12-2004 Endohedral Fullerenes - University of Tennessee system

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Fall 12-2004

Endohedral FullerenesMaria Danielle GarrettUniversity of Tennessee - Knoxville

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Recommended CitationGarrett, Maria Danielle, "Endohedral Fullerenes" (2004). University of Tennessee Honors Thesis Projects.https://trace.tennessee.edu/utk_chanhonoproj/740

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Abstract:

"Endohedral Fullerenes"

Fall 2003

Danielle Garrett

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

12 I I F dO S Tab e • Mo ecu es oun In spectra 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

Figure 1. Vacuum Ionization Pump

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Vacuum gauge

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Vacuum Ionization Pump

Danielle Garrett

Tip coated with e60 Iwrap{)I~,j wtth e')pper WIre)

Figure 2. Vacuum Ionization Pump Danielle Garrett

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32 E 6263 Voyager-DE PRO C:\VOYAGER\1oo weill UT-Knoxville

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Sample well: 32 Plate 10: E Serial number: 6263 Instrument name: Voyager-DE PRO Plate type filename: C:\VOYAGER\1oo well, Lab name: UT-Knoxville

Absolute x-position: 9136.93 Absolute y-position; 32803.2 Relative x-position: 2469.43 Relative y-posititon: 735.75 Shots in spectrum: 200 Source pressure: 1.381e-007 Mirror pressure: 1.471e-008 TC2 pressure: 0.002237 TIS gate width: 8 TIS flight length: 687


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20000 V 74% 1.12 0% 200 nsee

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737.3152

-.


Accelerating voltage: _ 4.6E+Prid voltage:

Mirror voltage ratio: - Guide wire 0:

Extraction delay time:


20000 V 74% 1.12 0% 200nsec

Acquisition mass range: 10 - 2000 Da Number of laser shots: 1oo/spectrum Laser intensity: 1569 Laser Rep Rate: 20.0 Hz Calibration type: Default Calibration matrix: 2,5-Dihydroxybenzoic E

Low mass gate: Off Timed ion selector: Off




3.284 0.5 nsec 82965 50mV -2.5% 500 MHz

32 E 6263 Voyager-DE PRO C:\VOYAGER\1oo well UT-Knoxville

9136.93 32803.2 2469.43 735.75 200 1.381e-007 1.471e-008 0.002237 8 687

"" -~.~.,." •.. ' ... , ." ,£,." .c;:_:~.~~" __ ' -'-0

747.2 762.0

Printed: 10:18. November 0

100, i

90

80i !

70-{ !

j I !

601 I

I

~ i 'iii c:

504 ~ I #-1 !

40i I

i I I

3O-j

I 20l

10~

Acquired: 14:37:00. October 31.2003 danielle's fitst run in negative ion A:\c60-1_ 0001.dat

Mode of operation:

Voyager Spec #1[BP = 720.3, 45991} Extraction mode: Polarity:


CEO 720.3321

721.2992

!

i ~ 722.2809

I I I

·722.5349

)

723.3513

722.8836

723.2184

! ~ i ~

i

~.! ,

723 Mass (mlz)

to /2=t/o3

C600 736.3177 !

737.3152

Acquisition control:

Accelerating voltage: 4 6E'prid voltage: r' Mirror voltage ratio:

! Guide wire 0: Extraction delay time:

20000 V 74% 1.12 0% 200 nsec

Acquisition mass range: 10 - 2000 Da Number of laser shots: 1001spectrum Laser intensity: 1569 Laser Rep Rate: 20.0 Hz catibration type: OefauH calibration matrix: 2.5-Dihydroxybenzoic a Low mass gate: Off Timed ion selector: Off

Digitizer start time: Bin size: Number of data points: Vertical scale 0: Vertical offset Input bandwidth 0:


Absolute x-positlon: Absolute y-position: Relative x-positlon: Relative y-posititon: Shots in spectrum: Source pressure: Mirror pressure: TC2 pressure: TIS gate width: TIS flight length:

3.284 O.5nsec 82965 SOmV -2.5% 500 MHz

32 E 6263 Voyager-DE PRO C:\vOYAGER\1oo weill UT -Knoxville

9136.93 32803.2 2469.43 735.75 200 1.381e-007 1.471e-008 0.002237 8 687

"~v~'/,~, ~ .. ,.,. ',."./.\ ~':." "V" r','-'" ~~~::,,:,:,~e:...:.. .. ::"'''2+0 731 739 747

Printed: 10:12, November m

b '0 c oS .E ?f<

1001 !

90~

! 80~ ;

i ,

70i

I 1 I

801

i , 1 i

5O~ [

40~ ,

1

~j 20~

! I

I

(600 736.3177

737.3152

I I ~ 1

i! l ,d! . 10' I.!" ,::':' I '

: '11",,1/, . ; ,I, I i,::tJJd, 'i!,' .,\;1., r '111d }iIH:j .. h~~~I~~ oJ", ~ ~ \ I,lj , f l l.t f·'."L 1.;1) .•

732.0 ::;''1~ ~

Acquired: 14:37:00. October 31, 2003 danielle's first run in negative ion A:\c60-1_0001.dat

Mode of operation: lixtraction mode:

Voyager Spec #1[BP = 720.3, 45991J Polarity:

Reflector Delayed Negative Manual Acquisition control:

Accelerating voltage: 7292.gGrid voltage:

i Mirror voltage ratio: I Guide wire 0:

20000 V 74% 1.12 0% 200nsec I Extraction delay time:

II I I , ' ,I

!! Iq ::!~ 1 il i! (J/';~' 'rj i\l~ll,' f,ll ,II, I It! In lit., il,: 'i ' ." I! 'i, ~, ! I:" "f 11 ], l, I I ,.I' '" ,i""" ,i" I, ,L

Acquisition mass range: 10 - 2000 Da Number of laser shots: 100/spectrum Laser intensity: 1569 Laser Rep Rate: 20.0 Hz Calibration type: Default Calibration matrix: 2,5-Dihydroxybenzoic Low mass gate: Off Timed ion selector: Off




3.284 0.5nsec 82965 50mV -2.5% 500 MHz

32 E 6263 Voyager-DE PRO C:WOYAGER\100 wei UT -Knoxville

9136.93 32803.2 2469.43 735.75 200 1.381e-007 1.471e-008 0.002237 8 687

',j ~ll",,!,!:np'l

' j ',,1'11:1 ",.'~,I; 'f~'~1: ii:" ~ ,.I~ivlY\IlI~'!~~\ &\li! " ;' ! i, : I It l! ~>1 ill,f\flI;~rl~' !'It/lit, " i 0

! • fld, tf ;il' 'i~~. 846.0 I 1!r.~lt·! Ii : __ ' ., 823.2 • I " !"U'd' ,:<Hf • ~ __

..- )11 1"0.1 \ff!l'j 800.4

Mass (mJz)

Printed: 10:19. November (

to /2. =r /03

100

90-;

!

801

70

601 I

~ £1 , c: i 2 50i .£ i

of

401

30

20~

;1

10,

'I . , '!

, !

,,, ....

I, ,

O!" .·r I. ,'-~I "f' >1"

796

!

fj

:~ J

Ii

L' I;

I

803

Acquired: 14:37:00. October 31. 2003 daniel/e's first run in negative ion A:\c6Q.1_0001.dat

-,,.,,,..,"""

1[': i.

Voyager Spec #1[8P::: 720.3, 45991]

n !

, i'

i .,. f t

II , I:·

I 'i

i i .,!r

i;' , ,I!: '::i ! , , ~

810 Mass (m/z)

to /2-=t 103

I; } r

:1'

,/,,'

. 'I ,I

I: j, ~> I i ':p

i'

i

I

,I ; 'j ·1 '

: !

I, :.1

r ~----T

817 824

J: ~ ,

I'

Iii

, !

II I ~ J

i :i


Accelerating voltage: 1998.rGrid voltage:

! Mirror voltage ratio: Guide wire 0: Extraction delay time:

Reflector(r Delayed Negative Manual

20000 V 74% 1.12 0% 200nsec

Acquisition mass range: 10 - 2000 Da Number of laser shots: 100/spectrum laser Intensity: 1569 laser Rep Rate: 20.0 Hz Calibration type: Default calibration matrix: 2.5-Dlhydroxybenzoic at low mass gate: Off Timed ion selector: Off

Digitizer start time: Bin size: Number of data points: Vertical scale 0: Vertical offset Input bandwidth 0:

Sample well: Plate 10: Serial number: Instrument name: Plate type filename: lab name:


3.284 0.5nsec 82965 50mV -2.5% SOOMHz

32 E 6263 Voyager-DE PRO C:\vOYAGER\100 well ~ UT-Knoxville

9136.93 32803.2 2469.43 735.75 200 1.381e-007 1.471e-008 0.002237 8 687

L~o 831


S~Y\'\,3 1001

j

90~

~ ~

80

70

60

S 50 .E ~

40

30

20

10 I Css

Voyager Spec #1 [BP = 720.2, 20995}

C60 720.1511

~ n 11 I: ,.

721.1~29

Ii II Ii

P II ~

I! ml~ ;1 II

!iii

HI ill 1\ 1

" II Ii 1'\7~1.3519 L I' I! " ~ )

eG.O 0 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

Mass (m/z)

800 shots D:\ ... \NaCOA2 0OO1.dat Acquired: 13:53:00. December 01. 2003 \\ t:t-/o~

77

~ III s::

S pedYUN\. t1 100

1 I

901

··1 ro1

60

~ 50 .5 #

40

30

I

2°1 j

((,0 720.2586

I

721.2592 !

! I i I I

H II II 722.2617 I ' , n

~ " I

vuyager ~pec 1flLI:W = ILU.J, 2~{Ulj

736.2527

C~O C6001.

10

CS8 696.2658 752.2338

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

100 Spe~5 C&o

720.2570

I I 721.2596

90

80

10

I II 722.2634 I

I III 60

~

~1 ! VI c .! I .E ~ j

l. 40-1 i

j

jll

~1 t~~

20-1 11,123.2751 C 660 736.2526

I 10-\ Csa lit J 737.2567 C ~ 22.817 I 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

100

90

80

70

60

;:.. :t::

'" c

i 50

~

40

30

20

10

<..~ 720.2570

I I 721.2596 p

II I' ~ ;1 i

I n I H

I II

I 'I

1 11 J 1!

I Ii , 11 H Ii II H :1 !I 722.2634

'111+ I.

Ii 4

1':1 i I .4615 , /' I ! I i ,

\

1 II

1:/1 I i I .1 I i. '

'I I , I'll, ! I· II 1 7~il.~762

f: I Ii

III i' t~' C~oO

736.2526 Ilf~IH232751 I II II 11 CS10 '0 'Z.. j ~~ \i \J2.8175 C 0 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~ ~ 707.0 719.2 l15 t,l 743 6 0 • .1 • 755.8 768.0

Mass (m/z)

00 shots :\. .. \NaCOC 0001.dat cquired: 13:58:00. Oecember01. 2003

\\ I r=r I 0'3

..----5pe.&~b 100]

CE,Q voyager ~pec 111LI:W = 12U.3, 55444]

720.~

I 722.2940 90

80

70

6°1 (58

j 696.3044

~ 1697.3008 III c

III i737.3019

0) 50 -.5 -.e.

40i II 117?~R~1

30

5101 C 0 19.....-"l 60 2.

20 C5' 672.3089 Cs,<x C-=to

CSq 10 673.3058 840.3215

648.3246

ok L~\JI.J'~l"""~~ v ~ ... -":, ... ·-_ ... ~· .. ""., __ I[ 632.0 705.8 779.6 853.4 927.2 1001.

Mass (m/z)

800 shots D:\ ... \NaCOC2 0001.dal Acquired: 14:00:00. December 01, 2003 l\/r:1-/D3

~ '" c: j! .5 '#-

100

1 90

80

70

60

50

40

30

20

.736.3008

~t.OO 11

1\ 737.3019

!J :1

I'I. t'

! ~ 11 Ii ,I II 11 'I·' II i II r! P It n II II I

!I II II I

II II II l741.3064

Ii I 7383025 I

vuyc&yttr .,pec R'ILI:W = I.o!U.;j, !>!>444J

I I ( "0 I i II S1] 'l.. ;1 I!, 740.~119 c 01-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 ~ 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 I ' ;i I I! i i !1!: 'I Ii I !1 i :\ 00 II lIt 735.b1182/ I ! I I! i ~ 1'1 ~l 1\ 746 3015 ' 'i ,\ C5G~3 758.2985 CfO " I I I II "I I I' il II 1',

I! :\ Ii I t ,I \ II \738 5344\ i \ 11.742.515J\ If ~ ii ,il II ?56. 58 ~ \761.2963 ~-~ ~ ! t I, :I I I, I\! I \ I \ I ~\ t. 1 i· Ii ,I i: 1 ~ 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, 1 i ~ 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

~ ell C

100

90

80

70

60

.! 50

.5 "e •

40

20·"

10

• V1U~t;;i' "'..,.:00,,", "" tL"". - t .. v.v, ""''''''''''I'''Y''''I'J

CS10, t04

·2643

I jf a II

~ !iill I iI

53053

804.~

f ,:1 iillli, Ii ii I ;

1,1 :1. 1'111 • i, I : I" 'I ,'f : i lid ,I . I"

i \ ! \i I II f I' \ I ,. I ,,, I til! 11 j I

797.307811\ \ 11 ,II, ,I ! i Ii! I Ii I I ! ~

Ill! III HI I \1 i I'

I I " II 787ijj I' ~

, \11

1111 ,! \ ! I I · il ii! I! III ii' Ill' ii',' ~I, ,1\1 K I' ~II ~ i I 1 '1 'I u ' "

" I' i ' , ' ' " I '

ir ~~LI iii 11 ~ " I i I :!I , , il! ~ I I" ,"' I J

I m I '1/ P Iii ~ '~I ~~~~~l ~f~ v

~ I!t III'

I r !III J I

III II ~!l~ Ii' I;! I

" i I I I i I I ; I ~ II ! ~ 1 \1/111 j

~h I I"

~\J!\~ ~il'~' 1~I,i J dl: l! I \ lA, :II~ g,

~ l'

Cb 840.3215

841.3276

842.3209

.1 , , , , I ( 782.0 799.4 816.8 834.2 851.6

Mass (mfz)

n/l=rI03 800 shots D:\ ... \NaCOC2 0001.dat Acquired: 14:00:00. December 01, 2003

~ Ui c CU -.5

:::!! 0

1001

~1 J

I

70

60

50

40

30

20

1.J

S?<2-~iV\. ~ 719.8467

CEO 720.8471

U 1721.8504 ,

I' ! , I

IiI II Ii 11121.0564

iLl Ijl 't'l I.jl

III 1.1 il!l II !11722.8628 II'

-~~-, --- --J

C600 736.8303

jlll~ H~

• 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

751.8096 ':I-5t C~~ C Oli ' C600z. 767.7845 1-61. --oil 60 892 796.8370

753.8215 I! -.:rvt785.7

I:\ ... \C60blank2 0OO1.dat .cquired: 13:49:00, December 01,2003

"B~"\\ Ir=t/03

Mass (mfz)

---.-----------------------------------------------------------

Works Cited

1. Allen, Kim. "Endohedral" Fullerenes. 2003. 27 November 2003

<http://www.mindspring.coml-kimalllFuller/endo.html>

Danielle Garrett

2. Cientifica. Fullerenes: Technology White Papers nr.7 October 2003. 3 December

2003 <http://nanotechweb.org/nanowhitepapers/fullerenes WP.pdf>

3. Fullerenes. 1 December 2003 <http://members.tripod.coml-chem7/007.html>

4. MALDI-TOF MS. 1 December 2003

<http://www.bbf.iu.edu/servicesIMALDIlOI.pdf>

- 10-

Documents

12-2004 Endohedral Fullerenes - University of Tennessee system