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Emission Studies (emission + studies)
Selected AbstractsNon-Covalent Aggregation of Discrete Metallo-Supramolecular Helicates into Higher Assemblies by Aromatic Pathways: Structural and Chemical Studies of New Aniline-Based Neutral Metal(II) DihelicatesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 17 2005Miguel Vázquez Abstract Neutral manganese(II), iron(II), cobalt(II), nickel(II), zinc(II) and cadmium(II) complexes with an N -tosyl-substituted N4 -donor Schiff base containing a 4,4'-methylenedianiline residue as spacer [H2La: N,N' -bis(2-tosylaminobenzylidene)-4,4'-methylenedianiline], and the zinc(II) complex with an analogous ligand [H2Lb: N,N' -bis(2-tosylaminobenzylidene)-4,4'-oxodianiline] have been prepared by an electrochemical procedure. FAB and ESI mass spectra of the complexes show peaks due to species corresponding to a general formula [M2(La,b)2 + H]+, thereby suggesting their dinuclear nature. A detailed study of the crystal packing in the unit cell of the zinc(II) complex with H2La shows that the helicates aggregate to form discrete prismatic moieties containing three molecules held together by ,,, and ,,, interactions. Moreover, the ZnII neutral dihelicate with H2Lb forms a 3D network in the solid state due to intermolecular ,-stacking interactions. 1H NMR studies of the diamagnetic compounds reported herein have been performed. Finally, the ligand H2La and its ZnII and CdII complexes have been studied by spectrophotometric and spectrofluorimetric techniques in order to get a better understanding of the formation mechanisms of the complexes and of the nature of their fluorescence emission. Emission studies show that the ZnII and CdII dihelicates with H2La display a green fluorescence in acetonitrile solution (, = 473 nm, , = 0.03 and , = 476 nm, , = 0.01, respectively). (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] A Novel Bis(zinc,porphyrin),Oxoporphyrinogen Donor,Acceptor Triad: Synthesis, Electrochemical, Computational and Photochemical StudiesEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 3 2006Jonathan P. Hill Abstract The first example of a porphyrin-quinonoid donor,acceptor triad featuring (tetraphenylporphinato)zinc(II) moieties covalently attached to an oxoporphyrinogen through its macrocyclic nitrogen atoms is reported. This arrangement of chromophores results in an interesting interplay between the electron-donating zinc,porphyrin(s) and the electron/energy accepting oxoporphyrinogen. The optical absorption of the triad reveals features corresponding to both the donor and acceptor entities. The geometry and electronic structure of the triad deduced from B3LYP/3-21G(*) calculations reveal an absence of inter-chromophoric interactions and localization of the HOMO on one zinc,porphyrin group and the LUMO on the oxoporphyrinogen scaffold. The electrochemical redox states of the triad were established from a comparative electrochemistry of the triad and the reference compounds. Both steady-state and time-resolved emission studies revealed quenching of the singlet excited state of zinc,porphyrin in the triad, and the free-energy calculations performed using Weller's approach indicate the possibility of electron transfer from the singlet excited zinc,porphyrin group to the oxoporphyrinogen in polar solvents. Time-resolved fluorescence studies reveal excited state energy transfer from zinc,porphyrin to oxoporphyrinogen in nonpolar solvents, while nanosecond transient absorption studies combined with time-resolved fluorescence studies in polar solvents are indicative of the occurrence of photoinduced charge separation from the singlet excited zinc,porphyrin to the oxoporphyrinogen. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Investigations on 1,5-diaminoanthraquinone by laser excitationJOURNAL OF RAMAN SPECTROSCOPY, Issue 1 2003M. Umadevi Abstract Optical absorption and fluorescence emission spectra of 1,5-diaminoanthraquinone (1,5-DAAQ) in different solvents and the surface-enhanced Raman scattering (SERS) spectrum of 1,5-DAAQ in silver sol were investigated. Optical absorption and fluorescence emission studies revealed that the internal and external hydrogen bonds and reorientation of the solvent molecule around the excited state fluorophore are responsible for the observed bathochromic shift and the non-radiative decay process in polar solvents. SERS studies showed that 1,5-DAAQ molecules are chemisorbed through carbonyl groups and the lone pair of electrons on the nitrogen. The orientation of the molecule on the silver surface is found to be stand-on. Copyright © 2002 John Wiley & Sons, Ltd. [source] Photosensitizing Properties of Triplet ,-Lapachones in Acetonitrile SolutionPHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 1 2009José Carlos Netto-Ferreira The photochemical reactivity of ,-lapachone (1), nor -,-lapachone (2) and 1,2-naphthoquinone (3) towards amino acids and nucleobases or nucleosides has been examined employing the nanosecond laser flash photolysis technique. Excitation (, = 355 nm) of degassed solutions of 1,3, in acetonitrile, resulted in the formation of their corresponding triplet excited states. These transients were efficiently quenched by l -tryptophan, l -tryptophan methyl ester, l -tyrosine, l -tyrosine methyl ester and l -cysteine (kq , 109 L mol,1 s,1). For l -tryptophan, l -tyrosine and their methyl esters new transients were formed in the quenching process, which were assigned to the corresponding radical pair resulting from an initial electron transfer from the amino acids or their esters to the excited quinone, followed by a fast proton transfer. No measurable quenching rate constants could be observed in the presence of thymine and thymidine. On the other hand, efficient rate constants were obtained when 1,3 were quenched by 2,-deoxyguanosine (kq , 109 L mol,1 s,1). The quantum efficiency of singlet oxygen (1O2) formation from 1 to 3 was determined employing time-resolved near-IR emission studies upon laser excitation and showed considerably high values in all cases (,, = 0.6), which are fully in accord with the ,,* character of these triplets in acetonitrile. [source] Ultrafast Energy Transfer from Bound Tetra(4- N,N,N,N -trimethylanilinium)porphyrin to Synthetic Dopa and Cysteinyldopa Melanins,PHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 1 2003Tong Ye ABSTRACT The binding of tetra(4- N,N,N,N -trimethylanilinium)porphyrin (TAP) to melanins quenches the porphyrin emission. Time-resolved femtosecond absorption spectroscopy reveals that the mechanism behind this quenching is ultrafast nonradiative energy transfer (,ET < 100 fs) from electronically excited TAP to melanin. Similar dynamics are observed for both dopa and cysteinyldopa melanins. Steady-state emission studies demonstrate that the emission from melanin increases upon excitation of bound TAP, thereby confirming that rapid energy transfer occurs. These results are consistent with previous photoacoustic studies, which revealed that the TAP,melanin complex behaves like a supermolecular system liberating heat as a whole. [source] Effect of ion energy on structural and electrical properties of intrinsic microcrystalline silicon layer deposited in a matrix distributed electron cyclotron resonance plasma reactorPHYSICA STATUS SOLIDI (A) APPLICATIONS AND MATERIALS SCIENCE, Issue 3 2010Sanjay K. Ram Abstract Microcrystalline silicon films were deposited in a matrix distributed electron cyclotron resonance (MDECR) plasma enhanced chemical vapor deposition (PECVD) system using pure silane, under varying substrate bias conditions. Microstructural characterization of the films shows a lower void fraction and a preponderance of nanograins in films deposited at negative bias, while in positive bias a thin incubation layer is seen with a higher void fraction. Plasma emission studies reveal higher electron temperature and more atomic H at positive bias, which lead to early onset of crystallization. The microstructural properties of the films are correlated with the dark and phototransport properties. Our study demonstrates the importance of substrate bias in controlling the ion energy and properties of films deposited in the MDECR reactor. [source] Field emission from single-wall nanotubes obtained from carbon and boron nitride mixturesPHYSICA STATUS SOLIDI (B) BASIC SOLID STATE PHYSICS, Issue 10 2008V. I. Kleshch Abstract Heterophase BN:C single-wall nanotubes are prospective as a material with a predicted possibility to vary the bandgap via changing a relative content of BN and C fractions in the nanotube walls. The challenge is both to find the ways of synthesis of such nanotubes and, in case of success, to confirm BN embedding. In this work field emission studies have been performed for revealing the difference between arc-produced pure carbon nanotubes and nanotubes grown from BN:C mixtures. The relative BN content in the mixtures was varied from 0% up to 50% (by mass). The materials have been characterized by a high resolution transmission electron microscopy, Raman scattering and UV-VIS-NIR optical absorption techniques. The single-wall nanotubes have been revealed in all samples synthesized, but their composition remained questionable. The field emission properties of the samples have been examined in a vacuum diode configuration. It has been found that the threshold fields and slopes of the Fowler,Nordheim plot, evaluated from the measured current,voltage dependences, increased with an enrichment of the starting mixtures with h-BN. This increase could be attributed to the work function rise due to h-BN embedding into the carbon nanotube walls. This result opens a way to use the field-emission characterization for an indirect confirmation of the heterophase BN:C nanotube formation. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Unique interactions between the chromophore and glutamate 16 lead to far-red emission in a red fluorescent proteinPROTEIN SCIENCE, Issue 2 2009Xiaokun Shu Abstract mPlum is a far-red fluorescent protein with emission maximum at ,650 nm and was derived by directed evolution from DsRed. Two residues near the chromophore, Glu16 and Ile65, were previously revealed to be indispensable for the far-red emission. Ultrafast time-resolved fluorescence emission studies revealed a time dependent shift in the emission maximum, initially about 625 nm, to about 650 nm over a period of 500 ps. This observation was attributed to rapid reorganization of the residues solvating the chromophore within mPlum. Here, the crystal structure of mPlum is described and compared with those of two blue shifted mutants mPlum-E16Q and -I65L. The results suggest that both the identity and precise orientation of residue 16, which forms a unique hydrogen bond with the chromophore, are required for far-red emission. Both the far-red emission and the time dependent shift in emission maximum are proposed to result from the interaction between the chromophore and Glu16. Our findings suggest that significant red shifts might be achieved in other fluorescent proteins using the strategy that led to the discovery of mPlum. [source] Dynamic Chemical Devices: Photoinduced Electron Transfer and Its Ion-Triggered Switching in Nanomechanical Butterfly-Type Bis(porphyrin)terpyridines,CHEMISTRY - A EUROPEAN JOURNAL, Issue 7 2006Myriam Linke-Schaetzel Dr. Abstract A series of butterfly-type molecular constructs has been prepared in good yield by using a double Stille coupling synthetic protocol. They are composed of a terpyridine (terpy) scaffold and two wings composed of appended porphyrins that are capable of switching from an extended W geometry to a compact U geometry upon cation coordination of the terpy unit. The porphyrin moieties exist in the constructs either as free bases or they can be sequentially metallated, thus giving rise to wings of different "colours". Stationary and time-resolved emission studies of the HZn, ZnAu and Zn2Au constructs show that the electronic properties are strongly dependent on the geometry. In the extended W conformation an energy-transfer process is seen from the free base to the Zn-metallated porphyrin. In the U conformation in Zn2Au the donor luminescence resulting from the singlet excited state of the Zn wing is strongly, quenched not only due to the heavy atom effect but also due to a fast electron-transfer process to the ground state of the Au wing. Furthermore, the binding of (,,,)-diamine substrates to the ZnII,porphyrin sites can also influence the conformation of the system. For the Zn2Zn construct, single-crystal diffraction experiments with synchrotron radiation allowed the structure to be solved by direct methods and fully refined; it shows the expected U conformation. The central Zn atom is six-coordinate, whereby the zinc atom is coordinated by the ,3 -terpy ligand as well by monodentate and semi-chelating acetate anions. The structure is made rigid by hydrogen bonds involving the aqua ligands on the outer Zn centres and acetate oxygen atoms. The present system thus represents a double-trigger-modulated optomechanical switching device with selective substrate binding for either metal atoms or tailored ligands. Both energy- and electron-transfer processes can be controlled opening a means of improving the on/off ratio in future constructs. Une série d'architectures moléculaires, présentant une forme de papillon, a été préparée avec de bons rendements en utilisant une méthodologie synthétique comprenant comme étape clé un double couplage de Stille. Ces architectures sont composées d'un squelette terpyridine (terpy), qui compose le torse du papillon, sur lequel deux ailes porphyriniques ont été greffées; la géométrie peut varier entre une conformation étendue en forme de W, et une conformation compacte en forme de U, dû à la complexation du torse terpy par un cation de taille et coordination adéquate. Les ailes porphyriniques se présentent soit comme bases libres ou, peuvent être métallées successivement avec différentes métaux, pouvant ainsi avoir différentes "couleurs". Des études de fluorescence non seulement stationnaire mais aussi résolues dans le temps sur les architectures HZn, ZnAu et Zn2Au, montrent que les propriétés électroniques sont très dépendantes de la géométrie adoptée. Dans la conformation W étendue, nous avons mis en évidence un processus de transfert d'énergie de la porphyrine base libre vers la porphyrine metalée avec du Zn. Dans la conformation U de Zn2Au la luminescence de l'aile donneuse, à cause de l'état excité singulet, est fortement éteinte, non seulement à cause de l'effet d'atome lourd, mais aussi à cause d'un processus de transfert d'électron vers l'état fondamental de l'aile metalée avec de l'or. De plus, par compléxation avec des (,,,)-diamines des atomes de ZnIIdans les tetrapyrroles porphyrinques, la conformation induite du système peut être profondément influencée. Pour le composé Zn2Zn, que nous avons pu obtenir en monocristaux, des expériences de diffraction en utilisant comme source lumineuse un synchrotron, ont fourni des données qui ont permis de résoudre la structure par des méthodes directes et de la raffiner pour montrer la conformation en U attendue. L'atome central de Zn a une coordination de six dont trois provenant du ligand ,3 -terpy, et les autres de deux anions acetates, un monodenté et l'autre semi-chelatizé. La structure est ligotée par des multiples liaisons hydrogène entre des ligands aqueux sur les atomes de Zn externes et les atomes d'oxygène des anions acetates. Le système présenté est un double effecteur qui montre une commutation opto-mechanique dirigée soit par des ions métalliques, soit par d'autres ligands de taille adaptée. En même temps, les processus de transfert d'énergie et d'électrons peuvent être commuté en laissant de la place pour améliorer le rapport "on/off" dans de futures architectures. Abstract in Romanian:O serie de arhitecturi moleculare având o form, de fluture au fost preparate cu randamente bune utilizând o metodologie sintetic, cuprinzând ca etap, cheie un dublu cuplaj Stille. Aceste architecturi sunt compuse dintr-un schelet terpiridinic (terpy) alc,tuind trupul fluturelui, la care au fost implementate dou, aripi porfirinice care sunt capabile sa varieze între o conforma,ie extins, în forma de liter, W ,i o conformai,ie compact, în form, de litera U, datorit, complexarii trupului terpy printr-un cation de talie ,i coordina,ie adecvat,. Aripile porfirinice se prezintã fie ca base libere sau, datorita unei metalari succesive cu diferite metale, pot avea diferite "culori". Studii de fluorescen,a atât sta,ionar, cât ,i rezolvat, în timp, asupra arhitecturilor HZn, ZnAu ,i Zn2Au, arat, c, proprit,,ile electronice sunt foarte dependente de geometria adoptat,. In conforma,ia W extins,, am putut pune în eviden,, un proces de transfer de energie dinspre baza liber, c,tre porfirina metalat, cu Zn. In conforma,ia U a Zn2Au luminescen,a aripei donoare, datorate st,rii singulet excitate, este puternic stins, nu numai datorit, efectului de atom greu, cât ,i a unui proces de transfer de electron c,tre starea fundamental, a aripei metalat, cu aur. Pe deasupra, complexând (,,,)-diamine c,tre atomii de ZnIIîntre tetrapirolii porfirinici, sunt induse profunde influen,e asupra conforma,iei sistemului. Pentru compusul Zn2Zn, care a putut fi crescut monocristalin, experimente de difrac,ie folosind ca surs, luminoas, un sincrotron au condus la un set de date care a permis ca structura sa fie elucidat, prin metode directe ,i rafinat,, ar,tând conforma,ia în U a,teptat,. Atomul central de Zn are o coordina,ie de sase unde pe lang, lignadul ,3 -terpy, atomul de Zn este coordinat de c,tre doi anioni acetat, unul monodentat, iar cel,lalt semi-chelatizant. Structura este br,zdat, de leg,turi de hidrogen care implic, liganzii apo,i situa,i pe centrii de Zn exteriori, ,i atomii de oxigen din ionii acetat. Sistemul prezentat este un dutblu efector, ar,tând comutare opto-mecanic,, datorat, fie lig,rii prin ioni metalici, fie prin al,i liganzi perfect croitori,i. In acel,i timp, atât procese de transfer de energie, cât ,i de electroni, pot fi perfect comutate, l,sând loc pentru imbun,t,,irea raportului "on/off" în arhitecturi viitoare. [source] | |||||||||||||