University of Tennessee, Knoxville TRACE: Tennessee Research and Creative Exchange
Supervised Undergraduate Student Research Chancellor’s Honors Program Projects and Creative Work
Fall 12-2004
Endohedral Fullerenes
Maria Danielle Garrett University of Tennessee - Knoxville
Follow this and additional works at: https://trace.tennessee.edu/utk_chanhonoproj
Recommended Citation Garrett, Maria Danielle, "Endohedral Fullerenes" (2004). Chancellor’s Honors Program Projects. https://trace.tennessee.edu/utk_chanhonoproj/740
This is brought to you for free and open access by the Supervised Undergraduate Student Research and Creative Work at TRACE: Tennessee Research and Creative Exchange. It has been accepted for inclusion in Chancellor’s Honors Program Projects by an authorized administrator of TRACE: Tennessee Research and Creative Exchange. For more information, please contact [email protected]. "Endohedral Fullerenes" Fall 2003 Danielle Garrett
Abstract:
The purpose of this research was to produce sodium filled endohedral fullerenes by injecting sodium ions into C60 molecules by laser ablation. After reproducing the experiment four times, it was found that Na@C60 (sodium endohedral fullerene) was not produced. However, many unexpected molecules were found in the spectra: (molecules found~ spectra #) (CS6 and C60~ 1), (Css, C6Q and C600~ 2), (Css, C60, C600 and C6002~ 3),
(Css, CssO, C6o, C6QO, CS902, C600 2, C6003 and C6004~ 4), (Css, C60, CS90, C600, CS90 2 and C6002~ 5), (Cs4, Cs6, Css, C60, CS902, C6Q02, C6003, CS90 6 and C70 ~ 6) and (C60, C600,
C6002, C6003 and C600 4; 7). After analyzing the spectra, the resolution was calculated
and found to be 1670 ± 178.
- 1 - Danielle Garrett
Introduction:
The purpose of this research was to try to form endohedral fullerenes by injecting
sodium ions into C60 molecules using a laser ablation technique. Endohedral fullerenes
are molecules in which an atom or several atoms have been captured within a fullerene's
caged structure. Endohedral fullerenes are typically made in two ways. Firstly, they can
be produced by striking an arc between graphite electrodes in an inert gas environment.
Secondly, they can be produced by bombarding a graphite target containing the element
to be entrapped in the fullerene with a high-powered laser. In both of these techniques, a
sizeable quantity of carbon soot is produced. Only a minute portion of the product
contains endohedral fullerenes.
Fullerenes are closed hollow caged structures that consist only of carbon atoms.
Every carbon atom in the structure is bonded to three other carbon atoms. Robert Curl,
Harry Kroto and Richard Smalley first discovered fullerenes in 1985. Curl and Smalley
were working at Rice University trying to reproduce the aggregation of carbon atoms in
cool giant red stars. However, in this process, they found traces of fullerenes: "Carbon
plasma generated by laser vaporization of graphite spontaneously formed large carbon
clusters upon cooling, and mass spectrometric analysis of the products showed that the
cluster ions 40 and C70 were particularly stable.,,3 It was not until 1990 that observable
quantities of fullerenes were produced by researchers at the Max Planck Institute in
Germany. Noticeable amounts of C60, C70 and other bigger fullerenes were discovered in
the soot produced by arc vaporization of graphite.
After laser ablation, the products can by analyze using matrix assisted laser
desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS).
-2- Danielle Garrett
In MALDI-TOF MS, a laser is pulsed at a surface containing the sample (analyte) mixed with a chemical matrix. A matrix is picked that will strongly absorb the energy from the
laser light. MALDI-TOF separates ions based on their mass/charge ratio. A pulse oflaser
light is used to ionize the molecules. A pulsed electric field then accelerates all ions to
the same kinetic energy into a region free from the electric field:
Kinetic energy = 1I2mv2 = q V,
where m = mass, v = velocity, q = charge and V = applied voltage.
Lighter ions have a higher velocity than heavier ions. Therefore, lighter ions reach the
detector sooner. The flight time is calculated by dividing the mass by their charge:
t = L/(2V/(m/q))1/2 = L/v,
where t = flight time and L = the length of the tube.
During desorption and ionization of the sample, some of the analyte can leave the
matrix surface with a minute quantity of variable kinetic energy as well as the energy
obtained by acceleration. The kinetic energy is the cause of band broadening in the
spectra: "This variable kinetic energy has the effect of "smearing" the mass-to-charge
ratio of a specific analyte fragment over a small time range, decreasing the signal-to
noise ratio and broadening the analyte bands.,,4 However, this band broadening can be
practically eliminated in two ways. First, delayed pulse extraction can be used to help
eliminate band broadening. In delayed pulse extraction, an acceleration voltage is
applied in a brief high voltage pulse a short time after the desorption/ionization laser has
been triggered. Second, changing the time-of-flight geometry by adding a reflectron to
the end of the flight tube and by moving the detector, the ion band will be focused. A
reflectron is made up of many electrostatic fields. These fields gather and redirect the
- 3 - Danielle Garrett ions: "Ions with a given mlz slow down as they approach the reflectron mirror, focus into a tighter packet, and are then repelled either at an angle toward a detector at the end of a
second stage of flight tube or backward along the same tube to a detector placed near the
ion source.,,4 Therefore, by reducing the effects of the differences in the original kinetic
energy, time-of-flight broadening is reduced. Reflectrons can also enhance the resolution
and increase the mass accuracy by doubling the flight path in time-of-flight mass
spectrometry.
Resolution is a dimensionless ratio mI~m, where m is mass and ~m is the full
width-half-maximum of the mass peak. Low mass resolution refers to a mI&n ratio that
is just high enough to separate ions differing by one amu (atomic mass unit). Often, high
mass resolution is required to separate ions that have almost identical masses or masses
with high molecular weight. Using the equation mI&n, resolution can be calculated from
spectra:
Resolution = mI&n = 2T/~T,
here ~T = 112 T~mlm = 'l2 ~mlm1l2 and k = L/(2eV)1/2,
where ~ T = change in flight time, T = flight time, &n = change in mass, m = mass, L =
length of flight path, e = electron charge and V = voltage
Experimental Procedure:
A solution ofC60 was prepared using O.069g ofC6o and toluene. The metal tip
and metal plate were removed from the ionization pump chamber (Figure 1). The metal
tips were coated with twenty-five layers of the C60 solution. Remove the faceplate from
-4- Danielle Garrett the metal plate. Smear the plate with solid sodium. Place the faceplate back over the
sodium. Place the metal tips and sodium-coated plate back in the vacuum chamber.
Turn the mechanical pump on. Allow the pump to run for at least twenty-four hours in
order to let the pressure drop to to-2 Torr. Set the wavelength of the Nd:YAG
(neodymium: yttrium-aluminum-garnet) laser to 532 nm. Turn the laser power to
approximately 40-45 JouleslPulse in order to focus the laser beam through the 25-cm
focal length lens onto the sodium coated plate. Once the laser beam is focused, turn the
power up to 80 milli-JouleslPulse and turn the amplifier on to 20 milli-JouleslPulse.
Allow the laser to run for ten minutes. After turning the laser off, remove the metal tip
and scrape the product off into a small vial. Then rinse the tip then off over the vial with
toluene. Dilute the product in the vial with toluene.
The next step is to analyze the product sample using MALDI-TOF MS. First,
clean the sample plate. Wash the plate with a detergent and then rinse it with water.
Next, rinse the plate with methanol. After that, dry the plate with a stream of nitrogen
air. Finally, place the plate in a vacuum-sealed container to dry completely. Place 1!JL
of the sample onto one of the spots on the sample plate. Repeat this on two or three more
spots on the sample plate. Place the plate back in the vacuum-sealed container to make
sure all the sample spots are completely dry. Then insert the sample plate into the mass
spectrometer. Apply the laser to each separate sample spot in order to ionize the
molecules. After firing the laser several times to one spot, move the laser to the next spot
containing the sample. Repeat this procedure with the laser until all sample spots have
been shot by the laser and enough data has been compiled to form an accurate spectrum
of the sample.
- 5 - Danielle Garrett
Results:
After running the experiment four times, it was concluded that Na@C60 molecules
(sodium endohedral fullerenes) were not produced. However, several interesting
compounds were found to he in the spectra. In the first set of spectra, CS6 and C60 were
discovered. In the second set of spectra, C58, C60 and C600 were found. C58, C60, C600
and C6002 were found in the third spectrum. In the fourth spectrum, C58, C580, C60,
C600, C590 2, C600 2, C6003 and C6004were found. In the fifth set of spectra, C58, C60,
C590, C600, C5902 and C6002 were discovered. C54, C56, C58, C60, C5902, C600 2, C6003,
C5906 and C70 were found in the sixth set of spectra. Finally, C60, C600, C6002, C6003 and
C600 4were were discovered in the seventh spectrum. The seventh spectrum is the blank.
It contained only the C60 solution. There are several plausible explanations for the
presence of many of these molecules in the spectra collected. The presence of smaller
fullerenes such as C54, C56 and C58 could be due to the high power of the laser. The high
power would cause the molecules to be in vibrationally excited states. If the molecules
were excited enough, carbons would be spit off from the original molecule. The presence
of C70 could be caused by ion bombardment. If this were the case, two C60 molecules
would combine to form C70. The presence of oxygen in the samples can be explained by
the ease with which C60 is oxidized. Since only the mechanical pump was used, it is
possible that the vacuum chamber had an air leak, therefore, exposing the C60 to oxygen.
Finally, fullerenes smaller than C60 with attached oxygen atoms could have been
produced by the oxygen knocking off a carbon atom and adding itself to the molecule.
By using the equation
Resolution = mJ L\m.
-6- Danielle Garrett where m = mass and ~m = change in mass, the resolution from the various spectra was calculated. After taking an average of several measurements (see Table 2), the resolution was determined to be 1670 .± 178. Improved resolution is achieved be delayed pulse extraction. Delayed pulse extraction reduces the resolution loss caused by the variable velocities of the ions as they are desorbed from the sample. Lower-velocity ions undergo a larger accelerating velocity than higher-velocity ions once the delayed pulse extraction voltage is applied. Lower velocity ions draw alongside the higher-velocity ions of equal mass by the time the ions get to the detector if the correct time delay is chosen. Delayed
pulse extraction diminishes the broadness of arrival times and increases the resolution.
Conclusions:
There are several things that could have been done to improve the experimental
procedure and possibly increase the chances of successful results. First, the wavelength
on the Nd: YAG laser could have been set to 355nm. Decreasing the wavelength from
532nm to 355nm would increase the energy of the ions:
').. = hlmv = hciE,
where').. = wavelength, h = Planck's constant, m = mass, v = velocity, c = speed of light
and E = energy. Increasing the energy and velocity of the ions would increase the chance
that they would penetrate the C60 molecules. Secondly, the diffusion pump should have
been used. Diffusion pumps capture gas molecules by vaporizing and condensing a
special type of oil. Diffusion pumps can attain vacuum pressures to the order of 10-4_10-7
mbar. This low pressure would keep the C60 and sodium from rapidly oxidizing. More
importantly, the relatively high pressure of background gas will cause energy loss of the
- 7- Danielle Garrett
Na+ ions resulting in low energy ions hitting the C60. Next, when performing MALDI
TOF MS, a matrix could have been used instead of merely placing the collected product
on the sample plate. The matrix absorbs photon energy from the laser. Therefore, since
the analyte does not directly absorb the energy, the matrix helps keep the analyte from
fragmenting or decomposing. Finally, a different fullerene solution could be used to coat
the metal tip. The C60 molecule could be replaced with a larger fullerene: "Even though
C60 is the most common fullerene, few endohedral materials have a C60 cage because it is
fairly small inside. Most of these materials are made out of C82, C84, or even higher
fullerenes. ,,1
Despite these changes, the probability of producing an endoherdal fullerene still
seems rather low. Not only is it difficult to get the atoms inside the caged molecule, but
it is also hard to get them to remain inside. There are only a few atoms that are known to
form stable endohedral fullerenes. Most molecules will break apart because the chemical
bonds will not develop at the right angles. It has been found that it is not easy to get an
atom inside a fullerene once the cage has already formed. Therefore, it would be better if
the atoms could be placed inside as the cages are forming: "the cage must "wrap around"
the atom as it comes together."l Currently, there is not much data available to study on
the production of endohedral fullerenes. Few experiments have been conducted because
endohedral fullerenes are still made in rather small amounts. Efficient methods of
production have not yet been discovered.
In spite of the lack of information available on endohedral fullerenes, they could
have a promising future in the field of medicine - "from delivery of radioisotopes, to
cancer cells, to MRI.,,2 Fullerenes have several advantages that would make them
- R - Danielle Garrett beneficial in the medical field. First, anything that is located within the fullerene cage would be protected from the body. Second, the body has a reasonably high tolerance for carbon. Finally, many fullerenes are small enough that once in the system, they could be easily expelled through the kidneys. One potential application would be to place a radioactive tracer atom inside a fullerene. Once injected into a person's bloodstream, the blood flow could be monitored. Another possible use would be to utilize the fullerene cage to carry a drug inside the body. Then, after a certain amount of time has passed, the drug would be released. The drug release would most probably occur by dissolution or breakdown by chemicals in the body. However, the medical field is still many years away from turning these ideas into practical applications.
-9- Danielle Garrett Table 1. Resolution Calculations
mass (m) change in resolution mass 720.257 0.3812
1973 1592 1600 1670 178 Deviation
m=mass ~m = change in mass = width of peak at 112 the height
Tab12 e • Mo Iecu Ies F oun dOIn Sspectra Spectra # 1 2 3 4 5 6 7 10/27/03 10/27/03 11/7/03 1117/03 11117/03 11117/03 11117/03 positive ion negative ion negative ion negative iOIJ Inegative ior negative ion negative ion sample sample sample sample sample sample blank
CS6 CS8 CS8 CS8 CS8 CS4 C60
C60 C60 C60 CS80 C60 CS6 C600
C600 C600 C60 CS90 CS8 C600 2
C600 2 C600 C600 C60 C600 3
CS90 2 CS90 2 CS90 2 C600 4
C600 2 C600 2 C600 2
C600 3 C600 3
C600 4 CS90 6
C70 Danielle Garrett Figure 1. Vacuum Ionization Pump
Tip coated with e60 Iwrap{)I~,j wtth e')pper WIre)
~"'-"-~-""'!I'-"-'-'-'" " ,
Vacuum gauge
~ •• -...... ,.., _____""....,.,,,"Ic
Vacuum Ionization Pump Danielle Garrett Figure 2. Vacuum Ionization Pump
Switches:
FI.)re opt'n close 'Rough Htvac All release Danielle Garrett Figure 3. Vacuum Ionization Pump
Chamber
Highvac• Trap
DiffuBion pump Mode of operation: Reflector Extraction mode: Delayed Voyager Spec #1[BP =720.3, 78S} Polarity: Jtl gil' '8 !? c :.1-: "''2.. S peon-o. \ Acquisition control: Manual ~ Accelerating voltage: 20000 V 783.0 Grid Voltage: 74% 100, 720.3123 C Mirror voltage ratio: 1.12 Guide wire 0: 0% Extraction delay time: 200nsec
9O~ Acquisition mass range: 10-1000 Da 283.9318 Number of laser shotS: SO/spectrum Laser intensity: 1151 Laser Rep Rate: 20.0 Hz Calibration type: Default so; Calibration matrix: 2,5-DihydroxybenzoiC ao Low mass gate: Off TImed ion selector. Off
Digitizer start time: 3.284 70~ 1722.2314 Bin size: 0.5nsec Number of data points: 56810 Vertical scale 0: SOmV Vertical offset -2.5% Input bandwidth 0: 500 MHz 60 J
;>, Sample well: 32 ~ Plate 10: E c , 6263 .s 50~ Serial number: .5 222.2481 Instrument name: Voyager-DE PRO o Plate type filename: C:\VOYAGER\1oo weill "'" Lab name: UT-Knoxville
40,, Absolute x-position: 8765.77 Absolute V-position: 32826.7 Relative x-position: 2098.27 308.1170 Relative y-posititon: 759.157 Shots in spectrum: SO 30~ Source pressure: 9.938-008 Mirror pressure: 1.338e-008 455.4090 TC2 pressure: 0.0019 TIS gate width: 8 687 20" u· TIS flight length: 671.8008 • ~ ~ it ~ 10·; < ~ 819.3720
O-r------L o 188.0 327.6 467.2 606.8 746.4 886.0 :v1ass {m/z)
Acquired: 15:05:00, October 31,2003 Printed: 10:08. November 0< danielle's first run in positive ion A:\c60-2_0001.dat \D /2..::r1 03 Mode of operation: Reflector Voyager Spec #1 [BP ::: 720.3, 783} Extract~n mode: Delayed Polarity. hlBidll"! f ()J J.' J 4- Acquisition control: Manual I,
~ Accelerating voltage: 20000 V 100, 720.3123 783.0 Grid voHage: 74% r Mirror voltage ratio: 1.12 Guide wire 0: 0% Extraction delay time: 200 nsec
90~ Acquisition mass range: 10 -1000 Da Number of laser shots: SO/spectrum Laser intensity: 1151 Laser Rep Rate: 20.0 Hz 80'; calibration type: Default , Calibration matrix: 2.5-0ihydroxybenzoic ae Low mass gate: Off Timed ion selector: Off
70~ 722.2314 Digitizer start time: 3.284 Bin size: 0.5 nsec Number of data points: 56810 Vertical scale 0: SO mV i Vertical offset: -2.5% 60i Input bandwidth 0: 500 MHz 720.5520 f ~.~ ~ 5j ! Plate 10: E :E SOl Serial number. 6263 ti< Instrument name: Voyager-DE PRO Plate type filename: C:WOVAGER\1oo well ~ Lab name: UT-Knoxville
40~ i Absolute x-position: 8765.77 Absolute y-position: 32826.7 Relative x-position: 2098.27 , Relative y-posititon: 759.157 30i Shots in spectrum: SO ; Source pressure: 9.93e-008 Mirror pressure: 1.338e-008 722.3407 TC2 pressure: 0.0019 . TIS gate width: 8 20i TIS flight length: 687
10~
709.0o--~------~------~------716.2 ·------~O 723.4 73o.s 737.8 745.0 ~\.~ass (m/Zj
Acquired: 15;05:00. October 31.2003 danielle's first run in positive ion Printed: 10:25, November 03 A:\d)()..2_0001.dat \o/z..:::r-/o'3 Mode of operation: Reflector extraction mode: Delayed Voyager Spec #1[BP::: 720.3,783] Polarity: ~r~~ . .J..:v~ Acquisition control: Manual
Accelerating voltage: 20000 V 74% 819.3720 .61.0 Grid voltage: 100, Mirror voltage ratio: 1.12 Guide wire 0: 0% Extraction delay time: 200 nsec
Acquisition mass range: 10 -- 1000 Da 901 Number of laser shots: 50/spectrum Laser intensity: 1151 Laser Rep Rate: 20.0 Hz Calibration type: Default i Calibration matrix: 2,5-Dihydroxybenzolc ae 801 Low mass gate: Off Timed ion seledor: Off
Digitizer start time: 3.284 70 Bin site: 0.5nsec 1 Number of data points: 56810 Vertical scale 0: SOmV Vertical offset: -2.5% Input bandwidth 0: 500 MHz 804
Sample well: 32 ~ Plate 10: E '0; co , Serial number: 6263 E'" 50": Instrument name: Voyager-DE PRO ;,e Plate type filename: C:\vOYAGER\1oo well ~ Lab name: UT-Knoxville
Absolute x-position: 8765.77 40 Absolute y-position: 32826.7 Relative x-position: 2098.27 Relative y-posititon: 759.157 Shots in spectrum: 50 30-1 Source pressure: 9.93e-008 Mirror pressure: 1.338e-008 Te2 pressure: 0.0019 TIS gate width: 8 TIS fliQht length: 687 201,
10i
o~.------~------~O 780.0 789.6 799.2 808.8 818.4 828.0 Mass (mIl:)
Printed: 10:25, November 0:: Acquired: 15:05:00, October 31, 2003 danielle's first run in positive ion \ 0 /2-;r/ ~3 A:\c60-2_0001.dat Mode of operation: Reflector Extraction mode: Delayed Voyager Spec #1 lBP := 720.3, 45991 J Polarity: Negative 5p~z Acquisition control: Manual (64) Accelerating voltage: 20000 V 720.3321 4.6E+prid voltage: 74% 100 r Mirror voltage ratio: 1.12 Guide wire 0: 0% 721.2992 Extraction delay time: 200 osee
Acquisition mass range: 10 - 2000 oa 90~ Number of laser shots: 100/spectrum Laser intensity: 1569 Laser Rep Rate: 20.0 Hz Calibration type: Default SOc Calibration matrix: 2,5·oihydroxybenzoic a Low mass gate: Off 1,,22"" Timed ion selector: Off Digitizer start time: 3.284 ! 0.5nsec 70~ I Bin size: Number of data points: 82965 l Vertical scale 0: 50mV i Vertical offset: -2.5% , ! Input bandwidth 0: 500 MHz 60 j i i I Sample well: 32 J:;. I Plate E 'tF. I 10: c Serial number: 6263 2 50 E ! Instrument name: Voyager-DE PRO <. Plate type filename: C:\VOYAGER\100 well "" Lab name: UT·Knoxville
40~ Absolute x-position: 9136.93 ! Absolute y-position: 32803.2 2469.43 1~ Relative x-position: Relative y·posititon: 735.75 ~723.3513 Shots in spectrum: 200 30~ Source pressure: 1.381e-007 Mirror pressure: 1.47190008 TC2 pressure: 0.002237 TIS gate width: 8 TIS flight length: 687 20-; 1(600 I 736.3177 i r... ',.737.3152 10" ~8 • 696.3015
, ~_ ,III j:a,tl ., ft,. ".~'i." " . 0,' .L, t.~" ... .. ".' ...... "MOO'; .'" •••• M"" I,· .0 '" .... ~_~~,It...... " ..... •,l~~~~O 210.0 346.2 482.4 618.6 754.8 891.0
r-..~a:ss (n-:/2)
Acquired: 14:37:00, October 31, 2003 Printed: 10:09, November 0 danielle's first run in negative ion \0/Z:=t/03 A;\c60- UJOQ~'Jdat \ ;~~ Mode of operation: Reflector Extraction mode: Delayed Voyager Spec #1(8P::: 720.3, 45991J Polarity: Negative Acquisition control: Manual C('o Accelerating voltage: 20000 V 720.3321 4.6E+(Grid voltage: 74% 100" i Mirror voltage ratio: 1.12 Guide wire 0: 0% Extraction delay time: 200 nsec
90-; Acquisition mass range: 10 - 2000 Da Number of laser shots: 100/spectrum Laser intensity: 1569 Laser Rep Rate: 20.0 Hz Calibration type: Default 80- Calibration matrix: 2.5-Dihydroxybenzoic a Low mass gate: Off Timed ion selector: Off
Digitizer start time: 3.284 70j Bin size: 0.5 nsec Number of data points: 82965 Vertical scale 0: 50mV Vertical offset: -2.5% 60~ I Input bandwidth 0: 500 MHz 1 I Sample well: 32 ~ ~22.5349 'i)i i Plate 10: E a'i 50J Serial number: 6263 E i Instrument name: Voyager-DE PRO ;{<. <> Plate type filename: C:\VOYAGER\1oo well, Lab name: UT-Knoxville
40" Absolute x-position: 9136.93 Absolute y-position; 32803.2 Relative x-position: 2469.43 Relative y-posititon: 735.75 Shots in spectrum: 200 30~ Source pressure: 1.381e-007 Mirror pressure: 1.471e-008 TC2 pressure: 0.002237 TIS gate width: 8 TIS flight length: 687 20" C600 736.3177
10'
~... 1ass fmlz)
Acquired: 14:37:00, October 31, 2003 Printed: 10:15, November 03 dan-ielle's first run in negative ion \o/2:t/o3 A:\c60.1_0001.dat Mode of operation: ReflectOr Extraction mode: Delayed Voyager Spec #1[8P '" 720.3, 45991] Polarity: Negative AcqUisition control: Manual
Accelerating voltage: 20000 V C&o 74% 720.3321 4 6E+o(Grid voltage: 100; :' Mirror voltage ratio: 1.12 Guide wire 0: 0% i 721.2992 Extraction delay time: 200 nsee
Acquisition mass range: 10 - 2000 Da 90" Number of laser shots: 100/spectrum Laser intensity: 1569 Laser Rep Rate: 20.0 Hz Calibration type: DafauH Calibration matrix: 2,5-Dihydroxybenzoic al 80c Low mass gate: Off Timed ion selector: Off 722.2809 Digitizer start time: 3.284 70-1 Bin size: 0.5 nsee Iii Number of data points: 82965 Vertical scale 0: 50mV Vertical offset: -2.5% Input bandwidth 0: 500 MHz 60-'
Sample well: 32 .€' 722.5349 Plate 10: E I c:OIl Serial number: 6263 2 5O~ .E I Instrument name: Voyager-DE PRO Plate type filename: C:\vOYAGER\100 weill 0 '" Lab name: UT-Knoxville 9136.93 40" Absolute x-position: Absolute y-position: 32803.2 Relative x-position: 2469.43 Relative y-posititon: 735.75 723.3513 Shots in spectrum: 200 30~ Source pressure: 1.381e-007 Mirror pressure: 1.471e-008 TC2 pressure: 0.002237 122.8836 TIS gate width: 8 TIS flight length: 687 20~ CGoO i i 736.3177
r~25 : 737.3152 10-' (58 696.3015 o-~_s,~."~. ilg,~",.,.i,~i'\" •..w~~~~'".kJi"",~f~\"'~I~~o 675 707 739 771 803 835 Mass Imlz)
Acquired: 14:37:00, October 31, 2003 Printed: 10:12, November 0: danielle's first run in negative ion \0/2.-::r/o3 A:\c60-1_0001.dat Mode of operation: Reflector Extraction mode: Delayed Voyager Spec #1 [BP = 720.3, 45991] Polarity: Negative Acquisition control: Manual
c~ Accelerating voltage: 20000 V 720.3321 _4.6E+Prid voltage: 74% 100" Mirror voltage ratio: 1.12 - Guide wire 0: 0% 721.2992 Extraction delay time: 200nsec
, Acquisition mass range: 10 - 2000 Da 90~ Number of laser shots: 1oo/spectrum Laser intensity: 1569 Laser Rep Rate: 20.0 Hz Calibration type: Default Calibration matrix: 2,5-Dihydroxybenzoic E 80i Low mass gate: Off 722.2809 Timed ion selector: Off I Digitizer start time: 3.284 0.5 nsec 70~, ! \ Bin size: Number of data points: 82965 Vertical scale 0: 50mV Vertical offset: -2.5% Input bandwidth 0: 500 MHz 60"
Sample well: 32 722.5349 ~ Plate 10: E II> I C Serial number: 6263 2 50·, Voyager-DE PRO E I j Instrument name: a::. Plate type filename: C:\VOYAGER\1oo well Lab name: UT-Knoxville
40'; Absolute x-position: 9136.93 Absolute y-position: 32803.2 Relative x-position: 2469.43 Relative y-posititon: 735.75 723.3513 Shots in spectrum: 200 301 Source pressure: 1.381e-007 Mirror pressure: 1.471e-008 722.8836 TC2 pressure: 0.002237 TIS gate width: 8 TIS flight length: 687 20: C'<)O 723.2184 736.3177
I: 737.3152 10., C58 .[' 696.3015 ';:,1" f!i.1 , ,/,',\ ..., ."."~'~~ '\"'~~""'~".: '11' ~. "" -~.~.,." •..' ... , ." ,£,." .c;:_:~.~~" __' -'-0 oi-·· - ".,. ,...... '_...:...:.1:.~.. .:,' -':..:, -. 688.0 702.8 717.6 732.4 747.2 762.0 ~}~ass (rn!z)
Printed: 10:18. November 0 Acquired: 14:37:00, October 31,2003 danielle's first run in negative ion \O{27J03 A:\c60-1_0001.dat Mode of operation: Reflector Extraction mode: Delayed Voyager Spec #1[BP =720.3, 45991} Polarity: Negative Acquisition control: Manual
CEO Accelerating voltage: 20000 V 74% 100, 720.3321 4 6E'prid voltage: r' Mirror voltage ratio: 1.12 i ! Guide wire 0: 0% 721.2992 Extraction delay time: 200 nsec ! 90 Acquisition mass range: 10 - 2000 Da Number of laser shots: 1001spectrum Laser intensity: 1569 Laser Rep Rate: 20.0 Hz catibration type: OefauH 80i calibration matrix: 2.5-Dihydroxybenzoic a ! Low mass gate: Off 722.2809 Timed ion selector: Off i ~ Digitizer start time: 3.284 70-{ I Bin O.5nsec ! I I size: Number of data points: 82965 j Vertical scale 0: SOmV I Vertical offset -2.5% ! Input bandwidth 0: 500 MHz 60 1I I Sample well: 32 ~ i ·722.5349 'iii Plate 10: c: E 504 Serial number: 6263 ~ Instrument name: Voyager-DE PRO #- I ) Plate type filename: C:\vOYAGER\1oo weill 1 Lab name: UT -Knoxville ! 40i Absolute x-positlon: 9136.93 I Absolute y-position: 32803.2 Relative x-positlon: 2469.43 iI Relative y-posititon: 735.75 I 723.3513 Shots in spectrum: 200 3O-j Source pressure: 1.381e-007 Mirror pressure: 1.471e-008 722.8836 TC2 pressure: 0.002237 I TIS gate width: 8 20l C600 TIS flight length: 687 723.2184 736.3177 ! ! ~ i ~ 737.3152 10~ i ~.! ,
"~v~'/,~, ~ .. ,.,. ',."./.\ ~':." "V" r','-'" ~~~::,,:,:,~e:...:.. .. ::"'''2+0 723 731 739 747 Mass (mlz)
Acquired: 14:37:00. October 31.2003 Printed: 10:12, November m danielle's fitst run in negative ion A:\c60-1_0001.dat to /2=t/o3 Mode of operation: Reflector lixtraction mode: Delayed Voyager Spec #1[BP = 720.3, 45991J Polarity: Negative Acquisition control: Manual (600 Accelerating voltage: 20000 V 736.3177 7292.gGrid voltage: 74% 1001 i Mirror voltage ratio: 1.12 ! I Guide wire 0: 0% I Extraction delay time: 200nsec
Acquisition mass range: 10 - 2000 Da 90~ Number of laser shots: 100/spectrum Laser intensity: 1569 Laser Rep Rate: 20.0 Hz ! Calibration type: Default Calibration matrix: 2,5-Dihydroxybenzoic 80~ ; Low mass gate: Off Timed ion selector: Off i , Digitizer start time: 3.284 70i Bin size: 0.5nsec 737.3152 Number of data points: 82965 I Vertical scale 0: 50mV 1 Vertical offset: -2.5% I Input bandwidth 0: 500 MHz 801 i, Sample well: 32 b 1 '0 Plate 10: E c i Serial number: 6263 oS 5O~ .E [ Instrument name: Voyager-DE PRO ?f< Plate type filename: C:WOYAGER\100 wei Lab name: UT-Knoxville
40~, Absolute x-position: 9136.93 Absolute y-position: 32803.2 Relative x-position: 2469.43 I Relative y-posititon: 735.75 1 Shots in spectrum: 200 Source pressure: 1.381e-007 ~j Mirror pressure: 1.471e-008 I TC2 pressure: 0.002237 II TIS gate width: 8 TIS flight length: 687 20~ ! I I I I , ' ,I !! 1 i! 1~ Iq ::!~ il 'rj f,ll I It! i! l ,d! . InJ/';~' lit.,i\l~ll,' il,:,II, 'i 10' I.!" ,::':' I ' ( ' ." I! 'i, ~, ! I:" "f 11 : '11",,1/, . ], l, I 1 I ,.I' '" ,i""" ,i" I, ,L ; ,I, I 1 i,::tJJd, 'i!,' ' j ',,1'1: ii:" &\li! " ;' ! i, : I It",.'~,I; l! ~>1'f~'~1: ~,.I~ivlY\IlI~'!~~\ ill,f\flI;~rl~' !'It/lit, " i 0 .,\;1., r'11 d }iIH:j.. h~~~I~~ I! • fld,1!r.~lt·! tf Ii ;il' : __'i~~. 846.0 oJ", ~ ~ \ I,lj , f l l.t f·'."L 1.;1) .• ',j ~ll",,!,!:np'l 1 • I " !"U'd' ,: Acquired: 14:37:00. October 31, 2003 Printed: 10:19. November ( danielle's first run in negative ion A:\c60-1_0001.dat to /2. =r /03 ,,, .... Mode of operation: Reflector(r Extraction mode: Delayed Voyager Spec #1[8P::: 720.3, 45991] Polarity: Negative Acquisition control: Manual Accelerating voltage: 20000 V 100 1998.rGrid voltage: 74% ! Mirror voltage ratio: 1.12 Guide wire 0: 0% Extraction delay time: 200nsec 90-; Acquisition mass range: 10 - 2000 Da Number of laser shots: 100/spectrum laser Intensity: 1569 laser Rep Rate: 20.0 Hz ! Calibration type: Default 801 calibration matrix: 2.5-Dlhydroxybenzoic at low mass gate: Off Timed ion selector: Off Digitizer start time: 3.284 70 Bin size: 0.5nsec ! Number of data points: 82965 Vertical scale 0: 50mV fj Vertical offset -2.5% 601 Input bandwidth 0: SOOMHz I :~ J ~ Sample well: 32 £1 , c: i Plate 10: E 2 50i 1[': i. Serial number: 6263 .£ i i' Instrument name: Voyager-DE PRO of Plate type filename: C:\vOYAGER\100 well ~ Ii lab name: UT-Knoxville 401 Absolute x-position: 9136.93 Absolute y-position: 32803.2 Relative x-position: 2469.43 Relative y-posititon: 735.75 I;L' Shots in spectrum: 30 200 I , Source pressure: 1.381e-007 ,I ; 'j ! Mirror pressure: 1.471e-008 i TC2 pressure: 0.002237 ·1 ' J: . I ~ , TIS gate width: 8 'I 20~ n I; ,I TIS flight length: 687 ! } r , i' II : ! I ~ J ;1 i .,. ,/,,' I' f t I: j, ~> :.1 10, , ! I i I, II 'i I i , , I:· ':p I, Iii :i .,!r 'I, .'! i i :1' I. ,'- i;' , ,I!: '::i !" .·r ! , ~I "f' >1" , ~ O r ~----T L~o 796 803 810 817 824 831 Mass (m/z) Acquired: 14:37:00. October 31. 2003 Printed: 10:15, November 03 daniel/e's first run in negative ion to /2-=t 103 A:\c6Q.1_0001.dat -,,.,,,..,""" Voyager Spec #1 [BP =720.2, 20995} S~Y\'\,3 C60 720.1511 1001 j 90~ 80 721.1~29 70 60 ~ ~ S 50 .E ~ n ~ 11 I:,. Ii II Ii 40 P II ~ 30 I! ml~ ;1 II !iii illHI 20 1\ 1 Ii" II1'\7~1.3519 I L I' I! eG.O 0 10 ) Css "lil~,11 ~ C Ii Ii ! 723.1544 &()O 'Z.. 696.1639 llt . 788 752.1235 I i~\ \ 1\ ~, ill'i~ ",.. i £~ ~~ n~ 736.4 756.2 77 Mass (m/z) 800 shots D:\ ... \NaCOA2 0OO1.dat Acquired: 13:53:00. December 01. 2003 \\ t:t-/o~ vuyager ~pec 1flLI:W = ILU.J, 2~{Ulj ((,0 S pedYUN\. t1 720.2586 100 I 1 I 901 721.2592 ! ··1 ro1 60 ~ IIIs:: ~ 50 .5 # ! I iI I 40 H II II 722.2617 I ' 30 , n ~ I " 2°1 I j C~O C6001. CS8 736.2527 696.2658 752.2338 10 1697.2606- CS80 II' C600 '3 I " 754.2498 o IU. II-I l 0 688.0 111.8 735.6 759.4 183.2 807.0 Mass (mlz) 100 shots ):\ ... \NaCOB_OOO1.dat \cquired: 13:55:00. December 01, 2003 \\/'1-/0?;' Voyager Spec #1[BP =720.3, 378981 C&o Spe~5 720.2570 100 I I 721.2596 90 80 10 II I 722.2634 I I III 60 ~ VIc .! ! .E ~1 ~ Ij l. i 40-1 j jll ~1 t~~ 20-1 11,123.2751 C 660 736.2526 I 737.2567 10-\ Csa lit 22.817 JI C~ 1. 696.2661 841.2627 o I M i J»., ,i.d,l\ tlJ I~~¥tt." Bitt. "1.",1h,,, ,L,:!l.! '-df,9k- ...... s; e .11, •• eli'" ' ..· .. 10 619.0 678.8 7~ R 198.4 858.2 918.0 Mass (mtz) 00 shots 1:\. .. lNaCOC 0001.dat ,cqulred: 13:58:00. December 01. 2003 \\/rt/o3 <..~ 720.2570 100 I I 721.2596 90 p II I' ~ ;1 i I n 80 I H I II 'I 1 11 J 1! I, Ii 11 70 H IIIi H :1 !I 722.2634 60 '111+I. ;:.. 4 :t:: Ii c '" 50 i I .4615 i !, /' I ~ 1':1i , 1 II 40 1:/1\ I i I .1 i. ' I 'I I , I'll, 30 ! I· II 1 7~il.~762 I Ii f:III i't~' 20 C~oO Ilf~IH232751 736.2526 10 j ~~ \i \J2.8175 C 0 I II II 11 CS10 '0 'Z.. I Ii ','\ n 724,2748 752.2321 I "ii! -L I 709.2800 71~.2677 717.246q i \\1\Vf3'f289 /" !J 754.2407757.2532 o I . .' ; i~,W,"'-p . 1\ j~ ~ • .1 • 707.0 719.2 l15 t,l 743 6 755.8 768.00 Mass (m/z) 00 shots :\. .. \NaCOC 0001.dat cquired: 13:58:00. Oecember01. 2003 \\ I r=r I 0'3 voyager ~pec 111LI:W =12U.3, 55444] ..---- CE,Q 100] 5pe.&~b 720.~ I 722.2940 90 80 70 (58 6°1 696.3044 ~ j III i737.3019 IIIc 1697.3008 0) 50 .5- -.e. 40i II 117?~R~1 30 5101 C 0 19.....-"l 60 2. 20 C5'672.3089 Cs, .736.3008 100 1 ~t.OO 11 1\ 737.3019 90 !J :1 'I. t' 80 I! ~ 11 Ii ,I II 11 'I·' II i II r! 70 P It nI III I !I II 60 II I II II ~ II l741.3064 c:'" j! 50 .5 i I 7383025 I '#- I I I ( I i II S1]"0 'l.. ;1 I!, 740.~119 c 01- 40 i : !,i'l' I Ii (J:> 7532804 II , i II ~ i o?r61.. I I \ \. /' I I ' 733.3066 Ii \1 i I! i! I, I ~ 30 I Il 1'1 Ii II 742.3086 ~I II !I 734.3152\ I ,1 1\ II il ~ 1 , 757.2872 'i I ! I ; I I :1 1'1' 745.3079 n il !. I 11 I Ii: 'I" t !' Ii 754.2863 !,I 1\' . I I \ d 1. Ii [I 744'f80 \ II 20 I ' ;i I I! i i !1!: 'I Ii I !1 i :\ 00 II lIt 735.b1182/ I I i 1'1 1\ 746 3015 ' 'i ,\ 758.2985 " I I I !II "II! ~I ~l I' il II 1',C5G~3 CfO I! :\ Ii I t ,I \ II \738 5344\ i \ 11.742.515J\ If ~ ii ,il II ?56. 58 ~ \761.2963 ~-~ 1 !t I, :I I I, I\! I \ I \ I ~\ t. 1 i· Ii ,I i: ~ I II "\ 10-1 I:' i' 1 1/ . \! ,\ r t I \ I ti Ii , I; II II :., \ 'I Ii I \r\ I~ ! \~ ; \. ;~\ ! V~ VJ ! /\ i I( ! i i \ 11\ I\ ! II. i ~ 1\ I ~ : ~ I ~l, 1i ~ r\ I\ 1\ t\ I: !I 1\ ~ it : \ IwJ \J ~ \J ,,~ V\J \,,} -V'-J \j ~J J \,~ \) \f'\.J \,~ '~\.~-J"'~ \\~ \;J \J lJ \"J \J \1 ~'"\J ~I \"'0 \J "l."A,~j\'-\~\j\rvJ\...J \ 01 I I ! I 10 731.0 738.6 746.2 753.8 761.4 769.0 Mass (m/z) 00 shots ':\. .. \NaCOC2 0OO1.dat cquired: 14:00:00. December 01. 2003 HI r::t-/03 • V1U~t;;i' "'..,.:00,,", "" tL"". - t .. v.v, ""''''''''''I'''Y''''I'J CS10, 04 2643 100 t · I jf Cb a II 53053 840.3215 90 ~ !iill iII 804.~ f ,:1 iillli, 841.3276 Ii ii I; 80 ~ 1,1• :1.i, 1'111I I!t : I" 'I ,'f III' : i . I"lid,I 70 i,.\ ! I \i I,,, II If I' \ I til! 11 j I Ir !III 797.307811\ \ 11,II, ,I ! i Ii! I Ii I I !~ 60 I IIIJ II Ill! III 842.3209 ~ HI ell I;! I C .! 50 I \1 i I' ~!l~Ii' .5 "I i i "e I I " II I I • I I 787ijj I' ~ ; I ~ 40 II ! ~ 1 , \1 1 \1/111 j 1111 ,! \ I I · il ii! I! III! ii' ~h I I" Ill'" ii',' ,1\1 I'KI' i 'i '1 ~I, u ' ~II" ~ , ' ' " I ' I 1 'I Jdl: l! I iii 11 ~\J!\~\ lA, ~il'~' 1~I,i:II~ g, ir ~~LI" I i :!I ~ , , Iil! I 20·" I" ,"' ~I J ~ l' Im I '1/ PIii ~ '~I v 10 ~~~~~l ~f~ .1 , , , , I( 782.0 799.4 816.8 834.2 851.6 Mass (mfz) 800 shots D:\ ... \NaCOC2 0001.dat Acquired: 14:00:00. December 01, 2003 n/l=rI03 -~~-, --- --J 719.8467 1001 S?<2-~iV\.~ CEO ~1 720.8471 JI 70 60 ~ Ui c CU 50 ,U 1721.8504 .5- 0:::!! , !I 40 ' IIiI II Ii 11121.0564 30 iLl Ijl 't'l I.jl 20 III 1.1 C600 il!l 736.8303 I !11722.8628 III' 1.J jlll~ 751.8096 ':I-5t C~~ C Oli H~ ' C600z. 767.7845 1-61. --oil 60 892 796.8370 753.8215 I! -.:rvt785.7 •I .. , ,.,.'" ,I, ... , .. "" . .J~ID:'l-' "HUL,... ..jU"lL '" ,,,.,IIL,. ..., ,• .1 .. " ...... I,. ,-'II.lW. 11.. •• ,.,••• ,J.!...... 1. 663.0 696.6 730.2 763.8 797.4 831.0 Mass (mfz) I:\ ... \C60blank2 0OO1.dat "B~" .cquired: 13:49:00, December 01,2003 \\ Ir=t/03 ---.------ Danielle Garrett Works Cited 1. Allen, Kim. "Endohedral" Fullerenes. 2003. 27 November 2003 2. Cientifica. Fullerenes: Technology White Papers nr.7 October 2003. 3 December 2003 3. Fullerenes. 1 December 2003 - 10-