Search results for "electron transfer"
showing 10 items of 282 documents
Decreased Electron Transfer Rates of Manganese Porphyrins with Conformational Distortion of the Macrocycle
1998
Slow electron transfer to manganese(iii) porphyrins results when the macrocycle deviates from planarity. This was demonstrated by measuring the kinetics of homogeneous electron transfer from a series of semiquinone radical anions to synthetic manganese porphyrins (shown schematically; R1 =H, Cl, F; R2 =H, F). Three of the four porphyrins studied have nonplanar macrocycles. These results could have implications for the role of manganese in biological electron transfer processes.
Carbene-metal complexes as molecular scaffolds for construction of through-space TADF emitters
2021
Through-space charge transfer (CT) process is observed in Cu(I) carbene-metal-amide complexes, where conventional imidazole or imidazoline N-heterocyclic (NHC) carbene fragments act as inert linkers and CT proceeds between a metal-bound carbazole donor and a distantly situated carbene-bound phenylsulfonyl acceptor. The resulting electron transfer gives a rise to efficient thermally activated delayed fluorescence (TADF), characterized with high photoluminescence quantum yields (ΦPL up to 90 %) and radiative rates (kr) up to 3.32×105 s-1. TADF process is aided by fast reverse intersystem crossing (rISC) rates of up to 2.56×107 s-1. Such emitters can be considered as hybrids of two existing TA…
Size-dependent electron transfer from atomically defined nanographenes to metal oxide nanoparticles.
2020
Atomically defined nanographenes (NGs) feature size-dependent energy gaps induced by, and tuneable through, quantum confinement. Their energy-tunability and robustness make NGs appealing candidates as active elements in sensitized geometries, where NGs functionalize a metal oxide (MO) film with large-area-to-volume ratio. Despite the prominent relevance of NG/MO interfaces for developing novel architectures for solar energy conversion, to date, little information is available regarding the fundamentals of electron transfer (ET) processes taking place from NG donors to MO acceptors. Here, we analyze the interplay between the size of atomically precise NGs and ET dynamics at NG/MO interfaces.…
ETD and ECD Mass Spectrometry Fragmentation for the Characterization of Protein Post Translational Modifications
2012
The introduction of electron capture dissociation (ECD) by McLafferty and co-workers, and further of electron transfer dissociation (ETD), mechanism allows gas-phase fragmentation of multiply charged protein and peptide ions upon capture of a low-energy (<1 eV) electron or electron transfer in a gas phase ion-ion chemistry. The odd-electron species then undergoes rearrangement with subsequent cleavage of N−Cα backbone. Peptide fragmentation can take place inducing the formation of cand ztype fragment ions without loss of the information on the PTM localization. The key to the success of this approach is the selection of intact protein molecular ions and its profound potential for PTM charac…
Gold nanoparticles/electrochemically expanded graphite composite: A bifunctional platform toward glucose sensing and SERS applications
2019
Abstract An integrated nanogold/expanded graphite based sensor was fabricated by a former electrochemical etching of the pencil lead electrode (PLE) and a later in-situ deposition of gold nanoparticles (AuNPs). The electrochemical pretreatment of PLE (EPLE) created a 3D graphene-like surface, enhanced the electrode surface area and facilitated the electron transfer ability within 5 min without any hazardous chemicals added. The obtained AuNPs/EPLE sensor had an excellent electrochemical response to glucose with a wide linear concentration range, from 0.05 to 38 mM and 38 to 60 mM, and a low detection limit of 5 μM (S/N = 3). Furthermore, the AuNPs/EPLE sensor was successfully employed to de…
Chemosensors displaying pH controlled multistage fluorescence emission
1999
A large number of systems displaying pH controlled multistages of fluorescence emission intensity, have not been recognized from this point of view. In this work we present two paradigmatic cases: (i) polyamine receptors linked to a fluorophore unit, in which the signal is modulated by an intra-molecular pH dependent electron transfer process, (ii) phenols presenting adiabatic excited state proton transfer. In the first example the chemosensors are constituted by a receptor unit containing a polyaza moiety suitable for binding protons (but also metal ions or anions). The receptor is linked to a benzene or naphthalene unit that acts as a fluorophore. The fluorescence signal is dependent on t…
Fluorescent Hg2+ Sensors: Synthesis and Evaluation of a Tren-Based Starburst Molecule Containing Fluorinated 1,2,4-Oxadiazoles.
2010
A new tren-based starburst molecule containing fluorinated 1,2,4-oxadiazoles as fluorophores has been synthesized and its sensing behavior toward several metal cations has been investigated by UV/Vis, fluorescence, 1 H NMR and 19 F NMR spectroscopy. Selective sensing for Hg 2+ ions through a PET-based mechanism was evidenced, suggesting application as fluorescent sensor for Hg 2+ of the off-on type.
Electron transfer in a supramolecular associate of a fullerene fragment
2014
Herein, we investigate the association of a fullerene fragment, hemifullerene C30H12, with an electron-donating bowl-shaped tetrathiafulvalene derivative (truxTTF). UV/Vis titrations and DFT calculations support formation of the supramolecular complex, for which an association constant of log Ka = 3.6±0.3 in CHCl3 at room temperature is calculated. Remarkably, electron transfer from truxTTF to C30H12 to form the fully charge-separated species takes place upon irradiation of the associate with light, constituting the first example in which a fullerene fragment mimics the electron-accepting behavior of fullerenes within a supramolecular complex.
Study of the electrochemical and optical properties of fullerene and methano[60]fullerenediphosphonate derivatives in solution and as self-assembled …
2014
Four methanofullerenes with phosphonate groups attached to a C60 core were synthesized to probe their electrochemical and optical properties both in solution and as self-assembled monolayer structures (SAMs). As the methano[60]fullerenediphosphonate is a water soluble derivative of the fullerene it has high potential as an imaging molecule in biological applications and in optoelectronics. For the processing of fullerene based SAMs different electrode substrates (ITO, Au and Si) with specific anchoring groups (zirconium, cysteamine and amino-silane) were used. The formation of the C60-SAMs to the surfaces were investigated by atomic force microscopy (AFM), infrared spectroscopy, contact ang…
Role of the bridge in photoinduced electron transfer in porphyrin-fullerene dyads.
2015
The role of π-conjugated molecular bridges in through-space and through-bond electron transfer is studied by comparing two porphyrin-fullerene donor-acceptor (D-A) dyads. One dyad, ZnP-Ph-C60 (ZnP = zinc porphyrin), incorporates a phenyl bridge between D and A and behaves very similarly to analogous dyads studied previously. The second dyad, ZnP-EDOTV-C60, introduces an additional 3,4-ethylenedioxythienylvinylene (EDOTV) unit into the conjugated bridge, which increases the distance between D and A, but, at the same time, provides increased electronic communication between them. Two essential outcomes that result from the introduction of the EDOTV unit in the bridge are as follows: 1) faster…