned to the Fe III-MeOH stretching vibration. The excitation profile of this band gave a peak around 585 nm and accordingly, the new absorption band at 584 nm was assigned to a charge-transfer (CT) band from MeOH to the Fe III ion. It was most unexpected that the photoreduction did not occur upon laser illumination within the CT band.

  10. Use of partial AUC (PAUC) to evaluate bioequivalence--a case study with complex absorption: methylphenidate.

    Science.gov (United States)

    Fourie Zirkelbach, Jeanne; Jackson, Andre J; Wang, Yaning; Schuirmann, Donald J

    2013-01-01

    Methylphenidate modified-release products produce early and late peak concentrations critical for treatment of morning and afternoon symptoms of attention deficit hyperactivity disorder (ADHD). Standard bioequivalence (BE) criteria cannot be applied to these products. The performance of partial area under the drug concentration-time curve (PAUC), Cmax and AUCINF to assess BE were independently evaluated for two products. A two-stage analysis was performed on plasma data for two methylphenidate modified-release products (Product 1 and 2). Simulations using the fitted parameters determined how changes in fast absorption rate constant (K0Fast) and fraction available (F1) affected curve shape and BE determination using Cmax, AUCINF and PAUC. The sensitivity of the mean PAUC(test)/PAUC(reference) ratios to changes in K0Fast(test) are product dependent. Product 1 mean PAUC(test)/PAUC(reference) ratios for PAUC0-4h are more responsive to both decreases and increases in K0Fast(test) than Product 2. Product 2 showed a greater response in the mean PAUC(test)/PAUC(reference) ratio for PAUC0-4h when the K0Fast(test) is decreased and less response as the value is increased. PAUC estimated curve shape is sensitive to changes in absorption and are product specific, and may require a new PAUC metric for each drug. A non-product specific metric to assess curve shape is warranted.

  11. Spin–Orbit TDDFT Electronic Structure of Diplatinum(II,II) Complexes

    Czech Academy of Sciences Publication Activity Database

    Záliš, Stanislav; Lam, Y.; Ch.; Gray, H. B.; Vlček, Antonín

    2015-01-01

    Roč. 54, č. 7 (2015), s. 3491-3500 ISSN 0020-1669 R&D Projects: GA MŠk LH13015 Institutional support: RVO:61388955 Keywords : BINUCLEAR PLATINUM(II) PHOTOCHEMISTRY * DENSITY-FUNCTIONAL THEORY * SPECTROSCOPIC PROPERTIES Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.820, year: 2015

  12. Antiviral activity of platinum (II) and palladium (II) complexes of dimethyl sulfoxide (DMSO) in vitro

    International Nuclear Information System (INIS)

    Al-Allaf, T.; Rashan, L

    1996-01-01

    The antiviral activity of complexes cis-[Pt(DMSO) 2 CI 2 ] and trans-[Pd(DMSO) 2 CI 2 ] against the reverse transcriptase enzyme, herpes and influenza viruses have been studied in vitro. Both complexes demonstrated some activity against the reverse transcriptase enzyme in which the inhibition concentration (IC 5 0) of the cis-Pt and the trans-Pd complexes were shown to be 37.6 and 35.5 μ g/ml respectively. This activity was compared with that of the standard reference; the phosphonoformate (PFA). On the other hand, both complexes have no antiviral activity against herpes and influenza viruses No cytotoxic effects on the three cell lines, Raji, K562 and Mrc-5 were demonstrated by these complexes at the concentrations studied in vitro. (authors). 16 refs., 1 tab., 2 figs

  13. Synthesis and crystal structure of two lead (II) complexes with 1,10-phenanthroline ligand

    International Nuclear Information System (INIS)

    Olivera, Fiorella L.; Santillan, Guillermo A.

    2012-01-01

    Two coordination complexes have been synthesized by the reaction of lead nitrate (II) with 1,10-phenanthroline in methanol/water. The crystals of these complexes were obtained by using the diffusion method and structurally characterized by X-ray single crystal diffraction. Both complexes crystallized in the monoclinic space group P2 1 /c. The analysis by crystal X-ray diffraction reveals that in both complexes the coordination around the lead (II) ion is a distorted octahedral structure where the ion is bonded to the heterocyclic nitrogen atoms of chelating ligand 1,10-phenanthroline, three oxygen atoms of three nitrate groups and one oxygen from the water molecule. The difference between the complexes lies in the way of nitrate ion in presence of carboxylic acid aromatics. In addition, the crystal structure of complexes can be regarded as a 3D coordination polymer through Pb-O weak interactions, hydrogen bonds and π-π stacking interactions. (author).

  14. Synthesis, spectral characterization, theoretical, antimicrobial, DNA interaction and in vitro anticancer studies of Cu(II and Zn(II complexes with pyrimidine-morpholine based Schiff base ligand

    Directory of Open Access Journals (Sweden)

    M. Sankarganesh

    2018-05-01

    Full Text Available Novel Cu(II (1 and Zn(II (2 complexes with 4-(1-(4-morpholinophenylethylideneaminopyrimidine-5-carbonitrile (L have been synthesized and characterized by various spectroscopic and analytical techniques. DFT (density functional theory studies result confirms that, LMCT mechanism have been done between L and M(II ions. The antimicrobial studies indicate that the ligand L and complexes 1 & 2 exhibit higher activity against the E. coli bacteria and C. albicans fungi. The groove binding mode of ligand L and complexes 1 & 2 with CT-DNA have been confirmed by electronic absorption, competitive binding, viscometric and cyclic voltammetric studies. The electronic absorption titration of ligand L and complexes 1 & 2 with DNA have been carried out in different buffer solutions (pH 4.0, 7.0 & 10.0. The Kb values of ligand L and complexes 1 & 2 are higher in acidic buffer at pH 4.0 (Kb = 2.42 × 105, L; 2.8 × 105, 1; 2.65 × 105, 2 and the results revealed that, the interaction of synthesized compounds with DNA were higher in the acidic medium than basic and neutral medium. Furthermore, CT-DNA cleavage studies of ligand L and complexes 1 & 2 have been studied. The in vitro anticancer activities results show that complexes 1 & 2 have moderate cytotoxicity against cancer cell lines and low toxicity on normal cell line than ligand L. Keywords: Pyrimidine, Morpholine, DFT, Antimicrobial, DNA binding, Anticancer studies

  15. The n-propyl 3-azido-2,3-dideoxy-β-D-arabino-hexopyranoside: Syntheses, crystal structure, physical properties and stability constants of their complexes with Cu(II), Ni(II) and VO(II)

    Science.gov (United States)

    Barabaś, Anna; Madura, Izabela D.; Marek, Paulina H.; Dąbrowska, Aleksandra M.

    2017-11-01

    The structure, conformation and configuration of the n-propyl 3-azido-2,3-dideoxy-β-D-arabino-hexopyranoside (BAra-nPr) were determined by 1H NMR, 13C NMR, and IR spectroscopy, as well as by optical rotation. The crystal structure was confirmed by single-crystal X-ray diffraction studies at room temperature. The compound crystallizes in P21 space group symmetry of the monoclinic system. The molecule has a 4C1 chair conformation with azide group in the equatorial position both in a solution as well as in the crystal. The spatial arrangement of azide group is compared to other previously determined azidosugars. The hydrogen bonds between the hydroxyl group of sugar molecules lead to a ribbon structure observed also for the ethyl homolog. The packing of ribbons is dependent on the alkyl substituent length and with the elongation changes from pseudohexagonal to lamellar. Acidity constants for the n-propyl 3-azido-2,3-dideoxy-β-D-arabino-hexopyranoside (BAra-nPr) in an aqueous solution were evaluated by the spectrophotometric and potentiometric titrations methods. Title compound exhibit blue absorption with the maximum wavelengths in the range of 266 nm and 306 nm. Based on these measurements we showed equilibria existing in a particular solution and a distribution of species which have formed during the titration. We also investigated interactions between Cu(II), Ni(II) and VO(II) and title compound (as ligand L) during complexometric titration. On these bases we identified that in [CuII-BAra-nPr]2+ the ratio of the ligand L to metal ion M(II) was 3:1, while in [NiII-BAra-nPr]2+ and [VOII-BAra-nPr]2+ complexes 2:1 ratios were found. The cumulative stability constants (as log β) occurring in an aqueous solution for the complexes of BAra-nPr with Cu(II), Ni(II) and VO(IV) were 14.57; 11.71 and 4.20, respectively.

  16. Synthesis, NMR characterization, X-ray crystal structure of Co(II) Ni(II) and Cu(II) complexes of a pyridine containing self-assembling

    International Nuclear Information System (INIS)

    Ranjbar, M.; Taghavipour, M.; Moghimi, A.; Aghabozorg, H.

    2002-01-01

    In the recent years, the self-assembling systems have been attracted chemists. The intermolecular bond in such systems mainly consists of ion pairing and hydrogen bonding [1,2]. The reaction between self-assembling system liquid LH 2 (py dc=2,6-pyridinedicarboxylic acid and py da=2,6- pyridine diamin) with cobalt (II) nitrate, nickel (II) chloride, and copper (II) acetate in water leads to the formation of self- assemble coordination complexes, [py da.H] 2 [M(py dc) 2 ]. H 2 O, M=Co(II),Ni(II), and Cu(II). The characterization was performed using elemental analysis, ESI mass spectroscopy, 1 H and 13 C NMR and X-ray crystallography. The crystal systems are monoclinic with space group P2 1 /n and four molecules per unit cell. These complexes shows 13 C NMR resonances of cationic counter ion [(py dc,H)] + in DMSO- d 6 but no signal corresponding to the two coordinated ligands [py dc] 2- The metal atoms are six-coordinated with a distorted octahedral geometry. The two [py de] 2- units are almost perpendicular to each other

  17. Plants lacking the main light-harvesting complex retain photosystem II macro-organization

    OpenAIRE

    Ruban, AV; Wentworth, M; Yakushevska, AE; Andersson, J; Lee, PJ; Keegstra, W; Dekker, JP; Boekema, EJ; Jansson, S; Horton, P

    2003-01-01

    Photosystem II (PSII) is a key component of photosynthesis, the process of converting sunlight into the chemical energy of life. In plant cells, it forms a unique oligomeric macrostructure in membranes of the chloroplasts(1). Several light-harvesting antenna complexes are organized precisely in the PSII macrostructure-the major trimeric complexes (LHCII)(2) that bind 70% of PSII chlorophyll and three minor monomeric complexes(3)-which together form PSII supercomplexes(4-6). The antenna comple...

  18. Hexacoordinated mixed-ligand complexes of vanadium(IV) and copper(II)

    International Nuclear Information System (INIS)

    Islam, M.S.; Motahera Begum; Roy, H.N.; Haroon, S.A.Q.M.

    1996-01-01

    The literature reports simple complexes of metal ions with Schiff bases derived from amino acids. But their mixed-ligand complexes are very rare. Keeping this fact in mind, some new mixed ligand complexes of V IV and Cu II with tridentate Schiff bases derived from glycine, salicylaldehyde and amino bases, e.g. quinoline (Q), isoquinoline (IQ), 2-picoline (2-pic), 4-picoline (4-pic) and pyridine (Py) were prepared and studied. 6 refs., 1 tab

  19. New octahedral ZnII and CdII complexes based on azo derivatives and azomethines of pyrazole-5-thione

    International Nuclear Information System (INIS)

    Uraev, A.I.; Vasil'chenko, I.S.; Borodkin, G.S.; Borodkina, I.G.; Vlasenko, V.G.; Burlov, A.S.; Divaeva, L.N.; Garnovskij, A.D.; Lysenko, K.A.; Antipin, M.Yu.

    2005-01-01

    New metal chelates of Zn II and Cd II (ML 2 ) based on (4Z)-3-methyl-1-phenyl-5-thioxo- 1,5-dihydro-4H-pyrazol-4-one quinolin-8-ylhydrazone (HL 1 ) and (4Z)-5-methyl-2-phenyl- 4-[(quinolin-8-ylimino)methyl]-2,4-dihydro-3H-pyrazole-3-thione (HL 2 ) were synthesized. The structures of the metal chelates were studied by EXAFS and NMR ( 1 H, 13 C, and 111 Cd) spectroscopy. The structure of the Cd(L 1 ) 2 complex was established by X-ray diffraction analysis. The complexes have pseudo octahedral structures with the N 4 S 2 ligand environment [ru

  20. Two-colour mid-infrared absorption in an InAs/GaSb-based type II and broken-gap quantum well

    International Nuclear Information System (INIS)

    Wei, X F; Xu, W; Zeng, Z

    2007-01-01

    We examine contributions from different transition channels to optical absorption in an InAs/GaSb-based type II and broken-gap quantum well (QW). In such a structure, because both electron and hole subbands are occupied by the conducting carriers, new channels open up for electronic transition via intra- and inter-layer scattering mechanisms. We find that two absorption peaks can be observed through inter-subband transitions within the same material layer. The absorption induced by the inter-layer transition is rather weak due to a small overlap of electron and hole wavefunctions. The results suggest that InAs/GaSb-based type II and broken-gap QWs can be employed as two-colour photodetectors working at mid-infrared bandwidth at relatively high temperatures up to room-temperature

  1. EPR study of complex formation between copper (II) ions and sympathomimetic amines in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Preoteasa, E.A. [Inst. of Atomic Physics, IFIN, Bucharest (Romania); Duliu, O.G.; Grecu, V.V. [Bucharest, Univ. (Romania). Dept. of Atomic and Nuclear Physics

    1997-07-01

    The complex formation between sympathomimetic amines (SA): adrenaline (AD), noradrenaline (NA), dopamine (DA), ephedrine (ED) and p-tyramine (pTA), and Cu(II) ion in aqueous solution has been studied by X-band EPR at room temperature. Excepting pTA, all investigated SA yielded two types of complexes in different pH domains. All complexes consistent with a ligand fields having a distorted octahedral symmetry, i.e., hexacoordination of Cu(II). The covalence coefficient calculated from the isotropic g and A values has shown strong ionic sigma-type ligand bonds. A structural model with the Cu(II) ion bound by four catecholic O(hydroxy) atoms for the low pH complexes of AD, NA and DA is proposed. For the high pH complexes of the former compounds as well as for both Ed complexes, the authors suppose Cu(II) bound by two N (amino) and two O (hydroxy) atoms. The spectra are consistent to water binding on the longitudinal octahedron axis in all compounds excepting the high pH complex of Ed, where OH2- ions are bound. Possible implications for the SA-cell receptors interactions are discussed.

  2. Simultaneous determination of Hg(II)-Ag(I)-Cd(II) by conductometric titration using the formation of ternary complex

    International Nuclear Information System (INIS)

    Hayashida, Ichiro; Yoshida, Hitoshi; Taga, Mitsuhiko; Hikime, Seiichiro

    1979-01-01

    A conductometric determination of Hg(II), Ag(I) and Cd(II) was carried out by using the insoluble ternary complex formation of the metal ions with iodide ion in the presence of 1,10-phenanthroline (phen). Recommended procedure is as follows; An aliquot of sample solution containing (14 -- 29) mg of Hg(II), (8 -- 16) mg of Ag(I), and (9 -- 17) mg of Cd(II) transfered into a 100 ml beaker. Add to acetate buffer and stoichiometric amounts of phen (40% ethanol-water solution). Amounts of nitrate ion which was estimated separately by other titration with 0.1 M Ag(phen) 2 complex (40% ethanol-water solution) are adjusted in the range of (4.0 -- 6.0) mM. The sample solution is titrated with 0.1 M KI standard solution at the rate of 0.20 ml/min or less. The titration curve showed three end-points corresponding to the formation of (1) Hg(phen) 2 I 2 , (2) Ag(phen)I, and (3) Cd(phen) 2 I 2 . The relative standard deviation was less than 0.8%, when the pH value was controlled at 4.0 -- 4.5 (acetate buffer) and the nitrate concentration was adjusted in the range of (4.0 -- 6.0)mM. The effect of diverse ions on the determination was also investigated in detail. (author)

  3. Synthesis, investigation and spectroscopic characterization of piroxicam ternary complexes of Fe(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) with glycine and DL-phenylalanine

    Science.gov (United States)

    Mohamed, Gehad G.; El-Gamel, Nadia E. A.

    2004-11-01

    The ternary piroxicam (Pir; 4-hydroxy-2-methyl- N-(2-pyridyl)-2H-1,2-benzothiazine-3-carboxamide 1,1-dioxide) complexes of Fe(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) with various amino acids (AA) such as glycine (Gly) or DL-phenylalanine (PhA) were prepared and characterized by elemental analyses, molar conductance, IR, UV-Vis, magnetic moment, diffuse reflectance and X-ray powder diffraction. The UV-Vis spectra of Pir and the effect of metal chelation on the different interligand transitions are discussed in detailed manner. IR and UV-Vis spectra confirm that Pir behaves as a neutral bidentate ligand coordinated to the metal ions via the pyridine- N and carbonyl group of the amide moiety. Gly molecule acted as a uninegatively monodentate ligand and coordinate to the metal ions through its carboxylic group, in addition PhA acted as a uninegatively bidentate ligand and coordinate to the metal ions through its carboxylic and amino groups. All the chelates have octahedral geometrical structures while Cu(II)- and Zn(II)-ternary chelates with PhA have square planar geometrical structures. The molar conductance data reveal that most of these chelates are non electrolytes, while Fe(III)-Pir-Gly, Co(II)-, Ni(II)-, Cu(II)- and Zn(II)-Pir-PhA cheletes were 1:1 electrolytes. X-ray powder diffraction is used as a new tool to estimate the crystallinity of chelates as well as to elucidate their geometrical structures.

  4. Hydride Reactivity of Ni-II-X-Ni-II Entities : Mixed-Valent Hydrido Complexes and Reversible Metal Reduction

    NARCIS (Netherlands)

    Gehring, Henrike; Metzinger, Ramona; Herwig, Christian; Intemann, Julia; Harder, Sjoerd; Limberg, Christian

    After the lithiation of PYR-H2 (PYR2-=[{NC(Me)C(H)C(Me)NC6H3(iPr)2}2(C5H3N)]2-), which is the precursor of an expanded beta-diketiminato ligand system with two binding pockets, its reaction with [NiBr2(dme)] led to a dinuclear nickel(II)bromide complex, [(PYR)Ni(mu-Br)NiBr] (1). The bridging bromide

  5. Asymmetric Ruthenium(II and Osmium(II Complexes with New Bidentate Polyquinoline Ligands. Synthesis and NMR Characterization

    Directory of Open Access Journals (Sweden)

    Antonino Mamo

    2010-03-01

    Full Text Available A series of Ru(II and Os(II tris-chelate complexes with new bidentate 2-pyridylquinoline ligands have been synthesized and fully characterized by EA,1H-NMR and FAB-MS techniques. The new ligands are: L1 = 4-p-methoxyphenyl-6-bromo-2-(2′- pyridylquinoline (mphbr-pq and L2 = 4-p-hydroxyphenyl-6-bromo-2-(2′-pyridyl-quinoline (hphbr-pq. The complexes studied are: [Ru(bpy2L1](PF62 (C1, [Ru(bpy2L2](PF62 (C2, [Os(bpy2L1](PF62 (C3, [Os(bpy2L2](PF62 (C4 (bpy = 2,2′-bipyridine, [Ru(dmbpy2L1](PF62 (C5, [Ru(dmbpy2L2](PF62 (C6, [Os(dmbpy2L1](PF62 (C7, and [Os(dmbpy2L2](PF62 (C8 (dmbpy = 4,4′-dimethyl-2,2′-bipyridine. Moreover, new functionalized complexes C9-C12 were obtained by the basecatalyzed direct alkylation of C2, C4, C6, and C8 with 6-bromo-1-hexene. The complete assignment of the 1H-NMR spectra for the two new ligands (L1 and L2, and their Ru(II or Os(II complexes has been accomplished using a combination of one- and two-dimensional NMR techniques. The JH,H values have been determined for the majority of the resonances.

  6. The dust, nebular emission, and dependence on QSO radio properties of the associated Mg II absorption line systems

    Energy Technology Data Exchange (ETDEWEB)

    Khare, Pushpa [CSIR Emeritus Scientist, IUCAA, Ganeshkhind, Pune 411007 (India); Daniel, Vanden Berk [Physics Department, St. Vincent College, Latrobe, PA 15650 (United States); Rahmani, Hadi [School of Astronomy, Institute for Research in Fundamental Sciences (IPM), P.O. Box 19395-5531, Tehran (Iran, Islamic Republic of); York, Donald G., E-mail: pushpakhare@gmail.com [Department of Astronomy and Astrophysics, University of Chicago, Chicago, IL 60637 (United States)

    2014-10-10

    We studied dust reddening and [O II] emission in 1730 Mg II associated absorption systems (AAS; relative velocity with respect to QSOs, ≤3000 km s{sup –1}; in units of velocity of light, β, ≤0.01) with 0.4 ≤z {sub abs} ≤ 2 in the Sloan Digital Sky Survey DR7, focusing on their dependence on the radio and other QSO properties. We used control samples, several with matching radio properties, to show that (1) AAS in radio-detected (RD) QSOs cause 2.6 ± 0.2 times higher dust extinction than those in radio-undetected (RUD) ones, which in turn cause 2.9 ± 0.7 times the dust extinction in the intervening systems; (2) AAS in core-dominated QSOs cause 2.0 ± 0.1 times higher dust extinction than those in lobe-dominated QSOs; (3) the occurrence of AAS is 2.1 ± 0.2 times more likely in RD QSOs than in RUD QSOs and 1.8 ± 0.1 time more likely in QSOs having black holes with masses larger than 1.23 × 10{sup 9} M {sub ☉} than in those with lower-mass black holes; and (4) there is excess flux in [O II]λ3727 emission in the composite spectra of the AAS samples compared with those of the control samples, which is at the emission redshift. The presence of AAS enhances the O II emission from the active galactic nucleus and/or the host galaxy. This excess is similar for both RD and RUD samples and is 2.5 ± 0.4 times higher in lobe-dominated samples than in core-dominated samples. The excess depends on the black hole mass and Eddington ratio. All these point to the intrinsic nature of the AAS except for the systems with z {sub abs} > z {sub em}, which could be infalling galaxies.

  7. Crystal structure, DNA binding, cleavage, antioxidant and antibacterial studies of Cu(II), Ni(II) and Co(III) complexes with 2-((furan-2-yl)methylimino)methyl)-6-ethoxyphenol Schiff base

    Science.gov (United States)

    Venkateswarlu, Kadtala; Kumar, Marri Pradeep; Rambabu, Aveli; Vamsikrishna, Narendrula; Daravath, Sreenu; Rangan, Krishnan; Shivaraj

    2018-05-01

    Three novel binary metal complexes; 1 [Cu(L)2], 2 [Ni(L)2] and 3 [Co(L)3] where, L (2-(((furan-2-yl) methylimino)methyl)-6-ethoxyphenol, C14H15NO3), were synthesized and characterized by various spectral techniques. Based on spectral studies square planar geometry is assigned for Cu(II) and Ni(II) complexes, whereas Co(III) owned octahedral geometry. Ligand, [Cu(L)2] and [Ni(L)2] are crystallized and found to be monoclinic crystal systems. CT-DNA absorption binding studies revealed that the complexes show good binding propensity (Kb = 5.02 × 103 M-1, 2.77 × 103 M-1, 1.63 × 104 M-1 for 1, 2 and 3 respectively). The role of these complexes in the oxidative and photolytic cleavage of supercoiled pBR322 DNA was studied and found that the complexes cleave the pBR322 DNA effectively. The catalytic ability of 1, 2 and 3 follows the order: 3 > 1 >2. Antioxidant studies of the new complexes revealed that they exhibit significant antioxidant activity against DPPH radical. The Schiff base and its metal complexes have been screened for antibacterial studies by Minimum Inhibitory Concentration method. It is observed that all metal complexes showed more activity than free ligand.

  8. Simultaneous preconcentration of Cu, Fe and Pb as methylthymol blue complexes on naphthalene adsorbent and flame atomic absorption determination

    International Nuclear Information System (INIS)

    Pourreza, Nahid; Hoveizavi, Reza

    2005-01-01

    A simultaneous preconcentration method was developed for determination of trace amounts of Cu, Fe and Pb by atomic absorption spectrometry. The method is based on the retention of their methylthymol blue complexes by naphthalene methyltrioctyl ammonium chloride adsorbent in a column. The adsorbed metal complexes were eluted from the column with nitric acid and Cu, Fe and Pb were determined by flame atomic absorption spectrometry. Several parameters such as pH of the sample solution, ligand concentration, volume of the sample and the amount of methyltrioctyl ammonium chloride loaded on naphthalene were evaluated. The effect of diverse ions on the preconcentration was also investigated. A preconcentration factor of up to 100 or more can easily be achieved depending on the volume of the sample taken. The calibration graphs were obtained in the range of 5-40, 10-100 and 10-200 ng ml -1 for Cu, Fe and Pb in the initial solution, respectively, when using 500 ml of the solution. The detection limit based on three standard deviations of the blank was 0.54, 3.1, and 4.5 ng ml -1 for Cu, Fe and Pb, respectively. The relative standard deviations (R.S.D.) of 0.62-1.4% for Cu, 1.9-3.4% for Fe and 1.0-2.2% for Pb were obtained. The method was applied to the determination of Cu, Fe and Pb in river and wastewater samples

  9. A study on complex formation of cadmium(II) ions, 8

    International Nuclear Information System (INIS)

    Matsui, Haruo; Hirabayashi, Yoshihiro

    1984-01-01

    In the potentiometric titration of the solution containing a cadmium(II) ion and an amino acid, white precipitates often appear in the test solution, and they disturb the emf measurements. Such precipitates were formes in the solutions, pH ranging 7.5--8.5, during the course of titrations of the test solutions containing cadmium(II) ion and amino acid such as glycine, α-alanine. 2-aminobutanoic acid, 3-aminobutanoic acid, 4-aminobutanoic acid, 2-aminopentanoic acid, 5-aminopentanoic acid, 2-aminohexanoic acid, 6-aminohexanoic acid, aspartic acid, glutamic acid, asparagine, or glutamine. The identification of the precipitates obtained from the solutions containing cadmium(II) ion and L-aspartic acid, 4-aminobutanoic acid, or 6-aminohexanoic acid were carried out by both of elemental analysis and the infrared spectroscopy. These results indicated that the precipitate obtained from the solution containing cadmium(II) ion and L-aspartic acid was 1:1 cadmium(II)-L-aspartic acid complex and did not contain any cadmium(II) hydroxide, and other two precipitates were mostly cadmium(II) hydroxide and contained a little cadmium(II)-amino acid complexes. (author)

  10. Ruthenium (II) complexes of thiosemicarbazone: Synthesis, biosensor applications and evaluation as antimicrobial agents

    Energy Technology Data Exchange (ETDEWEB)

    Yildirim, Hatice [Dokuz Eylul University, The Graduate School of Natural and Applied Sciences, Department of Chemistry, 35160 Buca, Izmir (Turkey); Guler, Emine [Ege University, Faculty of Science, Department of Biochemistry, 35100 Bornova, Izmir (Turkey); Yavuz, Murat, E-mail: myavuz@dicle.edu.tr [Ege University, Faculty of Science, Department of Biochemistry, 35100 Bornova, Izmir (Turkey); Dicle University, Faculty of Science, Department of Chemistry, 21280 Diyarbakir (Turkey); Ozturk, Nurdan; Kose Yaman, Pelin [Dokuz Eylul University, The Graduate School of Natural and Applied Sciences, Department of Chemistry, 35160 Buca, Izmir (Turkey); Subasi, Elif; Sahin, Elif [Dokuz Eylul University, Faculty of Science, Department of Chemistry, 35160 Buca, Izmir (Turkey); Timur, Suna [Ege University, Faculty of Science, Department of Biochemistry, 35100 Bornova, Izmir (Turkey); Ege University, Institute on Drug Abuse, Toxicology and Pharmaceutical Science (BATI), 35100 Bornova, Izmir (Turkey)

    2014-11-01

    A conformationally rigid half-sandwich organoruthenium (II) complex [(η{sup 6}-p-cymene)RuClTSC{sup N–S}]Cl, (1) and carbonyl complex [Ru(CO)Cl(PPh{sub 3}){sub 2}TSC{sup N–S}] (2) have been synthesized from the reaction of [{(η"6-p-cymene)RuCl}{sub 2}(μ-Cl){sub 2}] and [Ru(H)(Cl)(CO)(PPh{sub 3}){sub 3}] with thiophene-2-carboxaldehyde thiosemicarbazon (TSC) respectively and both novel ruthenium (II) complexes have been characterized by elemental analysis, FT-IR and NMR spectroscopy. The peripheral TSC in the complexes acts as an electrochemical coupling unit providing the ability to carry out electrochemical deposition (ED) and to form an electro-deposited film on a graphite electrode surface. The biosensing applicability of complexes 1 and 2 was investigated by using glucose oxidase (GOx) as a model enzyme. Electrochemical measurements at − 0.9 V versus Ag/AgCl electrode by following the ED Ru(II) reduction/oxidation due to from the enzyme activity, in the presence of glucose substrate. The designed biosensor showed a very good linearity for 0.01–0.5 mM glucose. The in vitro antimicrobial activities of complexes 1 and 2 were also investigated against nine bacterial strains and one fungus by the disc diffusion test method. No activity was observed against the Gram-negative strains and fungus, whereas complex 1 showed moderate antibacterial activities against Gram-positive bacterial strains. - Highlights: • Novel Ru (II) thiosemicarbazone complexes were synthesized and characterized. • Electrochemical depositions were performed. • Rigid half-sandwich Ru (II) complex showed enhanced antibacterial activity.

  11. Ruthenium (II) complexes of thiosemicarbazone: Synthesis, biosensor applications and evaluation as antimicrobial agents

    International Nuclear Information System (INIS)

    Yildirim, Hatice; Guler, Emine; Yavuz, Murat; Ozturk, Nurdan; Kose Yaman, Pelin; Subasi, Elif; Sahin, Elif; Timur, Suna

    2014-01-01

    A conformationally rigid half-sandwich organoruthenium (II) complex [(η 6 -p-cymene)RuClTSC N–S ]Cl, (1) and carbonyl complex [Ru(CO)Cl(PPh 3 ) 2 TSC N–S ] (2) have been synthesized from the reaction of [{(η 6 -p-cymene)RuCl} 2 (μ-Cl) 2 ] and [Ru(H)(Cl)(CO)(PPh 3 ) 3 ] with thiophene-2-carboxaldehyde thiosemicarbazon (TSC) respectively and both novel ruthenium (II) complexes have been characterized by elemental analysis, FT-IR and NMR spectroscopy. The peripheral TSC in the complexes acts as an electrochemical coupling unit providing the ability to carry out electrochemical deposition (ED) and to form an electro-deposited film on a graphite electrode surface. The biosensing applicability of complexes 1 and 2 was investigated by using glucose oxidase (GOx) as a model enzyme. Electrochemical measurements at − 0.9 V versus Ag/AgCl electrode by following the ED Ru(II) reduction/oxidation due to from the enzyme activity, in the presence of glucose substrate. The designed biosensor showed a very good linearity for 0.01–0.5 mM glucose. The in vitro antimicrobial activities of complexes 1 and 2 were also investigated against nine bacterial strains and one fungus by the disc diffusion test method. No activity was observed against the Gram-negative strains and fungus, whereas complex 1 showed moderate antibacterial activities against Gram-positive bacterial strains. - Highlights: • Novel Ru (II) thiosemicarbazone complexes were synthesized and characterized. • Electrochemical depositions were performed. • Rigid half-sandwich Ru (II) complex showed enhanced antibacterial activity

  12. Syntheses, structures, and properties of imidazolate-bridged Cu(II)-Cu(II) and Cu(II)-Zn(II) dinuclear complexes of a single macrocyclic ligand with two hydroxyethyl pendants.

    Science.gov (United States)

    Li, Dongfeng; Li, Shuan; Yang, Dexi; Yu, Jiuhong; Huang, Jin; Li, Yizhi; Tang, Wenxia

    2003-09-22

    The imidazolate-bridged homodinuclear Cu(II)-Cu(II) complex, [(CuimCu)L]ClO(4).0.5H(2)O (1), and heterodinuclear Cu(II)-Zn(II) complex, [(CuimZnL(-)(2H))(CuimZnL(-)(H))](ClO(4))(3) (2), of a single macrocyclic ligand with two hydroxyethyl pendants, L (L = 3,6,9,16,19,22-hexaaza-6,19-bis(2-hydroxyethyl)tricyclo[22,2,2,2(11,14)]triaconta-1,11,13,24,27,29-hexaene), have been synthesized as possible models for copper-zinc superoxide dismutase (Cu(2),Zn(2)-SOD). Their crystal structures analyzed by X-ray diffraction methods have shown that the structures of the two complexes are markedly different. Complex 1 crystallizes in the orthorhombic system, containing an imidazolate-bridged dicopper(II) [Cu-im-Cu](3+) core, in which the two copper(II) ions are pentacoordinated by virtue of an N4O environment with a Cu.Cu distance of 5.999(2) A, adopting the geometry of distorted trigonal bipyramid and tetragonal pyramid, respectively. Complex 2 crystallizes in the triclinic system, containing two similar Cu-im-Zn cores in the asymmetric unit, in which both the Cu(II) and Zn(II) ions are pentacoordinated in a distorted trigonal bipyramid geometry, with the Cu.Zn distance of 5.950(1)/5.939(1) A, respectively. Interestingly, the macrocyclic ligand with two arms possesses a chairlike (anti) conformation in complex 1, but a boatlike (syn) conformation in complex 2. Magnetic measurements and ESR spectroscopy of complex 1 have revealed the presence of an antiferromagnetic exchange interaction between the two Cu(II) ions. The ESR spectrum of the Cu(II)-Zn(II) heterodinuclear complex 2 displayed a typical signal for mononuclear trigonal bipyramidal Cu(II) complexes. From pH-dependent ESR and electronic spectroscopic studies, the imidazolate bridges in the two complexes have been found to be stable over broad pH ranges. The cyclic voltammograms of the two complexes have been investigated. Both of the two complexes can catalyze the dismutation of superoxide and show rather high activity.

  13. Synthesis, characterization, spectroscopic and theoretical studies of new zinc(II), copper(II) and nickel(II) complexes based on imine ligand containing 2-aminothiophenol moiety

    Science.gov (United States)

    Shafaatian, Bita; Mousavi, S. Sedighe; Afshari, Sadegh

    2016-11-01

    New dimer complexes of zinc(II), copper(II) and nickel(II) were synthesized using the Schiff base ligand which was formed by the condensation of 2-aminothiophenol and 2-hydroxy-5-methyl benzaldehyde. This tridentate Schiff base ligand was coordinated to the metal ions through the NSO donor atoms. In order to prevent the oxidation of the thiole group during the formation of Schiff base and its complexes, all of the reactions were carried out under an inert atmosphere of argon. The X-ray structure of the Schiff base ligand showed that in the crystalline form the SH groups were oxidized to produce a disulfide Schiff base as a new double Schiff base ligand. The molar conductivity values of the complexes in dichloromethane implied the presence of non-electrolyte species. The fluorescence properties of the Schiff base ligand and its complexes were also studied in dichloromethane. The products were characterized by FT-IR, 1H NMR, UV/Vis spectroscopies, elemental analysis, and conductometry. The crystal structure of the double Schiff base was determined by single crystal X-ray diffraction. Furthermore, the density functional theory (DFT) calculations were performed at the B3LYP/6-31G(d,p) level of theory for the determination of the optimized structures of Schiff base complexes.

  14. The CO_2 absorption spectrum in the 2.3 µm transparency window by high sensitivity CRDS: (II) Self-absorption continuum

    International Nuclear Information System (INIS)

    Mondelain, D.; Vasilchenko, S.; Čermák, P.; Kassi, S.; Campargue, A.

    2017-01-01

    The CO_2 absorption continuum near 2.3 µm is determined for a series of sub atmospheric pressures (250–750 Torr) by high sensitivity Cavity Ring Down Spectroscopy. An experimental procedure consisting in injecting successively a gas flow of CO_2 and synthetic air, keeping constant the gas pressure in the CRDS cell, has been developed. This procedure insures a high stability of the spectra baseline by avoiding changes of the optical alignment due to pressure changes. The CO_2 continuum was obtained as the difference between the CO_2 absorption coefficient and a local lines simulation using a Voigt profile truncated at ±25 cm"−"1. Following the results of the preceding analysis of the CO_2 rovibrational lines (Vasilchenko S et al. J Quant Spectrosc Radiat Transfer (10.1016/j.jqsrt.2016.07.002), a CO_2 line list with intensities obtained by variational calculations and empirical line positions was preferred to the HITRAN line list. A quadratic pressure dependence of the absorption continuum is observed, with an average binary absorption coefficient increasing from 2 to 4×10"−"8 cm"−"1 amagat"−"2 between 4320 and 4380 cm"−"1. The obtained continuum is found in good agreement with a previous measurement using much higher densities (20 amagat) and a low resolution grating spectrograph and is consistent with values currently used in the analysis of Venus spectra. - Highlights: • The CO_2 absorption continuum is measured by CRDS in the 2.3 µm window. • The achieved sensitivity and stability allow measurements at sub-atmospheric pressure. • The absorption coefficient is on the order of 3×10"−"8 cm"−"1 amagat"−"2 near 4350 cm"−"1. • A good agreement is obtained with previous results at much higher density (20 amagat).

  15. Complexation of buffer constituents with neutral complexation agents: part II. Practical impact in capillary zone electrophoresis.

    Science.gov (United States)

    Beneš, Martin; Riesová, Martina; Svobodová, Jana; Tesařová, Eva; Dubský, Pavel; Gaš, Bohuslav

    2013-09-17

    This article elucidates the practical impact of the complexation of buffer constituents with complexation agents on electrophoretic results, namely, complexation constant determination, system peak development, and proper separation of analytes. Several common buffers, which were selected based on the pH study in Part I of this paper series (Riesová, M.; Svobodová, J.; Tošner, Z.; Beneš, M.; Tesařová, E.; Gaš, B. Anal. Chem., 2013, DOI: 10.1021/ac4013804); e.g., CHES, MES, MOPS, Tricine were used to demonstrate behavior of such complex separation systems. We show that the value of a complexation constant determined in the interacting buffers environment depends not only on the analyte and complexation agent but it is also substantially affected by the type and concentration of buffer constituents. As a result, the complexation parameters determined in the interacting buffers cannot be regarded as thermodynamic ones and may provide misleading information about the strength of complexation of the compound of interest. We also demonstrate that the development of system peaks in interacting buffer systems significantly differs from the behavior known for noncomplexing systems, as the mobility of system peaks depends on the concentration and type of neutral complexation agent. Finally, we show that the use of interacting buffers can totally ruin the results of electrophoretic separation because the buffer properties change as the consequence of the buffer constituents' complexation. As a general conclusion, the interaction of buffer constituents with the complexation agent should always be considered in any method development procedures.

  16. Synthesis, characterization and biological studies of 2-(4-nitrophenylamino-carbonyl)benzoic acid and its complexes with Cr(III), Co(II), Ni(II), Cu(II) and Zn(II)

    International Nuclear Information System (INIS)

    Imran, M; Nazir, S.; Latif, S.; Mahmood, Z.

    2010-01-01

    Cr(III), Co(II), Ni(II), Cu(II) and Zn(II) complexes of 2-(4-Nitrophenyl aminocarbonyl)benzoic acid were synthesized and characterized on the basis of physical, analytical and spectroscopic data. The ligands, as well as its metal complexes were checked for their in-vitro antimicrobial activity against three bacterial strains, Mycobacterium smegmatis, Escherichia coli, Pseudomonas aeuroginosa, and three fungal strains, Nigrospora oryzae, Aspergillus niger and Candida albicans. Disc diffusion method and Tube diffusion test were used for antibacterial and antifungal activities, respectively. The synthesized complexes only show significant antifungal activity but inactive for antibacterial, however, in general, the metal complexes were found to be more active against antimicrobial activities as compared to their un complexed ligand. (author)

  17. Solar photocatalytic removal of Cu(II), Ni(II), Zn(II) and Pb(II): Speciation modeling of metal-citric acid complexes

    International Nuclear Information System (INIS)

    Kabra, Kavita; Chaudhary, Rubina; Sawhney, R.L.

    2008-01-01

    The present study is targeted on solar photocatalytic removal of metal ions from wastewater. Photoreductive deposition and dark adsorption of metal ions Cu(II), Ni(II), Pb(II) and Zn(II), using solar energy irradiated TiO 2 , has been investigated. Citric acid has been used as a hole scavenger. Modeling of metal species has been performed and speciation is used as a tool for discussing the photodeposition trends. Ninety-seven percent reductive deposition was obtained for copper. The deposition values of other metals were significantly low [nickel (36.4%), zinc (22.2%) and lead (41.4%)], indicating that the photocatalytic treatment process, using solar energy, was more suitable for wastewater containing Cu(II) ions. In absence of citric acid, the decreasing order deposition was Cu(II) > Ni(II) > Pb(II) > Zn(II), which proves the theoretical thermodynamic predictions about the metals

  18. Synthesis and characterization of monomeric and dimeric manganese(II and zinc(II complexes of pyridine-2-carbaldoxime

    Directory of Open Access Journals (Sweden)

    Jørgen Glerup

    2000-12-01

    Full Text Available The syntheses and characterization of two complexes of manganese(II and one complex of zinc(II with the ligand pyridine-2-carbaldoxime, C6H6N2O, are described. The monomeric manganese(II complex cis-[Mn(C6H6N2O 2Cl2] (1 crystallizes in the orthorhombic space group Pbcn with 4 formula units in a cell of dimensions a = 12.479(3 Å, b = 10.348(2 Å, and c = 11. 974(2 Å. The structure has been refined to a final value of the conventional R-factor of 0.0330 based on 1513 observed independent reflections. The analogous zinc(II complex, cis-[Zn(C6H6N2O2Cl2] (2 also crystallizes in the orthorhombic space group Pbcn with 4 formula units in a cell of dimensions a = 12.215(2 Å, b = 10.383(2 Å, and c = 12. 016(2 Å. The structure has been refined to a final value of the conventional R-factor of 0.0377 based on 1117 observed independent reflections. The two complexes are isostructural, with the central metal atom lying on a crystallographic 2-fold axis. Both complexes are approximately octahedral, the coordination being provided by two trans pyridine nitrogen atoms and two cis amine nitrogen atoms from the oxime ligands, and by two cis chlorides. The dimeric manganese(II complex [(C6H6N2O(CH3OHClMnCl2MnCl(CH3OH(C6H6N2O] (3 crystallizes in the monoclinic space group P21/n with 2 formula units in a cell of dimensions a = 7.895(2 Å, b = 11.196(3 Å, and c = 12. 544(2 Å, and b = 98.39(2o. The structure has been refined to a final value of the conventional R-factor of 0.0312 based on 1568 observed independent reflections. There is a crystallographic inversion center in the middle of the dimer relating one manganese center to the other. The geometry at each manganese(II center is again roughly octahedral, coordination being provided by two nitrogen atoms from the oxime ligand, a terminal chloride ion trans to the amine nitrogen, the oxygen atom of the coordinated methanol molecule, and two bridging chlorides that link the two halves of the dimer. The Mn

  19. Study of the interaction between two newly synthesized cyclometallated platinum (II) complexes and human serum albumin: Spectroscopic characterization and docking simulation

    Energy Technology Data Exchange (ETDEWEB)

    Yousefi, Reza, E-mail: ryousefi@shirazu.ac.ir [Protein Chemistry Laboratory (PCL), Department of Biology, College of Sciences, Shiraz University, Shiraz (Iran, Islamic Republic of); Mohammadi, Roghayeh [Protein Chemistry Laboratory (PCL), Department of Biology, College of Sciences, Shiraz University, Shiraz (Iran, Islamic Republic of); Taheri-Kafrani, Asghar [Department of Biotechnology, Faculty of Advanced Sciences and Technologies, University of Isfahan, Isfahan 81746-73441 (Iran, Islamic Republic of); Bagher Shahsavani, Mohammad [Protein Chemistry Laboratory (PCL), Department of Biology, College of Sciences, Shiraz University, Shiraz (Iran, Islamic Republic of); Dadkhah Aseman, Marzieh; Masoud Nabavizadeh, S.; Rashidi, Mehdi [Department of Chemistry, College of Sciences, Shiraz University, Shiraz (Iran, Islamic Republic of); Poursasan, Najmeh; Moosavi-Movahedi, Ali-Akbar [Institute of Biochemistry and Biophysics (IBB), the University of Tehran, Tehran (Iran, Islamic Republic of)

    2015-03-15

    This study describes HSA binding properties of two cyclometalated platinum (II) complexes with non-leaving lipophilic ligands; deprotonated 2-phenylpyridine (ppy): C{sub 1} and deprotonated benzo [h]quinolone (bhq): C{sub 2}, using UV–vis, fluorescence and circular dichroism (CD) spectroscopy. The absorption spectra of HSA decreased in the presence of increasing concentration of these complexes, reflecting HSA structural alteration after drug's binding. Also the thermodynamic parameters (ΔG, ΔH and ΔS) that obtained from Trp fluorescence study revealed that the interaction between these complexes and HSA were spontaneous. In addition, C{sub 1} with flexible chemical structure indicated significantly higher fluorescence quenching and binding affinity to HSA than C{sub 2} which possesses a higher structural rigidity. The ANS fluorescence results also indicated that two Pt (II) complexes were competing for binding to the hydrophobic regions of HSA. Moreover, CD results demonstrated that C{sub 2} complex induced alteration of HSA conformation to more significant extent compared to C{sub 1}. The molecular docking results revealed the involvement of π–π stacking and hydrophobic interaction between these complexes and the protein. Overall, this study may highlight the significance of structural flexibility in designing of future anticancer Pt (II) complexes with improved binding affinity for HSA. - Highlights: • HSA is a general transport carrier for a wide variety of ligands such as metabolites and pharmaceutical drugs. • The HSA binding properties of two structurally related cyclometallated platinum (II) complexes (C{sub 1} and C{sub 2}) were studied. • The complexes can bind to HSA and induce structural alteration in this protein. • The thermodynamic parameters revealed that the interactions were spontaneous and mainly hydrophobic driven. • C{sub 1} with flexible chemical structure indicated a higher binding affinity for HSA than C{sub 2}.

  20. Facile synthesis of RuII Schiff base complexes: spectral characterization and antimicrobial applications

    International Nuclear Information System (INIS)

    Arunachalam, S.; Padma Priya, N.; Shahul Meeran, H.

    2014-01-01

    Diamagnetic ruthenium (II) complexes of the type (RuCl (CO) (pyridine) (L)) (where L = monobasic tridentate Schiff base ligands) were synthesized by the reactions of Schiff bases derived from the reactions of o-aminobenzoic acid and Knovenegal condensate of β - ketoesters and appropriate ruthenium metal precursor (RuHCl (CO) (PPh 3 ) 2 (py)). Elemental analyses and spectral (FT-IR, UV-Vi s and 1 H, 31 P NMR) studies of all the new synthesized complexes suggest the presence of an octahedral environment around the Ru II ion. Cyclic voltammograms of all the complexes display oxidation and reduction potentials. Superoxide dismutase activity (SOD) of these complexes has also been examined. These complexes were also subjected to study their biocidal activity against Staphylococcus epidermidis, Escherichia coli, Botrytis cinerea and Aspergillus niger. (author)

  1. Copper (II) and zinc (II) complexes with flavanone derivatives: Identification of potential cholinesterase inhibitors by on-flow assays.

    Science.gov (United States)

    Sarria, André Lucio Franceschini; Vilela, Adriana Ferreira Lopes; Frugeri, Bárbara Mammana; Fernandes, João Batista; Carlos, Rose Maria; da Silva, Maria Fátima das Graças Fernandes; Cass, Quezia Bezerra; Cardoso, Carmen Lúcia

    2016-11-01

    Metal chelates strongly influence the nature and magnitude of pharmacological activities in flavonoids. In recent years, studies have shown that a promising class of flavanone-metal ion complexes can act as selective cholinesterase inhibitors (ChEIs), which has led our group to synthesize a new series of flavanone derivatives (hesperidin, hesperetin, naringin, and naringenin) complexed to either copper (II) or zinc (II) and to evaluate their potential use as selective ChEIs. Most of the synthesized complexes exhibited greater inhibitory activity against acetylcholinesterase (AChE) than against butyrylcholinesterase (BChE). Nine of these complexes constituted potent, reversible, and selective ChEIs with inhibitory potency (IC 50 ) and inhibitory constant (K i ) ranging from 0.02 to 4.5μM. Copper complexes with flavanone-bipyridine derivatives afforded the best inhibitory activity against AChE and BChE. The complex Cu(naringin)(2,2'-bipyridine) (11) gave IC 50 and K i values of 0.012±0.002 and 0.07±0.01μM for huAChE, respectively, which were lower than the inhibitory values obtained for standard galanthamine (IC 50 =206±30.0 and K i =126±18.0μM). Evaluation of the inhibitory activity of this complex against butyrylcholinesterase from human serum (huBChE) gave IC 50 and K i values of 8.0±1.4 and 2.0±0.1μM, respectively. A Liquid Chromatography-Immobilized Capillary Enzyme Reactor by UV detection (LC-ICER-UV) assay allowed us to determine the IC 50 and K i values and the type of mechanism for the best inhibitors. Copyright © 2016 Elsevier Inc. All rights reserved.

  2. Solvent effects on the fluorescence and effective three-photon absorption of a Zn(II)-[meso-tetrakis(4-octyloxyphenyl)porphyrin

    Science.gov (United States)

    Wan, Yong; Xue, Yuxiong; Sheng, Ning; Rui, Guanghao; Lv, Changgui; He, Jun; Gu, Bing; Cui, Yiping

    2018-06-01

    The fluorescence and effective three-photon absorption (3PA) properties of Zn(II)-[meso-tetrakis(4-octyloxyphenyl)porphyrin] (labeled Zn(II)-porphyrin) dissolved in three different polar solvents were systematically investigated. The electrochemical and photophysical properties of Zn(II)-porphyrin were investigated by 1H NMR spectra, IR spectra, mass spectroscopy, and electronic absorption spectra. The fluorescence emission of Zn(II)-porphyrin in three different solvents excited at the wavelengths of 420 nm (Soret band) and 550 nm (Q-band) were analyzed. By performing Z-scan experiments with femtosecond laser pulses at a wavelength of 800 nm, the effective 3PA process of Zn(II)-porphyrin in three different solvents was observed and the underlying mechanism was discussed in detail. It is found that the fluorescence spectra slightly depend on the polarity of the solvent. Interestingly, the effective 3PA properties of Zn(II)-porphyrin strongly depend on the solvent polarity. The lower the solvent polarity is, the larger effective 3PA cross-section is. Low polar solvents are beneficial to applications of Zn(II)-porphyrin in optical limiting, photodynamic therapy, etc.

  3. THE END OF HELIUM REIONIZATION AT z ≅ 2.7 INFERRED FROM COSMIC VARIANCE IN HST/COS He II Lyα ABSORPTION SPECTRA

    International Nuclear Information System (INIS)

    Worseck, Gabor; Xavier Prochaska, J.; McQuinn, Matthew; Dall'Aglio, Aldo; Wisotzki, Lutz; Fechner, Cora; Richter, Philipp; Hennawi, Joseph F.; Reimers, Dieter

    2011-01-01

    We report on the detection of strongly varying intergalactic He II absorption in HST/COS spectra of two z em ≅ 3 quasars. From our homogeneous analysis of the He II absorption in these and three archival sightlines, we find a marked increase in the mean He II effective optical depth from eff,He i i >≅1 at z ≅ 2.3 to eff,He i i >∼>5 at z ≅ 3.2, but with a large scatter of 2∼ eff,He i i ∼ 2.7, probably indicating He II reionization was incomplete at z reion ∼> 2.7. Likewise, recent three-dimensional numerical simulations of He II reionization qualitatively agree with the observed trend only if He II reionization completes at z reion ≅ 2.7 or even below, as suggested by a large τ eff,He i i ∼>3 in two of our five sightlines at z < 2.8. By doubling the sample size at 2.7 ∼< z ∼< 3, our newly discovered He II sightlines for the first time probe the diversity of the second epoch of reionization when helium became fully ionized.

  4. Synthesis and photoinduced electron transfer in platinum(II) bis(N-(4-ethynylphenyl)carbazole)bipyridine fullerene complexes.

    Science.gov (United States)

    Lee, Sai-Ho; Chan, Chris Tsz-Leung; Wong, Keith Man-Chung; Lam, Wai Han; Kwok, Wai-Ming; Yam, Vivian Wing-Wah

    2014-12-21

    Platinum(ii) bis(N-(4-ethynylphenyl)carbazole)bipyridine fullerene complexes, (Cbz)2-Pt(bpy)-C60 and ((t)BuCbz)2-Pt(bpy)-C60, were synthesized. Their photophysical properties were studied by electronic absorption and emission spectroscopy and the origin of the transitions was supported by computational studies. The electrochemical properties were also studied and the free energies for charge-separation and charge-recombination processes were evaluated. The photoinduced electron transfer reactions in the triads were investigated by femtosecond and nanosecond transient absorption spectroscopy. In dichloromethane, both triads undergo ultrafast charge separation from the (3)MLCT/LLCT excited state within 300 fs to yield their respective triplet charge-separated (CS) states, namely (Cbz)2˙(+)-Pt(bpy)-C60˙(-) and ((t)BuCbz)2˙(+)-Pt(bpy)-C60˙(-), and the CS states would undergo charge recombination to give the (3)C60* state, which subsequently decays to the ground state in 22-28 μs.

  5. Shrinking the Synchrotron : Tabletop Extreme Ultraviolet Absorption of Transition-Metal Complexes

    NARCIS (Netherlands)

    Zhang, Kaili; Lin, Ming Fu; Ryland, Elizabeth S.; Verkamp, Max A.; Benke, Kristin; De Groot, Frank M F; Girolami, Gregory S.; Vura-Weis, Josh

    2016-01-01

    We show that the electronic structure of molecular first-row transition-metal complexes can be reliably measured using tabletop high-harmonic XANES at the metal M2,3 edge. Extreme ultraviolet photons in the 50-70 eV energy range probe 3p → 3d transitions, with the same selection rules as soft X-ray

  6. Stirring of the propagation and the absorption of light in complex nanophotonic media

    NARCIS (Netherlands)

    Ojambati, Oluwafemi Stephen

    2016-01-01

    This thesis presents experimental investigations into the propagation of light inside both disordered and ordered complex photonic systems. The experimental results are interpreted using theoretical and numerical models. One of the main focus of this thesis is to determine experimentally and

  7. Metal based pharmacologically active complexes of Cu(II), Ni(II) and Zn(II): synthesis, spectral, XRD, antimicrobial screening, DNA interaction and cleavage investigation.

    Science.gov (United States)

    Raman, Natarajan; Mahalakshmi, Rajkumar; Arun, T; Packianathan, S; Rajkumar, R

    2014-09-05

    The present contribution reports a thorough characterization of newly obtained metallointercalators incorporating Schiff bases, formed by the condensation of N-acetoacetyl-o-toluidine with 1-amino-4-nitrobenzene (L(1))/1-amino-4-chlorobenzene (L(2)) as main ligand and 1,10-phenanthroline as co-ligand respectively. The characterization of newly formed metallointercalators has been done by (1)H NMR, UV-Vis, IR, EPR spectroscopy and molar conductivity studies. X-ray powder diffraction illustrates that they are crystalline nature. Binding interaction of these complexes with calf thymus (CT-DNA) has been investigated by emission, absorption, viscosity, cyclic voltammetry and differential pulse voltammetry. DNA binding experiments results reveal that the synthesized complexes interact with DNA through intercalative mode. The in vitro antibacterial and antifungal assay indicate that these complexes are good antimicrobial agents against various pathogens. The DNA cleavage exhibits that they act as efficient cleaving agents. Copyright © 2014 Elsevier B.V. All rights reserved.

  8. Complex dynamics in diatomic molecules. Part II: Quantum trajectories

    International Nuclear Information System (INIS)

    Yang, C.-D.; Weng, H.-J.

    2008-01-01

    The second part of this paper deals with quantum trajectories in diatomic molecules, which has not been considered before in the literature. Morse potential serves as a more accurate function than a simple harmonic oscillator for illustrating a realistic picture about the vibration of diatomic molecules. However, if we determine molecular dynamics by integrating the classical force equations derived from a Morse potential, we will find that the resulting trajectories do not consist with the probabilistic prediction of quantum mechanics. On the other hand, the quantum trajectory determined by Bohmian mechanics [Bohm D. A suggested interpretation of the quantum theory in terms of hidden variable. Phys. Rev. 1952;85:166-179] leads to the conclusion that a diatomic molecule is motionless in all its vibrational eigen-states, which also contradicts probabilistic prediction of quantum mechanics. In this paper, we point out that the quantum trajectory of a diatomic molecule completely consistent with quantum mechanics does exist and can be solved from the quantum Hamilton equations of motion derived in Part I, which is based on a complex-space formulation of fractal spacetime [El Naschie MS. A review of E-Infinity theory and the mass spectrum of high energy particle physics. Chaos, Solitons and Fractals 2004;19:209-36; El Naschie MS. E-Infinity theory - some recent results and new interpretations. Chaos, Solitons and Fractals 2006;29:845-853; El Naschie MS. The concepts of E-infinity. An elementary introduction to the cantorian-fractal theory of quantum physics. Chaos, Solitons and Fractals 2004;22:495-511; El Naschie MS. SU(5) grand unification in a transfinite form. Chaos, Solitons and Fractals 2007;32:370-374; Nottale L. Fractal space-time and microphysics: towards a theory of scale relativity. Singapore: World Scientific; 1993; Ord G. Fractal space time and the statistical mechanics of random works. Chaos, Soiltons and Fractals 1996;7:821-843] approach to quantum

  9. γ-Diimine palladium(II based complexes mediated polymerization of methyl methacrylate

    Directory of Open Access Journals (Sweden)

    Mahmoud Sunjuk

    2017-02-01

    Full Text Available The synthesis of new palladium(II complexes of the type [Pd(A–NC–ph–CN–ACl2] (4a–e (A = cyclohexyl (a, 2-isoprpropyl (b, pyrenyl (c, naphthyl (d, and 2,6-diisopropyl (e is described. The isolated γ-diimine ligands and their corresponding palladium(II complexes were characterized by their physical properties, elemental analysis, 1H NMR-, 13C NMR, and infrared spectroscopy. The palladium(II complexes (4a–e were employed successfully as catalysts for atom transfer radical polymerization (ATRP of methyl methacrylate (MMA in the presence of ethyl-2-bromoisobutyrate (EBIB as initiator at 90 °C. Polymerization with these catalyst systems afforded polymers with low molecular weight distribution (Mw/Mn and syndio-rich atactic poly (MMA with relatively higher [rr] diads.

  10. Antibacterial activity of Pd(II) complexes with salicylaldehyde-amino acids Schiff bases ligands.

    Science.gov (United States)

    Rîmbu, Cristina; Danac, Ramona; Pui, Aurel

    2014-01-01

    Palladium(II) complexes with Schiff bases ligands derived from salicylaldehyde and amino acids (Ala, Gly, Met, Ser, Val) have been synthesized and characterized by Fourier transform (FT)-IR, UV-Vis and (1)H-NMR spectroscopy. The electrospray mass spectrometry (ES-MS) spectrometry confirms the formation of palladium(II) complexes in 1/2 (M/L) molar ratio. All the Pd(II) complexes 1, [Pd(SalAla)2]Cl2; 2, [Pd(SalGly)2]Cl2; 3, [Pd(SalMet)2]Cl2; 4, [Pd(SalSer)2]Cl2; 5, [Pd(SalVal)2]Cl2; have shown antibacterial activity against Gram-positive bacteria Staphylococcus aureus and Gram-negative bacteria Escherichia coli.

  11. Surface complexation modeling calculation of Pb(II) adsorption onto the calcined diatomite

    Science.gov (United States)

    Ma, Shu-Cui; Zhang, Ji-Lin; Sun, De-Hui; Liu, Gui-Xia

    2015-12-01

    Removal of noxious heavy metal ions (e.g. Pb(II)) by surface adsorption of minerals (e.g. diatomite) is an important means in the environmental aqueous pollution control. Thus, it is very essential to understand the surface adsorptive behavior and mechanism. In this work, the Pb(II) apparent surface complexation reaction equilibrium constants on the calcined diatomite and distributions of Pb(II) surface species were investigated through modeling calculations of Pb(II) based on diffuse double layer model (DLM) with three amphoteric sites. Batch experiments were used to study the adsorption of Pb(II) onto the calcined diatomite as a function of pH (3.0-7.0) and different ionic strengths (0.05 and 0.1 mol L-1 NaCl) under ambient atmosphere. Adsorption of Pb(II) can be well described by Freundlich isotherm models. The apparent surface complexation equilibrium constants (log K) were obtained by fitting the batch experimental data using the PEST 13.0 together with PHREEQC 3.1.2 codes and there is good agreement between measured and predicted data. Distribution of Pb(II) surface species on the diatomite calculated by PHREEQC 3.1.2 program indicates that the impurity cations (e.g. Al3+, Fe3+, etc.) in the diatomite play a leading role in the Pb(II) adsorption and dominant formation of complexes and additional electrostatic interaction are the main adsorption mechanism of Pb(II) on the diatomite under weak acidic conditions.

  12. In silico prediction of drug dissolution and absorption with variation in intestinal pH for BCS class II weak acid drugs: ibuprofen and ketoprofen.

    Science.gov (United States)

    Tsume, Yasuhiro; Langguth, Peter; Garcia-Arieta, Alfredo; Amidon, Gordon L

    2012-10-01

    The FDA Biopharmaceutical Classification System guidance allows waivers for in vivo bioavailability and bioequivalence studies for immediate-release solid oral dosage forms only for BCS class I. Extensions of the in vivo biowaiver for a number of drugs in BCS class III and BCS class II have been proposed, in particular, BCS class II weak acids. However, a discrepancy between the in vivo BE results and in vitro dissolution results for BCS class II acids was recently observed. The objectives of this study were to determine the oral absorption of BCS class II weak acids via simulation software and to determine if the in vitro dissolution test with various dissolution media could be sufficient for in vitro bioequivalence studies of ibuprofen and ketoprofen as models of carboxylic acid drugs. The oral absorption of these BCS class II acids from the gastrointestinal tract was predicted by GastroPlus™. Ibuprofen did not satisfy the bioequivalence criteria at lower settings of intestinal pH of 6.0. Further the experimental dissolution of ibuprofen tablets in a low concentration phosphate buffer at pH 6.0 (the average buffer capacity 2.2 mmol l (-1) /pH) was dramatically reduced compared with the dissolution in SIF (the average buffer capacity 12.6 mmol l (-1) /pH). Thus these predictions for the oral absorption of BCS class II acids indicate that the absorption patterns depend largely on the intestinal pH and buffer strength and must be considered carefully for a bioequivalence test. Simulation software may be a very useful tool to aid the selection of dissolution media that may be useful in setting an in vitro bioequivalence dissolution standard. Copyright © 2012 John Wiley & Sons, Ltd.

  13. In Silico Prediction of Drug Dissolution and Absorption with variation in Intestinal pH for BCS Class II Weak Acid Drugs: Ibuprofen and Ketoprofen§

    Science.gov (United States)

    Tsume, Yasuhiro; Langguth, Peter; Garcia-Arieta, Alfredo; Amidon, Gordon L.

    2012-01-01

    The FDA Biopharmaceutical Classification System guidance allows waivers for in vivo bioavailability and bioequivalence studies for immediate-release solid oral dosage forms only for BCS class I. Extensions of the in vivo biowaiver for a number of drugs in BCS Class III and BCS class II have been proposed, particularly, BCS class II weak acids. However, a discrepancy between the in vivo- BE results and in vitro- dissolution results for a BCS class II acids was recently observed. The objectives of this study were to determine the oral absorption of BCS class II weak acids via simulation software and to determine if the in vitro dissolution test with various dissolution media could be sufficient for in vitro bioequivalence studies of ibuprofen and ketoprofen as models of carboxylic acid drugs. The oral absorption of these BCS class II acids from the gastrointestinal tract was predicted by GastroPlus™. Ibuprofen did not satisfy the bioequivalence criteria at lower settings of intestinal pH=6.0. Further the experimental dissolution of ibuprofen tablets in the low concentration phosphate buffer at pH 6.0 (the average buffer capacity 2.2 mmol L-1/pH) was dramatically reduced compared to the dissolution in SIF (the average buffer capacity 12.6 mmol L -1/pH). Thus these predictions for oral absorption of BCS class II acids indicate that the absorption patterns largely depend on the intestinal pH and buffer strength and must be carefully considered for a bioequivalence test. Simulation software may be very useful tool to aid the selection of dissolution media that may be useful in setting an in vitro bioequivalence dissolution standard. PMID:22815122

  14. The CO2 absorption spectrum in the 2.3 μm transparency window by high sensitivity CRDS: (II) Self-absorption continuum

    Science.gov (United States)

    Mondelain, D.; Vasilchenko, S.; Čermák, P.; Kassi, S.; Campargue, A.

    2017-01-01

    The CO2 absorption continuum near 2.3 μm is determined for a series of sub atmospheric pressures (250-750 Torr) by high sensitivity Cavity Ring Down Spectroscopy. An experimental procedure consisting in injecting successively a gas flow of CO2 and synthetic air, keeping constant the gas pressure in the CRDS cell, has been developed. This procedure insures a high stability of the spectra baseline by avoiding changes of the optical alignment due to pressure changes. The CO2 continuum was obtained as the difference between the CO2 absorption coefficient and a local lines simulation using a Voigt profile truncated at ±25 cm-1. Following the results of the preceding analysis of the CO2 rovibrational lines (Vasilchenko S et al. J Quant Spectrosc Radiat Transfer 10.1016/j.jqsrt.2016.07.002, a CO2 line list with intensities obtained by variational calculations and empirical line positions was preferred to the HITRAN line list. A quadratic pressure dependence of the absorption continuum is observed, with an average binary absorption coefficient increasing from 2 to 4×10-8 cm-1 amagat-2 between 4320 and 4380 cm-1. The obtained continuum is found in good agreement with a previous measurement using much higher densities (20 amagat) and a low resolution grating spectrograph and is consistent with values currently used in the analysis of Venus spectra.

  15. Adsorption of uranium(VI) to manganese oxides: X-ray absorption spectroscopy and surface complexation modeling.

    Science.gov (United States)

    Wang, Zimeng; Lee, Sung-Woo; Catalano, Jeffrey G; Lezama-Pacheco, Juan S; Bargar, John R; Tebo, Bradley M; Giammar, Daniel E

    2013-01-15

    The mobility of hexavalent uranium in soil and groundwater is strongly governed by adsorption to mineral surfaces. As strong naturally occurring adsorbents, manganese oxides may significantly influence the fate and transport of uranium. Models for U(VI) adsorption over a broad range of chemical conditions can improve predictive capabilities for uranium transport in the subsurface. This study integrated batch experiments of U(VI) adsorption to synthetic and biogenic MnO(2), surface complexation modeling, ζ-potential analysis, and molecular-scale characterization of adsorbed U(VI) with extended X-ray absorption fine structure (EXAFS) spectroscopy. The surface complexation model included inner-sphere monodentate and bidentate surface complexes and a ternary uranyl-carbonato surface complex, which was consistent with the EXAFS analysis. The model could successfully simulate adsorption results over a broad range of pH and dissolved inorganic carbon concentrations. U(VI) adsorption to synthetic δ-MnO(2) appears to be stronger than to biogenic MnO(2), and the differences in adsorption affinity and capacity are not associated with any substantial difference in U(VI) coordination.

  16. Synthesis, characterization, DNA binding and cleavage studies of mixed-ligand copper (II complexes

    Directory of Open Access Journals (Sweden)

    M. Sunita

    2017-05-01

    Full Text Available New two copper complexes of type [Cu(Bzimpy(LH2O]SO4 (where L = 2,2′ bipyridine (bpy, and ethylene diamine (en, Bzimpy = 2,6-bis(benzimidazole-2ylpyridine have been synthesized and characterized by elemental analyses, molar conductance measurements, magnetic susceptibility measurements, mass, IR, electronic and EPR spectral studies. Based on elemental and spectral studies six coordinated geometries were assigned to the two complexes. DNA-binding properties of these metal complexes were investigated using absorption spectroscopy, fluorescence spectroscopy, viscosity measurements and thermal denaturation methods. Experimental studies suggest that the complexes bind to DNA through intercalation. These complexes also promote the cleavage of plasmid pBR322, in the presence of H2O2.

  17. Evaluation of DNA binding, DNA cleavage, protein binding, radical scavenging and in vitro cytotoxic activities of ruthenium(II) complexes containing 2,4-dihydroxy benzylidene ligands

    Energy Technology Data Exchange (ETDEWEB)

    Mohanraj, Maruthachalam; Ayyannan, Ganesan; Raja, Gunasekaran; Jayabalakrishnan, Chinnasamy, E-mail: drcjbstar@gmail.com

    2016-12-01

    The new ruthenium(II) complexes with hydrazone ligands, 4-Methyl-benzoic acid (2,4-dihydroxy-benzylidene)-hydrazide (HL{sup 1}), 4-Methoxy-benzoic acid (2,4-dihydroxy-benzylidene)-hydrazide (HL{sup 2}), 4-Bromo-benzoic acid (2,4-dihydroxy-benzylidene)-hydrazide (HL{sup 3}), were synthesized and characterized by various spectro analytical techniques. The molecular structures of the ligands were confirmed by single crystal X-ray diffraction technique. The DNA binding studies of the ligands and complexes were examined by absorption, fluorescence, viscosity and cyclic voltammetry methods. The results indicated that the ligands and complexes could interact with calf thymus DNA (CT-DNA) through intercalation. The DNA cleavage activity of the complexes was evaluated by gel electrophoresis assay, which revealed that the complexes are good DNA cleaving agents. The binding interaction of the ligands and complexes with bovine serum albumin (BSA) was investigated using fluorescence spectroscopic method. Antioxidant studies showed that the complexes have a strong radical scavenging properties. Further, the cytotoxic effect of the complexes examined on cancerous cell lines showed that the complexes exhibit significant anticancer activity. - Highlights: • Synthesis of ruthenium(II) hydrazone complexes • Molecular structure of the ligands was elucidated by single crystal X-ray diffraction method. • The ligands and complexes interact with CT-DNA via intercalation. • The complexes possess significant antioxidant activity against DPPH, OH and NO radicals. • The complex 6 shows higher IC{sub 50} value than the other complexes against cancer cells.

  18. Metal based biologically active compounds: Design, synthesis, DNA binding and antidiabetic activity of 6-methyl-3-formyl chromone derived hydrazones and their metal (II) complexes.

    Science.gov (United States)

    Philip, Jessica Elizabeth; Shahid, Muhammad; Prathapachandra Kurup, M R; Velayudhan, Mohanan Puzhavoorparambil

    2017-10-01

    Two chromone hydrazone ligands HL 1 and HL 2 were synthesized and characterized by elemental analyses, IR, 1 H NMR & 13 C NMR, electronic absorption and mass spectra. The reactions of the chromone hydrazones with transition metals such as Ni, Cu, and Zn (II) salts of acetate afforded mononuclear metal complexes. Characterization and structure elucidation of the prepared chromone hydrazone metal (II) complexes were done by elemental, IR, electronic, EPR spectra and thermo gravimetric analyses as well as conductivity and magnetic susceptibility measurements. The spectroscopic data showed that the ligand acts as a mono basic bidentate with coordination sites are azomethine nitrogen and hydrazonic oxygen, and they exhibited distorted geometry. The biological studies involved antidiabetic activity i.e. enzyme inhibition of α-amylase and α-glucosidase, Calf Thymus - DNA (CT-DNA) interaction and molecular docking. Potential capacity of synthesized compounds to inhibit the α-amylase and α-glucosidase activity was assayed whereas DNA interaction studies were carried out with the help UV-Vis absorption titration and viscosity method. The docking studies of chromone hydrazones show that they are minor groove binders. Complexes were found to be good DNA - intercalates. Chromone hydrazones and its transition metal complexes have shown comparable antidiabetic activity with a standard drug acarbose. Copyright © 2017 Elsevier B.V. All rights reserved.

  19. X-ray diffraction study of phase transitions in iron(II) trisnioximate hexadecylboronate clathrochelate complex

    International Nuclear Information System (INIS)

    Vorontsov, I.I.; Antipin, M.Yu.; Dubovik, I.I.; Papkov, V.S.; Potekhin, K.A.; Voloshin, Ya.Z.; Stash, A.I.; Belsky, V.K.

    2001-01-01

    Crystals of the iron(II) nioximate hexadecylboronate clathrochelate complex-FeNx 3 (BHd ) 2 [tris(μ-1,2-cyclohexanedionedioximato-O:O ' )di-n-hexadecyldiborato(2-) - N,'''N''',N''',N''',N''',N ' ]iron(II) - are investigated by differential scanning calorimetry and X-ray diffraction. Two structural phase transitions are revealed at T cr1 = 290(3) K and T cr2 = 190(3) K. The crystal structures of phases I, II, and III are determined by X-ray diffraction analysis at 303, 243, and 153 K, respectively. It is demonstrated that the I ↔ II phase transition is due to a change in the system of translations, and the II ↔ III phase transition is accompanied only by a jumpwise change in the unit cell parameters. The possible mechanisms of phase transitions are discussed in terms of geometry and molecular packing of FeNx 3 (BHd) 2 in all three phases

  20. New copper(II) complexes with dopamine hydrochloride and vanillymandelic acid: Spectroscopic and thermal characterization

    Science.gov (United States)

    Mohamed, Gehad G.; Nour El-Dien, F. A.; El-Nahas, R. G.

    2011-10-01

    The dopamine derivatives participate in the regulation of wide variety of physiological functions in the human body and in medication life. Increase and/or decrease in the concentration of dopamine in human body reflect an indication for diseases such as Schizophrenia and/or Parkinson diseases. The Cu(II) chelates with coupled products of dopamine hydrochloride (DO.HCl) and vanillymandelic acid (VMA) with 4-aminoantipyrine (4-AAP) are prepared and characterized. Different physico-chemical techniques namely IR, magnetic and UV-vis spectra are used to investigate the structure of these chelates. Cu(II) forms 1:1 (Cu:DO) and 1:2 (Cu:VMA) chelates. DO behave as a uninegative tridentate ligand in binding to the Cu(II) ion while VMA behaves as a uninegative bidentate ligand. IR spectra show that the DO is coordinated to the Cu(II) ion in a tridentate manner with ONO donor sites of the phenolic- OH, -NH and carbonyl- O, while VMA is coordinated with OO donor sites of the phenolic- OH and -NH. Magnetic moment measurements reveal the presence of Cu(II) chelates in octahedral and square planar geometries with DO and VMA, respectively. The thermal decomposition of Cu(II) complexes is studied using thermogravimetric (TG) and differential thermal analysis (DTA) techniques. The activation thermodynamic parameters, such as, energy of activation, enthalpy, entropy and free energy change of the complexes are evaluated and the relative thermal stability of the complexes are discussed.

  1. Anti-Leishmania activity of new ruthenium(II) complexes: Effect on parasite-host interaction.

    Science.gov (United States)

    Costa, Mônica S; Gonçalves, Yasmim G; Nunes, Débora C O; Napolitano, Danielle R; Maia, Pedro I S; Rodrigues, Renata S; Rodrigues, Veridiana M; Von Poelhsitz, Gustavo; Yoneyama, Kelly A G

    2017-10-01

    Leishmaniasis is a parasitic disease caused by protozoa of the genus Leishmania. The many complications presented by the current treatment - including high toxicity, high cost and parasite resistance - make the development of new therapeutic agents indispensable. The present study aims to evaluate the anti-Leishmania potential of new ruthenium(II) complexes, cis‑[Ru II (η 2 -O 2 CR)(dppm) 2 ]PF 6 , with dppm=bis(diphenylphosphino)methane and R=4-butylbenzoate (bbato) 1, 4-(methylthio)benzoate (mtbato) 2 and 3-hydroxy-4-methoxybenzoate (hmxbato) 3, in promastigote cytotoxicity and their effect on parasite-host interaction. The cytotoxicity of complexes was analyzed by MTT assay against Leishmania (Leishmania) amazonensis, Leishmania (Viannia) braziliensis, Leishmania (Leishmania) infantum promastigotes and the murine macrophage (RAW 264.7). The effect of complexes on parasite-host interaction was evaluated by in vitro infectivity assay performed in the presence of two different concentrations of each complex: the promastigote IC 50 value and the concentration nontoxic to 90% of RAW 264.7 macrophages. Complexes 1-3 exhibited potent cytotoxic activity against all Leishmania species assayed. The IC 50 values ranged from 7.52-12.59μM (complex 1); 0.70-3.28μM (complex 2) and 0.52-1.75μM (complex 3). All complexes significantly inhibited the infectivity index at both tested concentrations. The infectivity inhibitions ranged from 37 to 85%. Interestingly, the infectivity inhibitions due to complex action did not differ significantly at either of the tested concentrations, except for the complex 1 against Leishmania (Leishmania) infantum. The infectivity inhibitions resulted from reductions in both percentage of infected macrophages and number of parasites per macrophage. Taken together the results suggest remarkable leishmanicidal activity in vitro by these new ruthenium(II) complexes. Copyright © 2017 Elsevier Inc. All rights reserved.

  2. Interfacial charge separation and recombination in InP and quasi-type II InP/CdS core/shell quantum dot-molecular acceptor complexes.

    Science.gov (United States)

    Wu, Kaifeng; Song, Nianhui; Liu, Zheng; Zhu, Haiming; Rodríguez-Córdoba, William; Lian, Tianquan

    2013-08-15

    Recent studies of group II-VI colloidal semiconductor heterostuctures, such as CdSe/CdS core/shell quantum dots (QDs) or dot-in-rod nanorods, show that type II and quasi-type II band alignment can facilitate electron transfer and slow down charge recombination in QD-molecular electron acceptor complexes. To explore the general applicability of this wave function engineering approach for controlling charge transfer properties, we investigate exciton relaxation and dissociation dynamics in InP (a group III-V semiconductor) and InP/CdS core/shell (a heterostructure beween group III-V and II-VI semiconductors) QDs by transient absorption spectroscopy. We show that InP/CdS QDs exhibit a quasi-type II band alignment with the 1S electron delocalized throughout the core and shell and the 1S hole confined in the InP core. In InP-methylviologen (MV(2+)) complexes, excitons in the QD can be dissociated by ultrafast electron transfer to MV(2+) from the 1S electron level (with an average time constant of 11.4 ps) as well as 1P and higher electron levels (with a time constant of 0.39 ps), which is followed by charge recombination to regenerate the complex in its ground state (with an average time constant of 47.1 ns). In comparison, InP/CdS-MV(2+) complexes show similar ultrafast charge separation and 5-fold slower charge recombination rates, consistent with the quasi-type II band alignment in these heterostructures. This result demonstrates that wave function engineering in nanoheterostructures of group III-V and II-VI semiconductors provides a promising approach for optimizing their light harvesting and charge separation for solar energy conversion applications.

  3. A bioaccumulative cyclometalated platinum(II) complex with two-photon-induced emission for live cell imaging.

    Science.gov (United States)

    Koo, Chi-Kin; Wong, Ka-Leung; Man, Cornelia Wing-Yin; Lam, Yun-Wah; So, Leo King-Yan; Tam, Hoi-Lam; Tsao, Sai-Wah; Cheah, Kok-Wai; Lau, Kai-Chung; Yang, Yang-Yi; Chen, Jin-Can; Lam, Michael Hon-Wah

    2009-02-02

    The cyclometalated platinum(II) complex [Pt(L)Cl], where HL is a new cyclometalating ligand 2-phenyl-6-(1H-pyrazol-3-yl)pyridine containing C(phenyl), N(pyridyl), and N(pyrazolyl) donor moieties, was found to possess two-photon-induced luminescent properties. The two-photon-absorption cross section of the complex in N,N-dimethylformamide at room temperature was measured to be 20.8 GM. Upon two-photon excitation at 730 nm from a Ti:sapphire laser, bright-green emission was observed. Besides its two-photon-induced luminescent properties, [Pt(L)Cl] was able to be rapidly accumulated in live HeLa and NIH3T3 cells. The two-photon-induced luminescence of the complex was retained after live cell internalization and can be observed by two-photon confocal microscopy. Its bioaccumulation properties enabled time-lapse imaging of the internalization process of the dye into living cells. Cytotoxicity of [Pt(L)Cl] to both tested cell lines was low, according to MTT assays, even at loadings as high as 20 times the dose concentration for imaging for 6 h.

  4. Luminescent pH sensor of a novel imidazole-containing hexanuclear Ru(II) polypyridyl complex

    Science.gov (United States)

    Cheng, Feixiang; Tang, Ning; Chen, Jishu; Chen, Guang

    2013-10-01

    Hexapodal ligand H6L containing imidazole rings has been prepared by the reaction of 1,10-phenanthroline-5,6-dione with 1,2,3,4,5,6-hexakis[(3-formylphenoxy)methyl]benzene. The Ru(II) polypyridyl complex [{Ru(bpy)2}6(μ6-H6L)](PF6)12 (bpy = 2,2'-bipyridine) has been synthesized by the reaction of Ru(bpy)2Cl2·2H2O with ligand H6L. The pH effects on the UV-vis absorption and emission spectra of the complex have been studied. The ground- and excited-state ionization constants of the acid-base equilibria have been calculated according to the absorbance and emission data. The complex acts as an off-on-off luminescent pH sensor through two successive deprotonation processes of imidazole rings, with a maximum on-off ratio of 5 in buffer solution.

  5. Synthesis and characterization of chromium(III), manganese(II), iron(III), cobalt(II), nickel(II), copper(II), cadmium(II) and dioxouranium(VI) complexes of 4(2-pyridyl)-1-(2,4-dihydroxybenzaldehyde)-3-thiosemicarbazone

    International Nuclear Information System (INIS)

    Abu El-Reash, G.M.; Ibrahim, M.M.; Kenawy; El-Ayaan, Usama; Khattab, M.A.

    1994-01-01

    A few complexes of Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and dioxouranium(VI) with 4(2-pyridyl)-1-(2,4-dihydroxybenzaldehyde)-3-thiosemicarbazone have been synthesised and characterized on the basis of elemental analysis, IR, electronic NMR, and magnetic moment data. An octahedral structure is proposed for the Cr(III), Fe(III), Co(II) and Ni(H 3 PBT) 2 Cl 2 .2H 2 O complexes; a tetrahedral structure for the Mn(II) and Ni 2 (PBT)OAc.H 2 0 complexes and a square planar structure for the Cu(II) complexes. The antimicrobial and antifungal activities of H 3 PBT and of its metal(II) complexes are investigated. The results reveal that H 3 PBT exhibits greater antimicrobial activities than its complexes. (author). 34 refs., 4 figs., 2 tabs

  6. Preconcentration of metallic elements by complexation with ammonium pyrrolidine dithiocarbamate (APDC) for atomic absorption analysis

    International Nuclear Information System (INIS)

    Santos Coelho, Ricardo dos; Dantas, Elizabeth S.K.

    1997-01-01

    Ammonium pyrrolidine dithiocarbamate (APDC) forms stable chelates with many metals being therefore, used in systems of preconcentration for determination of heavy metals in water. In this work, the metals were complexed with APDC and extracted with methyl isobutyl ketone (MIBK). The results showed that the studied metals (Co, Cu, Fe, Ni, Pb, Cr and Cd), in the range of 2 to 5 μg, in 100 ml of sample, were quantitatively extracted in only one stage using 10 ml of MIBK and 5 ml of 4% APDC. The pH must be between 4 and 5. The complexes stability was also studied. The proposed method can be applied to pre concentrate heavy metals in natural waters. (author). 4 refs., 1 fig., 3 tabs

  7. Towards the Development of Functionalized PolypyridineLigands for Ru(II Complexes as Photosensitizers inDye-Sensitized Solar Cells (DSSCs

    Directory of Open Access Journals (Sweden)

    Adewale O. Adeloye

    2014-08-01

    Full Text Available A number of novel ruthenium(II polypyridine complexes have been designedand synthesized for use as photosensitizers in dye-sensitized solar cells (DSSCs due totheir rich photophysical properties such as intense absorption, long-lived lifetimes, highemission quantum yields and unique redox characteristics. Many of these complexesexhibit photophysical behavior that can be readily controlled through a careful choice ofligands and/or substituents. With this perspective, we review the design and general syntheticmethods of some polypyridine ligands based on bipyridine, phenanthroline, terpyridine andquaterpyridine with/without anchoring groups with a view to correlate functionality ofligand structures with the observed photophysical, electroredox and power conversionefficiency of some examples of Ru(II polypyridyl complexes that have been reported andparticularly used in the DSSCs applications. The main interest, however, is focused onshowing the development of new polypyridine ligand materials containing long-rangeelectron transfer motifs such as the alkenyl, alkynyl and polyaromatic donor functionalities.

  8. Label free luminescence strategy for sensitive detection of ATP using aptamer-Ru(II) complexes

    Energy Technology Data Exchange (ETDEWEB)

    Babu, Eththilu [Department of Physical Che mistry, School of Chemistry, Madurai Kamaraj University, Madurai 625021, Tamil Nadu (India); Muthu Mareeswaran, Paulpandian [Department of Physical Che mistry, School of Chemistry, Madurai Kamaraj University, Madurai 625021, Tamil Nadu (India); Department of Industrial Chemistry, Alagappa Univesity, Karaikudi 630003, Tamil Nadu (India); Ramdass, Arumugam [Department of Physical Che mistry, School of Chemistry, Madurai Kamaraj University, Madurai 625021, Tamil Nadu (India); Research Department of Chemistry, Aditanar College of Arts and Science, Tiruchendur 628216, Tamil Nadu (India); Ramesh, Pandian [UCIBIO-REQUIMTE, Departmento de Química, Faculdade de Ciências e Tecnologia, Universidade NOVA de Lisboa, 2829-516 Caparica (Portugal); Rajagopal, Seenivasan, E-mail: rajagopalseenivasan@yahoo.com [Department of Physical Che mistry, School of Chemistry, Madurai Kamaraj University, Madurai 625021, Tamil Nadu (India)

    2016-07-15

    A simple and sensitive aptamer-based luminescence strategy for ATP detection is developed using Ru(II) complexes as probe molecule. It is based on the fact that Ru(II)-dppz complexes show the light switching behavior with DNA aptamers and found to show significant luminescence spectral change on the addition of ATP molecules. The binding efficiencies of aptamer with ATP, ADP and AMP are calculated and compared. The structural change of aptamer is also studied using circular dichroism (CD) spectral techniques. Moreover, the binding nature of aptamer with ATP, ADP and AMP is demonstrated by computational techniques. The proposed strategy was successfully applied to the detection of ATP.

  9. Synthesis and physicochemical analysis of Sm (II, III) acetylacetone chelate complexes

    International Nuclear Information System (INIS)

    Kostyuk, N.N.; Dik, T.A.; Trebnikov, A.G.

    2004-01-01

    Sm (II, III) acetylacetone chelate complexes were synthesized by electrochemical method. It was shown that anode dissolution of the metal samarium over acetylacetone leads to formation of the Sm (II, III) chelate complexes: xSm(acac)2 · ySm(acac)3 · zH(acac). Factors x, y and z depend on quantity of the electricity, which flew through the electrolysis cell. The compositions of the obtained substances were confirmed by the physicochemical analysis (ultimate analysis, IR-, mass spectroscopy and thermal analysis (thermogravimetric, isothermal warming-up and differential scanning colorimetry). (Authors)

  10. Surface Structures Formed by a Copper(II Complex of Alkyl-Derivatized Indigo

    Directory of Open Access Journals (Sweden)

    Akinori Honda

    2016-10-01

    Full Text Available Assembled structures of dyes have great influence on their coloring function. For example, metal ions added in the dyeing process are known to prevent fading of color. Thus, we have investigated the influence of an addition of copper(II ion on the surface structure of alkyl-derivatized indigo. Scanning tunneling microscope (STM analysis revealed that the copper(II complexes of indigo formed orderly lamellar structures on a HOPG substrate. These lamellar structures of the complexes are found to be more stable than those of alkyl-derivatized indigos alone. Furthermore, 2D chirality was observed.

  11. Label free luminescence strategy for sensitive detection of ATP using aptamer-Ru(II) complexes

    International Nuclear Information System (INIS)

    Babu, Eththilu; Muthu Mareeswaran, Paulpandian; Ramdass, Arumugam; Ramesh, Pandian; Rajagopal, Seenivasan

    2016-01-01

    A simple and sensitive aptamer-based luminescence strategy for ATP detection is developed using Ru(II) complexes as probe molecule. It is based on the fact that Ru(II)-dppz complexes show the light switching behavior with DNA aptamers and found to show significant luminescence spectral change on the addition of ATP molecules. The binding efficiencies of aptamer with ATP, ADP and AMP are calculated and compared. The structural change of aptamer is also studied using circular dichroism (CD) spectral techniques. Moreover, the binding nature of aptamer with ATP, ADP and AMP is demonstrated by computational techniques. The proposed strategy was successfully applied to the detection of ATP.

  12. Insights into functional-group-tolerant polymerization catalysis with phosphine-sulfonamide palladium (II) complexes

    KAUST Repository

    Jian, Zhongbao; Falivene, Laura; Wucher, Philipp; Roesle, Philipp; Caporaso, Lucia; Cavallo, Luigi; Gç ttker-Schnetmann, Inigo; Mecking, Stefan

    2014-01-01

    Two series of cationic palladium(II) methyl complexes {[(2-MeOC6H4)2PC6H4SO2NHC6H3(2,6-R1,R2)]PdMe}2[A]2 (X1+-A: R1=R2=H: H1+-A; R1=R2=CH(CH3)2: DIPP1+-A; R1=H, R2=CF3: CF31+-A; A=BF4 or SbF6) and neutral palladium(II) methyl complexes {[(2-MeOC6H4

  13. Investigation on biomolecular interactions of nickel(II) complexes with monoanionic bidentate ligands

    Science.gov (United States)

    Jayamani, Arumugam; Sethupathi, Murugan; Ojwach, Stephen O.; Sengottuvelan, Nallathambi

    2018-01-01

    Reactions of monoanionic bidentate ligands 5-methylsalicylaldehyde (5-msal), 5-bromosalicylaldehyde (5-brsal), 5-nitrosalicylaldehyde (5-nsal) and 2-hydroxy-1-naphthaldehyde (2-hnap) with nickel perchlorate hexahydrate produced nickel(II) complexes 1-4, respectively. Single crystal X-ray analyses of complexes 1 and 2 confirmed bidentate mode of the ligands with O˄O coordination to give square planar geometry around nickel atoms. Complexes 1-4 showed one quasi-reversible redox peak at cathodic region (-0.67 to -0.80 V) and one redox peak at anodic region (+1.08 to +1.44 V) assignable to the Ni(II)/Ni(I) and Ni(II)/Ni(III) redox couples, respectively. The complexes exhibited good bovine serum albumin (BSA) binding abilities with a maximum binding constant of 1.96 × 105 M-1. The binding of complexes with calf thymus DNA (ctDNA) showed that the binding affinity is consistent with an increase in steric bulk of the ligands. The nuclease activity of the complexes showed efficient oxidative cleavage in the presence of hydrogen peroxide as an oxidizing agent. The complexes showed higher zone of inhibition when screened for antimicrobial activity against bacteria and human pathogenic fungi.

  14. Synthesis, structure and luminescence properties of zinc (II) complexes with terpyridine derivatives as ligands

    International Nuclear Information System (INIS)

    Chen Xuegang; Zhou Quanguo; Cheng Yanxiang; Geng Yanhou; Ma Dongge; Xie Zhiyuan; Wang Lixiang

    2007-01-01

    Five zinc (II) complexes (1-5) with 4'-phenyl-2,2':6',2''-terpyridine (ptpy) derivatives as ligands have been synthesized and fully characterized. The para-position of phenyl in ptpy is substituted by the group (R), i.e. tert-butyl (t-Bu), hexyloxy (OHex), carbazole-9-yl (Cz), naphthalen-1-yl-phenyl-amine-N-yl (NPA) and diphenyl amine-N-yl (DPA), with different electron-donating ability. With increasing donor ability of the R, the emission color of the complexes in film was modulated from violet (392 nm) to reddish orange (604 nm). The photoexcited luminescence exhibits significant solvatochromism because the emission of the complexes involves the intra-ligand charge transfer (ILCT) excited state. The electrochemical investigations show that the complexes with stronger electro-donating substituent have lower oxidation potential and then higher HOMO level. The electroluminescence (EL) properties of these zinc (II) complexes were studied with the device structure of ITO/PEDOT/Zn (II) complex: PBD:PMMA/BCP/AlQ/LiF/Al. Complexes 3, 4 and 5 exhibit EL wavelength at 552, 600 and 609 nm with maximum current efficiency of 5.28, 2.83 and 2.00 cd/A, respectively

  15. Spectrochemical study the effect of high energetic ionization radiation on Ru(III, Pd(II and Hg(II complexes

    Directory of Open Access Journals (Sweden)

    Samar A. Aly

    2017-04-01

    Thermal studies of these chelates before and after γ-irradiation stable that the complexes of Ru(III and Pd (II after γ-irradiation are more thermal show than Hg(II complexes before and after γ-irradiation.

  16. Mechanism of enhanced oral absorption of morin by phospholipid complex based self-nanoemulsifying drug delivery system.

    Science.gov (United States)

    Zhang, Jinjie; Li, Jianbo; Ju, Yuan; Fu, Yao; Gong, Tao; Zhang, Zhirong

    2015-02-02

    Phospholipid complex (PLC) based self-nanoemulsifying drug delivery system (PLC-SNEDDS) has been developed for efficient delivery of drugs with poor solubility and low permeability. In the present study, a BCS class IV drug and a P-glycoprotein (P-gp) substrate, morin, was selected as the model drug to elucidate the oral absorption mechanism of PLC-SNEDDS. PLC-SNEDDS was superior to PLC in protecting morin from degradation by intestinal enzymes in vitro. In situ perfusion study showed increased intestinal permeability by PLC was duodenum-specific. In contrast, PLC-SNEDDS increased morin permeability in all intestinal segments and induced a change in the main absorption site of morin from colon to ileum. Moreover, ileum conducted the lymphatic transport of PLC-SNEDDS, which was proven by microscopic intestinal visualization of Nile red labeled PLC-SNEDDS and lymph fluids in vivo. Low cytotoxicity and increased Caco-2 cell uptake suggested a safe and efficient delivery of PLC-SNEDDS. The increased membrane fluidity and disrupted actin filaments were closely associated with the increased cell uptake of PLC-SNEDDS. PLC-SNEDDS could be internalized into enterocytes as an intact form in a cholesterol-dependent manner via clathrin-mediated endocytosis and macropinocytosis. The enhanced oral absorption of morin was attributed to the P-gp inhibition by Cremophor RH and the intact internalization of M-PLC-SNEDDS into Caco-2 cells bypassing P-gp recognition. Our findings thus provide new insights into the development of novel nanoemulsions for poorly absorbed drugs.

  17. Preparation and characterization of Schiff base Cu(II) complex and its applications on textile materials

    Science.gov (United States)

    Oylumluoglu, G.; Oner, J.

    2017-10-01

    Schiff base ligands are regarded as an important class of organic compounds on account of the fact that their complexation ability with transition metal ions. A new monomeric Schiff base Cu(II) complex, [Cu(HL)2], 1 [H2L = 2-((E)-(2-hydroxypropylimino)methyl)-4-nitrophenol] has been synthesized and characterized by elemental analysis, UV and IR spectroscopy, single crystal X-ray diffraction and photoluminescence study. While the Schiff base ligand and its Cu(II) complex are excited at λex = 349 nm in UV region, the Schiff base ligand shows a blue emission band at λmax = 480 nm whereas its Cu(II) complex shows a strong green emission band at λmax = 520 nm in the solid state at room temperature. The luminescent properties showed that the Schiff base ligand and its Cu(II) complex can be used as novel potential candidates for applications in textile such as UV-protection, antimicrobial, laundry and functional bleaching treatments.

  18. SPITZER VIEW OF YOUNG MASSIVE STARS IN THE LARGE MAGELLANIC CLOUD H II COMPLEXES. II. N 159

    International Nuclear Information System (INIS)

    Chen, C.-H. Rosie; Indebetouw, Remy; Chu, You-Hua; Gruendl, Robert A.; Seale, Jonathan P.; Testor, Gerard; Heitsch, Fabian; Meixner, Margaret; Sewilo, Marta

    2010-01-01

    The H II complex N 159 in the Large Magellanic Cloud is used to study massive star formation in different environments, as it contains three giant molecular clouds (GMCs) that have similar sizes and masses but exhibit different intensities of star formation. We identify candidate massive young stellar objects (YSOs) using infrared photometry, and model their spectral energy distributions to constrain mass and evolutionary state. Good fits are obtained for less evolved Type I, I/II, and II sources. Our analysis suggests that there are massive embedded YSOs in N 159B, a maser source, and several ultracompact H II regions. Massive O-type YSOs are found in GMCs N 159-E and N 159-W, which are associated with ionized gas, i.e., where massive stars formed a few Myr ago. The third GMC, N 159-S, has neither O-type YSOs nor evidence of previous massive star formation. This correlation between current and antecedent formation of massive stars suggests that energy feedback is relevant. We present evidence that N 159-W is forming YSOs spontaneously, while collapse in N 159-E may be triggered. Finally, we compare star formation rates determined from YSO counts with those from integrated Hα and 24 μm luminosities and expected from gas surface densities. Detailed dissection of extragalactic GMCs like the one presented here is key to revealing the physics underlying commonly used star formation scaling laws.

  19. Stability of binary complexes of Pb(II), Cd(II) and Hg(II) with maleic ...

    African Journals Online (AJOL)

    The trend in variation of complex stability constants with change in the mole fraction of the medium is explained on the basis of prevailing electrostatic and non-electrostatic forces. The species distribution as a function of pH at different compositions of TX100-water mixtures and plausible speciation equilibria are presented ...

  20. Synthesis and Characterization of Cu(II), Co(II) and Ni(II) Complexes of Trithiocyanuric Acid: The Structure of {N,N'-Bis(3-Aminopropyl)-1,3-Propanediamine}-(Trithiocyanurato)Nickel(II)

    Czech Academy of Sciences Publication Activity Database

    Kopel, P.; Trávníček, Zdeněk; Kvítek, L.; Černošek, Z.; Wrzeszcz, G.; Marek, J.

    2003-01-01

    Roč. 56, č. 1 (2003), s. 1-11 ISSN 0095-8972 R&D Projects: GA ČR GA203/00/0152; GA AV ČR IBS5038351 Institutional research plan: CEZ:AV0Z5038910 Keywords : Copper(II) * cobalt(II) and nickel(II) complexes * Trithiocyanuric acid Subject RIV: CE - Biochemistry Impact factor: 0.841, year: 2003

  1. Critical coupling and coherent perfect absorption for ranges of energies due to a complex gain and loss symmetric system

    International Nuclear Information System (INIS)

    Hasan, Mohammad; Ghatak, Ananya; Mandal, Bhabani Prasad

    2014-01-01

    We consider a non-Hermitian medium with a gain and loss symmetric, exponentially damped potential distribution to demonstrate different scattering features analytically. The condition for critical coupling (CC) for unidirectional wave and coherent perfect absorption (CPA) for bidirectional waves are obtained analytically for this system. The energy points at which total absorption occurs are shown to be the spectral singular points for the time reversed system. The possible energies at which CC occurs for left and right incidence are different. We further obtain periodic intervals with increasing periodicity of energy for CC and CPA to occur in this system. -- Highlights: •Energy ranges for CC and CPA are obtained explicitly for complex WS potential. •Analytical conditions for CC and CPA for PT symmetric WS potential are obtained. •Conditions for left and right CC are shown to be different. •Conditions for CC and CPA are shown to be that of SS for the time reversed system. •Our model shows the great flexibility of frequencies for CC and CPA

  2. Thiolato-bridged RuIIAgIRuII trinuclear complex composed of bis(bipyridine)ruthenium(II) units with chelating 2-aminoethanethiolate: conversion to a disulfide-bridged RuIIRuII dinuclear complex.

    Science.gov (United States)

    Tamura, Motoshi; Matsuura, Noriyuki; Kawamoto, Tatsuya; Konno, Takumi

    2007-08-20

    The reaction of [Ru(solvent)2(bpy)2]2+ (bpy = 2,2'-bipyridine) with Haet (2-aminoethanethiol) in ethanol/water in the presence of Ag+ gave a thiolato-bridged RuIIAgIRuII trinuclear complex, [Ag{Ru(aet)(bpy)2}2]3+, in which two [RuII(aet)(bpy)2]+ units are linked by an AgI atom. When this complex was treated with HCl in acetonitrile/water, a disulfide-bridged RuIIRuII dinuclear complex, [Ru2(cysta)(bpy)4]4+ (cysta = cystamine), was produced as a result of the removal of an AgI atom and the autoxidation of thiolato groups. It was found that the dinuclear structure in [Ru2(cysta)(bpy)4]4+ is reverted back to [Ag{Ru(aet)(bpy)2}2]3+ by treatment with Ag+ assisted by Zn reduction.

  3. Solid solutions of platinum(II) and palladium(II) oxalato-complex salt as precursors of nanoalloys

    Science.gov (United States)

    Zadesenets, A. V.; Asanova, T. I.; Vikulova, E. S.; Filatov, E. Yu.; Plyusnin, P. E.; Baidina, I. A.; Asanov, I. P.; Korenev, S. V.

    2013-03-01

    A solid solution of platinum (II) and palladium (II) oxalato-complex salt, (NH4)2[Pt0.5Pd0.5(C2O4)2]·2H2O, has been synthesized and studied as a precursor for preparing bimetallic PtPd nanoparticles through its thermal decomposition. The smallest homogenous bimetallic PtPd nanoparticles were found to form in hydrogen and helium atmospheres. The annealing temperature and time have low effect on the bimetallic particles size. Comparative analysis of structural and thermal properties of the solid solution and individual Pt, Pd oxalato-complex salts was performed to investigate a mechanism of thermal decomposition of (NH4)2[Pt0.5Pd0.5(C2O4)2]·2H2O. Based on in situ X-ray photoemission spectroscopy investigation it was proposed a mechanism of formation of bimetallic PtPd nanoparticles from the solid-solution oxalato-complex salt during thermal decomposition.

  4. Folate absorption

    International Nuclear Information System (INIS)

    Baker, S.J.

    1976-01-01

    Folate is the generic term given to numerous compounds of pteroic acid with glutamic acid. Knowledge of absorption is limited because of the complexities introduced by the variety of compounds and because of the inadequacy of investigational methods. Two assay methods are in use, namely microbiological and radioactive. Techniques used to study absorption include measurement of urinary excretion, serum concentration, faecal excretion, intestinal perfusion, and haematological response. It is probably necessary to test absorption of both pteroylmonoglutamic acid and one or more polyglutamates, and such tests would be facilitated by availability of synthesized compounds labelled with radioactive tracers at specifically selected sites. (author)

  5. Local 3d Electronic Structures of Co-Based Complexes with Medicinal Molecules Probed by Soft X-ray Absorption

    Science.gov (United States)

    Yamagami, Kohei; Fujiwara, Hidenori; Imada, Shin; Kadono, Toshiharu; Yamanaka, Keisuke; Muro, Takayuki; Tanaka, Arata; Itai, Takuma; Yoshinari, Nobuto; Konno, Takumi; Sekiyama, Akira

    2017-07-01

    We have examined the local 3d electronic structures of Co-Au multinuclear complexes with the medicinal molecules d-penicillaminate (d-pen) [Co{Au(PPh3)(d-pen)}2]ClO4 and [Co3{Au3(tdme)(d-pen)3}2] by Co L2,3-edge soft X-ray absorption (XAS) spectroscopy, where PPh3 denotes triphenylphosphine and tdme stands for 1,1,1-tris[(diphenylphosphino)methyl]ethane. The Co L2,3-edge XAS spectra indicate the localized ionic 3d electronic states in both materials. The experimental spectra are well explained by spectral simulation for a localized Co ion under ligand fields with the full multiplet theory, which verifies that the ions are in the low-spin Co3+ state in the former compound and in the high-spin Co2+ state in the latter.

  6. Effect of carboxylatozinc(II) and halogencarboxylatozinc(II) complexes on photosensitising organisms

    International Nuclear Information System (INIS)

    Kralova, K.; Gaplovsky, A.; Masarovicova, E.; Gyoeryova, K.

    2001-01-01

    The inhibition of oxygen evolution rate (OER) and Chlorophyll-a (Chl) synthesis in green alga Chlorella vulgaris as well as inhibition of root growth of Sinapis alba caused by carboxylatozinc(lI) and halogencarboxylatozinc(ll) complexes was investigated. The studied zinc(ll) complexes were as follows: Zn(HCOO) 2 , Zn(CH 3 COO) 2 .2.5H 2 O, Zn(CH 3 CH 2 COO) 2 , Zn(CH 3 CH 2 CH 2 COO) 2 , Zn((CH 3 ) 2 CHCOO) 2 , Zn(ClCH 2 COO) 2 .2H 2 0, Zn(ClCH 2 CH 2 COO) 2 , Zn(ICH 2 CHCOO) 2 . The inhibitory activity determined for OER inhibition (pH = 7.2) in suspensions of Chlorella vulgaris (Chl content in the suspension 18 mg dm -3 ) expressed by IC 50 values varied in the range of 0.112 -1.362 mmol dm -3 and it showed a decrease in the following order: Zn(lCH 2 COO) 2 > Zn(CICH 2 CH 2 COO) 2 > Zn(CICH 2 COO) 2 > Zn(CH 3 CH 2 COO) 2 > Zn(CH 3 CH 2 CH 2 COO) 2 > Zn(CH 3 COO) 2 .2.5H 2 0 > Zn((CH 3 CHCOO) 2 > Zn(HCOO) 2 indicating a quasi-parabolic course of OER-inhibiting activity on the lipophilicity of carboxylatozinc(ll) complexes. The branching of the alkyl chain was connected with decreased solubility of the compound and resulted in decreased biological activity of studied compounds. On the other hand, the insertion of Cl or I atoms led to the increase of their activity. The studied compounds also inhibited growth of sinapis alba roots. Similarly, the halogencarboxylatozinc(lI) complexes exhibited higher inhibitory activity than the corresponding carboxylatozinc(ll) compounds. In the suspensions of Chlorella vulgaris the compound Zn(CH 3 CH(Cl)COO) 2 caused fluorescence quenching at λ = 334 nm (λ ex = 275 nm). The emission band at Aλ = 334 nm belongs mainly to the tryptophan residues. The decay of this emission band is a direct evidence for interaction of this Zn(lI) compound with residues of aromatic amino acids present in photosynthetic centres of Chlorella vulgaris

  7. UNIFORM INFALL TOWARD THE COMETARY H II REGION IN THE G34.26+0.15 COMPLEX?

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Tie; Wu, Yuefang; Zhang, Huawei, E-mail: liutiepku@gmail.com, E-mail: ywu@pku.edu.cn [Department of Astronomy, Peking University, 100871 Beijing (China)

    2013-10-10

    Gas accretion is a key process in star formation. However, gas infall detections in high-mass, star-forming regions with high spatial resolution observations are rare. Here, we report the detection of gas infall toward a cometary ultracompact H II region ({sup C)} in the G34.26+0.15 complex. The observations were made with the IRAM 30 m, the James Clerk Maxwell Telescope 15 m telescope, and the Submillimeter Array (SMA). The hot core associated with 'C' has a mass of ∼76 ± 11 M{sub ☉} and a volume density of (1.1 ± 0.2) × 10{sup 8} cm{sup –3}. The HCN (3-2) and HCO{sup +} (1-0) lines observed by single dishes and the CN (2-1) lines observed by the SMA show redshifted absorption features, indicating gas infall. We found a linear relationship between the line width and optical depth of the CN (2-1) lines. Those transitions with larger optical depths and line widths have larger absorption areas. However, the infall velocities measured from different lines seem to be constant, indicating that the gas infall is uniform. We also investigated the evolution of gas infall in high-mass, star-forming regions. A tight relationship was found between the infall velocity and the total dust/gas mass. At stages prior to the hot core phase, the typical infall velocity and mass infall rate are ∼1 km s{sup –1} and ∼10{sup –4} M{sub ☉} yr{sup –1}, respectively. While in more evolved regions, the infall velocity and mass infall rates can reach as high as several km s{sup –1} and ∼10{sup –3}-10{sup –2} M{sub ☉} yr{sup –1}, respectively. Accelerated infall has been detected toward some hypercompact H II and ultracompact H II regions. However, the acceleration phenomenon is not seen in more evolved ultracompact H II regions (e.g., G34.26+0.15)

  8. Halide/pseudohalide complexes of cadmium(II) with benzimidazole: Synthesis, crystal structures and fluorescence properties

    Science.gov (United States)

    Zhao, Hai-Yan; Yang, Fu-Li; Li, Na; Wang, Xiao-Jing

    2017-11-01

    Two new dinuclear Cd(II) complexes, [CdL1Cl2]2·H2O (1) and [CdL1(N3)2]2·CH3OH (2) and one dicyanamide bridged one-dimensional polynuclear network [CdL1(μ1,5-dca)dca]n (3) of the potentially tridentate NNN-donor Schiff base 2-((1H-benzimidazol-2-yl-ethylimino)-methyl)pyridine (L1) and another dinucler Cd(II) complex [CdL2Cl(dca)]2 (4) of a similar NNN-donor Schiff base ligand 2-((1H-benzimidazol-2-yl-propylimino)-methyl)pyridine (L2), have been synthesized and characterized by elemental analyses, IR and single crystal X-ray crystallography. The ligands L1 and L2 are [1 + 1] condensation products of pyridine-2-carbaldehyde with 2-aminoethyl-1H-benzimidazole and 2-aminopropyl-1H-benzimidazole, respectively. In the complexes 1 and 4 the two Cd(II) centers are held together by the bridged chloride ligands, while in 2 the two Cd(II) centers are bridged by μ1,1-azide ions. Complex 3 has a one-dimensional infinite chain structure in which Cd(II) ions are bridged by single dicyanamide groups in end-to-end fashion. All the metal centers have a distorted octahedral geometry and H-bonding or π⋯π interactions are operative to bind the complex units in the solid state. Furthermore, these complexes have been investigated by thermogravimetric analyses and fluorescence spectra.

  9. Comparative studies on P-vanillin and O-vanillin of 2-hydrazinyl-2-oxo-N-phenylacetamide and their Mn(II) and Co(II) complexes

    Science.gov (United States)

    Yousef, T. A.; El-Reash, G. M. Abu; El-Tabai, M. N.

    2018-05-01

    Synthesis of complexes derived from hydrazones derived from both P-vanillin (H2L1) and its isomer O-vanillin (H2L2) of 2-hydrazinyl-2-oxo-N-phenylacetamide that coordinated with high magnetic metal ions of both Mn(II) and Co(II) were performed and characterized by different physicochemical methods, elemental analysis, (1H NMR, IR, and UV-visible spectra), also thermal analysis (TG and DTG) techniques and magnetic measurements. The molecular structures of the ligands and their Mn(II) and Co(II) complexes were optimized theoretically and the quantum chemical parameters were calculated. IR spectra suggest that the H2L1 behaved in a mononegative bidentate manner with both but H2L2 coordinated as mononegative tridentate with both Mn(II) and Co(II). The electronic spectra of the complexes as well as their magnetic moments suggested octahedral geometries for all the isolated complexes. The calculated values of binding energies indicated the stability of complexes is higher than that of ligand. The kinetic and thermodynamic parameters for the different decomposition steps in complexes were calculated using Coats-Redfern and Horowitz-Metzger equations. Moreover, the prepared ligands and their Mn(II) and Co(II) complexes were individually tested against a panel of gram positive Bacillus Subtilis and negative Escherichia coli microscopic organisms. Additionally cytotoxicity assay of two human tumor cell lines namely; hepatocellular carcinoma (liver) HePG-2, and mammary gland (breast) MCF-7 were tested.

  10. Synthesis and Characterization of the Adducts of Morpholinedithioccarbamate Complexes of Oxovanadium (IV, Nickel(II, and Copper(II with Piperidine and Morpholine

    Directory of Open Access Journals (Sweden)

    Mousami Sharma

    2012-01-01

    Full Text Available A series of 1:1 adducts of bis(morpholinedithiocarbamato complex of VO(IV, 1:1 and 1:2 adducts of bis(morpholinedithiocarbamato complexes of Ni(II and Cu(II with piperidine and morpholine have been synthesized and characterized by elemental analysis, molar conductance, magnetic susceptibility, IR, UV-Vis, and TGA/DTA techniques. Analytical data reveals that VO(IV complex forms only 1:1 adducts with the formula [VO(morphdtc2L].H2O while Ni(II and Cu(II complexes form both 1:1 and 1:2 adducts with 1:1 adducts having general formula Ni(morphdtc2.L and Cu(morphdtc2.L and 1:2 adducts having general formula Ni(morphdtc2.L2 and Cu(morphdtc2.L2 (morphdtc = morpholinedithiocarbamate, L = morpholine and piperidine. Antifungal activity of some complexes has been carried out against the fungal strain Fusarium oxysporium. Thermal studies indicate a continuous weight loss. A square pyramidal geometry has been proposed for the 1:1 adducts of Ni(II and Cu(II complexes while an octahedral geometry has been proposed for the 1:1 adducts of VO(IV and for the 1:2 adducts of Ni(II and Cu(II complexes.

  11. Cycloplatinated(II) complexes containing bridging bis(diphenylphosphino)acetylene: Photophysical study

    Energy Technology Data Exchange (ETDEWEB)

    Jamshidi, Mahboubeh [Department of Chemistry, College of Sciences, Shiraz University, Shiraz 71467-13565 (Iran, Islamic Republic of); Nabavizadeh, S. Masoud, E-mail: nabavizadeh@shirazu.ac.ir [Department of Chemistry, College of Sciences, Shiraz University, Shiraz 71467-13565 (Iran, Islamic Republic of); Sepehrpour, Hajar [Department of Chemistry, College of Sciences, Shiraz University, Shiraz 71467-13565 (Iran, Islamic Republic of); Hosseini, Fatemeh Niroomand [Department of Chemistry, Shiraz Branch, Islamic Azad University, Shiraz 71993-37635 (Iran, Islamic Republic of); Kia, Reza [Department of Chemistry, Sharif University of Technology, Tehran 11155-3516 (Iran, Islamic Republic of); Rashidi, Mehdi, E-mail: rashidi@chem.susc.ac.ir [Department of Chemistry, College of Sciences, Shiraz University, Shiraz 71467-13565 (Iran, Islamic Republic of)

    2016-11-15

    Reaction of the known cycloplatinated (II) complexes [PtAr(C^N)(SMe{sub 2})], in which Ar=p–MeC{sub 6}H{sub 4} or p–MeOC{sub 6}H{sub 4} and C^N= 2-phenylpyridinate (ppy) or benzo[h]quinolinate (bhq), with 0.5 equivalent of the bidentate phosphine ligand 1,1′–bis(diphenylphosphino)acetylene, dppac, in acetone at room temperature gave the symmetrical binuclear cycloplatinated(II) complexes [Pt{sub 2}Ar{sub 2}(C^N){sub 2}(μ–dppac)], 1–4, in which dppac acts as a bridging bidentate ligand. All the complexes were fully characterized using multinuclear ({sup 1}H, {sup 31}P and {sup 195}Pt) NMR spectroscopy and the complex [Pt{sub 2}(p–MeC{sub 6}H{sub 4}){sub 2}(ppy){sub 2}(μ–dppac)], 1, was further identified by single crystal X-ray structure determination. Additional information about the geometries and electronic spectra of these cycloplatinated (II) complexes are discussed. Effects of aryl and C^N ligands on the luminescent properties of the complexes were also investigated that are complying well with the related DFT/TD-DFT calculations.

  12. Architecture of the RNA polymerase II-Mediator core initiation complex.

    Science.gov (United States)

    Plaschka, C; Larivière, L; Wenzeck, L; Seizl, M; Hemann, M; Tegunov, D; Petrotchenko, E V; Borchers, C H; Baumeister, W; Herzog, F; Villa, E; Cramer, P

    2015-02-19

    The conserved co-activator complex Mediator enables regulated transcription initiation by RNA polymerase (Pol) II. Here we reconstitute an active 15-subunit core Mediator (cMed) comprising all essential Mediator subunits from Saccharomyces cerevisiae. The cryo-electron microscopic structure of cMed bound to a core initiation complex was determined at 9.7 Å resolution. cMed binds Pol II around the Rpb4-Rpb7 stalk near the carboxy-terminal domain (CTD). The Mediator head module binds the Pol II dock and the TFIIB ribbon and stabilizes the initiation complex. The Mediator middle module extends to the Pol II foot with a 'plank' that may influence polymerase conformation. The Mediator subunit Med14 forms a 'beam' between the head and middle modules and connects to the tail module that is predicted to bind transcription activators located on upstream DNA. The Mediator 'arm' and 'hook' domains contribute to a 'cradle' that may position the CTD and TFIIH kinase to stimulate Pol II phosphorylation.

  13. Adsorption of lead(II) and copper(II) on activated carbon by complexation with surface functional groups

    International Nuclear Information System (INIS)

    Pesavento, Maria; Profumo, Antonella; Alberti, Giancarla; Conti, Fabio

    2003-01-01

    The adsorption of lead(II) and copper(II) on an activated carbon (Filtrasorb 300, Chemviron) was characterized assuming that it takes place by formation of complexes with functional groups, present in the activated carbon. Their concentration and conditional adsorption coefficients were determined for each metal by titration of the carbon in suspension in aqueous phase, at constant acidity, with the metal itself. For each titration point, the concentration of the metal in the solution phase after equilibration was determined, and the data were processed by the Ruzic linearization method, to obtain the concentration of the active sites involved in the sorption, and the conditional constant. The effect of the pH was also examined, in the range 4-6, obtaining that the adsorption increases at increasing pH. The protonation and adsorption constants were determined from the conditional adsorption coefficients obtained at the different acidities. The concentration of the active sites is 0.023 and 0.042 mmol g -1 , and the protonation constants are 1.0x10 6 and 4.6x10 4 M -1 for Pb(II) and Cu(II). The corresponding adsorption constants are respectively 1.4x10 5 and 6.3x10 3 M -1 . All the parameters are affected by a large uncertainty, probably due to the heterogeneity of the active groups in the activated carbon. Even if so, these parameters make it possible a good prediction of the adsorption in a wide range of conditions. Other sorption mechanism can be set up at different conditions, in particular at different pH, as it has been demonstrated in the case of copper(II)

  14. Adsorption of lead(II) and copper(II) on activated carbon by complexation with surface functional groups

    Energy Technology Data Exchange (ETDEWEB)

    Pesavento, Maria; Profumo, Antonella; Alberti, Giancarla; Conti, Fabio

    2003-03-17

    The adsorption of lead(II) and copper(II) on an activated carbon (Filtrasorb 300, Chemviron) was characterized assuming that it takes place by formation of complexes with functional groups, present in the activated carbon. Their concentration and conditional adsorption coefficients were determined for each metal by titration of the carbon in suspension in aqueous phase, at constant acidity, with the metal itself. For each titration point, the concentration of the metal in the solution phase after equilibration was determined, and the data were processed by the Ruzic linearization method, to obtain the concentration of the active sites involved in the sorption, and the conditional constant. The effect of the pH was also examined, in the range 4-6, obtaining that the adsorption increases at increasing pH. The protonation and adsorption constants were determined from the conditional adsorption coefficients obtained at the different acidities. The concentration of the active sites is 0.023 and 0.042 mmol g{sup -1}, and the protonation constants are 1.0x10{sup 6} and 4.6x10{sup 4} M{sup -1} for Pb(II) and Cu(II). The corresponding adsorption constants are respectively 1.4x10{sup 5} and 6.3x10{sup 3} M{sup -1}. All the parameters are affected by a large uncertainty, probably due to the heterogeneity of the active groups in the activated carbon. Even if so, these parameters make it possible a good prediction of the adsorption in a wide range of conditions. Other sorption mechanism can be set up at different conditions, in particular at different pH, as it has been demonstrated in the case of copper(II)

  15. Ruthenium(II) bipyridine complexes bearing quinoline-azoimine (NN'N″) tridentate ligands: synthesis, spectral characterization, electrochemical properties and single-crystal X-ray structure analysis.

    Science.gov (United States)

    Al-Noaimi, Mousa; Abdel-Rahman, Obadah S; Fasfous, Ismail I; El-khateeb, Mohammad; Awwadi, Firas F; Warad, Ismail

    2014-05-05

    Four octahedral ruthenium(II) azoimine-quinoline complexes having the general molecular formula [Ru(II)(L-Y)(bpy)Cl](PF6) {L-Y=YC6H4N=NC(COCH3)=NC9H6N, Y=H (1), CH3 (2), Br (3), NO2 (4) and bpy=2,2'-bipyrdine} were synthesized. The azoimine-quinoline based ligands behave as NN'N″ tridentate donors and coordinated to ruthenium via azo-N', imine-N' and quinolone-N″ nitrogen atoms. The composition of the complexes has been established by elemental analysis, spectral methods (FT-IR, electronic, (1)H NMR, UV/Vis and electrochemical (cyclic voltammetry) techniques. The crystal structure of complex 1 is reported. The Ru(II) oxidation state is greatly stabilized by the novel tridentate ligands, showing Ru(III/II) couples ranging from 0.93-1.27 V vs. Cp2Fe/Cp2Fe(+). The absorption spectrum of 1 in dichloromethane was modeled by time-dependent density functional theory (TD-DFT). Copyright © 2014 Elsevier B.V. All rights reserved.

  16. Synthesis, crystal structure and excellent photoluminescence properties of copper (II and cobalt (II complexes with Bis(1[(4-butylphenylimino]methyl naphthalen-2-ol Schiff base

    Directory of Open Access Journals (Sweden)

    V.B. Nagaveni

    2018-03-01

    Full Text Available Copper (II and Cobalt (II metal complexes (4a- and 4b-complexes using Schiff base ligand 1-[(4-butylphenylimino]methyl naphthalen-2-ol (3 have been synthesized. The single crystals of Copper (II and Cobalt (II complex phosphors were grown and characterized by Fourier-Transform Infrared (FT-IR, single crystal X-ray diffraction (XRD, SEM (Scanning Electron Microscope and EDS (Energy Dispersive X-ray spectroscopy. Photoluminescence study of the phosphors revealed the presence of excitation peaks at 333 nm and 360 nm for 4a-complex (λemi = 495 nm and excitation peaks at 300 nm and 360 nm for 4b-complex (λemi = 496 nm. The calculated CCT values of the complexes pointed out that these materials can be used to obtain cold white light from the light emitting devices. Diffuse reflectance spectra (DRS showed the measured band gap energies of 1.78 eV and 1.44 eV for Cu (II and Co (II complexes, respectively. It is concluded that the 4a- and 4b-complexes become white and blue green light emitting diodes respectively and will be useful in the development of strong electroluminescent materials. Keywords: 1[(4-butylphenylimino]methylnaphthalen-2-ol, Schiff base, Cu (II and Co (IIcomplex, Photoluminescence, Single crystal XRD, OLED

  17. Microwave assisted synthesis, spectral, magnetic and bioevolution of few Mn (II)-amide complexes

    Energy Technology Data Exchange (ETDEWEB)

    Joshi, Gaurav [Department of Chemistry, Govt. Engineering College, Bikaner (India); Verma, K. K.; Gudesaria, D. D.; Bhojak, N., E-mail: drbhojak@rediffmail.com [GCRC, Department of Chemistry, Govt Dungar College, Bikaner-334003, Rajasthan (India)

    2016-05-06

    The importance and versatility of amide group containing ligands have promoted the selection of this class of ligands and their complexes for the study. The present work describes the synthesis, spectral and biological investigations on the complexes of amides derived from heterocyclic amines with Mn (II) ions. Four ligands derived 2-aminopyridine and their complexes with Mn (II) have been synthesized. A method for the synthesis of complexes has been developed by the use of microwave irradiation which is in agreement to Green chemistry approach. The complexes have been characterized on the basis of elemental analysis, infrared, electronic, ESR spectra and magnetic susceptibility studies. The diffuse reflectance spectrum of the complexes show bands in the region 20,000 cm{sup −1} to 26,000 cm{sup −1} assignable to {sup 6}A{sub 1g} → {sup 4}T{sub 2g} and {sup 6}A{sub 1g} → {sup 4}E{sub 1g} transitions. These are also typical of tetrahedral environment around the manganese. The magnetic moment (5.80 BM) of the complex indicates high spin tetrahedral environment. The microwave method of synthesis of complexes have been found easier, convenient and ecofriendly. Antimicrobial activities of compounds were also carried out against bacteria and fungi. Further minimal inhibitory concentration (MIC) was also determined for each compound.

  18. Photodynamic effect of light-harvesting, long-lived triplet excited state Ruthenium(II)-polyimine-coumarin complexes: DNA binding, photocleavage and anticancer studies.

    Science.gov (United States)

    Nomula, Raju; Wu, Xueyan; Zhao, Jianzhang; Munirathnam, Nagegownivari R

    2017-10-01

    Two coumarin based Ru II -polyimine complexes (Ru-1 and Ru-2) showing intense absorption of visible light and long-lived triplet excited states (~12-15μs) were used for study of the interaction with DNA. The binding of the complexes with CT-DNA were studied by UV-vis, fluorescence and time-resolved nanosecond transient absorption (ns-TA) spectroscopy. The results suggesting that the complexes interact with CT-DNA by intercalation mode of binding, showing the binding constants (K b ) 6.47×10 4 for Ru-1 and 5.94×10 4 M -1 for Ru-2, in contrast no such results were found for Ru-0. The nanosecond transient absorption spectra of these systems in the presence of CT-DNA showing a clear perturbation in the bleaching region was observed compare to buffer alone. Visible light photoirradiation DNA cleavage was investigated for these complexes by treating with the supercoiled pUC19 DNA and irradiated at 450nm. The reactive species produced upon irradiation of current agents is singlet oxygen ( 1 O 2 ), which results in the generation of other reactive oxygen species (ROS). The complexes shown efficient cleavage activity, converted complete supercoiled DNA to nicked circular at as low as 20μM concentration in 30min of light irradiation time. Significant amount of linear form was generated by Ru-1 at the same conditions. Even though Ru-0 has significant 1 O 2 quantum yield but shown lower cleavage activity compared to other two analogs is due the miserable interaction (binding) with DNA. The cytotoxicity in vitro of the complexes toward HeLa, BEL-7402 and MG-63 cells was assessed by MTT assay. The cellular uptake was observed on BEL-7402 cells under fluorescence microscope. The complexes shown appreciable cytotoxicity towards the cancer cell lines. Copyright © 2017 Elsevier B.V. All rights reserved.

  19. Copper(II)–imida‐salen Complexes Encapsulated into NaY Zeolite for Oxidations Reactions

    DEFF Research Database (Denmark)

    Kuźniarska‐Biernacka, Iwona; Carvalho, M. Alice; Rasmussen, Søren Birk

    2013-01-01

    The oxidation of phenol, cychohexanol and hydroquinone has been screened in the presence of copper(II) complexes with the Schiff‐base salen ligand, 1,5‐bis[(E)‐5‐chloro‐2‐hydroxybenzylideneamino]‐1H‐imidazole‐4‐carbonitrile, and encapsulated into NaY zeolite by using two different methods. The new...

  20. Photoenhanced Oxidative DNA Cleavage with Non-Heme Iron(II) Complexes

    NARCIS (Netherlands)

    Li, Qian; Browne, Wesley R.; Roelfes, Gerard

    2010-01-01

    The DNA cleavage activity of iron(II) complexes of a series of monotopic pentadentate N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine (N4Py)-derived ligands (1-5) was investigated under laser irradiation at 473, 400.8, and 355 nm in the absence of a reducing agent and compared to that under

  1. CD1 and major histocompatibility complex II molecules follow a different course during dendritic cell maturation

    NARCIS (Netherlands)

    van der Wel, Nicole N.; Sugita, Masahiko; Fluitsma, Donna M.; Cao, Xaiochun; Schreibelt, Gerty; Brenner, Michael B.; Peters, Peter J.

    2003-01-01

    The maturation of dendritic cells is accompanied by the redistribution of major histocompatibility complex (MHC) class II molecules from the lysosomal MHC class IT compartment to the plasma membrane to mediate presentation of peptide antigens. Besides MHC molecules, dendritic cells also express CD1

  2. Plants lacking the main light-harvesting complex retain photosystem II macro-organization

    NARCIS (Netherlands)

    Ruban, A.V.; Wentworth, M.; Yakushevska, A.E.; Andersson, J.; Lee, P.J.; Keegstra, W.; Dekker, J.P.; Boekema, E.J.; Jansson, S.; Horton, P.

    2003-01-01

    Photosystem II (PSII) is a key component of photosynthesis, the process of converting sunlight into the chemical energy of life. In plant cells, it forms a unique oligomeric macrostructure in membranes of the chloroplasts. Several light-harvesting antenna complexes are organized precisely in the

  3. Plants lacking the main light-harvesting complex retain photosystem II macro-organization

    NARCIS (Netherlands)

    Ruban, AV; Wentworth, M; Yakushevska, AE; Andersson, J; Lee, PJ; Keegstra, W; Dekker, JP; Boekema, EJ; Jansson, S; Horton, P

    2003-01-01

    Photosystem II (PSII) is a key component of photosynthesis, the process of converting sunlight into the chemical energy of life. In plant cells, it forms a unique oligomeric macrostructure in membranes of the chloroplasts(1). Several light-harvesting antenna complexes are organized precisely in the

  4. A saponification-triggered gelation of ester-based Zn(II) complex through conformational transformations.

    Science.gov (United States)

    Kumar, Ashish; Dubey, Mrigendra; Kumar, Amit; Pandey, Daya Shankar

    2014-09-11

    Novel saponification-triggered gelation in an ester-based bis-salen Zn(II) complex (1) is described. Strategic structural modifications induced by NaOH in 1 tune the dipolar-/π-interactions leading to J-aggregation and the creation of an inorganic gel material (IGM), which has been established by photophysical, DFT and rheological studies.

  5. Mixed-ligand complexes of ruthenium(II) incorporating a diazo ...

    Indian Academy of Sciences (India)

    Unknown

    Dedicated to the memory of the late Professor Bhaskar G Maiya. *For correspondence. Mixed-ligand complexes of ruthenium(II) incorporating a diazo ligand: Synthesis .... water (1 : 1) for 5 h to give a dark red solution. The solution was cooled to room temperature. After eva- poration of the solvent, the solid was collected,.

  6. C60 Recognition from Extended Tetrathiafulvalene Bis-acetylide Platinum(II) Complexes.

    Science.gov (United States)

    Bastien, Guillaume; Dron, Paul I; Vincent, Manon; Canevet, David; Allain, Magali; Goeb, Sébastien; Sallé, Marc

    2016-11-18

    The favorable spatial organization imposed by the square planar 4,4'-di(tert-butyl)-2,2'-bipyridine (dbbpy) platinum(II) complex associated with the electronic and shape complementarity of π-extended tetrathiafulvalene derivatives (exTTF) toward fullerenes is usefully exploited to construct molecular tweezers, which display good affinities for C 60 .

  7. Evaluating the response of complex systems to environmental threats: the Σ II method

    International Nuclear Information System (INIS)

    Corynen, G.C.

    1983-05-01

    The Σ II method was developed to model and compute the probabilistic performance of systems that operate in a threatening environment. Although we emphasize the vulnerability of complex systems to earthquakes and to electromagnetic threats such as EMP (electromagnetic pulse), the method applies in general to most large-scale systems or networks that are embedded in a potentially harmful environment. Other methods exist for obtaining system vulnerability, but their complexity increases exponentially as the size of systems is increased. The complexity of the Σ II method is polynomial, and accurate solutions are now possible for problems for which current methods require the use of rough statistical bounds, confidence statements, and other approximations. For super-large problems, where the costs of precise answers may be prohibitive, a desired accuracy can be specified, and the Σ II algorithms will halt when that accuracy has been reached. We summarize the results of a theoretical complexity analysis - which is reported elsewhere - and validate the theory with computer experiments conducted both on worst-case academic problems and on more reasonable problems occurring in practice. Finally, we compare our method with the exact methods of Abraham and Nakazawa, and with current bounding methods, and we demonstrate the computational efficiency and accuracy of Σ II

  8. NHC Versus Pyridine: How “Teeth” Change the Redox Behavior of Iron(II) Complexes

    KAUST Repository

    Weiss, Daniel T.; Anneser, Markus R.; Haslinger, Stefan; Pö thig, Alexander; Cokoja, Mirza; Basset, Jean-Marie; Kü hn, Fritz E.

    2015-01-01

    A series of octahedral iron(II) complexes with tetradentate NHC/pyridine hybrid ligands containing up to three pyridyl units was designed to study the influence of NHC and pyridine donors on the electronic structure of the metal center. Structural

  9. Lipids in the Structure of Photosystem I, Photosystem II and the Cytochrome b6f Complex

    NARCIS (Netherlands)

    Kern, Jan; Zouni, Athina; Guskov, Albert; Krauss, Norbert; Wada, Hajime; Murata, Norio

    2009-01-01

    This chapter describes the data accumulated in the last decade regarding the specific function of lipids in oxygenic photosynthesis, based on crystal structures of at least 3.0 Å resolution of the main photosynthetic membrane protein—pigment complexes, photosystem I, photosystem II and cytochrome

  10. Carotenoid-binding sites of the major light-harvesting complex II of higher plants

    NARCIS (Netherlands)

    Croce, Roberta; Weiss, Saskia; Bassi, Roberto

    1999-01-01

    Recombinant light-harvesting complex II (LHCII) proteins with modified carotenoid composition have been obtained by in vitro reconstitution of the Lhcb1 protein overexpressed in bacteria. The monomeric protein possesses three xanthophyll-binding sites. The L1 and L2 sites, localized by electron

  11. Pigment binding sites occupancy and functional architecture of the Photosystem II antenna complex Lhcb5

    NARCIS (Netherlands)

    Ballottari, M.; Mozzo, M.; Croce, R.; Morosinotto, T.; Bassi, R.

    2009-01-01

    Lhcb5 is an antenna protein that is highly conserved in plants and green algae. It is part of the inner layer of photosystem II antenna system retained in high light acclimated plants. To study the structure-function relation and the role of individual pigments in this complex, we (i) "knocked out"

  12. Some thiocyanato complexes of cadmium(II) with substituted pyridines and imidazoles

    Energy Technology Data Exchange (ETDEWEB)

    Mishra, B P; Ramana Rao, D V [Regional Engineering Coll., Rourkela (India). Dept. of Chemistry

    1979-05-01

    The complexes formed by cadmium(II) thiocyanate with 3-acetyl-, 3-bromo-, 3-methyl-, 4-acetyl-, 4-cyano-, 4-benzoyl pyridines, isoquinoline, 3,5-lutidine and imidazole, 2-methyl imidazole, 2-methyl benzimidazoles have been characterised through elemental analysis and molar conductance data. On the basis of infra-red spectroscopic studies, probable structures are discussed.

  13. Study of the emission oxidative reactions of ruthenium (II) complex by cationic compounds in anionic micelles

    International Nuclear Information System (INIS)

    Bonilha, J.B.S.

    1985-01-01

    The oxidative quenching of the emission of the tetraanionic complex tris (4,4' dicarboxylate - 2,2' - bipyridine ruthenium (II) in aqueous solution, by both organic and inorganic compounds in presence of anionic detergents, above and below the critical micelle concentration is studied. The organic cations, the inorganic ion and detergents used are shown. (M.J.C.) [pt

  14. Synthesis and properties of a trinuclear copper(II) complex with trithiocyanurate bridge

    Czech Academy of Sciences Publication Activity Database

    Kopel, P.; Čermáková, Š.; Doležal, Karel; Kalińska, B.; Bieńko, A.; Mroziński, J.

    2007-01-01

    Roč. 81, č. 3 (2007), s. 327-335 ISSN 0137- 5083 Institutional research plan: CEZ:AV0Z50380511 Keywords : copper(II) * trithiocyanuric acid complexes * magnetic properties Subject RIV: CA - Inorganic Chemistry Impact factor: 0.483, year: 2007 http://ichf.edu.pl/pjch/pj-2007/pj-2007-03a.pdf

  15. Spectrophotometric Determination of Metoprolol Tartrate in Pharmaceutical Dosage Forms on Complex Formation with Cu(II

    Directory of Open Access Journals (Sweden)

    Mustafa Cesme

    2011-06-01

    Full Text Available A new, simple, sensitive and accurate spectrophotometric method has been developed for the assay of metoprolol tartrate (MPT, which is based on the complexation of drug with copper(II [Cu(II] at pH 6.0, using Britton-Robinson buffer solution, to produce a blue adduct. The latter has a maximum absorbance at 675 nm and obeys Beer’s law within the concentration range 8.5-70 mg/mL. Regression analysis of the calibration data showed a good correlation coefficient (r = 0.998 with a limit of detection of 5.56 mg/mL. The proposed procedure has been successfully applied to the determination of this drug in its tablets. In addition, the spectral data and stability constant for the binuclear copper(II complex of MPT (Cu2MPT2Cl2 have been reported.

  16. One-Pot Synthesis of Cu(II Complex with Partially Oxidized TTF Moieties

    Directory of Open Access Journals (Sweden)

    Hiroki Oshio

    2012-07-01

    Full Text Available The one-pot synthesis of a Cu(II complex with partially oxidized tetrathiafulvalene (TTF moieties in its capping MT-Hsae-TTF ligands, [CuII(MT-sae-TTF2] [CuICl2] was realized by the simultaneous occurrence of Cu(II complexation and CuIICl2 mediated oxidation of TTF moieties. The crystal structure was composed of one-dimensional columns formed by partially oxidized TTF moieties and thus the cation radical salt showed relatively high electrical conductivity. Tight binding band structure calculations indicated the existence of a Peierls gap due to the tetramerization of the TTF moieties in the one-dimensional stacking column at room temperature, which is consistent with the semiconducting behavior of this salt.

  17. Preparations and characterization of some carbonyl-(1-cyanoethyl)ruthenium(II) complexes

    Energy Technology Data Exchange (ETDEWEB)

    Hiraki, Katsuma; Ochi, Naoyuki; Kitamura, Tsuneyuki; Sasada, Yoko [Nagasaki Univ. (Japan); Shinoda, Sumio

    1982-08-01

    A hydridoruthenium(II) complex (RuClH(CO)(PPh/sub 3/)/sub 3/) reacted easily with acrylonitrile and fumaronitrile to give chloro-bridged binuclear (1-cyanoethyl)ruthenium(II) complexes, ((Ru(MeCHCN)Cl(CO)(PPh/sub 3/)/sub 2/)/sub 2/) (2) and ((Ru(NCCH/sub 2/CHCN)Cl(CO)(PPh/sub 3/)/sub 2/)/sub 2/), respectively. Complex 2 reacted with 4-picoline (pic), Na(BHPz/sub 3/) (Pz = 1-pyrazolyl), Na(BPz/sub 4/), and Na(Et/sub 2/NCS/sub 2/).3H/sub 2/O to afford the corresponding (1-cyanoethyl)ruthenium(II) complexes, ((Ru(MeCHCN)Cl(CO)(pic)(PPh/sub 3/))/sub 2/) (3), (Ru(MeCHCN)(BHPz/sub 3/)(CO)(PPh/sub 3/)) (accompanied by a small amount of (Ru/sub 2/(MeCHCN)/sub 2/Cl(BHPz/sub 3/)(CO)/sub 2/(PPh/sub 3/)/sub 4/)), (Ru/sub 2/(MeCHCN)/sub 2/Cl(BPz/sub 4/)(CO)/sub 2/(PPh/sub 3/)/sub 2/), and Na(Ru(MeCHCN)Cl(Et/sub 2/NCS/sub 2/)(CO)(PPh/sub 3/)), respectively. Complex 3 reacted with thallium (I) acetylacetonate (Tl(acac)), resulting in the formation of ((Ru(MeCHCN)(acac)(CO)(PPh/sub 3/))/sub 2/) and (Ru(MeCHCN)(acad)(CO)(pic)(PPh/sub 3/)). These new complexes were characterized by means of elemental analysis and spectroscopic data. The diastereoisomerism was also discussed as regards these (1-cyanoethyl)ruthenium(II) complexes.

  18. Flame atomic absorption spectrometric determination of heavy metals in aqueous solution and surface water preceded by co-precipitation procedure with copper(II) 8-hydroxyquinoline

    Science.gov (United States)

    Ipeaiyeda, Ayodele Rotimi; Ayoade, Abisayo Ruth

    2017-12-01

    Co-precipitation procedure has widely been employed for preconcentration and separation of metal ions from the matrices of environmental samples. This is simply due to its simplicity, low consumption of separating solvent and short duration for analysis. Various organic ligands have been used for this purpose. However, there is dearth of information on the application of 8-hydroxyquinoline (8-HQ) as ligand and Cu(II) as carrier element. The use of Cu(II) is desirable because there is no contamination and background adsorption interference. Therefore, the objective of this study was to use 8-HQ in the presence of Cu(II) for coprecipitation of Cd(II), Co(II), Cr(III), Ni(II) and Pb(II) from standard solutions and surface water prior to their determinations by flame atomic absorption spectrometry (FAAS). The effects of pH, sample volume, amount of 8-HQ and Cu(II) and interfering ions on the recoveries of metal ions from standard solutions were monitored using FAAS. The water samples were treated with 8-HQ under the optimum experimental conditions and metal concentrations were determined by FAAS. The metal concentrations in water samples not treated with 8-HQ were also determined. The optimum recovery values for metal ions were higher than 85.0%. The concentrations (mg/L) of Co(II), Ni(II), Cr(III), and Pb(II) in water samples treated with 8-HQ were 0.014 ± 0.002, 0.03 ± 0.01, 0.04 ± 0.02 and 0.05 ± 0.02, respectively. These concentrations and those obtained without coprecipitation technique were significantly different. Coprecipitation procedure using 8-HQ as ligand and Cu(II) as carrier element enhanced the preconcentration and separation of metal ions from the matrix of water sample.

  19. Expression of major histocompatibility complex class II and costimulatory molecules in oral carcinomas in vitro.

    Science.gov (United States)

    Villarroel-Dorrego, Mariana; Speight, Paul M; Barrett, A William

    2005-01-01

    Recognition in the 1980 s that keratinocytes can express class II molecules of the Major Histocompatibility Complex (MHC) first raised the possibility that these cells might have an immunological function, and may even act as antigen presenting cells (APC). For effective T lymphocyte activation, APC require, in addition to MHC II, appropriate costimulatory signals. The aim of this study was to determine the expression of MHC class II and the co-stimulatory molecules CD40, CD80 and CD86 in keratinocytes derived from healthy oral mucosa and oral carcinomas. Using flow cytometry, it was confirmed that oral keratinocytes, switch on, expression of MHC class II molecules after stimulation with IFNgamma in vitro. All keratinocyte lines expressed CD40 constitutively; by contrast, CD80 and CD86 were universally absent. Loss of CD80 and CD86 may be one means whereby tumours escape immunological surveillance.

  20. Organometallic complexes of thiocarbanilides and substituted thiocarbanilides using manganese (II) chloride

    International Nuclear Information System (INIS)

    Babiker, Musa Elaballa Mohamed

    2000-01-01

    Organo-metallic complexes of substituted thiocarbanilide using manganese (II) chloride were prepared, these are: (VIII) 3:3'-Dichloro thiocarbanilide. Manganese (II) chloride. (IX) 3:3'-Dimethyl thiocarbanilide. Manganese (II) chloride. (X) 2:2'-dimethyl thiocarbanilide. Manganese (II) chloride. These compounds are coloured, soluble in most organic solvents, insoluble in water, decomposed by hot solvents. The physical properties of compounds (IX) and (X) were studied by UV and IR spectra, and the physical properties of compound (VIII) were studied by UV, IR, mass spectra and NMR. The molecular weight of the compound (VIII) was determined by three different methods; Rast's camphor method, mass spectra and the nitrogen contents. The stoichiometry of the reaction was found to be 2:1, and the coordination is from sulphur atom more than nitrogen.(Author)

  1. New bioactive silver(I) complexes: Synthesis, characterization, anticancer, antibacterial and anticarbonic anhydrase II activities

    Science.gov (United States)

    Ozdemir, Ummuhan O.; Ozbek, Neslihan; Genc, Zuhal Karagoz; İlbiz, Firdevs; Gündüzalp, Ayla Balaban

    2017-06-01

    Silver(I) complexes of alkyl sulfonic acide hydrazides were newly synthesized as homologous series. Methanesulfonic acide hydrazide (L1), ethanesulfonic acide hydrazide (L2), propanesulfonic acide hydrazide (L3) and butanesulfonic acide hydrazide (L4) were used for complexation with Ag(I) ions. The silver complexes obtained in the mol ratio of 1:2 have the structural formula as Ag(L1)2NO3 (I), Ag(L2)2NO3 (II), Ag(L3)2NO3(III), (Ag(L4)2NO3 (IV). The Ag(I) complexes exhibit distorted linear two-fold coordination in [AgL2]+ cations with uncoordinated nitrates. Ligands are chelated with silver(I) ions through unsubstituted primary nitrogen in hydrazide group. Ag(I) complexes were characterized by using elemental analysis, spectroscopic methods (FT-IR, LC-MS), magnetic susceptibility and conductivity measurements. Silver(I) complexes were optimized using PBEPBE/LanL2DZ/DEF2SV basic set performed by DFT method with the Gaussian 09 program package. The geometrical parameters, frontier molecular orbitals (HOMOs and LUMOs) and molecular electrostatic potential (MEP) mapped surfaces of the optimized geometries were also determined by this quantum set. The anticancer activities of silver(I) complexes on MCF-7 human breast cancer cell line were investigated by comparing IC50 values. The antibacterial activities of complexes were studied against Gram positive bacteria; S. aureus ATCC 6538, B. subtilis ATCC 6633, B. cereus NRRL-B-3711, E. faecalis ATCC 29212 and Gram negative bacteria; E. coli ATCC 11230, P. aeruginosa ATCC 15442, K. pneumonia ATCC 70063 by using disc diffusion method. The inhibition activities of Ag(I) complexes on carbonic anhydrase II enzyme (hCA II) were also investigated by comparing IC50 and Ki values. The biological activity screening shows that Ag(I) complex of butanesulfonicacidehydrazide (IV) has the highest activity against tested breast cancer cell lines MCF-7, Gram positive/Gram negative bacteria and carbonic anhydrase II (hCA II) isoenzyme.

  2. Synthesis, characterization and biological studies of 2-(4-nitro phenylaminocarbonyl)benzoic acid and its complexes with Cr(III), Co(II), Ni(II), Cu(II) and Zn(II)

    International Nuclear Information System (INIS)

    Aqeel Ashraf, M.; Jamil Maah, M.; Yusuf, I.

    2012-01-01

    Cr(III), Co(II), Ni(II), Cu(II) and Zn(II) salts of 2-(4-nitro phenylaminocarbonyl)benzoic acid were characterized by physical, analytical and spectroscopic studies and checked for their in-vitro antimicrobial activity against three bacterial strains, Mycobacterium smegmatis (Gram +ve), Escherichia coli (Gram -ve), Pseudomonas aeuroginosa (Gram -ve) and three fungal strains, Nigrospora oryzae, Aspergillus niger and Candida albicans. The antimicrobial activities of the metal complexes - were found to be greater than those of 2-(4-nitro phenylaminocarbonyl)benzoic acid alone.

  3. NMR investigation of dynamic processes in complexes of nickel(II) and zinc(II) with iminodiacetate, n-methyliminodiacetate and n-ethyliminodiacetate

    International Nuclear Information System (INIS)

    Wagner, M.R.

    1985-11-01

    Analysis of oxygen-17 bulk water relaxation rates with an aqueous solution of 1:1 Ni(II):ida reveals that two rate-limiting processes are involved with solvent exchange. Analysis of carbon-13 longitudinal relaxation rates of the bis-ligand complexes with zinc(II) are used to determine molecular tumbling rates and methyl rotation rates. The carbon-13 transverse relaxation rates for the carbons in the bis-ligand complex with Ni(II) are adequately fitted to the Solomon-Bloembergen equation. Three carboxylate carbon peaks are seen with the 13 C spectrum of the 1:2 Ni(II):ida complex, which coalesce into a single peak above about 360 K. The mechanism and rate of ligand exchange are determined for the complexes Zn(II)L 2 -2 (L = mida, eida) in aqueous solution by total lineshape analysis of the proton spectrum at 500 MHz

  4. The synthesis and characterization of 1,2-dihydroxyimino-3,6-di-aza-8,9-O-iso-butylidene nonane and its complexes with Ni(II), Cu(II), Zn(II) and Cd(II)

    International Nuclear Information System (INIS)

    Canpolat, E.; Kaya, M.; Gorgulu, A.O.

    2002-01-01

    1,2-dihydroxyimino-3,6-di-aza-8,9-O-iso-butylidene nonane (H 2 L) was synthesized starting from 1,2-O-iso-butylidene-4-aza-6-amino hexane (RNH 2 ) and antichloroglyoxime. Ni(II) and Cu(II) complexes of H 2 L have a metal:ligand ratio 1:2 and the ligand coordinates through two N atoms, as do most of the vic-dioximes. However, Zn(II) and Cd(II) complexes of H 2 L have a metal: ligand ratio 1:1 and one chloride ion and one water molecule are also coordinated to the metal ion. Structures of the ligand and its transition-metal complexes are proposed, according to elemental analysis, IR, 13 C and 1 H NMR spectra, magnetic susceptibility measurements and thermogravimetric analyses (TGA). (author)

  5. Mechanisms of energy transfer and conversion in plant Light-Harvesting Complex II

    Energy Technology Data Exchange (ETDEWEB)

    Barros, Tiago Ferreira de

    2009-09-24

    The light-harvesting complex of photosystem II (LHC-II) is the major antenna complex in plant photosynthesis. It accounts for roughly 30% of the total protein in plant chloroplasts, which makes it arguably the most abundant membrane protein on Earth, and binds about half of plant chlorophyll (Chl). The complex assembles as a trimer in the thylakoid membrane and binds a total of 54 pigment molecules, including 24 Chl a, 18 Chl b, 6 lutein (Lut), 3 neoxanthin (Neo) and 3 violaxanthin (Vio). LHC-II has five key roles in plant photosynthesis. It: (1) harvests sunlight and transmits excitation energy to the reaction centres of photosystems II and I, (2) regulates the amount of excitation energy reaching each of the two photosystems, (3) has a structural role in the architecture of the photosynthetic supercomplexes, (4) contributes to the tight appression of thylakoid membranes in chloroplast grana, and (5) protects the photosynthetic apparatus from photo damage by non photochemical quenching (NPQ). A major fraction of NPQ is accounted for its energy-dependent component qE. Despite being critical for plant survival and having been studied for decades, the exact details of how excess absorbed light energy is dissipated under qE conditions remain enigmatic. Today it is accepted that qE is regulated by the magnitude of the pH gradient ({delta}pH) across the thylakoid membrane. It is also well documented that the drop in pH in the thylakoid lumen during high-light conditions activates the enzyme violaxanthin de-epoxidase (VDE), which converts the carotenoid Vio into zeaxanthin (Zea) as part of the xanthophyll cycle. Additionally, studies with Arabidopsis mutants revealed that the photosystem II subunit PsbS is necessary for qE. How these physiological responses switch LHC-II from the active, energy transmitting to the quenched, energy-dissipating state, in which the solar energy is not transmitted to the photosystems but instead dissipated as heat, remains unclear and is the

  6. Synthesis, Photophysical and Electrochemical Properties of a Mixed Bipyridyl-Phenanthrolyl Ligand Ru(II Heteroleptic Complex Having trans-2-Methyl-2-butenoic Acid Functionalities

    Directory of Open Access Journals (Sweden)

    Adewale O. Adeloye

    2011-09-01

    Full Text Available In this work, two ligands: 4-(trans-2-Methyl-2-butenoic acid-2,2'-bipyridine (L1 and 5-(trans-2-methyl-2-butenoic acid-1,10-phenanthroline (L2, with the corresponding mixed-ligand heteroleptic Ru(II complex were synthesized and characterized by FT-IR, 1H-, 13C-NMR spectroscopy and elemental analysis. The influence of the mixed functionalized polypyridyl ruthenium(II complex on the photophysical and electrochemical properties were investigated and compared to individual single-ligand homoleptic complexes. Interestingly, the mixed-ligand complex formulated as [RuL1L2(NCS2] exhibits broad and intense metal-to-ligand charge transfer (MLCT absorption with a high molar extinction coefficient (λmax = 514 nm, ε = 69,700 M−1 cm−1, better than those of individual single-ligand complexes, [Ru(L12(NCS2] and [Ru(L22(NCS2], and a strong photoluminescence intensity ratio in the red region at λem = 686 nm. The electrochemical properties of the complex indicated that the redox processes are ligand-based.

  7. Structural, spectral, DFT and biological studies on macrocyclic mononuclear ruthenium (II) complexes

    Science.gov (United States)

    Muthukkumar, M.; Kamal, C.; Venkatesh, G.; Kaya, C.; Kaya, S.; Enoch, Israel V. M. V.; Vennila, P.; Rajavel, R.

    2017-11-01

    Macrocyclic mononuclear ruthenium (II) complexes have been synthesized by condensation method [Ru (L1, L2, L3) Cl2] L1 = (C36 H31 N9), L2= (C42H36N8), L3= (C32H32 N8)]. These ruthenium complexes have been established by elemental analyses and spectroscopic techniques (Fourier transform infrared spectroscopy (FT-IR), 1H- nuclear magnetic resonance (NMR), 13C- NMR and Electrospray ionization mass spectrometry (ESI-MS)). The coordination mode of the ligand has been confirmed and the octahedral geometry around the ruthenium ion has been revealed. Binding affinity and binding mode of ruthenium (II) complexes with Bovine serum Albumin (BSA) have been characterized by Emission spectra analysis. UV-Visible and fluorescence spectroscopic techniques have also been utilized to examine the interaction between ligand and its complexes L1, L2, & L3 with BSA. Chemical parameters and molecular structure of Ru (II) complexes L1H, L2H, & L3H have been determined by DFT coupled with B3LYP/6-311G** functional in both the gaseous and aqueous phases.

  8. The electric and thermoelectric properties of Cu(II)-Schiff base nano-complexes

    Science.gov (United States)

    Ibrahim, E. M. M.; Abdel-Rahman, Laila H.; Abu-Dief, Ahmed M.; Elshafaie, A.; Hamdan, Samar Kamel; Ahmed, A. M.

    2018-05-01

    The physical properties, such as electric and optical properties, of metal-Schiff base complexes have been widely investigated. However, their thermoelectric (TE) properties remain unreported. This work presents Cu(II)-Schiff base complexes as promising materials for TE power generation. Therefore, three Cu(II)-Schiff base complexes (namely, [Cu(C32H22N4O2)].3/2H2O, [Cu(C23H17N4O7Br)], and [Cu(C27H22N4O8)].H2O) have been synthesized in nanosized scale. The electric and TE properties have been studied and comprehensive discussions have been presented to promote the nano-complexes (NCs) practical applications in the field of TE power generation. The electrical measurements confirm that the NCs are semiconductors and the electrical conduction process is governed by intermolecular and intramolecular transfer of the charge carriers. The TE measurements reveal that the Cu(II)-Schiff base NCs are nondegenerate P-type semiconductors. The measured Seebeck coefficient values were higher compared to the values reported in previous works for other organic materials indicating that the complexes under study are promising candidates for theremoelectric applications if the electrical conductivity could be enhanced.

  9. Spectroscopic, thermal, catalytic and biological studies of Cu(II) azo dye complexes

    Science.gov (United States)

    El-Sonbati, A. Z.; Diab, M. A.; El-Bindary, A. A.; Shoair, A. F.; Hussein, M. A.; El-Boz, R. A.

    2017-08-01

    New complexes of copper(II) with azo compounds of 5-amino-2-(aryl diazenyl)phenol (HLn) are prepared and investigated by elemental analyses, molar conductance, IR, 1H NMR, UV-Visible, mass, ESR spectra, magnetic susceptibility measurements and thermal analyses. The complexes have a square planar structure and general formula [Cu(Ln)(OAc)]H2O. Study the catalytic activities of Cu(II) complexes toward oxidation of benzyl alcohol derivatives to carbonyl compounds were tested using H2O2 as the oxidant. The intrinsic binding constants (Kb) of the ligands (HLn) and Cu(II) complexes (1-4) with CT-DNA are determined. The formed compounds have been tested for biological activity of antioxidants, antibacterial against Gram-positive (Staphylococcus aureus) and Gram-negative (Escherichia coli) bacteria and yeast Candida albicans. Antibiotic (Ampicillin) and antifungal against (Colitrimazole) and cytotoxic compounds HL1, HL2, HL3 and complex (1) showed moderate to good activity against S. aureus, E. coli and Candida albicans, and also to be moderate on antioxidants and toxic substances. Molecular docking is used to predict the binding between the ligands with the receptor of breast cancer (2a91).

  10. Complex Formation in a Liquid-Liquid Extraction System Containing Cobalt(II, 4-(2-Pyridylazoresorcinol, and Nitron

    Directory of Open Access Journals (Sweden)

    Petya Vassileva Racheva

    2013-01-01

    Full Text Available Complex formation and liquid-liquid extraction were studied in a system containing cobalt(II, 4-(2-pyridylazoresorcinol (PAR, 1,4-diphenyl-3-(phenylamino-1H-1,2,4-triazole (Nitron, Nt, water, and chloroform. The effect of some experimental parameters (pH, shaking time, concentration of PAR, and concentration of Nt was systematically investigated, and the optimum conditions for cobalt extraction as an ion-association complex, (NtH+[Co3+(PAR2], were found. The following key equilibrium constants were calculated: constant of association (Log β=4.77±0.06, constant of distribution (LogKD=1.34±0.01, and constant of extraction (LogKex=6.11±0.07. Beer’s law was obeyed for Co concentrations up to 1.7 μg mL−1 with a molar absorptivity of 6.0×104 L mol−1 cm−1 at λmax=520 nm. Some additional characteristics, such as limit of detection, limit of quantification, and Sandell’s sensitivity, were estimated as well.

  11. Copper(II)-bis(thiosemicarbazonato) complexes as anti-chlamydial agents.

    Science.gov (United States)

    Marsh, James W; Djoko, Karrera Y; McEwan, Alastair G; Huston, Wilhelmina M

    2017-09-29

    Lipophilic copper (Cu)-containing complexes have shown promising antibacterial activity against a range of bacterial pathogens. To examine the susceptibility of the intracellular human pathogen Chlamydia trachomatis to copper complexes containing bis(thiosemicarbazone) ligands [Cu(btsc)], we tested the in vitro effect of CuII-diacetyl- and CuII-glyoxal-bis[N(4)-methylthiosemicarbazonato] (Cu(atsm) and Cu(gtsm), respectively) on C. trachomatis. Cu(atsm) and to a greater extent, Cu(gtsm), prevented the formation of infectious chlamydial progeny. Impacts on host cell viability and respiration were also observed in addition to the Chlamydia impacts. This work suggests that copper-based complexes may represent a new lead approach for future development of new therapeutics against chlamydial infections, although host cell impacts need to be fully explored. © FEMS 2017. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

  12. Bioinorganic Relevance of Some Cobalt(II Complexes with Thiophene-2-glyoxal Derived Schiff Bases

    Directory of Open Access Journals (Sweden)

    Prashant Singh

    2009-01-01

    Full Text Available Complexes of Co(II with two new Schiff bases TEAB [2-hydroxy-4-{[2-oxo-2-(thiophen-2-ylethylidene]amino}benzoic acid] and TEPC [N-[2-oxo-2-(thiophen-2-ylethylidene]pyridine-3-carboxamide] have been synthesized and characterized with the help of elemental analysis, magnetic, mass, 1H-NMR, 13C-NMR, IR and electronic spectral data. IR spectra manifest the coordination of the ligand to the metal ion through the carbonyl oxygen, azomethine nitrogen and thienyl sulphur atoms. With the help of electronic spectral data various ligand field parameters were also calculated. All these studies reveal the distorted octahedral Co(II complexes. Synthesized compounds have also been screened against some micro organisms viz, Escherichia coli, Proteus vulgaris, Aspergillus niger and Aspergillus flavus with the help of ‘filter paper disc’ technique. It has been observed that the antimicrobial activities of metal complexes are higher than that of the free ligand.

  13. Cobalt(II), nickel(II), copper(II), zinc(II) and hafnium(IV) complexes of N'-(furan-3-ylmethylene)-2-(4-methoxyphenylamino)acetohydrazide.

    Science.gov (United States)

    Emam, Sanaa M; El-Saied, Fathy A; Abou El-Enein, Saeyda A; El-Shater, Heba A

    2009-03-01

    Cobalt(II), nickel(II), copper(II), zinc(II) and hafnium(IV) complexes of furan-2-carbaldehyde 4-methoxy-N-anilinoacetohydrazone were synthesized and characterized by elemental and thermal (TG and DTA) analyses, IR, UV-vis and (1)H NMR spectra as well as magnetic moment and molar conductivity. Mononuclear complexes are obtained with 1:1 molar ratio except complexes 3 and 9 which are obtained with 1:2 molar ratios. The IR spectra of ligand and metal complexes reveal various modes of chelation. The ligand behaves as a neutral bidentate one and coordination occurs via the carbonyl oxygen atom and azomethine nitrogen atom. The ligand behaves also as a monobasic tridentate one and coordination occurs through the enolic oxygen atom, azomethine nitrogen atom and the oxygen atom of furan ring. Moreover, the ligand behaves as a neutral tridentate and coordination occurs via the carbonyl oxygen, azomethine nitrogen and furan oxygen atoms as well as a monobasic bidentate and coordination occurs via the enolic oxygen atom and azomethine nitrogen atom. The electronic spectra and magnetic moment measurements reveal that all complexes possess octahedral geometry except the copper complex 10 possesses a square planar geometry. The thermal studies showed the type of water molecules involved in metal complexes as well as the thermal decomposition of some metal complexes.

  14. Expanding rare-earth oxidation state chemistry to molecular complexes of holmium(II) and erbium(II).

    Science.gov (United States)

    MacDonald, Matthew R; Bates, Jefferson E; Fieser, Megan E; Ziller, Joseph W; Furche, Filipp; Evans, William J

    2012-05-23

    The first molecular complexes of holmium and erbium in the +2 oxidation state have been generated by reducing Cp'(3)Ln [Cp' = C(5)H(4)SiMe(3); Ln = Ho (1), Er (2)] with KC(8) in the presence of 18-crown-6 in Et(2)O at -35 °C under argon. Purification and crystallization below -35 °C gave isomorphous [(18-crown-6)K][Cp'(3)Ln] [Ln = Ho (3), Er (4)]. The three Cp' ring centroids define a trigonal-planar geometry around each metal ion that is not perturbed by the location of the potassium crown cation near one ring with K-C(Cp') distances of 3.053(8)-3.078(2) Å. The metrical parameters of the three rings are indistinguishable within the error limits. In contrast to Ln(2+) complexes of Eu, Yb, Sm, Tm, Dy, and Nd, 3 and 4 have average Ln-(Cp' ring centroid) distances only 0.029 and 0.021 Å longer than those of the Ln(3+) analogues 1 and 2, a result similar to that previously reported for the 4d(1) Y(2+) complex [(18-crown-6)K][Cp'(3)Y] (5) and the 5d(1) La(2+) complex [K(18-crown-6)(Et(2)O)][Cp″(3)La] [Cp″ = 1,3-(Me(3)Si)(2)C(5)H(3)]. Surprisingly, the UV-vis spectra of 3 and 4 are also very similar to that of 5 with two broad absorptions in the visible region, suggesting that 3-5 have similar electron configurations. Density functional theory calculations on the Ho(2+) and Er(2+) species yielded HOMOs that are largely 5d(z(2)) in character and supportive of 4f(10)5d(1) and 4f(11)5d(1) ground-state configurations, respectively.

  15. Synthesis, characterization, and biological activity of a new palladium(II) complex with deoxyalliin

    Energy Technology Data Exchange (ETDEWEB)

    Corbi, P.P.; Massabni, A.C. [Inst. de Quimica - UNESP, Dept., Dept. de Quimica Geral e Inoganica, Araraquara (Brazil)]. E-mail: pedrocorbi@yahoo.com; Moreira, A.G. [Inst. de Quimica - UNESP, Dept. de Quimica Geral e Inoganica, Araraquara (Brazil); Faculdade de Medicina de Ribeirao Preto - USP, Dept. de Bioquimica e Imunologia, Ribeirao Preto (Brazil); Medrano, F.J. [Laboratorio Nacional de Luz Sincrotron - LNLS, Campinas (Brazil); Jasiulionis, M.G. [Escola Paulista de Medicina - UNIFESP, Dept. de Micro-Imuno-Parasitologia, Sao Paulo (Brazil); Costa-Neto, C.M. [Faculdade de Medicina de Ribeirao Preto - USP, Dept. de Bioquimica e Imunologia, Ribeirao Preto (Brazil)

    2005-02-15

    Synthesis, characterization, and biological activity of a new water-soluble Pd(II)-deoxyalliin (S-allyl-L-cysteine) complex are described in this article. Elemental and thermal analysis for the complex are consistent with the formula [Pd(C{sub 6}H{sub 10}NO{sub 2}S){sub 2}]. {sup 13}C NMR, {sup 1}H NMR, and IR spectroscopy show coordination of the ligand to Pd(II) through S and N atoms in a square planar geometry. Final residue of the thermal treatment was identified as a mixture of PdO and metallic Pd. Antiproliferative assays using aqueous solutions of the complex against HeLa and TM5 tumor cells showed a pronounced activity of the complex even at low concentrations. After incubation for 24 h, the complex induced cytotoxic effect over HeLa cells when used at concentrations higher than 0.40 mmol/L. At lower concentrations, the complex was nontoxic, indicating its action is probably due to cell cycle arrest, rather than cell death. In agreement with these results, the flow cytometric analysis indicated that after incubation for 24 h at low concentrations of the complex cells are arrested in G0/G1. (author)

  16. Structure and Function of p97 and Pex1/6 Type II AAA+ Complexes.

    Science.gov (United States)

    Saffert, Paul; Enenkel, Cordula; Wendler, Petra

    2017-01-01

    Protein complexes of the Type II AAA+ (ATPases associated with diverse cellular activities) family are typically hexamers of 80-150 kDa protomers that harbor two AAA+ ATPase domains. They form double ring assemblies flanked by associated domains, which can be N-terminal, intercalated or C-terminal to the ATPase domains. Most prominent members of this family include NSF (N-ethyl-maleimide sensitive factor), p97/VCP (valosin-containing protein), the Pex1/Pex6 complex and Hsp104 in eukaryotes and ClpB in bacteria. Tremendous efforts have been undertaken to understand the conformational dynamics of protein remodeling type II AAA+ complexes. A uniform mode of action has not been derived from these works. This review focuses on p97/VCP and the Pex1/6 complex, which both structurally remodel ubiquitinated substrate proteins. P97/VCP plays a role in many processes, including ER- associated protein degradation, and the Pex1/Pex6 complex dislocates and recycles the transport receptor Pex5 from the peroxisomal membrane during peroxisomal protein import. We give an introduction into existing knowledge about the biochemical and cellular activities of the complexes before discussing structural information. We particularly emphasize recent electron microscopy structures of the two AAA+ complexes and summarize their structural differences.

  17. Ni(II) complexes of arginine Schiff-bases and its interaction with DNA

    Energy Technology Data Exchange (ETDEWEB)

    Sallam, S.A., E-mail: shehabsallam@yahoo.com [Chemistry Department, Faculty of Science, Suez Canal University, Isamilia (Egypt); Abbas, A.M. [Chemistry Department, Faculty of Science, Suez Canal University, Isamilia (Egypt)

    2013-04-15

    Ni(II) complexes with Schiff-bases obtained by condensation of arginine with salicylaldehyde; 2,3-; 2,4-; 2,5-dihydroxybenzaldehyde and o-hydroxynaphthaldehyde have been synthesized using the template method in ethanol or ammonia media. They were characterized by elemental analyses, conductivity measurements, magnetic moment, UV, IR and {sup 1}H NMR spectra as well as thermal analysis (TG, DTG and DTA). The Schiff-bases are dibasic tridentate donors and the complexes have diamagnetic square planar and octahedral structures. The complexes decompose in three steps where kinetic and thermodynamic parameters of the decomposition steps were computed. The interactions of the formed complexes with FM-DNA were monitored by UV and fluorescence spectroscopy. -- Highlights: ► Arginine Schiff-bases and their nickel(II) complexes have been synthesized. ► Magnetic and spectral data show diamagnetic square planar and octahedral complexes. ► The complexes thermally decompose in three stages. Interaction with FM-DNA shows hyperchromism with blue shift.

  18. Ni(II) complexes of arginine Schiff-bases and its interaction with DNA

    International Nuclear Information System (INIS)

    Sallam, S.A.; Abbas, A.M.

    2013-01-01

    Ni(II) complexes with Schiff-bases obtained by condensation of arginine with salicylaldehyde; 2,3-; 2,4-; 2,5-dihydroxybenzaldehyde and o-hydroxynaphthaldehyde have been synthesized using the template method in ethanol or ammonia media. They were characterized by elemental analyses, conductivity measurements, magnetic moment, UV, IR and 1 H NMR spectra as well as thermal analysis (TG, DTG and DTA). The Schiff-bases are dibasic tridentate donors and the complexes have diamagnetic square planar and octahedral structures. The complexes decompose in three steps where kinetic and thermodynamic parameters of the decomposition steps were computed. The interactions of the formed complexes with FM-DNA were monitored by UV and fluorescence spectroscopy. -- Highlights: ► Arginine Schiff-bases and their nickel(II) complexes have been synthesized. ► Magnetic and spectral data show diamagnetic square planar and octahedral complexes. ► The complexes thermally decompose in three stages. Interaction with FM-DNA shows hyperchromism with blue shift

  19. Preparation and properties of a calcium(II)-based molecular chain decorated with manganese(II) butterfly-like complexes.

    Science.gov (United States)

    Benniston, A C; Melnic, S; Turta, C; Arauzo, A B; Bartolomé, J; Bartolomé, E; Harrington, R W; Probert, M R

    2014-09-21

    The room temperature reaction of [Mn2O2(bipy)4](ClO4)3 (bipy = 2,2'-bipyridine) with Ca(CHCl2COO)2 in methanol produced a yellow crystalline material. The X-ray determined structure comprises of a multiple calcium(II) carboxylate bridged chain-like structure which is decorated with [Mn(bipy)2(OH2)](2+) subunits. The redox behaviour for the complex in H2O and MeCN is reported. In the latter solvent the oxidation of the manganese ions appears to be facilitated by the presence of the calcium ions. Magnetic susceptibility and low temperature magnetization measurements show that the Mn moment is isotropic, with g = 1.99(1) and S = 5/2, confirming it is in the 2+ oxidation state. A very weak antiferromagnetic interaction is also detected. Frequency-dependent ac measurements evidence slow magnetic relaxation of the Mn(bipy)2 units. Two relaxation mechanisms are identified: a very slow direct process and a faster one caused by the Resonant Phonon Trapping mechanism. This is the first example of field-induced single ion magnet (SIM) behavior in a mononuclear Mn(II) complex.

  20. Synthesis, characterization, DFT calculations and antibacterial activity of palladium(II) cyanide complexes with thioamides

    Science.gov (United States)

    Ahmad, Saeed; Nadeem, Shafqat; Anwar, Aneela; Hameed, Abdul; Tirmizi, Syed Ahmed; Zierkiewicz, Wiktor; Abbas, Azhar; Isab, Anvarhusein A.; Alotaibi, Mshari A.

    2017-08-01

    Palladium(II) cyanide complexes of thioamides (or thiones) having the general formula PdL2(CN)2, where L = Thiourea (Tu), Methylthiourea (Metu), N,N‧-Dimethylthiourea (Dmtu), Tetramethylthiourea (Tmtu), 2-Mercaptopyridine (Mpy) and 2-Mercaptopyrimidine (Mpm) were prepared by reacting K2[PdCl4] with potassium cyanide and thioamides in the molar ratio of 1:2:2. The complexes were characterized by elemental analysis, thermal and spectroscopic methods (IR, 1H and 13C NMR). The structures of three of the complexes were predicted by DFT calculations. The appearance of a band around 2100 cm-1 in IR and resonances around 120-130 ppm in the 13C NMR spectra indicated the coordination of cyanide to palladium(II). More than one resonances were observed for CN- carbon atoms in 13C NMR indicating the existence of equilibrium between different species in solution. DFT calculations revealed that in the case of the palladium(II) complex of Tmtu, the ionic dinuclear [Pd(Tmtu)4][Pd(CN)4] form was more stable than the dimer of mononuclear complex [Pd(Tmtu)2(CN)2] by 0.91 kcal mol-1, while for the complexes of Tu or Mpy ligands, the nonionic [Pd(L)2(CN)2] forms were more stable than the corresponding [Pd(L)4][Pd(CN)4] complexes by 1.26 and 6.49 kcal mol-1 for L = Tu and Mpy, respectively. The complexes were screened for antibacterial effects and some of them showed significant activities against both gram positive as well as gram negative bacteria.