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Cite this: Nanoscale, 2012, 4, 7727

Interaction of L-cysteine with naked gold nanoparticles

supported on HOPG: a high resolution XPS
investigation
Laura Caprile,a Albano Cossaro,b Ermelinda Falletta,c Cristina Della Pina,c
Ornella Cavalleri,a Ranieri Rolandi,a Silvana Terreni,a Riccardo Ferrando,a
Michele Rossi,c Luca Floreanob and Maurizio Canepa*a
We report the results of a synchrotron-based high-resolution XPS study of the interaction of L-cysteine (Cys)
with well-characterized colloidal gold nanoparticles (NPs, typical size 34 nm), which were pre-deposited
on highly oriented pyrolytic graphite and then brought into contact with the aqueous solution of Cys
by drop-casting. By comparison with data previously obtained for Cys deposition on at Au substrates
(single crystals and high quality lms), we demonstrate the formation of a strong Cys/NP thiolate bond.
The analysis of the line shape and adsorbate-induced Au 4f core level shift, backed by simulations of the

Received 31st May 2012

Accepted 9th October 2012

NP structure, reveals the interaction of Cys with low-coordinated Au atoms belonging to the NP edge
and corners. The analysis of the N 1s core-level indicates that neutral molecules are the most abundant
species. The small facet size limits the formation of extended networks of zwitterionic molecules, typical

DOI: 10.1039/c2nr32741d
www.rsc.org/nanoscale

of single crystal surfaces. This study provides a spectroscopic insight into the intense poisoning eect
caused by a limited amount of Cys on Au catalysts described in previous reports.

Introduction

Cysteine [Cys, HSCH2CH(NH2)COOH] is a fundamental amino

acid where the thiol side-chain is capable of forming covalent
bonds with metal surfaces.13 For this property Cys residues play
an important role in biomolecules anchoring to surfaces46 and
Cys is oen used to modify electrodes for bio-sensing.7,8
Seminal studies of the CysAu interaction date back to the
early 90s9 and since then this system has attracted a continuous
ow of interest. Experiments regarding single crystals and at
lms evidenced a variety of Cys self-assembled monolayers
(SAMs), whose formation and order properties are inuenced by
the lattice symmetry, the surface morphology and by the interplay between molecule and Au adatoms mobility. Molecular
beam deposition under ultra high vacuum (UHV) was exploited
to study enantioselectivity processes on well-dened
surfaces;1015 the popular CysAu(111) system has been also
proposed as a case study to investigate hydrogen bonds in 2D
networks16 and the molecular diusion processes leading to the
formation of 2D assemblies.17,18 When deposited from the
a

CNISM and Dipartimento di Fisica, Universit

a di Genova, via Dodecaneso 33, Genova,
Italy. E-mail: canepa@sica.unige.it; Tel: +39 010 3536242

b
c

CNR-IOM, Trieste, Italy

Dipartimento di Chimica, Universit

a di Milano, Milano, Italy

Electronic supplementary information (ESI) available: NP size distribution

statistics obtained by AFM measurements. Comparison with measurements on
a bulk Au(111) sample. See DOI: 10.1039/c2nr32741d

This journal is The Royal Society of Chemistry 2012

liquid phase, the networking properties of Cys SAMs may be

tuned by varying the electrochemical conditions.1922
Regarding, more specically, nano-chemistry applications, the
CysAu interaction plays an important role in many contexts. Gold
nanoparticles and nanorods are employed for selective detection
of Cys in colloidal solutions by measuring the shi of the plasmonic spectral features (sometimes called colorimetric analysis).23 Cys has been used in the formation of gold NPs, as a watersoluble capping/cross-linking agent24,25 able to tailor the size,
aspect ratio and optical properties of NPs24,26,27 and to mediate NP
assembly through interaction of Cys zwitterions.28 Cys was also
proposed as a linker between an oxidic support and gold clusters
as well as a factor of size control of gold clusters deposited under
UHV conditions on the TiO2 surface.29 The interaction of Cys with
gold NPs has been exploited to link and spatially orient biomolecules on surfaces.3032 Finally, the interaction of Cys with supported gold colloids has been exploited in catalytic studies33 and,
particularly, in selective oxidation processes concerning the
synthesis of organic compounds.34,35
In this eld, a recent study outlined the selective deactivation of NP gold nano-catalysts (typical size 34 nm) caused by
Cys (and other molecules containing sulfur) during the aerobic
oxidation of glucose.36 The observed strong poisoning eect was
assigned to the perturbation of the electronic properties of the
NP through a long range eect which overlaps the expected
subtraction of active sites. In this paper we report on the
synchrotron-based XPS investigation on the interaction of Cys

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with the same colloidal Au nanoparticles used in ref. 36. For this
purpose the NPs have been pre-deposited on the basal plane of
Highly Oriented Pyrolytic Graphite (HOPG). High-resolution
HR-XPS measurements, complemented with TEM measurements and molecular dynamics simulations of the NP structure,
were aimed to get information on the nature of the CysNP
bond, possibly deriving clues also on the CysCys assembly
properties on the small facets of NPs. By comparing data
regarding the CysNP interaction with those obtained, under
similar XPS experimental conditions, for deposition on at Au
surfaces (single crystals, high quality lms),37,38 this work is
intended to provide experimental spectroscopic support to
kinetic models of catalyst deactivation, investigating the role of
low-coordinated Au atoms belonging to NP edges and corners.39

Materials and methods

2.1

Nanoparticle preparation

The NP preparation followed well-known procedures.36 We

report here only a few notes. In a 150 ml ask, D-glucose monohydrate (2.4 g, 99% purity, Fluka) and 0.3 g of aqueous HAuCl4
(1% Au; 3 mg Au) were dissolved in 120 ml of MilliQ water
(Academic A-10 Millipore) and treated with 0.8 ml of 0.1 M
NaBH4 (96% purity Fluka) under vigorous stirring at room
temperature and under N2 atmosphere, obtaining a tea-coloured colloidal dispersion. HAuCl4 was prepared by dissolving
the metal (99.999% purity in sponge, Fluka) in aqua regia; aer
thermal evaporation of the liquid, the solid was puried by
several cycles of dissolution in water followed by evaporation.
Glucose plays the role of a weak stabilizer, scarcely interacting
with NPs.34
The particle size has been checked by UV-VIS transmission
spectroscopy, TEM and, aer deposition on HOPG, by AFM
measurements. Optical transmission spectra, recorded with a
Woollam M-2000 ellipsometer, are shown in Fig. 1a. The data
presented the typical prole consisting of a well-dened surface
plasmon resonance superimposed to a monotonically decaying
absorption from UV towards the visible region. The resonance,
with a maximum at z510 nm, is in the range expected for
clusters of 25 nm size.40 TEM characterizations were performed with a LEO 912AB microscope. Measurements were
done by depositing a drop of the solid ultrasonically dispersed
in water onto a carbon coated copper grid (FCF 200 mesh) and
allowing it to dry at 60
C for 2 h. Measurements showed a
narrow statistic size distribution (ESI), comprised between 2
and 5 nm, with an average diameter of 3.6 nm.34 TEM
measurements provided also useful clues on the NP shape.
Fig. 1b shows a single NP (size z 3.5 nm) of evident quasispherical polyhedral shape. In order to get more insight on the
NPs shape, simulations have been also performed and presented in Section 3.
2.2

Nanoparticles deposition on graphite

HOPG, a convenient substrate for UHV electron spectroscopy

studies of NPs,4143 was prepared by scotch-tape exfoliation on
both sides of the sample; this procedure allows the formation of

7728 | Nanoscale, 2012, 4, 77277734

Fig. 1 (a) Optical transmission measurements of Au NPs in liquid. The surface

plasmon resonance is in the wavelength range expected for NPs of 25 nm size.
(b) TEM (magnication 800k) image of a single Au-NP. The image suggests a
polyhedral shape. (c) Typical AFM (tapping mode) height image of a NP/HOPG
sample. A rather uniform coverage was routinely obtained (ESI).

large at domains in the micron scale. The particles have been

deposited on HOPG (ZYB type, 1  1 cm2) by dip-and-dry
methods. A freshly cleaved substrate was usually dipped in the
colloidal suspension for 4560 minutes and dried under N2 ux
aer extraction from the liquid. For brevity, in the remaining
part of the paper we will refer to the NP assembly on HOPG,
before interaction with cysteine, as NP/HOPG. Tapping mode
AFM measurements of the NP/HOPG system were performed
using a Dimension 3100/Nanoscope III system (Digital Instruments-Veeco) and Si cantilevers (OMCL-AC160TS, Olympus).
The deposition procedure provided a rather uniform NP density
(Fig. 1c), generally high enough to perform high-resolution XPS
measurements with a good signal-to-noise ratio. The analysis of
z-proles was consistent with the TEM characterization of the
particle size (ESI).
NP/HOPG substrates were exposed to a 25 ml drop of 0.1 M
aqueous solution of cysteine (>99.5% purity), then dried under
N2 ux. L-Cysteine was used aer re-crystallization in Milli-Q
water.
2.3

Synchrotron measurements

High-resolution XPS measurements were performed at the

beam-line ALOISA of the ELETTRA synchrotron (Trieste, Italy).44
The measurement protocols were similar to those used in
previous experiments on Cys deposition on at gold surfaces37,38
to which we address for additional details. Measurements have
been performed with a linearly polarized X-ray beam at a
grazing incidence angle of 3
in transverse magnetic polarization. This scattering geometry determined a reduced ux
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density of 1 to 2  1012 ph s1 mm2. In order to minimize the
irradiation damage, sequential measurements were taken on
fresh sample areas. The time necessary to get a full set of high
resolution spectra with a reasonably good signal-to-noise ratio
ranged from 3 to 5 min, i.e. about one order of magnitude
smaller than the time scale of a sizeable irradiation damage
(cf. ref. 37, 38 and 46). The high resolution photoemission
spectra have been collected at normal emission by means of a
hemispherical electron analyzer (angular acceptance of 1.5
),
equipped with a 2D multichannel detector. The core level
photoemission spectra shown hereaer have been taken at a
photon energy of 500 eV (for N 1s, C 1s, S 2p, Au 4f) and 200 eV
(for the ne structure of the Au 4f peak) with a corresponding
overall energy resolution of 450 and 120 meV, respectively. The
experimental spectra, normalized to the X-ray beam ux, are
reported in the next section as a function of the binding energy
(BE). The BE scale was calibrated with respect to the maximum
of the C 1s peak at 284.5 eV, according to the NIST reference for
the HOPG surface.45 The spectra are presented aer subtraction
of a Shirley-type background to account for inelastically scattered photoelectrons. The energy position and width of XPS
peaks indicated in the text were derived from a multipeak
analysis fully convoluted to a Gaussian curve in order to take
into account the instrumental broadening. Only the deconvoluted components are shown in the gures. As a matter of fact,
full free tting parameters yielded an overall Gaussian contribution of 160 meV for the Au 4f doublets taken at a photon
energy of 200 eV, i.e. only slightly larger than the nominal
energy resolution. The dierent Au 4f components were constrained to have the same spinorbit splitting, which yielded a
3.69 eV value with a branching ratio of 0.66  0.03, in agreement
with previous reports. The S 2p spectra at hn 500 eV display a
very large and dominating Lorentzian shape. In contrast, the N
1s peaks are only reproduced by purely Gaussian curves. The
multicomponent S 2p doublets were tted to pairs of peaks with
the constraints of having the same full width at half maximum
(fwhm), the standard spinorbit splitting of 1.2 eV, and a
statistical branching ratio of 1/2. The position of the S 2p
doublet will be conveniently identied by the position of the
2p3/2 component.

3 Shape of nanoparticles: numerical

simulation
In view of TEM results and the weak glucosegold interaction34,35 the simulations were performed for bare NPs with a
typical size of 34 nm. The most favourable structures (icosahedral, decahedral and fcc truncated octahedral, see Fig. 2)
were singled out following the methodology outlined in ref. 47.
The cluster energetics was evaluated by means of atomistic
potentials derived within the second-moment approximation to
the tight-binding model.47 In the diameter range between 3 and
4 nm, the most energetically favourable clusters have either a
decahedral or truncated octahedral shape. However, the presence of icosahedra, possibly formed by kinetic trapping
phenomena,48 should be considered. Most favourable clusters
are therefore compact and quasi-spherical polyhedra, in good

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Nanoscale

Fig. 2 Structure of the most energetically favourable Au cluster in the diameter

range between 3 and 4 nm. Clusters of about 4 nm size are represented. Tables
report the number of atoms (N) and the percentage on the total (%), for each
atomic coordination in the cluster. (A) Decahedral, total of 1228 atoms. (B)
Truncated octahedral, total of 1289 atoms. The icosahedral (923 atoms) (C) is less
favourable. The inset allows comparison of the size of cysteine with the Au(111)
facet size. For details see the text.

agreement with the shapes that are experimentally observed

(see the TEM image in Fig. 1).
In Fig. 2, the tables indicate the number of atoms of a given
coordination and their percentage with respect to the total
number of atoms. The surfaces of the clusters mostly consist of
(111) facets (coordination 9) that are strained in decahedra and
icosahedra. A much smaller proportion of the surface is made of
(100) facets. The lateral size of facets, of the order of 1.5 nm, is
comparable with molecular dimensions (about 0.5 nm, as
shown in the inset). Note that in the case of the most energetically favourable clusters (Fig. 2a and b) the number of atoms
with low-coordination (e.g. 6 and 7) is a sizeable fraction (25
27%) of all surface atoms.

Results and discussion

Fig. 3 shows representative HR-XPS measurements regarding

the spectral region of the S 2p core level, obtained aer interaction of Cys with NP/HOPG samples. Both spectra show a
prominent doublet with evident side shoulders. In the upper
panel the data have been decomposed into a set of three
doublets with the same full width at half maximum (fwhm 
0.85  0.05 eV).
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Fig. 3 Representative HR-XPS measurements of the S 2p core level obtained

after interaction of Cys with the NP-covered HOPG samples. Photon energy
500 eV. (A) Pristine sample. Low level of damage (B) data obtained after prolonged irradiation. The vertical scale is the same for the two panels. For details on
prole decomposition into sub-components see the text.

The main doublet (S1) occurs at 162.25  0.1 eV while two

minor doublets S2 and S3 are located at 163.8  0.15 eV and
161.5  0.15 eV, respectively. Prolonged irradiation (panel B)
induced an enhancement of both peaks S2 and S3. The t was
performed imposing that the fwhm of sub-components was the
same as in panel A. With this constraint, a fourth sub-component (S4) was required, located at 163.2  0.15 eV. Considering
the broad literature on the interaction of Cys (and other thiols)
with at and nanostructured gold surfaces,9,37,38,4952 the S1 state
can be assigned to a thiolate compound formed aer the reaction of the SH molecular termination with the atoms of the
particle. The S1 width appears somewhat larger than the typical
values (0.70.8 eV) found in similar experiments, for Cys
adsorption (and related molecules such as mercapto-propionic
acid (MPA) or cysteamine) on at Au(111) surfaces.37,38,53,54 Such
a broadening may indicate therefore the occurrence of chemisorbed states with slightly dierent bond congurations or
dierent absorption sites. The intensity behaviour in Fig. 3
suggests that the S2, S3 and S4 states are aected by irradiation.
The S3 state in particular could be at least partly due to molecules damaged by low energy photo-electrons (e.g. molecule
cleavage) as oen reported in experiments on thiols.38,53,5557
Regarding S2, we note that in experiments of Cys adsorption on
gold from the vacuum phase (both on single crystal surfaces16,58
and small clusters29) a state at about 164.1 eV was ascribed to
unbound sulfur, where unbound means that the molecule is not
bound to gold through a direct SAu link. Here the dierent BE
energies could be related to the dierent ambient conditions.
Control experiments revealed that adsorption of Cys on bare
HOPG from aqueous solutions is questionable; XPS results

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Fig. 4 Representative HR-XPS measurements, taken under the same experimental conditions, of the Au 4f core level (photon energy 200 eV) obtained (A)
before and (B) after exposure of the NPs to cysteine. In both panels the intensity is
normalized to the peak maximum. The low-BE side peak asymmetry in panel (A) is
related to the contributions of low-coordination Au atoms. In (B) the peak is
symmetric. The peaks are represented only by their Lorentzian component after
deconvolution by a 160 meV Gaussian broadening.

showed very low-intensity and broad S 2p signals which could

only slightly perturb the results of Fig. 3. Regarding the minor
S4 contribution, though a damage-induced state is fully
conceivable,59,60 caution is necessary due to the above
mentioned constraint on peak broadening applied to the t.
The intensity of S4 decreases if S1 and S2 states in Fig. 3B are
allowed to get broader than in panel A. Finally we mention that
we did not observe in these experiments peaks related to oxidised sulphur.52
The formation of strong SAu bonds is conrmed by the
analysis of the Au 4f core level lineshape reported in Fig. 4.
Panel A shows a representative spectrum recorded from the NP/
HOPG system, before interaction with Cys. The peaks present
an evident asymmetry towards the lowest BE side. According to
experiments on single crystal substrates, this shape suggests the
occurrence of sub-components associated with low coordination atoms, like surface and step atoms.6165 Note that, to our
knowledge, these measurements represent the rst determination of the surface core level shi of naked colloidal particles.
The term naked here can be fairly used due to the very weak
interaction with the glucose capping as derived by kinetic
determinations.34 Previous HR-XPS measurements on colloidal
gold NPs, e.g. ref. 61 considered, in fact, as-grown thiolatepassivated NPs.
Given the shape of the core level, we attempted a decomposition with the least number of sub-components, tentatively
representing the bulk and surface contributions. The two
sub-components, reported in the gure, have been found at 84.0
 0.1 eV and 84.3  0.1 eV, respectively. The surface core level
shi (0.30 eV) would be consistent with experimental values

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found for the surface component shi of Au(111) (ESI) and
vicinal single-crystal surfaces, in the 0.3 to 0.4 eV range.6267
Note that the bulk component, measured under conditions
comparable to the present experiment, is located at about
84.0 eV on at Au(111) surfaces64 and it is known to shi to
higher binding energy as nanoparticles of decreasing size are
considered.68
For the sake of discussion, it is worthwhile mentioning a
signicant dierence between NPs and at low-Miller index
surfaces of single crystals. Long range ordered, ideally at
fcc(111) surfaces present essentially two kinds of atoms characterized by a dierent coordination, i.e. bulk (coordination 12)
and surface atoms (coordination 9). As reported in the previous
section, in the case of NPs one may have bulk atoms with the
highest fcc coordination (12), as well as facet atoms (coordination 9 and 8) and a signicant fraction of atoms with lower
coordination (7 and 6), which are expected to show the highest
chemical activity.69,70 XPS emission from under-coordinated Au
atoms has been specically addressed, e.g., in high resolution
studies of the catalytic behaviour of low symmetry surfaces
(Au(310), Au(321)) of single crystals.67 In the case of very small
clusters, their XPS BE is expected to be substantially lower than
the one of facet atoms.71 In detail, calculations of ref. 71 for a
147-atom cluster reported surface core level shis of 0.43, 0.59
and 0.93 eV for facet, edge and corner atoms, respectively; note
however that the same calculations predicted a sizeable
decrease of these shis with increasing cluster size, such as
those of this experiment, and that the calculation procedure did
not include nal state eects.
The surface component of Fig. 4 (fwhm 0.35 eV) turns out
narrower than the bulk component (fwhm 0.46 eV). This
nding would contradict the results established on Au(111)
single crystals, where the surface component turned out
broader than the bulk component (0.48 eV vs. 0.43,63 0.45 vs.
0.40 eV (ref. 64)), the broadening being assigned to crystal eld
splitting and to surface defects (presumably atoms of lower
coordination located at steps and kinks).63,64 A similar trend was
observed for relatively small Au clusters grown on CeO2.65 In
addition, in the present experiment the bulk component
(fwhm 0.46) is broader than the counterpart of the single crystal
Au(111) surface measured under comparable experimental
conditions (0.40 eV (ref. 64)).
The contradiction can be solved assuming that the bulk NP
component is in turn the superposition of unresolved subcomponents. Based on simulated NP structures and calculations on small clusters,71 and relying on HR-XPS results of
vicinal gold surfaces,67 we advance the hypothesis that the
surface component bears information mainly related to
atoms of the lowest coordination, such as edge or corner atoms
(coordination 7 and 6), while the bulk component could
actually derive from the superposition of emission from those
surface atoms sharing the highest coordination (9 and 8) and
highly coordinated inner atoms (coordination 12), thus
producing a relatively broadened feature. In this respect we will
re-denominate the bulk and the surface sub-components as
HC and LC, respectively. The NP size distribution, though
rather narrow, represents a source of XPS line-broadening,

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Nanoscale
limiting the resolution for detecting the HC and LC subcomponents. Our interpretation is however consistent with a
recent XPS experiment dealing with Au NPs (typical size 4.7 nm,
synthesized by the gas phase condensation method) deposited
on HOPG.43 In that work, the authors observed a neat upward
shi of the Au 4f binding energy (about 0.3 eV) when increasing
the incident photon energy from 180 to 1486.6 eV. Considering,
as suggested by the authors, the importance of the coordination
number to local screening conditions, it appears reasonable to
hypothesize that measurements taken at the largest and
smallest photon energies were mostly inuenced by bulk (e.g.
HC) and surface (including LC) atoms respectively.
The adsorption of Cys leads to substantial modication of
the Au 4f line-shape as shown in panel B of Fig. 4, where data
have been measured under strictly comparable experimental
conditions of panel A. The Au 4f feature became narrower and
symmetric thus indicating a denite shi of the LC component
towards the highest BE side, induced by the formation of SAu
bonds. The peak prole was accurately tted by a single, relatively broad component, peaked at 84.3 eV. However, the fwhm
of this single component (0.50 eV) is larger than the HC
component of naked particles, suggesting that also in this case
the prole is the result of unresolved sub-components. The Au
4f data conrm that cysteine strongly interacted with LC atoms
at NP edges and corners. This interpretation is in agreement
with studies on vicinal Au surfaces emphasizing the importance
of low-coordinated atoms for enhanced catalytic activity72 and is
also in agreement with calculations of Cys enantio-specic
adsorption on a chiral 55-atom Au cluster.73
Chemisorption of Cys at NP facets, though plausible, is more
dicult to be assessed. We did not observe those low-intensity
high-BE shoulders found, in UHV deposition experiments, for
high density thiolate phases on Au(111)63,64 and for adsorption
of CO on vicinal surfaces.67 However, the symmetric shape is in
accordance with results for thiol-passivated NPs.61 Note that
formation of a strong SAu bond on the Au(111) surface can be
still considered a partially open problem; the process can be in
fact aected by many factors including, e.g., the deposition
temperature, the deposition ambient (UHV vs. liquid solution),
the molecular density, and the defect density of the actual
surface under consideration. Both STM17 and XPS measurements16,58 for Cys deposition in vacuum on the single crystal
(111) surface have been interpreted in terms of weakly adsorbed
species; also recent STM measurements on the early stage of Cys
adsorption on Au(111) reported on a high surface mobility of
the molecule.18 The thiolate CysAu bond was clearly observed
in UHV for deposition at higher temperatures (330380 K)16,17,58
and for deposition from liquid on ame-annealed Au lms with
a (111) dominant texture. Compared with a single crystal
surface, the latter substrate is rich in defects. In this context, it
could be useful to note that whenever in our experiments on the
CysAu(111) (and Au(110)) system we have observed a main S 2p
component related to a strong SAu bond, we neatly observed
an upward BE shi of the Au 4f surface component (ESI).
These annotations suggest that the chemical activity of
atoms belonging to facets could be signicantly lower than
those endowed with a lower coordination, a fact which has been

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Fig. 5 Representative HR-XPS measurements of the N 1s core level, obtained

after interaction of Cys with the NP covered HOPG samples. Photon energy
500 eV. (A) Pristine sample. Low level of damage (B) data obtained after prolonged irradiation. Data were obtained on the same samples of panels A and B of
Fig. 3. Note the broad feature suggesting the occurrence of several sub-components. The reported t assumed two sub-components. For details on prole
decomposition into sub-components see the text.

already noted in chemisorption studies on Au vicinal surfaces.72

Note nally that in spite of the weak coupling with the NP, the
glucose capping could represent an obstacle along the path to
Cys chemisorption at facets, e.g. contrasting the high molecular
mobility which was observed for early stages of adsorption on
single crystal Au(111) surfaces.18
The analysis of N 1s, C 1s and O 1s core levels may provide
additional information on CysCys interactions and the Cys
substrate bond.37,38,76 In the present experiment the C 1s and the
O 1s signals were strongly aected by contributions from both
the substrate and the glucose protective layer. In particular the
relatively weak and broadened COOH group features were
superimposed on the intense tail of the graphite signal. We
therefore preferred to concentrate the attention on the N 1s
data, presented in Fig. 5. One can observe a broad, asymmetric
feature in the BE range (398403 eV) expected for CysAu
systems.37,38
Both the width and the line shape asymmetry suggest the
occurrence of at least two sub-components. The comparison
between panel A and B indicates that the highest BE side
components are signicantly aected by irradiation time. In the
gure we show the results of the best decomposition into two subcomponents. The two components are peaked at 399.5399.6 eV
(N1) and 401.1401.2 eV (N2) with a fwhm of 1.8  0.1 eV. Both N1
and N2 peaks are substantially broader than the counterparts
found in previous experiments performed under comparable
conditions on at substrates (typically less than 1.5 eV).37,38
The position of N1 is in reasonable agreement with peaks
found at about 399.3399.5 BE in our previous experiments on

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Cys deposition on at Au substrates37,38 and with the value 399.6
found for Cys adsorption on a chiral vicinal surface (Au(17
11 9));14 further, it nicely matches the results of a recent experiment of Cys UHV adsorption on small gold clusters predeposited on TiO2 (ref. 29) where a prominent peak was
observed at 399.65 eV BE. An intense, dominant peak at 399.7 
0.1 eV BE was also observed for monolayer adsorption of a
related molecule (cysteamine) on Au(111).54
The energy position of N2, which is aected by background
subtraction to a greater extent than N1, appears slightly
dierent from previous determinations of Cys adsorption on
at substrates, where a second component was generally well
resolved in the 401.3401.6 eV range.37,38 The N1/N2 intensity
ratio (from 1.5 to 1.9 on pristine and irradiated samples,
respectively) deserves further comments. Our ndings (N1 > N2)
are similar to the data obtained in the mentioned recent
experiments on small clusters29 where N2 was observed, above
401 V BE, as a shoulder of the most intense N1 peak. A similar
N1 to N2 ratio was also observed at early stages of UHV deposition of Cys on Au(110),38 likely aected by surface defects. The
N1 peak was denitely more intense than N2 also for the
mentioned experiment on the Au(17 11 9) surface, rich in kink
sites.14 Instead, data obtained on at Au(111) and Au(110)
surfaces at the monolayer coverage, where extended 2D
molecular networks were formed,16,38 showed a prominent N2
peak, far more intense than N1.
In previous works, N1 was assigned to the amine nitrogen
(NH2), mainly belonging to neutral molecules.14,37,38,54 Intense
N2 peaks were generally assigned to protonated amine nitrogen
(NH3+) of zwitterionic Cys typical of powders74 and 2D
networks.12,18,38 We opt for the same assignments here, though
the width of N 1s sub-components makes the interpretation less
sharp. The broadening of N1 can be explained by the occurrence
of dierent chemical congurations, likely including the direct
interaction of amine groups with gold atoms of dierent coordinations10,75 and, to a limited extent, NH2 interaction with
graphite. The position and broadening of N2 can be ascribed to
several factors. We can mention the formation of zwitterionic
pairs cross-linking NPs as proposed in ref. 28. The perturbing
inuence of the capping glucose layer and/or of the colloidal
solution should be also taken into consideration. In fact, owing
to the acidic nature of the latter, due to residual HCl, the
presence of protonated nitrogen possibly aects the N2 state.
Overall the data indicate that neutral molecules are 50 to
100% more abundant, though they are not conclusive of the
direct interaction of the amino group with Au. The small facet
size probably limits the formation of extended networks
involving zwitterionic molecules, typical of well-dened single
crystal surfaces.12,18 Only small size networks are conceivable,
such as e.g. Cys dimers10 or trimers proposed to rationalise
some high resolution STM structures observed for Cys adsorption on Au(111).18

Concluding remarks

While previous HR-XPS experiments on metal colloidal NPs

regarded particles capped (and passivated) with strongly bound

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molecules, such as thiols, the present research focused on the
interaction with cysteine of weakly protected nanoparticles
assimilable to naked entities. Besides the basic information,
this synchrotron-based study was intended to obtain spectroscopic interpretation of the kinetic deactivation caused on gold
catalysts (34 nm, containing ca. 1000 atoms) by a limited
amount of sulphur-poisoning agents, observed during glucose
oxidation.34,36 The deactivating eect of one molecule of
cysteine on a single NP amounted to 9% when compared to a
very small variation of the molecular surface composition
(0.27%).36 Such a relevant poisoning eect was ascribed to
electron withdrawal from the metal to the sulphur atom via dp
pp orbitals.36
In this investigation we were able to observe the Au 4f corelevel shi related to the NP Au atoms of the lowest coordination
and the line shape changes induced by the formation of a strong
bond with foreign molecules. From a thorough comparison
with the extended database regarding the cysteine interaction
with at Au substrates (several surfaces of single crystals and
well-dened lms, several methods of molecule deposition) and
considering previous works on the catalytic properties of Au
vicinal surfaces, our investigation sheds light on the cysteine
NP interaction, outlining the relevance of the bond between the
Cys sulphur termination and the low-coordination Au atoms
behaving as reactive Lewis acids either in the catalytic cycle or
towards poisoning species. In the light of the present investigation, indicating that cysteine strongly interacts with LC
atoms, and considering that the amount of cysteine molecules
needed for inhibiting the catalytic eect is much smaller than
the total number of surface atoms, we can consider two
dierent deactivation models. According to the electronic
perturbation model,36 a long range perturbation of the entire
particle occurs owing to the electron withdrawing property of
cysteine (so base), which would cause the poisoning eect.
This model was supported by the fact that the poisoning eect
increases with the power of the so basic character, while hard
bases (e.g. OH), having electron donor ability but no electron
withdrawing eect, show no poisoning eects but behave as a
catalytic promoter. In another view, the occupation of a few
highly active sites could lead to a severe poisoning of the nanocatalysts. Irrespective of the model, our data, in line with many
experiments on vicinal surfaces (e.g. (ref. 67)), enlighten the role
of the NP atoms with the lowest coordination, endowed with a
pronounced chemical activity. The analysis of the N 1s core-level
indicates that neutral cysteine molecules are the most abundant
species. The small facet size represents an intrinsic limit to the
formation of the extended 2D networks involving zwitterionic
molecules observed for Cys deposition on at ordered surfaces.

Acknowledgements
Funding from University of Genova (PRA) and support from
Sincrotrone Trieste are acknowledged. Mirko Prato, L. Lavagnino, M. Fiammarelli and A. Penco are acknowledged for
experimental assistance in some stages of experiments. A.
Morgante, D. Cvetko and L. Pasquali are acknowledged for
many discussions on the cysteineAu system.

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Nanoscale

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