Chemistry - A European Journal,
Год журнала:
2024,
Номер
30(29)
Опубликована: Март 19, 2024
Free
radicals
are
increasingly
recognized
as
active
intermediate
reactive
species
that
can
participate
in
various
redox
processes,
significantly
influencing
the
mechanistic
pathways
of
reactions.
Numerous
researchers
have
investigated
generation
one
or
more
distinct
photogenerated
radicals,
proposing
hypotheses
to
explain
reaction
mechanisms.
Notably,
recent
research
has
demonstrated
emergence
innovative
including
organic
chemical
reactions
and
photocatalytic
dissolution
precious
metals.
To
harness
potential
these
free
effectively,
it
is
imperative
consolidate
analyze
processes
action
modes
radicals.
This
conceptual
paper
delves
into
latest
advancements
understanding
mechanics
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(7), С. 4081 - 4087
Опубликована: Фев. 13, 2023
The
highly
oxygen-dependent
nature
of
photodynamic
therapy
(PDT)
limits
its
therapeutic
efficacy
against
hypoxic
solid
tumors
in
clinics,
which
is
an
urgent
problem
to
be
solved.
Herein,
we
develop
oxygen-independent
supramolecular
agent
that
produces
hydroxyl
radical
(•OH)
by
oxidizing
water
the
presence
intracellularly
abundant
pyruvic
acid
under
oxygen-free
conditions.
A
fluorene-substituted
BODIPY
was
designed
as
electron
donor
and
coassembled
with
perylene
diimide
acceptor
form
quadruple
hydrogen-bonded
agent.
Detailed
mechanism
studies
reveal
intermolecular
transfer
charge
separation
upon
light
irradiation
result
efficient
generation
ion
pairs.
Under
conditions,
cationic
radicals
directly
oxidize
generate
cytotoxic
•OH,
anionic
electrons
acid,
realizing
catalytic
cycle.
Thus,
this
exhibited
superb
photocytotoxicity
even
severe
environments
excellent
vivo
antitumor
on
HeLa-bearing
mouse
models.
This
work
provides
a
strategy
for
constructing
agents,
opens
up
avenue
effective
PDT
tumors.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(15)
Опубликована: Фев. 14, 2023
Abstract
Although
metallacycle‐based
supramolecular
photosensitizers
(PSs)
have
attracted
increasing
attention
in
biomedicine,
their
clinical
translation
is
still
hindered
by
inherent
dark
toxicity.
Herein,
we
report
what
to
our
knowledge
the
first
example
of
a
molecular
engineering
approach
building
blocks
metallacycles
for
constructing
series
PSs
(
RuA–RuD
),
with
aim
simultaneously
reducing
toxicity
and
enhancing
phototoxicity,
consequently
obtaining
high
phototoxicity
indexes
(PI).
Detailed
vitro
investigations
demonstrate
that
display
cancer
cellular
uptake
remarkable
antitumor
activity
even
under
hypoxic
conditions.
Notably,
RuD
exhibited
no
displayed
highest
PI
value
(≈406).
Theoretical
calculations
verified
has
largest
steric
hindrance
lowest
singlet‐triplet
energy
gap
(Δ
E
ST
,
0.61
eV).
Further
vivo
studies
confirmed
allows
safe
effective
phototherapy
against
A549
tumors.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Март 21, 2024
Abstract
Photodynamic
therapy
(PDT)
is
a
promising
cancer
treatment
but
has
limitations
due
to
its
dependence
on
oxygen
and
high-power-density
photoexcitation.
Here,
we
report
polymer-based
organic
photosensitizers
(PSs)
through
rational
PS
skeleton
design
precise
side-chain
engineering
generate
•O
2
−
•OH
under
oxygen-free
conditions
using
ultralow-power
808
nm
photoexcitation
for
tumor-specific
photodynamic
ablation.
The
designed
skeletons
can
electron-hole
pairs
sensitize
H
O
into
with
photoexcitation,
achieving
NIR-photoexcited
oxygen-independent
production.
Further,
compared
commonly
used
alkyl
side
chains,
glycol
oligomer
as
the
chain
mitigates
recombination
offers
more
molecules
around
generated
from
hydrophobic
skeletons,
which
yield
4-fold
stronger
production,
thus
allowing
an
high
PDT
effect.
Finally,
feasibility
of
developing
activatable
PSs
in
female
mice
further
demonstrated
irradiation
15
mW
cm
−2
.
study
not
only
provides
insights
mechanism
also
general
guideline
develop
NIR
PDT.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(13), С. 8991 - 9003
Опубликована: Март 21, 2024
Though
immunogenic
cell
death
(ICD)
has
garnered
significant
attention
in
the
realm
of
anticancer
therapies,
effectively
stimulating
strong
immune
responses
with
minimal
side
effects
deep-seated
tumors
remains
challenging.
Herein,
we
introduce
a
novel
self-assembled
near-infrared-light-activated
ruthenium(II)
metallacycle,
Ru1105
(λem
=
1105
nm),
as
first
example
Ru(II)
supramolecular
ICD
inducer.
synergistically
potentiates
immunomodulatory
and
reduces
adverse
through
multiple
regulated
approaches,
including
NIR-light
excitation,
increased
reactive
oxygen
species
(ROS)
generation,
selective
targeting
tumor
cells,
precision
organelle
localization,
improved
penetration/retention
capabilities.
Specifically,
demonstrates
excellent
depth-activated
ROS
production
(∼1
cm),
resistance
to
diffusion,
anti-ROS
quenching.
Moreover,
exhibits
promising
results
cellular
uptake
generation
cancer
cells
multicellular
spheroids.
Importantly,
induces
more
efficient
an
ultralow
dose
(10
μM)
compared
conventional
agent,
oxaliplatin
(300
μM).
In
vivo
experiments
further
confirm
Ru1105's
potency
inducer,
eliciting
CD8+
T
depleting
Foxp3+
effects.
Our
research
lays
foundation
for
design
secure
exceptionally
potent
metal-based
agents
immunotherapy.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(12)
Опубликована: Янв. 23, 2024
We
herein
present
an
approach
of
photo-induced
disproportionation
for
preparation
Type-I
photodynamic
agents.
As
a
proof
concept,
BODIPY-based
photosensitizers
were
rationally
designed
and
prepared.
The
intermolecular
electron
transfer
between
homotypic
chromophores
leads
to
the
reaction,
resulting
in
formation
charged
intermediates,
cationic
anionic
radicals.
radicals
efficiently
oxidize
cellularimportant
coenzyme,
tetrahydrobiopterin
(BH
