Thermodynamic properties of the C70(OH)12 fullerenol in the temperature range T = 9.2 K to 304.5 K

Journal Pre-proofs Thermodynamic properties of the C70(OH)12 fullerenol in the temperature range T = 9.2 K to 304.5 K Nikita E. Podolsky, Maxim I. Lelet, Sergei V. Ageev, Andrey V. Petrov, Anton S. Mazur, Nailia R. Iamalova, Dmitry N. Zakusilo, Nikolay A. Charykov, Lubov V. Vasina, Konstantin N. Semenov, Igor V. Murin PII: DOI: Reference:

S0021-9614(19)30417-3 https://doi.org/10.1016/j.jct.2019.106029 YJCHT 106029

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J. Chem. Thermodynamics

Received Date: Revised Date: Accepted Date:

8 May 2019 25 November 2019 11 December 2019

Please cite this article as: N.E. Podolsky, M.I. Lelet, S.V. Ageev, A.V. Petrov, A.S. Mazur, N.R. Iamalova, D.N. Zakusilo, N.A. Charykov, L.V. Vasina, K.N. Semenov, I.V. Murin, Thermodynamic properties of the C70(OH)12 fullerenol in the temperature range T = 9.2 K to 304.5 K, J. Chem. Thermodynamics (2019), doi: https://doi.org/ 10.1016/j.jct.2019.106029

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Thermodynamic properties of the C70(ОН)12 fullerenol in the temperature range T = 9.2 K to 304.5 K Nikita E. Podolskya, Maxim I. Leletb, Sergei V. Ageeva, Andrey V. Petrova, Anton S. Mazura, Nailia R. Iamalovaa, Dmitry N. Zakusiloa, Nikolay A. Charykovc, Lubov V. Vasinad,e, Konstantin N. Semenovd,a,c*, Igor V. Murina aInstitute

of Chemistry, Saint Petersburg State University, Universitetskii pr. 26, Saint Petersburg

198504, Russia bResearch

Institute for Chemistry, Lobachevsky State University of Nizhny Novgorod, Gagarin

Ave. 23, Nizhny Novgorod 603950, Russia cSaint

Petersburg State Technological Institute (Technical University), Moskovskii pr. 26, Saint

Petersburg 190013, Russia dPavlov

First Saint Petersburg State Medical University, L’va Tolstogo str. 6–8, Saint Petersburg

197022, Russia eAlmazov

National Medical Research Centre, Akkuratova str. 2, Saint Petersburg 197341,

Russia

*Corresponding

author.

Tel.:

(812)4284109;

fax:

(812)2349859;

e-mail

address:

[email protected] (K. N. Semenov)

1

Abstract The paper is devoted to thermodynamic investigation of polyhydroxylated fullerene C70(OH)12. The measurement of fullerenol’s isobaric heat capacity in the temperature range T = 9.2 K– 304.5 K was performed, as well as the standard thermodynamic functions: Sm°, [Hm°(T) − Hm°(0)] and [Фm°(T) − Фm°(0)] were calculated. Additionally, the complex thermal analysis was conducted for investigation of thermal properties of C70(OH)12. The quantum chemistry approach was used in order to calculate the electronic structure, thermodynamic properties, and NMR spectra for C70(OH)12 isomers. Keywords: fullerenol, isobaric heat capacity, DFT, Gibbs energy, entropy

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1. Introduction Water-soluble fullerene derivatives, especially polyhydroxylated fullerenes (fullerenols), have potential of application in different areas of science and technology, mainly in nanobiomedicine [1–3]. This is due to the fact that these compounds possess antitumor [4–6], antioxidant [7,8], antitoxic [9,10], radio protective [11,12], photosensitive properties [13], as well as can be used for targeted drug delivery [14,15] and as contrasting agents for cancer treatment [16,17]. In addition, fullerene derivatives positively effect on plants and fungi [18–20] and can be applied as nanomodifiers of polyelectrolytes [1,21], polymers [1,22,23], paints [1] and construction materials [24]. Nowadays, there is a considerable number of articles, which are devoted to physicochemical investigation of water-soluble fullerenols. However, most of them are focused on the study of C60 fullerene derivatives, and only a few conduct experiments with C70 fullerenols. Physicochemical study of this class of compounds underlies the optimisation of fullerenols’ application in various fields of science and technology. Analysis of literature revealed the following directions of polyhydroxylated fullerenes (C60 and C70) physicochemical investigation: — physicochemical study of aqueous solutions, namely temperature and concentration dependences of viscosity, density, electric conductivity, refractive index, nanoparticles size distribution, as well as calculation of the excess thermodynamic functions of C60(OH)22–24 and C70(OH)12 [1,25–28]; — kinetics investigation of the heterogeneous catalytic reactions of fullerenol formation under different conditions (oxidizers, phase-transfer catalysts, heating modes etc.) [29,30]; — investigation of phase equilibria in systems containing water-soluble fullerenols. To this time, binary C60(OH)22–24–H2O [25] and C70(OH)12–H2O systems were studied in the temperature range T = 293.15 K–353.15 K [27] and such ternary systems, as C60(OH)22–24–inorganic salt

3

(SmCl3, Pr(NO3)3, YCl3, CuCl2, UO2SO4)–H2O were studied under isothermal conditions at T = 298.15 K [31,32]; — theoretical studies, as well as computer simulation of the fullerenol properties. Present-day methods for calculation of the electronic structure allow to predict equilibrium geometry, total energy, electron density distribution, thermodynamic functions and different spectra of the polyhydroxylated fullerenes (NMR, infrared, Raman). Authors of [33] studied various models of the C60(OH)24 isomers with the use of the density functional theory method (DFT). It was found that the isomer, which has Saturn-like distribution of hydroxyl groups (along the equator of the fullerene core), was the most energetically stable. The same result concerning the fullerenol geometry was obtained using the continual (PCM model) and cluster approaches for the solvent behaviour modelling by Maciel et al. [34]. Dawid et al. [35] performed the calculations of the infrared and Raman spectra of C60(OH)24 with the use of DFT method. Concerning the investigation of thermodynamic properties of the fullerenols, we can sight only ref. [36] which is devoted to the study of isobaric heat capacities of C60(OH)40 in the temperature range T = 5 K to 326 K and calculation of the standard thermodynamic functions (Sm°, [Hm°(T) − Hm°(0)] and [Фm°(T) − Фm°(0)]). The present paper is focused on the thermodynamic study of C70(OH)12. As a result, the standard thermodynamic functions, namely Gibbs energy, enthalpy and entropy were calculated in the temperature interval from T → 0 K to 304 K. Additionally, the standard entropy of C70(OH)12 formation, ΔfSmo, in the crystalline state at T = 298.15 K was calculated, as well as complex thermal analysis of the fullerenol sample was conducted in the temperature range T = 293.15 K–873.15K. Finally, using DFT method, the electronic structure of the fullerenol was calculated and temperature dependence of heat capacity was obtained under harmonic approximation. 2. Experimental

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2.1. Materials The polyhydroxylated fullerenol C70(OH)12 with mass fraction purity 0.998 produced from MST “Nano” (St. Petersburg) was used for thermodynamic investigation. The fullerenol under study represents a mixture of isomers, and no mixture composition experiment was conducted. We performed the identification of purchased sample with the use of IR spectroscopy (Shimadzu FTIR-8400S spectrometer), mass spectrometry (Bruker Daltonik MaXis ESI-QTOF spectrometer), elemental analysis (Euro EA3028-HT) and

13C

NMR spectroscopy (NMR-

spectrometer Bruker Avance III 400 WB, USA). FTIR: 3420 cm–1 (νO–H), 1625 cm–1 (νC=C), 1381 cm–1 (δSC–O–H) and 1073 cm–1 (νC–O) (see Figure S1 of Supplementary Material). The positive ion ESI mass spectrum of fullerenol demonstrates ion fragmentation and, at the same time, detection of a molecular ion at m/z equal to 1043.03 indicates that fullerenol formula corresponds to C70(OH)12 (see Figure S2). Experimental data on elemental analysis: (C 80.44; H 1.18)%, calc.: (C 80.46; H 1.15)%. When providing the NMR study, the sample of C70(OH)12 was placed in a zirconium oxide rotor having an outer diameter of 4 mm and rotated with a frequency equal to 12.5 kHz at a magic angle to the direction of a constant magnetic field. Cross-polarisation excitation pulse sequence (CP/MAS) and direct excitation (DE) techniques were used for obtaining the 13C NMR spectra. In the case of CP/MAS method, the contact time was (7-10) μs, the relaxation delay time was 2 s, the number of accumulations was 2000 in experiments with varying constant time and 16000 in experiments with a large ratio signal-to-noise. For providing DE technique, the following conditions were used: the relaxation delay of 30 s, the duration of exciting pulse of 3.2 μs, the number of accumulations of 4000. Tetramethylsilane was used as an external standard compound. Figure 1 shows the 13C NMR spectra obtained using the DE and CP/MAS techniques at a contact time of 2000 μs. Analysis of the obtained spectra allows to characterise the C70(OH)12 sample: (i) the peak at 140.5 ppm corresponds to the structurally “pure” state of the carbon 5

nuclei in the stoichiometric C70 fullerene molecule; (ii) the peak with a chemical shift of 74.5 ppm is referred to hydroxylated carbon atoms. The HPLС analysis of the C70(OH)12 derivative was performed using Shimadzu LC-20 Prominence apparatus with UV-detection at 300 nm equipped with “Phenomenex® NH2” (150 mm × 2.0 mm, 5 μm, 100 A) column, injection volume was equal to 210−8 m3, injection speed 0.2 mL·min−1, eluent with water/acetonitrile (1/1). The chromatogram of C70(OH)12 derivative reveals that the purity of the sample is equal to 99.8% (see Figure S3). Figure 2 shows the results of the complex thermal analysis of C70(OH)12 sample. These experimental data reveal the following features: (i) the fullerenol C70(OH)12 is thermally stable up to the temperature T = 345 K; (ii) the decomposition of the fullerenol starts at T = 345 K and may consist of the following processes: pinacol type rearrangement of hydroxyl groups, hemiketal formation, dihydroxylation and degradation of hydroxyl groups. The loss of mass in the temperature interval T = 345 K–873 K is equal to 19.54%, which corresponds to the loss of 12 hydroxyl groups of the fullerenol molecule. The obtained data of the complex thermal analysis are agreed well with the literature value [42]. Based on these results, we can conclude that the thermal analysis can be used as a method for fullerenols’ identification. 2.2. Heat capacity measurements and thermal analysis The C70(OH)12 isobaric heat capacity measurements in the temperature range T = 9.2 K to 304.5 K were performed with the use of adiabatic calorimetry (“AK-9.02/BCT-21”-type calorimeter, TERMAX, Russia). Ref. [37] describes the calorimeter setup and the measurement technique. The isobaric heat capacities of benzoic acid (mass fraction purity 0.99998) and synthetic sapphire α-Al2O3 (mass fraction purity 0.99999) as standard samples were measured during the calibration of the apparatus. The Cp,m° values between T = 5 K and T = 330 K for benzoic acid compared to literature data [38] are shown in Figure S4 and in the Table S1 of Supplementary Material. The Cp,m° values between T = 81 K and T = 270 K for synthetic sapphire compared to literature data [39] are shown in Figure S5 and in the Table S2. The 6

agreement between experimental and literature data is better than 0.5% at T > 20 K and 2.1% at T < 20 K for benzoic acid and better than 0.2% at T > 81 K for sapphire. As a result, the Cp,m°(T) experimental values can be determined with the following combined expanded uncertainties: Uc,r(Cp) = 0.021 for T < 20 K, 0.005 for T = 20 K–60 K, 0.003 for T = 60 K–330 K at the 0.95 level of confidence (k = 2). The mass of C70(OH)12 solid sample used for conducting experiments was equal to 0.4333 g (0.4335 g after air buoyancy correction). The buoyancy correction for the sample mass was not applied during the experiments. Liquid helium and nitrogen were used for the measurements of heat capacities in the temperature ranges T = 81.6 K to 304.5 K and T = 9.2 K to 78.1 K. The determination of heat capacity was carried out in a vacuum ampoule, which was later filled with dry helium (room temperature and 4 kPa pressure). The ampoule was hermetically sealed with the use of indium. Heat capacity values of the C70(OH)12 fullerenol corresponded to (30-40)% of the total heat capacity of the loaded ampoule in the temperature range T = 9.2 K to 304.5 K. Shimadzu DTG-60H apparatus was used for carrying out the thermal properties of C70(OH)12 derivative over the temperature range T = 293.15 K to 873.15 K in the air at the heating rate 5 K∙min–1. 2.3. Computer simulation The electronic structure of C70(OH)12 isomers was obtained by DFT method implemented into DMol3 module in Materials Studio software package. The atomic basis of DNP 4.4 and PBE functional were applied for heat capacity calculation. For calculation of NMR spectra, we used DFT approach in CASTEP module of Materials Studio software package with plane basis and PBE functional (cutoff = 610 eV, total energy/atom convergence tolerance = 5·10–7 eV). 3. Results and discussion

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3.1. Heat capacity behaviour Raw molar heat capacity (Cp,m°) data for the C70(OH)12 derivative over the range of temperatures T = 9.2 K to 304.5 K are given in Supplementary Material (see Table S3) and Figure 3. It can be seen that the obtained results are well behaved. Moreover, we did not observe any phase transitions or Cp,m° dependence abnormal behaviour. In order to extrapolate the heat capacity dependence to T = 0 K, we used the Debye model of heat capacity [40]:

  C p  nD  D  T 

(1),

where D is the symbol of the Debye function, n and ΘD are specially selected parameters. For the investigated sample, n = 3 and ΘD = 62.42 K in the temperature interval from T = 9.2 K to T = 10 K. The experimental Cp° values of copolymer were described by the above equation with the relative standard uncertainty ur(Cp°) = 0.081. The Cp,m° data were fitted over five different temperature ranges using the method of nonlinear least squares, with the polynomial [41]: C p ,m  J  K 1  mol 1

3

2

T  T  T   k0  k1     k2     k3    K K K

0.5

2

T  T  T   k 4     k5     k 6    K K K

3

(2).

The five temperature segments are from (9.2 to 13) K, (14 to 17) K, (18 to 29) K, (30 to 70) K, and (71 to 304.5) K. The final best-fit values for the various k terms are given in Supplementary Table S4. Figure S6 shows the difference between the experimental Cp,m° data and the fitted Cp,m° values for C70(OH)12. 3.2. Standard third-law entropy and Gibbs energy of formation The standard molar entropy of C70(OH)12 at T = 298.15 K (Sm°) was calculated using the heat capacity data by numerical integrating according to Eq. 5 assuming that ST=0K = 0: S   S T 0 K 

298.15

 0

C p T

dT

(5).

We determined the values of the standard molar entropy (Sm°) of C70(OH)12 at T = 298.15 K, which was equal to Sm° = (1161.2±7.0) J∙K–1∙mol–1. 8

The absolute entropies of C70(OH)12 fullerenol and elemental substances (C(gr, cr), H2(g), O2(g)) were used for calculation of C70(OH)12 standard entropy of formation in crystalline state at T = 298.15 K according to the following equation (see Table 2): 70∙C(gr) + 6∙H2(g) + 6∙O2(g) = C70(OH)12(cr)

(6),

where gr is graphite, cr is crystal, and g is gas. Finally, we obtained the following value of the C70(OH)12 standard molar entropy of formation: ΔfSm°(298.15 K, C70(OH)12, cr) = –(1245.8±8.2) J∙K–1∙mol–1

(7).

Table 3 summarises the smoothed Cp,m°(T) values of the C70(OH)12 derivative in the temperature range T → 0 K to T = 304 K, as well as the values of standard molar entropy Sm°, enthalpy [Hm°(T) − Hm°(0)] and Gibbs function [Фm°(T) − Фm°(0)] at p = 0.1 MPa. 3.3. Electronic structure calculation Figure 1 presents the experimental 13C NMR data for C70(OH)12 in comparison with the calculated data for the I–V isomers (Figure 4) obtained with quantum chemical calculations. The difference in the structure of the C70(OH)12 isomers shown in Figure 4 is that hydroxyl groups are bonded to carbon atoms in non-equivalent positions a, c, d, e, and also to all non-equivalent carbon atoms a–e in the case of equatorial arrangement of hydroxyl groups. The data obtained for structures II, III, and V most closely correspond to the experimental 13C NMR spectra of the fullerenol. Table 4 presents calculated data on charge states, HOMO-LUMO energies and total energy of isomers with different arrangement of hydroxyl groups (Figure 4). Analysis of the total energy calculated values of the I–V isomers reveals that structures IV and V are the least energetically profitable. At the same time, the structures I, II, and III have close values of the total energies that may indicate equal probability of their formation during synthesis. Structures II and III were chosen for further calculation of isobaric heat capacities, since they correspond to

9

the minimum of energy and they are also most consistent with the experimental data on NMR spectroscopy (Figure 1). Figure 5 presents a comparison of heat capacities data for individual fullerene C70, namely, the recommended values of the heat capacities of crystalline fullerene C70 (monoclinic phase) [43], values obtained in the ideal gas state (P = 101325 Pa) [43] and DFT-calculated values. We can state the good agreement between DFT-calculated values and the data presented in ref. [44] using the method of statistical thermodynamics. At the same time, the discrepancy between the calculated and experimental values does not exceed 5% in the temperature range T = 50 K–275 K. In addition, Figure 5 shows the DFT-calculated values of the isobaric heat capacity of C70(OH)12 isomers II and III in comparison with the experimental ones. It is clearly seen that the PBE functional describes the temperature dependence of heat capacities for C70(OH)12 in a less adequate way. The latest fact can be associated with the anharmonicity of oscillations and the influence of vibrations of OH-groups increase with the temperature rise. 4. Conclusions With the use of the adiabatic calorimetry, the isobaric heat capacities of C70(OH)12 in the temperature interval T = 9.2 K–304.5 K were obtained. In addition, we performed the calculations of the standard thermodynamic functions (molar third law entropy, Sm°, Gibbs energy, [Фm°(T) − Фm°(0)], and enthalpy, [Hm°(T) − Hm°(0)]) of crystalline C70(OH)12 in the temperature range T → 0 K to 304 K. By performing the complex thermal analysis of C70(OH)12, it was shown that the fullerene derivative is stable up to T = 345 K. The isobaric heat capacity experimental data showed good agreement with the values calculated by DFT method in the temperature range T = (25-125) K (isomers II, III). With increasing temperature, it is necessary to take into account those isomers that make the largest contribution to the energy of interatomic vibrations and the impact of amendments on anharmonism. Acknowledgements

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This work was supported by Grants of RFBR (18-33-20238, 18-08-00143, 16-08-01206) and by the Grant of the President of the Russian Federation for young scientists MD2175.2018.3. MIL is grateful to the Ministry of Science and Higher Education of the Russian Federation for financial support through grant 4.5510.2017/8.9. Research was carried out using computational resources provided by Resource Center “Computer Center of SPbU” and the Collective Usage Center “New Materials and Energy Saving Technologies” of Lobachevsky State University of Nizhny Novgorod. The authors are grateful to the partner Research & Production Company “Modern Synthesis Technology” (www.mstnano.com) for participation in conducting of experiments and for provided samples of the fullerenol.

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References [1]

K.N. Semenov, N.A. Charykov, V.N. Postnov, V.V. Sharoyko, I.V. Vorotyntsev, M.M. Galagudza, I.V. Murin, Fullerenols: Physicochemical properties and applications, Prog. Solid State Chem. 44 (2016) 59–74. doi:10.1016/j.progsolidstchem.2016.04.002.

[2]

K.N. Semenov, E. V. Andrusenko, N.A. Charykov, E. V. Litasova, G.G. Panova, A. V. Penkova, I. V. Murin, L.B. Piotrovskiy, Carboxylated fullerenes: Physico-chemical properties and potential applications, Prog. Solid State Chem. 47–48 (2017) 19–36. doi:10.1016/J.PROGSOLIDSTCHEM.2017.09.001.

[3]

F. Cataldo, T. Da Ros, Medicinal chemistry and pharmacological potential of fullerenes and carbon nanotubes, Springer Netherlands, Dordrecht, 2008. doi:10.1007/978-1-40206845-4.

[4]

X. Zhu, S. Cirovic, A. Shaheen, W. Xu, Investigation of fullerenol-induced changes in poroelasticity of human hepatocellular carcinoma by AFM-based creep tests, Biomech. Model. Mechanobiol. 17 (2018) 665–674. doi:10.1007/s10237-017-0984-5.

[5]

P.T.T. Bernardes, B.M. Rezende, C.B. Resende, T.P. De Paula, A.C. Reis, W.A. Gonçalves, E.G. Vieira, M.V.B. Pinheiro, D.G. Souza, M.G.M. Castor, M.M. Teixeira, V. Pinho, Nanocomposite treatment reduces disease and lethality in a murine model of acute graft-versus-host disease and preserves anti-tumor effects, PLoS One. 10 (2015) e0123004. doi:10.1371/journal.pone.0123004.

[6]

J. Tang, R. Zhang, M. Guo, L. Shao, Y. Liu, Y. Zhao, S. Zhang, Y. Wu, C. Chen, Nucleosome-inspired nanocarrier obtains encapsulation efficiency enhancement and side effects reduction in chemotherapy by using fullerenol assembled with doxorubicin, Biomaterials. 167 (2018) 205–215. doi:10.1016/j.biomaterials.2018.03.015.

[7]

R.D.N. Arifa, T.P. de Paula, M.F.M. Madeira, R.L. Lima, Z.M. Garcia, T.V. Ÿvila, V. Pinho, L.S. Barcelos, M.V.B. Pinheiro, L.O. Ladeira, K. Krambrock, M.M. Teixeira, D.G. Souza, The reduction of oxidative stress by nanocomposite Fullerol decreases mucositis 12

severity and reverts leukopenia induced by Irinotecan, Pharmacol. Res. 107 (2016) 102– 110. doi:10.1016/j.phrs.2016.03.004. [8]

P. Roy, S. Bag, D. Chakraborty, S. Dasgupta, Exploring the inhibitory and antioxidant effects of fullerene and fullerenol on Ribonuclease A, ACS Omega. 3 (2018) 12270– 12283. doi:10.1021/acsomega.8b01584.

[9]

J.-Y. Xu, Y.-Y. Su, J.-S. Cheng, S.-X. Li, R. Liu, W.-X. Li, G.-T. Xu, Q.-N. Li, Protective effects of fullerenol on carbon tetrachloride-induced acute hepatotoxicity and nephrotoxicity

in

rats,

Carbon

N.

Y.

48

(2010)

1388–1396.

doi:10.1016/J.CARBON.2009.12.029. [10]

M. Slavic, A. Djordjevic, R. Radojicic, S. Milovanovic, Z. Orescanin-Dusic, Z. Rakocevic, M.B. Spasic, D. Blagojevic, Fullerenol C60(OH)24 nanoparticles decrease relaxing effects of dimethyl sulfoxide on rat uterus spontaneous contraction, J. Nanoparticle Res. 15 (2013) 1650. doi:10.1007/s11051-013-1650-1.

[11]

S. Trajković, S. Dobrić, V. Jaćević, V. Dragojević-Simić, Z. Milovanović, A. Đorđević, Tissue-protective effects of fullerenol C60(OH)24 and amifostine in irradiated rats, Colloids Surfaces B Biointerfaces. 58 (2007) 39–43. doi:10.1016/j.colsurfb.2007.01.005.

[12]

J. Grebowski, P. Kazmierska, G. Litwinienko, A. Lankoff, M. Wolszczak, A. Krokosz, Fullerenol C60(OH)36 protects human erythrocyte membrane against high-energy electrons,

Biochim.

Biophys.

Acta

-

Biomembr.

1860

(2018)

1528–1536.

doi:10.1016/j.bbamem.2018.05.005. [13]

P. Chaudhuri, A. Paraskar, S. Soni, R.A. Mashelkar, S. Sengupta, Fullerenol−cytotoxic conjugates

for

cancer

chemotherapy,

ACS

Nano.

3

(2009)

2505–2514.

doi:10.1021/nn900318y. [14]

N. Thotakura, G. Sharma, B. Singh, V. Kumar, K. Raza, Aspartic acid derivatized hydroxylated fullerenes as drug delivery vehicles for docetaxel: an explorative study, Artif.

Cells,

Nanomedicine,

Biotechnol.

46

(2017)

1–10. 13

doi:10.1080/21691401.2017.1392314. [15]

D. Petrovic, M. Seke, M.L. Borovic, D. Jovic, I. Borisev, B. Srdjenovic, Z. Rakocevic, V. Pavlovic, A. Djordjevic, Hepatoprotective effect of fullerenol/doxorubicin nanocomposite in acute treatment of healthy rats, Exp. Mol. Pathol. 104 (2018) 199–211. doi:10.1016/j.yexmp.2018.04.005.

[16]

Y. Liu, F. Jiao, Y. Qiu, W. Li, F. Lao, G. Zhou, B. Sun, G. Xing, J. Dong, Y. Zhao, Z. Chai, C. Chen, The effect of Gd@C82(OH)22 nanoparticles on the release of Th1/Th2 cytokines and induction of TNF-α mediated cellular immunity, Biomaterials. 30 (2009) 3934–3945. doi:10.1016/j.biomaterials.2009.04.001.

[17]

É. Tóth, R.D. Bolskar, A. Borel, G. González, L. Helm, A.E. Merbach, B. Sitharaman, L.J. Wilson, Water-soluble gadofullerenes: toward high-relaxivity, pH-responsive MRI contrast agents, J. Am. Chem. Soc. 127 (2005) 799–805. doi:10.1021/ja044688h.

[18]

T. Kovač, I. Borišev, B. Crevar, F. Čačić Kenjerić, M. Kovač, I. Strelec, C.N. Ezekiel, M. Sulyok, R. Krska, B. Šarkanj, Fullerol C60(OH)24 nanoparticles modulate aflatoxin B1 biosynthesis in Aspergillus flavus, Sci. Rep. 8 (2018) 12855. doi:10.1038/s41598-01831305-9.

[19]

G.G. Panova, I.N. Ktitorova, O.V. Skobeleva, N.G. Sinjavina, N.A. Charykov, K.N. Semenov, Impact of polyhydroxy fullerene (fullerol or fullerenol) on growth and biophysical characteristics of barley seedlings in favourable and stressful conditions, Plant Growth Regul. 79 (2016) 309–317. doi:10.1007/s10725-015-0135-x.

[20]

T. Kovač, B. Šarkanj, T. Klapec, I. Borišev, M. Kovač, A. Nevistić, I. Strelec, Fullerol C60(OH)24 nanoparticles and mycotoxigenic fungi: a preliminary investigation into modulation of mycotoxin production, Environ. Sci. Pollut. Res. 24 (2017) 16673–16681. doi:10.1007/s11356-017-9214-z.

[21]

K. Tasaki, R. DeSousa, H. Wang, J. Gasa, A. Venkatesan, P. Pugazhendhi, R.O. Loutfy, Fullerene composite proton conducting membranes for polymer electrolyte fuel cells 14

operating under low humidity conditions, J. Memb. Sci. 281 (2006) 570–580. doi:10.1016/j.memsci.2006.04.052. [22]

A. V. Penkova, S.F.A. Acquah, M.E. Dmitrenko, B. Chen, K.N. Semenov, H.W. Kroto, Transport properties of cross-linked fullerenol–PVA membranes, Carbon N. Y. 76 (2014) 446–450. doi:10.1016/J.CARBON.2014.04.053.

[23]

T. V. Plisko, A.S. Liubimova, A. V. Bildyukevich, A. V. Penkova, M.E. Dmitrenko, V.Y. Mikhailovskii, G.B. Melnikova, K.N. Semenov, N. V. Doroshkevich, A.I. Kuzminova, Fabrication and characterization of polyamide-fullerenol thin film nanocomposite hollow fiber membranes with enhanced antifouling performance, J. Memb. Sci. 551 (2018) 20– 36. doi:10.1016/J.MEMSCI.2018.01.015.

[24]

A.A. Zolotarev, A.I. Lushin, N.A. Charykov, K.N. Semenov, V.I. Namazbaev, V.A. Keskinov, A.S. Kritchenkov, Impact resistance of cement and gypsum plaster nanomodified by water-soluble fullerenols, Ind. Eng. Chem. Res. 52 (2013) 14583–14591. doi:10.1021/ie400245c.

[25]

K.N. Semenov, N.A. Charykov, V.N. Keskinov, Fullerenol synthesis and identification. Properties of the fullerenol water solutions, J. Chem. Eng. Data. 56 (2011) 230–239. doi:10.1021/je100755v.

[26]

K.N. Semenov, D.G. Letenko, N.A. Charykov, V.A. Nikitin, M.Y. Matuzenko, V.A. Keskinov, V.N. Postnov, A.A. Kopyrin, Electrochemical properties of aqueous solutions of fullerenol-d, Russ. J. Appl. Chem. 84 (2011) 79–83. doi:10.1134/S1070427211010137.

[27]

K.N. Semenov, N.A. Charykov, I. V. Murin, Y. V. Pukharenko, Physico-chemical properties of the fullerenol-70 water solutions, J. Mol. Liq. 202 (2015) 1–8. doi:10.1016/J.MOLLIQ.2014.12.002.

[28]

N.A. Charykov, K.N. Semenov, E.R. López, J. Fernández, E.B. Serebryakov, V.A. Keskinov, I. V. Murin, Excess thermodynamic functions in aqueous systems containing soluble

fullerene

derivatives,

J.

Mol.

Liq.

256

(2018)

305–311. 15

doi:10.1016/J.MOLLIQ.2018.01.177. [29]

M. Gigov, J. Jovanović, B. Adnađević, Isothermal kinetics of C60 polyhydroxylation in a two-phase system in the presence of tetrabutylammonium hydroxide, React. Kinet. Mech. Catal. 122 (2017) 741–755. doi:10.1007/s11144-017-1268-x.

[30]

B. Adnadjevic, M. Gigov, J. Jovanovic, The effects of external physical fields on the isothermal kinetics of fullerol formation, React. Kinet. Mech. Catal. 123 (2018) 269–286. doi:10.1007/s11144-017-1326-4.

[31]

G.O. Yur’ev, V.A. Keskinov, K.N. Semenov, N.A. Charykov, Phase equilibria in a ternary fullerenol-d(C60(OH)22–24)–SmCl3–H2O system at 25°C, Russ. J. Phys. Chem. A. 91 (2017) 797–799. doi:10.1134/S0036024417050326.

[32]

K.N. Semenov, N.A. Charykov, V.A. Keskinov, A.S. Kritchenkov, I. V. Murin, Fullerenol-d solubility in fullerenol-d–inorganic salt–water ternary systems at 25°C, Ind. Eng. Chem. Res. 52 (2013) 16095–16100. doi:10.1021/ie401590g.

[33]

H. He, L. Zheng, P. Jin, M. Yang, The structural stability of polyhydroxylated C60(OH)24: Density functional theory characterizations, Comput. Theor. Chem. 974 (2011) 16–20. doi:10.1016/j.comptc.2011.07.005.

[34]

C. Maciel, E.E. Fileti, R. Rivelino, Assessing the solvation mechanism of C60(OH)24 in aqueous

solution,

Chem.

Phys.

Lett.

507

(2011)

244–247.

doi:10.1016/J.CPLETT.2011.03.080. [35]

A. Dawid, K. Górny, Z. Gburski, Water solvent effect on infrared and raman spectra of C60(OH)24 fullerenol isomers - DFT study, J. Phys. Chem. C. 121 (2017) 2303–2315. doi:10.1021/acs.jpcc.6b06484.

[36]

N.E. Podolsky, M.I. Lelet, S. V. Ageev, A.G. Novikov, A. V. Petrov, A.S. Mazur, K.N. Semenov, N.A. Charykov, L. V. Vasina, I. V. Murin, Thermodynamic properties from calorimetry and density functional theory and the thermogravimetric analysis of the fullerene derivative C60(OH)40, J. Chem. Eng. Data. 64 (2019) 1480–1487. 16

doi:10.1021/acs.jced.8b01075. [37]

R.M. Varushchenko, A.I. Druzhinina, E.L. Sorkin, Low-temperature heat capacity of 1bromoperfluorooctane,

J.

Chem.

Thermodyn.

29

(1997)

623–637.

doi:10.1006/JCHT.1996.0173. [38]

G.T. Furukawa, R.E. McCoskey, G.J. King, Calorimetric properties of benzoic acid from 0°

to

410°

K,

J.

Res.

Natl.

Bur.

Stand.

(1934).

47

(1951)

256–261.

https://nvlpubs.nist.gov/nistpubs/jres/47/jresv47n4p256_a1b.pdf. [39]

D.A. Ditmars, S. Ishihara, S.S. Chang, G. Bernstein, E.D. West, Enthalpy and heatcapacity standard reference material: Synthetic sapphire (α-Al2O3) from 10 to 2250 K, J. Res. Natl. Bur. Stand. (1934). 87 (1982) 159. doi:10.6028/jres.087.012.

[40]

P. Debye, Zur Theorie der spezifischen Wärmen, Ann. Phys. 344 (1912) 789–839. doi:10.1002/andp.19123441404.

[41]

E. Dachs, C.A. Geiger, Heat capacities and entropies of mixing of pyrope-grossular (Mg3Al2Si3O12-Ca3Al2Si3O12) garnet solid solutions: A low-temperature calorimetric and a

thermodynamic

investigation,

Am.

Mineral.

91

(2006)

894–906.

doi:10.2138/am.2006.2005. [42]

T.H. Goswami, R. Singh, S. Alam, G.N. Mathur, Thermal analysis: a unique method to estimate the number of substituents in fullerene derivatives, Thermochim. Acta. 419 (2004) 97–104. doi:10.1016/j.tca.2004.02.001.

[43]

K.B. Zhogova, B.V. Lebedev, Thermodynamics of C70 fullerence in the 0–390 K temperature range, Russ. Chem. Bull. 47 (1998) 625–628. doi:10.1007/BF02495966.

[44]

V. V. Diky, G.J. Kabo, Thermodynamic properties of C60 and C70 fullerenes, Russ. Chem. Rev. 69 (2000) 95–104. doi:10.1070/RC2000v069n02ABEH000535.

[45]

NIST Chemistry WebBook, (n.d.). doi:10.18434/T4D303.

17

Table 1. Provenance and mass fraction purity of the reagents. Mass fraction №

Sample

Supplier

Method of analysis purity

1

C70

MST “Nano”, Russia

≥0.999

liquid chromatography

MST “Nano”, Russia

≥0.998

liquid chromatography

C70(OH)12 2

(mixture of isomers)

3

C6H5COOH

Ltd. “Vecos”

0.99998

—

4

α-Al2O3

Ltd. “Vecos”

0.99999

—

18

Table 2. Standard entropies of elemental substancesa [45].

a0.95

Substance

Sm(298 K) / J∙K–1∙mol–1

C, cr (graphite)

5.60.5

H2, g

130.6800.003

O2, g

205.1520.005

level of confidence (k = 2)

19

Table 3. Standard molar thermodynamic functions of C70(OH)12 derivative (mixture of isomers) at p = 0.1 MPaa.

T0 H m (T )  (T )   S (T )  T  m

T/K

C p ,m (T ) / J  K 1  mol 1

T 0

 m

H m (T )  H m (0) / J  mol 1

S m (T ) / J  K 1  mol 1

 m (T )   m (0) / J  K 1  mol 1

[0]

[0]

[0]

[0]

[0]

5

0.504

0.509

0.127

0.025

10

5.523

12.358

1.592

0.356

15

20.04

75.60

6.523

1.483

20

36.53

215.8

14.47

3.676

25

55.34

444.7

24.59

6.804

30

79.06

777.0

36.66

10.76

35

104.9

1235

50.71

15.43

40

130.3

1823

66.39

20.81

45

157.2

2541

83.28

26.80

50

187.5

3401

101.4

33.35

60

247.9

5584

141.0

47.93

70

302.6

8341

183.4

64.24

80

358.0

11656

227.6

81.88

90

406.1

15479

272.6

100.6

100

452.6

19773

317.8

120.0

110

497.7

24526

363.0

140.1

120

540.9

29721

408.2

160.5

130

582.0

35338

453.1

181.3

140

621.2

41355

497.7

202.3

20

150

658.8

47756

541.9

223.5

160

695.3

54527

585.5

244.7

170

731.3

61660

628.8

266.1

180

767.1

69152

671.6

287.4

190

803.2

77003

714.0

308.7

200

839.9

85218

756.2

330.1

210

877.1

93803

798.0

351.4

220

915.0

102763

839.7

372.6

230

953.5

112105

881.2

393.8

240

992.5

121835

922.6

415.0

250

1031.5

131955

963.9

436.1

260

1070.4

142465

1005.2

457.2

270

1108.7

153361

1046.3

478.3

273.15

1120.5

156872

1059.2

484.9

280

1145.8

164635

1087.3

499.3

290

1181.4

176272

1128.1

520.3

298.15

1208.7

186013

1161.2

537.3

300

1214.7

188255

1168.7

541.2

304

1227.2

193139

1184.9

549.6

aStandard

uncertainties, u, are u(T) = 0.05 K, u(p) = 0.001 MPa. The combined expanded

uncertainties, Uc are Uc,r(Cp,m°(T)) = 0.022 for T < 20 K, 0.009 from T = 20 K to 60 K, 0.006 between T = 60 K and 330 K, Uc,r(Δ0TSm°(T)) = 0.022 for T < 20 K, 0.009 between T = 20 K and 60 K, 0.006 between T = 60 K and 330 K, Uc,r(Δ0THm°(T)) = 0.022 for T < 20 K, 0.009 between T = 20 K and 60 K, 0.006 between T = 60 K and 330 K, Uc,r(Δ0TΦm°(T)) = 0.022 for T < 20 K, 0.009 between T = 20 K and 60 K, 0.006 between T = 60 K and 330 K (0.95 level of confidence). 21

22

Table 4. Results of calculations of the electronic structure of the fullerenol C70(OH)12 isomers. Caverage /(e)

Oaverage /(e)

Haverage /(e)

0.034

–0.523

0.324

Total energy /(eV) –97344.140

I

–5.263

LUMO /(eV) –4.955

II

–5.464

–4.019

0.035

–0.489

0.287

–97344.154

III

–5.592

–4.667

0.036

–0.509

0.302

–97344.154

IV

-5.494

–4.876

0.034

–0.485

0.289

–97340.072

V

–5.314

–4.765

0.035

–0.503

0.297

–97341.977

HOMO /(eV)

23

140.5 74.5 DE CP C70 I III IV II V 200

Figure 1. Experimental

180

13C

160

140

120

100

 / ppm

80

60

40

20

NMR spectra of C70(OH)12 obtained using DE (solid line) and

CP/MAS (dashed line) techniques.

Conta-6ct

time = 2000 µs. The lower spectrum represents non-

modified C70 molecule. Note 1 ppm = 10-6.

24

0

3

2.0

DSC / mkV mg-1

1.5

5

2

1.0

0.5

0.0

1

TG / %

-1.0 300

400

500

600

700

T/ K

10

800

900

0 -1

15

DTG / %min-1

-0.5

-2 -3

20 300

400

500

600

700

800

-4 900

T/K

Figure 2. Complex thermal analysis of the C70(OH)12 derivative in the temperature range from T = 293.15 K to 873.15 K. TG curve — solid line, DTG curve — dotted line.

25

Figure 3. Temperature dependence of isobaric heat capacity Ср,m / J·K–1·mol–1 of C70(OH)12 in the temperature range from T = 9.2 K to 304.5 K. Experimental data obtained using liquid helium (T = 9.2 K to 78.1 K) are shown as rings (○) and experimental data using liquid nitrogen (T = 81.6 K to 304.5 K) are shown as solid circles (●). The solid curve corresponds to extrapolation of experimental data using Eq. 2.

26

Figure 4. Structures of several C70(OH)12 fullerenol isomers. Structures I–IV correspond to distribution of hydroxyl groups according to carbon atom positions a, c, d, e. Structure V corresponds to equatorial distribution of hydroxyl groups including inequivalent carbon atom positions a–e.

27

1400

Cp,m°(T) / JK -1mol -1

1200 1000 800 600 400 200 0 0

50

100

150

200

250

300

T/K

Figure 5. Temperature dependence of heat capacity (Ср,m / J·K–1·mol–1). ● — C70(OH)12 experimental data,  — DFT-calculated data for C70(OH)12 (isomer II),  — DFT-calculated data for C70(OH)12 (isomer III), ■ — C70 experimental data obtained in ref. [43], ● — C70 calculated data obtained in ref. [44], ● — DFT-calculated data for fullerene C70. Highlights

Heat capacities of C70(OH)12 derivative were measured between T = 9.2 K and T = 304.5 K.

Standard thermodynamic functions of crystalline C70(OH)12 were calculated.

Thermodynamic and spectral characteristics of various C70(OH)12 isomers were obtained using quantum chemistry approach.

28

Declaration of interests

☒ The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

☐The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:

Authors Statement Nikita E. Podolsky — Software, Investigation, Formal analysis Maxim I. Lelet — Investigation, Resources, Formal analysis Sergei V. Ageev — Writing (Original Draft, Review & Editing), Data Curation, Visualisation Andrey V. Petrov — Software, Investigation Anton S. Mazur — Investigation, Resources Nailia R. Iamalova — Investigation Dmitry N. Zakusilo — Investigation Nikolay A. Charykov — Methodology, Investigation Lubov V. Vasina — Conceptualisation, Methodology, Funding acquisition Konstantin N. Semenov — Conceptualisation, Validation, Supervision, Project administration 29

Igor V. Murin — Project administration, Funding acquisition

30