Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Oct. 25, 2024
Abstract
Comprehending
the
underlying
factors
that
govern
photoluminescence
(PL)
in
metal
nanoclusters
(NCs)
under
physiological
conditions
remains
a
highly
intriguing
and
unresolved
challenge,
particularly
for
their
biomedical
applications.
In
this
study,
we
evaluate
critical
role
of
excited‐state
proton‐coupled
electron
transfer
emission
NCs.
Our
findings
demonstrate
hydronium
ion
(H
3
O
+
)
binding
can
trigger
nonlinear,
pH‐dependent
concerted
proton
(CEPT)
reaction.
This
involves
simultaneous
from
Au(0)
core
to
Au(I)−ATT
(ATT
denotes
6‐aza‐2‐thiothymidine)
surface
H
ATT
ligand
single
step,
greatly
promoting
vibrations
rotations
surface,
resulting
substantial
PL
quenching
Au
10
(ATT)
6
Further
analyses
show
unique
CEPT
dynamics
are
strongly
influenced
by
opposing
effects
increased
reorganization
energy
larger
pre‐exponential
factor
on
rate.
Moreover,
proposed
process
is
found
be
prevalent
core–shell
relaxation
NCs,
such
as
25
(SR)
18
(SR
thiolate)
serves
an
important
limiting
emission.
By
simply
controlling
p
K
ligands,
performance
easily
regulated
environments.
Sustainable Energy & Fuels,
Journal Year:
2024,
Volume and Issue:
8(9), P. 1944 - 1952
Published: Jan. 1, 2024
The
tetraruthenium
polyoxometalate
Ru
4
POM
shows
sequential
oxidative
proton
coupled
electron
transfer
(PCET)
events
in
a
[Ru(bpy)
3
]
2+
/S
2
O
8
2−
photochemical
cycle
for
catalytic
water
oxidation,
reaching
quantum
efficiency
approaching
14%.
Chemical Science,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
The
mechanism
of
proton-coupled
electron
transfer
at
the
surface
titanium-substituted
polyoxovanadate-alkoxide
clusters
can
be
tuned
by
judicious
selection
substrate.
Chemical Science,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
Lytic
polysaccharide
monooxygenases
(LPMOs)
are
a
unique
group
of
monocopper
enzymes
that
exhibit
remarkable
ability
to
catalyze
the
oxidative
cleavage
recalcitrant
carbohydrate
substrates,
such
as
cellulose
and
chitin,
by
utilizing
O2
or
H2O2
oxygen
source.
One
key
challenges
in
understanding
catalytic
mechanism
LPMOs
lies
deciphering
how
they
activate
dioxygen
using
diverse
reductants.
To
shed
light
on
this
intricate
process,
we
conducted
in-depth
investigations
quantum
mechanical/molecular
mechanical
(QM/MM)
metadynamics
simulations,
molecular
dynamics
(MD)
density
functional
theory
(DFT)
calculations.
Specifically,
our
study
focuses
elucidating
situ
formation
presence
cellobiose
dehydrogenase
(CDH),
proposed
natural
reductant
LPMOs.
Our
findings
reveal
proton-coupled
electron
transfer
(PCET)
process
generating
Cu(ii)-hydroperoxide
intermediate
from
Cu(ii)-superoxide
intermediate.
Subsequently,
direct
proton
proximal
results
LPMO-Cu(ii).
Notably,
significantly
differs
LPMO/ascorbate
system,
where
two
hydrogen
atom
reactions
responsible
for
LPMO-Cu(i).
Based
propose
LPMO
CDH
substrate,
which
involves
competitive
binding
substrate
reduced
While
CDH-bound
can
generate
H2O2,
substrate-bound
employ
generated
LPMO/CDH
system
perform
peroxygenase
substrate.
work
not
only
provides
valuable
insights
into
reductant-dependent
mechanisms
activation
but
also
holds
implications
functions
these
their
environment.
Precision Chemistry,
Journal Year:
2025,
Volume and Issue:
3(5), P. 233 - 260
Published: March 11, 2025
Hydrogen
transfer
is
a
fundamental
chemical
process
critical
to
the
design
and
application
of
organic
molecules
functional
devices.
By
uncovering
dynamic
interactions
between
atoms
within
molecules,
hydrogen
research
offers
innovative
pathways
for
creating
advanced
materials
These
advancements
have
driven
progress
in
areas
such
as
optoelectronics,
molecular
switches,
bioimaging.
This
review
explores
various
forms
transfer,
including
atom,
proton,
hydride
highlighting
their
mechanisms
key
reactions.
It
also
examines
integration
these
processes
into
devices,
single-molecule
systems,
films,
frameworks.
Future
directions
emphasize
precise
control
pathways,
development
highly
selective
efficient
reaction
robust
devices
based
on
processes.
efforts
aim
enhance
device
performance
broaden
applications
intelligent
materials,
integrated
functions,
information
technology.
Inorganic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: May 23, 2025
The
oxidation
of
metal-aquo
and
-hydroxo
complexes
to
generate
the
high-valent
metal-oxo
species
used
in
oxidative
catalysis
is
often
kinetically
slow
due
sluggish
proton
transfer
between
ligated
-H2O/-OH
proton-coupled
electron
(PCET)
chemistry.
In
this
research,
a
ruthenium
water
catalyst
anchored
conductive
tin-doped
indium
oxide
(ITO)
thin
film,
abbreviated
ITO|RuII-OH2,
was
characterized
by
spectroscopic
electrochemical
methods
acetate
or
phosphate
buffers.
deprotonated
intermediate,
RuII-OH,
observed
spectroscopically
PCET
half-reaction
ITO(e-)|RuIII-OH
+
H+
→
ITO|RuII-OH2
indicating
an
underlying
stepwise
ET-PT
mechanism.
contrast,
at
elevated
buffer
concentrations,
intermediate
absent,
2-4
order
magnitude
increase
rate
constant
observed.
Kinetic
data
for
reaction
measured
as
function
driving
force
provided
reorganization
energy
λ
=
1.05
eV
assigned
concerted
electron-proton
(EPT)
addition,
standard
heterogeneous
constants
two
equilibria,
RuIII-OH
e-
⇌
RuII-OH2
RuIV
O
were
enhanced
these
same
Collectively,
show
that
added
buffers
can
enhance
kinetics
thermodynamics
reactions
relevant
catalysis.
The Journal of Chemical Physics,
Journal Year:
2024,
Volume and Issue:
160(17)
Published: May 2, 2024
Understanding
the
dynamics
of
photoinduced
processes
in
complex
systems
is
crucial
for
development
advanced
energy-conversion
materials.
In
this
study,
we
investigate
nonadiabatic
using
time-convolution
(TC)
and
time-convolutionless
(TCL)
quantum
master
equations
(QMEs)
based
on
treating
electronic
couplings
as
perturbation
within
framework
multistate
harmonic
(MSH)
models.
The
MSH
model
Hamiltonians
are
mapped
from
all-atom
simulations
such
that
all
pairwise
reorganization
energies
consistently
incorporated,
leading
to
a
heterogeneous
environment
couples
multiple
states
differently.
Our
exploration
encompasses
charge
transfer
organic
photovoltaic
carotenoid–porphyrin–C60
triad
dissolved
liquid
solution
excitation
energy
(EET)
photosynthetic
Fenna–Matthews–Olson
complexes.
By
systematically
comparing
perturbative
TC
TCL
QME
approaches
with
exact
quantum-mechanical
various
semiclassical
approximate
kernels,
demonstrate
their
efficacy
accuracy
capturing
essential
features
dynamics.
calculations
show
QMEs
generally
yield
more
accurate
results
than
QMEs,
especially
EET,
although
both
methods
offer
versatile
adaptable
across
different
systems.
addition,
approximations
featuring
Wigner-transformed
classical
nuclear
densities
well
governing
during
coherence
period,
highlighting
trade-off
between
computational
cost.
This
work
provides
valuable
insights
into
applicability
performance
via
model,
offering
guidance
realistic
applications
condensed-phase
atomistic
level.
Small,
Journal Year:
2024,
Volume and Issue:
20(47)
Published: Aug. 24, 2024
The
introduction
of
noble
metal
into
spinel
structure
is
an
effective
strategy
to
develop
efficient
oxygen
evolution/reduction
reaction
(OER/ORR)
catalysts.
Herein,
surface
Co
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Oct. 31, 2024
Comprehending
the
underlying
factors
that
govern
photoluminescence
(PL)
in
metal
nanoclusters
(NCs)
under
physiological
conditions
remains
a
highly
intriguing
and
unresolved
challenge,
particularly
for
their
biomedical
applications.
In
this
study,
we
evaluate
critical
role
of
excited-state
proton-coupled
electron
transfer
emission
NCs.
Our
findings
demonstrate
hydronium
ion
(H
