69 research outputs found
Disparate roles of ATR and ATM in immunoglobulin class switch recombination and somatic hypermutation
Introduction to the LLM Special Issue 2012 on the History, contact and classification of Papuan languages
Harald Hammarström and Wilco van den Heuvel organized a conference on the History, contact, and classification of Papuan languages, and edited this peer-reviewed special issue of the journal Languages and Linguistics in Melanesia following the conference
The Rate Ladder of Proton-Coupled Tyrosine Oxidation in Water: A Systematic Dependence on Hydrogen Bonds and Protonation State
Ultrafast Electron Transfer Dynamics in a Series of Porphyrin/Viologen Complexes: Involvement of Electronically Excited Radical Pair Products
Ultrafast
electron transfer was studied for a series of metalloporphyrin/bipyridinium
complexes in aqueous solution, using laser excitation in the Soret
or Q-bands of the porphyrin. Electron transfer occurred before electronic
and vibrational relaxation of the initial excited state. This allowed
for a thorough investigation of the dependence of electron transfer
rate constants on the driving force and the nature of the product
state. The driving force dependence showed that electron transfer
from the S<sub>2</sub> state occurred to an electronically excited
radical pair state, and the present results provide the most direct
evidence to date for the formation of such states in photoinduced
electron transfer reactions. We also found that subsequent recombination
of the radical pair produced vibrationally excited ground states;
the excess energy of the radical pair generated from the initial state
is not completely dissipated during the lifetime of the radical pair.
The porphyrin/bipyridinium complexes where recombination lies deeper
in the Marcus inverted region show <i>less</i> formation
of unrelaxed ground states, contrary to what is expected from equilibrium
electron transfer theories. Instead, the rate of the electron transfer,
which competes with vibrational relaxation, was the main parameter
controlling the relative yield of unrelaxed ground states within this
series of complexes
Direct Evidence of a Tryptophan Analogue Radical Formed in a Concerted Electron−Proton Transfer Reaction in Water
Proton-coupled
electron transfer (PCET) is a fundamental reaction
step of many chemical and biological processes. Well-defined biomimetic
systems are promising tools for investigating the PCET mechanisms
relevant to natural proteins. Of particular interest is the possibility
to distinguish between stepwise and concerted transfer of the electron
and proton, and how PCET is controlled by a proton acceptor such as
water. Thus, many tyrosine and phenolic derivatives have been shown
to undergo either stepwise or concerted PCET, where the latter process
is defined by simultaneous tunneling of the electron and proton from
the same transition state. For tryptophan instead, it is theoretically
predicted that a concerted pathway can never compete with the stepwise
electron-first mechanism (ETPT) when neat water is the primary proton
acceptor. The argument is based on the radical p<i>K</i><sub>a</sub> (∼4.5) that is much higher than that for water
(p<i>K</i><sub>a</sub>(H<sub>3</sub>O<sup>+</sup>) = 0),
which thermodynamically disfavors a concerted proton transfer to H<sub>2</sub>O. This is in contrast to the very acidic radical cation of
tyrosine (p<i>K</i><sub>a</sub> ∼ −2). However,
in this study we show, by direct time-resolved absorption spectroscopy
on two [RuÂ(bpy)<sub>3</sub>]<sup>2+</sup>−tryptophan (bpy =
2,2′-bipyridine) analogue complexes, that also tryptophan oxidation
with water as a proton acceptor can occur via a concerted pathway,
provided that the oxidant has weak enough driving force. This rivals
the theoretical predictions and suggests that our current understanding
of PCET reactions in water is incomplete
Competitive Hole Transfer from CdSe Quantum Dots to Thiol Ligands in CdSe-Cobaloxime Sensitized NiO Films Used as Photocathodes for H<sub>2</sub> Evolution
Quantum dot (QD)
sensitized NiO photocathodes rely on efficient
photoinduced hole injection into the NiO valence band. A system of
a mesoporous NiO film co-sensitized with CdSe QDs and a molecular
proton-reduction catalyst was studied. While successful electron transfer
from the excited QDs to the catalyst is observed, most of the photogenerated
holes are instead quenched very rapidly (ps) by hole trapping at the
surface thiols of the capping agent used as linker molecules. We confirmed
our conclusion by first using a thiol free capping agent and second
varying the thiol concentration on the QD’s surface. The later
resulted in faster hole trapping as the thiol concentration increased.
We suggest that this hole trapping by the linker limits the H<sub>2</sub> yield for this photocathode in a device
Competitive Hole Transfer from CdSe Quantum Dots to Thiol Ligands in CdSe-Cobaloxime Sensitized NiO Films Used as Photocathodes for H<sub>2</sub> Evolution
Quantum dot (QD)
sensitized NiO photocathodes rely on efficient
photoinduced hole injection into the NiO valence band. A system of
a mesoporous NiO film co-sensitized with CdSe QDs and a molecular
proton-reduction catalyst was studied. While successful electron transfer
from the excited QDs to the catalyst is observed, most of the photogenerated
holes are instead quenched very rapidly (ps) by hole trapping at the
surface thiols of the capping agent used as linker molecules. We confirmed
our conclusion by first using a thiol free capping agent and second
varying the thiol concentration on the QD’s surface. The later
resulted in faster hole trapping as the thiol concentration increased.
We suggest that this hole trapping by the linker limits the H<sub>2</sub> yield for this photocathode in a device
State-Selective Electron Transfer in an Unsymmetric Acceptor−Zn(II)porphyrin−Acceptor Triad: Toward a Controlled Directionality of Electron Transfer from the Porphyrin S 2 and S 1 States as a Basis for a Molecular Switch
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