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Electronic Interactions (electronic + interaction)
Selected AbstractsEnhancing Learners' Communication Skills through Synchronous Electronic Interaction and Task-Based InstructionFOREIGN LANGUAGE ANNALS, Issue 1 2002Lina Lee ABSTRACT: Online interactive exchange offers the learner many opportunities to use the target language to negotiate both meaning and form in a social context that is crucial for second language acquisition. This paper discusses a pilot study using synchronous electronic chats combined with task-based instruction (TBI) to enhance learners' communication skills. TBI focuses on the two-way exchange of information on real-life topics. This pilot study shows that computer-mediated communication using less structure-controlled but more open-ended exchange had a significant impact on the process of language learning. Students benefited from online task-based activities because they had to access different functional skills to construct and negotiate meaning collaboratively. However, foreign language educators need to be aware that the quick cyberspace interactions impeded students from producing correct and coherent discourse, especially during learner-learner interaction. One corrective technique is to make students reexamine and revise their exchanges with guided instruction. [source] ChemInform Abstract: ipso-Acylation of 5,13-Di-tert-butyl-8,16-dimethyl[2.2]metacyclophane with Acid Anhydrides: Through-Space Electronic Interaction Among the Two Benzene Rings.CHEMINFORM, Issue 44 2009Tomoe Shimizu 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] Electronic Interactions in Ferrocene- and Ruthenocene-Functionalized Tetraazamacrcocyclic Ligand Complexes of FeII/III, CoII, NiII, CuII and ZnIIEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 2 2005Peter Comba Abstract The syntheses of ferrocene- and ruthenocene-functionalized tetraazamacrocyclic ligands and their corresponding transition metal complexes are described. Reaction of N,N, -bis(2-aminoethyl)-1,3-propanediamine (2,3,2-tet) with 1,1,-diformylferrocene and 1,1,-diformylruthenocene produces the ligands fcmac and rcmac in 81,85% yield. Examination of their CuII, NiII, CoII, ZnII and FeII/III complexes by IR, UV/Vis, EPR and Mössbauer spectroscopy as well as by electrochemical studies suggests electronic communication between the two metal centers of each complex. The molecular structure of [CuII(fcmac)(FBF3)]BF4, determined by X-ray structure analysis, is reported and shows that the distance between the two metals is 4.54 Å. Stability constants, determined by potentiometric titration, indicate that the copper(II) complexes are of similar stability as those with unfunctionalized tetraazamacrocyclic ligands (e.g. cyclam = 1,4,8,11-tetraazacyclotetradecane); stability constants of cobalt(II) complexes are about 2 log units smaller, those of nickel(II) and zinc(II) complexes are reduced by more than 10 log units. This selectivity is discussed on the basis of the structural studies. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Modulating Electronic Interactions between Closely Spaced Complementary , Surfaces with Different Outcomes: Regio- and Diastereomerically Pure Subphthalocyanine,C60 Tris Adducts,ANGEWANDTE CHEMIE, Issue 43 2009David González-Rodríguez Dr. Stark gekoppelte, regio- und diastereomerenreine Subphthalocyanin-C60 -Dyaden (siehe Kalottenmodell; B orange, C hellblau, H grau, N blau, O rot), die durch dreifache Addition erhalten wurden, können, abhängig vom Abstand zwischen den beiden komplementären ,-Oberflächen, auf Photoanregung unterschiedlich reagieren (mit Elektronen- oder mit Energietransfer). [source] Di- and Trinuclear [70]Fullerene Complexes: Syntheses and Metal,Metal Electronic Interactions,ANGEWANDTE CHEMIE, Issue 34 2009Yutaka Matsuo Prof. Buckyballs mit Spikes: [70]Fulleren wurde in die Zwei- und Dreikernkomplexe [M2(C70Ar6)Cp2], [M2(C70Ar7H)Cp2] und [M3(C70Ar7)Cp3] überführt (M=Fe, Ru; Ar=Aryl; Cp=C5H5; siehe Bild: M,violett, C,rosa, blau, grau), in denen die Metallatome über das ,-konjugierte System des Fullerens elektronisch wechselwirken. Die Komplexe sollten sich wegen ihrer Strukturen und elektrochemischen Eigenschaften für den Einsatz in der molekularen Elektronik eignen. [source] Multicomponent Supramolecular Devices: Synthesis, Optical, and Electronic Properties of Bridged Bis-dirhodium and -diruthenium Complexes,EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 19 2006Anne Petitjean Abstract Four ruthenium- and rhodium-based metal,metal-bonded multicomponent systems have been synthesized, and their absorption, redox, spectroelectrochemical and structural properties have been studied. The absorption spectra of the four bis-dimetallic compounds M2LM2, where L is a bridging ligand and M is rhodium or ruthenium, exhibit very strong bands in the UV, visible and, for the diruthenium species, near-IR region. The low-energy absorption bands are assigned to charge-transfer transitions involving a metal,metal bonding orbital as the donor and an orbital centered on the bis-tetradentate aromatic ligands as the acceptor (metal,metal to ligand charge transfer, M2LCT). Each compound exhibits reversible bridging-ligand-centered reductions at mild potentials and several reversible oxidation processes. The oxidation signals of the two equivalent dimetallic centers of each bis-dimetallic compound are split, with the splitting , a measure of the electronic coupling , depending on both the metal and bridging ligand. The mixed-valence species of the dirhodium species was investigated, and the electronic coupling matrix element calculated from the experimental intervalence band parameters for one of them (86 cm,1) indicates a significant inter-component electronic interaction which compares well with good electron conducting anionic bridges such as cyanides. Although none of these compounds is luminescent, the M2LCT excited state of one of the bis-dirhodium complexes is relatively long-lived (about 6 ,s) in degassed acetonitrile at room temperature. The results presented here are promising for the development of linear poly-dimetallic complexes built on longer naphthyridine-based strands, with significant long-range electronic coupling and molecular-wire-like behavior. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Trust, power and interorganizational information systems: the case of the electronic trading community TransLeaseINFORMATION SYSTEMS JOURNAL, Issue 1 2000David K. Allen Abstract. This paper focuses on Cap Gemini's electronic commerce system, TransLease. TransLease is an interorganizational information system (IOS), which facilitates electronic commerce between motor vehicle leasing and repair companies. During our investigation, the system was used by approximately 1000 repair agents working for seven of the UK's leading vehicle leasing and contract hire companies. This system was originally developed by AT&T and acquired by Cap Gemini in July 1998. At the time of acquisition, the system was seen as being of high strategic value, although it was also seen as underperforming. This paper reports the results of an action research project, which formed one element of the process by which Cap Gemini investigated the former problem. In the paper, TransLease is described as a complex electronic community, dependent upon the existence of symbiotic relationships. As such, the problems that the system users and developers experienced can be attributed to factors that impeded the mutual benefit accruing from participation in the system. The efficacy of the terms of exchange and the degree to which participants mutually benefit through electronic interaction is determined by the complex interplay of a number of relational and organizational factors. The research therefore illustrates the importance of the ,soft' organizational issues in IOS management and development, and suggests a conceptual model of the factors relevant in this case. At the time of this study, TransLease was still in the early stages of its life cycle, having only been available in the marketplace for approximately 18 months. During this time, through recognizing the complex problems and issues detailed in this paper, Cap Gemini accordingly redressed the way in which the system was managed and maintained. TransLease is now seen as having matured into a highly successful example of an IOS , a view reflected by its position as market leader in the industry. As this paper will show, the key to improving the existing service has been the emphasis Cap Gemini now places on managing the ,soft' aspects of the electronic community. [source] In situ generated diphenylsiloxane-polyimide adduct-based nanocompositesPOLYMER ENGINEERING & SCIENCE, Issue 1 2005Manisha G. Goswami Arylsiloxane was incorporated into polyimide (PI) via electronic interaction with polyamic acid (PAA)/PI, and a wide spectrum of properties were evaluated for different compositions. The samples prepared with relatively low concentrations (0.0001,0.1%) of oligomers showed unusual synergism, which is attributed to the generation of nanostructures dispersed in the continuous PI matrix. The incorporation of siloxane with bulky phenyl groups contributed to enhanced thermal stability as determined by thermogravimetric analysis. Water uptake and methanol absorption by these composites were evaluated and correlated with the underlying micro- and nanostructures. Fourier Transform Infrared (FTIR) spectroscopy was used to elucidate the probable reaction mechanism (including in situ polymerization of arylsilanol), and to study the synthetic aspects associated with the molecular composites and nanocomposites formation. POLYM. ENG. SCI., 45:142,152, 2005. © 2004 Society of Plastics Engineers [source] Ruthenium-to-Platinum Interactions in ,6,,1 NCN-Pincer Arene Heterobimetallic Complexes: An Experimental and Theoretical StudyEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 29 2010Sylvestre Bonnet Abstract A series of ,6,,1 -heterobimetallic complexes have been prepared in which a [Ru(,6 -arene)(C5R5)]+ fragment (R = H or Me) and an ,1 -NCN-pincer platinum fragment are combined within the same molecule. In complexes [2]+ and [3]+, the ruthenium and platinum centers are ,6 and ,1 coordinated, respectively, to the same arene ring, whereas in [4A]+ and [5A]+ they are coordinated to two different arene rings that are linked with a covalent bond ([4A]+) or an ethyl bridge ([5A]+). Upon changing the organic manifold between both metal centers, very strong ([2]+) to very weak ([5A]+) ruthenium-to-platinum interactions are obtained. Experimentally, X-ray crystal structures show an increaing steric hindrance when the Ru,Pt distance diminishes, and electrochemical and 195Pt NMR spectroscopic studies show a decreasing electron density on platinum from [5A]+ to [2]+. Theoretical DFT calculations were undertaken, which show an increasing charge on platinum from [5A]+ to [2]+. Our theoretical analysis shows that the particularly strong ruthenium-to-platinum electronic interactions in [2]+ and [3]+ do not come from binding of ruthenium to platinum, but from the pincer Cipso sharing its electron density between both metal centers, which decreases the , donation to platinum, and from increased backdonation of the platinum d electrons into the , system of the arene ring. [source] Magneto,Structural Correlations in Discrete MnII -WV Cyano-Bridged Assemblies with Polyimine LigandsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 26 2010Robert Podgajny Abstract We present the magneto,structural correlations for two novel discrete cyano-bridged assemblies based on cationic complexes of manganese(II) with diimine ligands and octacyanotungstate(V) ions. The crystal structure of [MnII(terpy)(dmf)(H2O)2][MnII(terpy)(H2O)(dmf)(,-NC)WV(CN)7]2·6H2O (1) (terpy = 2,2,;6,,2,-terpyridine, dmf = dimethylformamide) contains dinuclear {MnIIWV}, cyano-bridged anions, while the crystal structure of [MnII(phen)3]2[MnII(phen)2(,-NC)2WV(CN)6]2(ClO4)2·9H2O (2) (phen = 1,10-phenanthroline) is built of tetranuclear {MnII2WV2}2, square anions. Intramolecular Mn,W magnetic interactions through the cyano bridges are represented by magnetic coupling constants J = ,39 cm,1 for the {MnIIWV}, unit in 1 and J1 = ,25.7 and J2 = ,16.7 cm,1 for the {MnII2WV2}2, unit in 2. J and J1 represent relatively strong W,CN,Mn interactions and are ascribed to the bridges in b positions of TPRS-8 (trigonal prism square-face bicapped) of [W(CN)8]3, polyhedra, favoring the strongest electronic interactions between the d,d orbital of W and the ,* orbitals of CN,, whereas J2 is related to the m vertex of [W(CN)8]3,. The magnetic properties of 1 and 2 are compared with reference compounds and discussed in the context of the type of coordination polyhedra of [W(CN)8]3, as well as the metric parameters of cyano-bridged W,CN,Mn linkages. We found the type of coordination polyhedra and bridging mode of [W(CN)8]3, to be the most important factors influencing the magnitude of the Mn,W magnetic interaction. [source] Chain-Like Tetra-, Penta- and Heptanuclear Cyanide-Bridged Complexes by Attachment of Organometallic Cyanides to M2, M3 and M5 UnitsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 20 2003Tianlu Sheng Abstract Attachment of the "ligands" [Cp(dppe)Fe-CN], [Cp(PPh3)2Ru-CN], [Cp(CO)2Fe-CN] and [(CO)5M-CN],, (where M = Cr, Mo, W) to the polymetallic centres [Ru2(OAc)4]+, [Co3(dpa)4]2+ and [Ni5(tdpa)4]2+ yielded two tetra-, three penta- and five heptanuclear complexes with chain-like linear arrangements of the metal ions and the bridging cyanide ligands, as proved by the structure determination of [Ni5(tdpa)4{Cp(dppe)2Fe-CN}2](PF6)2. IR and CV data show that the Ru2, Co3 and Ni5 centres of these complexes withdraw electron density from the external organometallic units. This prevents electronic interactions between the two terminal metal ions, yet allows multistep one- and two-electron redox processes. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] 2,5-Disubstituted Pyrrolidines as Chiral Auxiliaries in Radical Reactions: A Theoretical ApproachEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 25 2010Miglena K. Georgieva Abstract The radical addition to amides derived from chiral 2,5-disubstituted pyrrolidines has been theoretically studied by the use of density functional methods and the results compared with known experimental data. The results agree quite well with those obtained experimentally and allow the full rationalization of the factors influencing the diastereoselectivity. Steric effects are the main factors determining the selectivity, but electronic interactions can also be very important when the attacking alkene is ,,,-conjugated, as in acrylic esters or acrylamides. Additions at the ,- and ,-positions of the amide chain in the auxiliary are subject to different rules, with the former usually yielding high diastereoselectivities both experimentally and theoretically, whereas the latter is theoretically predicted to occur with low selectivity. We fully rationalize these two opposite behaviours and suggest several ways to circumvent this limitation, thus strongly increasing the interest of this type of structure as chiral auxiliaries in radical reactions. [source] Multicyclic polyethers by the polycondensation of 1,2- or 1,3-dicyanotetrafluorobenzene with flexible diphenolsJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 19 2006Hans R. Kricheldorf Abstract 1,2-Dicyanotetrafluorobenzene (1,2-DCTB) was polycondensed with various flexible diphenols in a molar ratio of 1:2, and experimental parameters such as the concentration and temperature were varied. Certain diphenols allowed a complete substitution of all CF bonds, so perfect multicyclic polyethers (BnCN, where B stands for bridge units, C represents cycles, and N is the degree of polymerization) were the main reaction products. Despite complete conversion, gelation was avoidable under optimized reaction conditions. However, in the case of 1,3-dicyanotetrafluorobenzene (1,3-DCTB), complete tetrasubstitution was not feasible with a feed ratio of 1:2. Yet, because of the inductive and mesomeric electronic interactions of all substituents in 1,3-DCTB, the three CF groups in the ortho position with respect to the cyano groups were significantly more reactive than the fourth CF bond. Therefore, polycondensations with diphenols in a 3:2 feed ratio showed a relatively clean course, yielding soluble multicycles of structure Bn /2CN. All the multicyclic polyethers were amorphous and possessed molar mass distributions with polydispersities greater than 2. Heating with Cu2+ salts caused crosslinking of the multicycles derived from 1,2-DCTB because of the formation of phthalocyanine complexes. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5546,5556, 2006 [source] Structural conformations and electronic interactions of the natural product, oroxylin: a vibrational spectroscopic studyJOURNAL OF RAMAN SPECTROSCOPY, Issue 12 2008Jose P. Abraham Abstract The oroxylin, 5,7-dihydroxy 6-methoxy flavone is a potent natural product extracted from ,Vitex peduncularis'. Density functional theory (DFT) at B3LYP/6-311G(d,p) level has been used to compute energies of different conformers of oroxylin to find out their stability, the optimized geometry of the most stable conformer and its vibrational spectrum. The conformer ORLN-1 with torsion angles 0, 180, 180 and 0 degrees, respectively, for H13O12C6C5, H14O10C4C5, H13O12C6C5 and H14O10C4C5 is found to be most stable. The optimized geometry reveals that the dihedral angle , between phenyl ring B and the chrome part of the molecule in , 19.21° is due to the repulsive force due to steric interaction between the ortho-hydrogen atom H29 of the B ring and H18 of the ring C (H29·H18 = 2.198 Å). A vibrational analysis based on the near-infrared Fourier transform(NIR-FT) Raman, Fourier transform-infrared (FT-IR) and the computed spectrum reveals that the methoxy group is influenced by the oxygen lone pair-aryl pz orbital by back donation. Hence the stretching and bending vibrational modes of the methoxy group possess the lowest wavenumber from the normal values of methyl group. The carbonyl stretching vibrations have been lowered due to conjugation and hydrogen bonding in the molecules. The intramolecular H-bonding and nonbonded intramolecular interactions shift the band position of O10H14 and O12H13 stretching modes, which is justified by DFT results. Copyright © 2008 John Wiley & Sons, Ltd. [source] Cyclic Polymers by Kinetically Controlled Step-Growth PolymerizationMACROMOLECULAR RAPID COMMUNICATIONS, Issue 5-6 2003Hans R. Kricheldorf Abstract The theory of step-growth polymerizations including the cascade theory is discussed in the light of new results focussing on the role of cyclization reactions. The identification of cyclic oligomers and polymers in reaction products of step-growth polymerizations has been eased considerably by means of MALDI-TOF mass spectrometry. Experimental examples concern syntheses of polyesters, polycarbonates, polyamides, polyimides, poly(ether sulfone)s, poly(ether ketone)s and polyurethanes. It was found in all cases that the percentage and molecular weight of the cycles increases when the reaction conditions favor high molecular weights. In the absence of side reactions all reaction products will be cycles when conversion approaches 100%. Cyclization may even take place in the nematic phase but even-numbered cycles are favored over odd-numbered ones due to electronic interactions between mesogens aligned in parallel. In contrast to Flory's cascade theory, cyclization also plays a decisive role in polycondensations of abn -type monomers, and at 100% conversion all hyperbranched polymers have a cyclic core. Furthermore, it is demonstrated that in a2+b3 polycondensations intensive cyclization in the early stages of the process has the consequence that either no gelation occurs or the resulting networks consist of cyclic and bicyclic oligomers as building blocks. Finally, a comparison between cyclization of synthetic polymers and biopolymers is discussed. Schematic representation of a network structure mainly consisting of cyclic oligomers and multicyclic building blocks as derived from "a2" + "b3" polycondensation. [source] Role of Environmental Factors on the Structure and Spectroscopic Response of 5,-DNA,Porphyrin Conjugates Caused by Changes in the Porphyrin,Porphyrin InteractionsCHEMISTRY - A EUROPEAN JOURNAL, Issue 44 2009Angela Mammana Dr. Abstract We have explored the utility, strength, and limitation of through-space exciton-coupled circular dichroism in determination of the secondary structure of optically active chromophoric nanoarrays using the example of end-capped porphyrin, and metalloporphyrin,oligodeoxynucleotide conjugates. We put special emphasis on the explanation of the origin and significance of the distinctive multiple bands in the CD spectra (trisignate and tetrasignate CD bands). Such CD profiles are often observed in chiral aggregates or multichromophoric arrays but have never before been studied in detail. We found that variation of temperature and ionic strength has a profound effect on the geometry of the porphyrin,DNA conjugates and thus the nature of electronic interactions. At lower temperatures and in the absence of NaCl all three 5,-DNA,porphyrin conjugates display negative bisignate CD exciton couplets of variable intensity in the Soret region resulting from through-space interaction between the electric transition dipole moments of the two end-capped porphyrins. As the temperature is raised these exciton couplets are transformed into single positive bands originating from the porphyrin,single-strand DNA interactions. At higher ionic strengths and low temperatures, multisignate CD bands are observed in the porphyrin Soret region. These CD signature bands originate from a combination of intermolecular, end-to-end porphyrin,porphyrin stacking between duplexes and porphyrin,DNA interactions. The intermolecular aggregation was confirmed by fluorescence and absorption spectroscopy and resonance light scattering. DeVoe theoretical CD calculations, in conjunction with molecular dynamics simulations and Monte Carlo conformational searches, were used to mimic the observed bisignate exciton-coupled CD spectra as well as multiple CD bands. Calculations correctly predicted the sign and shape of the experimentally observed CD spectra. These studies reveal that the exciton-coupled circular dichroism is a very useful technique for the determination of the structure of optically active arrays. [source] Single-Step Electron Transfer on the Nanometer Scale: Ultra-Fast Charge Shift in Strongly Coupled Zinc Porphyrin,Gold Porphyrin DyadsCHEMISTRY - A EUROPEAN JOURNAL, Issue 11 2008Jérôme Fortage Dr. Abstract The synthesis, electrochemical properties, and photoinduced electron transfer processes of a series of three novel zinc(II),gold(III) bisporphyrin dyads (ZnPSAuP+) are described. The systems studied consist of two trisaryl porphyrins connected directly in the meso position via an alkyne unit to tert -(phenylenethynylene) or penta(phenylenethynylene) spacers. In these dyads, the estimated center to center interporphyrin separation distance varies from 32 to 45,Å. The absorption, emission, and electrochemical data indicate that there are strong electronic interactions between the linked elements, thanks to the direct attachment of the spacer on the porphyrin ring through the alkyne unit. At room temperature in toluene, light excitation of the zinc porphyrin results in almost quantitative formation of the charge shifted state .+ZnPSAuP., whose lifetime is in the order of hundreds of picoseconds. In this solvent, the charge-separated state decays to the ground state through the intermediate population of the zinc porphyrin triplet excited state. Excitation of the gold porphyrin leads instead to rapid energy transfer to the triplet ZnP. In dichloromethane the charge shift reactions are even faster, with time constants down to 2,ps, and may be induced also by excitation of the gold porphyrin. In this latter solvent, the longest charge-shifted lifetime (,=2.3,ns) was obtained with the penta-(phenylenethynylene) spacer. The charge shift reactions are discussed in terms of bridge-mediated super-exchange mechanisms as electron or hole transfer. These new bis-porphyrin arrays, with strong electronic coupling, represent interesting molecular systems in which extremely fast and efficient long-range photoinduced charge shift occurs over a long distance. The rate constants are two to three orders of magnitude larger than for corresponding ZnPAuP+ dyads linked via meso -phenyl groups to oligo-phenyleneethynylene spacers. This study demonstrates the critical impact of the attachment position of the spacer on the porphyrin on the electron transfer rate, and this strategy can represent a useful approach to develop molecular photonic devices for long-range charge separations. [source] Photosensitization and the Photocurrent Switching Effect in Nanocrystalline Titanium Dioxide Functionalized with Iron(II) Complexes: A Comparative StudyCHEMISTRY - A EUROPEAN JOURNAL, Issue 20 2007Wojciech Macyk Dr. Abstract Selected iron(II) complexes (ferrocene, ferrocenylboronic acid, hexacyanoferrate(II)) have been used as photosensitizers of titanium dioxide. Various types of electronic interactions between the surface complex and the semiconducting support are reflected in different yields of photocurrent generated upon visible-light irradiation and different efficiencies of the photosensitization effect. The studied systems, showing the photocurrent switching upon changes of electrode potential and energy of photons (the PEPS effect), are good models of simple photoelectrochemical logic devices. The mechanism of photosensitization and photocurrent switching is discussed with respect to the type of surface-complex,support interaction. Quantum-mechanical calculations support the proposed mechanisms. Wybrane kompleksy ,elaza(II) (ferrocen, kwas ferrocenyloboronowy i heksacyjano,elazian(II)) zosta,y u,yte jako fotosensybilizatory dwutlenku tytanu. Ró,ne typy oddzia,ywa, elektronowych pomi,dzy kompleksami powierzchniowymi a pod,o,em pó,przewodnikowym znajduj, odbicie w ró,nych wydajno,ciach generacji fotopr,du i ró,nym stopniu fotosensybilizacji materia,ów na ,wiat,o widzialne. Wszystkie badane uk,ady wykazuj, efekt fotoelektrochemicznego prze,,czenia fotopr,du na skutek zmian potencja,u fotoelektrody i zmian d,ugo,ci fali ,wiat,a padaj,cego (efekt PEPS), dlatego te, stanowi, bardzo dobre modele prostych prze,,czników fotoelektrochemicznych. Niniejsza praca szczegó,owo okre,la mechanizm fotosensybilizacji i prze,,czenia fotopr,du na podstawie analizy oddzia,ywa, pomi,dzy kompleksem a powierzchni, pó,przewodnika. Obliczenia kwantowo-mechaniczne potwierdzaj, postulowany mechanizm. [source] An Experimental and Computational Study on Intramolecular Charge Transfer: A Tetrathiafulvalene-Fused Dipyridophenazine MoleculeCHEMISTRY - A EUROPEAN JOURNAL, Issue 13 2007Chunyang Jia Prof. Abstract To study the electronic interactions in donor,acceptor (D,A) ensembles, D and A fragments are coupled in a single molecule. Specifically, a tetrathiafulvalene (TTF)-fused dipyrido[3,2- a:2,,3,- c]phenazine (dppz) compound having inherent redox centers has been synthesized and structurally characterized. Its electronic absorption, fluorescence emission, photoinduced intramolecular charge transfer, and electrochemical behavior have been investigated. The observed electronic properties are explained on the basis of density functional theory. [source] Reactions of Th and U Atoms with C2H2: Infrared Spectra and Relativistic Calculations of the Metallacyclopropene, Actinide Insertion, and Ethynyl ProductsCHEMISTRY - A EUROPEAN JOURNAL, Issue 32 2006Lester Andrews Prof. Dr. Abstract Reactions of laser-ablated Th and U atoms with C2H2 during condensation with excess argon at 7 K give several new product species. The metallacyclopropene, inserted hydride, and actinide ethynyl are identified from isotopic frequencies and relativistic DFT calculations. The higher-energy vinylidine isomer was not observed. These actinide metallacyclopropenes exhibit substantially stronger bonding interactions than found recently for the Pd and Pt metals. In the case of Th(C2H2) the argon matrix interaction is strong enough to reverse the computed order of states (MR-CISD) in favor of a triplet ground state for the (Ar)n(Th(C2H2)) complex. The nature of the electronic interactions between various metal atoms and acetylene is compared and the origin of the particularly strong interaction for U and Th is traced to the higher energy of their 6d orbitals. The ThCCH and UCCH actinide ethynyl products are also observed and characterized by CC stretching modes 38±2 cm,1 lower than acetylene itself. [source] Synthesis and Pharmacological Evaluation of 8- and 9-Substituted Benzolactam-V8 Derivatives as Potent Ligands for Protein Kinase,C, a Therapeutic Target for Alzheimer's DiseaseCHEMMEDCHEM, Issue 3 2006Ulrich Abstract A central element in the pathophysiology of Alzheimer's disease (AD) is the formation of amyloid plaques, which result from abnormal processing of the amyloid precursor protein (APP). The processing of APP is largely provided by three key enzymes, namely the ,-, ,-, and ,-secretases. As the latter two contribute to the formation of neurotoxic A, fragments while ,-secretase does not, a decrease in the amyloidogenic products can be brought about either by inhibition of the ,- and ,-secretases or through the activation of ,-secretase. It is now known that the activation of protein kinase,C (PKC) enhances ,-secretase activity and therefore represents a possible target for the development of agents urgently needed for the treatment of this devastating neurodegenerative disorder. In the present study, new benzolactam-V8-based PKC activators were synthesized and tested for their binding affinity toward PKC,. All compounds tested showed binding values in the nanomolar concentration range. In accordance with previous publications, 9-substitution dramatically increased PKC binding affinity in comparison with the corresponding 8-substituted analogues. In addition to the location of the side chain on the aromatic ring, the binding affinities of these benzolactams were found to depend on the orientation, length, and electronic properties of this appendage. An interesting decrease in binding affinity was found for the 9-thienyl analogue 13, suggesting adverse electronic interactions of the sulfur atom with PKC or parts of the cellular membrane. [source] | ||||||||||||||||||||||||||||