Chemical
modification
of
carbonaceous
materials
is
a
convenient
and
reliable
approach
for
the
permanent
fabrication
functional
moieties.
Among
different
linkers,
diazirines
offer
photogenerated
reactive
carbene
that
can
insert
into
X–H
(X;
O,
N)
add
to
π
bonds
tether
variety
moieties
on
surface
materials.
Explicitly,
3‐phenyl‐3‐(trifluoromethyl)‐3H‐diazirine
more
thermally
chemically
stable
within
diazirine
family.
Here,
we
synthesized
3‐(ferrocenylalkyloxy)‐3‐(trifluoromethyl)‐diazirine
derivatives
utilized
them
covalently
modify
glassy
carbon
(GC).
The
enabled
tethering
ferrocene
(Fc)
GC
electrode
(GCE).
modified
properties
were
investigated
using
electrochemical
techniques,
ellipsometry
spectroscopy,
scanning
electron
microscopy.
Electrochemical
responses
in
KCl
Ru(NH
3
)
6
3+
solutions
clearly
exhibited
redox
behavior
blocking
during
modification,
respectively.
Surface
analysis
results
revealed
clear
correlation
between
thickness
capacitance
current
surface.
More
importantly,
obtained
electrochemistry
data
show
substantial
chemical
stability
tethered
Fc
GCE
both
aqueous
nonaqueous
media.
presented
work
offers
an
on‐demand
photochemical
formation
from
functionality
applications
electrodes
electrocatalysis
sensing.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(24), С. 16670 - 16680
Опубликована: Июнь 7, 2024
To
unravel
why
computational
design
fails
in
creating
viable
enzymes,
while
directed
evolution
(DE)
succeeds,
our
research
delves
into
the
laboratory
of
protoglobin.
DE
has
adapted
this
protein
to
efficiently
catalyze
carbene
transfer
reactions.
We
show
that
previously
proposed
enhanced
substrate
access
and
binding
alone
cannot
account
for
increased
yields
during
DE.
The
3D
electric
field
entire
active
site
is
tracked
through
dynamics,
clustered
using
affinity
propagation
algorithm,
subjected
principal
component
analysis.
This
analysis
reveals
notable
changes
with
DE,
where
distinct
topologies
influence
transition
state
energetics
mechanism.
A
chemically
meaningful
emerges
takes
lead
facilitates
crossing
barrier
transfer.
Our
findings
underscore
intrinsic
dynamic's
on
enzyme
function,
ability
switch
mechanisms
within
same
protein,
crucial
role
design.
Chemical Society Reviews,
Год журнала:
2024,
Номер
53(22), С. 11004 - 11044
Опубликована: Янв. 1, 2024
This
review
provides
a
mechanistic
overview
of
asymmetric
Fe,
Cu,
Pd,
Rh,
Au
and
heme-based
enzymes
catalyzed
carbene
insertion
reactions
to
construct
C–X
(X
=
O,
N,
S,
etc.
)
C–C
bonds,
focusing
on
the
stereochemical
models.
Digital Discovery,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
Steric
molecular
descriptors
designed
for
machine
learning
(ML)
applications
are
critical
connecting
structure–function
relationships
to
mechanistic
insight.
Chemistry - Methods,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 31, 2025
Abstract
In
its
ongoing
development,
mechanochemistry
is
becoming
equipped
with
additional
energy
inputs
such
as
light.
this
work
we
demonstrate
a
proof‐of‐principle
setup
for
real‐time
in
situ
Raman
monitoring
of
photomechanochemical
reactions.
Using
photoisomerization
azobenzenes,
and
photolysis
adamantane
diazirine
model
reactions,
show
that
multiple
cycles
can
be
performed
monitored
ball
mill,
highlight
reaction
selectivity
achieved
by
photomechanochemistry.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 12, 2025
The
creation
of
enzymes
with
abiological
abilities
offers
exciting
opportunities
to
access
new-to-nature
biocatalysis
beyond
that
found
in
nature.
Here,
we
repurpose
a
novel
protein
scaffold,
CTB10,
as
an
artificial
photoenzyme
through
genetic
code
expansion.
It
enables
catalytic
deracemization
cyclopropane,
process
remains
inaccessible
traditional
due
its
thermodynamically
unfavorable
Following
structural
optimization
directed
evolution,
broad
substrate
scope
high
enantioselectivities
is
achieved.
Furthermore,
the
crystal
structure
CTB10-based
photoenzyme-substrate
complex
well
demonstrates
how
chiral
cavity
sculpted
promote
efficient
and
selective
light-enabled
deracemization.
Therefore,
this
study
unlocks
potential
for
achieving
challenging
biocatalysis.
Chemical
modification
of
carbonaceous
materials
is
a
convenient
and
reliable
approach
for
the
permanent
fabrication
functional
moieties.
Among
different
linkers,
diazirines
offer
photogenerated
reactive
carbene
that
can
insert
into
X–H
(X;
O,
N)
add
to
π
bonds
tether
variety
moieties
on
surface
materials.
Explicitly,
3‐phenyl‐3‐(trifluoromethyl)‐3H‐diazirine
more
thermally
chemically
stable
within
diazirine
family.
Here,
we
synthesized
3‐(ferrocenylalkyloxy)‐3‐(trifluoromethyl)‐diazirine
derivatives
utilized
them
covalently
modify
glassy
carbon
(GC).
The
enabled
tethering
ferrocene
(Fc)
GC
electrode
(GCE).
modified
properties
were
investigated
using
electrochemical
techniques,
ellipsometry
spectroscopy,
scanning
electron
microscopy.
Electrochemical
responses
in
KCl
Ru(NH
3
)
6
3+
solutions
clearly
exhibited
redox
behavior
blocking
during
modification,
respectively.
Surface
analysis
results
revealed
clear
correlation
between
thickness
capacitance
current
surface.
More
importantly,
obtained
electrochemistry
data
show
substantial
chemical
stability
tethered
Fc
GCE
both
aqueous
nonaqueous
media.
presented
work
offers
an
on‐demand
photochemical
formation
from
functionality
applications
electrodes
electrocatalysis
sensing.
To
unravel
why
computational
design
fails
in
creating
viable
enzymes,
while
directed
evolution
(DE)
succeeds,
our
research
delves
into
the
laboratory
of
Protoglobin.
DE
has
adapted
this
protein
to
efficiently
catalyze
carbene
transfer
reactions.
We
show
that
previously
proposed
enhanced
substrate
access
and
binding
alone
cannot
account
for
increased
yields
during
DE.
The
3D
electric
field
entire
active
site
is
tracked
through
dynamics,
clustered
using
affinity
propagation
algorithm,
subjected
principal
component
analysis.
This
analysis
reveals
notable
changes
with
DE,
where
distinct
topologies
influence
transition
state
energetics
mechanism.
A
chemically
meaningful
emerges
takes
lead
facilitates
crossing
barrier
transfer.
Our
findings
underscore
intrinsic
dynamic's
on
enzyme
function,
ability
switch
mechanisms
within
same
protein,
crucial
role
design.
An
intriguing
P–H
insertion
of
arylhalodiazirines
with
H-phosphorus
oxides
under
ultraviolet-light
irradiation
is
described.
This
methodology
provides
an
efficient
and
straightforward
route
to
the
construction
a
variety
α-halophosphorus
in
good
yields
(≤95%),
which
represents
unique
example
α-halocarbenes
for
C–P
bond
formation.
The
metal-free
protocol
features
advantages
mild
reaction
conditions,
high
atom
economy,
environmental
friendliness.
