The only stable isomer of the higher fullerene C76 of D2 symmetry was isolated from carbon soot by the new and advanced extraction and chromatographic methods and processes. Characterization of the isolated C76-D2 was performed by the IR(KBr) and UV/VIS method in the absorption mode. All of the experimentally observed infrared and electronic absorption bands are in excellent agreement with the theoretical calculations for this fullerene. The molar absorptivity ε and the integrated molar absorptivity Ψ of the observed entire new series of various characteristic, both deconvoluted and convoluted IR absorption bands of the C76-D2 isomer, in different integration ranges were determined. In addition, the molar extinction coefficients of its UV/VIS absorption bands were determined. The obtained novel IR and UV/VIS spectroscopic parameters are significant for the quantitative assessment of C76-D2. All the presented data are important both for its qualitative and quantitative determination, either in natural resources on Earth and in space or in artificially synthesized materials, electronic and optical devices, optical limiters, sensors, polymers, solar cells, nanophotonic lenses, diagnostic and therapeutic agents, pharmaceutical substances, for targeted drug delivery, incorporation of metal atoms, in biomedical engineering, industry, applied optical science, batteries, catalysts and so forth.
Ministarstvo Prosvete, Nauke i Tehnološkog RazvojaUniversity of Belgrade450091. Introduction
Fullerenes C60 and C70 were first detected in space [1–14] and quantified [5, 6] by means of IR spectroscopy [1–27]. They were found in a series of space environments and astrophysical objects [1–27], such as certain planetary [4–7] and protoplanetary nebulae [7], carbon-rich stars including also R-Coronae Borealis stars [8, 9], postasymptotic giant branch stars, and young stellar objects [10], in the interstellar medium, in reflection nebulae [1–3, 11–14], as well as in some resources on Earth [3, 15].
For the identification of the basic fullerenes, the knowledge of the infrared band position and band widths as well as the evolution of these parameters with temperature was necessary [1–25]. Quantitative assessment of fullerenes C60 and C70 required knowledge about intensities of their IR absorption bands [3, 5, 6, 26–28].
Their relative abundance in space, for example, an abundance of about 0.35% in certain planetary nebulae, was estimated through the molar absorptivity and integrated molar absorptivity of the infrared maxima measured in laboratory [5, 6].
Another useful method for the identification and quantitative determination of fullerenes can be electronic absorption spectroscopy due to their transitions in the spectral range comprised between 190 and 1500 nm, where it is known that the space is rich in a number of yet unassigned electronic transitions belonging to molecules and radicals [28, 29].
It should be expected also that the higher fullerenes can be found and quantified in space because of their exceptional stability toward high temperatures and cosmic rays [1–3, 30–34], as well as the possibilities of their formation through coalescence of smaller fullerenes by laser ablation of carbon and dehydrogenation of hydrogenated fullerenes, fulleranes [1–3, 30–37].
The IR and electronic absorption spectra as well as their dependence on temperature that are necessary for the qualitative detection of the higher fullerenes, such as C76-D2, the only stable C76 isomer of D2 symmetry [1–3, 38–61], isolated by the new advanced chromatographic methods [2, 3, 38–45], were studied in the previous works [2, 3, 38–61].
It is important to mention that all of the experimentally observed infrared and electronic absorption bands of the isolated C76-D2 in this research [2, 3, 38–44] are in excellent agreement with the theoretical calculations for this molecule [46–49].
The aim of this study was to determine the novel IR and UV/VIS spectroscopic parameters that are necessary for the quantitative assessment of C76-D2.
In the previous work [3], the molar extinction coefficients and the integrated molar extinction coefficients of the main convoluted or integral IR absorption bands with some shoulders of this fullerene were determined and reported together with the relative intensities.
Excellent agreement was found between the relative intensities of the main characteristic absorption maxima calculated from ελ and from the Ψλ values in adequate integration ranges [3].
In this article, the molar absorptivity and the integrated molar absorptivity of the entire series of all the observed various characteristic and new deconvoluted or separated absorption maxima and shoulders were determined. In addition, the integrated molar absorptivity of several convoluted absorption bands with some shoulders of C76-D2 in different and new relevant integration ranges were determined. The molar extinction coefficients of its UV/VIS absorption bands were also determined.
The molar absorptivity and the integrated molar absorptivity in the applied integration ranges of the corresponding main and characteristic absorption bands, both separated and integral, in all the IR and UV/VIS spectra of the chromatographically purified C76-D2 samples from this research [2, 3, 38–44] are in excellent agreement.
The obtained new research results in the recent [3] and current IR and UV/VIS spectroscopic study of the higher fullerene C76-D2 are important for its quantitative determination.
All the presented IR and UV/VIS data will significantly contribute to better understanding of the spectroscopic properties of C76-D2, which is important both for its identification and quantitative assessment, either in natural resources or in artificially synthesized materials.
2. Experimental Methods
In the first phase of this research, C60, C70 [21–23], and the higher fullerenes, mainly C76 and C84 [2, 3, 38–45], were Soxhlet extracted with a series of different and previously unapplied solvents or combinations of solvents from the samples of the carbon soot produced by an electric arc (MER Corporation, Tucson, USA). The extraction procedures were performed until the complete disappearance of color in a Soxhlet extraction thimble. Solvents used were n-heptane, toluene, chlorobenzene, p-xylene, a mixture of o/m/p-xylene, and pyridine, as well as the successive use of toluene and chlorobenzene and p-xylene and pyridine. The yields as well as the compositions of all the extracts were determined by spectroscopic and chromatographic methods. The procedures for increases of fullerene yields and for additional selective extraction of higher order fullerenes were found [2, 3, 21–23, 38–45].
In the second phase, C60, C70, and the higher fullerenes C76 and C84 (the only stable C60-Ih, C70-D5h, and C76-D2 isomers of the first three mentioned fullerenes and the most abundant, stable C84 isomer of D2 symmetry) were chromatographically separated from the obtained extracts of the carbon soot on the activated Al2O3 columns by new and advanced methods [2, 3, 38–45].
The main difference and advantage of these methods [2, 3, 38–45], in comparison to previous methods under pressure [53–61], is the isolation of the purified stable isomers of the higher fullerenes C76 and C84 (the C76-D2 and C84-D2:22 isomers) successively after the basic fullerenes in one phase of each of the processes under atmospheric pressure and smaller flow of 1.5 mL/min in increased milligram yields. The elution was performed continuously with several different original, defined gradients of solvents: from pure hexane or 5% toluene in hexane to pure toluene. The amounts of the initial materials used were as follows: fullerene extracts, 10 mg, and finely granulated Al2O3, 50 g, activated for 2 h at 105°C, and eluent (1.5 to 1.75 L) per chromatographic separation [2, 3, 38–45]. Starting from 10 mg of the soluble soot extract, in average ca. 1 mg of C76 and ca. 1 mg of C84 were isolated in purified form per one chromatographic process or up to few milligrams in some cases. The time spent on the purification processes was from 16.7 to 19.4 h [3, 42, 43].
The other advantages of the developed methods [2, 3, 38–45], in comparison to previous methods [53–61], are the use of significantly smaller amounts of the initial materials as well as less expensive laboratory equipment. In these methods [2, 3, 38–45], the entire materials and energy expense, the time spent on the purification processes, and environmental pollution were decreased using smaller amounts of less toxic solvents. The yields and the purities of the isolated fullerenes were increased or maximized [2, 3, 42, 43].
Purification of the higher fullerenes under pressure on a preparative scale, either by flash chromatography or by HPLC, generally required larger amounts of the initial materials repeated chromatography, and the fullerenes were obtained in smaller yields [53–61] compared to our results [2, 3, 38–45]. This was discussed and presented in more detail in the previous articles [3, 42, 43].
2.1. Measurement of the IR Spectra, the Molar Absorptivity, and Integrated Molar Absorptivity of Deconvoluted and Convoluted Absorption Bands of C76-D2
The IR spectra of the C76-D2 samples, isolated by the new and advanced chromatographic methods and processes [2, 3, 38–44], were recorded on a Thermo Scientific FT-IR spectrometer Nicolet IR-6700 by the KBr disk technique in the range of 400–2000 cm−1 at a resolution of 1 cm−1 in the transparence mode formerly for its qualitative detection [2]. In the previous [3] and this article, the IR spectra of the isolated C76-D2 samples were recorded in the absorption mode for determination of novel parameters for its quantitative determination.
Chromatographically isolated C76-D2 sample (0.196 mg) was mixed with 100.4 mg of KBr. The obtained powder was compressed at 4 tons/cm2 with the Perkin Elmer press. The resulting pellet was placed in the FT-IR spectrometer. Measurement of the intensities (heights) of the entire new series of C76-D2 absorption bands as well as of the integrated intensities of both all deconvoluted absorption maxima and shoulders and of convoluted absorption bands with some shoulders of this fullerene in different integration ranges with automatic subtraction of the baseline was made possible through the OMNIC software from Thermo Scientific, dedicated to the FT-IR spectrometer. The method and software used in this study have also been recently used for the measurement of relative intensities of IR absorption bands of the basic fullerenes C60, C70, and their hydrogenated derivative fulleranes [25–27], as well as of the main convoluted absorption bands of the higher fullerenes C76-D2 and C84-D2:22 [3].
The mass of the resulting pellet was 100.6 mg, and the percentage of carbon determined by the elemental analysis was 0.195. Its measured thickness (b) was 1.205 mm~0.1205 cm, diameter (R) was 0.7 cm, and the half diameter (r) was 0.35 cm.
The volume of the pellet (V) was determined from the abovementioned r and b parameters by the equation V=r2πb. The obtained values of the volume and the thickness of the pellet were also confirmed using KBr density (2.753 g/cm3) [3, 26] and the mass of the pellet.
Concentration (c) of fullerene C76 in this pellet was calculated using the above given mass of C76 in the pellet, its molar mass of 912.76 g/mol, and the volume of the pellet. The bc−1 value determined for the applied C76-D2 sample in KBr pellet from the abovementioned experimental parameters was 1409.9 L cm−1 mol−1, ca. 1410 L cm−1 mol−1.
2.2. Measurement of the UV/VIS Spectra and the Molar Absorptivity of Absorption Bands of C76-D2
The UV/VIS spectra of the chromatographically isolated C76-D2 samples by the new improved methods were recorded on the GBC Cintra 40 spectrophotometer in the region from 200 to 900 nm for its qualitative detection previously [2, 38–43], as well as for the quantitative determination in this article. Solutions of fullerene C76 in hexane, conc. 10−5 mol/dm3 were used. The thickness of the cuvette was 1 cm.
The bc−1 value determined for the C76-D2 sample in n-hexane from the abovementioned experimental parameters was 100,000 L cm−1 mol−1.
3. Results and Discussion
In this article, the molar absorptivity and the integrated molar absorptivity of the observed series of various characteristic and new for both deconvoluted and convoluted IR absorption bands in different integration ranges of the C76-D2 isomer were determined. The molar absorptivity of its UV/VIS absorption bands was also determined.
The original characteristic and new IR spectrum of the chromatographically isolated C76-D2 sample are obtained in the absorption mode in this article, Figure 1, in order to find the abovementioned novel parameters for its quantitative determination. This spectrum was previously provided in transparence mode [2] for its qualitative determination.
The IR(KBr) absorption spectrum of the isolated C76-D2 sample.
The main three most intense dominant C76 maxima registered in this research [2, 3, 38–44] appear at 967 cm−1; 1082 cm−1 with the shoulders at 1122, 1101, 1056, and 1024 cm−1; and at 1187 cm−1 with the shoulders at 1209 and 1162 cm−1 in the central part of the region relevant for the identification of fullerenes from ca. 400 to 1800 cm−1. Characteristic absorption bands unique to C76 are present in the first relevant part of the spectrum at 892 and 823 cm−1 with a neighboring band at 789 cm−1, at 705 cm−1 with the shoulders at 743 and 729 cm−1, at 646 cm−1 with a shoulder at 661 cm−1, followed by a maximum at 603 cm−1. Several other C76 absorption bands appear at 533 cm−1 with a shoulder at 555 cm−1, at 487 cm−1 with a shoulder at 507 cm−1, at 436 cm−1 with a shoulder at 461 cm−1, and at 405 cm−1. Pronounced and intense maxima are present in the higher frequency region at 1386 cm−1 with the shoulders at 1399 and 1364 cm−1, at 1461 cm−1 with a neighboring band at 1493 cm−1, and at 1633 and 1734 cm−1 with the shoulders at 1681 cm−1 and 1713 cm−1, respectively. Maximum at 1312 cm−1 appears, followed by the bands at 1276 cm−1, with a shoulder at 1291 cm−1 and at 1247 cm−1. Weak absorption features are also observed at 1552, 1533, and 1339 cm−1. Complete absorption [2] in this spectrum corresponds to the theoretical predictions for C76-D2, as well as for its dianion [46, 47].
The IR spectra of all the chromatographically isolated C76-D2 samples from this research have similar properties. All the observed vibrational frequencies and the general pattern of these spectra [2, 3, 38–44] are in agreement with the semiempirical QCFF/PI and DFT theoretical calculations for C76-D2, as well as for its dianion C76-D22− [2, 3, 42–44, 46, 47].
From the presented IR absorption spectrum Figure 1, the values of absorbance Aλ have been determined for all the separated absorption maxima and shoulders using the OMNIC software subtracting automatically the base line. Determination of molar absorptivity of the entire series of deconvoluted IR absorption bands of the C76-D2 isomer at a given wave number ελ was achieved through (1), previously applied for its main convoluted infrared absorption bands for C60 and C70, as well as hydrogenated fullerenes [3, 25–27, 62], according to Lambert and Beer law using the absorbance Aλ read at a given wave number.
(1)ελ=Aλbc−1.
It was found that the peak height measurements that correspond to the absorbance A are sensitive to changes in the resolution of the spectrometers used [25–27, 62] and to changes in temperature and smaller chemical shifts of characteristic absorption bands (within 1–3 cm−1) in some cases. Theoretical calculations [46, 47] also predict the possibility of appearance of very close or different out of the numerous possible IR vibration modes C76-D2. The measurement of the integrated intensity that represents the area below a corresponding absorption band measured in adequate integration range is much less sensitive to instrumental resolution [25–27, 62] and temperature as well as smaller shifts of absorption bands than the peak height measurement.
Thus in this article also, the integrated intensity of both deconvoluted and convoluted absorption bands in different integration ranges was determined from the presented infrared spectrum in a mode of the isolated C76-D2 sample, Figure 1, using the OMNIC software and subtracting automatically the baseline. The integrated molar absorptivity expressed in cm mol−1 or 10−5 Km mol−1 was calculated by (2), previously applied for its main convoluted absorption bands for the basic fullerenes as well as for fulleranes [3, 25–27, 62].
(2)Ψ=∫ελdλ.
In this equation, λ is the wavelength, and ελ is the molar absorptivity integrated over the whole band. In practice, by substituting (1) into (2), we get [3, 25–27, 62]
(3)Ψ=bc−1∫Aλdλ.
The molar absorptivity and the integrated molar absorptivity in adequate integration range calculated according to (1) and (2) of all the observed [2, 3] deconvoluted absorption bands of the higher fullerene C76-D2 in this spectrum are reported in Table 1.
The molar absorptivity and the integrated molar absorptivity in adequate integration range of deconvoluted absorption bands of C76-D2.
νa,b(cm−1)
ελ(L cm−1 mol−1)
Int. range(cm−1)
Ψ(Km mol−1)
1733.8
129.711
1758–1721
1.097
1712.6
81.774
1721–1699
0.017
1680.7
91.643
1684–1678
0.004
1633.1
188.927
1678–1573
6.549
1551.6
16.919
1562–1543
0.022
1533.4
14.099
1542–1513
0.025
1493.4
252.372
1512–1481
2.242
1461.1
320.047
1478–1432
3.953
1398.7
270.701
1416–1396
0.265
1385.6
303.128
1393–1371
0.850
1364.2
146.630
1368–1349
0.230
1338.7
29.608
1349–1326
0.024
1312.4
112.792
1326–1300
0.884
1290.5
81.774
1296–1283
0.010
1275.6
91.643
1282–1263
0.096
1247.6
111.382
1260–1231
0.568
1208.6
174.828
1222–1202
0.234
1187.0
384.903
1200–1168
3.423
1161.6
159.319
1167–1141
0.254
1122.0
131.121
1139–1112
0.219
1101.0
140.990
1110–1099
0.028
1081.6
370.804
1098–1063
3.810
1056.4
112.792
1062–1048
0.027
1024.2
115.612
1039–1005
0.179
967.0
634.455
996–926
13.765
892.2
88.824
908–871
1.107
823.4
64.855
848–809
1.376
788.8
43.707
803–774
0.219
742.9
54.986
750–736
0.010
729.3
67.675
736–717
0.014
704.8
84.594
715–679
0.460
661.1
66.265
678–655
0.240
645.8
76.135
655–632
0.031
602.9
132.531
627–575
1.246
555.5
112.792
570–548
0.038
532.7
126.891
545–520
0.300
507.1
104.333
518–499
0.062
486.6
107.152
499–471
0.344
460.6
71.905
469–453
0.037
436.0
102.923
450–422
0.637
405.2
179.057
421–400
1.799
a[2]. b[3].
The integrated molar absorptivity of convoluted absorption maxima with some absorption shoulders of C76-D2 in determined, different, and new relevant integration ranges for its quantitative determination as well as identification is presented in Table 2.
The integrated molar absorptivity in determined integration ranges of convoluted absorption maxima with some absorption shoulders of C76-D2.
ν(cm−1)
Int. range(cm−1)
Ψ(Km mol−1)
1733.8–1712.6
1757–1699
2.163
1633.1–1680.7
1683–1573
6.861
1461.1–1493.4
1512–1432
9.907
1385.6–1398.7
1423–1371
4.457
1385.6–2 ab. shouldersa
1421–1349
13.163
1275.6–1290.5
1298–1264
0.341
1187.0–2 ab. shouldersb
1222–1143
8.481
1081.6–4 ab. shouldersc
1139–1004
7.979
704.8–742.9
774–681
2.168
645.8–661.1
678–632
0.587
532.7–555.5
571–518
0.735
486.6–507.1
518–470
0.746
436.0–460.6
468–422
0.946
aAbsorption maximum at 1386 cm−1 with two absorption shoulders at 1399 and 1364 cm−1. bAbsorption maximum at 1187 cm−1 with two absorption shoulders at 1209 and 1162 cm−1. cAbsorption maximum at 1081.6 cm−1 with four absorption shoulders at 1122, 1101, 1056, and 1024 cm−1.
The molar absorptivity and the integrated molar absorptivity in the mentioned adequate integration ranges of the corresponding main and characteristic absorption bands, both deconvoluted and convoluted, in all the obtained IR spectra of the chromatographically purified C76-D2 samples from this research [2, 3, 38–44] are in excellent agreement.
In this article also, the original UV/VIS spectrum of the chromatographically isolated C76-D2 sample previously applied for its identification [39, 40] is presented in Figure 2 for determination of the abovementioned parameters for its quantitative assessment.
The UV/VIS spectrum of the isolated C76-D2 sample [39, 40].
Relevant C76 absorption maxima [2, 38–43] of decreased relative intensity in comparison to the spectra of the previous fractions C60 and C70 [21–23] appear at 258 and 328 nm [39, 40]. An inflection point occurs at 210 nm, whereas the most intense dominant UV absorption is moved to the region below 200 nm, which is characteristic for C76. Pronounced C76 absorption shoulder is present at 275 nm followed by less intense shoulders at 358 and 378 nm. In the visible part, weak absorption band appears at 405 nm; the absorption is prolonged to 900 nm. Complete absorption in this spectrum [39, 40] corresponds to the theoretical predictions for C76-D2 [48, 49].
The UV/VIS spectra of all the chromatographically isolated C76-D2 samples from this research have similar properties. All the observed absorption bands and the general pattern of these spectra [2, 3, 38–44] are in agreement with the semiempirical QCFF/PI and DFT theoretical calculations for C76-D2 [2, 42, 43, 48, 49].
From the UV/VIS spectrum [39, 40] presented in Figure 2, the values of absorbance Aλ of the absorption bands of C76 have been determined. The values of molar absorptivity ελ were calculated according to (1) previously applied for the basic fullerenes and their radical cations as well as fulleranes [28, 29, 62] and reported in Table 3.
The molar absorptivity of absorption bands of C76-D2.
λa,b(nm)
ελ(L cm−1 mol−1)
210.0
140,000
257.7
41,500
275.0
26,500
327.8
11,000
358.0
6000
378.0
4500
405.0
3100
a[39]. b[40].
The molar absorptivity of the observed main and characteristic absorption bands in all the obtained UV/VIS spectra of the chromatographically purified C76-D2 samples from this research [2, 38–43] is in excellent agreement.
The aforementioned change of the spectral parameters of the C76-D2 isomer compared to C60 and C70 can also lead to changes of refraction features that can be useful for its application in the fullerene-based optoelectronic materials and devices, such as nanophotonic lenses with advanced properties. The results of the recent investigations [63–67] show also that fullerene nanomaterials incorporated in standard, basic (commercial) materials, such as poly(methyl methacrylate) for the rigid gas permeable and poly(2-hydroxyethyl methacrylate) for the soft contact lenses, improve their wettability.
4. Conclusion
In this study, the only stable isomer of the higher fullerene C76 of D2 symmetry was isolated from the carbon soot by new and advanced extraction and chromatographic methods and processes [2, 3, 38–44]. The original and new IR and UV/VIS spectra [39, 40] of the isolated C76-D2 sample were obtained in the absorption mode over the relevant regions from 400 to 2000 cm−1, as well as from 200 to 900 nm, and presented for determination of novel parameters for its quantitative assessment.
All of the experimentally observed infrared and electronic absorption bands of the isolated C76-D2 samples from this research [2, 3, 38–44] are in excellent agreement with the theoretical calculations for this molecule [46–49], which is important for the qualitative detection [2, 3].
In the previous article [3], the molar extinction coefficients and the integrated molar extinction coefficients of the main convoluted IR absorption bands of the higher fullerene C76-D2 were determined and reported together with the relative intensities.
Excellent agreement was obtained between the relative intensities of the main absorption maxima calculated from ελ and from the Ψλ values in adequate integration ranges [3].
In this article, the molar absorptivity and the integrated molar absorptivity of the entire series of the observed various characteristic and new deconvoluted IR absorption maxima and shoulders of the isolated C76-D2 isomer were determined at room temperature in the KBr matrix. In addition, the integrated molar absorptivity of several convoluted absorption bands with some shoulders in different and relevant integration ranges was determined. The molar absorptivity of its UV/VIS absorption bands was also determined.
It should be mentioned that the molar extinction coefficients and the integrated molar extinction coefficients in the mentioned adequate integration ranges of the corresponding main and characteristic absorption bands, both separated and convoluted, in all the IR and UV/VIS spectra of the chromatographically purified C76-D2 samples from this research [2, 3, 38–44] are in excellent agreement.
The obtained new IR and UV/VIS spectroscopic results and parameters of the higher fullerene C76-D2 are important for its quantitative determination.
All the presented data will significantly contribute to better understanding of the IR and UV/VIS spectroscopic properties of the C76-D2 isomer. This is important both for its identification and quantitative assessment, either in natural resources or in artificially synthesized materials, electronic and optical devices, optical limiters, sensors, polymers, solar cells, nanophotonic lenses, diagnostic and therapeutic agents such as for diabetes, incorporation of metal atoms, targeted drug delivery in biomedical engineering, industry, applied optical science, batteries, catalysts, synthesis of diamond, and so forth.
Additional Points
Figure 2 is an intellectual property of Tamara Jovanovic and Djuro Koruga. The new technological process for extraction, chromatography, and characterization of the basic and the higher fullerenes from carbon soot, the intellectual property office of Serbia, Belgrade, no. 985/09 A-59/09, 2009.
Conflicts of Interest
The authors declare that there are no conflicts of interest regarding the publication of this paper.
Acknowledgments
The authors are grateful to Professor Dr. Branimir Jovancicevic, Department of Applied Chemistry, Faculty of Chemistry, University of Belgrade, for valuable help and support during the experimental part of the work and to the Ministry of Education, Science and Technological Development of the Republic of Serbia and the University of Belgrade for financial support of this research (Project III 45009).
CataldoF.HafezY.Iglesias-GrothS.FT-IR spectra of fullerenes C76, C78 and C84 at temperatures between −180°C and +250°C2014221090191310.1080/1536383X.2012.7494552-s2.0-84898063156JovanovićT.KorugaĐ.JovančićevićB.Recent advances in IR and UV/VIS spectroscopic characterization of the C76 and C84 isomers of D2 symmetry201420141170131210.1155/2014/7013122-s2.0-84963902497JovanovićT.KorugaĐ.JovančićevićB.The IR spectra, molar absorptivity, and integrated molar absorptivity of the C76-D2 and C84-D2:22 isomers2017201710436074610.1155/2017/43607462-s2.0-85018833283CamiJ.Bernard-SalasJ.PeetersE.MalekS. E.Detection of C60 and C70 in a young planetary nebula201032959961180118210.1126/science.11920352-s2.0-7795629642820651118García-HernándezD. A.Iglesias-GrothS.Acosta-PulidoJ. A.ManchadoA.García-LarioP.StanghelliniL.VillaverE.ShawR. A.CataldoF.The formation of fullerenes: clues from new C60, C70, and (possible) planar C24 detections in Magellanic cloud planetary nebulae20117372L3010.1088/2041-8205/737/2/L302-s2.0-80051775182García-HernándezD. A.VillaverE.García-LarioP.Acosta-PulidoJ. A.ManchadoA.StanghelliniL.ShawR. A.CataldoF.Infrared study of fullerene planetary nebulae2012760210710.1088/0004-637X/760/2/1072-s2.0-84869176374ZhangY.KwokS.Detection of C60 in the protoplanetary nebula IRAS 01005+79102011730212610.1088/0004-637X/730/2/1262-s2.0-79953698762García-HernándezD. A.RaoN. K.LambertD. L.Are C60 molecules detectable in circumstellar shells of r coronae borealis stars?2011729212610.1088/0004-637X/729/2/1262-s2.0-79952180037ClaytonG. C.KellyD. M.LacyJ. H.Little-MareninI. R.FeldmanP. A.BernathP. F.A mid-infrared search for C60 in R Coronae Borealis stars and IRC+10216199510952096210310.1086/1174352-s2.0-0010112636RobertsK. R. G.SmithK. T.SarreP. J.Detection of C60 in embedded young stellar objects, a Herbig Ae/Be star and an unusual post‐asymptotic giant branch star201242143277328510.1111/j.1365-2966.2012.20552.x2-s2.0-84863411148SellgrenK.WernerM. W.IngallsJ. G.SmithJ. D. T.CarletonT. M.JoblinC.Confirmation of C60 in the reflection nebula NGC 702320114620921410.1051/eas/11460222-s2.0-84874355342HerbigG. H.The search for interstellar C602000542133434310.1086/309523Iglesias-GrothS.Fullerenes and the 4430 Å diffuse interstellar band20076612L167L17010.1086/5188322-s2.0-34250879524FoingB. H.EhrenfreundP.Detection of two interstellar absorption bands coincident with spectral features of C60+1994369647829629810.1038/369296a02-s2.0-0028243430Hameroff S.WithersJ.LouftyR.SundareshanM.KorugaD.1993Amsterdam, The NetherlandsElsevier Science PublishersKrätschmer W.LambL. D.FostiropoulosK.HuffmanD. R.Solid C60: a new form of carbon1990347629135435810.1038/347354a02-s2.0-0025187901KrätschmerW.FostiropoulosK.HuffmanD. R.The infrared and ultraviolet absorption spectra of laboratory produced carbon dust: evidence for the presence of the C60 molecule19901702-316717010.1016/0009-2614(90)87109-52-s2.0-25044479020CoxD. M.BehalS.DiskoM.GorunS. M.GreaneyM.HsuC. S.KollinE. B.MillarJ.RobbinsJ.Characterization of C60 and C70 clusters199111382940294410.1021/ja00008a0232-s2.0-5244369769BethuneD. S.MeijerG.TangW. C.RosenH. J.GoldenW. G.SekiH.BrownC. A.de VriesM. S.Vibrational Raman and infrared spectra of chromatographically separated C60 and C70 fullerene clusters19911791-218118610.1016/0009-2614(91)90312-W2-s2.0-33751290408HareJ. P.DennisT. J.KrotoH. W.TaylorR.AllafA. W.BalmS.WaltonD. R. M.The IR spectra of fullerene-60 and -701991641210.1039/c399100004122-s2.0-37049078263JovanovicT.KorugaD.JovancicevicB.Simic-KrsticJ.Modifications of fullerenes extractions and chromatographies with different solvents200311438339410.1081/FST-1200258572-s2.0-0348146152JovanovićT.KorugaD.PolićP.DevićG.Extraction, separation and characterization of fullerenes from carbon soot2003413596410.4028/www.scientific.net/msf.413.59JovanovicT.KorugaD.JovancicevicB.Simic-KrsticJ.Improvement in separation of nanostructured carbon clusters C60 and C7020032312914010.1142/S0219581X03001188CataldoF.Iglesias-GrothS.ManchadoA.Low and high temperature infrared spectroscopy of C60 and C70 fullerenes201018322423510.1080/153638310037829402-s2.0-77954283138Iglesias-GrothS.CataldoF.ManchadoA.Infrared spectroscopy and integrated molar absorptivity of C60 and C70 fullerenes at extreme temperatures2011413121322210.1111/j.1365-2966.2011.18124.x2-s2.0-84863839683CataldoF.Iglesias-GrothS.ManchadoA.On the molar extinction coefficient and integrated molar absorptivity of the infrared absorption spectra of C60 and C70 fullerenes201220319119910.1080/1536383X.2010.5333132-s2.0-84856336142CataldoF.Iglesias-GrothS.Garcia-HernandezD. A.ManchadoA.Determination of the integrated molar absorptivity and molar extinction coefficient of hydrogenated fullerenes201321541742810.1080/1536383X.2011.6297562-s2.0-84868128694CataldoF.García-HernándezD. A.ManchadoA.Iglesias-GrothS.Spectroscopy of fullerenes, fulleranes and PAHs in the UV, visible and near infrared spectral range20139S29729429610.1017/S17439213130160252-s2.0-84894678583Cataldo F.Iglesias-GrothS.HafezY.On the molar extinction coefficients of the electronic absorption spectra of C60 and C70 fullerenes radical cation201321210.17628/ecb.2013.2.1013-1018CioslowskiJ.Heats of formation of higher fullerenes from ab initio Hartree-Fock and correlation energy functional calculations19932163–638939310.1016/0009-2614(93)90114-G2-s2.0-0000784106CataldoF.StrazzullaG.Iglesias-GrothS.Stability of C60 and C70 fullerenes toward corpuscular and γ radiation2009394261562310.1111/j.1365-2966.2008.14369.x2-s2.0-62549104193Iglesias-GrothS.Hydrogenated fulleranes and the anomalous microwave emission of the dark cloud LDN 1622200636841925193010.1111/j.1365-2966.2006.10272.x2-s2.0-33744547135CataldoF.Iglesias-GrothS.On the action of UV photons on hydrogenated fulleranes C60H36 and C60D362009400129129810.1111/j.1365-2966.2009.15457.x2-s2.0-70449564547CataldoF.Iglesias-GrothS.2009Berlin, GermanySpringerYeretzianC.HansenK.DiederichiF.WhettenR. L.Coalescence reactions of fullerenes19923596390444710.1038/359044a02-s2.0-0002460492KublerB.MillonE.GaumetJ. J.MullerJ. F.Formation of high mass Cn clusters (n > 100) by laser ablation/desorption coupled with mass spectrometry1996461247126110.1080/106412296080011772-s2.0-0030401774CataldoF.KeheyanY.On the mechanism of carbon clusters formation under laser irradiation. The case of diamond grains and solid C60 fullerene200210431333210.1081/FST-1200164522-s2.0-0036910052JovanovicT.KorugaD.JovancicevicB.Simic-KrsticJ.Advancement of the process for extraction, chromatography and characterization of fullerenes200917213515010.1080/153638308026717592-s2.0-61649092878JovanovicT.KorugaD.The new technological process for extraction, chromatography and characterization of the basic and the higher fullerenes from carbon soot2009The intellectual property office of the Republic of Serbia, Belgrade. Faculty of Mechanical Engineering, University of BelgradeNumber 985/09 A-59/09JovanovicT.KorugaD.JovancicevicB.VajsV.DevicG.Comparative spectroscopic characterization of the basic and the higher fullerenes2013211647410.1080/1536383X.2011.5888122-s2.0-84867081691JovanovicT.KorugaD.JovancicevicB.Isolation and characterization of the higher fullerenes from carbon soot201119430931610.1080/153638310037218722-s2.0-79953127237JovanovicT.KorugaD.JovancicevicB.Advances in chromatographic separation on Al2O3 and spectroscopic characterization of the higher fullerenes201422438439610.1080/1536383X.2012.6904612-s2.0-84893026944JovanovicT.KorugaD.Recent advances in chromatographic separation and spectroscopic characterization of the higher fullerenes C76 and C84201481627510.2174/18722105089991401301224542-s2.0-8489637217524635208JovanovicT.KorugaD.The electronic structure and vibrational frequencies of the stable C76 isomer of D2 symmetry: theory and experiment2013577687010.1016/j.cplett.2013.05.0152-s2.0-84879692825JovanovicT.KorugaD.JovancicevicB.The electronic structure and vibrational frequencies of the stable C84 isomer of D2 symmetry: theory and experiment201444444810.1016/j.diamond.2014.02.0042-s2.0-84897722333OrlandiG.ZerbettoF.FowlerP. W.ManolopoulosD. E.The electronic structure and vibrational frequencies of the stable C76 isomer of D2 symmetry19932085-644144510.1016/0009-2614(93)87170-82-s2.0-0000115935HampeO.NeumaierM.BoeseA. D.LemaireJ.Niedner-SchatteburgG.KappesM. M.Infrared multiphoton electron detachment spectroscopy of C762−20091311212430610.1063/1.32241302-s2.0-7034962896319791880HarigayaK.AbeS.Optical absorption spectra and geometric effects in higher fullerenes19968428057806610.1088/0953-8984/8/42/0232-s2.0-0030260111SaitoS.SawadaS. I.HamadaN.Electronic and geometric structures of C76 and C8419924523138451384810.1103/PhysRevB.45.138452-s2.0-0000045647ManolopoulosD. E.Faraday communications. Proposal of a chiral structure for the fullerene C76199187172861286210.1039/ft99187028612-s2.0-37049071972ManolopoulosD. E.FowlerP. W.Molecular graphs, point groups, and fullerenes199296107603761410.1063/1.4624132-s2.0-0040262629EhrlerO. T.FurcheF.Mathias WeberJ.KappesM. M.Photoelectron spectroscopy of fullerene dianions C76(2-), C78(2-), C84(2-)20051229, article 09432110.1063/1.18592722-s2.0-2294445240915836142DiederichF.EttlR.RubinY.WhettenR. L.BeckR.AlvarezM.AnzS.SensharmaD.WudlF.KhemaniK. C.KochA.The higher fullerenes: isolation and characterization of C76, C84, C90, C94, and C70O, an oxide of D5h-C701991252500554855110.1126/science.252.5005.5482-s2.0-034415095217838488JinnoK.MatsuiH.OhtaH.SaitoY.NakagawaK.NagashimaH.ItohK.Separation and identification of higher fullerenes in soot extract by liquid chromatography-mass spectrometry1995415-635336010.1007/BF026880512-s2.0-0028866367JinnoK.SatoY.NagashimaH.ItohK.Separation and identification of higher fullerenes by high-performance liquid chromatography coupled with electrospray ionization mass spectrometry1998101798810.1002/(SICI)1520-667X(1998)10:1<79::AID-MCS11>3.0.CO;2-HKikuchiK.NakaharaN.HondaM.SuzukiS.SaitoK.ShiromaruH.YamauchiK.IkemotoI.KuramochiT.HinoS.AchibaY.Separation, detection and UV/Visible absorption spectra of fullerenes: C76, C78, and C8419912091607161010.1246/cl.1991.1607KikuchiK.NakaharaN.WakabayashiT.HondaM.MatsumiyaH.MoriwakiT.SuzukiS.ShiromaruH.SaitoK.YamauchiK.IkemotoI.AchibaY.Isolation and identification of fullerene family: C76, C78, C82, C84, C90 and C9619921883-417718010.1016/0009-2614(92)90005-82-s2.0-44049119538EttlR.ChaoI.DiederichF.WhettenR. L.Isolation of C76, a chiral D2 allotrope of carbon1991353634014915310.1038/353149a02-s2.0-0001614818MichelR. H.SchreiberH.GierdenR.HennrichF.RockenbergerJ.BeckR. D.KappesM. M.LehnerC.AdelmannP.ArmbrusterJ. F.Vibrational spectroscopy of purified C76199498797597810.1002/bbpc.199409807142-s2.0-0028466080AventA. G.DuboisD.PénicaudA.TaylorR.The minor isomers and IR spectrum of [84]fullerene1997101907191010.1039/a703697c2-s2.0-0001601319DennisT. J. S.HulmanM.KuzmanyH.ShinoharaH.Vibrational infrared spectra of the two major isomers of [84] fullerene: C84D2(IV) and C84D2d(II)2000104235411541310.1021/jp0006835ColthupN. B.DalyL. H.WiberleyS. E.19903rdSan Diego, California, USAAcademic PressJovanovićT.KorugaD.Optical absorption properties and applications of fullerenesProceedings of the 14th Yougoslav Materials Research Society Conference “YUCOMAT ‘12”2012Herceg-Novi, MontenegroMaterials Research Society of Serbia122StamenkovićD.JagodićN.ConteM.IlankovićN.JovanovićT.KorugaD.Optical properties of nanophotonic contact lensesProceedings of the 12th Yougoslav Materials Research Society Conference "YUCOMAT '10"2010Herceg-Novi, MontenegroMaterials Research Society of Serbia177MitrovićA.PopovićD.MiljkovićV.KorugaD.Mechanical properties of nanophotonic soft contact lenses based on poly (2-hydrohzethil methacrylate) and fullerenes20161613942JovanovicT.KorugaD.JovancicevicB.StamenkovicD.IR spectroscopy of the higher fullerene C76-D2 for its qualitative and quantitative determinationInnovation Center of Faculty of Mechanical Engineering, Faculty of Mechanical Engineering, University of Belgrade2017Zlatribor, Serbia24Proceedings of the International Conference on Experimental and Numerical Investigations and New Technologies “CNN TECH 2017”JovanovićT.KorugaD.JovančićevićB.MitrovićA.StamenkovićD.RakonjacI.Comparative spectroscopic characterization of fullerene nanomaterialsProceedings of the 19th Yougoslav Materials Research Society Conference “YUCOMAT ‘17”2017Herceg-Novi, Montenegro107Materials Research Society of Serbia