Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 23, 2024
Abstract
Owing
to
the
inaccessibility
of
β1–4‐
N
‐acetylgalactosaminyltransferase
for
direct
glycan
chain
elongation,
enzymatic
synthesis
0‐series
gangliosides
with
extended
backbones
has
not
been
explored.
In
this
study,
sialic
acid
was
enzymatically
introduced
as
an
auxiliary
group
overcome
limitation
substrate
specificity
Campylobacter
jejuni
(CjCgtA)
achieve
desired
ganglioside
core
structures,
and
could
be
removed
by
sialidase
at
appropriate
stages.
A
bacterial
α2–6‐sialyltransferase
from
Photobacterium
damselae
(Pd2,6ST)
exhibited
unexpected
acceptor
providing
ready
access
complex
bearing
sialyl
‐acetylgalactosamine
unit.
The
structures
key
substrates
were
further
diversified
sequential
modular
assembly
generate
a
collection
31
glycans
after
removal
sugar
stage.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 10, 2025
Sulfation
is
a
common,
but
poorly
understood,
post-glycosylational
modification
(PGM)
used
to
modulate
biological
function.
To
deepen
our
understanding
of
the
roles
various
sulfated
glycoforms
and
their
relevant
binding
proteins,
we
must
expand
enzymatic
toolkit
for
synthesis.
Here,
bypass
need
both
sulfotransferases
glycosyltransferases
by
engineering
series
mutants
6-SulfoGlcNAcase,
from
Streptococcus
pneumoniae,
directly
efficiently
synthesize
not
only
ubiquitous
6S-GlcNAc-β-1,3-Gal
linkage
prevalent
within
host
glycans,
also
6S-GlcNAc-β-1,6-GalNAc
commonly
observed
core-6
O-glycans,
more
exotic
6S-GlcNAc-β-1,4-GalNAc
linkage.
We
further
elaborate
these
into
complex
N-glycan
O-glycan
structures
relevance.
By
utilizing
cost-effective
activated
donor
pNP-6S-GlcNAc
in
conjunction
with
mutant
GH185
6-SulfoGlcNAcases
demonstrate
simple
yet
powerful
vitro
method
generating
well-defined
oligosaccharides
use
variety
applications
including
glycan
arrays,
remodeling,
specificity
studies
carbohydrate
proteins
such
as
lectins.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 25, 2025
Natural
polysaccharides
possess
various
biological
functions
and
have
become
increasingly
important
as
drug
candidates
for
biomedical
development.
However,
the
accessibility
to
multiple-branched
large-sized
acidic
with
well-defined
structures
identification
of
related
active
glycan
domains
remain
challenging.
Here,
we
report
precision
synthesis
a
highly
branched
pectin
polysaccharide
up
63-mer
containing
10
different
glycosidic
linkages
from
Lycium
barbarum.
The
synthetic
strategy
relies
on
stereoselective
modular
assembly
an
orthogonally
protected
decasaccharide
backbone,
efficient
three
side
chain
glycans
by
integration
stereocontrolled
one-pot
chemoselective
glycosylations
hydrogen-bond-mediated
aglycone
delivery
approach,
convergent
target
in
site-specific
glycosylation
manner
via
flexible
orthogonal
protecting
group
manipulations.
Structure–activity
relationship
studies
its
short
fragments
(9-mer,
10-mer,
11-mer,
33-mer)
suggest
that
domain
exhibits
better
antiliver
fibrosis
activity.
Nature Communications,
Journal Year:
2025,
Volume and Issue:
16(1)
Published: May 10, 2025
Fucoidan,
a
sulfated
glycan
derived
from
brown
algae,
has
garnered
significant
attention
for
its
anticoagulant
properties.
However,
the
structural
complexity
and
heterogeneity
of
naturally
extracted
fucoidan
have
hindered
comprehensive
understanding
structure-activity
relationship,
limiting
development
fucoidan-based
drugs.
To
address
this
challenge,
we
synthesize
diverse
library
58
distinct
fucoidans
with
multiple
contiguous
1,2-cis
glycosidic
bonds,
ranging
disaccharides
to
dodecasaccharides,
using
highly
efficient
preactivation-based
one-pot
glycosylation
strategy.
This
includes
compounds
various
sulfation
patterns
(2,3-O-di-,
3,4-O-di-,
2,3,4-O-tri-sulfation)
encompassing
nearly
all
possible
structures.
In
vitro
assays
demonstrate
that
both
molecular
size
degree
play
crucial
roles
in
potency.
Notably,
29,
30,
37,
significantly
prolong
human
plasma
activated
partial
thromboplastin
time
(APTT),
comparable
effect
enoxaparin,
without
affecting
prothrombin
(PT)
or
thrombin
(TT).
selective
inhibition
intrinsic
coagulation
pathway
suggests
reduced
risk
bleeding,
highlighting
therapeutic
potential
these
as
safer
agents.
Chemical Science,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
Decarboxylative
radical
sulfation
is
achieved
with
persulfates
functioning
as
both
oxidants
and
sulfating
agents
to
facilitate
C–OSO
3
−
bond
formation.
Synthesis
of
organosulfates
from
carboxylic-acid-based
drugs
may
improve
their
metabolic
profiles.
The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: June 4, 2025
Sulfation
is
a
crucial
transformation
in
both
pathological
and
physiological
processes.
However,
the
conventional
synthesis
of
organosulfates
primarily
relies
on
O-sulfonation,
which
limited
to
hydroxyl-containing
substrates.
Here,
we
developed
practical
cost-efficient
method
for
electrochemical
decarboxylative
sulfation.
This
approach
opens
new
avenues
access
from
readily
available
carboxylic
acids
with
broad
substrate
scope
good
functional
group
compatibility.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: June 4, 2025
The
assembly-line
strategy
serves
as
an
effective
way
for
optimizing
tandem
steps
in
the
fields
of
enzyme
catalysis
and
homogeneous
catalysis.
Herein,
we
rationally
construct
efficient
Ru/TiO2
catalysts
important
industrial
heterogeneous
reaction
Fischer-Tropsch
synthesis
(FTS),
involving
CO
dissociation,
hydrogenation,
C-C
coupling
complex
processes.
These
feature
"assembly-line"
structure
composed
oxygen
vacancies
(Ov),
interfacial
Ru
(RuIδ+
at
RuIδ+-Ov-Ti3+),
exposed
(RuE0)
sites.
Both
experimental
theoretical
results
demonstrate
that
RuIδ+
sites
with
assistance
Ov
primarily
contribute
to
dissociation
hydrogenation
C1
monomers
(workshop
1),
while
RuE0
predominantly
drive
above
intermediates
carbon
chain
growth
2).
We
interestingly
discover
besides
performance
two
workshops
themselves,
their
coordination
is
key
improve
activity
long-chain
hydrocarbon
selectivity
FTS.
Optimizing
this
trisite
catalytic
system
via
tuning
prereduction
time
TiO2
support
robustly
achieves
ultrahigh
FTS
(180.8
molCO
molRu-1
h-1)
maintaining
impressive
C5+
(90.1%),
outperforming
vast
majority
state-of-the-art
Ru-based
catalysts.
This
work
not
only
clearly
clarifies
synergistic
mechanisms
multiple
active
but
also
offers
valuable
guidance
application
reactions.
Advanced Science,
Journal Year:
2024,
Volume and Issue:
12(2)
Published: Nov. 18, 2024
Abstract
In
the
present
work,
bacterial
glycosyltransferases
are
utilized
to
construct
ganglioside
glycans
in
a
convergent
approach
via
sugar‒nucleotide
regeneration
system
and
one‐pot
multienzyme
reactions.
Starting
from
β‐lactoside
enables
diversification
of
both
glycan
moieties
linkages
lower
α‐arm
upper
β‐arm.
Overall,
comprehensive
panel
24
natural
a‐series
(GM3,
GM2,
GM1a,
GD1a,
GT1a,
fucosyl‐GM1),
b‐series
(GD3,
GD2,
GD1b,
GT1b,
GQ1b),
c‐series
(GT3,
GT2,
GT1c,
GQ1c,
GP1c),
α‐series
(GM1α,
GD1aα,
GT1aα),
o‐series
(GA2,
GA1,
GM1b,
GalNAc‐GM1b,
GD1c)
prepared,
which
suitable
for
biological
studies
further
applications.
Moreover,
microarray
is
constructed
with
these
synthesized
investigate
their
binding
specificity
recombinant
Fc‐fused
Siglec‐7
Siglec‐9,
immune
checkpoint‐like
recognition
proteins
on
killer
cells.
The
results
reveal
that
GD3
GT1aα
specific
ligands
respectively,
this
discovery
can
lead
identification
appropriate
investigating
roles
Siglecs
immunomodulation.
