Molecular Recognition-Mediated Transformation of Single-Chain Polymer Nanoparticles into Crosslinked Polymer Films

Article abstract of DOI:10.1002/anie.201706379

We describe single-chain polymer nanoparticles (SCNPs) possessing intramolecular dynamic covalent crosslinks that can transform into polymer films through a molecular recognition-mediated crosslinking process. The SCNPs utilise molecular recognition with surface-immobilised proteins to concentrate upon a substrate, bringing the SCNPs into close spatial proximity with one another and allowing their dynamic covalent crosslinkers to undergo intra- to interpolymer chain crosslinking leading to the formation of polymeric film. SCNPs must possess both the capacity for specific molecular recognition and a dynamic nature to their intramolecular crosslinkers to form polymer films, and an investigation of the initial phase of film formation indicates it proceeds from features which form upon the surface then grow predominantly in the xy directions. This approach to polymer film formation presents a potential method to “wrap” surfaces displaying molecular recognition motifs—which could potentially include viral, cellular and bacterial surfaces or artificial surfaces displaying multivalent recognition motifs—within a layer of polymer film.

Full text of DOI:10.1002/anie.201706379

A Journal of the Gesellschaft Deutscher Chemiker
Angewandte
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Accepted Article
Title: Molecular-recognition mediated transformation of single-chain
polymer nanoparticles into crosslinked polymer films
Authors: Clare Sarah Mahon, Christopher J McGurk, Scott M D
Watson, Martin A Fascione, Chadamas Sakonsinsiri, William
Bruce Turnbull, and David Andrew Fulton
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201706379
Angew. Chem. 10.1002/ange.201706379
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10.1002/anie.201706379
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Molecular recognition-mediated transformation of single-chain
polymer nanoparticles into crosslinked polymer films
Clare S. Mahon,[a,b,c] Christopher J. McGurk,[a] Scott M. D. Watson,[a] Martin A. Fascione,[c] Chadamas
Sakonsinsiri[b,d] W. Bruce Turnbull*[b] and David A. Fulton*[a]
crosslinked nature to the coating is desired. Here, we report a
method for polymer film formation in which so-called single-chain
polymer nanoparticles (SCNPs)[7] are transformed into
crosslinked polymeric films. We show that film formation only
occurs in the presence of complementary molecular recognition
between the SCNPs and functionalities displayed on the surface,
and that the dynamic covalent nature of intramolecular crosslinks
contained within the SCNPs is crucial for film formation. We
anticipate that this method will enable the ‘wrapping’ of a variety
of surfaces displaying molecular recognition motifs—which could
include the surfaces of viruses, cellular and bacterial surfaces or
artificial surfaces displaying multivalent recognition motifs—within
a layer of polymer film.
We utilise SCNPs (Fig. 1(a), top right) which are
nanostructures composed of intramolecularly crosslinked linear
polymer chains. We use dynamic covalent acylhydrazone bonds
as intramolecular cross-linkers within our SCNPs on account of
the well-known ability of this bond to undergo component
exchange processes in aqueous solution (Fig. 1(b)).[8] The
dynamic nature of the acylhydrazone linkage endows SCNPs with
the capacity for structural reconfiguration, facilitating intra- to
intermolecular crosslinking of polymer chains. In dilute solution
SCNPs possessing dynamic covalent crosslinks have been
shown[9] to display good kinetic stability, but when the SCNPs are
concentrated their dynamic crosslinks undergo intra- to interchain
cross-linking.[9b] We anticipated that dynamic covalent SCNPs
Abstract: We describe single-chain polymer nanoparticles
(SCNPs) possessing intramolecular dynamic covalent crosslinks
that can transform into polymer films through a molecular
recognition-mediated crosslinking process. The SCNPs utilise
molecular recognition with surface-immobilised proteins to
concentrate upon a substrate, bringing the SCNPs into close
spatial proximity with one another and allowing their dynamic
covalent crosslinkers to undergo intra-to interpolymer chain
crosslinking leading to the formation of polymeric film. SCNPs
must possess both the capacity for specific molecular recognition
and a dynamic nature to their intramolecular crosslinkers to form
polymer films, and an investigation of the initial phase of film
formation indicates it proceeds from features which form upon the
surface then grow predominantly in the xy directions. This
approach to polymer film formation presents a potential method
to ‘wrap’ surfaces displaying molecular recognition motifs—which
could potentially include viral, cellular and bacterial surfaces or
artificial surfaces displaying multivalent recognition motifs—within
a layer of polymer film.
Polymer films are ubiquitous in the modern world, acting as
barriers to protect objects from their environments or improve
performance.[1] A plethora of methods exist to prepare polymer
films upon surfaces such as solvent casting,[2] thermal spraying[3]
or by vapour deposition techniques[4] and self-assembly methods
such as Langmuir-Blodgett[5] or Layer-by-layer[6] approaches. A
limitation of these methods is that deposition of polymers upon
the surfaces is driven by relatively unselective interactions and
additional chemical processes may have to be performed if a
could be concentrated upon
a surface, encouraging their
crosslinking to form polymer films. Consequently, our SCNPs are
decorated with carbohydrate residues which bind (Fig. 1(c))
through specific molecular recognition to complementary surface-
immobilised carbohydrate-binding proteins (lectins). This process
concentrates the SCNPs upon the surface where their increased
spatial proximity with one another allows intra- to inter-polymer
chain reorganization of their dynamic cross-linkers, leading to
formation of polymer film. This topological transformation may be
considered as a macromolecular “metamorphosis”.[10] Galactose
and mannose were chosen on account of their specific molecular
recognition capabilities with complementary lectins E. coli heat
labile toxin (LTB) and Concanavalin A (Con A) (Fig. 1),
respectively. LTB[11] belongs to the AB5 family of toxins[12] and
exhibits recognition behaviour identical to that of cholera toxin,
binding to galactose-terminated gangliosides on cellular surfaces
to facilitate entry, with the naturally-occurring toxin proceeding to
disrupt cellular biochemistry and cause disease. A non-toxic B5
variant of the toxin displaying five circularly arranged galactose
binding sites approximately 30 Å apart has been used for this
study. Con A[13] is isolated from Canavalia ensiformis (Jack
bean), and exists under the conditions of our experiment as a
dimer of two 26 kDa subunits which recognises mannose at two
binding sites.
[a]
Dr Clare S. Mahon, Dr Christopher J. McGurk, Dr Scott M. D.
Watson, Dr David A. Fulton
Chemical Nanoscience Laboratory, School of Chemistry
Newcastle University
Newcastle-upon-Tyne, NE1 7RU, UK
E-mail: david.fulton@ncl.ac.uk
Dr Clare S. Mahon, Chadamas Sakonsinsiri, Prof Dr W. Bruce
Turnbull
[b]
School of Chemistry and Astbury Centre for Structural Molecular
Biology
University of Leeds
Leeds, LS2 9JT, UK
E-mail: w.b.turnbull@ncl.ac.uk
Dr Clare S. Mahon, Dr Martin A. Fascione
Department of Chemistry
University of York,
Heslington, York, YO10 5DD, UK
Dr Chadamas Sakonsinsiri
[c]
[d]
SCNPs were prepared from linear polymer scaffold P1[14]
(Fig. 1(a)) containing pendant aldehyde functionalities allowing
for the conjugation of carbohydrate units[14b] GAL and MAN
through acylhydrazone linkages, yielding glycopolymers P1-GAL
and P1-MAN. Treatment of P1-GAL and P1-MAN with succinic
Department of Biochemistry,
Faculty of Medicine
Khon Kean University,
Muang District,
dihydrazide induces component exchange through
a
Khon Kaen 40002 Thailand
transimination-type process,[15] resulting in intra-polymer chain
Supporting information for this article is given via a link at the end of
the document.
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Fig. 1 (a) Construction of single-chain polymer nanoparticles (SCNPs): MAN and GAL, acylhydrazide derivatives of mannose and galactose, were appended onto
an aldehyde functionalised polymer scaffold P1, producing linear glycopolymers P1-MAN and P1-GAL. Addition of succinic dihydrazide induces intra-chain
crosslinking to yield SCNP1-MAN and SCNP1-GAL. LTB is shown with five associated galactose residues (blue) and Con A shown in its tetrameric form with four
associated mannose residues (red). (b) Component exchange of dynamic covalent acylhydrazone bonds to form new bonds. (c) A combination of specific molecular
recognition and rearrangement of dynamic covalent bonds allows SCNPs to cross-link into polymeric films. Binding to a 'Velcro'-like layer of complementary lectins
through specific molecular recognition leads to their concentration upon the surface. The surface-bound SCNPs are now spatially close, and their intra-molecular
dynamic covalent linkages undergo component exchange to form inter-chain crosslinks, resulting in formation of polymer film.
crosslinking to yield the glycosylated SCNPs SCNP1-MAN and
SCNP1-GAL. The crosslinking process was monitored by gel
permeation chromatography (GPC) which revealed increases in
retention time compared to P1-GAL and P1-MAN (Fig. S4), an
observation which indicates collapse of polymer chains to form
species of decreased volume and is consistent with successful
SCNP formation.[7b, 9a, 16]
linkages (ESI). Film formation was performed by immersing the
surfaces in solutions (9 mg/mL) of their complementary SCNP
(SCNP1-GAL in the case of LTB, and SCNP1-MAN in the case
of Con A) for 18 h at 5 °C. Visual inspection suggested the
formation of a very thin layer of polymer film which demonstrated
no solubility in H2O, DMF or DMSO, in contrast to SCNP1-MAN
and SCNP1-GAL which possess good solubility in these solvents,
The kinetic stability of SCNP1-MAN and SCNP1-GAL
observations suggesting the polymer films possessed a
in solution (9 mg/mL) was monitored by GPC over a 24 h period
(Fig. S3), during which time no aggregation was observed,
indicating SCNPs in solution possess good kinetic stability.
Surfaces displaying complementary carbohydrate recognition
motifs were prepared by immobilising LTB or Con A onto
streptavidin-coated polystyrene by means of biotin-streptavidin
crosslinked nature. The polymer films were imaged by AFM (Fig.
2). Analysis of the surface treated with SCNP1-MAN (Fig. 2c)
revealed feature heights of up to ~650 nm and and significant
differences in appearance to the ConA-functionalised substrate
(Fig. 2b) and also the underlying streptavidin-functionalised
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polystyrene (Fig. 2a), observations consistent with the formation
of polymer film.
Likewise, analysis of the LTB-functionalised polystyrene
after treatment with a solution of SCNP1-GAL (Fig. 2f) indicated
the formation of film displaying feature heights up to ~500 nm and
differences in appearance to the underlying LTB-functionalised
(Fig. 2e) and streptavidin-functionalised polystyrene (Fig. 2d).
Control experiments were performed to gain further insights as to
the nature of these polymer films. No significant changes in the
nature of streptavidin-functionalised polystyrene surfaces
incubated in solutions of SCNP1-MAN and SCNP1-GAL were
observed by AFM (Fig. S4a,b). Likewise, no film formation was
observed when each lectin-functionalised polystyrene sample
was immersed in a solution of the non-complementary SCNP, i.e.
Con A-functionalised polystyrene with SCNP1-GAL, or LTB-
functionalised polystyrene with SCNP1-MAN (Fig. S4c,d). These
observations demonstrate that films are only formed when the
SCNP displays complementary carbohydrates for the immobilised
lectin and that in the absence of specific molecular recognition
films do not form. Samples of SCNP1-MAN and SCNP1-GAL
were then treated with NaCNBH3 to reduce their acylhydrazone
bonds thus rendering them unable to undergo intra- to
interpolymer reconfiguration. Exposure of these ‘static’ SCNPs to
complementary lectin-functionalised polystyrene did not lead to
notable changes in appearance of surfaces as determined by
AFM (Fig. S4e,f), demonstrating that dynamic covalent exchange
processes are required for film formation. These observations
also indicate that the films are not simply a collection of
intramolecularly cross-linked SCNPs deposited upon a surface,
and that reorganization has indeed occurred to afford
intermolecularly cross-linked polymers. Taken together, these
control experiments demonstrate that both molecular recognition
and dynamic covalent crosslinking are required to drive the
transformation of SCNPs into cross-linked films, and that in the
absence of either feature film formation does not occur.
Fig. 2. AFM images of a 15.0 x 15.0 µm region of streptavidin-coated
polystyrene surfaces (a),(d) prior to any modification; (b) after functionalisation
with Con A; (c) after functionalisation with Con A and incubation in a solution of
SCNP1-MAN for 18 h at 5 °C; (e) after functionalisation with LTB via biotin-
streptavidin linkage; (f) after functionalisation with LTB and incubation in a
solution of SCNP1-GAL for 18 h at 5 °C.
To further support this hypothesis, we exposed pre-formed
polymer films to conditions that would remove the molecular
recognition and/or crosslinks. Films of SCNP1-MAN on Con A-
functionalised polystyrene (Fig. 3a,c) were incubated in a solution
of hydroxylamine to exchange acylhydrazone bonds into more
stable oxime bonds[17] thus releasing the succinic dihydrazide
crosslinker along with MAN. After 18 h at 5 °C optical microscopy
(Fig. S5) revealed surfaces free from film. AFM imaging (Fig. 3b)
revealed surfaces identical to those observed prior to film
formation, suggesting the removal of the cross-links has led to the
disassembly of the polymeric film. This finding demonstrates that
acylhydrazone linkages are essential to maintain the structure of
films, and that films maintain the dynamic character of their
crosslinks.
A control experiment was also performed to
investigate the importance of the carbohydrate-protein
interactions in adhering films to the surfaces. Thus, polymer films
prepared from SCNP1-MAN on Con A functionalised polystyrene
were incubated at 5 °C for a total of 3d in a buffered saturated
methyl α-mannoside (a ligand for Con A) solution at pH 4.5. After
incubation, microscopy revealed the absence of film, with AFM
again showing a surface (Fig. 3d) similar in appearance to that
observed prior to film formation. These results demonstrate that
undermining molecular recognition processes triggers release of
films from surfaces. We hypothesise that the longer timescale
required for the removal of films following exposure to methyl α-
mannoside arises because of difficulties in the diffusion of the
sugar through the film to reach the recognition sites of Con A units
upon the surface. A pre-formed polymer film was also subjected
to mechanical damage (ESI) by using an AFM tip to scratch the
surface. After incubation in 100 mM NH4OAc (pH 4.5) for 24 h,
AFM imaging showed repair of the damaged area, again
highlighting the dynamic nature of the material.
Fig. 3 AFM imaging of 15.0 x 15.0 µm regions of surfaces displaying: (a)
polymer film produced by exposure of SCNP1-MAN to a Con A functionalised
surface; (b) the same surface after exposure to hydroxylamine; (c) polymer film
produced by exposure of SCNP1-MAN to a Con A functionalised surface; (d)
the same surface after exposure to methyl α-mannoside.
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Fig. 5. AFM images of (a) ConA-functionalised Si; (b) polymer film obtained
upon ConA-functionalised Si at 5 min; (c) polymer film obtained upon ConA-
functionalised Si at 60 min; (d) polymer film obtained upon ConA-functionalised
Si at 360 min.
-
Fig. 4. AFM images of (a) ConA-functionalised Si; (b) polymer film obtained
upon ConA-functionalised Si; (c) the ‘mask-etched’ polymer film. (d) A height
profile of the etched polymer film.
speculate these features occur when two (or more) of the smaller
features are sufficiently close together that they merge, or are
smaller features that have grown by sequestering and
incorporating SCNPs from solution. Analysis of the image
obtained at 60 min (Fig. 5c) reveals a greater number of the larger
irregular features and that these features have increased their
average areas, with fewer of the smaller features. At 360 min (Fig.
5d) the surface was dominated by larger irregular features and
even fewer of the smaller features were present. Taken together,
these observations indicate that film formation does not occur
through a layer-by-layer approach where a continuous thin layer
is formed which then grows in thickness. Instead, the film is
formed in a process where SCNPs concentrate and crosslink at
‘hotspots’ on the surface to form features which then grow
predominately in the xy plane in an irregular fashion to form larger
features. We suggest that feature growth occurs when a SCNP
binds to the surface adjacent to a feature and then becomes
covalently ‘trapped’ within the feature. Feature growth continues,
and in the latter phase of film formation we presume the features
merge into a continuous film. A full understanding of the
mechanism by which the SCNPs form films is beyond the scope
of this work and will be the subject of future experiments.
The mechanical properties of the films were investigated by AFM
nanoindentation analysis. The Young’s moduli for polymer
surfaces (Table 1) were similar in magnitude to those obtained for
plastics such as LDPE or poly(vinyl alcohol),[19] demonstrating
that rearrangement of SCNPs forms a ‘plastic-like’ coating. Films
generated on lectin-functionalised silicon wafer displayed greater
Young’s moduli than those corresponding films generated on
polystyrene, an observation we attribute to the more uniform lectin
coverage expected upon silicon leading to the formation of more
homogenous films. Films generated using Con A-functionalised
surfaces and SCNP1-MAN displayed higher Young’s moduli than
those generated using LTB and SCNP1-GAL, a factor which may
complement our visual observation that more extensive film
formation was noted on Con A-functionalised surfaces than on
LTB-functionalised surfaces. We believe that these observations
can be accounted for by considering differences in the
orientations of binding sites in each lectin (Fig. 1). The binding
sites of LTB are circularly arranged on one face of the pentamer,
whilst the binding sites of Con A point in opposing directions. We
propose that the remote geometry of recognition sites in Con A
We then investigated film formation upon lectin-
functionalised silicon wafer, through the formation of a self
assembled monolayer (SAM) on the Si surface to which lectins
are covalently attached (ESI). This substrate is considerably
flatter and smoother than polystyrene, and a surface-masked
plasma etching process (see ESI) can be performed for the
removal of organic material from areas of the substrate, allowing
film thickness to be determined by AFM. The polymer film
obtained from treatment of Con A-functionalised silicon with
SCNP1-MAN for 18 h displays (Fig. 4b) a surface topology which
is only subtly different from the underlying ConA-functionalised
silicon (Fig. 4a). The ‘mask-etch’ procedure was performed and
AFM (Fig. 4c) revealed an even film thickness of mean height 17
nm ( 7 nm) (Fig. 4d). The immobilisation of Con A onto the
surface through the formation of a SAM and subsequent
modification with the lectin is expected to account for ~5 nm of
organic matter upon the surface,[18] suggesting a polymer film
thickness of ~10 nm. This observation contrasts polymer films
obtained upon polystyrene whose feature heights suggest films
significantly thicker than those obtained upon ConA-
functionalised silicon. The reasons for this difference are
currently unclear; we consider it likely that lectin attachment via
organic films onto silicon wafer leads to a more uniform display of
protein, providing the foundation for more uniform and thin film
formation.
Commercially-sourced streptavidin-functionalised
polystyrene substrates, on the other hand, may display
inhomogeneous lectin coverage which leads to less uniform and
and thicker films.
To gain insights to the growth of films, multiple samples of
ConA-functionalised silicon wafer were treated in solutions of
SCNP1-MAN and wafers removed at time points, rinsed and
analysed by AFM. Comparison of the sample at 5 min (Fig. 5b)
with the untreated ConA-functionalised substrate (Fig. 5a) reveals
a relatively flat surface upon which has formed a population of
features that are ~5-10 nm in height and ~200-400 nm in diameter
(circled in purple). We postulate that these features have formed
when multiple SCNPs bind upon areas of the surface where there
is an ‘optimal’ display in terms of densities, spacings and
orientations of carbohydrate binding sites that promote SCNP
concentration and subsequent cross-linking. There is also a
smaller population of larger irregular features (circled in green) of
heights ~15-30 nm and ~0.4-1.0 µm in diameter, and we
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Table 1. Mechanical properties of polymer films, as determined by
nanoindentation analysis. In each case a minimum of 200 measurements
were made, with standard deviations quoted in parentheses.
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Substrate
SCNP
Young’s modulus of film /
GPa
[10]
[11]
Si-Con A
SCNP1-MAN
SCNP1-GAL
SCNP1-MAN
SCNP1-GAL
1.34 (0.521)
0.458 (0.091)
0.847 (0.309)
0.131 (0.041)
Si-LTB
[12]
[13]
[14]
Polystyrene-Con A
Polystyrene-LTB
[15]
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may be better suited to facilitate the formation of more extensive
films, and that the resultant films may display improved
homogeneity in crosslinking, leading to stiffer materials.
In conclusion, we have demonstrated how a combination of
molecular recognition and dynamic covalent chemistry can be
used to drive the transformation of SCNPs into cross-linked
polymeric films. In this work we have utilised recognition between
carbohydrate residues and lectins, however, in principle a variety
of well-understood and highly selective molecular recognition
motifs could be applied, increasing substantially the scope of the
concept. We also propose that the concept could be extended to
form films around 3-dimensional objects displaying high densities
of receptors, such as bacteria or viral capsids, thus allowing the
application of a ‘wrapping’ of polymer coating which may help to
sequester pathogens or possibly even protect and stabilise
biological objects. To explore this idea we are investigating the
‘shrink-wrapping’ of virus-like particles.
[17]
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[19]
Experimental Section
Experimental Details may be found in the Electronic Supporting
Information file.
Acknowledgements
This work was supported by EPSRC (EP/G066507/1 and
EP/G043302/1) and BBSRC (BB/M005666/1). CSM wishes to
thank EPSRC and the University of Leeds for the award of a
Doctoral Prize Fellowship which enabled this work. The authors
wish to thank Dr Peng Bao, University of Leeds, for experimental
advice.
Keywords • adaptive materials • carbohydrates • dynamic
covalent chemistry • polymer films • polymer nanoparticles
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Entry for the Table of Contents
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C. S. Mahon, C. J. McGurk, S. M. D.
Watson, M. A. Fascione, C.
Sakonsinsiri, W. B. Turnbull* and D. A.
Fulton*
Page No. – Page No.
Molecular-recognition mediated
transformation of single-chain
polymer nanoparticles into
crosslinked polymer films
Single-chain polymer nanoparticles possessing intramolecular dynamic covalent
crosslinks can transform into polymer films through a molecular-recognition-
mediated crosslinking process.
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