Journal of

MASS
Research article SPECTROMETRY
Received: 1 June 2015 Revised: 8 October 2015 Accepted: 19 October 2015 Published online in Wiley Online Library

(wileyonlinelibrary.com) DOI 10.1002/jms.3718

Depth profiling of inks in authentic and

counterfeit banknotes by electrospray laser
desorption ionization/mass spectrometry
Yi-Ying Kao,a Sy-Chyi Cheng,b Chu-Nian Chengb and Jentaie Shieab,c*
Electrospray laser desorption ionization is an ambient ionization technique that generates neutrals via laser desorption and
ionizes those neutrals in an electrospray plume and was utilized to characterize inks in different layers of copy paper and banknotes
of various currencies. Depth profiling of inks was performed on overlapping color bands on copy paper by repeatedly scanning
the line with a pulsed laser beam operated at a fixed energy. The molecules in the ink on a banknote were desorbed by irradiating
the banknote surface with a laser beam operated at different energies, with results indicating that different ions were detected at
different depths. The analysis of authentic $US100, $100 RMB and $1000 NTD banknotes indicated that ions detected in ‘color-
shifting’ and ‘typography’ regions were significantly different. Additionally, the abundances of some ions dramatically changed with
the depth of the aforementioned regions. This approach was used to distinguish authentic $1000 NTD banknotes from counterfeits.
Copyright © 2015 John Wiley & Sons, Ltd.

Keywords: banknote; electrospray laser desorption ionization; ambient mass spectrometry; money counterfeiting; depth profiling

Introduction surfaces without sample preparation.[12–17] Illegal drugs, explosives

To prevent money counterfeiting, several security features such as
watermarks, security threads, color-shifting printed patterns and
foils are applied to banknotes so they are easily recognized by
the naked eye.[1,2] However, when a banknote circulates in the
market for an extended period of time, these anti-counterfeit
markers fade and lose their effectiveness. Spectroscopic techniques
(ultraviolet, infrared and Raman) and microscopic examinations are
widely used to assist in identification of counterfeit banknotes
because of their cost-effective, simple and non-destructive
features.[3–6] Unfortunately, it is difficult for these techniques to
distinguish aged banknotes from high-quality counterfeits (such
as supernotes) that share very similar spectroscopic features with
authentic notes. Characterizing chemical compounds in banknotes
using mass spectrometry (MS) provides molecular information for
identification, which can overcome the shortcomings of the spec-
troscopic methods mentioned earlier.
Extraction and concentration, followed by gas chromatography/
MS or liquid chromatography/MS, are common approaches to
characterize inks and chemical compounds on banknotes.[7–10]
Recently, a solvent-free gold nanoparticle-assisted laser desorp-
tion ionization mass spectrometric approach was used to image
a $20 HKD (Hong Kong dollar) banknote.[11] Nevertheless, there
are several shortcomings for using conventional MS techniques,
as (1) tedious and time-consuming sample pretreatment is re-
quired, (2) large sample areas are explored, which results in low
analyte spatial resolution, (3) sampling will permanently damage
samples, and (4) depth profiling of inks in the banknote cannot
be achieved.
Ambient MS (AMS) includes techniques that characterize sam-
ples in their native environment and has been applied in forensic
20
and proteins on the surfaces of paper, stainless steel plates and
plastics were characterized by various AMS techniques including di-
rect analysis in real time, desorption electrospray ionization (DESI),
easy ambient sonic spray ionization (EASI), low-temperature plasma
and electrospray laser desorption ionization (ELDI).[18–22] However,
only inks on paper and banknote surfaces have been characterized
by these AMS techniques.[23–27] Some counterfeit banknotes may
have very similar surface ink compositions as those of authentic
ones. In this case, analysis of surface ink composition is not enough
to effectively distinguish between counterfeit and authentic notes.
Because banknote printing contains a series of processes such as
offset lithographic and intaglio printing to transfer different inks
from the printing plates to different layers of a banknote,[2] bank-
notes can be definitively distinguished by characterizing the inks
in different printed layers.
Laser ablation inductively coupled plasma MS (LA-ICP-MS) uses a
pulsed laser beam to ablate elements from samples, which are then
transported by a carrier gas stream to inductively coupled plasma-
MS for ionization and detection.[28,29] LA-ICP-MS allows analysis to
be performed under ambient conditions with high spatial resolu-
tion. The technique has been applied in biology and the forensic
and material sciences for bulk analysis and depth profiling of
* Correspondence to: Jentaie Shiea, Department of Chemistry, National Sun Yat-Sen
University, Kaohsiung, 804 Taiwan. E-mail: jetea@mail.nsysu.edu.tw
a Investigation Bureau, Ministry of Justice, New Taipei, Taiwan
b Department of Chemistry, National Sun Yat-Sen University, Kaohsiung, Taiwan
c Department of Medicinal and Applied Chemistry, Kaohsiung Medical University,

science to rapidly characterize chemical compounds on various Kaohsiung, Taiwan

J. Mass Spectrom. 2016, 51, 20–27 Copyright © 2015 John Wiley & Sons, Ltd.
 Journal of
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ELDI was used to analyze inks at different layers SPECTROMETRY

elements in conducting and nonconducting materials such as tissue
sections, wafers and thin films.[29–33] The experimental processes of
ELDI/MS are similar to those of LA-ICP-MS, except that the post-
ionization mechanism of the former is performed using electrospray
ionization of organic compounds instead of elements.[21,24,26,34,35]
Because a focused pulsed laser beam is used to ablate analytes over
very small sampling areas, depth profiling of inks in the banknote is
achievable by ELDI/MS. Herein, we demonstrated ELDI/MS analysis
of banknotes by (1) repeatedly scanning the sample surface with a
pulsed laser at a fixed energy and (2) varying the pulsed laser energy
to desorb inks located at different depths of the sample. Banknotes
were analyzed using the latter mode to characterize the inks in print-
ing layers inside the banknotes.
Experimental
High-performance liquid chromatography-grade methanol and
reagent-grade acetic acid were purchased from Merck (Darmstadt,
Germany) and J. T. Baker (Phillipsburg, NJ, United States), respec-
tively. Distilled deionized water (produced by a Milli-Q Plus water
purification system, Millipore, Molsheim, France) was used to pre-
pare the stock solutions. New authentic banknotes, including
$US100 (United States dollar), $100 RMB (Renminbi) and $1000
NTD (New Taiwan dollar) were obtained from the Bank of Taiwan
and placed in paper bags before analysis. Counterfeit $1000 NTD
banknotes printed by a laserjet printer were obtained from the In-
vestigation Bureau of the Ministry of Justice, Taiwan. A line was drawn
with a ballpoint pen (KB-15AL, Kangher, Japan) on top of two colored
bands printed by a laser printer (CLC 1120, Canon, Japan) and a color
laserjet printer (HP 5550, Hewlett-Packard, TX, United States), respec-
tively. The first band (5 cm long and 1 cm wide) was printed on copy
paper using yellow ink, while the second band was printed using ma-
genta ink. A blue line (10 mm long and 0.7 mm wide) was then drawn
over the magenta-yellow bands with a ballpoint pen. The line on the
copy paper was analyzed using ELDI/MS without cutting, folding or
applying any matrix. To prevent variations in desorption efficiency
due to laser energy fluctuations (particularly when the laser was
switched on and off), all analyses were performed and completed
in one assay without turning off the laser power.
The detailed configurations of ELDI/MS can be found in previous
publications.[21,24,26,34,35] In this study, the sample (i.e. banknote and
copy paper) was placed on an XYZ stage. The stage was moved at a
speed of 0.03 cm/s during analysis. A pulsed Nd:YAG laser beam
(266 nm, MINILITE I, Continuum Electro-Optics Inc., United States)
was used to irradiate the sample surface at an incident angle of
45°. The laser was operated at a repetition rate of 5 Hz, a pulse du-
ration of 5 ns and a pulse energy from 80 μJ to 10 mJ. The irradia-
tion spot was focused to ca. 300 μm. The laser-desorbed
molecules moved upward to join in an electrospray ionization
(ESI) plume generated from a capillary; the capillary tip was located
approximately 3 mm from the sample spot, and an acidic methanol
solution (MeOH with 0.1% acetic acid) was used to generate the ESI
plume. The analyte ions generated in the ESI plume were detected
by a quadrupole time-of-flight mass spectrometer (microTOF-QII,
Bruker Daltonics, MA, United States) operated in positive ion mode.

Figure 1. (a to c) Photographs of a blue line drawn over magenta and yellow bands on copy paper. The line was scanned by a pulsed laser beam (a) before
the laser scan, (b) after the first laser scan, (c) after the second laser scan and (d) after the 15th laser scan. (e–h) electrospray laser desorption ionization mass
21

spectra from the line on the copy paper after (e) the first laser scan, (f) the second laser scan, (g) the fourth laser scan and (h) the 15th laser scan.

J. Mass Spectrom. 2016, 51, 20–27 Copyright © 2015 John Wiley & Sons, Ltd. wileyonlinelibrary.com/journal/jms
 Journal of
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SPECTROMETRY Y.-Y. Kao et al.

Mass spectra were recorded from m/z 100 to 1200 with a scan rate
of 0.5 Hz. The line on the copy paper was repeatedly scanned by a
pulsed laser beam with a fixed laser energy (80 μJ) to acquire infor-
mation on the ink compositions at different depths. The banknote
surfaces were scanned by a pulsed laser beam over a distance of
0.5 cm. The laser energy was changed from 2.5 to 10 mJ to observe
the influence of the laser energy on analyte ion signals.
Results and discussion
To demonstrate the capability of ELDI/MS to obtain depth profiles
of ink layers on copy paper, a blue line drawn over a magenta band
drawn over a yellow band on copy paper was analyzed. Figure 1(a)–(d)
shows the photographs of the line before and after repeated
scanning by a pulsed laser beam. The ELDI mass spectrum obtained
from the first laser scan is shown in Fig. 1(e), where the ion signals
of blue ink components including methyl violet (m/z 372) and basic
blue 26 (m/z 470) were detected, as well as their degradation prod-
ucts (m/z 344 and 358 from methyl violet and m/z 456 from basic
blue 26). After the first scan, the blue ink depleted to reveal the
underlying magenta ink layer (Fig. 1(b)). The ELDI mass spectrum
obtained from the second laser scan is shown in Fig. 1(f). Ions from
magenta ink (i.e. m/z 337, 359, 383 and 493) were predominant,
while ion signals from the blue ink (i.e. m/z 372 and 470) were still
detected. Figure 1(g) displays the ELDI mass spectrum of ions gen-
erated from the fourth laser scan, where ions from both magenta
and yellow inks were detected. The photograph in Fig. 1(c) reveals
the yellow ink layer under the magenta ink. After 15 laser scans, the
inks on the copy paper were almost entirely depleted, with only
weak ion signals from the yellow ink being detected (Fig. 1(d)
and (h)). In summary, ions from the blue, blue and magenta,
magenta and yellow and yellow inks were detected between the
first and third, second and fifth and fourth to 15th laser scans,
respectively. These results reflect the composition of inks with
respect to depth on the paper. In a previous work, ELDI/MS was used
to analyze crossed ink lines made by different pens.[26] Although not
reported in this study, ELDI/MS is capable of characterizing crossed
lines made produced by laserjet and inkjet printers.
It is known that the laser spot depth is dependent on laser
energy;[36] thus, the laser energy of ELDI/MS was adjusted from
2.5 to 10 mJ to desorb and characterize analytes at both exterior

Figure 2. (a) Photograph of an authentic $US100 banknote. (b to d) Recorded electrospray laser desorption ionization mass spectra for the ‘color-shifting’
22

region of an authentic $US100 banknote. The pulsed laser energy was set at (b) 2.5 mJ, (c) 7 mJ and (d) 10 mJ, respectively.

wileyonlinelibrary.com/journal/jms Copyright © 2015 John Wiley & Sons, Ltd. J. Mass Spectrom. 2016, 51, 20–27
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ELDI was used to analyze inks at different layers SPECTROMETRY

and interior levels. Although a high-energy laser was used, the ion signals produced by photon ionization processes were not de-
destroyed area was barely observable to the naked eye because tected, as the direct current voltage for the ESI source was turned
the small laser spot had a micrometer-range diameter; furthermore, off. Figure 2 shows the ELDI mass spectra recorded at the ‘color-

Figure 3. Recorded electrospray laser desorption ionization mass spectra for the ‘typography’ region of an authentic $US100 banknote. The pulsed laser
energy was set at (a) 2.5 mJ, (b) 7 mJ and (c) 10 mJ, respectively.

Figure 4. Recorded electrospray laser desorption ionization mass spectra for the ‘intaglio’ region of an authentic $US100 banknote. The pulsed laser energy
23

was set at (a) 2.5 mJ, (b) 7 mJ and (c) 10 mJ, respectively.

J. Mass Spectrom. 2016, 51, 20–27 Copyright © 2015 John Wiley & Sons, Ltd. wileyonlinelibrary.com/journal/jms
 Journal of
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shifting’ region. When the laser energy was set at 2.5 mJ, four series
of polymer ion signals – m/z 309 + 58n, m/z 331 + 58n, m/z
405 + 58n and m/z 442 + 58n as well as dibutyl phthalate (m/z
279) – were detected as the predominant ions on the ELDI mass
spectrum (Fig. 2(b)). The mass difference (Δm) between the adja-
cent polymeric ion peaks was 58, indicating these polymers could
be either polypropylene glycol (PPG) or polymers with a PPG
branch chain. Ion signals at m/z 309 + 58n, 331 + 58n and
405 + 58n were tentatively identified as protonated [(M + H)+, M:
analyte], sodiated (M + Na)+ and potassiated (M + K)+ polymers, re-
spectively. The identification was based on a Δm of 22 between
(M + H)+ and (M + Na)+ and a Δm of 16 between (M + Na)+ and
(M + K)+. Ion series detected by ELDI/MS were previously detected
on authentic $US50 banknotes using EASI/MS; these ions were
characterized as oligomeric series of ethoxylated/propoxylated
alcohols.[23] As the ink in the ‘color-shifting’ region was analyzed
at higher laser energies (i.e. 7 and 10 mJ), the prominent ion sig-
nals and their relative intensities on the ELDI mass spectra did
not change much, although the abundance of sodiated PPG (m/z
331 + 58n) and potassiated PPG ions (m/z 405 + 58n) decreased by
approximately three times (Fig. 2(c) and (d)). These results implied
that the ‘color-shifting’ region in the $US100 banknote was printed
using a single ink, although somehow the sodium and potassium
contents of the paper material inside the banknote were lower than
those at the surface. An increase in the laser desorption energy did
Figure 5. (a) Photograph of an authentic $100 RMB banknote. (b to g) Recorded electrospray laser desorption ionization mass spectra for (b–d) the ‘color-shifting’
24
and (e–g) the ‘intaglio’ regions of a $100 RMB banknote. The pulsed laser energy was set at (b and e) 2.5 mJ, (c and f) 7 mJ and (d and g) 10 mJ, respectively.
wileyonlinelibrary.com/journal/jms Copyright © 2015 John Wiley & Sons, Ltd.
Y.-Y. Kao et al.
not induce the formation of new compounds by the reactions
between inks and other materials in the laser desorption area.
The PPG ion series detected in the ‘typography’ region were sim-
ilar to those in the ‘color-shifting’ region on the same banknote, as
the laser energy was set at 2.5 mJ (compare the mass spectra on
Figs. 2(b) and 3(a)). However, several ion signals at m/z 159, 177,
191, 209 + 18n (i.e. m/z 209, 227 and 245) and m/z 257 + 18n
(i.e. m/z 257, 275 and 293) were only detected in the ‘typography’
region. As the pulsed laser energy was increased to 7 mJ, the abun-
dance of PPG-related ion signals decreased, and the ion at m/z 191
became the predominant ion signal on the ELDI spectrum. In addi-
tion, a new ion series at m/z 257 + 18n (i.e. m/z 257, 275 and 293)
were the second most predominant ions on the ELDI mass
spectra.
To validate the experimental results obtained by ELDI/MS, the ink
compounds in the ‘typography’ region were extracted by applying
a drop of acidic methanol solution (0.1% acetic acid) on the bank-
notes. The inks were extracted in the methanol solution by repeat-
edly pipetting the methanol droplet on the banknote surfaces for
ten times. The extracted solution was spotted on a stainless steel
plate, and when dried, was analyzed by ELDI/MS using three differ-
ent laser energies (2.5, 7 and 10 mJ). The ELDI mass spectra of the
dried extracts did not change with the laser energies, indicating
that degradation of molecules in the ink with an increase of laser
energy did not occur (data not shown). Thus, the PPG ion signals
J. Mass Spectrom. 2016, 51, 20–27
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Figure 6. (a) Photograph of an authentic $1000 NTD banknote. (b to g) Recorded electrospray laser desorption ionization mass spectra for (b–d) the ‘color-
shifting’ and (e–g) the ‘intaglio’ regions of a $1000 NTD banknote. The pulsed laser energy was set at (b and e) 2.5 mJ, (c and f) 7 mJ and (d and g) 10 mJ,
respectively.

Figure 7. Recorded electrospray laser desorption ionization mass spectra for (a–c) the ‘color-shifting’ and (d–f) the ‘intaglio’ regions of a counterfeit $1000
25

NTD banknote. The pulsed laser energy was set at (a and d) 2.5 mJ, (b and e) 7 mJ and (c and f) 10 mJ, respectively.

J. Mass Spectrom. 2016, 51, 20–27 Copyright © 2015 John Wiley & Sons, Ltd. wileyonlinelibrary.com/journal/jms
 Journal of
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detected at 2.5 mJ from the ink printed on the surface of the ‘typog-
raphy’ region (Fig. 3(a)), and at m/z 159, 177, 191, 209 + 18n (i.e. m/z
209, 227 and 245) and 257 + 18n (i.e. m/z 257, 275 and 293) were
not degradation products; instead, they were from the inks from
the inside layers of the banknote (Fig. 3).
The ‘intaglio’ region on the same $US100 banknote was analyzed
by ELDI/MS operated at different laser energies (Fig. 4). At a lower
laser energy (2.5 mJ), the ELDI mass spectra recorded from the
‘typography’ and ‘intaglio’ areas were very similar (compare Fig. 3(a)
with Fig. 4(a)). However, the abundance of the ion series at m/z
405 + 58n (i.e. m/z 405, 463, 521, 579, 637, 695 and 753) increased
and became the predominant ion series as the laser energy was
increased up to 7 mJ. When the laser energy was increased to 10 mJ,
new ion series at m/z 538 + 18n (i.e. m/z 538, 556 and 574) were
detected and became the predominant ion signal on the ELDI mass
spectrum (Fig. 4(c)).
For ELDI/MS analysis of the authentic $US100 banknote, ion se-
ries for protonated, sodiated and potassiated PPG molecules were
detected as the predominant ion signals in the ‘color-shifting’,
‘typography’ and ‘intaglio’ regions when the laser desorption
energy was set at 2.5 mJ (Figs. 2(b), 3(a) and 4(a)). These ions were
from inks applied on the surface or the top layer of the banknote.
When the laser desorption energy was increased to 7 and 10 mJ,
the predominant PPG ion series detected in ‘typography’ and
‘intaglio’ regions were different from those at 2.5 mJ, indicating that
the composition of the inks in the inner layers of the authentic
$US100 banknote was different from those on the surface. In a pre-
vious study, droplet pick-up techniques such as EASI and DESI were
used to characterize oligomeric series of ethoxylated/propoxylated
alcohols on a $US50 banknote,[23] where results were similar to
those obtained by ELDI at a laser energy of 2.5 mJ. Additionally,
the ink composition at deeper levels was successfully characterized
by ELDI/MS at a higher laser energy. This implied that DESI and EASI
are useful to characterize the protecting film on banknotes, while
ELDI is useful for characterizing the protecting film and deeper
ink composition of banknotes.
Similar experiments as those performed on the $US100 bank-
note were applied to $100 RMB and $1000 NTD banknotes. Again,
three laser energies (2.5, 7 and 10 mJ) were used to desorb the inks
on the banknotes. Because color-shifting and intaglio printing are
common and important security features applied to banknotes,
only the inks on ‘color-shifting’ and ‘intaglio’ regions were analyzed
(Figs. 5(a) and 6(a)). Figure 5(b)–(g) shows the ELDI mass spectra re-
corded from the $100 RMB banknote. The predominant ion series
detected from ‘color-shifting’ regions were m/z 437 + 14n (Fig. 5(b)).
As the laser desorption energy was increased from 2.5 to 7 and
10 mJ, the ion at m/z 177 was predominant on the ELDI mass spectra
(Fig. 5(c) and (d)). The predominant ions detected in the ‘color-
shifting’ region were different from those in the ‘intaglio’ region,
where ions at m/z 384 + 58n were predominant on the ELDI mass
spectrum (Fig. 5(e)). However, the ion series detected in the ‘inta-
glio’ region did not change with the laser energy, indicating the
ink composition throughout the $100 RMB banknote was the same
(Fig. 5(f) and (g)).
Figure 6(b)–(g) shows the ELDI mass spectra recorded from the
‘color-shifting’ and ‘intaglio’ regions on a $1000 NTD banknote with
different laser energies. It was found that the ion pattern on the
ELDI mass spectra did not change much at different laser energies.
The predominant ions detected in the ‘color-shifting’ region in-
cluded m/z 315 (M + Na)+ and 331 (M + K)+ (Fig. 6(b)–(d)). The abun-
dance of (M + H)+ (m/z 283) of this ink compound was low, to the
26
point it was nearly undetectable. Although their abundances were
wileyonlinelibrary.com/journal/jms Copyright © 2015 John Wiley & Sons, Ltd.
Y.-Y. Kao et al.
low, two PPG-related ion series (m/z 403 + 14n and 552 + 58n) were
detected on the surface of the ‘color-shifting’ region at a laser en-
ergy 2.5 mJ (Fig. 6(b)). The ions of m/z 403 + 14n were not detected
at all when the laser energy was increased to 7 and 10 mJ (Fig. 6(c)
and (d)). The predominant ions detected in the ‘intaglio’ region
were m/z 399 (M + H)+, 421 (M + Na)+ and 437 (M + K)+ (Fig. 6(e)–(g)),
which were different from those found in the ‘color-shifting’ region.
Again, the ion pattern of the ‘intaglio’ region did not change much
with an increase of laser energy, except that the ion at m/z 497
was detected when the laser energy was increased up to 10 mJ
(Fig. 6(g)). Two ion series with relatively low abundance (m/z
484 + 44n and m/z 502 + 44n) were also detected in the ‘intaglio’
region (Fig. 6(e)–(g)).
Electrospray laser desorption ionization/mass spectrometry was
able to characterize different inks at different depths of authentic
banknotes (Figs. 3 and 4) and can be used to characterize counter-
feit banknotes. Figure 7 shows the ELDI mass spectra recorded from
the ‘color-shifting’ and ‘intaglio’ regions from a counterfeit $1000
NTD banknote under different laser energies. A predominant ion
at m/z 667 that is different from the ions detected in the authentic
banknote was detected in both regions, and the mass spectra
remained unchanged even when the laser energy was increased
from 2.5 to 10 mJ. These results indicate that the counterfeit bank-
note made by a laserjet printer used the same ink in both its ‘color-
shifting’ and ‘intaglio’ regions regardless of depth. However, we did
demonstrate depth profiling with authentic banknotes using differ-
ent laser energies (Figs. 3 and 4), so that we could use depth profil-
ing to distinguish authentic from counterfeit banknotes if better
counterfeits are found.
Conclusion
This study demonstrated the feasibility of using ELDI/MS to profile
inks at different depths in copy papers and authentic and counter-
feit banknotes. The results showed that ELDI mass spectra reflected
the ink composition at both exterior and deeper levels. Several
unique ions corresponding to specific regions and layers were de-
tected so that they can be used as money security features to distin-
guish authentic banknotes from counterfeits. During ELDI/MS
analysis, it was unnecessary to fold, cut or extract the banknotes;
thus, samples were well-preserved and can be subjected to addi-
tional physical tests such as nondestructive microscopic examina-
tion or spectroscopic analysis. Furthermore, the ESI emitter in the
ELDI source could be replaced with an atmospheric pressure chem-
ical ionization source to post-ionize laser-ablated analytes, which is
useful for analyzing nonpolar ink compounds and is currently un-
dergoing development in our laboratory.
Acknowledgements
This study was partially supported by grants provided by the Minis-
try of Science and Technology, Taiwan: NSC 102-1301-05-04-05.
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