Selective sensing of sulfate anions in water with cyclopeptide-decorated gold nanoparticles

Article abstract of DOI:10.1039/d0cc04796a

The interaction of cyclopeptides bound to the surface of mixed monolayer-protected gold nanoparticles with sulfate anions causes the crosslinking and concomitant precipitation of the nanoparticles from aqueous solutions even in presence of an excess of competing anions, thus allowing the naked eye detection of sulfate in water.

Full text of DOI:10.1039/d0cc04796a

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DOI: 10.1039/D0CC04796A
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Selective sensing of sulfate anions in water with cyclopeptide-
decorated gold nanoparticles
a
a
b
,a
Julia Bartl, Lena Reinke, Marcus Koch and Stefan Kubik*
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
6
The interaction of cyclopeptides bound to the surface of mixed sensing can rely on their intensive colour. Analytes inducing
monolayer-protected gold nanoparticles with sulfate anions causes AuNP crosslinking, for example, either cause the
the crosslinking and concomitant precipitation of the nanoparticles decolourisation of the solution due to nanoparticle
from aqueous solutions even in presence of an excess of competing precipitation, or the shift of the characteristic surface plasmon
anions, thus allowing the naked eye detection of sulfate in water.
resonance (SPR) band in the UV-vis spectrum. This concept,
7
a
illustrated in Fig. 1a, has been used to detect metal ions,
Optical probes are useful tools to assess the quality of water.
Acid-base indicators allow the rapid determination of the pH,
for instance, while probes relying on supramolecular principles
can be used to detect organic compounds, or inorganic cations
7b
7c-e
7e,f
7g,h
carboxylic acids, amino acids, peptides, proteins, and
7i,j
nucleic acids but not often to sense inorganic anions.
(a)
(b)
1
or anions. Especially when it comes to anions there are a
2
number of relevant analytes. Examples are phosphate and
analyte
nitrate, which are responsible for the eutrophication of rivers
and lakes, toxic anions such as cyanide, chromate, or arsenate,
radioactive pertechnetate anions, and also perchlorate, sulfate
3
and others. Probes for these anions can be based on receptors
whose binding to the substrate triggers a change in the optical
Fig. 1 Illustration of the analyte-induced crosslinking of gold nanoparticles with
properties of an attached chromophore (direct sensing) or a surface-bound receptors of which two units are required for analyte recognition
a). To illustrate the binding mode of the receptor used in this work, the structure
(
1
d
non-covalently bound dye (indirect sensing). A challenge of the 2:1 cyclopeptide/sulfate complex is depicted in (b), which was calculated
1
4c
on the basis of the crystal structure of the respective iodide complex. Protons
when designing such probes is that they have to overcome the except those on nitrogen atoms are omitted for reasons of clarity.
intrinsic difficulties associated with the recognition of inorganic
4
anions in water, but existing optical probes demonstrate that Examples are AuNPs with surface-bound amide groups that
2
c
anion sensing in water is possible.
aggregated in dichloromethane in the presence of various
–
8
Optical probes can also be based on polymeric materials or oxoanions, especially H
nanoparticles.5 These systems potentially benefit from the fact groups that responded to the presence of PF
2
PO
4
,
or those with imidazolium
,6
–
9
6
anions. Kim et
that binding takes place not in water but in an environment al. found that the cyanide-induced dissociation of the
characterised also by the polymeric matrix or the nanoparticle copper(II)-phenanthroline complex induced the aggregation of
1
0
ligands. Other advantages are the modular synthesis that an ATP-stabilised AuNP, and the Mirkin group showed that
facilitates structural variations and the relatively easy nitrite anions mediated the covalent crosslinking of
integration into devices. Gold nanoparticles (AuNPs) are a appropriately functionalised AuNPs.11
A
calix[4]pyrrole-
particularly attractive basis for such probes because they can be decorated AuNP was furthermore shown by the Sessler group
decorated with a wide variety of recognition units and because to aggregate in dichloromethane in the presence of a
bis(imidazolium) ion and halides, especially chloride and
1
2
a. Technische Universität Kaiserslautern, Fachbereich Chemie - Organische Chemie,
fluoride.
Erwin-Schrödinger-Straße, 67663 Kaiserslautern, Germany. E-mail:
kubik@chemie.uni-kl.de.
INM – Leibniz Institute for New Materials, Campus D2 2, 66123 Saarbrücken,
Note that other strategies to detect anions by surface-modified
AuNPs exist. Anion binding can alternatively be sensed
electrochemically, by the effects of anion binding on the
b.
1
3a
Germany.
Electronic Supplementary Information (ESI) available: synthetic details, NMR, and
mass spectra of compounds 1-5, nanoparticle synthesis, characterisation, and
results of the binding studies. See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
Chem. Commun., 2020, 00, 1-3 | 1
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Journal Name
1
3b
optical properties of a surface-bound chromophore,
indirectly by the release of a nanoparticle-bound dye.
or (R)-lipoic acid via a C
6
spacer unit to ensure a sufficient distance
View Article Online
DOI: 10.1039/D0CC04796A
1
3c,d
of the receptor from the AuNP surface and to thus allow two
We expected the anion-binding cyclopeptide developed some cyclopeptides on different particles to simultaneously interact
time ago in our group to also represent a useful building block with an anion. An excess of 1 was used to reduce the probability
for AuNP-based optical probes because its propensity to form of the formation of AuNPs in which receptors residing on the
sandwich complexes in aqueous media, with the anion bound same nanoparticle engage in analyte binding. The number of
between two cyclopeptide rings, should allow it to induce AuNP cyclopeptide residues should still be high enough to ensure that
crosslinking (Fig. 1b).1 Complex formation moreover proceeds AuNP crosslinking benefits from multivalent interactions. The
cooperatively (the formation of the 2:1 complex from the 1:1 NMR spectroscopic characterisation of the obtained AuNPs
4
complex has a significantly larger K
a
than the formation of the unfortunately showed that they contained no cyclopeptide or
1
:1 complex) so that 2:1 complexes dominate even if the anion only a small amount. One reason for the lack of reaction of 2
is present in excess. Here we shown that immobilising the with the AuNP could have been the low solubility of the
cyclopeptide onto AuNPs together with solubilising triethylene cyclopeptide-containing ligand in the aqueous medium in which
glycol units indeed affords mixed monolayer-protected AuNPs the exchange reaction was performed, but the presence of co-
that precipitate from water upon the addition of a sulfate salt, solvents such as methanol or DMF did not improve the
thus allowing the detection of this strongly hydrated and outcome. We therefore chose another strategy to access the
1
5
therefore difficult to bind anion with the naked eye.
mixed monolayer-protected nanoparticle.
COOH
The synthesis was based on citrate-protected AuNPs prepared In this approach, a mixed monolayer-protected AuNP NP
by a modified Turkevich method that involved rapidly adding a containing a mixture of ligands 1 and the carboxylic acid 3 was
COOH
hot aqueous solution of tetrachloroauric(III) acid to aqueous initially prepared. NP
was then treated as described
1
6
19
sodium citrate at 100 °C. The resulting AuNPs were initially previously for the synthesis of other systems with an amine
treated with ligand 1, containing a triethylene glycol unit linked and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) as
to (R)-lipoic acid via an amide group, which was prepared in a the coupling reagent to obtain the corresponding functionalised
COOH
four-step synthesis (Fig. 2). We chose lipoic acid as the anchor AuNP. To test the feasibility of this approach, NP
was first
group because of the simpler synthesis (no deprotection is reacted with the benzylamine derivative 4 (Fig. 2). Signals in the
1
required prior to immobilisation as in the case of thiols), the aromatic region of the H NMR spectrum of the purified product
Bn
small tendency of lipoic acid-derived ligands to migrate on the NP demonstrated that the coupling reaction indeed yielded
AuNP surface, and the higher stability of the corresponding the desired mixed product. Relating the integrals of the signals
1
7
AuNPs with respect to thiol-containing ones. The resulting to those of ligand 1 furthermore showed that the ratio of 1 and
TEG
AuNPs NP
did not contain citrate after purification and the functionalised ligand amounted to ca. 2:1 (Fig. S2a).
dispersed freely in water. They had an average diameter of 10.2 Considering that a 9:1 ratio of 1 and 3 was used in the synthesis
COOH
Bn
±
1.8 nm according to transmission electron microscopy (TEM) of NP
, the degree of functionalisation of NP was higher
(Fig. 3a), consistent with the maximum of the SPR band in the than expected, suggesting that 3 had a larger tendency to react
UV-vis spectrum at 523 nm (Fig. S1).
with the citrate-protected AuNP than 1. No further variation of
the reaction conditions was nevertheless performed but we
instead tested whether the cyclopeptide-derived amine 5 could
O
O
O
1
N
H
O
O
COOH
also be coupled with NP
NP
. Gratifyingly, the treatment of
S
S
S
S
O
O
O
HN
N
COOH
with an excess of 5 in the presence of EDC afforded the
AuNP NPCP with surface-bound TEG and cyclopeptide residues
H
N
N
N
H
N
O
in the expected 2:1 ratio as a water-soluble and stable product.
O
NH
2
Bn
CP
The average diameters of NP and NP were similar to those
N
N
TEG
of NP as were the wavelengths of the absorption maxima of
O
HN
OH
N
the SPR bands (Fig. 3b,c, Fig. S2, Fig. S3).
N
H
O
O
S
S
O
O
3
(a)
(b)
O
HN
O
N
H
N
N
HClH2N
N
O
O
NH
5
H
N
HClH2N
N
N
250 nm
250 nm
O
HN
4
N
(c)
(d)
(e)
O
O
Fig. 2 Molecular structures of ligands 1–3 and amines 4 and 5.
The simultaneous immobilisation of 1 and the cyclopeptide-
containing ligand 2 was attempted in a similar manner. Ligand
250 nm
250 nm
250 nm
1
8
2
contained the known anion-binding cyclopeptide linked to
2
| Chem. Commun., 2017, 00, 1-3
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TEG
Bn
Fig. 3 Transmission electron microscopic images of nanoparticles NP (a), NP
CP
CP
the hallmark of multivalent systems whose final state is
(
b), and NP in the absence of anions (c) and of NP 5 min (d) and 30 min (e) after
View Article Online
the addition of Na SO . Further TEM images are depicted in the ESI.
2
4
stabilized by multiple cooperative interacDtOioI:n1s0..1
20
039/D0CC04796A
No changes in the UV-vis spectrum were observed when the
solution contained 2.5 mM NaI instead of Na SO (Fig. S6). This
With two AuNPs in hand, one containing a receptor known to
interact with anions in water, especially sulfate and iodide, and
one lacking specific receptor units, we evaluated how their
solutions responded to potential analytes. To this end, a series
2
4
lack of response to iodide was unexpected because the
immobilised cyclopeptide normally also possesses affinity for
1
4
this anion in water. Some cyclopeptide derivatives even have
CP
of NP solutions were prepared in water. Increasing amounts
1
4b
a similar affinity for iodide in water as for sulfate. In aqueous
solvent mixtures containing, for example, methanol as the
organic component, sulfate affinity of the cyclopeptides is,
however, always substantially higher than iodide affinity and
–
–
–
2–
2–
of the sodium salts of various anions (Cl , Br , I , SO
4
, CO
3
,
2
–
2–
4–
–
HPO
4 4 2 7 3
, HAsO , P O , NO ) were added, and their effects on
the colour of the solutions inspected. No effects were observed
during the initial additions until a salt concentration of 2.5 mM
was reached, when the solution containing sodium sulfate
became turbid (Fig. 4a). When left standing, the AuNPs in this
solution settled at the bottom of the vial as a black precipitate,
while the supernatant solution remained light purple (Fig. 4b).
No changes were visible at the same salt concentration in the
other solutions, even when they were kept overnight. Under
CP
the high sulfate selectivity of NP could therefore be due to a
reduced permittivity of the environment close to the
nanoparticle surface with respect to that of water.
The Na SO addition mainly affected the intensity of the SPR
2 4
band but not the absorption wavelength, showing that the
anion caused nanoparticle precipitation rather than the
formation of soluble aggregates. TEM images supported this
assumption. In the absence of sulfate anions, individual
Bn
the same conditions, NP reacted to none of the tested anions
(
Fig. 4c), showing that the cyclopeptides immobilised on the
CP
nanoparticles of NP were dispersed in solution (Fig. 3c). The
CP
surface of NP were responsible for the response to an anion
for which the cyclopeptide is known to have a pronounced
affinity.14
addition of sodium sulfate induced aggregation, initially leading
to the formation of smaller aggregates comprising 20–60
nanoparticles (Fig. 3d, Fig. S7a). After 30 min, large globular
aggregates dominated with only a few individual AuNPs left that
did not participate in the interaction (Fig. 3e, Fig. S7b). These
images thus demonstrated that the cyclopeptides indeed
induced the expected nanoparticle crosslinking.
(a)
(b)
(c)
CP
To test whether NP responded to sulfate also in the presence
of an excess of competing anions, a solution of the AuNPs was
prepared in which NaCl and Na HPO were present at
2 4
concentrations of 23 mM each. This solution did not differ in
CP
colour from a solution of NP in water, showing that both salts
did not induce nanoparticle aggregation even at concentrations
substantially higher than in the other binding study. A distinct
Cl–
Br–
I–
SO42–
CO32– HPO42– HAsO42– P2O74– NO3–
blank
Fig. 4 Photographs of the series of experiments used to qualitatively assess the colour change was observed, however, when sodium sulfate
CP
Bn
response of NP and NP to the presence of various anions. The image in (a) was
CP
was additionally present at a concentration of 2.3 mM (Fig. 5). A
ten times higher concentration of chloride and hydrogen
phosphate anions thus did not interfere in the interaction of
taken 5 min after the addition of the anions specified below the vials to NP and
the image in (b) 30 min after the salt addition. The image in (c) shows the response
Bn
of NP to the same anions after 30 min. The amount of AuNP was 0.25 mg/mL
and the salt concentrations were 2.5 mM in each sample. All salts were used as
sodium salts.
CP
NP with sulfate anions.
To determine the minimum sulfate concentration required to
induce a colour change, UV-vis spectra were recorded of a series
CP
of solutions containing NP and varying concentrations of
2 4
Na SO (0–12.5 mM). An AuNP concentration of 0.25 mg/mL
was chosen to ensure that the absorption of the solution
without salt at the wavelength of the SPR band was <1. Spectral contains NP (0.25 mg/mL) the centre vial additionally contains NaCl and
changes were observed in this experiment only when the and Na SO (2.3 mM).
Fig. 5 Photograph of the solutions of the competition experiment. The left vial only
CP
2 4 2 4
Na HPO (23.3 mM each), and the right vial NaCl (23.3 mM), Na HPO (23.3 mM),
2
4
2 4
Na SO concentration was at least 2 mM (Fig. S4a), with higher
sulfate concentrations mainly causing the rate but not the Our investigations thus demonstrated that immobilising
extent of precipitation to increase. The solution with the sulfate receptors on the surface of nanoparticles known to form
concentration that just induced precipitation thus afforded a complexes in which two receptor units have to come together
spectrum after 30 min that was similar to the one obtained after to interact with an anion represents a promising strategy to
5
min at a 5 mM sulfate concentration (Fig. S5b). Accordingly, achieve anion detection in water. The advantage of this
the extent of precipitation did not shift continuously when approach is that the selectivity of anion detection can easily be
increasing the analyte concentration but exhibited a relatively tuned by the nature of the immobilised receptor. While the
CP
sharp transition from the non-associated to the associated state sulfate selectivity of NP can be attributed to the intrinsic
once a certain limiting concentration was surpassed, which is selectivity of the immobilised cyclopeptide, for example, we
already have evidence that nanoparticles containing zinc(II)-
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7
(a) G. Sener, L. Uzun and A. Denizli, ACS Appl. Mater.
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dipicolylamine residues on the surface can sense
pyrophosphate (but not sulfate), consistent with the affinity of
Interfaces, 2014, 6, 18395–18400; (b) S. Sistach, K. Rahme, N.
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Mingotaud, Chem. Mater., 2008, 20, 1221–1223; (c) H. M.
Zakaria, A. Shah, M. Konieczny, J. A. Hoffmann, A. J. Nijdam
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1
such zinc complexes for pyrophosphate anions. Sensing also
benefits from the multiple interactions of the receptor units
immobilised on the nanoparticles, which act cooperatively and
thus cause nanoparticle precipitation to occur at a certain
analyte concentration. The easily discernible change of the
AuNP aggregation state thus not only qualitatively provides
evidence that the analyte is present but also that its
6
87–690; (g) M. Retout, H. Valkenier, E. Triffaux, T. Doneux,
CP
concentration exceeds a certain value. In the case of NP , this
K. Bartik and G. Bruylants, ACS Sens., 2016, 1, 929–933; (h)
M. J. Eibling, C. M. MacDermaid, Z. Qian, C. J. Lanci, S.-J. Park
and J. G. Saven, J. Am. Chem. Soc., 2017, 139, 17811–17823;
concentration amounts to ca. 2 mM (when using 0.25 mg/mL of
CP
NP ), which is close to the threshold concentration at which
(i) R. Elghanian, J. J. Storhoff, R. C. Mucic, R. L. Letsinger and
mineral water is considered to be sulfate-rich and thus slightly
C. A. Mirkin, Science, 1997, 277, 1078–1080; (j) C. S. Thaxton,
D. G. Georganopoulou and C. A. Mirkin, Clin. Chim. Acta,
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2
2
bitter tasting (>200 mg/L or >2.1 mM). In terms of selectivity
CP
and sensitivity, NP is therefore useful for practical applications
8
9
S. Watanabe, M. Sonobe, M. Arai, Y. Tazume, T. Matsuo, T.
Nakamura and K. Yoshida, Chem. Commun., 2002, 2866–
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varying the content or the structure of the cyclopeptide-
containing ligand on the nanoparticle surface or the nature of
the ligand that mediates water solubility.
2
867.
H. Itoh, K. Naka and Y. Chujo, J. Am. Chem. Soc., 2004, 126,
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We thank Dr. Disha Mungalpara and Dr. Fabian Sommer for help 10 M. H. Kim, S. Kim, H. H. Jang, S. Yi, S. H. Seo, M. S. Han,
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in early experiments. This work was funded by the Deutsche
Forschungsgemeinschaft (KU 925/10-1). The generous support
is greatly appreciated.
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DOI: 10.1039/D0CC04796A
Julia Bartl, Lena Reinke, Marcus Koch and Stefan Kubik "Selective sensing of sulfate anions in
water with cyclopeptide-decorated gold nanoparticles"
Gold nanoparticles containing surface-bound cyclopeptides precipitate from an aqueous solution in
the presence of sulfate ions, thus allowing the selective detection of this anion with the naked eye.
Na SO4
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