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Model Compounds (model + compound)
Kinds of Model Compounds Selected AbstractsSubcritical Water Reaction Behavior of D -Glucose as a Model Compound for Biomass Using Two Different Continuous-Flow Reactor ConfigurationsCHEMICAL ENGINEERING & TECHNOLOGY (CET), Issue 4 2009T. Saito Abstract Recently, cellulosic materials have been considered as a useful resource for the recovery of valuable chemicals and liquid fuels, etc. Cellulose is a homopolymer of D -glucose, which is often used as a model compound for biomass. Reactions of D -glucose in subcritical water as the reaction solvent were conducted using a single-flow-type reactor (S1) and an admixture-type reactor with feed and preheated-water flow (S2) at temperatures from 200 to 240,°C, pressures from 15 to 20 MPa, residence times from 40 to 120 s, and initial feed concentrations of 1.5,10 wt %. D -Glucose was converted into aldehydes, organic acids and furans, with mainly organic acids obtained at 240,°C. D -Glucose decomposition using reactors S1 and S2 revealed that the conversion rate of D -glucose was promoted more using S2 than by S1. The yield of furans with S1 was higher than with S2, while the yield of organic acids from S1 was lower than that from S2. [source] Decomposition of a Lignin Model Compound under Hydrothermal ConditionsCHEMICAL ENGINEERING & TECHNOLOGY (CET), Issue 8 2007Wahyudiono Abstract Lignin, which is the second most abundant polymeric aromatic organic substance in wood biomass after cellulose, and contains many oxygen-based functional groups, has been proposed as an alternative source of chemical compounds. Guaiacol, a model compound for lignin, was reacted in supercritical water using a batch-type reactor at temperatures of 653,673,K and various pressures under an argon atmosphere. The effects of temperature and reaction time at the same pressure were combined into a single severity parameter that was used to monitor the decomposition of guaiacol to its derived compounds. The main products in aqueous solution were catechol, phenol, and o -cresol. The amounts present approached 40.73,wt,%, 14.18,wt,%, and 4.45,wt,%, respectively. With an increase in the reaction time at the same conditions, the amount of guaiacol decreased and the quantity of derived compounds of guaiacol increased. Based on the experimental results, a reaction mechanism for the decomposition of guaiacol was proposed. The process investigated in this study may form the basis for an efficient method of wood biomass decomposition. [source] Transition Metal Complexes Coordinated by an NAD(P)H Model Compound and their Enhanced Hydride-Donating Abilities in the Presence of a BaseCHEMISTRY - A EUROPEAN JOURNAL, Issue 14 2005Atsuo Kobayashi Dr. Abstract The ruthenium(II) and rhenium(I) complexes containing an NAD(P)H model compound, 1-benzyl-1,4-dihydronicotinamide (BNAH), as ligand, [Ru(tpy)(bpy)(BNAH)]2+ (1,a) and [Re(bpy)(CO)3(BNAH)]+ (1,b), were quantitatively produced by the reaction of the corresponding metal hydrido complexes with BNA+ (1-benzylnicotinamidium cation). In the presence of base with pKa=8.9, 1,a and 1,b have much greater reducing power than "free" BNAH. The oxidation potentials of 1,a in the absence and the presence of triethylamine were 0.55 V and ,0.04 V, respectively, versus Ag/AgNO3, whereas that of "free" BNAH was 0.30 V. Spectroscopic results clearly showed that the base extracts a proton from the carbamoyl group on 1,a and 1,b to give the deprotonated BNAH coordinating to the transition-metal complexes [Ru(tpy)(bpy)(BNAH,H+)]+ (3,a) and [Re(bpy)(CO)3(BNAH,H+)] (3,b); this deprotonation underlies the enhancement in reducing ability. The deprotonated forms 3,a and 3,b can efficiently reduce other NAD(P) models to give the corresponding 1,4-dihydro form, resulting in the deprotonated BNA+ being coordinated to the metal complexes [Ru(tpy)(bpy)(BNA+,H+)]2+ (2,a) and [Re(bpy)(CO)3(BNA+,H+)]+ (2,b); "free" BNAH and the protonated adducts 1,a and 1,b cannot act in this way. X-ray crystallography was performed on the PF6, salt of 2,a, and showed that the deprotonated nitrogen atom on the carbamoyl group coordinates to the ruthenium(II) metal center with a bond length of 2.086(3) Å. Infrared spectral data suggested that the deprotonated carbamoyl group on the reduced forms 3,a and 3,b is converted to the imido group, and that the oxygen atom coordinates to the metal center. [source] Minerals as Model Compounds for Cu/ZnO Catalyst Precursors: Structural and Thermal Properties and IR Spectra of Mineral and Synthetic (Zincian) Malachite, Rosasite and Aurichalcite and a Catalyst Precursor MixtureEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 10 2009Malte Behrens Abstract The Cu/ZnO system is a model for Cu/ZnO/Al2O3 catalysts, which are employed industrially for the synthesis of methanol. These catalysts are usually prepared from mixed basic carbonate precursors. A complex phase mixture, with constituents structurally related to the minerals rosasite andaurichalcite, is present at the industrially applied composition (Cu/Zn , 70:30). Using minerals and phase-pure synthetic samples as references, a comprehensive characterisation of such a phase mixture, including the determination of the individual compositions of the different phases, has been attempted by complementary analytical laboratory techniques (XRD, TGA, IR). The results are critically discussed in light of the complexity of the system. A thermally very stable carbonate species , well-known for mixed synthetic systems , is also detected for the mineral reference samples. Significant amounts of amorphous phases are found to be present in the synthetic zincian malachite sample but not in synthetic aurichalcite or the catalyst precursor. A simplified explanation for the shift of the characteristic 20 reflection of the malachite structure as a function of Zn incorporation based on the varying average Jahn,Teller distortion of the MO6 octahedra is proposed. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Polyfluorene Light-Emitting Diodes: Understanding the Nature of the States Responsible for the Green Emission in Oxidized Poly(9,9-dialkylfluorene)s: Photophysics and Structural Studies of Linear Dialkylfluorene/Fluorenone Model Compounds (Adv. Funct.ADVANCED FUNCTIONAL MATERIALS, Issue 13 2009Mater. Polyfluorenes, whilst attractive candidates for polymer light-emitting diodes, are susceptible to oxidative degradation. This degradation results in significant green emission. Although it has been linked to the formation of fluorenones, the precise relationship between fluorenones and the observed color shift remains widely debated. On page 2147, Chan et al. report a study on this relationship with the use of a series of model compounds. Inter-molecular fluorenone,fluorenone interaction is reported to be an essential requirement for the color shift. [source] Understanding the Nature of the States Responsible for the Green Emission in Oxidized Poly(9,9-dialkylfluorene)s: Photophysics and Structural Studies of Linear Dialkylfluorene/Fluorenone Model CompoundsADVANCED FUNCTIONAL MATERIALS, Issue 13 2009Khai Leok Chan Abstract Here, the optical properties of a series of structurally well-defined model compounds for oxidatively degraded poly(dialkylfluorenes) (PFs) are reported. Specifically, linear compounds comprising one, two, or four dihexylfluorene (F) moieties together with one fluorenone (O) moiety placed either at the end or in the center of each chain (i.e., FO, FFO, FOF, FFOFF) are studied. The results support the recent observation that the photophysics of the fluorenone-centered "pentamer" (FFOFF) is most similar to that of oxidized PFs. They further demonstrate that molecule,molecule interaction is essential to activate the green emission band. Investigations by X-ray diffraction (XRD) identify the solid-state structure of a representative member of this class of compounds and reveal inter-molecular interaction through dipole,dipole coupling between neighboring fluorenone moieties. [source] Natural Abundance 43Ca NMR Spectroscopy of Tobermorite and Jennite: Model Compounds for C,S,HJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 2 2009Geoffrey M. Bowers There are few effective methods for characterizing the molecular scale structural environments of Ca2+ in hydrated cements, which has limited our ability to understand the structure of, for example, Ca,silicate hydrate (C,S,H). 43Ca nuclear magnetic resonance (NMR) spectroscopy has long been considered too insensitive to provide useful data in this regard, but 43Ca magic angle spinning (MAS) NMR spectra reported here for synthetic tobermorite and jennite with naturally abundant levels of 43Ca demonstrate that this is a viable approach. We show that spectra with useful signal/noise ratios can be obtained in a reasonable acquisition period (,2 days) using an H0 field strength of 21.1 T, 5 mm rotors spinning at a frequency of 5 kHz, and a double frequency sweep preparatory pulse sequence. Tobermorite and jennite produce relatively broad resonances due to their complex structures and structural disorder, however, the chemical shift differences between six-coordinate 43Ca in jennite and seven-coordinate 43Ca in 11 Å tobermorite are large enough that the signals are entirely resolved at this field. These data suggest that signal from ideal tobermorite-like and jennite-like sites in cement C,S,H can most likely be distinguished by 43Ca NMR and that this method will be a powerful approach for studying cement-based ceramic materials in the coming decade. [source] Degradation of Poly(methyl methacrylate) Model Compounds Under Extreme Environmental ConditionsMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 13 2010Francesca Bennet No abstract is available for this article. [source] Downsizing of Enzymes by Chemical Methods: Arginine Mimics with Low pKa,Values Increase the Rates of Hydrolysis of RNA Model CompoundsANGEWANDTE CHEMIE, Issue 36 2009Johan Ein talentierter Imitator: Sehr viel schneller werden katalytische Reaktionen von RNA-Modellen, wenn zwei Argininreste und zwei Histidinreste in einem gefalteten Polypeptidkatalysator durch Reste mit einer Guanidiniocarbonylpyrrol(Gcp)-Seitenkette (siehe Struktur) ersetzt werden. Gcp übernimmt nicht nur die Funktionen von Arg und His, sondern übertrifft diese sogar leistungsmäßig. [source] ChemInform Abstract: Synthesis of Dendritic Iron(II) Porphyrins with a Tethered Axial Imidazole Ligand Designed as New Model Compounds for Globins.CHEMINFORM, Issue 18 2001Philipp Weyermann 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] Theoretical Study of One-electron Redox Potentials of Some NADH Model CompoundsCHINESE JOURNAL OF CHEMISTRY, Issue 1 2010Huajing Wang Abstract Several 1-benzyl-1,4-dihydronicotinamide derivatives, which are important NADH model compounds were studied theoretically in acetonitrile. The performances of various DFT methods including B3LYP, B1B95, B3PW91, MPW1B95, MPWKCIS, and M06 were tested to calculate the redox potentials. The first theoretical protocol to predict the redox potentials of these derivatives is B1B95, whose reliability has been tested against almost all the available experimental data. Strikingly, the mean absolute derivations (MAD) and root mean square (RMS) error of the current theoretical model equal 0.015 and 0.017, respectively. By using this method, the important thermodynamic properties of BNAHs were investigated and the mechanisms of hydride transfer progress were explained. Besides, para -substituents that have a big effect on these redox potentials of BNAH were systematically studied and carefully demonstrated. [source] Synthesis and light-emitting properties of carbazole-based copolymers bearing cyano-substituted arylenevinylene chromophoreJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 1 2010Koji Takagi Abstract Two arylenevinylene compounds bearing the cyano group at ,-position (6) and ,-position (9) from the dialkoxylphenylene unit were synthesized, in which the molecular termini were functionalized with 3-bromocarbazole. The Suzuki coupling copolymerization of these compounds with 1,4-bis[(3,-bromocarbazole-9,-yl)methylene]-2,5-didecyloxybenzene and 9,9-dihexylfluorene-2,7-bis(boronic acid) was carried out to obtain copolymers (cp67 and cp97) containing the cyano-substituted arylenevinylene fluorophore of 7 mol %. Model compounds (6, and 9,) corresponding to the arylenevinylene fluorophore were also prepared. The UV spectra of copolymers resembled that of homopolymer hp with no arylenevinylene segment in both CHCl3 solution and thin film. The emission maxima of copolymers in CHCl3 (394 nm) agreed with that of homopolymer indicating that the emission bands originated from the carbazole-fluorene-carbazole segment. The emission maximum wavelength of copolymer cp67 in thin film (477 nm) indicated fluorescence from the cyano-substituted arylenevinylene fluorophore because of the occurrence of fluorescence resonance electron transfer. In contrast, copolymer cp97 showed fluorescence at 528 nm to suggest the formation of a new emissive species such as a charge-transfer complex (exciplex). © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 91,98, 2010 [source] Synthesis and properties of novel polyimides derived from 2,2,,3,3,-benzophenonetetracarboxylic dianhydrideJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 9 2004Xing-Zhong Fang Abstract A new synthetic route to 2,2,,3,3,-BTDA (where BTDA is benzophenonetetracarboxylic dianhydride), an isomer of 2,3,,3,,4,-BTDA and 3,3,,4,4,-BTDA, is described. Single-crystal X-ray diffraction analysis of 2,2,,3,3,-BTDA has shown that this dianhydride has a bent and noncoplanar structure. The polymerizations of 2,2,,3,3,-BTDA with 4,4,-oxydianiline (ODA) and 4,4,-bis(4-aminophenoxy)benzene (TPEQ) have been investigated with a conventional two-step process. A trend of cyclic oligomers forming in the reaction of 2,2,,3,3,-BTDA and ODA has been found and characterized with IR, NMR, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry, and elemental analyses. Films based on 2,2,,3,3,-BTDA/TPEQ can only be obtained from corresponding polyimide (PI) solutions prepared by chemical imidization because those from their polyamic acids by thermal imidization are brittle. PIs from 2,2,,3,3,-BTDA have lower inherent viscosities and worse thermal and mechanical properties than the corresponding 2,3,,3,,4,-BTDA- and 3,3,,4,4,-BTDA-based PIs. PIs from 2,2,,3,3,-BTDA and 2,3,,3,,4,-BTDA are amorphous, whereas those from 3,3,,4,4,-BTDA have some crystallinity, according to wide-angle X-ray diffraction. Furthermore, PIs from 2,2,,3,3,-BTDA have better solubility, higher glass-transition temperatures, and higher melt viscosity than those from 2,3,,3,,4,-BTDA and 3,3,,4,4,-BTDA. Model compounds have been prepared to explain the order of the glass-transition temperatures found in the isomeric PI series. The isomer effects on the PI properties are discussed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2130,2144, 2004 [source] Perfluoroalkyl Phosphonic and Phosphinic Acids as Proton Conductors for Anhydrous Proton-Exchange MembranesCHEMPHYSCHEM, Issue 13 2010Mahesha B. Herath Abstract A study of proton-transport rates and mechanisms under anhydrous conditions using a series of acid model compounds, analogous to comb-branch perfluorinated ionomers functionalized with phosphonic, phosphinic, sulfonic, and carboxylic acid protogenic groups, is reported. Model compounds are characterized with respect to proton conductivity, viscosity, proton, and anion (conjugate base) self-diffusion coefficients, and Hammett acidity. The highest conductivities, and also the highest viscosities, are observed for the phosphonic and phosphinic acid model compounds. Arrhenius analysis of conductivity and viscosity for these two acids reveals much lower activation energies for ion transport than for viscous flow. Additionally, the proton self-diffusion coefficients are much higher than the conjugate-base self-diffusion coefficients for these two acids. Taken together, these data suggest that anhydrous proton transport in the phosphonic and phosphinic acid model compounds occurs primarily by a structure-diffusion, hopping-based mechanism rather than a vehicle mechanism. Further analysis of ionic conductivity and ion self-diffusion rates by using the Nernst,Einstein equation reveals that the phosphonic and phosphinic acid model compounds are relatively highly dissociated even under anhydrous conditions. In contrast, sulfonic and carboxylic acid-based systems exhibit relatively low degrees of dissociation under anhydrous conditions. These findings suggest that fluoroalkyl phosphonic and phosphinic acids are good candidates for further development as anhydrous, high-temperature proton conductors. [source] Development of a Controlled Release System for Risperidone Using Polypyrrole: Mechanistic StudiesELECTROANALYSIS, Issue 4 2010Darren Svirskis Abstract Polypyrrole (PPY) film has been selected as a platform material for drug delivery due to its inherent conductivity, ease of preparation and apparent biocompatibility. PPY films were prepared containing the antipsychotic drug risperidone as a model compound. Drug release profiles could be altered by applying different electrical stimulation to these films. Atomic force microscopy was used to investigate changes in PPY film thickness when different stimuli were applied. The highest levels of drug release were observed when PPY was reduced; this was accompanied by expansion of the film. Technology such as this could be utilized for implantable drug delivery devices, where the dose could be adjusted by external signaling. [source] Carbon Ceramic Electrodes Modified with Laccase from Trametes hirsuta: Fabrication, Characterization and Their Use for Phenolic Compounds DetectionELECTROANALYSIS, Issue 9 2007Behzad Haghighi Abstract Fungal laccase (Lc) from the basidiomycete Trametes hirsuta was immobilized on top of a carbon ceramic electrode using physical absorption. Direct, unmediated heterogeneous electron transfer between Lc and the carbon ceramic electrode (CCE) under aerobic conditions was shown. The bioelectrocatalytic reduction of oxygen on Lc-CCE started at about 430,mV vs. Ag|AgCl|KClsat at pH,3.5 and moved with about 57,mV in the cathodic region per pH unit. The Lc-modified CCE was then used as a biosensing detection element in a single line flow injection system for the amperometric determination of a variety of phenolic substrates of the enzyme. The experimental conditions were studied and optimized for catechol serving as a model compound. Statistical aspects were applied and the sensor characteristics and Michaelis-Menten constants of the investigated phenolic compounds were calculated and compared with those obtained for solid graphite electrodes modified with Trametes hirsuta laccase. The results showed that the CCE based biosensor in comparison with the solid graphite based biosensor offers a lower detection limit, a wider linear dynamic range, and excellent operational stability with no sensor passivation, indicating that the sol,gel lattice improves the electrochemical behavior of the biosensor. [source] Supramolecular Derivatives of 9,10-Anthraquinone.ELECTROANALYSIS, Issue 5-6 2003Complexing Properties, Electrochemistry at Regular-, Low Ionic Strength Abstract Three newly synthesized polyanthraquinone derivatives: 7,13-bis(9,10-dioxo-1-anthryl)-1,4,10-trioxa-7,13-diazacyclopentadecane, (AQ)A215C5, 7,16-bis(9,10-dioxo-1-anthryl)-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane, (AQ)A218C6, and tris[(9,10-diokso-1-antryl)-aminoethyl]amine, (AQNet)3N, were examined by cyclic and normal pulse voltammetry. All anthraquinone groups in these compounds were electroactive and formed the radicals and dianions similarly to simple anthraquinone. The differences between the voltammograms obtained in the absence and presence of supporting electrolyte are discussed, and the diffusion coefficients of the compounds and the rates of the chemical reactions following the first reduction step were evaluated. (AQNet)3N appears to be a good model compound for multi electron transfers in aprotic solvents. It offers two consecutive nearly reversible 3-electron redox systems: 0/,3 and ,3/,6. The interactions of the radicals and dianions of the above compounds with alkali metal cations were examined. [source] CE-ESI-MS/MS as a rapid screening tool for the comparison of protein,ligand interactionsELECTROPHORESIS, Issue 7 2010Thomas Hoffmann Abstract In drug development, the combinatorial synthesis of drug libraries is common use, therefore efficient tools for the characterization of drug candidates and the extent of interaction between a drug and its target protein is a central question of analytical interest. While biological activity is tested today by enzyme assays, MS techniques attract more and more attention as an alternative for a rapid comparison of drug,target interactions. CE enables the separation of proteins and drug,enzyme complexes preserving their physiological activity in aqueous media. By hyphenating CE with ESI-MS/MS, the binding strength of enzyme inhibitors can be deduced from MS/MS experiments, which selectively release the inhibitor from the drug,target complex after CID. In this study, ,-chymotrypsin (CT), a serine protease, was chosen as a model compound. Chymostatin is a naturally occurring peptide aldehyde binding to CT through a hemiacetal bond and electrostatic interaction. First, a CE separation was developed, which allows the analysis of ,-CT and a chymotrypsin,chymostatin complex under MS-compatible conditions. The use of neutral-coated CE capillaries was mandatory to reduce analyte,wall interactions. ESI-quadrupole ion trap-MS was worked out to demonstrate the selective drug release after CID. Fragmentation of the drug,enzyme complex was monitored in dependence from the excitation energy in the ion trap, leading to the V50 voltage that enables 50% complex fragmentation as a reference value for chymotrypsin,chymostatin complex. A stable CE-ESI-MS/MS setup was established, which preserves the drug,enzyme complexes during ionization,desolvation processes. With this optimized setup, different CT inhibitors could be investigated and compared. [source] Bacterioplankton assemblages transforming dissolved organic compounds in coastal seawaterENVIRONMENTAL MICROBIOLOGY, Issue 8 2007Xiaozhen Mou Summary To characterize bacterioplankton functional assemblages that transform specific components of the coastal seawater dissolved organic carbon (DOC) pool, bromodeoxyuridine (BrdU) was used to label the bacterioplankton cells that were active following addition of single-DOC model compounds: two organic osmolytes [dimethylsulfoniopropionate (DMSP) and glycine betaine (GlyB)] and two aromatic monomers [para -hydroxybenzoic acid (pHBA) and vanillic acid (VanA)]. Bacterial populations were analysed based on in situ fluorescent immunodetection of BrdU incorporation followed by fluorescence-activated cell sorting (FACS). Sorted cells were then characterized by 16S rDNA-based analysis. Populations with high BrdU incorporation level (HI) developed within 8 h of introduction of 100 nM model compound. Terminal restriction fragment length polymorphisms (T-RFLP) analysis indicated that the HI populations in all four amendments were composed of bacteria from the same major taxa (phylum and subphylum levels), but the relative abundance of each differed. High-resolution clone libraries (each containing ,200 clones) showed that the HI populations in the GlyB and VanA amendments consisted of both metabolic generalists and specialists within the , -Proteobacteria (mainly members of the Roseobacter clade), , -Proteobacteria and , -Proteobacteria (mainly members of Altermonadaceae, Chromatiaceae, Oceanospirillaceae and Pseudomonadaceae). The presence of members of OM60/241, OM185, SAR11, SAR86 and SAR116 in the HI populations indicated that members of these groups can assimilate the model DOC compounds, providing some of the first glimpses into heterotrophy by members of these poorly understood environmental clusters. [source] Phage display as a novel screening tool for primary toxicological targetsENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 2 2010Bieke Van Dorst Abstract In the present study the use of phage display as a screening tool to determine primary toxicological targets was investigated. These primary toxicological targets are the targets in the cell with which a chemical compound initially interacts and that are responsible for consecutive (toxic) effects. Nickel was used as model compound for the present study. By selection of Ni-binding peptides out of a 12-mer peptide phage library, it was possible to identify primary toxicological targets of Ni (and other metals). The selected Ni-binding peptides showed similarities to important primary toxicological targets of Ni, such as the hydrogenase nickel incorporation protein (hypB) and the Mg/Ni/Co transporter (corA). This shows that phage display, which is already widely used in other research fields, also has potential in ecotoxicology, as a novel screening tool with which to determine primary toxicological targets of chemical compounds. Environ. Toxicol. Chem. 2010;29:250,255. © 2009 SETAC [source] A New Spherical Metallacryptate Compound [Na{Cu6(Thr)8(H2O)2(ClO4)4}]·ClO4·5,H2O: Magnetic Properties and DFT CalculationsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 13 2005Sheng-Chang Xiang Abstract The hexanuclear copper(II) complex with threoninato acid has been synthesized. Its structure can be described as an octahedron cage with D2h symmetry in which six copper ions are bound by eight threoninato acids with a [3.11223130] coordination mode and one Na+ cation being captured within the center of the cage. In contrast with other hexanuclear copper compounds containing amino acids, the title compound has a prolate Cu6 octahedron with the longest axial distance and a rectangle equatorial plane, as well as special coordinated perchlorate ions. Compared with classic cryptate, hexanuclear copper(II) compounds with amino acids can be regarded as a new topologic type of spherical macrotricyclic metallacryptates [2,2,2,2] whose cages have a high selectivity for sodium ions. The analysis of magnetic susceptibility data shows that the threoninato compound has a ground state with spin S = 3. The computing coupling constant between the equatorial Cu centers and the axial ones is 4.4 cm,1,calculated by using DFT methods for a model compound. This is close to three known experimental values of 1.39, 0.56 or 0.43 cm,1 for complexes with 4-hydroxy- L -prolinato, L -prolinato or L -threoninato acid as ligands, respectively. The dominant ferromagnetic interactions for these complexes can be essentially attributed to the orthogonality between the magnetic orbitals, dxz or dyz orbitals for the equatorial CuII centers and d orbitals for the axial ones. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Columnar Mesomorphism in Hexacatenar Tetrahedral (2,2,-Bipyridine)zinc Complexes and Homologous Palladium DerivativesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 1 2005Giovanna Barberio Abstract The synthesis and characterisation of novel liquid crystals which display columnar mesomorphism induced upon complexation of a series of nonmesomorphic hexacatenar 4,4,-disubstituted 2,2,-bipyridines (Ln) are reported. The introduction of different metal centres (Zn, Pd) causes the appearance of mesomorphism in all complexes regardless of the geometry around the metal ion. We therefore report the first examples of mesomorphism in tetrahedral zinc derivatives. The nature of the columnar phases is related to the self-assembly of the half-disc shaped [LnMCl2] (M = Zn, Pd) complexes into full disc-shaped supramolecules. The molecular organisation in the mesophase is mainly driven by intermolecular attractive interactions, as shown by the crystal structure of the model compound [LPdCl2]. Preliminary measurements of photoconductivity have been performed on samples of [LnMCl2] complexes doped with C60 to increase absorption. Promising results were obtained. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Specific Ca2+ Fluorescent Sensor: Signaling by Conformationally Induced PET Suppression in a Bichromophoric AcridinedioneEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 34 2009Pichandi Ashokkumar Abstract A series of acridinedione-based bichromophoric podand systems 1a,c were synthesized and characterized. Among these, bichromophore 1c shows specific binding of Ca2+ in the presence of other biologically important metal ions like Na+, K+, Mg2+, and Zn2+. The selective complexation was proved by steady-state emission, time-resolved emission, and 1H NMR titration. Signaling of the binding event was achieved by Ca2+ -induced folding of the bichromophore, resulting in PET suppression in the acridinedione chromophore. Involvement of a PET process in the optical signaling was confirmed by comparing bichromophores 1a,c with non-PET compound 2 and monochromophore model compound 3. Non-PET compound 2 failed to give optical response upon Ca2+ binding as a result of the absence of a PET process in the Ca2+ -bound complex. Monochromophore 3 shows a similar optical response, which is the same as that in 1c. Titration of the metal-ion-bound complex of 1c with EDTA released the metal ion from the complex, thereby regaining the original photophysical properties of the bichromophore.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Oligophenylcalix[4]arenes as Potential Precursors for Funnelenes and Calix[4]triphenylenes: Syntheses and Preliminary Cyclodehydration StudiesEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 21 2006Michael Mastalerz Abstract The concept for a new class of nonplanar polyaromatic hydrocarbons , the funnelenes , is presented. Retrosynthetic considerations lead to polyphenyl- and oligophenylcalix[4]arenes as potential precursors. In this paper we describe the synthesis of these calixarenes and the first cyclodehydration studies on a model compound which leads to a hexabenzocoronene derivative. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] C-Glycosidations of a 2-Ketohexosyl Bromide with Electrophilic, Radical, and Nucleophilic Anomeric CarbonsEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 16 2003Frieder W. Lichtenthaler Abstract The susceptibility of acylated 2-ketohexosyl halides to C-homologation is demonstrated with the easily accessible tri- O -benzoyl-,- D - arabino -hexos-ulosyl bromide 1 as the model compound. C-Glycosidation with an electrophilic anomeric carbon requires prior carbonyl protection, to avoid carbonyl addition by the C-nucleophile, for example, as the cyanohydrin. Silver triflate-promoted reaction with the silylenol ether of acetophenone then efficiently yields the ,-phenacyl product. With thermal (AIBN) or photochemical induction, 1 smoothly generates an anomeric radical , comparatively electrophilic, due to its capto-dative substitution , which exclusively traps hydrogen in the presence of tributyltin and electron-deficient alkenes. With allyltributylstannanes, however, it reacts with high stereoselectivity to afford ,- C -allyl glycosiduloses. The ,-bromoketone functionality in ulosyl bromide 1 is susceptible to Reformatsky conditions: treatment with zinc-copper couple readily generates the 1,2-enolate, a most simple anomeric nucleophile, which effectively adds to aldehydes to give ,- C -hydroxyalkyl glycosiduloses or ,- C -disaccharides (with sugar aldehydes) with a high degree of double stereoselection. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] Charging of tRNA with non-natural amino acids at high pressureFEBS JOURNAL, Issue 13 2006Malgorzata Giel-Pietraszuk We show a simple and reliable method of tRNA aminoacylation with natural, as well as non-natural, amino acids at high pressure. Such specific and noncognate tRNAs can be used as valuable substrates for protein engineering. Aminoacylation yield at high pressure depends on the chemical nature of the amino acid used and it is up to 10%. Using CoA, which carries two potentially reactive groups -SH and -OH, as a model compound we showed that at high pressure amino acid is bound preferentially to the hydroxyl group of the terminal ribose ring. [source] Red,Yellow Fluorescence Patterning of a Polymer Film Containing Phthalimido Carbamate GroupsADVANCED FUNCTIONAL MATERIALS, Issue 17 2007H. Chae Abstract Bicolor fluorescent micro-patterns in the polymer film are prepared through the use of a new group of photobase generator containing phthalimido carbamate groups. The photobase generation from phthalimide carbamates is studied by examining the changes in pH, fluorescence intensity, and photo-crosslinking of poly(glycidyl methacrylate). The product analysis of a model compound indicates that amine groups are produced from the photolytic cleavage of the C,N bond of the phthalimide carbamate groups. A copolymer containing phthalimide carbamate groups is applied to a bicolor fluorescent imaging material. Red-yellow fluorescent micropatterns are obtained by treating the copolymer film, which is irradiated with 254 nm UV light through a photomask, with fluorescamine and rhodamine, consecutively. Various colored fluorescent micropatterns , green, red, or red-yellow, are obtained on a single polymer film by varying the excitation wavelength. [source] The Reaction of Peroxynitrite with Morpholine (Secondary Amines) Revisited: The Overlooked Hydroxylamine FormationHELVETICA CHIMICA ACTA, Issue 10 2006Michael Kirsch Abstract The reaction of peroxynitrite/peroxynitrous acid with morpholine as a model compound for secondary amines is reinvestigated in the absence and presence of carbon dioxide. The concentration- and pH-dependent formation of N -nitrosomorpholine and N -nitromorpholine as reported in three previous papers ([25],[26],[14]) is basically confirmed. However, 13C-NMR spectroscopic product analysis shows that, in the absence of CO2, N -hydroxymorpholine is, at pH,,,7, the major product of this reaction, even under anaerobic conditions. The formation of N -hydroxymorpholine has been overlooked in the three cited papers. Additional (ring-opened) oxidation products of morpholine are also detected. The data account for radical pathways for the formation of these products via intermediate morpholine-derived aminyl and , -aminoalkyl radicals. This is further supported by EPR-spectrometric detection of morpholine-derived nitroxide radicals, i.e., morpholin-4-yloxy radicals. N -Nitrosomorpholine, however, is very likely formed by electrophilic attack of peroxynitrite-derived N2O4. 15N-CIDNP Experiments establish that, in the presence of CO2, N -nitro- and C -nitromorpholine are generated by radical recombination. The present results are in full accord with a fractional (28,±,2%) homolytic decay of peroxynitrite/peroxynitrous acid with release of free hydroxyl and nitrogen dioxide radicals. [source] A Macrocyclic Model Dodecamer for Polyfluorenes,ADVANCED MATERIALS, Issue 1 2009Sascha C. Simon A , -conjugated, cyclododeca-2,7-fluorene macrocycle is synthesized as a new model compound for polyfluorenes. The structure formation is demonstrated by 1H NMR spectroscopy, MALDI-TOF, and STM measurements, and the optical properties of this monodisperse cycle are investigated using UV-vis and fluorescence spectroscopy. [source] Theory of chemical bonds in metalloenzymes III: Full geometry optimization and vibration analysis of ferredoxin-type [2Fe,2S] clusterINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 1 2007Mitsuo Shoji Abstract The nature of chemical bonds in a ferredoxin-type [2Fe,2S] cluster has been investigated on the basis of natural orbitals and several bond indices developed in Parts I and II of this study. The broken-symmetry hybrid density functional theory (BS-HDFT) with spin projection approach has been applied to elucidate the natural orbitals and occupation numbers for a model compound [Fe2S2(SCH3)4] (1), which is used to calculate the indices. The molecular structure, vibration frequencies, electronic structures, and magnetic properties in both oxidized and reduced forms of 1 have been calculated and compared with the experimental values. The optimized molecular structures after approximate spin projection have been in good agreement with experimental data. The structure changes upon one-electron reduction have been slight (<0.1 Å) and only limited around one side of the Fe atom. Raman and infrared (IR) spectra have been calculated, and their vibration modes have been assigned using the bridging 34S isotope substitution. Their magnetic properties have been examined in terms of spin Hamiltonians that contain exchange interactions and double exchange interactions. The BS-HDFT methods have provided the magnetic parameters; i.e., effective exchange integral (J) values and valence delocalization (B) values, which agree with the experimental results. It is found that large charge transfer (CT) from the bridging sulfur to the iron atoms has led to the strong antiferromagnetic interactions between iron atoms. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 [source] | ||||||||||||||||||||||||||||||||||||||||||||||