Feature

pubs.acs.org/ac

Application of Mass Spectrometry in the Synthesis and

Characterization of Metal Nanoclusters
In recent years, mass spectrometry has been widely used in the characterization of metal nanoclusters.
In this Feature, we first give an introductory tutorial on mass spectrometry and then highlight the
versatile applications of mass spectrometry in accurately analyzing core size, atom-level composition,
charge states, etc. of metal nanoclusters and size evolution during synthesis. Finally, some
perspectives on the future applications of mass spectrometry in nanocluster research are given.
Yizhong Lu and Wei Chen*
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State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences,
Changchun, Jilin 130022, China
gaps, photoluminescence, and enhanced catalytic activity of
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Dr. Dingyi Tong
D ue to the unique electronic structures and thus the
unusual physical and chemical properties different from
the corresponding bulk materials and atoms, metal nano-
particles exhibit potential applications in wide fields such as
optoelectronic devices, catalysis, nanoelectronics, chemical
sensors, nanomedicine, etc.1−5 As elementary building blocks
of nanostructured materials, understanding the formation,
structure, and properties of metal nanoparticles is extremely
important from the scientific and technological points of
view.6,7 One of the structural characteristics of nanoparticles is structures of metal nanoclusters is of fundamental importance
the presence of a high percentage of atoms exposed on the
particle surface. More importantly, the surface atoms on a
particle usually play a decisive role in determining its chemical control and identify the numbers of metal atoms in the core
and physical properties and the fraction of surface atoms
increases sharply with the particle size decreasing. Therefore,
the chemical and optical properties of metal nanoparticles are
strongly dependent on their core size. Among the investigated
metal particles in the nanosized regime, metal nanoclusters
consisting of only several to tens of metal atoms have attracted
a great deal of attention in recent years because of the
dramatically unique properties.6,8,9 For example, their discrete
energy levels and the small size comparable to the Fermi
wavelength of the electron result in the molecule-like energy
metal nanoclusters.
Following the landmark synthesis of alkanethiolate-protected
gold nanoparticles by Brust and co-workers, considerable
interest has been shown in the research field of Au
nanoparticles with core dimension smaller than 5 nm.10−12
For the monolayer-protected gold clusters (Au MPCs) with
core diameters d > ∼2 nm, obvious surface plasmon resonance
(SPR) can be observed at around 520 nm in their UV−vis
absorption spectra. Instead, single band or multibands of UV−
vis absorption can be observed for the subnanometer sized
metal clusters.13 On the other hand, quantized capacitance
charging has been observed for metal MPCs with core
diameters between ∼1.5 and ∼2.5 nm in both scanning
tunneling microscope (STM) and electrochemical measure-
ments, attributed to the single electron charging of MPC with a
very small capacitance.14−16 With the metal core size further
decreasing (d < ∼1.5 nm), the Au MPCs show a highest
occupied molecular orbital (HOMO)−lowest unoccupied
molecular orbital (LUMO) energy gap and exhibit molecular-
like rather than metallic behaviors. Thus, metal nanoclusters,
especially subnanometer sized metal clusters, bridge the gap
between metal atom and large metal nanoparticles. In recent
years, various synthetic methods have been developed for the
preparation of subnanometer sized metal clusters and their
novel optical and electronic properties have been examined
extensively.7,17,18 Since the properties of subnanometer sized
clusters are greatly core size-dependent, elucidation of the
to understand the origin of the unique physicochemical
properties of these compounds.19 Therefore, how to precisely
and monolayer molecules covered on the cluster surface is still
a big challenge for the research of subnanometer sized metal
clusters.
It should be noted that, due to the extremely tiny size of
subnanometer metal clusters and the limited resolution of
electron microscopy, traditional techniques for the size
characterization of large metal nanoparticles, including scanning
electron microscopy (SEM), transmission electron microscopy
Published: June 18, 2015

© 2015 American Chemical Society 10659 DOI: 10.1021/acs.analchem.5b00848

Anal. Chem. 2015, 87, 10659−10667
Analytical Chemistry
(TEM), or high-resolution TEM (HR-TEM), and powder X-
ray diffraction (XRD) are actually not very reliable for
evaluating the core diameters of metal clusters.20−22 In the
1990s, mass spectrometry (MS) was successfully applied to the
determination of chemical compositions of gold nanoclusters
by Whetten and co-workers.23−28 Since then, MS has been
considered a powerful tool for the core size characterization of
various types of metal nanoclusters. Subsequently, careful
studies on high resolution mass spectrometry from Murray’s
and Tsukuda’s groups, among others, have unraveled the
molecular formulas (compositions) of metal nanoclusters.29−34
More recently, MS has also been used to probe the charge
states and to study the growth mechanism of metal nano-
clusters. This Feature article focuses on the application of MS
in the synthesis and structural characterization of metal
nanoclusters with typical characterization examples.
■ MASS SPECTROMETRY AND MASS
SPECTROMETER
As one of the most important traditional spectroscopy
analytical techniques, MS has been widely used to analyze the
chemical structures of organic compounds and small biological
molecules. Moreover, MS can provide information on the
molecular mass of a sample. Since Thomson discovered
isotopes of Ne by mass spectrometry in 1912, the MS
technique has been developed rapidly in physics, chemistry,
biology, and environmental and material sciences. The modern
MS techniques allow more precise determination of atomic
masses and analysis of compound structures. More importantly,
with the discoveries of two soft ionization techniques, i.e.,
electrospray and matrix-assisted laser desorption/ionization in
the late 1980s, MS can be successfully applied to analyze the
mass of high molecular weight compounds, such as polymers,
proteins, nucleic acids (DNA and RNA), etc.33−35
For the mass spectrometry measurement, samples have to be
ionized first by a beam of high energy electrons or other
ionization techniques to generate (positively or negatively)
charged molecular ions and the possible following fragments
ions. After ionization, the charged molecular ions are then
separated by acceleration under an electronic or electro-
magnetic field according to their mass-to-charge ratios (m/z).
The separated ions and fragments are detected and analyzed.
The output signals are finally transmitted to the data system,
producing a mass spectrum.33 A mass spectrum is usually
presented as a plot of ion abundance versus mass-to-charge
ratio. The relative amount of the ionized molecules and
fragments is reflected from the height of each peak
corresponding to the particular m/z values. In a mass spectrum,
the strongest peak is called the base peak and assigned the
relative abundance of 100%. The abundance of all the other
peaks is given their proportionate values, as a percentage of the
base peak.
A mass spectrometer works on the basis of the ionized
molecules which should provide information concerning the
nature and structure of the corresponding precursor molecule.
Therefore, in the spectrum of a pure compound, the highest
value of m/z should correspond to the molecular ion and the
mass of the compound can be derived from the peak. To avoid
the collisions with other air molecules during the traveling of
molecular ions to the detector, a mass spectrometer, including
the ionization sources, analyzer, and detector, is maintained
under high vacuum (low pressure). In fact, possible collisions
would make the molecular ions deviate from the original
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Feature
trajectory, and the ions would lose their charge against the walls
of the instrument. On the other hand, collisions could produce
unwanted species and hence increase the complexity of the
spectrum and mass analysis.
To date, various ionization techniques have been developed
for mass spectrometry, including electron ionization (EI),
chemical ionization (CI), field ionization (FI), fast atom
bombardment (FAB), electrospray ionization (ESI), plasma
desorption (PD), matrix-assisted laser desorption ionization
(MALDI), laser desorption (LD), thermospray ionization (TI),
atmosphere pressure chemical ionization (APCI), etc. Each
ionization method has its own advantages and disadvantages, so
they can be used selectively on the basis of the types of
analyzed sample and the mass spectrometer. For example, FD
can only be used to analyze the molecules with low-mass ions
(m/z ∼ <5000), while MALDI mass spectrometers have been
successfully applied to the analysis of high-mass molecules, such
as proteins, polymers, large organimetallic compounds, and
metallic clusters up to approximately m/z of 500 000. It should
be noted that some ionization techniques are very energetic and
lead to the formation of extensive fragmentations. Other
techniques, however, are softer and produce predominantly the
molecular ions, such as FAB, ESI, and MALDI. Due to the little
fragmentation, one of the advantages of the soft ionization
methods is that the mass spectra are relatively easy to analyze
and interpret. Sector, quadrupole, ion trap (IT), time-of-flight
(TOF), and Fourier transform ion cyclotron resonance
(FTICR) are the main types of mass analysers used currently
in mass spectrometers. The ion energy of the fragments with
different mass-to-charge ratios are then converted into electrical
signals by the detector. The mass spectra were finally produced
and analyzed with the data system. For more details about the
principles of mass spectrometry and the structure of mass
spectrometers, please refer to the comprehensive reference
books.36−40
■
DETERMINATION OF CORE SIZE AND
COMPOSITION OF METAL NANOCLUSTERS BY
MASS SPECTROMETRY
Among the nanometer sized metal clusters, Au is the most
extensively studied metal partly because of its high stability,
easy preparation, and biocompatibility.41 Except for the size-
controlled synthesis and potential applications, the property
characterization, especially the determination of core size and
composition, is one of the most important research topics.
Until now, various types of MS techniques, such as FAB-MS,
MALDI-MS, laser desorption/ionization time-of-flight (LDI-
TOF), and ESI-MS in positive- or negative-ion modes, have
been used as efficient techniques for the analysis of core size
and composition of metal nanoclusters.6,42 In the studies of
metal nanoclusters, MS can not only provide the size and
composition information of the as-synthesized products but
also evaluate the size separation techniques and provide the
optimal reaction parameters to produce specific cluster
compounds in high yield.
Whetten’s group first found the application of LDI-MS in
gold nanoclusters.23 In their work, the crude product with
mixed core sizes was first separated through cycles of fractional
crystallization from solution and then monitored at each stage
by laser desorption/ionization and time-of-flight mass spectro-
metric analysis. For the MS analysis, neat or matrix-diluted
films were prepared on a steel rod tip by vacuum-drying the
toluene solutions of alkylthiol passivated nanocrystals. The
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Analytical Chemistry
sample hold was inserted into the ion-source region of a TOF
mass spectrometer. The gold nanoclusters are irradiated by a
frequency-doubled Nd:YAG laser (532 nm, 5 ns) at a pulse
fluence of 20 mJ/cm2. Figure 1 shows a series of mass spectra of
Figure 1. Mass spectra (abundance vs mass, in k = 103 amu and in
mass-equivalent number N of gold atoms) for a crude mixture (a), of
separated fractions (b−e), and a mixture of the two lightest fractions
(f) of gold nanocrystals passivated by dodecanethiolate monolayers.
The inset structures were predicted optimal core structures containing
N = 459, 314, etc. gold atoms. Spectra were plotted versus cube-root of
mass to facilitate comparison with measurements of linear dimension.
The inset to frame (e) is a high-resolution mass spectrum plotted on a
linear mass scale, with an arrow marking the first peak at 27 609 ± 2
amu. Reprinted with permission from ref 23. Copyright 1996 Wiley-
VCH.
the dominant separated fractions. The mass spectra were
collected for negatively charged nanoclusters, in which case a 15
kV initial acceleration and a 30 kV postflight acceleration were
provided prior to impact on a conversion-type detector. Digital
TOF waveforms were averaged, calibrated against those of
biomolecules in the range of 10−60 k and corrected for
desorption ejection velocity, and converted to a mass-scale.
From the MS spectrum of each fractionation, the core number
of Au atoms (N) in the gold nanocrystals and the
corresponding lattice structure can be well evaluated, which
can be verified from extensive high resolution TEM. From
Figure 1, it can be seen that the mass gradually decreased with
the different separated fractions, indicating the effective
separation for the crude Au nanocluster mixture and the
effective size determination of metal nanoclusters from LDI
mass spectrometry measurements. In another study, Tsukuda
and co-workers prepared thiolate-protected gold nanoclusters
by thiolation of aqueous polymer (poly(N-vinyl-2-pyrrodi-
done), PVP)-stabilized Au clusters.43 Four fractions with
different Au core size were separated from the crude mixture
with gel permeation chromatography (GPC) fractionation. The
fraction containing only 11 kDa species was assigned to
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Feature
Au55(SC18)32 clusters (∼1.3 nm) through the LDI mass
spectrometry characterization. These results indicate that
LDI-MS could be an efficient and direct method to identify
the purity and size (number of metal atoms and the surface
protecting ligands) of metal nanoclusters.
Arnold and Reilly analyzed the composition of gold
nanoclusters by using high-resolution TOF mass spectrome-
try.44 From the fine spectral structures shown in the high-
resolution MS spectrum, the spacing between the labeled
clusters was measured to be about 197 Da, which matches very
well with the mass of a gold atom. Meanwhile, the spacing of 32
Da within the clusters corresponds to the mass of a sulfur atom.
The obtained mass spectra indicated clearly that the clusters
contain different numbers of gold atoms in the metal cores and
the peaks within each cluster correspond to different numbers
of sulfur atoms bound to metal cores. From this study, it can
also be seen that laser irradiation in TOF-MS can efficiently
cleave the S−C and Au−S bonds or even cause loss of gold
atoms; hence, it is not a perfect mode to determine the intact
cluster mass and to further deduce the formula. In such a
situation, the choice of matrix will be very important in
MALDI-MS measurements. Recently, Dass et al. demonstrated
that almost no fragmentation of Au nanoclusters was observed
in the MALDI-TOF mass spectra of Au25(SC2H4Ph)18 clusters
by using trans-2-[3-(4-tert-butylphenyl)-2-methyl-2-propenyldi-
dene] malononitrile (DCTB) as matrix.30 When DCTB was
used as matrix, only a dominant peak around 7391 Da was
produced, corresponding well to the molecular ion of the
Au25(SC2H4Ph)18 cluster, indicating that the ligands remain
intact on the gold cluster core. Moreover, the high-resolution
MALDI spectrum agrees well with the simulated isotopic
distribution. The authors also found that, except for matrix,
laser pulse intensity and ion modes (positive or negative) also
play important roles in MALDI-TOF-MS measurements.
Generally, given a good choice of matrix, lowering the laser
pulse intensity can produce dominant nanocluster intact ions
with minimal fragmentation. Since then, the nondestructive
MALDI mass spectrometry using DCTB as matrix has been
widely used to precisely determine the chemical composition of
metal clusters.45−49
ESI is another important ionization technique in mass
spectrometry.33 Compared to LDI and MALDI, electrospray
ionization mass spectrometry (ESI-MS) is a much softer
ionization technique that tends to produce abundant molecular
ions and little or no fragmentation. Thus, the application of
ESI-MS in metal nanocluster analysis allows one to determine
the exact structure, mass, and composition of metal nano-
clusters. Whetten and co-workers26,28 and subsequently
Tsukuda and co-workers50,51 successfully introduced ESI-MS
in the studies of very small glutathionate-protected gold
nanoclusters. From then on, ESI-MS has been widely adopted
to characterize and determine the compositions of the metal
core and ligand monolayer of metal nanoclusters. In the work
of Whetten’s group, water-soluble gold nanoclusters protected
by tripeptide glutathione (GSH = y-Glu-Cys-Gly) were
synthesized.26 The as-prepared clusters were then isolated by
polyacrylamide gel electrophoresis (PAGE). The most
abundant fraction was characterized by both MALDI and ESI
mass spectrometry. The MALDI mass spectrum indicated that
the gold cluster core is fragmenting extensively in the
desorption/ionization process. The peaks spaced by 197 and
32 amu were ascribed to the various AuS cluster fragmentation
produced by laser desorption, while in the ESI mass
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Analytical Chemistry Feature

spectrometry measurements, the molecular weight of the intact

cluster compound was determined to be 10.4 kDa, correspond-
ing to the cluster with a formula of Au25(SG)18.
Following Whetten’s work, Tsukuda and co-workers studied
the Aun(SG)m system carefully and analyzed all the separated
cluster species with ESI spectrometry.50 Aun(SG)m clusters
were first synthesized and then fractionated into six cluster
components by a high resolution PAGE. On the basis of the
devonvoluted spectra, six highly pure cluster species corre-
sponding to Au 18 (SG) 11 , Au 21 (SG) 12 , Au 25±1 (SG) 14±1 ,
Au28(SG)16, Au32(SG)18, and Au39(SG)23 were obtained. One
year later, Negishi et al. reassessed the chemical compositions
of the fractionated clusters by using freshly prepared samples,
high-resolution ESI mass spectrometry, and more accurate mass
calibrations.51 Nine isolated cluster species were reassigned to
Au10(SG)10, Au15(SG)13, Au18(SG)14, Au22(SG)16, Au22(SG)17,
Au25(SG)18, Au29(SG)20, Au33(SG)22, and Au39(SG)24, respec-
tively. In the study, the Au25(SG)18 cluster was for the first time
identified and confirmed by detailed ESI-MS analysis.
As is known, thiolates-passivated metal clusters are typically
hydrophobic and were considered to be only suitable for laser
desorption ionization mass spectrometry characterization.
Meanwhile, the LDI technique is very energetic and often
results in fragmentation of metal nanoclusters, including the
loss of thiolate ligands, breaking of Au−S or S−C bonds, and
loss of metal atoms, even under threshold laser intensity. Figure 2. (a) Full scan of m/z, acquired using 0.44 mg of NaOAc per
Therefore, it is difficult to determine exactly the intact cluster mg of gold nanoclusters. The peak for TOA+ is truncated. (b) Set of
mass and the chemical composition. The soft ionization 3+ peaks acquired using 1.78 mg of NaOAc or 4.16 mg of CsOAc per
technique with a nonfragmenting process could make it mg of nanoclusters. Insets show more details in selected regions. (c)
possible to produce only ions of the molecular species and High-resolution analysis of several prominent 3+ ions acquired using
thus to analyze the exact composition of nanoclusters, which is 0.44 to 1.78 mg of NaOAc per mg of nanoclusters (in color).
very helpful to study the size-dependent properties of (surface Simulations (black): x3+ = Na4Au25(SC2Ph)18−x(S-PEG)x3+. Reprinted
from ref 29. Copyright 2007 American Chemical Society.
functionalized) metal nanoclusters. An important breakthrough
was made by Murray’s group in 2007.29 In their work, by
tagging clusters with readily ionizable methoxy penta(ethylene switching, and Cs+ adduction, the formula of Au nanoclusters
glycol) thiolate ligands (-S-PEG) via ligand exchange, the core was determined to be Au329(SR)84.
It should be noted that ESI is usually used for composition
size and ligand shell compositions of Au25(SR)18 nanoclusters
assignment, and MALDI is useful for the analysis of the purity
were successfully measured and unambiguous assignments were
of metal nanoclusters.53−56 Thus, in order to get comprehen-
achieved by high-resolution ESI-MS. Figure 2a shows the
sive and accurate data of nanoclusters, the combination of
typical mass spectrum of the Au nanoclusters acquired using
MALDI and ESI MS is necessary. In a recent report, Dass’s
NaOAc, where the two sets of peaks represent 3+ and 4+ group, for the first time, obtained 14 kDa gold nanoclusters
cluster ions. It can be seen that, at each charge state, a set of ion with high-yield and purity. As can be seen from the MALDI-
masses were formed due to the different ligands exchanged on TOF MS analysis shown in Figure 3, there are no other peaks
Au nanoclusters. On the basis of the mass difference of 130 Da corresponding to Au25 or Au102 which always appeared in
between -S-PEG (267 Da) and -SC2Ph (137 Da), a periodic earlier studies, indicating the high purity of the nanoclusters.57
130 Da difference between prominent neighboring peaks is By using the high-resolution ESI-MS of two different thiolate
expected. By comparing the spectra of 3+ peak set obtained ligands, the cluster composition was accurately determined to
with Na+ and Cs+ (Figure 2b), we can see that each 3+ ion has be Au67(SR)35.
4 coordinated M+ and the Au core has a −1 charge. As can be Except for gold, significant efforts have also been devoted to
seen from the high-resolution analysis of three main peaks the synthesis and characterization of silver nanoclusters. The
acquired with different amounts of Na+ shown in Figure 2c, the structure and composition of silver nanoclusters have also been
experimental data match excellently with the simulated ones. analyzed by ESI mass spectrometry. Recently, Jin’s group
Together with the data for different extents of ligand exchange, succeeded in ESI-MS analysis of Ag7 nanoclusters for the first
all the ESI-MS results verified that Au25(ligand)18 is the correct time.21 From the base peak at m/z 1520.4 corresponding to the
assignment. Since then, scientists began to use mass true molecular ion mass, the formula of silver nanoclusters was
spectrometry in organic solvent to determine the chemical precisely determined to be Ag7(DMSA)4, where DMSA is 2,3-
composition of hydrophobic metal nanoclusters. Note that, in dimercaptosuccinic acid. Guo et al. made the formula
2014, Dass’ group reported the application of the electrospray assignment for a large ligand-protected silver magic-number
ionization quadrupole-time-of-flight (ESI Q-TOF) MS techni- Ag32(SG)19 cluster by optimizing ESI-MS conditions.58 They
que in determining the chemical composition of faradaurate provided a general strategy that enables the acquisition of high-
76.3 kDa Au nanoclusters.52 Through the analysis of mass shifts quality mass spectra of fragile metal clusters that are needed to
caused by changing the mass of ligands, ionization mode make reliable mass and formula assignments. More recently,
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Analytical Chemistry
Figure 3. (A) Positive mode MALDI-TOF and ESI-MS of
Au67(SC2H4Ph)35. (B) Positive mode MALDI-TOF and the negative
mode ESI-MS of Au67(SC6H13)35. (C) Positive mode and negative
mode ESI-MS of Au67(SC6H13)35. (D) ESI-MS of Au67(SR)35
protected by phenylethanethiolate and n-hexanethiolate showing a
mass difference of 350 Da. The number of ligands in the Au67 was
calculated to be 35. Reprinted from ref 57. Copyright 2013 American
Chemical Society.
Ag44(SR)30 nanoclusters have also been synthesized in high
yield and the composition was identified by ESI-MS.59−63
Moreover, Cu and Pt clusters have also been successfully
identified by ESI-MS during the past years.64−66 For example,
we synthesized subnanometer sized copper nanoclusters based
on wet chemical reduction.65 The chemical composition of the
2-mercapto-5-n-propylpyrimidine-protected nanoclusters was
analyzed by positive-ion ESI-MS. The result showed that Cu8
clusters are the dominant component in the colloid solution.
The experimental MS spectra are consistent with the simulated
isotopic patterns. From above, it can be seen that ESI-MS is a
powerful tool for the precise analysis of core and shell
compositions of monolayer-protected metal nanoclusters and
even for the mixed monolayer-functionalized ones.
In addition to the above MALDI-MS and ESI-MS, fast atom
bombardment (FAB) ionization mass spectrometry was also
applied to the size and composition characterization of gold
nanoclusters. The FAB technique is realized by employing a
discharged beam of fast atoms of an inert gas to bombard the
sample. With this ionization technique, the sample must be
dissolved in a liquid matrix which should be nonvolatile, of low
viscosity, and chemically inert. Murray and co-workers analyzed
Au25(SR)18 (R = C2H4Ph and (CH2)9CH3) nanoclusters with
FAB-MS by using 3-nitrobenzene alcohol as matrix.67 They
compared the FAB-MS, MALDI-MS, and ESI-MS of
Au25(SC2H4Ph)18 nanoclusters and found that the ESI-MS
spectrum exhibits a very clean pattern with only the molecular
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Feature
ion of the nanocluster at 7394 Da. In the case of MALDI-MS
measurements, dependent on the selected matrix and threshold
laser pulse intensity, the MALDI spectrum shows the parent
ion and a series of fragments corresponding to the losses of
Au(SR) units, with the loss of Au4(SR)4 being favored.
However, the FAB-MS spectrum exhibits significant fragmen-
tation, producing rich peaks due to the serial losses of gold
atoms, protecting ligands and sulfur atoms. This result well
demonstrated the characteristics of the most used mass
spectrometry techniques in metal nanoclusters.
Taken together, size and composition of metal nanoclusters
could be determined by MS techniques. In addition, to further
confirm the purity and composition of metal nanoclusters,
thermogravimetric analysis (TGA) and X-ray photoelectron
spectroscopy (XPS) were usually performed.68−70 Taking
Au102(p-MBA)44 (p-MBA, p-mercaptobenzoic acid) nano-
cluster as an example, the ratio of metal to organic component
(ligands) can be determined by TGA, and the atomic number
ratio of Au/S can be determined by XPS.70 TGA of the purified
Au102(p-MBA)44 clusters shows a weight loss of 23 wt %, close
to the theoretical weight loss (25.2 wt %) between 260 and 360
°C. On the other hand, from the integration of Au 4f and S 2p
peak intensities in the high-resolution XPS spectra, the
percentages of Au and S were calculated to be 72.8% and
27.2%, respectively. The values for Au102(p-MBA)44 are 69.9%
Au and 30.1% S. Note that these methods rely on the purity of
nanoclusters. If nanoclusters are pure, these approaches readily
give a precise formula. However, for a size-mixed sample, such
approaches are less useful in determining the composition
because these methods only provide an average value of all
clusters in a sample. More recently, the structure of
Au25−nAgn(SCH2CH2Ph)18− alloy was determined by Dass
and co-workers by X-ray crystallography. The obtained
composition of Au18.3Ag6.7(SCH2CH2Ph)18 agrees well with
that from ESI-MS measurement.71
■ ANALYSIS OF THE COMPOSITION OF MIXED
PROTECTING LIGANDS ON CLUSTER SURFACE
To tune the surface structure and properties of metal
nanoclusters, surface modification with specific functional
groups is an effective approach for practical applications.72
Metal nanoclusters capped with multiple protecting ligands can
be realized by ligand exchange on the already formed
nanoclusters with the desired functional ligands. These
functionalized nanoclusters are of importance in both
fundamental studies and technological applications. Spectral
analysis, such as FT-IR and NMR can provide the average
surface compositions of the mixed protecting ligands. However,
how to get the accurate composition information on the
individual nanocluster is still a big challenge.
Murray and co-workers studied the structure of Au
nanoclusters capped with mixed ligands by using positive-
mode ESI-MS.73 The core size and ligand shell composition of
benzeneethanethiolate (SC2Ph)-protected gold nanoclusters
were analyzed by purposeful incorporation of methoxy penta
(ethylene glycol) thiolate ligands (-S-PEG) via ligand exchange
reaction. Subsequently, by using DCTB as matrix, Murray’s
group found that MALDI-TOF MS is another ideal tool for
measuring mixed monolayer compositions on the nanocluster
surface.30 Figure 4 shows a MALDI-TOF mass spectrum (the
middle one) of Au25(SC2H4Ph)18 clusters with a small amount
of fragmentation at ∼6060 Da. The top and bottom mass
spectra correspond to Au25 clusters that had been subjected to
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Analytical Chemistry
Figure 4. MALDI-TOF-MS of Au25(SCH2CH2Ph)18 (middle curve)
in positive linear mode and ligand exchange products (after 22 h) with
methoxy pentaethylene glycol thiol (PEG5-SH, top curve) and with
methoxy ethylene glycol thiol (PEG1-SH, bottom curve) in negative
linear mode. Reprinted from ref 30. Copyright 2008 American
Chemical Society.
the ligand exchange with CH3(OCH2CH2)5SH (PEG5-SH)
and CH3(OCH2CH2)SH (PEG1-SH), respectively. Because
PEG5-SH is heavier by 130 Da and PEG1-SH is lighter by 46
Da than the original phenylethanethiolate ligand, respectively, a
series of peaks at higher (top spectrum) and lower (bottom
spectrum) mass were observed, corresponding to different
numbers of PEG5-S- and PEG1-S- ligands incorporated into
the surface protecting ligand monolayer. From the top mass
spectrum, there are 12 peaks for molecular ions, corresponding
to 12 nanoclusters with different numbers of exchanged ligands.
The corresponding nanoclusters with mixed ligands can be
assigned to formula Au25(SC2H4Ph)18−x(PEG5-S)x, where x is
the labeled number for the peaks. This example clearly shows
that MALDI-TOF-MS under nonfragmenting conditions can
be used to analyze the metal clusters with the same metal core
atoms capped with different mixed protecting ligands.
■
COMPOSITION DETERMINATION OF BIMETALLIC
NANOCLUSTERS
As we all know, bimetallic nanostructure materials are of great
interest because they not only show a combination of the
properties associated with two different metals but also usually
present improved optical, electronic, magnetic, and catalytic
properties. Moreover, substituting one or more gold atoms with
metal heteroatom(s) (such as Pt, Pd, Ag, and Cu) could
provide exciting opportunities to tune the electronic, optical,
and catalytic properties of nanoclusters truly at the single-atom
level as well as a deep understanding of the stability of
nanoclusters.45,46,74,75 Therefore, synthesis and composition
characterization of bimetallic nanoclusters are quite necessary
from both scientific and practical aspects.
In 2009, Murray and co-workers reported that Pd-doped
[Pd1Au24(SC2H4Ph)18]0 bimetallic nanocluster could be
synthesized by using the coreduction method.76 Subsequently,
Negishi et al. successfully synthesized Au25−nAgn(SC12H25)18
bimetallic clusters with various Au−Ag mixing ratios.77 All the
peaks in the MALDI-MS spectra can be assigned to a series of
Au25−nAgn(SC12H25)18 (n = 0−11) bimetallic clusters. More
recently, Qian et al. reported the synthesis, isolation, and
characterization of monoplatinum-doped Pt1Au24(SR)18 nano-
clusters.74 First, a modified one-phase method with THF as
solvent was used to prepare a mixture of Au25(SR)18 and Pt-
10664
Feature
doped clusters. The mixed clusters were then treated with
concentrated H2O2 (30 wt %), where Au25(SR)18 clusters were
selectively decomposed. Finally, pure Pt1Au24(SR)18 composi-
tion was obtained after being purified by size-exclusion
chromatography (SEC). Due to the very small mass difference
(1.89 Da) between Au (196.97 Da) and Pt (195.08 Da), high-
precision ESI-MS was used to analyze the composition of
Pt1Au24(SR)18 clusters. As can be seen from the ESI mass
spectrum (Figure 5A), an intense peak at m/z 7524.8 Da (the
Figure 5. (A) ESI-MS of Pt1Au24(SR)18 nanoclusters. (B) Exper-
imental and simulated isotope patterns of Pt1Au24(SR)18Cs+ and
Au25(SR)18Cs+ (a resolving power of 9500 was used in the simulation).
Reprinted from ref 74. Copyright 2012 American Chemical Society.
most abundant isotope peak) was observed. Since cesium
acetate was added to form Cs+ adducts during the measure-
ments, this peak could be assigned to Pt1Au24(SR)18Cs+
(7524.8 Da). Moreover, it was found that the experimental
isotopic pattern was superimposable with the simulated one but
different from that of Au25(SR)18Cs+ (Figure 5B), confirming
the monoplatinum-doped Pt1Au24(SC2H4Ph)18 nanoclusters.
On the basis of experimental and DFT calculations, the authors
further found that the Pt1Au24(SC2H4Ph)18 cluster possesses a
Pt-centered icosahedal core capped by six Au2(SC2H4Ph)3
staples. In another work, Negishi et al. precisely determined
the chemical composition of Pd1Au24(SC12H25)18 clusters using
nondestructive MALDI mass spectrometry with DCTB as the
matrix.45 In order to minimize the possible dissociation of
clusters caused by laser irradiation, a cluster-to-matrix ratio of
1:1000 was used in the study. Simultaneously, the laser fluence
was decreased to the lowest value. More recently, Wu and co-
workers successfully synthesized atomically monodisperse
Au25Ag2(SC2H4Ph)18 in high yield (89%) within 2 min via a
unique antigalvanic reduction method.78 In contrast with the
earlier reports, the authors found that the two silver atoms in
Au25Ag2(SC2H4Ph)18 do not replace the gold atoms in the
precursor particle Au25(SC2H4Ph)18 but collocate on Au25. In
the MALDI-MS of the as-synthesized Au25Ag2(SC2H4Ph)18
nanoclusters, a distinct peak at ∼7610 Da (the highest intensity
in the mass spectrum) appeared and the unity spacing of
isotopes implies that the ionized clusters bear a +1 charge
(acquired in the positive ion mode); the m/z value of the peak
therefore represents the molecular ion mass. Compared with
the formula weight of Au25(SC2H4Ph)18 (∼7394 Da), a 216 Da
deviation, which is equal to the mass of two Ag atoms, was
observed. Thus, the formula of Au25Ag2(SC2H4Ph)18 could be
readily deduced from such MS results, which is further
supported by the excellent agreement of the isotopic patterns
from experiments and calculations.
Except for doped Au25 nanoclusters, Au144−xMx (M = Ag, Cu,
and Pd) bimetallic nanoclusters have also been synthesized and
characterized by mass spectrometry.79−81 For example, for the
first time, Dass and co-workers successfully synthesized and
DOI: 10.1021/acs.analchem.5b00848
Anal. Chem. 2015, 87, 10659−10667
Analytical Chemistry
isolated (AuAg)144(SR)60 nanoclusters. The ESI-MS results
indicated that the fraction of Ag in the nanoalloy does not
reflect the mole fraction of the precursors and seems to plateau
at 37% for the 1:0.75 Au/Ag incoming mole ratio.79
■
PROBING THE CHARGE STATES OF METAL
NANOCLUSTERS
Charged active sites are hypothesized as key reaction centers in
heterogeneously catalyzed reactions.82 For instance, positively
charged Auδ+ species have been identified as active sites for the
CO oxidation reaction. Recently, anionically charged Au25−
nanoclusters have been demonstrated to facilitate the
adsorption and activation of molecular species, such as O2
and CO2, and thus improve the reactivity of the clusters.47,83
Therefore, how to probe the charge states of metal nanoclusters
is critical to investigate their potential application.
Generally, the charge state of metal nanoclusters could be
easily determined by the known nuclear magnetic resonance
(NMR) and optical absorption spectroscopy.84 For example,
the charge state of Au25 nanoclusters could be conveniently
identified from the relative intensities of the 400 and 450 nm
peaks as well as the presence or absence of the 800 nm
shoulder peak in the UV−vis spectrum.85 Recently, Tsukuda
a n d c o - w o r k e r s d i s c u s s e d t h e c h a r g e st at es o f
[Au25(SC6H13)18]q (q = −1, 0, +1) on the basis of detailed
ESI-MS analysis. 8 6 In their study, charge neutral
[Au25(SC6H13)18]0 clusters were subjected to oxidation by
Ce(SO 4 ) 2 and reduction by NaBH 4 to obtain the
[Au25(SC6H13)18]+1 and [Au25(SC6H13)18]−1, respectively. As
can be seen from Figure 6b (top), a single peak assigned to
Figure 6. (a) Optical spectra and (b) ESI mass spectra of positive- and
negative-charged (3, top; 4, bottom) [Au25(SC6H13)18]x clusters.
Reprinted from ref 86. Copyright 2007 American Chemical Society.
[Au25(SC6H13)18]+1 was observed in the positive-ion ESI mass
spectra, where no anions were detected. In contrast, only a
single [Au25(SC6H13)18]−1 species was detected in the negative-
ion ESI mass spectrum (Figure 6b (bottom)). Subsequently,
Murray’s group reported the use of alkali metal salt for
adduction formation to determine the charge states of
Au25(SR)18 nanoclusters (−1, 0, +1, +2).73 In a recent work,
Dass and co-workers also determined the charge states of
Au133(SPh-tBu)52 nanoclusters through the use of Cs+ as
adduction.87 In addition, Wu et al. successfully determined the
charge states of clusters by using LDI-MS combined with NMR
and UV−vis spectroscopy.84 All these results indicate that mass
spectrum could be used as an efficient tool to probe the charge
states of metal nanoclusters.
10665
Feature
■ MECHANISM STUDY OF NANOCLUSTER
FORMATION
Despite significant progress having been achieved in the
synthesis of monodisperse metal nanoclusters, the formation
mechanism of clusters is still unclear. In 2009, by using the
UV−vis technique, Wu et al. found that the initially formed
mixture of different sized Aun nanoclusters slowly converted
into uniform Au25 nanoclusters via the so-called “size-focusing”
process.72 On the basis of Wu’s work, Dass and co-workers
carried out a systematic mass spectrometric investigation on
monodisperse Au25 nanoclusters during the synthesis.88
Through the MALDI-TOF MS, they observed that, at earlier
reaction times, a mixture of Au25, Au38, Au∼44, Au68, and Au102
was formed, and subsequently, size evolution led to the
formation of highly monodisperse Au25 (Figure 7). For the first
Figure 7. MALDI-TOF mass spectra of the as-prepared gold
nanoclusters using DCTB matrix and operating at threshold laser
fluence. Samples were purified and analyzed at 5 min, 1 h, 6 h, and 3
days. Peaks marked by an asterisk are fragments. Reprinted from ref
88. Copyright 2009 American Chemical Society.
time, they demonstrated that MALDI-TOF MS could be used
effectively to monitor the formation progress of metal
nanoclusters. In another work, through thiol etching, Qian et
al. developed a facile and large-scale method for synthesizing
truly monodisperse Au38(SC2H4Ph)24 nanoclusters in high
yield.68 To investigate the evolution of the starting Aun(SG)m
mixture to monodisperse Au38(SC2H4Ph)24 nanoclusters
induced by thermal thiol etching, Qian et al. performed the
UV−vis and MALDI-MS analysis. The obtained MALDI mass
spectra revealed that, with the reaction time increasing, the
relatively large Au nanoclusters (n > 38) seem to decompose
and convert gradually to Au38 nanoclusters. After ∼40 h, very
clean Au38(SC2H4Ph)24 nanoclusters (10 780 Da, z = 1) were
obtained. Since then, MS has been widely used to detect the
core size evolution of metal nanoclusters.48,89 More recently,
for the first time, Xie’s group performed detailed studies on the
formation of Au25 nanoclusters by monitoring the evolution of
Au(I) precursor and intermediates with ESI-MS.54 Meanwhile,
by using high resolution ESI-MS and MALDI-TOF MS, Dass’s
group reported the size evolution from Au144(SR)60 to
Au99(SR)42 and the synthesis of Au38(SR)24 or Au40(SR)24
without interference from each other.90,91
■ CONCLUSION AND PERSPECTIVES
In this Feature article, we demonstrate the capabilities of mass
spectrometry in identifying the size, composition, and charge
states of nanometer-sized metal clusters, as well as the size
DOI: 10.1021/acs.analchem.5b00848
Anal. Chem. 2015, 87, 10659−10667
Analytical Chemistry
evolution during the synthesis. All these studies have shown
that MS has now become an indispensable tool in metal
nanocluster research. During the past decade, various MS
techniques have been used in the studies of gold, silver, copper,
noble metals, and their doped or alloyed nanoclusters.
However, high-quality MS spectra of cluster samples need
optimized MS experimental conditions. For different cluster
systems, how to get the optimal conditions, such as the type of
MS, selection of matrix, etc., is the critical step to easily obtain
the correct composition information on metal nanoclusters. We
believe that MS will have more wide applications in the field of
metal nanoclusters in the future.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: weichen@ciac.ac.cn.
Notes
The authors declare no competing financial interest.
Biographies
Dr. Yizhong Lu received his Ph.D. in electroanalytical chemistry from
Changchun Institute of Applied Chemistry, Chinese Academy of
Sciences. His research involves the size-controlled synthesis, character-
ization, and size-dependent property study of metal nanoclusters.
Prof. Wei Chen received his Ph.D. in electrochemistry from Xiamen
University in 2003. Following his graduate studies, he began working
as a postdoctoral associate in the area of synthesis and the property
studies of metal nanoclusters at University of California-Santa Cruz.
He is currently a full professor at Changchun Institute of Applied
Chemistry, Chinese Academy of Sciences. His research interests
include electroanalytical chemistry, surface electrochemistry, electro-
catalysis, photoelectrocatalysis, the controlled synthesis, character-
ization, and application of nanomaterials in energy storage and
conversion.
■
ACKNOWLEDGMENTS
The authors thank Dr. Dingyi Tong for designing the TOC
graphic. This work is supported by grants from the National
Natural Science Foundation of China (Nos. 21275136,
21043013).
■
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10667 DOI: 10.1021/acs.analchem.5b00848

Anal. Chem. 2015, 87, 10659−10667