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Adsorption of ibuprofen on silicon decorated fullerenes and single walled carbon nanotubes: A comparative DFT study
Journal of Molecular Structure 1184 (2019) 110e113
Contents lists available at ScienceDirect
Journal of Molecular Structure journal homepage: http://www.elsevier.com/locate/molstruc
Adsorption of ibuprofen on silicon decorated fullerenes and single walled carbon nanotubes: A comparative DFT study € Cemal Parlak a, Ozgür Alver b, * a b
Department of Physics, Science Faculty, Ege University, Izmir, 35100, Turkey Department of Physics, Science Faculty, Eskisehir Technical University, Eskisehir, 26555, Turkey
a r t i c l e i n f o
a b s t r a c t
Article history: Received 15 December 2018 Received in revised form 5 February 2019 Accepted 6 February 2019 Available online 7 February 2019
Ibuprofen (IBP) is known as a widely prescribed drug for its non-steroidal, anti-inflammatory, analgesic, and antipyretic effects. Carbon nanotubes and fullerenes are the novel elements of drug delivery and sensor applications. In this work using M062X and B3LYP functionals with 6-31G(d) basis set, adsorption energies, possible sensor applications or sensitivity of single walled carbon nanotube (SWCNT) and fullerene C60 to IBP along with some electronic properties including conductivity, gap energies of frontier orbitals and natural bond orbital (NBO) analyses were reported in comparison. It was found that SiC59 is more strongly interacts with IBP and electronic sensitivity of it higher than that of Si@SWCNT system. © 2019 Elsevier B.V. All rights reserved.
Keywords: Ibuprofen Fullerene Carbon nanotube DFT
1. Introduction Drug delivery and sensor applications of carbon nanotube and fullerene based materials have been paid increasing attention lately. Due to their remarkable electronic and mechanical properties carbon nanotube based materials have been used in the variety of fields such as in the anticancer researches, liposome and near infrared light triggered drug delivery platforms in the literature [1e4]. They were also included in the search for electrochemical biosensors and optical sensors [5,6]. Furthermore, fullerenes have been widely studied for biomedical and sensor applications such as enzyme inhibition, imaging radiotherapy and work function type sensors [7e9]. Ibuprofen (IBP) which is also named as 2-(4-isobutylphenyl) propanoic acid is known with its non-steroidal, anti-inflammatory, analgesic and antipyretic effects [10]. It is first introduced in 1969 and known as an alternative to aspirin and the most frequently encountered side effects of it are gastric discomfort, nausea and vomiting [11,12]. It is also among the most frequently prescribed drugs [13,14]. Density functional theory (DFT) is widely used to assess the
* Corresponding author. Department of Physics, Science Faculty, Eskis¸ehir Technical University, Eskis¸ehir, 26555, Turkey. € Alver). E-mail address: [email protected] (O. https://doi.org/10.1016/j.molstruc.2019.02.023 0022-2860/© 2019 Elsevier B.V. All rights reserved.
chemical stability, adsorption energies (Eads), reactivity and sensitivity properties of fullerene and carbon nanotube related systems in the literature [15e19]. Two level adsorption study of IBP on C60 fullerenes for transdermal delivery purpose was reported before [20]. In the scope of this work, we aimed to investigate the interaction between silicon decorated fullerene C60, armchair type single walled carbon nanotube (SWCNT) and IBP drug molecule based on the DFT approach. The main motivation of this work is to analyze the possible drug delivery and sensor applications of IBP interacted fullerene and SWCNT systems by DFT methods. 2. Computational methods First, all the optimizations and vibrational frequency calculations to check the convergence of true structural minima were carried out with M062X functional and 6-31G(d) basis set. M062X is known as a hybrid type of Minnesota functional providing very good results for especially adsorption energies [21,22]. For the search of stable configurations, first, IBP, C60 and armchair type SWCNT were optimized and then one carbon atom located on the C60 and SWCNT was replaced by silicon atom. The resultant structures were optimized again. Having found the energetically stable configurations, the possible IBP and Si-doped fullerene and SWCNT interactions were searched. Electron density which is projected onto an electrostatic potential isosurface for IBP was reported by Hadad et al. [20]. Based on this report, two possible interaction sites
€ Alver / Journal of Molecular Structure 1184 (2019) 110e113 C. Parlak, O.
111
were taken into account for IBP as OH and C¼O edges. The structures were built with GaussView [23] including optimized fragments and then optimized again. The process was repeated along with frequency calculations until no imaginary frequencies yielded at the end. In the literature it was pointed out that although M062X produces very acceptable adsorption energies it overestimates the gap energies (Eg) when compared to the experimental results [22]. Therefore, for gap energy of the highest occupied and the lowest unoccupied molecular orbitals (HOMO-LUMO), chemical hardness (h), electrophilicity index(u), Wiberg bond index (WBI) and Fuzzy bond order (FBO) calculations B3LYP/6-31G(d) level of theory was preferred. Henceforth, all the calculations including optimizations of each structure and the complex system and the frequency calculations were repeated again with B3LYP/6-31G(d). Multiwfn program was used to get WBI and FBO parameters to analyze the bond characteristics where the interaction occurs [24]. Gaussian program was used for the optimizations and the frequency calculations of the examined structures [25]. 3. Results and discussions In this part interactions between IBP and SiC59 and SWCNT were examined based on structural, chemical, and infrared spectroscopic means. During the search for possible stable structures, two scenarios were taken into account. According to this procedure, oxygens of IBP and dopant silicon atom were chosen as interaction sites. If the interaction occurs between oxygen of OH of IBP and the dopant silicon atom (Fig. 1), for SiC59/O (OH) IBP and Si@SWCNT … O (OH) IBP systems adsorption energies were found as 12.86 and 7.76 kcal/mol, respectively. The Si/O (OH) bond distances were reported as 1.91 and 1.96 Å, respectively, as seen in Fig. 1. In order to investigate the electronic sensitivity of silicon doped C60 and SWCNT to IBP drug molecule, the widely used correlation between the gap energy and the electronic conductivity (s) was included as following [26e28]:
s a exp(-Eg/2 kT)
(1)
In equation (1), it is clearly seen that there is an exponential correlation between Eg and s. Henceforth, a possible change in Eg by modifying the population of conduction electrons will alter the conductivity of the system which can be used to produce an electrical signal for possible sensor and detector applications. The sensitivity of Si doped C60 and SWCNT was also examined by calculating the work function F which is theoretically defined as the minimum energy required to elevate one electron from the Fermi level (EF) of the system to infinity as described below [9].
F ¼ V(∞)-EF
(2)
Fig. 1. Optimized structures of SiC59/O (OH) IBP and Si@SWCNT … O (OH) IBP with M062X/6-31G(d).
of view. The optimized energy of the system given in Fig. 2 after the basis set superposition error (BSSE) correction was found as 25.59 kcal/mol which lies in the range of chemisorption indicating that the interaction is quite strong [31]. The Si … O (C¼O) distance was calculated as 1.85 Å which is in the acceptable range for possible strong interactions as reported in the previous works [9,32]. Among the vibrational bands of IBP carbonyl and hydroxyl
In here, V is the electrostatic potential energy of the electron at infinity. By analyzing the change in the work function F due to interaction with the title molecule (in here IBP), sensitivity assessments are possible [29,30]. If the interaction occurs from carbonyl oxygen of IBP stronger adsorption energies and larger alterations in the gap energies were observed. Therefore, in the following sections and in the rest of the discussions the carbonyl site interactions were considered for the examined systems. 3.1. SiC59 and IBP interaction First, it is better to discuss what happens when IBP interacts with SiC59 in chemical, structural, and infrared spectroscopic point
Fig. 2. Optimized structure of SiC59…IBP with M062X/6-31G(d).
€ Alver / Journal of Molecular Structure 1184 (2019) 110e113 C. Parlak, O.
112
stretching vibrations are particularly important since where the interaction takes place. For the isolated single IBP, n(C¼O) and n(OH) were calculated as 1870 and 3682 cm1. Following the interaction with SiC59, the related bands shifted to 1690 and 3515 cm1, correspondingly. It is possibly due to the weakening bond character of carbonyl and hydroxyl groups as a result of charge flow or redistribution of charges after the interaction. Gap energy was calculated as 1.668 eV for SiC59…IBP system and percent change from SiC59 to SiC59…IBP was found as 23.10%. The examination of charge transfer rate (DN) between the IBP and SiC59 showed that IBP behaves as electron donor with a DN value of 0.179 [33,34]. Upon interaction with IBP chemical hardness and electrophilic characters of the system were reduced by 0.251 and 2.698 eV, respectively. The Fermi level of SiC59 was shifted from 4.734 to 3.568 eV following the adsorption of IBP molecule. As seen in equation (2), EF has a direct correlation with work function F. The larger changes in EF means larger changes in F and less negative EF following the interaction with IBP contributes the electron emission possibility. Interaction of SiC59 with IBP produced 24.63% change in the work function F. Therefore, possible electron emission from the EF level will be favored significantly which can be converted into an electronic signal for detection of IBP. WBI and FBO values can be thought as the descriptor of the strength of the bond character [35,36]. WBI and FBO values were calculated as 0.605 and 0.901 for Si/O (C¼O) IBP. Further they were calculated as 0.031 and 0.059 for Si/O (OH) IBP. This fact reflects that dopand silicon atom and the oxygen of carbonyl group in IBP shows more covalent character with higher WBI and FBO values. 3.2. Si@SWCNT and IBP interaction The optimized energy of the Si@SWCNT … IBP system (Fig. 3) after BSSE correction was found as 16.73 kcal/mol which is 8.86 kcal/mol less in magnitude than the previous SiC59…IBP system. Further, Si/O (C¼O) distance was calculated as 1.89 Å which is 0.04 Å larger than the Si/O (C¼O) distance in SiC59…IBP system. Following the interaction with Si@SWCNT, n(C¼O) and n(OH) stretching bands of IBP moved to 1699 and 3543, respectively. As compared with SiC59…IBP, the alteration of the vibrational wavenumbers of the mentioned bands are less with Si@SWCNT … IBP system. Eg energy was calculated as 1.412 eV for Si@SWCNT … IBP system and percent change from Si@SWCNT to Si@SWCNT … IBP was
found as 17.86% which is 5.24% less than SiC59…IBP system. DN value here again shows negative trend with a value of 0.060 indicating that IBP acts as electron donor as it happens with silicon doped fullerene system. Interaction with IBP reduced the chemical hardness and electrophilic character of the system like silicon decorated fullerene system by 0.154 and 1.274 eV, respectively. However, the reduction is less when compared to silicon decorated system. The Fermi level of Si@SWCNT was shifted to higher energy level 3.591 to 2.965 eV after the adsorption of IBP molecule. This change in the EF means 17.43% change in the work function F. If considered together with SiC59 system with 24.63% change in F, it seems that SiC59 is more sensitive than Si@SWCNT to the detection of IBP molecule. For the SWCNT system, WBI and FBO values were calculated as 0.538 and 0.835 for Si/O (C¼O) IBP. In addition to that, they were calculated as 0.029 and 0.055 for Si/O (OH) IBP. This fact also reflects that as it happens with Si doped fullerene systems dopant silicon atom and the oxygen of carbonyl group in IBP possesses more covalent character indicating that main interaction occurs at this site. 4. Conclusions The following results can be summed up in brief: i. IBP more strongly interacts with SiC59 when compared to Si@SWCNT with adsorption energies 25.59 (SiC59…IBP) and 16.73 kcal/mol (Si@SWCNT … IBP). Further, interaction with carbonyl oxygen of IBP yields higher adsorption energies in magnitude when compared to its hydroxyl edge. ii The stronger adsorption energies led to higher shift in the stretching vibrations of n(C¼O) and n(OH) of IBP. Therefore, larger shifts were observed with SiC59…IBP system. Further, it was observed that as the adsorption energy increases Si/O distances which were calculated as 1.85 Å for SiC59…IBP and 1.89 Å for Si@SWCNT … IBP systems decreased. iii Due to their different strength in adsorption energies, using both SiC59…IBP and Si@SWCNT … IBP systems at the same time might open a way for controlled delivery purposes of IBP drug molecule in various environments. iv Percent gap energy (DEg) and wok function (DF) changes are larger with silicon decorated fullerene system (23.10 & 24.63%) when compared to silicon doped single walled carbon nanotube system (17.86 & 17.43%) which reflects that SiC59 is more sensitive to the presence of IBP than Si@SWCNT. Acknowledgments We would like to show a warm thank to the Scince Faculty of Ege University for the provided computational resources. References
Fig. 3. Optimized structure of Si@SWCNT … IBP with M062X/6-31G(d).
[1] C. Tripisciano, K. Kraemer, A. Taylor, E. Borowiak-Palen, Chem. Phys. Lett. 478 (2009) 200. [2] N. Pippaa, Demetrios D. Chronopoulosa, D. Stellas, R. Fern andez-Pacheco, R. Arenal, C. Demetzos, N. Tagmatarchis, Int. J. Pharm. 528 (2017) 429. [3] X. Dong, C. Wei, J. Liang, T. Liu, D. Kong, F. Lv, Colloids Surf., B 154 (2017) 253. [4] J.J. Gooding, Electrochim. Acta 50 (2005) 3049. [5] G.A. Rivas, M.C. Rodríguez, M.D. Rubianes, F.A. Gutierrez, M. Eguílaz, P.R. Dalmasso, E.N. Primo, C. Tettamanti, M.L. Ramírez, A. Montemerlo, P. Gallay, C. Parrado, Appl. Mater. Today 9 (2017) 566. [6] P. Sehrawat Abid, S.S. Islam, P. Gulati, M. Talib, P. Mishra, M. Khanuja, Sens. Actuators, A 269 (2018) 62. [7] S.H. Friedman, D.L. DeCamp, R.P. Sijbesma, G. Srdanov, F. Wudl, G.L. Kenyon, J. Am. Chem. Soc. 115 (1993) 6506. [8] L.J. Wilson, D.W. Cagle, T.P. Thrash, S.J. Kennel, S. Mirzadeh, J.M. Alford,
€ Alver / Journal of Molecular Structure 1184 (2019) 110e113 C. Parlak, O. G.J. Ehrhardt, Coord. Chem. Rev. 190e192 (1999) 199. [9] S. Bashiri E. Vessally, A. Bekhradnia, A. Hosseinian, L. Edjlali, Vacuum 136 (2017) 156. [10] J.J. Lazarevi c, S. Uskokovi ceMarkovi c, M. Jeliki ceStankov, M. Radonji c, D. Tanaskovi c, N. Lazarevi c, Z.V. Popovi c, Spectrochim. Acta 126 (2014) 301. [11] R. Bushra, N. Aslam, Oman Med. J. 25 (3) (2010) 155. [12] K.D. Tripathi, Non steroidal anti inflammatory drugs and anti pyretic analgesics, in: Essentials of Medical Pharmacology, fifth ed., Jaypee Brothers, New Delhi, 2003, p. 176. [13] P. Abraham, K. Indirani, K. Desigamani, Dig. Dis. Sci. 50 (9) (2005) 1632. [14] F. Bradbury, Int. J. Clin. Prat. 144 (2004) 27. € Alver, Chem. Phys. Lett. 678 (2017) 85. [15] C. Parlak, O. € Alver, P. Ramasami, J. Cluster Sci. 28 (5) (2017) 2645. [16] C. Parlak, O. € Alver, M. Bilge, N. Atar, C. Parlak, M. S¸enyel, J. Mol. Liq. 231 (2017) 202. [17] O. [18] M.T. Baei, Fullerenes, Nanotub. Carbon Nanostruct. 20 (8) (2012) 681. [19] H. Bai, N. Yuan, Y. Wu, J. Li, Y. Ji, Fullerenes, Nanotub. Carbon Nanostruct. 23 (3) (2015) 203. [20] A. Hadad, D.L. Azevedo, E.W.S. Caetano, V.N. Freire, G.L.F. Mendonça, P.L. Neto, E.L. Albuquerque, R. Margis, C. Gottfried, J. Phys. Chem. C 115 (2011) 24501. [21] A.M. El Mahdy, Appl. Surf. Sci. 383 (2016) 353. [22] M.K. Hazrati N.L. Hadipour, Comput. Theor. Chem. 1098 (2016) 63.
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[23] R.D. Dennington, T.A. Keith, J.M. Millam, GaussView 5.0.8, Gaussian Inc., 2008. [24] T. Lu, F. Chen, J. Comput. Chem. 33 (2012) 580. [25] M.J. Frisch, G.W. Trucks, H.B. Schlegel, et al., Gaussian 09, Revision A.1, Gaussian Inc., Wallingford, 2009. [26] A. Ahmadi, N.L. Hadipour, M. Kamfiroozi, Z. Bagheri, Sensor. Actuator. B Chem. 161 (2012) 1025. [27] A. Ahmadi Peyghan, N.L. Hadipour, Z. Bagheri, J. Phys. Chem. C 117 (2013) 2427. [28] A.A. Peyghan, S.A. Aslanzadeh, H. Soleymanabadi, Mon. für Chem.-Chem. Mon. 145 (2014) 1253. [29] I. Baikie, S. Mackenzie, P. Estrup, J. Meyer, Rev. Sci. Instrum. 62 (1991) 1326. [30] P. Bergstrom, S. Patel, J. Schwank, K. Wise, Sensor. Actuator. B Chem. 42 (1997) 195. [31] B. Bhushan, Principles and Applications of Tribology, first ed., Wiley-Interscience, Ohio, 1999. [32] M.K. Hazrati, N.L. Hadipour, Phys. Lett. 380 (2016) 937. [33] R.G. Parr, L.V. Szentpaly, S. Liu, J. Am. Chem. Soc. 121 (1999) 1922. [34] J. Padmanabhan, R. Parthasarathi, V. Subramanian, P.K. Chattaraj, J. Phys. Chem. 111 (2007) 1358. [35] Z. Mahdavifar, M. Poulad, Sensor. Actuator. B Chem. 205 (2014) 26. [36] J. Du, X. Sun, C. Zhang, Int. J. Hydrog. Energy 41 (2016) 11301.
Contents lists available at ScienceDirect
Journal of Molecular Structure journal homepage: http://www.elsevier.com/locate/molstruc
Adsorption of ibuprofen on silicon decorated fullerenes and single walled carbon nanotubes: A comparative DFT study € Cemal Parlak a, Ozgür Alver b, * a b
Department of Physics, Science Faculty, Ege University, Izmir, 35100, Turkey Department of Physics, Science Faculty, Eskisehir Technical University, Eskisehir, 26555, Turkey
a r t i c l e i n f o
a b s t r a c t
Article history: Received 15 December 2018 Received in revised form 5 February 2019 Accepted 6 February 2019 Available online 7 February 2019
Ibuprofen (IBP) is known as a widely prescribed drug for its non-steroidal, anti-inflammatory, analgesic, and antipyretic effects. Carbon nanotubes and fullerenes are the novel elements of drug delivery and sensor applications. In this work using M062X and B3LYP functionals with 6-31G(d) basis set, adsorption energies, possible sensor applications or sensitivity of single walled carbon nanotube (SWCNT) and fullerene C60 to IBP along with some electronic properties including conductivity, gap energies of frontier orbitals and natural bond orbital (NBO) analyses were reported in comparison. It was found that SiC59 is more strongly interacts with IBP and electronic sensitivity of it higher than that of Si@SWCNT system. © 2019 Elsevier B.V. All rights reserved.
Keywords: Ibuprofen Fullerene Carbon nanotube DFT
1. Introduction Drug delivery and sensor applications of carbon nanotube and fullerene based materials have been paid increasing attention lately. Due to their remarkable electronic and mechanical properties carbon nanotube based materials have been used in the variety of fields such as in the anticancer researches, liposome and near infrared light triggered drug delivery platforms in the literature [1e4]. They were also included in the search for electrochemical biosensors and optical sensors [5,6]. Furthermore, fullerenes have been widely studied for biomedical and sensor applications such as enzyme inhibition, imaging radiotherapy and work function type sensors [7e9]. Ibuprofen (IBP) which is also named as 2-(4-isobutylphenyl) propanoic acid is known with its non-steroidal, anti-inflammatory, analgesic and antipyretic effects [10]. It is first introduced in 1969 and known as an alternative to aspirin and the most frequently encountered side effects of it are gastric discomfort, nausea and vomiting [11,12]. It is also among the most frequently prescribed drugs [13,14]. Density functional theory (DFT) is widely used to assess the
* Corresponding author. Department of Physics, Science Faculty, Eskis¸ehir Technical University, Eskis¸ehir, 26555, Turkey. € Alver). E-mail address: [email protected] (O. https://doi.org/10.1016/j.molstruc.2019.02.023 0022-2860/© 2019 Elsevier B.V. All rights reserved.
chemical stability, adsorption energies (Eads), reactivity and sensitivity properties of fullerene and carbon nanotube related systems in the literature [15e19]. Two level adsorption study of IBP on C60 fullerenes for transdermal delivery purpose was reported before [20]. In the scope of this work, we aimed to investigate the interaction between silicon decorated fullerene C60, armchair type single walled carbon nanotube (SWCNT) and IBP drug molecule based on the DFT approach. The main motivation of this work is to analyze the possible drug delivery and sensor applications of IBP interacted fullerene and SWCNT systems by DFT methods. 2. Computational methods First, all the optimizations and vibrational frequency calculations to check the convergence of true structural minima were carried out with M062X functional and 6-31G(d) basis set. M062X is known as a hybrid type of Minnesota functional providing very good results for especially adsorption energies [21,22]. For the search of stable configurations, first, IBP, C60 and armchair type SWCNT were optimized and then one carbon atom located on the C60 and SWCNT was replaced by silicon atom. The resultant structures were optimized again. Having found the energetically stable configurations, the possible IBP and Si-doped fullerene and SWCNT interactions were searched. Electron density which is projected onto an electrostatic potential isosurface for IBP was reported by Hadad et al. [20]. Based on this report, two possible interaction sites
€ Alver / Journal of Molecular Structure 1184 (2019) 110e113 C. Parlak, O.
111
were taken into account for IBP as OH and C¼O edges. The structures were built with GaussView [23] including optimized fragments and then optimized again. The process was repeated along with frequency calculations until no imaginary frequencies yielded at the end. In the literature it was pointed out that although M062X produces very acceptable adsorption energies it overestimates the gap energies (Eg) when compared to the experimental results [22]. Therefore, for gap energy of the highest occupied and the lowest unoccupied molecular orbitals (HOMO-LUMO), chemical hardness (h), electrophilicity index(u), Wiberg bond index (WBI) and Fuzzy bond order (FBO) calculations B3LYP/6-31G(d) level of theory was preferred. Henceforth, all the calculations including optimizations of each structure and the complex system and the frequency calculations were repeated again with B3LYP/6-31G(d). Multiwfn program was used to get WBI and FBO parameters to analyze the bond characteristics where the interaction occurs [24]. Gaussian program was used for the optimizations and the frequency calculations of the examined structures [25]. 3. Results and discussions In this part interactions between IBP and SiC59 and SWCNT were examined based on structural, chemical, and infrared spectroscopic means. During the search for possible stable structures, two scenarios were taken into account. According to this procedure, oxygens of IBP and dopant silicon atom were chosen as interaction sites. If the interaction occurs between oxygen of OH of IBP and the dopant silicon atom (Fig. 1), for SiC59/O (OH) IBP and Si@SWCNT … O (OH) IBP systems adsorption energies were found as 12.86 and 7.76 kcal/mol, respectively. The Si/O (OH) bond distances were reported as 1.91 and 1.96 Å, respectively, as seen in Fig. 1. In order to investigate the electronic sensitivity of silicon doped C60 and SWCNT to IBP drug molecule, the widely used correlation between the gap energy and the electronic conductivity (s) was included as following [26e28]:
s a exp(-Eg/2 kT)
(1)
In equation (1), it is clearly seen that there is an exponential correlation between Eg and s. Henceforth, a possible change in Eg by modifying the population of conduction electrons will alter the conductivity of the system which can be used to produce an electrical signal for possible sensor and detector applications. The sensitivity of Si doped C60 and SWCNT was also examined by calculating the work function F which is theoretically defined as the minimum energy required to elevate one electron from the Fermi level (EF) of the system to infinity as described below [9].
F ¼ V(∞)-EF
(2)
Fig. 1. Optimized structures of SiC59/O (OH) IBP and Si@SWCNT … O (OH) IBP with M062X/6-31G(d).
of view. The optimized energy of the system given in Fig. 2 after the basis set superposition error (BSSE) correction was found as 25.59 kcal/mol which lies in the range of chemisorption indicating that the interaction is quite strong [31]. The Si … O (C¼O) distance was calculated as 1.85 Å which is in the acceptable range for possible strong interactions as reported in the previous works [9,32]. Among the vibrational bands of IBP carbonyl and hydroxyl
In here, V is the electrostatic potential energy of the electron at infinity. By analyzing the change in the work function F due to interaction with the title molecule (in here IBP), sensitivity assessments are possible [29,30]. If the interaction occurs from carbonyl oxygen of IBP stronger adsorption energies and larger alterations in the gap energies were observed. Therefore, in the following sections and in the rest of the discussions the carbonyl site interactions were considered for the examined systems. 3.1. SiC59 and IBP interaction First, it is better to discuss what happens when IBP interacts with SiC59 in chemical, structural, and infrared spectroscopic point
Fig. 2. Optimized structure of SiC59…IBP with M062X/6-31G(d).
€ Alver / Journal of Molecular Structure 1184 (2019) 110e113 C. Parlak, O.
112
stretching vibrations are particularly important since where the interaction takes place. For the isolated single IBP, n(C¼O) and n(OH) were calculated as 1870 and 3682 cm1. Following the interaction with SiC59, the related bands shifted to 1690 and 3515 cm1, correspondingly. It is possibly due to the weakening bond character of carbonyl and hydroxyl groups as a result of charge flow or redistribution of charges after the interaction. Gap energy was calculated as 1.668 eV for SiC59…IBP system and percent change from SiC59 to SiC59…IBP was found as 23.10%. The examination of charge transfer rate (DN) between the IBP and SiC59 showed that IBP behaves as electron donor with a DN value of 0.179 [33,34]. Upon interaction with IBP chemical hardness and electrophilic characters of the system were reduced by 0.251 and 2.698 eV, respectively. The Fermi level of SiC59 was shifted from 4.734 to 3.568 eV following the adsorption of IBP molecule. As seen in equation (2), EF has a direct correlation with work function F. The larger changes in EF means larger changes in F and less negative EF following the interaction with IBP contributes the electron emission possibility. Interaction of SiC59 with IBP produced 24.63% change in the work function F. Therefore, possible electron emission from the EF level will be favored significantly which can be converted into an electronic signal for detection of IBP. WBI and FBO values can be thought as the descriptor of the strength of the bond character [35,36]. WBI and FBO values were calculated as 0.605 and 0.901 for Si/O (C¼O) IBP. Further they were calculated as 0.031 and 0.059 for Si/O (OH) IBP. This fact reflects that dopand silicon atom and the oxygen of carbonyl group in IBP shows more covalent character with higher WBI and FBO values. 3.2. Si@SWCNT and IBP interaction The optimized energy of the Si@SWCNT … IBP system (Fig. 3) after BSSE correction was found as 16.73 kcal/mol which is 8.86 kcal/mol less in magnitude than the previous SiC59…IBP system. Further, Si/O (C¼O) distance was calculated as 1.89 Å which is 0.04 Å larger than the Si/O (C¼O) distance in SiC59…IBP system. Following the interaction with Si@SWCNT, n(C¼O) and n(OH) stretching bands of IBP moved to 1699 and 3543, respectively. As compared with SiC59…IBP, the alteration of the vibrational wavenumbers of the mentioned bands are less with Si@SWCNT … IBP system. Eg energy was calculated as 1.412 eV for Si@SWCNT … IBP system and percent change from Si@SWCNT to Si@SWCNT … IBP was
found as 17.86% which is 5.24% less than SiC59…IBP system. DN value here again shows negative trend with a value of 0.060 indicating that IBP acts as electron donor as it happens with silicon doped fullerene system. Interaction with IBP reduced the chemical hardness and electrophilic character of the system like silicon decorated fullerene system by 0.154 and 1.274 eV, respectively. However, the reduction is less when compared to silicon decorated system. The Fermi level of Si@SWCNT was shifted to higher energy level 3.591 to 2.965 eV after the adsorption of IBP molecule. This change in the EF means 17.43% change in the work function F. If considered together with SiC59 system with 24.63% change in F, it seems that SiC59 is more sensitive than Si@SWCNT to the detection of IBP molecule. For the SWCNT system, WBI and FBO values were calculated as 0.538 and 0.835 for Si/O (C¼O) IBP. In addition to that, they were calculated as 0.029 and 0.055 for Si/O (OH) IBP. This fact also reflects that as it happens with Si doped fullerene systems dopant silicon atom and the oxygen of carbonyl group in IBP possesses more covalent character indicating that main interaction occurs at this site. 4. Conclusions The following results can be summed up in brief: i. IBP more strongly interacts with SiC59 when compared to Si@SWCNT with adsorption energies 25.59 (SiC59…IBP) and 16.73 kcal/mol (Si@SWCNT … IBP). Further, interaction with carbonyl oxygen of IBP yields higher adsorption energies in magnitude when compared to its hydroxyl edge. ii The stronger adsorption energies led to higher shift in the stretching vibrations of n(C¼O) and n(OH) of IBP. Therefore, larger shifts were observed with SiC59…IBP system. Further, it was observed that as the adsorption energy increases Si/O distances which were calculated as 1.85 Å for SiC59…IBP and 1.89 Å for Si@SWCNT … IBP systems decreased. iii Due to their different strength in adsorption energies, using both SiC59…IBP and Si@SWCNT … IBP systems at the same time might open a way for controlled delivery purposes of IBP drug molecule in various environments. iv Percent gap energy (DEg) and wok function (DF) changes are larger with silicon decorated fullerene system (23.10 & 24.63%) when compared to silicon doped single walled carbon nanotube system (17.86 & 17.43%) which reflects that SiC59 is more sensitive to the presence of IBP than Si@SWCNT. Acknowledgments We would like to show a warm thank to the Scince Faculty of Ege University for the provided computational resources. References
Fig. 3. Optimized structure of Si@SWCNT … IBP with M062X/6-31G(d).
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