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Covalent Functionalization of Multi-Layer Fullerenes (Carbon Nano-Onions)

Covalent Functionalization of Multi-Layer Fullerenes (Carbon Nano-Onions)

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An essay for the 2011 Undergraduate Awards Competition by Eoghan Delany. Originally submitted for Thesis at Trinity College, Dublin, with lecturer Dr. Silvia Giordani in the category of Life Sciences
An essay for the 2011 Undergraduate Awards Competition by Eoghan Delany. Originally submitted for Thesis at Trinity College, Dublin, with lecturer Dr. Silvia Giordani in the category of Life Sciences

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Published by: Undergraduate Awards on Aug 29, 2012
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10/27/2013

 
Covalent Functionalization of Multilayer Fullerenes (CarbonNano-Onions) using a Fluorescein-modified PolyethyleneGlycol Chain
ABSTRACTTwo contrasting methods for covalently functionalizingmultilayer fullerenes (carbon nano-onions) using a fluo-rescein-terminated polyethylene glycol (PEG) chain weredesigned and carried out. The first involved independentsynthesis of the fluorescein-PEG molecule with subsequentattachment to the carbon nano-onion, while the second in-volved its stepwise construction on the carbon nano-onionsurface. Subsequent characterization was used to compareand contrast both the effectiveness and efficiency of theabove methods. The resulting species display significantlyenhanced solubility and, with further functionalization,may have potentially attractive biomedical applications.
The extensive research and interest revolving around syntheticcarbon allotropes in the past two decades owes much to the dis-covery of the buckminsterfullerene in 1985
1
and carbon nanotubes(CNTs) in 1991
2
. The period described as the
―era of 
syntheticcarbon allotropes
3
has also seen the discovery of other, less fa-miliar carbon nanostructures such as the multilayer fullerene
4
,more commonly referred to as the carbon nano-onion (CNO) dueto its shell-like structure. It is reasonable to conclude that CNOshave not been subjected to similar research efforts as their fulle-rene or CNT relatives based upon the limited publications dealingwith these curious allotropes. However, despite this, possessionof several singular properties such as a graphene-like network of carbon atoms, a large surface area to volume ratio (934 m
2
 /kg), lowdensity and a multilayer morphology
5
mean CNOs are indepen-dently beginning to generate increasing interest regarding potentialapplications.A further advantage of CNOs is the diversity of their chemistry.Depending upon their method of formation, different trends inreactivity are apparent when dealing with CNOs. Small CNOs (6
 – 
8 shells, produced through annealing of nanodiamonds
6
) behavechemically in a manner similar to fullerenes, being predominantlyreactive towards nucleophiles. Their reactivity tends to decreasewith increasing shell number, however, as less strain is incurred onthe outermost surface and so larger CNOs (20
 – 
30 shells, pro-duced through arc discharge of graphite
7
) display a graphite-likereactivity.
8
Unlike CNTs, no helicity arises within the structure of a nano-onion and so the reactivity of a given sample is generallyuniform.This diversity in chemical reactivity is important when exploringpotential applications for CNOs. Applications in catalysis
9
, elec-tromagnetic shielding
10
, gas storage
7
and optical limiting
11
havebeen investigated previously. However, biomedical applicationsfor CNOs are essentially non-existent due to the ambiguity sur-rounding their cytotoxicity. Equally, like CNTs, CNOs displaypoor solubility and dispersibility in aqueous and organic solventsand so, in their pristine form, are not ideal biomedical agents.However, given the contrasts in reactivity between CNOs of dif-ferent sizes, a wide variety of methods are viable to chemicallyfunctionalize the surface of a CNO with simple hydrophilic moie-ties and subsequently increase its solubility. Methods previouslysuccessful in this regard include the 1,3-dipolar cycloaddition,
12
 direct fluorination,
13
[2 + 1] cycloaddition of nitrenes
14
or therecently developed
in situ
diazonium addition.
15
 Overcoming solubility issues gives rise to numerous biomedicalpossibilities involving CNOs. In our work, we explored the no-tion of CNOs as a novel cellular imaging unit or an agent of drugdelivery through design and synthesis of CNOs chemically func-tionalized with a fluorescein-terminated polyethylene glycol(PEG) chain. Initial functionalization involved the introduction of benzoic acid moieties onto the external surface of the CNOs
via
 the aforementioned
in situ
diazonium generation by Flavin
et al
 (Scheme 1). Whilst increasing the relative solubility of the sample,the modified CNOs also retained the potential for further functio-nalization. Exploiting this, two methods were investigated forintroduction of the fluorescein-PEG (Figure 1) onto the CNOsurface:1.
 
independent construction of the fluorescein-PEG andsubsequent attachment (through the formation of anamide bond) to the benzoic acid-functionalized CNOs.2.
 
stepwise construction of the fluorescein-PEG on thesurface of the benzoic acid-functionalized CNOs.In characterizing the resulting species, we considered not only theeffectiveness, but equally the efficiency, of each method in cova-lently functionalizing the CNOs.
 
2 _______________________________________ 
 
Scheme 1.
Benzoic acid functionalization of CNOs by in situ gener-ation of a diazonium species
 
 _______________________________________ 
Figure 1.
Fluorescein-PEG molecule as used in experimentalprocedures
 _______________________________________ 
The introduction of defects onto the graphitic surface (i.e. conver-sion of an sp
2
to an sp
3
carbon atom) of the CNOs can be visua-lized using Raman spectroscopic measurements. As fluorescencecauses significant background overtones and distortion, spectra areobtainable for the pristine CNOs (p-CNOs) and benzoic acid-functionalized CNOs (f-CNOs 1) only. Figure 2 compares spectrafor the CNOs prior to and after first functionalization, normalizedwith respect to the G band (1569 cm
-1
). A significant enhance-ment of the D-band (1352 cm
-1
) upon functionalization is indica-tive of disruption of the graphitic surface due to covalent functio-nalization. The increase in the D/G ratio from 0.27 to 0.60 sup-ports this conclusion further.
_______________________________________
Figure 2.
Raman spectra (
λ 
exc = 457 nm) of pristine CNOs and f-CNOs (1), focusing on the D and G bands.
 _______________________________________ 
Infrared (IR) spectra obtained for both methods establish covalentattachment with each step of either functionalization process.Figure 3 illustrates IR spectra corresponding to method 1, wherethe formation of the amide bond following attack of the primaryamine upon the acid carbonyl group, paramount to the validity of the method, is highlighted through the appearance of the C-NHstretch for an amide (1491 cm
-1
) within the f-CNOs (2) spectra.Further indication is seen with the C=O stretch for the amide at1663 cm
-1
.
 _______________________________________ 
Figure 3.
IR spectra of pristine CNOs, f-CNOs (1) and f-CNOs (2)in the solid state (KBr, 0.1%). For clarity purposes, the spectra havebeen baseline corrected.
 
 _______________________________________ 
 Figure 4 provides IR data obtained from the method 2*. Again,amide bond formation, observable through the C-NH at 1471cm-1 and C=O stretch at 1651 cm-1, upon addition of the mono-protected PEG chain (f-CNOs 3) establishes initial covalentfunctionalization. Subsequent removal of the Boc-protectinggroup is indicated through the disappearance of the C-C3 band(1193 cm-1) seen in the f-CNOs (3) spectrum and correspondingappearance of the C-NH2 stretch (1213 cm-1) for a primary aminein the f-CNOs (4) spectrum. [*Please consult the SupportingInformation for further notes regarding Figure 3].The primary means of estimating the efficiency of either methodinvolved thermogravimetric analysis. First derivative weight losscurves for method 1 (Figure 5) identify two distinct regions of weight loss upon combustion, namely the decomposition of thesurface functionalities (<400
o
C) and subsequently the graphiticscaffold (>500
o
C). With each functionalization process, initiallywith the benzoic acid moiety and finally the fluorescein-PEG (f-CNOs 2), it is evident that there is an increase in weight loss oc-curring below 400
o
C, indicative of the greater degree of surfacefunctionalization with each step.Further indication of successful functionalization is observablewith the distinct shift in the graphitic decomposition temperatureupon introduction of surface functionalities, attributable to thefact that defects disrupt the stable aromatic nature of the surfacebut also to the more oxidizable nature of the functionalities. Firstderivative TGA curves (Supporting Information) present similartrends for method 2, indicating that stepwise construction of the
 
3
fluorescein-PEG on the CNO surface is also a viable method of synthesising the final product.
_______________________________________
 
Figure 4.
IR spectra of f-CNOs (1), f-CNOs (3) and f-CNOs (4) inthe solid state (KBr, 0.1%). For clarity purposes, the spectra havebeen baseline corrected and plotted on two separate axes.
_______________________________________
 
Figure 5.
First derivative TGA weight-loss curves for p-CNOs, f-CNOs (1) and f-CNOs (2) as synthesised through method 1.
 
 _______________________________________ 
 
Table 1 details the efficiency of both methods, based upon theirrespective final functionalization steps, by estimating the numberof functionalities per CNO as previously reported by Cioffi
et al
.
5
The results clearly suggest that the efficiency of method 2 (86%)is slightly superior to that of method 1 (72%), although the novelnature of the synthesis means optimisation may be required toverify this suggestion. Simple repetition of the functionalizationprocess might increase the respective values even further.However, based upon present data, it could be argued that thesuperiority of method 2 reflects the contrasting sterics involved ineither method.
 
UV-Vis measurements confirm the presence of the fluorophorewithin the final product for both methods. Both spectra display acharacteristic band at ~495 nm in the absorption spectra thatcorrelate well to the observed peaks at 521 nm in the emissionspectra, the excitation and emission wavelengths respectively forfluorescein. With regard to potential biomedical applications, thepresence of the emission peak is significant in demonstrating thatthe proximity of the fluorophore to the extensive aromatic scaffoldof the carbon nano-onion does not negate or dampen itsfluorescent ability.
_______________________________________
 
Table 1.
Degree of Functionalization of f-CNOs (1), f-CNOs (2), f-CNOs (4) and f-CNOs (5)
Sample Weight loss (%) Functionalities100
 – 
400
o
C per CNO
Method 1f-CNOs (1) 11.40 73f-CNOs (2) 32.30 52Method 2f-CNOs (4) 26.67 80f-CNOs (5) 40.38 69
_______________________________________
In conclusion, we have demonstrated two separate methods forcovalently attaching a fluorescein-modified PEG chain to thesurface of pristine CNOs. Both methods show reasonableefficiency based upon TGA estimations, with a stepwiseconstruction of the fluorescein-PEG upon the CNO surfacedisplaying a slightly superior efficiency. The result is a novelCNO species that display significantly enhanced solubility and,with further investigation into the toxicological properties andcontinued functionalization, may have potential biomedicalapplications in the future.
Supporting Information Available:
Experimental procedures,synthetic mechanisms and characterization are given for all syn-thesized compounds including IR, Raman, TGA, UV-Vis absorp-tion and emission where relevant for the f-CNOs, as well as fur-ther notes regarding Figure 4. This information is available free of charge via the Internet at http://pubs.acs.org 
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