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Absorption Spectroscopy (absorption + spectroscopy)
Kinds of Absorption Spectroscopy Terms modified by Absorption Spectroscopy Selected AbstractsIntracavity Laser Absorption Spectroscopy for flame diagnosticsISRAEL JOURNAL OF CHEMISTRY, Issue 2 2007Igor Rahinov Intracavity Laser Absorption Spectroscopy (ICLAS) is one of the most sensitive techniques in absorption spectroscopy. Application of this technique to combustion diagnostics offers many important advantages. Since ICLAS is an absorption-based method, it is not limited by the quenching and predissociation effects that compromise the sensitivity of Laser Induced Fluorescence (LIF), one of the most sensitive and widespread techniques applied in combustion diagnostics. For that reason, radicals that are subject to strong collisional quenching or predissociation, such as 1CH2 and HCO, can be measured by ICLAS with sensitivity much greater than that of LIF. For the same reason, ICLAS also possesses better sensitivity for NH and HNO. The present paper overviews the ICLAS measurements performed during the last decade in our laboratory and also presents recent results: first-time detection of the HSO radical in flames by ICLAS and application of Fiber Laser Intracavity Absorption Spectroscopy (FLICAS) based on Er-doped fiber laser for in-situ detection of ammonia and hydrogen cyanide in a low-pressure methane/air flame doped with a small amount of ammonia. Avenues for future research are discussed. [source] Investigation into the Chemical Reactivity of Plasma-Deposited Perfluorophenyl Methacrylate Using Infrared Reflection Absorption Spectroscopy and Microcantilever StudiesPLASMA PROCESSES AND POLYMERS, Issue S1 2007Nuria Queralto Abstract Perfluorophenyl methacrylate (pp-PFM) was plasma-polymerized using low duty cycle conditions to yield a surface rich in active ester groups. The reactivity of this surface towards different primary amines was investigated using infrared reflection absorption spectroscopy (IRRAS) and micromechanical cantilever (MC) sensors. While IRRAS provided information on the chemistry, the MC sensors technique gave insights into volume changes induced by the reactions of the polymer film. We found that the volume change upon reaction was different for each of the amines studied and correlated this to the ability of the amines to diffuse into the polymer matrix. The changes observed can be related to reactions occurring either at the liquid,solid interface or to reactions occurring within the matrix of the polymer and appear to be related to the chemical structure of the amines. [source] ChemInform Abstract: Pd,C,Fe Nanoparticles Investigated by X-Ray Absorption Spectroscopy as Electrocatalysts for Oxygen Reduction.CHEMINFORM, Issue 49 2009Yun-Chieh Yeh 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] ChemInform Abstract: Electronic Absorption Spectroscopy of Cobalt Ions in Diluted Magnetic Semiconductor Quantum Dots: Demonstration of an Isocrystalline Core/Shell Synthetic Method.CHEMINFORM, Issue 15 2002Pavle V. Radovanovic Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 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] ChemInform Abstract: Preparation of Nanocrystalline BaTiO3 Characterized by in situ X-Ray Absorption Spectroscopy.CHEMINFORM, Issue 39 2001Holger Rumpf Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 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] Description of the Ground-State Covalencies of the Bis(dithiolato) Transition-Metal Complexes from X-ray Absorption Spectroscopy and Time-Dependent Density-Functional CalculationsCHEMISTRY - A EUROPEAN JOURNAL, Issue 10 2007Kallol Ray Dr. Abstract The electronic structures of [M(LBu)2], (LBu=3,5-di- tert -butyl-1,2-benzenedithiol; M=Ni, Pd, Pt, Cu, Co, Au) complexes and their electrochemically generated oxidized and reduced forms have been investigated by using sulfur K-edge as well as metal K- and L-edge X-ray absorption spectroscopy. The electronic structure content of the sulfur K-edge spectra was determined through detailed comparison of experimental and theoretically calculated spectra. The calculations were based on a new simplified scheme based on quasi-relativistic time-dependent density functional theory (TD-DFT) and proved to be successful in the interpretation of the experimental data. It is shown that dithiolene ligands act as noninnocent ligands that are readily oxidized to the dithiosemiquinonate(,) forms. The extent of electron transfer strongly depends on the effective nuclear charge of the central metal, which in turn is influenced by its formal oxidation state, its position in the periodic table, and scalar relativistic effects for the heavier metals. Thus, the complexes [M(LBu)2], (M=Ni, Pd, Pt) and [Au(LBu)2] are best described as delocalized class,III mixed-valence ligand radicals bound to low-spin d8 central metal ions while [M(LBu)2], (M=Cu, Au) and [M(LBu)2]2, (M=Ni, Pd, Pt) contain completely reduced dithiolato(2,) ligands. The case of [Co(LBu)2], remains ambiguous. On the methodological side, the calculation led to the new result that the transition dipole moment integral is noticeably different for S1s,valence-, versus S1s,valence-, transitions, which is explained on the basis of the differences in radial distortion that accompany chemical bond formation. This is of importance in determining experimental covalencies for complexes with highly covalent metal,sulfur bonds from ligand K-edge absorption spectroscopy. [source] Organoplatinum(II) Complexes with Chromophore,Acceptor Dyad Studied by Ultrafast Time-Resolved Absorption SpectroscopyCHEMISTRY - AN ASIAN JOURNAL, Issue 1 2010Siu-Wai Lai Dr. Femtosecond time-resolved absorption revealed the formation of charged-separated [ClPtIII{C,N,N(PhMV+,)}] species (left) with a forward rate constant of about 1012,s,1, which is more rapid than that of the back electron-transfer process (k,1=1.6×109,s,1). Similar slower back ET reaction than forward light-induced ET reaction of [Pt(MV-bpy)(CCPh)2](PF6)2 (right) has been observed. MV=methyl viologen. [source] X-Ray Absorption Spectroscopy of Cuprous-Thiolate Clusters in Saccharomyces cerevisiae MetallothioneinCHEMISTRY & BIODIVERSITY, Issue 10 2008Limei Zhang Abstract Copper (Cu) metallothioneins are cuprous-thiolate proteins that contain multimetallic clusters, and are thought to have dual functions of Cu storage and Cu detoxification. We have used a combination of X-ray absorption spectroscopy (XAS) and density-functional theory (DFT) to investigate the nature of Cu binding to Saccharomyces cerevisiae metallothionein. We found that the XAS of metallothionein prepared, containing a full complement of Cu, was quantitatively consistent with the crystal structure, and that reconstitution of the apo-metallothionein with stoichiometric Cu results in the formation of a tetracopper cluster, indicating cooperative binding of the Cu ions by the metallothionein. [source] Size-dependent Raman and infrared studies of PbSe nanoparticlesJOURNAL OF RAMAN SPECTROSCOPY, Issue 9 2008F. S. Manciu Abstract Micro-probe Raman and far-infrared absorption spectroscopies were used to prove the existence of optical phonon modes of PbSe nanoparticles prepared by colloidal chemistry and preliminarily characterized by transmission electron microscopy. To the best of our knowledge, this is the first time that evidence of the surface phonon (SP) mode by Raman spectroscopy has been experimentally observed. The wavenumber of the SP mode is consistent with its prediction by a dielectric continuum model. While for different PbSe nanoparticle sizes the observed SP mode does not show any obvious change in its position, there is a clear shift by approximately 4 cm,1 toward higher wavenumber in the appearance of the LO(,) in the Raman spectra from the 3 nm to the 7 nm PbSe nanoparticles. Far-infrared measurements demonstrate the presence of the transverse optical TO(,) and of the coupled phonon modes. Copyright © 2008 John Wiley & Sons, Ltd. [source] Molecular structure study of dimethoxyphenyl-substituted phosphonodipeptides by infrared, Raman, and surface enhanced Raman spectroscopiesJOURNAL OF RAMAN SPECTROSCOPY, Issue 5 2006Edyta Podstawka Abstract In this study, Fourier-transform Raman (FT-RS) and infrared (FT-IR) absorption spectroscopies were employed to characterize the molecular structures of L -Ala-(3,4-dimethoxy)- L -Phe-PO3H2 (A) and L -Ala-(3,4-dimethoxy)-(des-CH2)- L -Phe-PO3H2 (B) phosphonodipeptides, where L -Phe denotes L -phenylalanine and L -Ala, L -alanine. The vibrational band assignments have been proposed. In order to determine the structures of these dimethoxyphenyl-substituted phosphonodipeptides adsorbed on a colloidal silver surface, surface enhanced Raman spectra (SERS) were measured. The analysis of SERS band intensities showed that these dimethoxyphenyl-substituted phosphonodipeptides directly interacted with the silver surface through the aromatic ring of Phe that adopted an orientation almost perpendicular to the silver surface. We also showed that intense enhancement of the ,as(NH2), ,as(PO32,), and ,(PO) modes of L -Ala-(3,4-dimethoxy)- L -Phe-PO3H2 suggested that these groups were mainly involved in the interaction with the silver colloid. Additionally, we proved that in the SERS spectrum of L -Ala-(3,4-dimethoxy)-(des-CH2)- L -Phe-PO3H2, several vibrations of the CH3 group were enhanced, indicating a flattened orientation of the peptide backbone on the silver surface. Copyright © 2005 John Wiley & Sons, Ltd. [source] On-line optical and X-ray spectroscopies with crystallography: an integrated approach for determining metalloprotein structures in functionally well defined statesJOURNAL OF SYNCHROTRON RADIATION, Issue 5 2008Mark J. Ellis X-ray-induced redox changes can lead to incorrect assignments of the functional states of metals in metalloprotein crystals. The need for on-line monitoring of the status of metal ions (and other chromophores) during protein crystallography experiments is of growing importance with the use of intense synchrotron X-ray beams. Significant efforts are therefore being made worldwide to combine different spectroscopies in parallel with X-ray crystallographic data collection. Here the implementation and utilization of optical and X-ray absorption spectroscopies on the modern macromolecular crystallography (MX) beamline 10, at the SRS, Daresbury Laboratory, is described. This beamline is equipped with a dedicated monolithic energy-dispersive X-ray fluorescence detector, allowing X-ray absorption spectroscopy (XAS) measurements to be made in situ on the same crystal used to record the diffraction data. In addition, an optical microspectrophotometer has been incorporated on the beamline, thus facilitating combined MX, XAS and optical spectroscopic measurements. By uniting these techniques it is also possible to monitor the status of optically active and optically silent metal centres present in a crystal at the same time. This unique capability has been applied to observe the results of crystallographic data collection on crystals of nitrite reductase from Alcaligenes xylosoxidans, which contains both type-1 and type-2 Cu centres. It is found that the type-1 Cu centre photoreduces quickly, resulting in the loss of the 595,nm peak in the optical spectrum, while the type-2 Cu centre remains in the oxidized state over a much longer time period, for which independent confirmation is provided by XAS data as this centre has an optical spectrum which is barely detectable using microspectrophotometry. This example clearly demonstrates the importance of using two on-line methods, spectroscopy and XAS, for identifying well defined redox states of metalloproteins during crystallographic data collection. [source] NMR in photo-induced chemical exchange systems.CONCEPTS IN MAGNETIC RESONANCE, Issue 5 2006-dipyridyl)ethene photoisomerization kinetics, Double-resonance inverse fractional population transfer application for investigation of Abstract The analytical expression describing the dynamics of nuclear magnetization with the use of double-resonance NMR by the procedure of inverse fractional population transfer in requirements of photo-induced chemical exchange (PICE) is obtained in this article. Laser-induced (, = 308 nm) photoisomerization of 1,2-(2,2,-dipyridyl)ethene was studied by NMR and UV absorption spectroscopy under irreversible and photostationary conditions. © 2006 Wiley Periodicals, Inc. Concepts Magn Reson Part A 28A: 337,346, 2006 [source] A New Amperometric Hydrazine Sensor Based on Prussian Blue/Single-walled Carbon Nanotube NanocompositesELECTROANALYSIS, Issue 16 2010Cong Wang Abstract A slow reaction process has been successfully used to synthesize Prussian blue/single-walled carbon nanotubes (PB/SWNTs) nanocomposites. Electrochemical and surface characterization by cyclic voltammetry (CV), scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV-vis absorption spectroscopy, Fourier transform infrared (FTIR) spectroscopy and X-ray diffraction (XRD) confirmed the presence of PB nanocrystallites on SWNTs. PB/SWNTs modified glassy carbon electrode (GCE) exhibits efficient electron transfer ability and high electrochemical response towards hydrazine. The fabricated hydrazine sensor showed a wide linear range of 2.0×10,6,6.0×10,3,M with a response time less than 4,s and a detection limit of 0.5,,M. PB/SWNTs modified electrochemical sensors are promising candidates for cost-effective in the hydrazine assays. [source] A Study of Nafion-Coated Bismuth-Film Electrode for the Determination of Zinc, Lead, and Cadmium in Blood SamplesELECTROANALYSIS, Issue 21 2008Benzhi Liu Abstract In this article a sensitive differential pulse stripping voltammetry technique on Nafion-coated bismuth-film electrode (NCBFE) was studied for the simultaneous determination of zinc, cadmium, and lead ions in blood samples at ultra trace levels. The measurement results were in excellent agreement with those obtained from atomic absorption spectroscopy. Various operational parameters were investigated and discussed in terms of their effect on the measurement signals. Under optimal conditions, calibration curves for the simultaneous determination of zinc, cadmium, and lead ions were achieved, based on three times the standard deviation of the baseline, the limits of detection were 0.09,,g L,1 for Cd(II), 0.13,,g L,1 for Pb(II), and 0.97,,g L,1 for Zn(II) respectively. [source] Multilayer Assembly of Hemoglobin and Colloidal Gold Nanoparticles on Multiwall Carbon Nanotubes/Chitosan Composite for Detecting Hydrogen PeroxideELECTROANALYSIS, Issue 19 2008Shihong Chen Abstract Chitosan (CS) was chosen for dispersing multi-wall carbon nanotubes (MWNTs) to form a stable CS-MWNTs composite, which was first coated on the surface of a glassy carbon electrode to provide a containing amino groups interface for assembling colloidal gold nanoparticles (GNPs), followed by the adsorption of hemoglobin (Hb). Repeating the assembly step of GNPs and Hb resulted in {Hb/GNPs}n multilayers. The assembly of GNPs onto CS-MWNTs composites was confirmed by transmission electron microscopy. The consecutive growth of {Hb/GNPs}n multilayers was confirmed by cyclic voltammetry and UV-vis absorption spectroscopy. The resulting system brings a new platform for electrochemical devices by using the synergistic action of the electrocatalytic activity of GNPs and MWNTs. The resulting biosensor displays an excellent electrocatalytic activity and rapid response for hydrogen peroxide. The linear range for the determination of H2O2 was from 5.0×10,7 to 2.0×10,3 M with a detection limit of 2.1×10,7 M at 3, and a Michaelis,Menten constant KMapp value of 0.19,mM. [source] Synthesis and Characterization of MWNTs/Au NPs/HS(CH2)6Fc Nanocomposite: Application to Electrochemical Determination of Ascorbic AcidELECTROANALYSIS, Issue 16 2008Jian-Ding Qiu Abstract In this article, a detailed electrochemical study of a novel 6-ferrocenylhexanethiol (HS(CH2)6Fc) self-assembled multiwalled carbon nanotubes-Au nanoparticles (MWNTs/Au NPs) composite film was demonstrated. MWNTs/Au NPs were prepared by one-step in situ synthesis using linear polyethyleneimine (PEI) as bifunctionalizing agent. HS(CH2)6Fc, which acted as the redox mediator, was self-assembled to MWNTs/Au NPs via Au-S bond. Transmission electron microscopy (TEM), energy-dispersive X-ray analysis (EDX), Fourier transformed infrared absorption spectroscopy (FT-IR), UV-visible absorption spectroscopy, and cyclic voltammetry were used to characterize the properties of the MWNTs/Au NPs/HS(CH2)6Fc nanocomposite. The preparation of the nanocomposite was very simple and effectively prevented the leakage of the HS(CH2)6Fc mediator during measurements. The electrooxidation of AA could be catalyzed by Fc/Fc+ couple as a mediator and had a higher electrochemical response due to the unique performance of MWNTs/Au NPs. The nanocomposite modified electrode exhibited excellent catalytic efficiency, high sensitivity, good stability, fast response (within 3,s) and low detection limit toward the oxidation of AA at a lower potential. [source] Properties of Poly(sodium 4-styrenesulfonate)-Ionic Liquid Composite Film and Its Application in the Determination of Trace Metals Combined with Bismuth Film ElectrodeELECTROANALYSIS, Issue 5 2008Jianbo Jia Abstract A new kind of bismuth film modified electrode to sensitively detect trace metal ions based on incorporating highly conductive ionic liquids 1-butyl-3-methyl-imidazolium hexafluorophosphate (BMIMPF6) in solid matrices at glassy carbon (GC) was investigated. Poly(sodium 4-styrenesulfonate) (PSS), silica, and Nafion were selected as the solid matrices. The electrochemical properties of the mixed films modified GC were evaluated. The electron transfer rate of Fe(CN)64,/Fe(CN)63, can be effectively improved at the PSS-BMIMPF6 modified GC. The bismuth modified PSS-BMIMPF6 composite film electrodes (GC/PSS-BMIMPF6/BiFEs) displayed high mechanical stability and sensitive stripping voltammetric performances for the determination of trace metal cations. The GC/PSS-BMIMPF6/BiFE exhibited well linear response to both Cd(II) and Pb(II) over a concentration range from 1.0 to 50,,g L,1. And the detection limits were 0.07,,g L,1 for Cd(II) and 0.09,,g L,1 for Pb(II) based on three times the standard deviation of the baseline with a preconcentration time of 120,s, respectively. Finally, the GC/PSS-BMIMPF6/BiFEs were successfully applied to the determination of Cd(II) and Pb(II) in real sample, and the results of present method agreed well with those of atomic absorption spectroscopy. [source] Halotaxis of cyanobacteria in an intertidal hypersaline microbial matENVIRONMENTAL MICROBIOLOGY, Issue 3 2010Katharina Kohls Summary An intertidal hypersaline cyanobacterial mat from Abu Dhabi (United Arab Emirates) exhibited a reversible change in its surface colour within several hours upon changes in salinity of the overlying water. The mat surface was orange-reddish at salinities above 15% and turned dark green at lower salinities. We investigated this phenomenon using a polyphasic approach that included denaturing gradient gel electrophoresis, microscopy, high-performance liquid chromatography, hyperspectral imaging, absorption spectroscopy, oxygen microsensor measurements and modelling of salinity dynamics. Filaments of Microcoleus chthonoplastes, identified based on 16S rRNA sequencing and morphology, were found to migrate up and down when salinity was decreased below or increased above 15%, respectively, causing the colour change of the mat uppermost layer. Migration occurred in light and in the dark, and could be induced by different salts, not only NaCl. The influence of salinity-dependent and independent physico-chemical parameters, such as water activity, oxygen solubility, H2S, gravity and light, was excluded, indicating that the observed migration was due to a direct response to salt stress. We propose to term this salinity-driven cyanobacterial migration as ,halotaxis', a process that might play a vital role in the survival of cyanobacteria in environments exposed to continuous salinity fluctuations such as intertidal flats. [source] Absorption of copper(II) by creosote bush (Larrea tridentata): Use of atomic and x-ray absorption spectroscopyENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 11 2001Jorge Luis Gardea-Torresdey Abstract Larrea tridentata (creosote bush), a common North American native desert shrub, exhibits the ability to take up copper(II) ions rapidly from solution. Following hydroponic studies, U.S. Environmental Protection Agency method 200.3 was used to digest the plant samples, and flame atomic absorption spectroscopy (FAAS) was used to determine the amount of copper taken up in different parts of the plant. The amount of copper(II) found within the roots, stems, and leaves was 13.8, 1.1, and 0.6 mg/g, respectively, after the creosote bush was exposed to a 63.5-ppm copper(II) solution for 48 h. When the plant was exposed to a 635-ppm copper(II) solution, the roots, stems, and leaves contained 35.0, 10.5, and 3.8 mg/g, respectively. In addition to FAAS analysis, x-ray microfluorescence (XRMF) analysis of the plant samples provided further confirmation of copper absorption by the various plant parts. X-ray absorption spectroscopy (XAS) elucidated the oxidation state of the copper absorbed by the plants. The copper(II) absorbed from solution remained as copper(II) bound to oxygen-containing ligands within the plant samples. The results of this study indicate that creosote bush may provide a useful and novel method of removing copper(II) from contaminated soils in an environmentally friendly manner. [source] meta -Terphenyl Phosphaalkenes Bearing Electron-Donating and -Accepting GroupsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 6 2010Vittal B. Gudimetla Abstract A set of para -substituted meta -terphenyl phosphaalkenes of the form 4-X-2,6-Mes2C6H2P=C(H)C6H4 -4-X, (X = H, MeO or NMe2; X, = H, CN, or NO2) have been synthesized to allow systematic studies of the impact of remote X and X, substituents on the phosphaalkene unit. The new compounds were characterized by 1H and 31P NMR spectroscopy, UV/Vis absorption spectroscopy, single X-ray crystal structures (for four compounds) and by electrochemical studies. The introduction of remote groups (X,) on the less hindered phenyl ring generated more significant effects on the physical properties of the materials than did substituents (X) on the hindered meta -terphenyl rings. These effects were also explored by computational methods in order to assess the influence of substituents on structures and properties. The polarization of these molecules is less than that produced for analogous alkenes, as the phosphaalkenes bear sterically demanding groups that constrain the systems to adopt conformations that are less than ideal for maximum ,-conjugation of the central , network [source] Ultrasound-Assisted Synthesis of CuO Nanorods in a Neat Room-Temperature Ionic LiquidEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 19 2009Tarek Alammar Abstract CuO nanorods were prepared via ultrasound-assisted synthesis in the room temperature ionic liquid (RTIL) 1-butyl-3-methylimidazoliumbis(trifluoromethylsulfonyl)imide [C4mim][Tf2N] as a reaction medium. The structure and morphology of CuO nanorods were characterized with X-ray powder diffraction (XRD), transmission electron microscopy (TEM), energy-dispersive X-ray analysis (EDX), X-ray photoelectron spectroscopy (XPS), vibrational and UV/Vis absorption spectroscopy. The synthesized CuO nanocrystals are of rod like shape with lengths from 30 to 100 nm and diameters of about 10 nm. Quantum size effects were observed as the bandgap of the CuO nanorods was determined to 2.41 eV from UV/Vis absorption measurements, which is significantly larger than the bulk value. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Synthesis and Characterization of Radical Cations Derived from Mono- and Biferrocenyl-Substituted 2-Aza-1,3-butadienes: A Study of the Influence of an Asymmetric and Oxidizable Bridge on Intramolecular Electron TransferEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 12 2005Vega Lloveras Abstract The synthesis and study of structural and electronic properties of mono-ferrocenyl ,-conjugated complexes 5a,d, whose electronic characteristics have been systematically varied by introducing an electron-donating or electron-withdrawing substituent either at the 1-position or at the 4-position of the 2-aza-1,3-butadiene moiety linked to the ferrocenyl unit, are presented. The structural and electronic properties of the homobimetallic complex 5f, with two ferrocene units linked through the asymmetric and oxidizable 2-aza-1,3-butadiene bridge, is also reported. The crystal structures of complexes 5b, 5d, and 5f show a large degree of conjugation in this family of compounds. Complexes 5 show a rich electrochemical behavior due both to the oxidation of ferrocenyl units and the 2-aza-1,3-butadiene bridge, as revealed by cyclic voltammetry. Radical cations 5+· were prepared from 5 by coulometric oxidations following their generation by absorption spectroscopy. The electronic properties of all reported neutral and oxidized ,-conjugated complexes have been investigated by means of UV/Vis,near-IR, EPR and 57Fe Mössbauer spectroscopy. The detailed study of mono-oxidized species 5a+·,5f+· has permitted the determination of the influence of an asymmetric bridge with an electroactive character on the intramolecular electron transfer (IET) phenomenon, thus demonstrating that the 2-aza-1,3-butadiene bridge promotes the IET between the two metallic units of 5f+· through two different pathways. The experimental data and conclusions are supported by DFT computations (B3LYP/3-21G*) and time-dependent DFT methods. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Dimeric 2,2,-Bipyridylruthenium(II) Complexes Containing 2,2,-Bis(1,2,4-triazin-3-yl)-4,4,-bipyridine-Like Bridging Ligands: Syntheses, Characterization and DNA BindingEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 11 2004Cai-Wu Jiang Abstract Three new bridging ligands 2,2,-bis(1,2,4-triazin-3-yl)-4,4,-bipyridine (btb), 2,2,-bis(1,2,4-triazino[5,6-f]acenaphthylen-3-yl)-4,4,-bipyridine (btapb), 2,2,-bis(5,6-diphenyl-1,2,4-triazin-3-yl)-4,4,-bipyridine (bdptb) and their dimeric 2,2,-bipyridylruthenium(II) complexes [Ru(bpy)2(btb)Ru(bpy)2]4+ (1), [Ru(bpy)2(btapb)Ru(bpy)2]4+ (2), [Ru(bpy)2(bdptb)Ru(bpy)2]4+ (3) have been synthesized and characterized by elemental analysis, fast atom bombardment (FAB) mass spectrometry or electrospray mass spectrometry (ES-MS), 1H NMR and UV/Visible spectroscopy. The binding behavior of these dimeric complexes with calf thymus DNA (CT-DNA) was investigated by electronic absorption spectroscopy, viscosity measurements, and equilibrium dialysis experiments. The hypochromism of the metal-ligand charge transfer (MLCT) band in the electronic absorption spectra of the dinuclear complexes 1, 2, and 3 is 8.7%, 19% and 33%, respectively, with bathochromic shifts of 5, 5 and 14 nm, respectively. The binding constants are 7.5×104M,1, 4.8×105M,1 and 7.6×105M,1, respectively. Increasing the size of the plane of the bridging ligand increases the hydrophobicity of their complexes, leading to stronger binding by the complexes to calf thymus DNA. The effect of increasing concentrations of these novel dimeric ruthenium(II) complexes on the relative viscosities of CT-DNA is less notable than that of well-known intercalators such as [Ru(bpy)2(dppz)]2+. The equilibrium experiments showed that ,,,3 binding is stronger than ,,,3 binding to CT-DNA. This is the first example of a dinuclear complex binding enantioselectively to CT-DNA measured by equilibrium dialysis. The experiments suggest that the three complexes may be DNA groove binders. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Oxidation of oleuropein studied by EPR and spectrophotometryEUROPEAN JOURNAL OF LIPID SCIENCE AND TECHNOLOGY, Issue 2 2008Evaggelia D. Tzika Abstract The autoxidation at alkaline pH and enzymatic oxidation by mushroom tyrosinase of oleuropein, the dominant biophenol present in the fruits and leaves of Olea europea, was followed by both electron paramagnetic resonance (EPR) and absorption spectroscopy. For comparison, the same oxidation processes were applied to 4-methylcatechol, a simple polyphenol present in olive mill wastewaters. EPR spectra of stable o -semiquinone radicals produced during autoxidation at pH,12 and short-lived o -semiquinone free radicals produced during autoxidation at pH,9.0 or tyrosinase action and stabilized by chelation with a diamagnetic metal ion (Mg2+) were recorded for both polyphenols, and the corresponding hyperfine splitting constants were determined. The UV-Vis spectral characteristics of the oxidation of polyphenols were highly dependent on the type of polyphenol, oxidant type and the pH of the reaction. The kinetic behavior of tyrosinase in the presence of oleuropein and 4-methylcatechol was followed by recording spectral changes at 400,nm (absorption maximum) over time. The tysosinase activity with oleuropein showed a pronounced pH optimum at pH,6.5 and a minor one around pH,8. From the data analysis of the initial rate at pH,6.5, the kinetic parameters Km = 0.34,±,0.03,mM and Vmax = 0.029,±,0.002 ,A400,min,1 were determined for oleuropein. [source] Surface Activation of a Ferrimagnetic Glass,Ceramic for Antineoplastic Drugs GraftingADVANCED ENGINEERING MATERIALS, Issue 7 2010Enrica Vernè A ferrimagnetic glass,ceramic, belonging to the system SiO2,Na2O,CaO,P2O5,FeO,Fe2O3, has been studied as potential carrier for antineoplastic agents, in order to exploit the combination of hyperthermia and chemotherapy. Different material pre-treatments, such as ultrasonic washing, water, or simulated body fluid dipping, were evaluated to promote the surface activation of the glass,ceramic, i.e., the hydroxyl groups formation on it. X-ray photoelectron spectroscopy, scanning electron microscopy, energy dispersion spectrometry, and wettability measurements were performed to observe the samples surface modification. The best results in terms of free hydroxyl groups exposition were obtained by dipping the samples in distilled water for 7 days at 37,°C. Two different anticancer drugs were selected in order to test the reactivity of the activated surface: cisplatinum and doxorubicin. The uptake and release of doxorubicin and cisplatinum were evaluated on glass,ceramic powders, by using UV,Visible spectrometry and graphite furnace atomic absorption spectroscopy, respectively. After 1 day of uptake at 37,°C, the quantity of doxorubicin incorporated into the glass,ceramic is 77,±,7 wt%, while only 42,±,9.6 wt% of cisplatinum is grafted onto the material surface. For both antitumoral agents, the maximum drug release after soaking in aqueous solutions at 37,°C was obtained in few hours, with a randomly distributed kinetics trend. [source] Off the Back or on the Side: Comparison of meso and 2-Substituted Donor-Acceptor Difluoroborondipyrromethene (Bodipy) DyadsEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 15 2010Andrew C. Benniston Abstract The preparation of several difluoroborondipyrromethene (Bodipy) dyads is described incorporating covalently attached hydroquinone/quinone groups at the 2-position (BD-SHQ, BD-SQ, BD-SPHQ, BD-SPQ). The compounds, currently under investigation as chemical sensors for reactive oxygen species, show various levels of fluorescence depending on the oxidation state of the appended group. The 19F NMR spectrum for BD-SHQ in CDCl3 at room temperature reveals the two fluorines are inequivalent on the NMR timescale. In contrast, the 19F NMR spectrum for the counterpart quinone compound, BD-SQ, is consistent with two equivalent fluorine atoms. The two results are interpreted as the quinone is free to rotate around the connector bond, whereas this motion is restricted for the hydroquinone group and makes the fluorines chemically inequivalent. Cyclic voltammograms recorded for all derivatives in CH2Cl2 electrolyte solution are consistent with typical Bodipy-based redox chemistry; the potentials of which depend on factors such as presence of the phenylene spacer and oxidation state of the appended group. A comparison of the electrochemical behaviour with the counterpart meso derivatives reveals some interesting trends which are associated with the location of the HOMO/LUMOs. The absorption profiles for the compounds in CH3CN are again consistent with Bodipy-based derivatives, though there are some subtle differences in the band-shapes of the closely-coupled systems. In particular, the absorption spectra for the dyad, BD-SQ, in a wide range of solvents are appreciably broader than for BD-SHQ. Femtosecond transient absorption spectroscopy performed on the hydroquinone derivatives, BD-SHQ and its meso analogue is interpreted as electron transfer occurs from the hydroquinone unit to the first-excited singlet (S1) state of the Bodipy center, followed by ultrafast charge recombination to reinstate the ground state. The coupling of OH vibrations to the return electron transfer process is invoked to explain the lack of clear identification of the charge-separated state in the transient records. [source] Thermodynamics of Complexes between Dibenzo-24-crown-8 Derivatives and 1,2-Bis(pyridinium)ethanesEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 27 2007Yu Liu Abstract The binding behavior of para -substituted 1,2-bis(pyridinium)ethane derivatives (X-PyCH2,CH2Py-X, X = H, Me, Ph, and Py) a,d with dibenzo-24-crown-8 (DB24C8, 1) and its derivatives, diformyldibenzo-24-crown-8 (2), dinitrodibenzo-24-crown-8 (3), dimethyldibenzo-24-crown-8 (4) and diaminodibenzo-24-crown-8 (5), has been comprehensively investigated by 1H NMR and UV absorption spectroscopy and isothermal titration microcalorimetry in acetonitrile. The results obtained indicated that some of the complexes constructed from DB24C8 derivatives and 1,2-bis(pyridinium)ethane derivatives resulted in visible color changes. For example, upon the addition of equimolar proportions of 5, the colorless CH3CN solution of d changed to red. Furthermore, we investigated the thermodynamics of the complexation of crown ethers 1,5 with guests a,d, and found that the nature of the substituents attached to 1,2-bis(pyridinium)ethanes and the catechol rings on DB24C8 dramatically affects the molecular recognition behavior and the binding thermodynamics. Thermodynamically, the formation of these complexes is an enthalpy-driven process. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Systematic Studies on Photoluminescence of Oligo(arylene-ethynylene)s: Tunability of Excited States and Derivatization as Luminescent Labeling Probes for ProteinsEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 14 2006Yong-Gang Zhi Abstract Functionalized oligo(phenylene-ethynylene)s (OPEs) with different conjugation lengths, p -X(C6H4C,C)nSiMe3 (n = 1,4; X = NH2, NMe2, H) were synthesized by Sonogashira coupling of (phenylene-ethynylene)s and 1-iodo-4-(trimethylsilylethynyl)benzene, followed by desilylation of the p -substituted (trimethylsilylethynyl)benzenes with potassium hydroxide. The photoluminescent properties for the OPE series with different chain lengths and their solvatochromic responses were examined. The absorption maxima were red-shifted with increasing numbers of ,(C6H4C,C), units (n), and a linear plot of the absorption energy maxima vs. 1/n was obtained for each series. The emission spectra in dichloromethane showed a broad and structureless band, the energies of which (in wavenumbers) also fit linearly with 1/n. Both the absorption and emission wavelength maxima of the NH2 - and NMe2 -substituted OPEs exhibited significant solvent dependence, whereas the parent OPEs (X = H) showed only minor shifts of the ,max values in different solvents. Substituent effects upon the photoluminescent characteristics of the OPEs and the tunability of the excited states were examined with the p -X(C6H4C,C)nSiMe3 (n = 2, 3; X = NH2, NMe2, H, SMe, OMe, OH, and F) series. The H- and F-substituted counterparts exhibited high-energy vibronically structured emissions attributed to the 3(,,*) excited states of the (arylene-ethynylene) backbone. For compounds bearing NH2 and NMe2 groups, a broad red-shifted emission with a remarkable Stokes shift from the respective absorption maximum was observed, which can be assigned to an n , ,* transition. The n , ,* assignment was supported by MO calculations on the model compounds p -X(C6H4C,C)2SiH3 (X = NH2, H). Functionalization of the oligo(arylene-ethynylene)s with the N -hydroxysuccinimidyl (NHS) moiety enabled covalent attachment of the fluorophore to HSA protein molecules. A series of fluorescent labels, namely p -X(C6H4C,C)nC6H4NHS, (n = 1, X = NH2, NMe2, SMe, OMe, OH, F; n = 2, X = NH2, NMe2) and p -Me2NC6H4C,C(C4H2S)C,CC6H4NHS were synthesized, and their conjugates with HSA (human serum albumin) were characterized by MALDI-TOF mass spectrometry, UV/Vis absorption spectroscopy, and gel electrophoresis. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Synthesis and Photophysical Properties of a Pyrazolino[60]fullerene with Dimethylaniline Connected by an Acetylene LinkageEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 10 2006Andreas Gouloumis Abstract A new triad based on pyrazolino[60]fullerene and a conjugated dimethylaniline group has been synthesized by a copper-free Sonogashira cross-coupling reaction using microwave irradiation as the source of energy. The electrochemical and photophysical properties of the triad were systematically investigated by techniques such as time-resolved fluorescence and transient absorption spectroscopy. Charge separation via the excited singlet state of the C60 moiety was confirmed in polar and nonpolar solvents and competes with triplet formation of the C60 moiety. The charge-separated state persisted for 91 ns. Such long lifetimes are characteristic of long distances between the radical anion of the pyrazolino[60]fullerene derivative and the radical cation of the dimethylaniline moiety. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Arborol-Functionalised Tetrathiafulvalene Derivatives: Synthesis and Thin-Film FormationEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 18 2003Thierry Le Gall Abstract The syntheses of a series of novel tetrathiafulvalene derivatives substituted with four side-chains terminating in hydrophilic amidoalcohol (arborol) groups are reported, for example the tetrathiafulvalene derivative 15. Some of these arborol derivatives formed thin films by spin-coating from methanol solution onto solid supports such as glass, ITO-coated glass and gold. The quality of the films improved markedly with an increasing number of alcohol substituents at the periphery of the molecule. Optical absorption spectroscopy showed that oxidative doping of these films could be achieved chemically and electrochemically. The observation of low-energy bands in the UV/Vis absorption spectra (,max = 820 nm tailing to ca. 1300 nm) and the moderate levels of conductivity (,rt , 10,4 S cm,1) in these doped films strongly suggest that a significant degree of supramolecular order is present, with ,-, stacking of the TTF cores. To the best of our knowledge this is the first time that semiconducting behaviour has been achieved in molecular arborol systems that possess an electroactive core unit. This work offers the prospect of using spin-coated films of TTF-arborols as semiconducting charge-transport layers in optoelectronic devices. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] | |||||||||||||||||||||||||||||||||||||||||||