Journal of the American Chemical Society,
Journal Year:
2021,
Volume and Issue:
143(37), P. 14939 - 14950
Published: Sept. 7, 2021
Decades
of
extensive
research
efforts
by
biochemists,
organic
chemists,
and
protein
engineers
have
led
to
an
understanding
the
basic
mechanisms
essentially
all
known
types
enzymes,
but
in
a
formidable
number
cases
essential
aspect
has
been
overlooked.
The
occurrence
short-lived
chiral
intermediates
formed
symmetry-breaking
prochiral
precursors
enzyme
catalyzed
reactions
systematically
neglected.
We
designate
these
elusive
species
as
fleeting
analyze
such
crucial
questions
"Do
occur
homochiral
form?"
If
so,
what
is
absolute
configuration,
why
did
Nature
choose
that
particular
stereoisomeric
form,
even
when
isolable
final
product
may
be
achiral?
Does
configuration
depend
any
way
on
precursor?
How
does
this
affect
catalytic
proficiency
enzyme?
issues
continue
unexplored,
then
many
remains
incomplete.
systematized
according
their
structures
types.
This
followed
critical
analyses
selected
case
studies
conclusions
perspectives.
hope
fascinating
concept
will
attract
attention
scientists,
thereby
opening
exciting
new
field.
Protein Engineering Design and Selection,
Journal Year:
2023,
Volume and Issue:
36
Published: Jan. 1, 2023
Abstract
Biocatalysis
has
become
a
powerful
alternative
for
green
chemistry.
Expanding
the
range
of
amino
acids
used
in
protein
biosynthesis
can
improve
industrially
appealing
properties
such
as
enantioselectivity,
activity
and
stability.
This
review
will
specifically
delve
into
thermal
stability
improvements
that
non-canonical
(ncAAs)
confer
to
enzymes.
Methods
achieve
this
end,
use
halogenated
ncAAs,
selective
immobilization
rational
design,
be
discussed.
Additionally,
specific
enzyme
design
considerations
using
ncAAs
are
discussed
along
with
benefits
limitations
various
approaches
available
enhance
Science Advances,
Journal Year:
2023,
Volume and Issue:
9(38)
Published: Sept. 20, 2023
Plastic
waste
management
is
a
pressing
ecological,
social,
and
economic
challenge.
The
saliva
of
the
lepidopteran
Galleria
mellonella
larvae
capable
oxidizing
depolymerizing
polyethylene
in
hours
at
room
temperature.
Here,
we
analyze
by
cryo-electron
microscopy
(cryo-EM)
G.
mellonella's
directly
from
native
source.
three-dimensional
reconstructions
reveal
that
buccal
secretion
mainly
composed
four
hexamerins
belonging
to
hemocyanin/phenoloxidase
family,
renamed
Demetra,
Cibeles,
Ceres,
previously
unidentified
factor
termed
Cora.
Functional
assays
show
this
factor,
as
its
counterparts
Demetra
also
able
oxidize
degrade
polyethylene.
cryo-EM
data
x-ray
analysis
purified
fractions
they
self-assemble
primarily
into
three
macromolecular
complexes
with
striking
structural
differences
likely
modulate
their
activity.
Overall,
these
results
establish
ground
further
explore
hexamerins'
functionalities,
role
vivo,
eventual
biotechnological
application.
Chemistry of Materials,
Journal Year:
2023,
Volume and Issue:
35(10), P. 3941 - 3950
Published: May 12, 2023
The
development
of
solar-driven
organic
synthesis
processes
as
an
alternative
to
conventional
thermo-catalytic
technologies
is
great
research
significance
in
academia
and
industry.
Herein,
we
looked
into
the
photoinduced
Baeyer–Villiger
oxidation
cyclohexanone
based
on
Mukaiyama
method
for
first
time.
We
fabricated
a
crystalline
polyoxometalate-based
metal–organic
framework
photocatalyst,
CR-SiW12,
which
represents
example
trinuclear
ruthenium
clusters
involved
construction
frameworks.
was
efficiently
converted
ε-caprolactone
under
visible
light
(>400
nm)
irradiation
with
CR-SiW12
catalyst,
reaction
turnover
number
frequency
recorded
941
274.5
h–1,
respectively,
apparent
quantum
yield
at
465
nm
measured
be
8.4%.
Moreover,
exhibited
high
structural
stability
reusability
where
remained
91.3%
after
five
consecutive
cycles.
This
work
offers
promising
strategy
accomplishing
reactions
green
conditions.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(48)
Published: Aug. 28, 2023
Biocatalytic
cascades
are
a
powerful
tool
for
building
complex
molecules
containing
oxygen
and
nitrogen
functionalities.
Moreover,
the
combination
of
multiple
enzymes
in
one
pot
offers
possibility
to
minimize
downstream
processing
waste
production.
In
this
review,
we
illustrate
various
recent
efforts
development
multi-step
syntheses
involving
C-O
C-N
bond-forming
produce
high
value-added
compounds,
such
as
pharmaceuticals
polymer
precursors.
Both
vitro
vivo
examples
discussed,
revealing
respective
advantages
drawbacks.
The
use
engineered
boost
outcome
is
also
addressed
current
co-substrate
cofactor
recycling
strategies
presented,
highlighting
importance
atom
economy.
Finally,
tools
overcome
challenges
multi-enzymatic
oxy-
amino-functionalization
reactions
including
flow
systems
with
immobilized
biocatalysts
confined
nanomaterials.
Heliyon,
Journal Year:
2023,
Volume and Issue:
10(1), P. e23416 - e23416
Published: Dec. 9, 2023
The
exploitation
of
natural
products
and
their
analogues
in
the
field
pharmacology
has
been
regarded
as
great
importance.
It
can
be
attributed
to
fact
that
these
scaffolds
exhibit
diverse
chemical
properties,
distinct
biological
activities
zenith
specificity
biochemical
processes,
enabling
them
act
favorable
structures
for
lead
compounds.
synthesis
a
crafty
hard-to-achieve
task.
Steglich
esterification
reaction
played
significant
role
area.
is
mild
efficient
technique
constructing
ester
linkages.
This
involves
establishment
moiety
via
carbodiimide-based
condensation
carboxylic
acid
with
an
alcohol,
thiol
or
amine
catalyzed
by
dimethyl
aminopyridine
(DMAP).
Specifically,
labile
reagents
multiple
reactive
sites
are
esterified
efficiently
classical
modified
conditions,
which
accounts
synthetic
utility.
review
encloses
performance
forging
linkage
executing
total
derivatives
since
2018.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(2), P. 797 - 811
Published: Jan. 3, 2024
An
atypical
nonheme
iron-dependent
dioxygenase
BTG13
with
a
rare
iron
coordination
of
four
histidine
residues
and
carboxylated-lysine
(Kcx)
was
recently
reported
to
catalyze
the
C4a–C10
bond
cleavage
anthraquinone.
However,
reaction
mechanism
remains
elusive.
Herein,
detailed
is
studied
using
molecular
dynamics
simulations
density
functional
theory
calculations.
The
comprehensive
mechanistic
study
shows
that
most
favorable
pathway
for
C–C
anthraquinone
involves
two
unusual
steps:
(1)
hydrogen
atom
abstraction
(HAA)
from
an
sp3-hybridized
carbon
substrate
by
FeIII–O2•–
(2)
oxygen
rebound
radical
via
homolytic
O–O
cleavage,
which
activates
FeIII–OOH
form
FeIV═O
species.
Furthermore,
our
results
reveal
Kcx
could
increase
electron-donating
ability
ferrous
iron,
thereby
boosting
activation
dioxygen
species
facilitating
following
HAA
processes.
This
advances
current
knowledge
reactions
catalyzed
oxygenases.
Journal of Chemical Information and Modeling,
Journal Year:
2024,
Volume and Issue:
64(8), P. 3123 - 3139
Published: April 4, 2024
Rapidly
predicting
enzyme
properties
for
catalyzing
specific
substrates
is
essential
identifying
potential
enzymes
industrial
transformations.
The
demand
sustainable
production
of
valuable
industry
chemicals
utilizing
biological
resources
raised
a
pressing
need
to
speed
up
biocatalyst
screening
using
machine
learning
techniques.
In
this
research,
we
developed
an
all-purpose
deep-learning-based
multiple-toolkit
(ALDELE)
workflow
catalysts.
ALDELE
incorporates
both
structural
and
sequence
representations
proteins,
alongside
ligands
by
subgraphs
overall
physicochemical
properties.
Comprehensive
evaluation
demonstrated
that
can
predict
the
catalytic
activities
enzymes,
particularly,
it
identifies
residue-based
hotspots
guide
engineering
generates
substrate
heat
maps
explore
scope
given
biocatalyst.
Moreover,
our
models
notably
match
empirical
data,
reinforcing
practicality
reliability
approach
through
alignment
with
confirmed
mutation
sites.
offers
facile
comprehensive
solution
integrating
different
toolkits
tailored
purposes
at
affordable
computational
cost
therefore
would
be
discovery
new
functional
their
exploitation
industry.
ACS Catalysis,
Journal Year:
2021,
Volume and Issue:
12(1), P. 66 - 72
Published: Dec. 10, 2021
Baeyer-Villiger
monooxygenases
(BVMOs)
catalyze
the
oxidation
of
ketones
to
lactones
under
very
mild
reaction
conditions.
This
enzymatic
route
is
hindered
by
requirement
a
stoichiometric
supply
auxiliary
substrates
for
cofactor
recycling
and
difficulties
with
supplying
necessary
oxygen.
The
recombinant
production
BVMO
in
cyanobacteria
allows
substitution
organic
cosubstrates
water
as
an
electron
donor
utilization
oxygen
generated
photosynthetic
splitting.
Herein,
we
report
identification
from
Burkholderia
xenovorans
(BVMO
Xeno
)
that
exhibits
higher
rates
comparison
currently
identified
BVMOs.
We
10-fold
increase
specific
activity
cyclohexanone
monooxygenase
(CHMO
Acineto
Synechocystis
sp.
PCC
6803
(25
vs
2.3
U
gDCW-1
at
optical
density
OD750
=
10)
initial
rate
3.7
±
0.2
mM
h-1.
While
cells
containing
CHMO
showed
considerable
reduction
cyclohexanol,
this
unwanted
side
was
almost
completely
suppressed
,
which
attributed
much
faster
lactone
formation
lower
KM
value
toward
cyclohexanone.
Furthermore,
whole-cell
catalyst
outstanding
stereoselectivity.
These
results
show
that,
despite
self-shading
cells,
high
activities
can
be
obtained
elevated
cell
densities
even
further
increased
through
manipulation
transport
chain
(PETC).
up
h-1
underline
usefulness
oxygenic
chassis
reactions.
evolution
contribute
alleviating
highly
problematic
mass-transfer
limitation
oxygen-dependent
processes.