CRYSTAL RESEARCH AND TECHNOLOGY, Issue 5 2006
Gülsün Göka
Abstract The crystal structure of [Cu(C6H2I3O)2(NH3)2] (CCDC 238896) has been determined by x-ray diffraction. This monomeric centrosymmetric Cu(II) complex crystallizes in the monoclinic system. The CuO2N2 coordination sphere is trans -planar, [Cu,O: 1.943(5) Å and Cu-N: 1.972(7)] with the fifth and sixth coordination sites occupied by I atoms from the phenoxide ions [Cu,I1: 3.3552(8) Å] to form a tetragonally elongated octahedral structure for CuO2N2I2 coordination. The complex molecules hold together in a one dimensional chain true [100] direction by intermolecular hydrogen bonds. Differantial scanning calorimeter, FTIR and magnetic susceptibility measurements were also performed in order to identify the title complex. (© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source]

Structural, Spectroscopic, and Proton-Coupled Electron-transfer Behavior of Pyrazolyl-3,5-bis(benzimidazole)-Bridged Homo- and Heterochiral RuIIRuII, OsIIOsII, and OsIIRuII 2,2,-Bipyridine Complexes

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 4 2010
Sujoy Baitalik
Abstract The homo- and heterobimetallic complexes [(bpy)2MII(H2pzbzim)M,II(bpy)2](ClO4)3·nH2O (1, 3, 5) and their corresponding deprotonated complexes [(bpy)2MII(pzbzim)M,II(bpy)2](ClO4)·nH2O (2, 4, 6) [where MII, M,II = Ru (1, 2) = Os (3, 4); MII = Os and M,II = Ru (3, 5); bpy = 2,2,-bipyridine; H3pzbzim = pyrazole-3,5-bis(benzimidazole)] were synthesized, separated to their heterochiral (a, ,,/,,) and homochiral (b, ,,/,,) diastereoisomers, and characterized by elemental analyses, ESI-MS, and 1H NMR spectroscopy. The X-ray structures of 1a, 3a, and 5a show the involvement of two pyridine rings of two bpy ligands in strong intramolecular nonbonded ,,, interaction. The occurrence of a C,H···, interaction between an aromatic C,H and the ,-cloud of a pyridine ring leads to strong electronic shielding of this proton (1H NMR). In all cases, the two diastereoisomers show practically no differences in their absorption spectra, redox potentials, and pK values. The large shifts in the E1/2 values to less positive potentials and substantial redshifts in the MLCT bands that occur on deprotonation of 1, 3, and 5 are energetically correlated. From the profiles of E1/2(1), (2) vs. pH over the pH range 1,12, the equilibrium constants and standard redox potentials for all the complex species in the metal oxidation states II·II, II·III, and III·III and the bridged ligand in the protonation states H2pzbzim,, Hpzbzim2,, and pzbzim3, have been evaluated. Using these values the bond dissociation free energies for the benzimidazole N,H bonds have been estimated. Spectroelectrochemical studies have been carried out for 1a, 3a, and 5a in the range 400,1100 nm. With stepwise oxidation of the metal centers replacement of MLCT bands by LMCT bands occur gradually with the observation of sharp isosbestic points. In the case of 1a, a band observed at ,max = 910 nm for the RuIIRuIII species has been ascribed to intervalence charge transfer (IVCT) transition. [source]

Spectroscopic and Computational Study on New Blue Emitting ReL(CO)3Cl Complexes Containing Pyridylimidazo[1,5- a]pyridine Ligands

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 23 2008
Claudio Garino
Abstract The structural and photophysical properties of three new ReL(CO)3Cl complexes (ReL1,ReL3) and their 1-(2-pyridyl)imidazo[1,5- a]pyridine ligands, namely 3-methyl-1-(2-pyridyl)imidazo[1,5- a]pyridine (L1), 1-(2-pyridyl)-3-[4-(trifluoromethyl)phenyl]imidazo[1,5- a]pyridine (L2), and 3-(4-nitrophenyl)-1-(2-pyridyl)imidazo[1,5- a]pyridine (L3), were studied by spectroscopy, X-ray diffraction, and computational methods. ReL1,ReL3 have high-energy singlet emissions arising from a , , ,* ligand-centered state. In oxygen-free acetonitrile solutions, the complexes display dual fluorescence due to intense ligand-centered triplet emission.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source]

A New Pentadentate Ligand Forms Both a Di- and a Mononuclear MnII Complex: Electrochemical, Spectroscopic and Superoxide Dismutase Activity Studies

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 28 2007
Federico Cisnetti
Abstract The X-ray crystal structure of the dinuclear complex[1(PF6)2] derived from a new ligand bearing both imidazole and phenolato moieties, namely N -(2-hydroxybenzyl)- N,N,-bis[2-(N -methylimidazolyl)methyl]ethane-1,2-diamine (LH), is described and its properties in organic solvent (CH3CN) investigated (EPR, electrochemistry). [1(PF6)2] is shown to be a mononuclear MnII species in aqueous solution and displays an efficient SOD-like activity, as measured by the McCord,Fridovich assay performed both in conventional phosphate buffer and in a noncoordinating buffer (PIPES). (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source]

Crystal Structure, Solid-State NMR Spectroscopic and Photoluminescence Studies of Organic-Inorganic Hybrid Materials (HL)6[Ge6(OH)6(hedp)6]·2(L)·nH2O, L = hqn or phen,

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 23 2006
Luís Mafra
Abstract Two germanium,hedp4, solids with heteroaromatic amines 8-hydroxyquinoline (hqn) and 1,10-phenanthroline (phen), (HL)6[Ge6(OH)6(hedp)6]·2(L)·nH2O (L = hqn or phen), in I and II respectively, have been prepared and characterised by single-crystal XRD, thermogravimetry, FTIR and UV/Vis spectroscopy. The complex hydrogen-bond networks, particularly in compound I, have been studied by advanced high-resolution solid-state NMR spectroscopy that combines homonuclear recoupling techniques (two-dimensional 1H- 1H DQF and 1H- 1H RFDR MAS NMR) and combined rotation and multiple-pulse spectroscopy (two-dimensional 1H- 1H FS-LG, 1H- 31P FS-LG). The fine details of the crystal structure of I have been elucidated, mainly those involving the ,,, stacking of 8-hydroxyquinoline and the relative orientation of adjacent such molecules. Compound II exhibits an emission from the lowest triplet-state energy (,,,* 0-phonon transition) of the aromatic rings at 320 nm (31250 cm,1) from 14 K to room temperature. In contrast, the triplet emission of I at 530 nm (18868 cm,1) is only detected at low temperature, because of thermally activated non-radiative mechanisms. The emission spectra of I and II display a lower-energy component with a larger life time, which results from the formation of an excimer state that originated from the ,,, phenanthroline and hydroxyquinoline interactions, respectively. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source]

Layered [BaM(C3H2O4)2(H2O)4] (M = Fe or Co) Complexes , Spectroscopic, Magnetic and Thermal Study

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 16 2003
Izaskun Gil de Muro
Abstract Complexes with formula [BaM(C3H2O4)2(H2O)4], where M = Fe or Co, were synthesised and characterised. These two types of complexes are isostructural and crystallise in the Pccn space group. Their structure consists of two-dimensional networks of octahedral MO6 polyhedra in which the transition metal ions are coordinated by bridging malonate ligands, through the O-C-O atoms. These M-malonate units are extended along the crystallographic [101] plane. Spectroscopic data are consistent with the cations being in a high-spin octahedral symmetry. The two types of compounds exhibit 2D antiferromagnetic interactions as well as weak ferromagnetism below the Néel temperature, as a result of an intralayer misalignment of the spins. Thermal treatment of the metallo-organic precursors gave rise to BaMO3,y oxides at lower temperatures and reaction times than those found in the literature using the ceramic method. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003). [source]

Spectroscopic and DNA-binding characterization of the isolated heme-bound basic helix,loop,helix-PAS-A domain of neuronal PAS protein 2 (NPAS2), a transcription activator protein associated with circadian rhythms

FEBS JOURNAL, Issue 11 2006
Yuji Mukaiyama
Neuronal PAS domain protein 2 (NPAS2) is a circadian rhythm-associated transcription factor with two heme-binding sites on two PAS domains. In the present study, we compared the optical absorption spectra, resonance Raman spectra, heme-binding kinetics and DNA-binding characteristics of the isolated fragment containing the N-terminal basic helix,loop,helix (bHLH) of the first PAS (PAS-A) domain of NPAS2 with those of the PAS-A domain alone. We found that the heme-bound bHLH-PAS-A domain mainly exists as a dimer in solution. The Soret absorption peak of the Fe(III) complex for bHLH-PAS-A (421 nm) was located at a wavelength 9 nm higher than for isolated PAS-A (412 nm). The axial ligand trans to CO in bHLH-PAS-A appears to be His, based on the resonance Raman spectra. In addition, the rate constant for heme association with apo-bHLH-PAS (3.3 × 107 mol,1·s,1) was more than two orders of magnitude higher than for association with apo-PAS-A (< 105 mol,1·s,1). These results suggest that the bHLH domain assists in stable heme binding to NPAS2. Both optical and resonance Raman spectra indicated that the Fe(II),NO heme complex is five-coordinated. Using the quartz-crystal microbalance method, we found that the bHLH-PAS-A domain binds specifically to the E-box DNA sequence in the presence, but not in the absence, of heme. On the basis of these results, we discuss the mode of heme binding by bHLH-PAS-A and its potential role in regulating DNA binding. [source]

Outer sphere mutagenesis of Lactobacillus plantarum manganese catalase disrupts the cluster core

FEBS JOURNAL, Issue 6 2003
Mechanistic implications
X-ray crystallography of the nonheme manganese catalase from Lactobacillus plantarum (LPC) [Barynin, V.V., Whittaker, M.M., Antonyuk, S.V., Lamzin, V.S., Harrison, P.M., Artymiuk, P.J. & Whittaker, J.W. (2001) Structure9, 725,738] has revealed the structure of the dimanganese redox cluster together with its protein environment. The oxidized [Mn(III)Mn(III)] cluster is bridged by two solvent molecules (oxo and hydroxo, respectively) together with a µ1,3 bridging glutamate carboxylate and is embedded in a web of hydrogen bonds involving an outer sphere tyrosine residue (Tyr42). A novel homologous expression system has been developed for production of active recombinant LPC and Tyr42 has been replaced by phenylalanine using site-directed mutagenesis. Spectroscopic and structural studies indicate that disruption of the hydrogen-bonded web significantly perturbs the active site in Y42F LPC, breaking one of the solvent bridges and generating an ,open' form of the dimanganese cluster. Two of the metal ligands adopt alternate conformations in the crystal structure, both conformers having a broken solvent bridge in the dimanganese core. The oxidized Y42F LPC exhibits strong optical absorption characteristic of high spin Mn(III) in low symmetry and lower coordination number. MCD and EPR measurements provide complementary information defining a ferromagnetically coupled electronic ground state for a cluster containing a single solvent bridge, in contrast to the diamagnetic ground state found for the native cluster containing a pair of solvent bridges. Y42F LPC has less than 5% of the catalase activity and much higher Km for H2O2 (,1.4 m) at neutral pH than WT LPC, although the activity is slightly restored at high pH where the cluster is converted to a diamagnetic form. These studies provide new insight into the contribution of the outer sphere tyrosine to the stability of the dimanganese cluster and the role of the solvent bridges in catalysis by dimanganese catalases. [source]

Cover Picture: Spectroscopic and Photophysical Properties of a Highly Derivatized C60 Fullerol (Adv. Funct.

ADVANCED FUNCTIONAL MATERIALS, Issue 1 2006
Mater.
Abstract The photo-oxidative stress in aqueous milieus can readily be generated in the presence of newly synthesized highly derivatized fullerenes (fullerols) reported in the Full Paper by Vileno and co-workers on p.,120. Their basic structural and photophysical properties were characterized using a range of methods, including X-ray photoelectron and IR spectroscopies, and electron spin resonance. Moreover, a significant drop of the local stiffness of a living cell was monitored using atomic force microscopy. This cell softening was attributed to the early effects of the photo-oxidative stress. Hydroxylated C60 molecules, also called fullerols, are a class of water-soluble fullerenes. Here we report the synthesis in acidic conditions of a highly derivatized fullerol (up to 36 carbons per C60 are oxidized). Spectroscopic investigations (X-ray photoelectron spectroscopy and infrared absorption) highlight the coexistence of both acidic and basic forms for the hydroxyl addends of derivatized C60. pH titrimetry reveals that, at millimolar concentrations, only ten protons per fullerol molecule are labile. Such a low value, as compared to 36 hydroxyl groups, is explained by the formation of clusters. A UV-vis absorption study performed over a large range of concentrations also points to the aggregation phenomenon. Moreover, this study shows that the clusters of fullerols appear at relatively low (micromolar) concentrations. An electron spin resonance (ESR) study, based on the attack of singlet oxygen (1,g) on 2,2,6,6-tetramethyl-4-piperidinol (TMP-OH), has proved the potential of hydroxylated C60 for performing efficient generation of singlet oxygen in aqueous solution. ESR measurements, which allow detection and quantification of 1,g, have also revealed the generation of reactive oxygen species (ROS). The yield of generation of 1,g and ROS is strongly correlated to the concentration of fullerol, thus also pointing to the aggregation of fullerol molecules. Exposing glioblastoma cells to oxidative stress in the presence of hydroxylated C60 and visible light has also been performed. Atomic force microscopy is used to monitor the relevant diminishment of the Young's modulus values for cells exposed to the oxidative stress. These results point to a possible application field of fullerols for performing bio-oxidations. [source]

Ghanaian Cocoa Bean Fermentation Characterized by Spectroscopic and Chromatographic Methods and Chemometrics

JOURNAL OF FOOD SCIENCE, Issue 6 2010
Patrick C. Aculey
Abstract:, Export of cocoa beans is of great economic importance in Ghana and several other tropical countries. Raw cocoa has an astringent, unpleasant taste, and flavor, and has to be fermented, dried, and roasted to obtain the characteristic cocoa flavor and taste. In an attempt to obtain a deeper understanding of the changes in the cocoa beans during fermentation and investigate the possibility of future development of objective methods for assessing the degree of fermentation, a novel combination of methods including cut test, colorimetry, fluorescence spectroscopy, NIR spectroscopy, and GC-MS evaluated by chemometric methods was used to examine cocoa beans sampled at different durations of fermentation and samples representing fully fermented and dried beans from all cocoa growing regions of Ghana. Using colorimetry it was found that samples moved towards higher,a* and,b* values as fermentation progressed. Furthermore, the degree of fermentation could, in general, be well described by the spectroscopic methods used. In addition, it was possible to link analysis of volatile compounds with predictions of fermentation time. Fermented and dried cocoa beans from the Volta and the Western regions clustered separately in the score plots based on colorimetric, fluorescence, NIR, and GC-MS indicating regional differences in the composition of Ghanaian cocoa beans. The study demonstrates the potential of colorimetry and spectroscopic methods as valuable tools for determining the fermentation degree of cocoa beans. Using GC-MS it was possible to demonstrate the formation of several important aroma compounds such 2-phenylethyl acetate, propionic acid, and acetoin and the breakdown of others like diacetyl during fermentation. Practical Application:, The present study demonstrates the potential of using colorimetry and spectroscopic methods as objective methods for determining cocoa bean quality along the processing chain. Development of objective methods for determining cocoa bean quality will be of great importance for quality insurance within the fields of cocoa processing and raw material control in chocolate producing companies. [source]

Functionalization of carbon nanofibers (CNFs) through atom transfer radical polymerization for the preparation of poly(tert -butyl acrylate)/CNF materials: Spectroscopic, thermal, morphological, and physical characterizations

JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 10 2008
Marcos Ghislandi
Abstract Vapor-grown carbon nanofibers (CNFs) were oxidized and functionalized for atom transfer radical polymerization (ATRP) of tert -butyl acrylate (t -BA) from the surface of the CNFs. The materials were characterized by solubility tests, Fourier-transform infrared (FTIR) spectroscopy, Raman spectroscopy, thermogravimetric analysis (TGA), X-ray diffraction (XRD), and scanning electron microscopy. The FTIR and electron microscopy results suggest that ATRP process was successfully used to graft poly(tert -butyl acrylate) (poly(t -BA)) chains from the surface of the fibers. Raman results strongly indicate the partial degradation of the graphitic layer of CNFs because of the chemical treatments. TGA results suggest that the presence of poly(t -BA) leads to a decrease of the initial degradation temperature of the fibers. XRD and electron microscopy results indicate that the microstructure of fibers was not destroyed because of the oxidation and functionalization processes. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3326,3335, 2008 [source]

Synthesis and characterization of polyaniline doped with organic acids

JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 8 2004
Milind V. Kulkarni
Abstract Spectroscopic [UV,visible and Fourier transform IR (FTIR)] and thermal properties of chemically synthesized polyanilines are found to be affected by varying the protonation media (acetic, citric, oxalic, and tartaric acid). The optical spectra show the presence of a greater fraction of fully oxidized insulating pernigraniline phase in polyaniline doped with acetic acid. In contrast, the selectivity in the formation of the conducting phase is higher in oxalic acid as a protonic acid media. The FTIR spectra of these polymers reveal a higher ratio of the relative intensities of the quinoid to benzenoid ring modes in acetic acid doped polyaniline. Scanning electron micrographs revealed a sponge-like structure derived from the aggregation of the small granules in acetic acid and oxalic acid doped polyaniline. A three-step decomposition pattern is observed in all the polymers, regardless of the protonic acid used for the doping. The second step loss related to the loss of dopant is found to be higher in the oxalic acid doped polymer. In accordance with these results the conductivity is also found to be higher in oxalic acid doped material. The temperature dependent conductivity measurements show the thermal activated behavior in all the polymers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2043,2049, 2004 [source]

Spectroscopic and computational studies on self-assembly complexes of bis(pyrrol-2- ylmethyleneamine) ligands linked by alkyl spacers with Cu(II)

JOURNAL OF RAMAN SPECTROSCOPY, Issue 5 2007
Wei Li
Abstract Bis(pyrrol-2-ylmethyleneamine) ligands and their mononuclear monomeric and dinuclear dimeric self-assembly complexes with Cu(II) were investigated by means of IR and Raman spectroscopies and density functional theory. The ground-state geometries were calculated by using the BeckeLeeYangParr composite exchange-correlation functional (B3LYP) and a combined basis set (LanL2DZ for Cu; 6,31G(d) for C, H, N), and they were compared with the single-crystal X-ray diffraction (XRD) structures. The DFT-calculated CuN bond lengths are generally higher by 0.001,0.040 Å than those determined through XRD. The vibrational spectra were also calculated at the same level of theory for the optimized geometries. The calculated wavenumbers were scaled by a uniform scaling factor and compared with the experimental fundamentals. The predicted spectra are in good agreement with the experimental ones with the deviations generally less than 30 cm,1. In comparison with the spectra of the ligands, the coordination effect shifts the ,(CN) wavenumber by about 50 cm,1 toward a lower value. Because of the weak intermolecular CH···Cu hydrogen bond, the CuN stretching mode is shifted toward a lower wavenumber. Copyright © 2006 John Wiley & Sons, Ltd. [source]

Spectroscopic and Thermal Properties of Ga2S3,Na2S,CsCl Glasses

JOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 3 2006
Luiz C. Barbosa
The synthesis and properties of the vitreous system (0.75,x)Ga2S3,0.25Na2S,xCsCl, with x varying from 0.1 to 0.2, are presented. Thermal, optical, and structural properties such as density, viscosity, thermal expansion coefficient, glass transition temperature, softening point temperature, refractive index, and absorption coefficient were measured using several techniques: X-ray diffraction, Raman scattering, differential thermal analysis, thermal mechanical analysis, and absorption spectroscopy. This glass system presents a high third-order non-linear optical susceptibility that can be significantly increased by increasing the CsCl content without affecting the low phonon frequency. [source]

Methacrylic Polymers Containing Optically Active Side-Chain Carbazole: Synthesis, Characterization and Photoconductive Properties

MACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 9 2008
Luigi Angiolini
Abstract Two novel optically active polymethacrylates bearing in the side chain a cyclic chiral group of one prevailing absolute configuration linked to the carbazole chromophore, deriving from the related monomers (S)-(,)-3-methacryloyloxy- N -[3-(9-ethylcarbazolyl)]pyrrolidine [(S)-(,)-MECP] and (S)-(+)-2-methacryloyloxy- N -[3-(9-ethylcarbazolyl)]succinimide [(S)-(+)-MECSI], have been prepared and characterized with the aim to obtain materials suitable to photoconductive applications. Poly[(S)-(,)-MECP] and poly[(S)-(+)-MECSI] exhibit remarkable thermal stability, with glass transition temperature around 200,°C and decomposition temperatures in the range 330,350,°C. Spectroscopic, thermal and chiroptical characterizations indicate the occurrence of dipolar interactions among the side chain moieties and the presence of chiral conformation at least for chain segments of the macromolecules. The photoconductive properties are discussed in terms of extent of conjugation in the side chain based on the electron-acceptor or electron-donator properties of the optically active ring linked to the carbazole group. [source]

Acorn-Shape Polymeric Nano-Colloids: Synthesis and Self-Assembled Films

MACROMOLECULAR RAPID COMMUNICATIONS, Issue 2 2010
Anuradha Misra
Abstract These studies show for the first time that the synthesis of two distinct phase-separated copolymers within one colloidal particle, i.e., poly(methyl methacrylate) (PMMA)/n -butylacrylate (nBA) and poly(nBA)/pentafluorostyrene (p-PFS) phases, results in unique acorn-shaped morphologies and are capable of coalescence. Spectroscopic and morphological analysis combined with contact angle measurements as well as thermodynamic modeling reveal that in an effort to create stable heterogeneous two-phase particle morphologies it is essential to provide desirable interfacial energetic conditions during polymerization and to utilise monomers that have a similar glass transition temperature (Tg). Such colloidal particles are stable and are able to self-assemble during coalescence, depending upon the surface energy of a substrate. When a particle monolayer coalesces on a high surface tension substrate, the p-PFS phase expresses itself near the film,air interface, whereas for low surface energy substrates, the p-PFS phase dominates the film,substrate interfacial regions. [source]

Global properties of the rich cluster ABCG 209 at z, 0.2. Spectroscopic and photometric catalogue

MONTHLY NOTICES OF THE ROYAL ASTRONOMICAL SOCIETY, Issue 4 2008
A. Mercurio
ABSTRACT This paper is aimed at giving an overview of the global properties of the rich cluster of galaxies ABCG 209. This is achieved by complementing the already available data with new medium-resolution spectroscopy and near-infrared (NIR) photometry which allow us to (i) analyse in detail the cluster dynamics, distinguishing among galaxies belonging to different substructures and deriving their individual velocity distributions, using a total sample of 148 galaxies in the cluster region, of which 134 belonging to the cluster; (ii) derive the cluster NIR luminosity function; (iii) study the Kormendy relation and the photometric plane of cluster early-type galaxies (ETGs). Finally we provide an extensive photometric (optical and NIR) and spectroscopic data set for such a complex system to be used in further analyses investigating the nature, formation and evolution of rich clusters of galaxies. The present study shows that the cluster is characterized by a very high value of the line-of-sight velocity dispersion: ,v= 1268+93,84 km s,1, that results in a virial mass of Mvir= 2.95+0.80,0.78× 1015 h,170 M, within Rvir= 3.42 h,170 Mpc. The analysis of the velocity dispersion profile shows that such high value of ,v is already reached in the central cluster region. There is evidence of three significant substructures, the primary one having a velocity dispersion of ,v= 847+52,49 km s,1, which makes it consistent with mass estimates from weak lensing analyses. This observational scenario confirms that ABCG 209 is presently undergoing strong dynamical evolution with the merging of two or more subclumps. This interpretation is also supported by the detection of a radio halo suggesting that there is a recent or ongoing merging. Cluster ETGs follow a Kormendy relation whose slope is consistent with previous studies both at optical and NIR wavelengths. We investigate the origin of the intrinsic scatter of the photometric plane due to trends of stellar populations, using line indices as indicators of age, metallicity and ,/Fe enhancement. We find that the chemical evolution of galaxies could be responsible for the intrinsic dispersion of the photometric plane. [source]

Spectroscopic and photometric observations of the selected Algol-type binaries , II.

MONTHLY NOTICES OF THE ROYAL ASTRONOMICAL SOCIETY, Issue 1 2008
V2080 Cygni, V2365 Ophiuchi
ABSTRACT This paper is the second in the planned series of investigations. We present new radial velocities and photometric observations of V2080 Cyg and V2365 Oph. New UBV photometric data and radial velocities were analysed for the systems' parameters. While V2080 Cyg consists of two nearly equal F-type main-sequence stars, V2365 Oph has two different components, namely an early A-type primary and a G-type secondary star. New ephemerides are calculated for both systems. The masses of the component stars have been derived as 1.19 ± 0.02 and 1.16 ± 0.02 M, for V2080 Cyg and 1.97 ± 0.02 and 1.06 ± 0.01 M, for V2365 Oph. The effective temperatures and reddening of the systems have been estimated from Johnson wide-band UBV photometric calibrations. The radii have been measured by simultaneous fitting the UBV light curves using Wilson,Devinney code and are 1.60 ± 0.01 R, for both components of V2080 Cyg and 2.19 ± 0.01 and 0.934 ± 0.004 R, for V2365 Oph. The absolute parameters of the stars in both systems lie within the same ranges in the mass,radius, mass,effective temperature, mass,luminosity and luminosity,effective temperature planes as in detached Algol systems. A comparison between the properties of the systems of interest and the predictions of theoretical evolutionary models is undertaken in the log g,logTeff, log R, log M and radius,log age diagrams. The model predictions match the measured properties of V2080 Cyg for an age of about 5.6 Gyr and a ,solar' metal abundance (Z= 0.019), indicating the components near the end of their core hydrogen-burning phases. However, the position of the components of V2365 Oph on the Hertzsprung,Russell (HR) diagram is best reproduced with evolutionary models for somewhat metal-deficient (Z= 0.004) stars. We found an age of about 700 Myr, with the primary component slightly evolved off the zero-age main-sequence and the secondary one still very close to it. From the basic stellar parameters we have also redetermined the distances to V2080 Cyg and V2365 Oph as 78 ± 1 and 251 ± 8 pc, which are in agreement with, and more accurate than, Hipparcos values. The observations show that at least one of the components of V2365 Oph is an intrinsic variable with a period and peak-to-peak amplitude of 0.07 d and 0.05 mag, respectively. In accordance with its position in the HR diagram, the primary component should be considered as a , Scuti star and it is believed to be the variable star in the system. [source]

FTIR Spectroscopic and Theoretical Study of the Photochemistry of Matrix-isolated Coumarin

PHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 5 2007
Nihal Ku
The infrared spectrum of monomeric unsubstituted coumarin (C9H6O2; 2H -1-benzopyran-2-one), isolated in solid argon at 10 K is presented and assigned. The UV-induced (, > 200 nm) unimolecular photochemistry of the matrix-isolated compound was studied experimentally. Three main photoreactions were observed: (a) decarboxylation of the compound and formation of benzocyclobutadiene and CO2, with the Dewar form of coumarin as intermediate; (b) isomerization of the compound, leading to production of a conjugated ketene; and (c) decarbonylation, leading to formation of CO and benzofuran complex. Further decomposition of benzofuran to produce ethynol is suggested. Photochannels (a) and (b) correspond to those previously observed for matrix-isolated ,- pyrone and its sulfur analogs (Phys. Chem. Chem. Phys. 2004, 6, 929; J. Phys. Chem. A 2006, 110, 6415), while route (c) is similar to the UV-induced photochemistry of coumarin in the gaseous phase (J. Phys. Chem. A 2000, 104, 1095). Interpretation of the experimental data is supported by extensive calculations performed at the B3LYP/6-311++G(d,p), MP2/6-31G(d,p) and MP2/6-311++G(d,p) levels. [source]

Supramolecular Structure of Self-assembled Synthetic Zinc-131 -oxo-chlorins Possessing a Primary, Secondary or Tertiary Alcoholic 31 -Hydroxyl Group: Visible Spectroscopic and Molecular Modeling Studies,

PHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 2 2001
Shiki Yagai
ABSTRACT Zinc-chlorin 3 (see Fig. 2 in text) possessing a tertiary 31 -hydroxyl group and a 13-keto group was synthesized as a model for the antenna chlorophylls of green bacteria. Self-aggregation of 3 in nonpolar organic media was examined and compared to 1 and 2 possessing a primary and secondary 31 -hydroxyl group, respectively. Zinc-chlorin 3 self-aggregated in 1 vol% CH2Cl2,hexane to form oligomers and showed a red-shifted Qy maximum at 704 nm compared to the monomer (648 nm in CH2Cl2). This red-shift is larger than that of 2S (648 , 697 nm) and comparable to that of 2R (648 , 705 nm), but smaller than that of 1 (648 , 740 nm), indicating that while a single 31 -methyl group (prim -OH ,sec -OH) suppressed close and/or higher aggregation, the additional 31 -methyl group (sec -OH ,tert -OH) did not further suppress aggregation. The relative stability of the aggregates was in the order 1 > 2R, 3 > 2S as determined by visible spectral analyses. Molecular modeling calculations on dodecamers of zinc-chlorins 1, 2R and 3 gave similar well-ordered energy-minimized structures, while 1 stacked more tightly than 2R and 3. In contrast, 2S gave a relatively disordered (twisted) structure. The calculated dodecameric structures could explain the visible spectral data of 1,3 in nonpolar organic media. [source]

Spectroscopic and thermal studies of poly[(N -vinylimidazole)- co -(maleic acid)] hydrogel and its quaternized form

POLYMER INTERNATIONAL, Issue 4 2008
Nursel Pekel
Abstract BACKGROUND: In this study, poly[(N -vinylimidazole)- co -(maleic acid)] (poly(VIm/MA)) hydrogels were prepared by ,-irradiation of ternary mixtures of N -vinylimidazole,maleic acid,water using a 60Co ,-source. Spectroscopic and thermal analyses of these hydrogels as a function of protonation showed that the results are consistent with the existence of an H-bridged complex when the imidazole rings are partially protonated. Finally, the efficiency and binding trends of Cu2+, Co2+, Cd2+ and Pb2+ ions with both protonated and unprotonated poly(VIm/MA) hydrogels were determined. RESULTS: Gelation of 90% was reached at around 180 kGy dose at the end of irradiation. The poly(VIm/MA) hydrogels synthesized were further protonated in HCl solutions with different concentrations. Hydrogels originally showed 450% volumetric swelling; this ratio reached 1900% after protonation at pH = 5.0. Fourier transform infrared spectral changes in the +NH stretching region (3200,3600 and 1173 cm,1) and the ring mode deformation at 915 cm,1 are consistent with the formation of an H-bridged complex between the protonated and unprotonated imidazole rings upon partial protonation. Similar changes were obtained from NMR spectra of both the protonated and unprotonated forms of the hydrogels. CONCLUSION: Protonated and unprotonated hydrogels have been used in heavy metal ion adsorption studies for environmental purposes. Adsorption decreased with decreasing pH value due to the protonation of the VIm ring. The adsorption of Me2+ ions decreased in the order Cu2+ > Co2+ > Cd2+ > Pb2+, which is related to the complexation stability as well as the ionic radius of the metal ions. These results show that P(VIm/MA) hydrogels can be used efficiently to remove heavy metal ions from aqueous solutions. However, the protonated form is a bad choice for heavy metal ion adsorption due to electrostatic repulsion forces; it can nevertheless be assumed to be a good choice for anion adsorption from environmental waste water systems. Copyright © 2007 Society of Chemical Industry [source]

Interpenetrating polymeric network hydrogels for potential gastrointestinal drug release

POLYMER INTERNATIONAL, Issue 11 2007
Sema Ekici
Abstract New interpenetrating polymeric network (IPN) hydrogels based on chitosan (C), poly(N -vinyl pyrrolidone) (PVP) and poly(acrylic acid) (PAAc), crosslinked with glutaraldehyde (G) and N,N,-methylenebisacrylamide (MBA), were prepared and investigated for potential gastrointestinal drug delivery vehicles utilizing a model drug, amoxicillin. IPN hydrogels were synthesized by simultaneous polymerization/crosslinking of acrylic acid monomer in the presence of another polymer (C) and crosslinker (G, MBA). Three different concentrations of glutaraldehyde were used (0.5, 1.0 and 2.0 w/w) to control the overall porosity of the hydrogels, named C-P-AAc/0.5, C-P-AAc/1.0 and C-P-AAc/2.0, respectively. Spectroscopic and thermal analyses such as Fourier transform infrared spectroscopy, thermogravimetric analysis and thermomechanical analysis were performed for IPN characterization. Equilibrium swelling studies were conducted for pH and temperature response behavior. Swelling studies were also carried out in simulated gastric fluid of pH = 1.1 and simulated intestinal fluid of pH = 7.4 to investigate possible site-specific drug delivery. It was found that the release behavior of the drug from these IPN hydrogels was dependent on the pH of the medium and the proportion of crosslinker in the IPN. It was observed that amoxicillin release at pH = 7.4 was higher than at pH = 1.1. The analysis of the drug release showed that amoxicillin was released from these hydrogels through a non-Fickian diffusion mechanism. Copyright © 2007 Society of Chemical Industry [source]

Spectroscopic and theoretical investigation of capillary-induced keto,enol tautomerism of phenacyl benzoylpyridinium-type photoinitiators

POLYMER INTERNATIONAL, Issue 4 2007
Nihan Yonet
Abstract Phenacyl benzoylpyridinium (PBP) salts are effective photoinitiatiors for cationic polymerization. In this study, it is shown that PBP salts are stable in their keto forms, and undergo a reversible keto,enol tautomerization reaction when a capillary action is applied. Spectroscopic and theoretical methods are used to explain the existence of the enol forms in the capillary tube. Copyright © 2006 Society of Chemical Industry Society of Chemical Industry [source]

Molecular interactions of isoxazolcurcumin with human serum albumin: Spectroscopic and molecular modeling studies

BIOPOLYMERS, Issue 2 2009
Bijaya Ketan Sahoo
Abstract Curcumin is a nontoxic natural product with diverse pharmacological potencies. We report the interaction of a potent synthetic derivative of curcumin, isoxazolcurcumin (IOC) with human serum albumin (HSA) using various biophysical methods. The observed fluorescence quenching of HSA by IOC is due to a complex formation by a static quenching process with a quenching constant of the order of 105M,1. The binding affinity and the number of binding sites were obtained from a Scatchard analysis. Thermodynamics reveals that the interaction is entropy driven with predominantly hydrophobic forces. From the observed Förster-type fluorescence resonance energy transfer (FRET), the donor (Trp 214 in HSA) to acceptor (IOC) distance is calculated to be 3.2 nm. The conformational changes of HSA due to the interaction were investigated qualitatively from synchronous fluorescence spectra along with a quantitative estimation of the secondary structure from Fourier Transform Infrared (FTIR) and circular dichroism (CD) spectroscopies. Molecular docking studies were performed to obtain information on the possible residues involved in the interaction process, and changes in accessible surface area of the interacting residues were calculated. The preferred binding site of IOC was analyzed by ligand displacement experiments with 1-anilino-8-naphthalenesulfonate (ANS) and warfarin-bound HSA. © 2008 Wiley Periodicals, Inc. Biopolymers 91: 108,119, 2009. This article was originally published online as an accepted preprint. The "Published Online" date corresponds to the preprint version. You can request a copy of the preprint by emailing the Biopolymers editorial office at biopolymers@wiley.com [source]

Spectroscopic and perfusion magnetic resonance imaging predictors of progression in pediatric brain tumors

CANCER, Issue 6 2004
A. Aria Tzika Ph.D.
Abstract BACKGROUND In vivo biomarkers to predict progression of brain tumors are of great value in clinical practice. Therefore, the authors tested the hypothesis that changes in choline ratios by magnetic resonance (MR) spectroscopic imaging and/or relative tumor blood volume (rTBV) can differentiate clinically stable from progressive pediatric brain tumors. METHODS MR spectroscopic imaging examinations were performed on 27 children with neuroglial brain tumors during therapy on a 1.5-Tesla MR system. Normalized rTBV values were measured in 11 of 27 patients. Each examination was rated as stable or progressive by clinical and imaging criteria. RESULTS The percent change in normalized choline (Cho) was significantly greater in patients who had progressive examinations compared with patients who had stable examinations (P = 0.03). The percent change in Cho/N-acetylaspartate (Cho/NAA) was significantly higher in patients who had progressive outcomes (n = 18 patients) compared with patients who had stable outcomes (n = 32 patients; P < 0.001; sensitivity, 0.89; specificity, 0.88) and was identified as the most important prognostic indicator of tumor progression by logistic regression (likelihood ratio test, 33.4; P < 0.001). The odds of tumor progression were approximately 55 times greater for patients who showed at least a 20% change in Cho/NAA. rTBV distinguished between progressing and stable tumors (P = 0.03), and Cho/NAA and rTBV values showed interaction to predict the probability of a progressing clinical outcome. CONCLUSIONS The percent change in Cho/NAA by proton MR spectroscopic imaging, assisted by rTBV, was useful in predicting tumor progression in children with brain tumors. Cancer 2004. © 2004 American Cancer Society. [source]

ChemInform Abstract: Matrix-Isolation Infrared Spectroscopic and Density Functional Theory Studies on Reactions of Laser-Ablated Lead and Tin Atoms with Water Molecules.

CHEMINFORM, Issue 3 2008
Yun-Lei Teng
Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source]

Spectroscopic and Magnetic Properties of Co1.7Mn0.3(OH)PO4.

CHEMINFORM, Issue 45 2007
I. de Pedro
Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF. [source]

A Photoelectron Spectroscopic and Computational Study of Sodium Auride Clusters, NanAun - (n = 1,3).

CHEMINFORM, Issue 42 2007
Li-Feng Cui
Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF. [source]

Synthesis and Spectroscopic and Structural Studies of Cross-Conjugated Dienones Derived from Cyclic Ketones and Aromatic Aldehydes.

CHEMINFORM, Issue 16 2007
S. Z. Vatsadze
Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF. [source]

On the Spectroscopic and Thermochemical Properties of ClO, BrO, IO, and Their Anions

CHEMINFORM, Issue 15 2007
Kirk A. Peterson
Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF. [source]