Dataset Information

D?f energy transfer in Ir(III)/Eu(III) dyads: use of a naphthyl spacer as a spatial and energetic "stepping stone".

ABSTRACT: A series of luminescent complexes based on {Ir(phpy)2} (phpy = cyclometallating anion of 2-phenylpyridine) or {Ir(F2phpy)2} [F2phpy = cyclometallating anion of 2-(2',4'-difluorophenyl)pyridine] units, with an additional 3-(2-pyridyl)-pyrazole (pypz) ligand, have been prepared; fluorination of the phenylpyridine ligands results in a blue-shift of the usual (3)MLCT/(3)LC luminescence of the Ir unit from 477 to 455 nm. These complexes have pendant from the coordinated pyrazolyl ring an additional chelating 3-(2-pyridyl)-pyrazole unit, separated via a flexible chain containing a naphthalene-1,4-diyl or naphthalene-1,5-diyl spacer. Crystal structures show that the flexibility of the pendant chain allows the naphthyl group to lie close to the Ir core and participate in a ?-stacking interaction with a coordinated phpy or F2phpy ligand. Luminescence spectra show that, whereas the {Ir(phpy)2(pypz)} complexes show typical Ir-based emission--albeit with lengthened lifetimes because of interaction with the stacked naphthyl group--the {Ir(F2phpy)2(pypz)} complexes are nearly quenched. This is because the higher energy of the Ir-based (3)MLCT/(3)LC excited state can now be quenched by the adjacent naphthyl group to form a long-lived naphthyl-centered triplet ((3)nap) state which is detectable by transient absorption. Coordination of an {Eu(hfac)3} unit (hfac = 1,1,1,5,5,5-hexafluoro-pentane-2,4-dionate) to the pendant pypz binding site affords Ir-naphthyl-Eu triads. For the triads containing a {Ir(phpy)2} core, the unavailability of the (3)nap state (not populated by the Ir-based excited state which is too low in energy) means that direct Ir?Eu energy-transfer occurs in the same way as in other flexible Ir/Eu complexes. However for the triads based on the{Ir(F2phpy)2} core, the initial Ir?(3)nap energy-transfer step is followed by a second, slower, (3)nap?Eu energy-transfer step: transient absorption measurements clearly show the (3)nap state being sensitized by the Ir center (synchronous Ir-based decay and (3)nap rise-time) and then transferring its energy to the Eu center (synchronous (3)nap decay and Eu-based emission rise time). Thus the (3)nap state, which is energetically intermediate in the {Ir(F2phpy)2}-naphthyl-Eu systems, can act as a "stepping stone" for two-step d?f energy-transfer.

SUBMITTER: Sykes D

PROVIDER: S-EPMC3971759 | biostudies-literature | 2013 Sep

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

d→f energy transfer in Ir(III)/Eu(III) dyads: use of a naphthyl spacer as a spatial and energetic "stepping stone".

Sykes Daniel D Parker Simon C SC Sazanovich Igor V IV Stephenson Andrew A Weinstein Julia A JA Ward Michael D MD

Inorganic chemistry 20130905 18

A series of luminescent complexes based on {Ir(phpy)2} (phpy = cyclometallating anion of 2-phenylpyridine) or {Ir(F2phpy)2} [F2phpy = cyclometallating anion of 2-(2',4'-difluorophenyl)pyridine] units, with an additional 3-(2-pyridyl)-pyrazole (pypz) ligand, have been prepared; fluorination of the phenylpyridine ligands results in a blue-shift of the usual (3)MLCT/(3)LC luminescence of the Ir unit from 477 to 455 nm. These complexes have pendant from the coordinated pyrazolyl ring an additional c ...[more]

PMID: 24007190

Similar Datasets

Project description:Compositionality refers to a structural property of human language, according to which the meaning of a complex expression is a function of the meaning of its parts and the way they are combined. Compositionality is a defining characteristic of all human language, spoken and signed. Comparative research into the emergence of human language aims at identifying precursors to such key features of human language in the communication of other primates. While it is known that chimpanzees, our closest relatives, produce a variety of gestures, facial expressions and vocalizations in interactions with their group members, little is known about how these signals combine simultaneously. Therefore, the aim of the current study is to investigate whether there is evidence for compositional structures in the communication of chimpanzees. We investigated two semi-wild groups of chimpanzees, with focus on their manual gestures and their combinations with facial expressions across different social contexts. If there are compositional structures in chimpanzee communication, adding a facial expression to a gesture should convey a different message than the gesture alone, a difference that we expect to be measurable by the recipient's response. Furthermore, we expect context-dependent usage of these combinations. Based on a form-based coding procedure of the collected video footage, we identified two frequently used manual gestures (stretched arm gesture and bent arm gesture) and two facial expression (bared teeth face and funneled lip face). We analyzed whether the recipients' response varied depending on the signaler's usage of a given gesture + face combination and the context in which these were used. Overall, our results suggest that, in positive contexts, such as play or grooming, specific combinations had an impact on the likelihood of the occurrence of particular responses. Specifically, adding a bared teeth face to a gesture either increased the likelihood of affiliative behavior (for stretched arm gesture) or eliminated the bias toward an affiliative response (for bent arm gesture). We show for the first time that the components under study are recombinable, and that different combinations elicit different responses, a property that we refer to as componentiality. Yet our data do not suggest that the components have consistent meanings in each combination-a defining property of compositionality. We propose that the componentiality exhibited in this study represents a necessary stepping stone toward a fully evolved compositional system.

Project description:BackgroundMultiple pathway databases are available that describe the human metabolic network and have proven their usefulness in many applications, ranging from the analysis and interpretation of high-throughput data to their use as a reference repository. However, so far the various human metabolic networks described by these databases have not been systematically compared and contrasted, nor has the extent to which they differ been quantified. For a researcher using these databases for particular analyses of human metabolism, it is crucial to know the extent of the differences in content and their underlying causes. Moreover, the outcomes of such a comparison are important for ongoing integration efforts.ResultsWe compared the genes, EC numbers and reactions of five frequently used human metabolic pathway databases. The overlap is surprisingly low, especially on reaction level, where the databases agree on 3% of the 6968 reactions they have combined. Even for the well-established tricarboxylic acid cycle the databases agree on only 5 out of the 30 reactions in total. We identified the main causes for the lack of overlap. Importantly, the databases are partly complementary. Other explanations include the number of steps a conversion is described in and the number of possible alternative substrates listed. Missing metabolite identifiers and ambiguous names for metabolites also affect the comparison.ConclusionsOur results show that each of the five networks compared provides us with a valuable piece of the puzzle of the complete reconstruction of the human metabolic network. To enable integration of the networks, next to a need for standardizing the metabolite names and identifiers, the conceptual differences between the databases should be resolved. Considerable manual intervention is required to reach the ultimate goal of a unified and biologically accurate model for studying the systems biology of human metabolism. Our comparison provides a stepping stone for such an endeavor.

Dataset Information

D?f energy transfer in Ir(III)/Eu(III) dyads: use of a naphthyl spacer as a spatial and energetic "stepping stone".

Publications

d→f energy transfer in Ir(III)/Eu(III) dyads: use of a naphthyl spacer as a spatial and energetic "stepping stone".

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets