of 5
Infrared
Photodissociation
Spectroscopy
of Water-Tagged
Ions with
a Widely
Tunable
Quantum
Cascade
Laser
for Planetary
Science
Applications
Tyler
M. Nguyen,
Douglas
C. Ober,
Aadarsh
Balaji,
Frank
W. Maiwald,
Robert
P. Hodyss,
Stojan
M. Madzunkov,
Mitchio
Okumura,
*
and Deacon
J. Nemchick
*
Cite This:
Anal.
Chem.
2024,
96, 8875−8879
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*
sı
Supporting
Information
ABSTRACT:
This
work
presents
a benchtop
method
for
collecting
the
room
temperature
gas
phase
infrared
(IR)
action
spectra
of
protonated
amino
acids
and
their
isomers.
The
adopted
setup
uses
a minimally
modified
commercial
electrospray
ionization
linear
ion
trap
mass
spectrometer
(ESI-
LIT-MS)
coupled
to a broadband
continuous
wave
(cw)
quantum
cascade
laser
(QCL)
source.
This
approach
leverages
messenger
assisted
action
spectroscopic
techniques
using
water-tagged
molecular
ions
with
complex
formation,
irradiation,
and
subsequent
analysis,
all
taking
place
within
a
single
linear
ion
trap
stage.
This
configuration
thus
circumvents
the
use
of
multiple
mass
selection
and
analysis
stages,
cryogenic
buffer
cells,
and
complex
high-power
laser
systems
typically
called
upon
to
execute
these
techniques.
The
benchtop
action
spectrometer
is used
to collect
the
935
−
1600
cm
−
1
(6.2
−
10.7
μ
m)
IR
action
spectrum
of a collection
of amino
acids
and
a dipeptide
with
results
cross
referenced
against
literature
examples
obtained
with
a free
electron
laser
source.
Recorded
IR
spectra
are
used
for
the
analysis
of binary
mixture
samples
composed
of constitutional
isomers
α
-alanine
and
β
-alanine
with
ratios
determined
to
∼
4%
measurement
uncertainty
without
the
aid
of a front-end
separation
stage.
This
turn-key
QCL-based
approach
is a major
step
in showing
the
viability
of tag-based
action
spectroscopic
techniques
for
use
in future
in situ
planetary
science
sensors
and
general
analytical
applications.
M
ass
spectrometer
(MS)
technologies
have
over
five
decades
of
success
in
remote
deployment
for
in
situ
planetary
science
applications.
1
Priorities
outlined
in
the
Planetary
Science
Decadal
Survey
encourage
the
development
of
sensor
platforms
capable
of
biomolecular
detection
in
physiochemically
relevant
environments
(icy
worlds,
Titan,
Mars
polar
regions)
with
several
concept
missions
encouraging
elements
that
include
mass
detection
and
liquid
sampling.
2
Mass
spectrometric
detection
alone
has
limitations
in
identifying
analytes
and
is thus
often
coupled
with
front-end
separation
techniques
with
such
platforms
already
in develop-
ment
for
planetary
science
applications.
3,4
A
possible
alternative
or
complement
to
front-end
separation
is
to
implement
action
spectroscopic
techniques
that
provide
vibrational
spectra
of
mass-selected
ions
with
ion-counting
sensitivity.
A spaceborne
in situ
sensor
could
then
supplement
information
from
traditional
one-dimensional
mass
analysis
with
an
orthogonal
infrared
(IR)
channel,
allowing
for
the
spectroscopic
identification
of
molecule
classes
or
even
the
quantification
of isomeric
mixture
components.
Wavelength
agile
IR
photodissociation
techniques
5
are
increasingly
showing
promise
as
analytical
tools
for
the
interrogation
of a variety
of biomolecule
classes
6
−
9
including
structural
isomer
differentiation.
10
−
12
Unfortunately,
most
implementations
present
insurmountable
barriers
for
adapta-
tion
to space-borne
sensors,
which
place
stringent
demands
on
system
size,
weight,
and
power.
Immediately
disqualified
are
direct
multiphoton
action
spectroscopic
techniques
which
require
intense
user
facility
photon
sources.
8
Perhaps
more
viable
are
messenger
assisted
techniques,
13
which
mechanisti-
cally
operate
by
dissociation
of a noncovalent
tag
species
from
a parent
analyte
ion
and
can
be
executed
with
laboratory-based
radiation
sources.
These
approaches
present
other
complica-
tions
in that
they
are
executed
with
multiple
ion
trap
or mass
analysis
stages,
often
deploying
cryogenic
buffer
cells
to boost
complex
formation
and
narrow
molecular
resonances.
This
work
adopts
a system
architecture
that
has
a
conceivable
path
to
planetary
science
sensor
development,
invoking
a widely
tunable
mid-IR
quantum
cascade
laser
(QCL)
array.
Such
sources
are
considered
in alignment
with
Received:
February
23,
2024
Revised:
May
6, 2024
Accepted:
May
6, 2024
Published:
May
22,
2024
Letter
pubs.acs.org/ac
© 2024
California
Institute
of
Technology.
Gov't
sponsorship
acknowledged.
Published
by American
Chemical
Society
8875
https://doi.org/10.1021/acs.analchem.4c01023
Anal.
Chem.
2024,
96, 8875
−
8879
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planetary
applications
owing
to their
intrinsic
lightweight
and
high
conversion
efficiencies.
Solid-state
semiconductor
lasers
have
an
established
record
for
planetary
science
application
such
as
the
3.27
μ
m
interband
cascade
lasers
used
by
the
tunable
laser
spectrometer
onboard
the
Mars
Curiosity
Rover.
14,15
Broadly
tunable
QCLs
have
been
demonstrated
as
viable
radiation
sources
for
numerous
portable
terrestrial
sensors
16
−
18
and
for
executing
cryogenic,
messenger
assisted
action
techniques
in laboratory
settings.
19
To
reduce
experimental
complexity,
this
work
uses
a single
room
temperature
ion
trap
for
complex
formation,
irradiation,
and
subsequent
reanalysis
with
a continuous
wave
(modulation
free)
tunable
QCL
source.
Observed
action
spectra
are
thus
the
kinetic
outcome
of the
competing
complex
formation
and
photodissociation
processes.
Related
continuous
wave
irradi-
ation
schemes
20
have
been
employed
for
tagged
species
in
cryogenic
(
∼
5
K)
ion
traps
where
the
role
of
competing
processes,
including
the
laser-induced
inhibition
of
complex
growth,
have
been
discussed
in
detail.
21,22
Amino
acid
test
cases
are
used
for
demonstrations
as they
are
a prime
target
for
future
planetary
science
missions,
23,24
with
observed
spectra
compared
to those
taken
with
much
more
complex
instrument
sets.
Recorded
infrared
action
spectra
are
used
for
the
analysis
of
sample
mixtures
containing
the
constitutional
isomers
α
-
alanine
and
β
-alanine,
both
of which
were
detected
in samples
returned
from
the
Ryugu
asteroid
by
laboratory
high-
performance
liquid
chromatography
techniques.
25
These
combined
results
show
that
IR
action
spectroscopy
can
be
executed
for
analytical
pursuits
with
an
instrument
set
that
could
potentially
serve
as
a platform
for
future
planetary
science
sensors.
The
experimental
setup
is composed
of
a Finnigan
LTQ
linear
ion
trap
MS
modified
to
incorporate
a zinc
selenide
(ZnSe)
window.
The
radiation
source
used
is
a Daylight
Solutions
MIRcat-QT
quantum
cascade
laser
having
>75
mW
(
∼
250
mW
peak)
power
output
over
the
operational
bandwidth
(6.2
−
10.7
μ
m).
Continuous
wave
radiation
was
injected
axially
through
the
end-caps
of the
ion
trap
with
an
externally
mounted
lens
used
to focus
radiation
in the
center
of
the
trap
(250
mm
focal
length
lens;
beam
waist
∼
0.6
mm).
A
pickoff
was
incorporated
into
the
beam
path
for
monitoring
laser
power
used
for
spectrum
normalization
(viz.
Supporting
Information).
Protonated
amino
acid
samples
were
prepared
using
standard
concentrations
of
100
μ
M
in
1:1
H
2
O:methanol
solutions
with
0.1%
formic
acid
and
ionized
via
electrospray
ionization
(ESI).
The
MS
collection
sequence
was
composed
of trap
fill
(
∼
1
−
100
ms),
hold
(500
ms),
eject
(20
ms),
and
dead
(20
ms)
periods
with
each
collection
taking
less
than
640
ms.
Analyte
ions
of
interest
are
preselected
by
mass
in
the
room-temperature
linear
quadrupole
ion
trap
with
complex
formation
aided
by
water
vapor
seeded
in helium
buffer
gas.
The
trapped
ion
cloud
is continuously
irradiated
by
the
QCL
source
during
the
complex
formation
(hold)
period,
with
counts
of
the
parent
and
complex
species
subsequently
analyzed.
Initial
experiments
were
performed
using
protonated
O
-
phospho-
L
-tyrosine
as
a parent
species
to
form
a singly
hydrated
complex,
pTyrH
+
(H
2
O).
This
chemical
system
serves
as a convenient
test
case
owing
both
to the
favorable
formation
of the
water
bound
adduct
and
previous
literature
spectra
of
this
species.
26
Figure
1a
details
single
mass
spectra
collected
in
both
the
presence
(red
trace)
and
absence
(blue
trace)
of QCL
generated
radiation
(100
mW)
tuned
to
a vibrational
resonance
at
1280
cm
−
1
. Similar
traces
were
collected
as
a
function
of
the
laser
power
to
generate
the
response
curves
shown
in
Figure
1b.
Here,
the
ion
ratios
are
defined
as
the
integral
of
the
parent
or
complex
species
signal
(S
P
or
S
C
)
divided
by
the
sum
of the
parent
and
complex
signals
(S
P
+
S
C
).
Figure
1b
highlights
the
favorable,
approximately
4:1
formation
of
the
complex
species
relative
to
the
parent.
Photodissociation
of the
hydrogen
bound
water
bound
adduct
at 1280
cm
−
1
is found
to be
highly
linear
with
laser
power
up
to
∼
75
mW
flattening
out
before
reaching
complete
saturation
at
∼
150
mW.
The
laser
power
axis
shown
in Figure
1b
does
not
include
corrections
for
reflective/transmissive
losses,
which
are
estimated
to
be
∼
30%.
Photodissociation
responses
can
thus
be
observed
with
laser
powers
at the
focal
point
inside
the
linear
ion
trap
as low
as 20
mW.
An
IR
action
spectrum,
depicted
in Figure
1c,
is obtained
by
recording
individual
photodissociation
mass
spectra
as
a
function
of
the
QCL
irradiation
frequency.
A single
action
Figure
1.
(a)
Mass
spectrum
showing
the
simultaneous
trapping
of pTyrH
+
(
m
/
z
= 262)
and
pTyrH
+
(H
2
O)
(
m
/
z
= 280)
with
(red
trace)
and
without
(blue
trace)
laser
irradiation.
(b)
Power
dependence
of the
proportion
of water-tagged
(complex)
and
bare
(parent)
taken
at 1280
cm
−
1
.
(c)
IRPD
spectrum
(gray
dots
raw
data;
red
trace
smoothed)
of pTyrH
+
(H
2
O)
with
comparison
to
a literature
spectrum
(black
trace)
and
a
spectrum
generated
from
density
functional
calculations
(blue
area).
Analytical
Chemistry
pubs.acs.org/ac
Letter
https://doi.org/10.1021/acs.analchem.4c01023
Anal.
Chem.
2024,
96, 8875
−
8879
8876
spectrum
is collected
by
stepping
the
radiation
source
over
a
935
−
1600
cm
−
1
(6.2
−
10.7
μ
m)
range
in 5 cm
−
1
steps
with
30
individual
photodissociation
mass
spectra
collected
at
each
frequency
setpoint
(
∼
4000
total
photodissociation
spectra).
For
this
example,
where
adduct
formation
is
favorable
(complex
tagging
ratio
> 0.1),
the
yield
axis
can
be
obtained
directly
by
plotting
the
integrated
parent
feature
at
m
/
z
= 262
as
a function
of
irradiation
frequency
with
the
response
normalized
to
laser
power.
The
experimental
result
(gray
points)
for
three
individual
action
spectra
are
presented
in
Figure
1c,
with
each
scan
constituting
a total
collection
time
of
∼
1
h. A smoothed
contour
of the
average
result
is also
shown
(red
trace).
The
broadband
QCL
action
spectra
obtained
as part
of this
work
is compared
against
a literature
example
of
the
same
chemical
system.
26
In
this
account,
water
tagged
ions
were
prepared
in a room
temperature
hexapole
collision
cell
before
injection
into
an
ion
cyclotron
resonance
mass
spectrometer
with
IR
radiation
generated
with
a free
electron
laser
(FEL)
source.
Despite
the
simplified
experimental
setup
implemented
in the
current
work,
Figure
1c
shows
good
agreement
in not
only
peak
positions
but
also
relative
intensities.
Furthermore,
the
current
spectrum
has
lower
levels
of
background
dissociation
with
several
features
appearing
to
be
narrower,
suggesting
a lower
ion
internal
temperature.
Figure
1c
also
depicts
a calculated
spectrum
of
pTyrH
+
(H
2
O)
at
a global
minimum
geometry
generated
by
scaling
harmonic
density
functional
calculations
(
ω
B97X-V/def2-QZVPP
27,28
) with
an
empirical
factor
(0.965)
and
applying
a Gaussian
function
with
a full
width
at half-maximum
of
20
cm
−
1
at each
vibrational
resonance.
The
cumulative
results
presented
in Figure
1 show
it is possible
to significantly
scale
down
experimental
size
and
complexity
typically
associated
with
infrared
action
spectro-
scopic
techniques,
making
them
viable
for
adaptation
to
planetary
science
applications.
The
benchtop
action
spectrometer
setup
was
used
to record
935
−
1600
cm
−
1
IR
spectra
of
a collection
of
water-tagged
protonated
amino
acids
(glycine
[GlyH
+
];
α
-alanine
[
α
-
AlaH
+
];
sarcosine
[SarcH
+
];
β
-alanine
[
β
-AlaH
+
];
phenyl-
alanine
[PheH
+
]; proline
[ProH
+
]) and
a dipeptide
(diglycine
[Gly
2
H
+
]) having
common
functional
moieties.
These
spectra
are
stacked
in Figure
2 along
with
the
result
for
pTyrH
+
with
plots
ordered
by
the
complex
tagging
ratio,
S
C
/(S
C
+ S
P
),
observed
in the
absence
of IR
radiation.
For
cases
where
the
tagging
ratio
is low
(<0.1),
photodissociation
yield
is based
on
the
depletion
of the
water
tagged
complex
and
calculated
using
a simple
variation
of
commonly
deployed
logarithm-based
approaches
(viz.
Supporting
Information).
29
In
the
same
fashion
as Figure
1, raw
spectral
data
points
are
presented
in
gray
for
three
individual
scans
with
a smoothed
contour
of the
average
result
in
dark
blue.
To
highlight
the
structural
information
encoded
in
these
spectra,
the
C
−
OH
bend
of
the
carboxyl
group
common
to all
species
is indicated
with
a
vertical
red
line
that
traverses
all
plots.
Similarly,
a green
vertical
line
is used
to
annotate
the
NH
3
umbrella
mode
present
in
all
species
with
the
exception
of
sarcosine
and
proline,
which
lack
this
functional
group.
As
also
observed
in Figure
1c,
the
spectra
in Figure
2 show
reasonable
agreement
with
the
calculated
results
of
the
corresponding
water
tagged,
protonated
amino
acids
(viz.
Supporting
Information).
With
the
exception
of
pTyrH
+
(H
2
O),
none
of
the
spectra
presented
in
Figure
2
can
be
directly
compared
against
the
literature
examples.
The
closest
analog
systems
are
multiphoton
spectra
of
untagged
amino
acids
collected
with
FEL
sources
where
spectral
profiles
are
much
broader
than
those
observed
in
this
work.
30
−
32
Signal-to-noise
ratios
for
the
spectra
presented
in Figure
2 can
be
traced
to
a variety
of
factors
including
parent
analyte
ionization
efficiency,
complex
formation
dynamics
(binding
affinity),
and
photodissociation
properties
(absorption
cross
section).
In
general,
the
signal-to-noise
ratio
of
these
room-
temperature
spectra
track
with
the
complex
formation
ratio
observed
in
the
absence
of
IR
radiation
which
scales
with
calculated
binding
energy
metrics
(viz.
Supporting
Informa-
tion).
The
lowest
signal-to-noise
spectrum
observed
for
ProH
+
(H
2
O)
also
has
the
lowest
calculated
binding
energy
of
∼
5000
cm
−
1
. Below
this
threshold,
the
total
linear
trap
ion
capacity
is insufficient
for
generating
enough
messenger
tagged
ions
to
execute
the
technique
at
room
temperature.
In
the
context
of
planetary
science
applications,
infrared
action
spectra
like
those
presented
in
Figure
2 can
be
used
to
identify
specific
molecules
or functional
groups
(e.g.,
carboxyl,
amino,
etc.)
in unknown
samples.
The
distinct
spectral
patterns
observed
in Figure
2 can
also
be
leveraged
to quantify
the
relative
proportion
of isomers
in
Figure
2.
Action
spectra
of various
singly
hydrated
protonated
amino
acids
ordered
by
complex
tagging
efficiency
(bracketed
value).
The
red
line
highlights
the
C
−
OH
bend
of the
carboxyl
and
green
line,
the
the
NH
3
umbrella
mode.
For
tagging
fraction
< 0.1,
normalized
yields
are
calculated
by
depletion
of the
complex
species
and
otherwise
by
growth
of the
parent
species.
Analytical
Chemistry
pubs.acs.org/ac
Letter
https://doi.org/10.1021/acs.analchem.4c01023
Anal.
Chem.
2024,
96, 8875
−
8879
8877
mixture
samples.
The
recorded
IR
spectra
of the
constitutional
isomers
α
-AlaH
+
and
β
-AlaH
+
are
highlighted
in blue
in Figure
2. The
NH
3
rocking
(1075
cm
−
1
) and
CH
2
wagging
(1425
cm
−
1
) vibrational
modes
in
β
-AlaH
+
are
largely
suppressed
in
α
-AlaH
+
making
this
spectral
region
viable
for
discerning
between
these
two
species.
A study
was
executed
by
preparing
five
mixture
samples
having
different
constituent
ratios
of
α
-
AlaH
+
:
β
-AlaH
+
and
collecting
their
corresponding
IR
action
spectrum.
The
relative
fraction
of
each
isomer
was
then
determined
by
least-squares
fitting
a linear
combination
of the
experimental
pure
sample
spectra
to the
observed
experimental
mixture
spectra.
An
example
action
spectrum
for
a 1:2
(
α
-AlaH
+
:
β
-AlaH
+
)
sample
mixture
is presented
in Figure
3a.
This
top
plot
shows
both
the
unsmoothed
average
of
five
action
spectra
(black
trace)
along
with
fit
result
obtained
from
the
least-squares
analysis
(red
trace;
α
-AlaH
+
= 34
±
3%).
The
residual
trace
lacks
a large
systemic
structure
with
some
noise
associated
with
power
normalization
of the
QCL
radiation
source
observable
at frequencies
> 1425
cm
−
1
. See
Supporting
Information
for
analogous
plots
for
all sample
mixtures
and
a description
of the
fitting
procedure.
Fitting
results
for
all
species
are
summarized
in
Figure
3b
which
shows
how
the
relative
fraction
of
each
isomer
as derived
from
the
analysis
of infrared
spectra
deviates
from
expectation.
The
error
bars
adopted
are
the
uncertainty
in
the
fit
parameter
from
the
least-squares
analysis
which
are
universally
within
±
4%
of
the
determined
value.
Figure
3b
shows
the
sample
composition
derived
from
QCL
IR
action
spectra
are
within
the
error
of expectation
for
all trials
with
the
exception
of
the
pure
α
-AlaH
+
sample
case
which
under-
estimates
(overestimates)
the
amount
of
α
-AlaH
+
(
β
-AlaH
+
)
by
approximately
9%.
A global
metric
is provided
in the
form
of a root-mean-square
deviation
(RMSD)
that
is calculated
to
be
4.1%.
These
results
highlight
the
ability
to
use
room
temperature
infrared
analysis
to
differentiate
mass
degenerate
constitutional
isomers
and
quantify
their
relative
abundances,
independent
of traditional
separation
techniques.
Infrared
action
techniques
with
wavelength
agile
radiation
sources
and
mass
gated
detection,
primarily
associated
with
fundamental
studies
of
molecular
structure,
are
increasingly
showing
promise
for
use
as analytical
tools.
This
work
distills
the
experimental
setup
to
essential
elements
deploying
a
slightly
modified
commercial
ESI
linear
ion
trap
mass
spectrometer
and
a CW
broadband
semiconductor-based
QCL
radiation
source.
This
implementation
thus
lacks
multiple
ion
trap/MS
stages,
cryogenic
buffer
cells,
and
high-
power
(FEL)
or
crystal-based
radiation
sources
that
are
commonly
deployed
to
boost
complex
formation
efficiency,
narrow
spectral
features,
and
achieve
sufficient
levels
of
photodissociation.
Despite
these
sacrifices,
action
spectra
collected
with
the
current
benchtop
setup
are
shown
to
reproduce
infrared
spectra
observed
with
more
complex
instrumentation,
clearly
showing
resolved
vibrational
structure
for
a collection
of amino
acid-based
test
cases.
Despite
lower
tagging
efficiencies
and
broadened
spectral
features
associated
with
these
room
temperature
measurements,
spectra
are
still
of
sufficient
quality
to
quantify
isomer
fractions
in
the
mixture
samples.
The
system
architecture
is fundamentally
compatible
with
liquid
sampling-based
planetary
science
platforms
where
multiple
fixed
frequency
QCL
sources
could
be
used
to
identify
functional
groups
or perform
targeted
sample
analysis.
Future
work
aims
to adapt
existing
flight
heritage
quadrupole
ion
trap
MS
systems
33
to
execute
photodissociation-based
analysis
routines
on
relevant
planetary
science
samples.
■
ASSOCIATED
CONTENT
*
sı
Supporting
Information
The
Supporting
Information
is available
free
of
charge
at
https://pubs.acs.org/doi/10.1021/acs.analchem.4c01023.
Experimental
and
computational
details,
infrared
action
spectra
compared
to
calculated
spectra,
all
spectra
mixture
trials,
and
thermodynamic
quantities
(binding
energy)
of
singly
hydrated,
protonated
amino
acids
(PDF)
■
AUTHOR
INFORMATION
Corresponding
Authors
Mitchio
Okumura
−
Division
of Chemistry
and Chemical
Engineering,
California
Institute
of Technology,
Pasadena,
California
91125,
United
States;
orcid.org/0000-0001-
6874-1137;
Email:
mo@caltech.edu
Deacon
J. Nemchick
−
NASA Jet Propulsion
Laboratory,
California
Institute
of Technology,
Pasadena,
California
91109,
United
States;
orcid.org/0000-0003-4760-4752;
Email:
Deacon.J.Nemchick@jpl.nasa.gov
Authors
Tyler M. Nguyen
−
Division
of Chemistry
and Chemical
Engineering,
California
Institute
of Technology,
Pasadena,
Figure
3.
IR
action
spectrum
(a)
of
a 1:2
α
-AlaH
+
(H
2
O):
β
-
AlaH
+
(H
2
O)
sample
mixture
(black
trace)
and
result
from
fitting
routine
(red
trace).
Deviation
of the
mixing
ratios
derived
from
least-
squares
fitting
analysis
from
expected
values
(b)
for
five
tested
samples
with
varying
mixing
fractions
having
a global
root
mean
squared
deviation
of 4.1%.
Analytical
Chemistry
pubs.acs.org/ac
Letter
https://doi.org/10.1021/acs.analchem.4c01023
Anal.
Chem.
2024,
96, 8875
−
8879
8878
California
91125,
United
States;
orcid.org/0000-0002-
9872-7149
Douglas
C. Ober
−
Division
of Chemistry
and Chemical
Engineering,
California
Institute
of Technology,
Pasadena,
California
91125,
United
States
Aadarsh
Balaji
−
Division
of Chemistry
and Chemical
Engineering,
California
Institute
of Technology,
Pasadena,
California
91125,
United
States
Frank
W. Maiwald
−
NASA Jet Propulsion
Laboratory,
California
Institute
of Technology,
Pasadena,
California
91109,
United
States
Robert
P. Hodyss
−
NASA Jet Propulsion
Laboratory,
California
Institute
of Technology,
Pasadena,
California
91109,
United
States
Stojan
M. Madzunkov
−
NASA Jet Propulsion
Laboratory,
California
Institute
of Technology,
Pasadena,
California
91109,
United
States
Complete
contact
information
is available
at:
https://pubs.acs.org/10.1021/acs.analchem.4c01023
Notes
The
authors
declare
no
competing
financial
interest.
■
ACKNOWLEDGMENTS
The
research
was
carried
out
at the
Jet
Propulsion
Laboratory,
California
Institute
of Technology,
under
a contract
with
the
National
Aeronautics
and
Space
Administration
(80NM0018F0613).
Additional
support
was
provided
from
the
National
Science
Foundation
Graduate
Research
Fellow-
ship
under
Grant
No.
2139433
and
the
John
Stauffer
SURF
Fellowship.
The
authors
thank
Dr.
Mona
Shahgholi
of
the
Caltech
Mass
Spectrometry
Facility,
Professor
J. L.
Beau-
champ,
Dr.
Charles
R.
Markus,
and
Dr.
Gregory
H.
Jones
for
useful
discussions
and
also
Dr.
Gilles
Ohanessian
for
the
reference
spectrum
plotted
in Figure
1.
■
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