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Molecule decomposition via plasma jet at atmospheric pressure
Journal of Molecular Liquids 277 (2019) 912–920
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Journal of Molecular Liquids journal homepage: www.elsevier.com/locate/molliq
Molecule decomposition via plasma jet at atmospheric pressure Murat Tanışlı a,⁎, Erol Taşal b, Neslihan Şahin a, Gökhan Dikmen c a b c
Eskişehir Technical University, Science Faculty, Department of Physics, Eskişehir 26470, Turkey Eskişehir Osmangazi University, Art and Sciences Faculty, Physics Department, Eskişehir, Turkey Eskişehir Osmangazi University, Central Research Laboratory, Application and Research Center, Eskişehir, Turkey
a r t i c l e
i n f o
Article history: Received 7 August 2018 Received in revised form 4 December 2018 Accepted 5 January 2019 Available online 07 January 2019 Keywords: NMR UV–Vis FT-IR spectra Drug molecule Chemical decomposing Plasma photoproduct
a b s t r a c t In this study, the 6-(4-fluorobenzoyl)-3-(2-(4-methylpiperazine-1-il)-2-oxoethyl)benzo [d]thiazole-2(3H) (briefly named as 6FPB) molecule structure and its properties have been investigated in detail. Fouriertransform infrared (FTIR), ultraviolet visible (UV–Vis) techniques were used to obtain the spectra of vibrational, absorption or emission and also the nuclear magnetic resonance (NMR) spectrum was provided in research for determining of the content of solid and liquid phases for the 6FPB molecule. Then, the atmospheric pressure plasma treatment (APPT) was applied to the 6FPB molecule in liquid phase. In this case, the NMR, UV–Vis and FT-IR spectra have been obtained and analyzed, again. According to the results, it is seen that the 6FPB molecule was decomposed after APPT. Some shifts and changes occurring in the peaks show that some bonds of 6FPB molecule have been broken. The electronic transitions as π-π* and n-π* were obtained at the 6FPB molecule. It is seen that the electronic transitions π-π* and n-π* are related to the isomerization process. NMR spectra show that all of the protons of title molecule except for protons of piperazine ring and CH2 group were eliminated by APPTs. © 2019 Elsevier B.V. All rights reserved.
1. Introduction It is well-known that plasma can be considered as a quasi-neutral ionized gas including very different particles such as photons, ions, free electrons, atoms [1]. Also, the generation of discharge in laboratory can be obtained with the different excitation frequency and electrode design. Direct current (DC), alternative current (AC), radio frequency (RF) and microwave power supplies are used to generate discharge at low and atmospheric pressures [2–4]. In the related literature, there are some studies about discharge at low pressure, but it is known that the vacuum systems, which are quite expensive in these systems, are needed for generating of discharge at low pressure. These vacuum systems need to be maintained. Additionally, the dimensions of the material to be applied are limited by the dimensions of the vacuum chamber. For these reasons, the discharges generated at atmospheric pressure can be preferred instead of the discharge generated at low pressure [5]. A classification of discharges is known as Corona, dielectric barrier discharge (DBD), atmospheric pressure plasma jet (APPJ) and microwave plasma in the GHz range [6]. In addition, non-local thermodynamic equilibrium (non-LTE) plasma jets are classified as dielectricfree electrode, DBD, DBD-like and single-electrode jets [7]. The room temperature has been accepted as the temperature of non-LTE plasma jets and the electron temperatures are around several electron volt
⁎ Corresponding author. E-mail addresses: [email protected] (M. Tanışlı), [email protected] (E. Taşal).
https://doi.org/10.1016/j.molliq.2019.01.026 0167-7322/© 2019 Elsevier B.V. All rights reserved.
(eV) and the reactive radicals, UV photons and metastable atoms are occurred in non-LTE plasma jets [8]. Over the years, the plasma physics has been considered for interdisciplinary studies. Nowadays, there are some industrial and medical applications of DBD and DBD-like jets at atmospheric pressure. The material modification, deposition, etching, nanomaterial synthesis and microorganism are the well-known for some of the most important applications [9,10]. For the low temperature, the studies on the bases of plasma formation at atmospheric pressure and effects on microspheres and bacteria inactivation have been carried out [6,11,12]. In recent years, there have also been studies with selective intramolecular vibration owing to vibration photochemistry. Apart from this, the effects of plasma on the molecules have been researched. Some studies have been investigated whether the plasma at atmospheric pressure changes the structure of the molecule or not. The changes in the structure of the molecule after APPT have been compared with the title molecule. Tanışlı and Taşal have applied argon and neon atmospheric pressure plasma jets on coumarin molecule. With argon plasma jet treatment on this molecule, the 1O\\2C single bond was broken, the 1O\\6C single bond became double bonded and also the 2C\\3C single-bond changed into 2C_3C double-bonds. With neon plasma jet treatment, some shifts and changes at specific wavenumbers were only been observed. The reason for this difference was related to the energy of the argon and neon plasmas [13]. In their other study, they investigated application of the argon atmospheric pressure plasma jet on C13H12N2O3 molecule which is dye molecule, two-photo products have been obtained as 12C_17O (strong, wide stretching peak) and 6C\\7N\\8N_9C
M. Tanışlı et al. / Journal of Molecular Liquids 277 (2019) 912–920
(strong, varying stretching peak). A new dye molecule has been seen with this application [14]. Durme and et al. attempted to give an overview of recently published on plasma catalysis. They have showed that the effect of hybrid plasma catalysis is on by-product. It can be concluded from this study that dielectric barrier discharges are most frequently used in recent plasma catalytic research [15]. Urashima and Chang have reviewed the gaseous pollution control technology based on discharge plasma. They investigated destruction of volatile organic compounds from air streams and industrial flue gases by non-thermal plasma [16]. Morent and et al. have given plasma treatment effects or results on the treatment of textiles with non-thermal plasmas in their study [17]. Ermolaeva and et al. have shown the effect of non-thermal argon plasma in removing pathogenic bacteria from biofilms and wound surface. Their studies present that non-thermal plasma is being important to sterilize [18]. Scally and et al. investigated the effects of atmospheric pressure non-equilibrium plasma discharge on polyethylene terephthalate samples [19]. In the literature, there are also many studies about cancer cell death. Liedtke and et al. have explored the application of an atmospheric pressure argon plasma jet on the pancreatic cancer. This study has represented suggestions about non-thermal plasma conditioned solutions for treatment of malignancies [20]. He and et al. have investigated the effects of cold atmospheric plasma on the gold nanoparticles. They have explored the mechanism of synergistic cytotoxic effects between cold atmospheric plasma and nanotechnologies [21]. Kumar and et al. compared the effects of plasma treated media and plasma treated water on two different pancreatic ductal adenocarcinomas and pancreatic stellate cells [22]. When the APPJ interacts with a molecule, the molecule can be converted to the other molecule by a new useful method in plasma physics field. Tanışlı and et al. show that the 7N\\8C bond at 6-(2-Fluorobenzoyl)-3-(2-(4-(4fluorophenyl)piperazin-1-yl)-2-oxoethyl)benzo[d]thiazol-2(3H)-one molecule has been broken after argon plasma jet treatment. The new photoproducts have been considered as stretching peaks at 17C\\18S_14C and 17C_19O [23]. In addition, the various applications of plasma occur in the industrial process. Because, non-thermal plasmas are high removal efficiency, energy yields and good economy. Sensitivity to pain is a hard case that people have been struggling for centuries. No drug has been discovered yet that is effective against pain and has no side effects. Today, the most drug group studied is analgesics. The main goal in pain research is to develop nonsteroidal antiinflammatory (NSAI) drugs and non-opiate analgesics that are as effective as opiates because of the least side effects. Also, non-acidic NSAIs have fewer side effects than acidic NSAIs [24]. In this context, benzothiazolinone derivatives are one of the promising groups for having analgesic activity. Benzothiazolinone derivatives are analogous molecules that are reference of NSAI drugs and are considered to be one of the promising groups because of their analgesic activity. They have heterocyclic ring systems with a wide range of biological activities such as antibacterial, analgesic, diuretic, antihistaminic, anticonvulsant, antiarrhythmic, antiasthmatic and central nervous system depressant [25–29]. Various biological effects of benzothiazolinone derivative molecules including analgesic and anti-inflammatory activities have been studied [30,31]. Benzothiazolinone derivatives have been reported to exhibit strong anti-inflammatory activity by inhibiting prostaglandin synthesis. It is also reported in the literature that there are fewer side effects compared to analgesic and anti-inflammatory drugs currently on the market [32]. Taking into account this information, some benzothiazolinone derivatives and studies on them have produced compounds with significant analgesic and anti-inflammatory activity. Some biologically active substituted benzothiazole derivatives can also be used in the treatment of breast cancer [33–40]. The organization of this study is the following: First of all, the introduction part is presented in Section 1. After that, Sections 2 and 3 describe the experimental setup, and molecule. In Sections 4 and 5, the experimental data have been presented with the assignment of spectra.
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And then, the results of NMR spectra are analyzed in Section 6. Finally, the innovation and importance for results are concluded in conclusions. 2. Experimental setup In this study, the dielectric barrier discharge-like (DBD-like) at atmospheric pressure is used for the experimental studies (Fig. 1). When the discharge does not interact with metals at the out of the discharge tube, this system is defined as DBD-like discharge without extra dielectric material. The presented system has two electrodes, whose geometries are different from each other. The discharge tube is also used as the dielectric material. The geometry of the grounded electrode made of aluminum is circular. The high voltage electrode was made of tungsten wire. Tungsten wire diameter and thickness are 0.16 and 170 mm, and the thickness and diameter of the aluminum electrode are 4 and 40 mm, respectively. The discharge tube has been made from a cylindrical quartz and it has a length of 17.3 cm. The outer and inner diameters of discharge tube are 8 and 6 mm. The high voltage and grounded electrodes are placed inside and outside of the discharge tube, respectively. The high voltage AC power supply was connected to the electrode to provide energy for discharge. The working frequency and voltage for power supply are between 10–25 kHz and 4–20 kV, respectively. For this study, the voltage of AC power supply has been adjusted as 16 kV at the 24 kHz frequency. The pure Ar has been sent into the discharge tube, which was held perpendicular in the system. The flow rate is controlled by Mass Flowmeter. For this study, the flow rate has also been selected as 4 l/min. The temperature of the plasma plume from the jet has been measured with Fluke CNXT3000 K-Type Wireless Temperature Module in 38–42 °C range. Tektronix Oscilloscope 500 MHz and AC current probe have also been used to measure current values of Ar atmospheric pressure plasma jet. Peak-to-peak and RMS currents have been measured as 14.60 and 1.37 mA, respectively. In the presented study, the 6FPB molecule has been tried to be modified with DBD-like discharge system. For this purpose, the solutions for the 6FPB molecule were prepared in liquid phase about 5 × 10−4 M with using two different solvents, which are ethanol and methanol. Also, the atmospheric pressure discharge has been used to apply the samples from the distances 1 cm with 3 min duration. The changes of molecule structure have been evaluated with FTIR, UV–Vis and NMR spectra. Infrared spectrum was obtained in the range 4000 and 300 cm−1 on a Perkin-Elmer two FT-IR System. The KBr pellet technique was used via this spectrophotometer. The absorbance spectra were also recorded in the range 200–800 nm with Shimadzu UV–Vis spectrophotometer and CPS-100 apparatus were used to keep the sample temperature constant at 22 °C during the experiment. NMRs were considered for both before and after APPT to the 6FPB molecule dissolved separately in ethanol and methanol. JEOL ECZ 500R spectrometer was used for NMR measurements at room temperature. The operating frequencies for 1H nucleus were 500.13 MHz. Deuterium oxide was chosen as solvent. All spectra were collected via standard pulse as 90° and the scan number has been adjusted to 32. 3. The structure and properties of the 6FPB molecule The optimized structure and atomic number for the 6FPB molecule are shown in Fig. 2. The properties of the molecular structure and FT-IR spectrum of solid phase for the 6FPB molecule have been represented in Table 1 and Fig. 3, respectively. The 6FPB molecule, which is given in Table 1, is a new molecule obtained by synthesizing in the Turkish Scientific Council (TÜBİTAK) Research Project (No: 108T192-2008). The molecule was not used in any study. All properties will be included in the literature for the first time and will contribute to a new benzothiazolinone derivative.
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Fig. 1. Schematic diagram of the plasma system.
4. Analysis of vibrational spectra before and after APPJ FT-IR spectra of 6FPB molecule dissolved in different solvents before and after Ar APPTs are given in Figs. 4 and 5. Also, the changes of molecule structure have been evaluated. In addition to this, some vibration modes of ethanol and methanol solvents have been clearly known in the literature [41]. A. The vibration modes of 6FPB molecule dissolved in ethanol before APPT are listed below: CH2 asymmetric stretching as sharp and strong was noticed at wavenumber 2975.37 cm−1. CH3 asymmetric stretching as sharp and medium was considered at wavenumber 2928.64 cm−1. CH3 symmetric stretching as narrow and strong was existed at wavenumber 2888.89 cm−1. A sharp and strong C _ C stretching was seen at wavenumber 1455.36 cm−1. A sharp and strong C\\C\\S\\N\\C stretching was recognized at wavenumber 1417.93 cm−1. C \\ C \\ C \\ C \\ C stretching was noticed as sharp and strong at wavenumbers 1417.93 and 1381.06 cm−1.
C _ C stretching was existed as sharp and strong at wavenumber 1381.06 cm−1 and it was seen as narrow and strong at wavenumber 1275.14 cm−1. C\\C\\C\\C\\C stretching was recognized as narrow and strong at wavenumber 1275.14 cm−1. C\\N stretching was noticed as sharp and medium at wavenumber 1330.72 cm−1. C \\ H stretching was existed as sharp and strong at wavenumbers 1090.87 and 1049.54 cm−1. C \\ N stretching as sharp and strong was recognized at wavenumbers 881.34 and 584.04 cm−1. C \\ S was noticed as medium and sharp at wavenumber 804.09 cm−1. CH2 scissoring as sharp and strong was recognized at wavenumber 1455.36 cm−1. C \\ H in-plane-bending was existed as sharp and strong at wavenumber 1417.93 cm−1. C\\H\\C\\C\\C\\S\\C\\N in-plane-bending stretching was noticed as sharp and strong at wavenumber 1090.87 cm−1. A sharp and strong C \\ H \\ C \\ C \\ C \\ S \\ C \\ N in-planebending was recognized at wavenumbers 1381.06 and 1049.54 cm−1. A narrow and strong CH2 wagging was noticed at wavenumber 1275.14 cm−1.
Fig. 2. a) The optimized structure and b) the atomic number for the 6FPB molecule.
M. Tanışlı et al. / Journal of Molecular Liquids 277 (2019) 912–920
CH2 wagging was existed as medium and sharp at wavenumber 1330.72 cm−1. A sharp and strong CH3 deformation was recognized at wavenumber 1090.87 cm−1. CH2 rocking was noticed as sharp and strong at wavenumber 1049.54 cm−1. A sharp and strong C\\C\\C\\C\\C deformation was noticed at wavenumber 1049.54 cm−1. C \\ H out-of-plane-bending was existed as sharp and strong at wavenumber 881.34 cm−1. C \\ H out-of-plane-bending was existed as medium and sharp at wavenumber 804.09 cm−1. A medium and strong C \\ C \\ C \\ C \\ C out of plane bending at wavenumber 665.80 cm−1 was noticed. C \\ C \\ S \\ C \\ N out of plane bending at wavenumber 665.80 cm−1 was existed as medium and strong. C\\H\\C\\C\\C\\C\\C was recognized as medium and strong at wavenumber 665.80 cm−1. A sharp and strong C\\C\\C\\C\\C out of plane bending was noticed at wavenumber 584.04 cm−1. C\\ C\\ S\\ C\\ N out of plane bending was existed as sharp and strong at wavenumber 584.04 cm−1. CH2 rocking was existed as sharp and strong at wavenumber 584.04 cm−1.
Table 1 The properties of the 6FPB molecule. QSAR and QSPR parameters and properties
6FPB molecule
Dot Group The weight of molecule Boiling point (K) Melting point (K) The formula of molecule The number of total electron The number for full molecular orbital The number for empty orbital The number for total molecular orbital Molecular polarizability Dipole moment (Debye) EHOMO (eV) ELUMO (eV) q− qH+ Vm (cm3/mol) Ionization potentials (eV) Electron affinity (eV) Electronegativity (eV) Hardness for molecule (eV) Softness for molecule (eV) Index for electrophilic Log P Molar refractivity (cm3/mol) Formation heat (298 K) (kcal/mol)
C1 413.47 1031.18 810.22 C21H20FN3O3S 216 108 371 479 274.507 7.1845 −6.005 −1.754 −0.502 0.214 274.316 6.005 1.754 −3.880 2.126 0.470 3.540 2.169 110.316 −162.960
Points Count
Data Spacing
7201
849.5 763
%T r ansmittance
584.5
755 802.5
1002
25
1234 1284.5 1295
1575 1590.5
30
964
1452
35
1140 1144 1154.5 1193.5
1311 1379
40
623.5 695.5
933
1096.5 1052.5
1505
45
495.5 511.5
917
414 437
1781 1853 1908 2015.5 2073.5
50
2799 2852.5
2931 2977
55
2750
60
3047.5 3098
3309
65
0.5000
2252.5 2382.5 2420.5 2456 2562.5 2617 2686
70
915
20
1672
1645.5
15 10 5 0 4000 No
cm-1
3000 %T
Intensity
No
cm-1
2000 Wavenumber (cm-1) %T
Intensity
No
cm-1
1000 %T
Intensity
Fig. 3. FT-IR spectrum of the 6FPB molecule in solid phase.
No
cm-1
%T
Intensity
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%T
107 100 95 90 85 80 75 70 65 60 55 50 46 108 105 100
2256.50cm-1, 102.12%T1925.66cm-1, 100.17%T
474.28cm-1, 100.94%T 506.74cm-1, 98.31%T
1660.54cm-1, 95.70%T
561.05cm-1, 92.46%T 521.48cm-1, 95.88%T 491.03cm-1, 99.16%T 458.92cm-1, 101.30%T
1330.72cm-1, 81.64%T 1417.93cm-1, 76.68%T 1455.36cm-1, 75.09%T 1381.06cm-1, 72.51%T 881.34cm-1, 63.23%T
2928.64cm-1, 60.97%T 3340.79cm-1, 47.91%T 2975.37cm-1, 49.49%T 2888.89cm-1, 58.63%T
1049.54cm-1, 49.45%T 1090.87cm-1, 55.19%T
1925.59cm-1, 102.88%T 2256.36cm-1, 104.05%T 1660.41cm-1, 99.74%T
95 90 %T
5 4 4 .0 7 c m -1 , 9 4 .0 6 % T
804.09cm-1, 89.88%T 584.04cm-1, 88.31%T 665.80cm-1, 84.66%T
1275.14cm-1, 87.00%T
459.47cm-1, 101.87%T 491.38cm-1, 99.74%T 521.75cm-1, 97.84%T 583.98cm-1, 92.63%T 659.86cm-1, 90.09%T 804.10cm-1, 94.70%T 506.74cm-1, 99.77%T
1275.15cm-1, 93.37%T
85
1330.39cm-1, 89.12%T 1455.46cm-1, 83.98%T 1380.98cm-1, 81.86%T 1423.82cm-1, 85.38%T
80 75 70
473.84cm-1, 100.83%T
881.34cm-1, 71.84%T
65 60 55 53 4000
2888.83cm-1, 68.56%T
3340.40cm-1, 54.01%T
2975.56cm-1, 56.93%T 2928.66cm-1, 70.90%T
3500
1049.63cm-1, 54.60%T 1090.94cm-1, 62.93%T
3000
2500
2000
cm-1
Name Description T3 ETH Sample 064 By Administrator Date Sunday, May 28 2017 T3 ETH AR Sample 065 By Administrator Date Sunday, May 28 2017
1500
1000
500450
Fig. 4. FT-IR spectra for interactions of plasma and 6FPB molecule dissolved in ethanol. The subfigures are combined into a whole one (The spectrum shown above in red indicates the state after argon plasma interaction.).
The wavenumber 544.07 cm−1 includes the N\\C_O stretching and CH2 rocking modes as sharp and weak. CH2 rocking was existed as sharp and weak at wavenumber 521.48 cm−1.
C\\ C\\ C\\ C\\ C out of plane bending was noticed as sharp and weak at wavenumber 561.04 cm−1. C \\ C \\ S \\ C \\ N out of plane bending was recognized as sharp and weak at wavenumber 561.04 cm−1.
485.51cm-1, 96.41%T
%T
102
2869.3
95 90 85 80 75 70 65 60 55 50
3706.86cm-1, 96.05%T 3681.22cm-1, 95.86%T
2525.63cm-1, 94.37%T
2917.1
2052.00cm-1, 95.95%T 1706.46cm-1, 97.16%T
1454.31cm-1, 84.56%T 2977.7
547.15cm-1, 93.24%T
669.22cm-1, 88.85%T
1347.9 2832.11cm-1, 71.14%T
3325.71cm-1, 65.67%T
2945.20cm-1, 66.37%T
516.36cm-1, 95.13%T
45 100
1414.8
95 2525.29cm-1, 96.77%T
90
2043.91cm-1, 97.50%T
1670.88cm-1, 96.53%T
1115.68cm-1, 91.86%T
85
%T
509.13cm-1, 94.74%T 1115.16cm-1, 88.88%T
1450.23cm-1, 87.82%T
669.15cm-1, 88.86%T
80 75 70
2 8 3 3 . 9 5 c m
- 1 ,
7 5 . 2 4 %
T
2946.35cm-1, 71.63%T
65 60
3338.11cm-1, 64.15%T
54 4000
3500
1031.53cm-1, 54.90%T
3000
Name Description T3 METH ARG Sample 077 By Administrator Date Sunday, May 28 2017 T3 METH Sample 076 By Administrator Date Sunday, May 28 2017
2500
cm-1
2000
1500
1000
500450
Fig. 5. FT-IR spectra for interactions of plasma and 6FPB molecule dissolved in methanol. The subfigures are combined into a whole one (The spectrum shown above in blue indicates the state after argon plasma interaction.).
M. Tanışlı et al. / Journal of Molecular Liquids 277 (2019) 912–920
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A sharp and weak C \\ C \\ C \\ C \\ C out of plane bending mode was noticed at wavenumber 506.74 cm−1. The wavenumber 521.48 cm−1 includes the sharp and weak C \\ S stretching and C\\ C\\ C\\ C\\ C out of plane bending modes. B. The vibration modes of the 6FPB molecule dissolved in ethanol after Ar APPT are listed below: CH2 asymmetric stretching was existed as sharp and strong at wavenumber 2975.56 cm−1. A narrow and medium CH3 asymmetric stretching was noticed at wavenumber 2928.66 cm−1. A narrow and strong CH3 symmetric stretching was existed at wavenumber 2888.83 cm−1 and also CH3 symmetric stretching was recognized as narrow and weak at wavenumber 2256.36 cm−1. The wavenumber 1455.46 cm−1 includes the CH2 scissoring and C _ C stretching modes as medium and sharp. The wavenumber 1423.82 cm−1 includes the C\\C\\S\\C\\N\\ C stretching, C \\ C \\ C \\ C \\ C stretching, and C \\ H in-planebending modes as narrow and medium. The sharp and strong C\\C\\C\\C\\C stretching, C\\H\\C\\C \\C\\S\\C\\N in-plane-bending, and C _ C stretching modes were noticed at wavenumber 1380.98 cm−1. CH2 wagging, C _ C stretching, and C\\ C\\ C \\ C\\ C stretching modes as narrow and strong were existed at wavenumber 1275.15 cm−1. The sharp and strong C\\N stretching and CH2 wagging modes were existed at wavenumber 1330.39 cm−1. The sharp and strong C \\ H \\ C \\ C \\ C \\ S \\ C \\ N in-planebending stretching, CH3 deformation, and C\\H stretching modes were noticed at wavenumber 1090.94 cm−1. CH2 rocking, C\\H stretching, C\\H\\C\\C\\C\\C\\C in plane bending, and C \\ C \\ C \\ C \\ C deformation modes as sharp and strong were recognized at wavenumber 1049.63 cm−1. C \\ N stretching and C \\ H out-of-plane-bending modes as sharp and strong were seen at wavenumber 881.34 cm−1. The medium and sharp C \\ S stretching and C \\ H out-of-planebending modes at wavenumber 804.10 cm−1 were existed. C\\C\\C\\C\\C out of plane bending, C\\C\\S\\C\\N out of plane bending, and C\\H\\C\\C\\C\\C\\C modes were existed as strong and medium at wavenumber 659.86 cm−1. The wavenumber 583.98 cm−1 includes the C\\N stretching, C\\C \\ C \\ C \\ C out of plane bending, C \\ C \\ S \\ C \\ N out of plane bending, and CH2 rocking modes as wide and strong. CH2 rocking was seen as sharp and weak at wavenumber 521.75 cm−1.
Fig. 6. UV–Vis for the 6FPB molecule dissolved in methanol before APPT.
Fig. 7. UV–Vis for the 6FPB molecule dissolved in methanol after Ar APPT.
C\\ C\\ C\\ C\\ C out of plane bending was noticed as sharp and weak at wavenumber 506.74 cm−1. C\\S stretching and C\\C\\C\\C\\C out of plane bending modes as sharp and weak were noticed at wavenumber 491.38 cm−1. A sharp and weak CH2 rocking was recognized at wavenumber 473.84 cm−1. CH2 rocking was noticed as sharp and weak at wavenumber 459.86 cm−1. The experimental vibration spectra of the 6FPB molecule dissolved in ethanol before and after APPT are given in Fig. 4. It is obvious that there is no break in the 6FPB molecule dissolved in ethanol before and after Ar APPT. After Ar APPT, some shifts and changes were only observed in the vibrational peaks. C. The vibration modes of 6FPB molecule dissolved in methanol before APPT are listed below: CH2 asymmetric stretching was existed as sharp and strong at wavenumber 2946.35 cm−1. CH3 asymmetric stretching was noticed as sharp and strong at wavenumber 2833.95 cm−1. A medium and wide CH3 symmetric stretching was noticed at wavenumber 2525.29 cm−1. CH3 symmetric stretching was existed as medium and wide at wavenumber 2043.91 cm−1.
Fig. 8. UV–Vis for the 6FPB molecule dissolved in ethanol before APPT.
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C\\C\\C\\C\\C out of plane bending, C\\C\\S\\C\\N out of plane bending, and C\\H\\C\\C\\C\\C\\C modes were existed as wide and strong at wavenumber 669.15 cm−1. D. The vibration modes of the 6FPB molecule dissolved in methanol after Ar APPT are listed below:
Fig. 9. UV–Vis for the 6FPB molecule dissolved in ethanol after Ar APPT.
C\\C\\S\\C\\N\\C stretching, C\\C\\C\\C\\C stretching, and C _ C stretching modes were recognized as narrow and medium at wavenumber 1450.23 cm−1. The wavenumber 1115.68 cm−1 includes the C\\C\\S\\C\\N\\ C stretching and C\\C\\C\\C\\C in plane bending modes as narrow and medium. CH2 rocking, C\\H stretching, C\\H\\C\\C\\C\\C\\C in plane bending, and C\\ C\\ C\\ C\\ C deformation modes were noticed as sharp and strong at wavenumber 1031.53 cm−1.
O\\H symmetric stretching modes were considered as narrow and medium at wavenumbers 3681.22 and 3706.86 cm−1. CH2 asymmetric stretching was acquired as strong and medium at wavenumber 2945.20 cm−1. CH3 asymmetric stretching was realized as sharp and strong at wavenumber 2832.11 cm−1. S_C stretching modes were existed as medium and wide at wavenumber 2052.00 and 2525.63 cm−1. CH2 scissoring and C _ C stretching modes were noticed as sharp and strong at wavenumber 1454.31 cm−1. CH3 deformation and C \\ H stretching modes were considered as strong and medium at wavenumber 1115.16 cm−1. CH2 rocking, C\\H stretching, C\\H\\C\\C\\C\\C\\C in plane bending, and C\\C\\C\\C\\C deformation modes were recognized as sharp and strong at wavenumber 1031.53 cm−1. C\\C\\C\\C\\C out of plane bending, and C\\H\\C\\C\\C\\ C \\ C modes were existed as wide and strong at wavenumber 669.22 cm−1. C \\ N \\ C \\ C \\ N stretching was noticed as weak and sharp at wavenumber 516.36 cm−1. CH2 rocking was acquired as sharp and weak at wavenumber 547.15 cm−1.
Fig. 10. a) 1H NMR spectra of the 6FPB molecule dissolved in methanol, b) after Ar APPT.
M. Tanışlı et al. / Journal of Molecular Liquids 277 (2019) 912–920
C\\ C\\ C\\ C\\ C out of plane bending was existed as sharp and weak at wavenumber 509.13 cm−1. C \\ H \\ C \\ C \\ C \\ C \\ C out of plane bending was noticed as sharp and weak at wavenumber 485.51 cm−1. As seen in Fig. 5, the following situations have occurred for the 6FPB molecule dissolved in methanol after Ar APPT: A very sharp and strong bond as 7N\\8 C_10O was broken at wavenumber 881 cm−1. The 9S\\8C peak was disappeared at wavenumber 804 cm−1. The 7N\\8 C_10O peak was disappeared at wavenumber 881 cm−1. A new peak as 5C\\9S\\8 C_10O bond occurred at wavenumber 2525.63 cm−1. A new peak as 9S_8C bond was observed at wavenumber 2052 cm−1. A new peak as a very sharp and strong C \\ C \\ S \\ C \\ N bond was seen at wavenumber 1090.87 cm−1.
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at wavelengths 275 and 320–325 nm for ethanol after Ar APPT are related with the electronic transition n-π*. The 6FPB molecule contains the fluorine (F) atom attached to the phenyl ring. The electronic transitions in the 6FPB molecule are π-π* transitions originating from the benzothiazole ring in the molecules. Transitions observed in the 6FPB molecule between the wavelengths 270 and 320 nm for ethanol are n-π* transitions originating from “lone-pair” electrons in carbonyl groups. It is more intense than the nπ* transitions observed for the 6FPB molecule. This is the F atom, which has weak electronegativity in the 6FPB molecule. However, the F atom does not have a significant effect on the absorption wavelength. As seen in figures, the electronic transitions as π-π* and n-π* occurred on the 6FPB molecule. 6. Analysis of NMR spectra
5. Assignment of UV–Visible spectra The absorbance spectra for the 6FPB molecule dissolved in ethanol and methanol before and after Ar APPTs are recorded in Figs. 6–9. As seen in Fig. 6, the first absorption bands of spectrum at wavelengths 235 and 325 nm and, the second absorption bands of spectrum at wavelengths 255 and 315 nm for methanol before Ar APPT are related with the electronic transition n-π*. As seen in Fig. 7, the first absorption bands of spectrum at wavelengths 240 and 325 nm and, in spectrum, the second absorption bands at wavelengths 255 and 315 nm for methanol after Ar APPT are related with the electronic transition n-π*. As seen in Fig. 8, the first absorption bands of spectrum at wavelengths 255 and 300 nm and, the second absorption bands of spectrum at wavelengths 270 and 320 nm for ethanol before APPT are related with the electronic transition n-π*. As seen in Fig. 9, the first absorption bands of spectrum at wavelengths 255 and 300 nm and, the second absorption bands of spectrum
Proton (1H) NMR spectra of the title molecule dissolved in the ethanol and methanol and 1H NMR spectra of the molecule in liquid phase after Ar APPT have been measured and presented in Figs. 10−11. As seen in Figs. 10–11, protons of phenyl ring bonded to carbonyl group were appeared at 8.06 and 7.21 ppm as doublets because of each other, respectively. Moreover, these peaks were appeared as multiplet due to fluorine atom. Protons of pyridine ring have been seen at 3.48 and 2.25 ppm. Peaks of these atoms were observed as triplet. Protons of methyl group bonded to piperazine ring and CH2 group bonded to carbonyl group have been observed at 2.18 and 4.52 ppm, respectively. After Ar discharge was applied to the title molecule, there were some changes in the NMR peaks. Especially, peaks of protons of piperazine ring were removed. The reason of this may be nitrogen atom, which is electronegative. Because of the one, Ar APPT may be more affected according to other atoms. On the other hand, protons of CH2 groups of pyridine ring near to methyl group were disappeared. Wherein said
Fig. 11. (a) 1H NMR spectra of the 6FPB molecule dissolved in ethanol, (b) after Ar APPT.
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nitrogen atom is the nitrogen atom in the title molecule. Because, nitrogen atom in the title molecule affects the chemical shift in the NMR spectrum. In plasma application, no nitrogen atom is attached to the molecule. However other CH2 group was not disappeared. Chemical shift was observed at protons of methyl group (Fig. 10). The APPJ of Ar was applied to the 6FPB molecule dissolved in ethanol, 1H NMR spectrum is represented in Fig. 11. According to the spectrum obtained, the chemical shifts were seen in almost all peaks. In contrast to sample dissolved in methanol, except for protons of piperazine ring, all of the proton peaks were not observed in the spectrum after applied Ar APPT. Another result to be extracted from here, it has also been observed that the APPT effect varies according to solvent. 7. Result and discussion It is well-known that there are some studies about the interactions of molecules and laboratory plasmas. The purpose of this study is to search for some effects on a new molecule. Here the peak shifts of molecular bonds, breakdowns, intensification of the peaks are looked, and how the more divergent changes of molecular bonds occur. As a result, the conditions for molecular dissociation will also be investigated. It is revealed under which conditions and plasma species will degrade the molecule. Thus, a new decompose method has emerged. The molecular structure was described in detail with the modes before discharge applied. Subsequently, the plasma interaction has been carried out and the same detailed examination has been carried out once again for the changes. In order to make sure of the results, three different spectra as FT-IR, UV–Vis and NMR were taken. According to the spectra, it can be seen that the 6FPB molecule varies under shifts for a given solvent. In this context, with this and similar studies, it will be given in an answer to the question which molecules interactions will arise in which energies. There was no break in the 6FPB molecule dissolved in ethanol before and after Ar APPT. However, some shifts and changes occurred in the peaks. Unlike, as seen in the related figures, the following situations have occurred for the 6FPB molecule dissolved in methanol after Ar APPT: The 7N\\8C_10O very strong sharp bond was broken at 881 cm−1. The 9S\\8C peak disappeared at wavenumber 804 cm−1. New peak as 5C\\9S\\8 C_10O occurred at wavenumber 2525.63 cm−1. New peak as 9S_8C was seen at wavenumber 2052 cm−1. New peak as very strong, sharp C\\C\\S\\C\\N was obtained at wavenumber 1090.87 cm−1. According to NMR spectra, protons of phenyl ring were more affected than other protons from Ar APPT and these protons are not observed after Ar APPT. Especially, protons of piperazine ring, methyl group and CH2 group bonded to carbonyl have not been affected from Ar APPT. It is clear that Ar APPT indicated different effects depending on the solvent. Acknowledgement We are grateful to Anadolu University via Research Project No: 1701F028, Turkish Scientific Council (TUBITAK) Research Fund Committee via the Research Project No: 108T192 (2008) and Eskişehir Osmangazi University Research Foundation via Research Project No: 2016-1089, 2017.
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Journal of Molecular Liquids journal homepage: www.elsevier.com/locate/molliq
Molecule decomposition via plasma jet at atmospheric pressure Murat Tanışlı a,⁎, Erol Taşal b, Neslihan Şahin a, Gökhan Dikmen c a b c
Eskişehir Technical University, Science Faculty, Department of Physics, Eskişehir 26470, Turkey Eskişehir Osmangazi University, Art and Sciences Faculty, Physics Department, Eskişehir, Turkey Eskişehir Osmangazi University, Central Research Laboratory, Application and Research Center, Eskişehir, Turkey
a r t i c l e
i n f o
Article history: Received 7 August 2018 Received in revised form 4 December 2018 Accepted 5 January 2019 Available online 07 January 2019 Keywords: NMR UV–Vis FT-IR spectra Drug molecule Chemical decomposing Plasma photoproduct
a b s t r a c t In this study, the 6-(4-fluorobenzoyl)-3-(2-(4-methylpiperazine-1-il)-2-oxoethyl)benzo [d]thiazole-2(3H) (briefly named as 6FPB) molecule structure and its properties have been investigated in detail. Fouriertransform infrared (FTIR), ultraviolet visible (UV–Vis) techniques were used to obtain the spectra of vibrational, absorption or emission and also the nuclear magnetic resonance (NMR) spectrum was provided in research for determining of the content of solid and liquid phases for the 6FPB molecule. Then, the atmospheric pressure plasma treatment (APPT) was applied to the 6FPB molecule in liquid phase. In this case, the NMR, UV–Vis and FT-IR spectra have been obtained and analyzed, again. According to the results, it is seen that the 6FPB molecule was decomposed after APPT. Some shifts and changes occurring in the peaks show that some bonds of 6FPB molecule have been broken. The electronic transitions as π-π* and n-π* were obtained at the 6FPB molecule. It is seen that the electronic transitions π-π* and n-π* are related to the isomerization process. NMR spectra show that all of the protons of title molecule except for protons of piperazine ring and CH2 group were eliminated by APPTs. © 2019 Elsevier B.V. All rights reserved.
1. Introduction It is well-known that plasma can be considered as a quasi-neutral ionized gas including very different particles such as photons, ions, free electrons, atoms [1]. Also, the generation of discharge in laboratory can be obtained with the different excitation frequency and electrode design. Direct current (DC), alternative current (AC), radio frequency (RF) and microwave power supplies are used to generate discharge at low and atmospheric pressures [2–4]. In the related literature, there are some studies about discharge at low pressure, but it is known that the vacuum systems, which are quite expensive in these systems, are needed for generating of discharge at low pressure. These vacuum systems need to be maintained. Additionally, the dimensions of the material to be applied are limited by the dimensions of the vacuum chamber. For these reasons, the discharges generated at atmospheric pressure can be preferred instead of the discharge generated at low pressure [5]. A classification of discharges is known as Corona, dielectric barrier discharge (DBD), atmospheric pressure plasma jet (APPJ) and microwave plasma in the GHz range [6]. In addition, non-local thermodynamic equilibrium (non-LTE) plasma jets are classified as dielectricfree electrode, DBD, DBD-like and single-electrode jets [7]. The room temperature has been accepted as the temperature of non-LTE plasma jets and the electron temperatures are around several electron volt
⁎ Corresponding author. E-mail addresses: [email protected] (M. Tanışlı), [email protected] (E. Taşal).
https://doi.org/10.1016/j.molliq.2019.01.026 0167-7322/© 2019 Elsevier B.V. All rights reserved.
(eV) and the reactive radicals, UV photons and metastable atoms are occurred in non-LTE plasma jets [8]. Over the years, the plasma physics has been considered for interdisciplinary studies. Nowadays, there are some industrial and medical applications of DBD and DBD-like jets at atmospheric pressure. The material modification, deposition, etching, nanomaterial synthesis and microorganism are the well-known for some of the most important applications [9,10]. For the low temperature, the studies on the bases of plasma formation at atmospheric pressure and effects on microspheres and bacteria inactivation have been carried out [6,11,12]. In recent years, there have also been studies with selective intramolecular vibration owing to vibration photochemistry. Apart from this, the effects of plasma on the molecules have been researched. Some studies have been investigated whether the plasma at atmospheric pressure changes the structure of the molecule or not. The changes in the structure of the molecule after APPT have been compared with the title molecule. Tanışlı and Taşal have applied argon and neon atmospheric pressure plasma jets on coumarin molecule. With argon plasma jet treatment on this molecule, the 1O\\2C single bond was broken, the 1O\\6C single bond became double bonded and also the 2C\\3C single-bond changed into 2C_3C double-bonds. With neon plasma jet treatment, some shifts and changes at specific wavenumbers were only been observed. The reason for this difference was related to the energy of the argon and neon plasmas [13]. In their other study, they investigated application of the argon atmospheric pressure plasma jet on C13H12N2O3 molecule which is dye molecule, two-photo products have been obtained as 12C_17O (strong, wide stretching peak) and 6C\\7N\\8N_9C
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(strong, varying stretching peak). A new dye molecule has been seen with this application [14]. Durme and et al. attempted to give an overview of recently published on plasma catalysis. They have showed that the effect of hybrid plasma catalysis is on by-product. It can be concluded from this study that dielectric barrier discharges are most frequently used in recent plasma catalytic research [15]. Urashima and Chang have reviewed the gaseous pollution control technology based on discharge plasma. They investigated destruction of volatile organic compounds from air streams and industrial flue gases by non-thermal plasma [16]. Morent and et al. have given plasma treatment effects or results on the treatment of textiles with non-thermal plasmas in their study [17]. Ermolaeva and et al. have shown the effect of non-thermal argon plasma in removing pathogenic bacteria from biofilms and wound surface. Their studies present that non-thermal plasma is being important to sterilize [18]. Scally and et al. investigated the effects of atmospheric pressure non-equilibrium plasma discharge on polyethylene terephthalate samples [19]. In the literature, there are also many studies about cancer cell death. Liedtke and et al. have explored the application of an atmospheric pressure argon plasma jet on the pancreatic cancer. This study has represented suggestions about non-thermal plasma conditioned solutions for treatment of malignancies [20]. He and et al. have investigated the effects of cold atmospheric plasma on the gold nanoparticles. They have explored the mechanism of synergistic cytotoxic effects between cold atmospheric plasma and nanotechnologies [21]. Kumar and et al. compared the effects of plasma treated media and plasma treated water on two different pancreatic ductal adenocarcinomas and pancreatic stellate cells [22]. When the APPJ interacts with a molecule, the molecule can be converted to the other molecule by a new useful method in plasma physics field. Tanışlı and et al. show that the 7N\\8C bond at 6-(2-Fluorobenzoyl)-3-(2-(4-(4fluorophenyl)piperazin-1-yl)-2-oxoethyl)benzo[d]thiazol-2(3H)-one molecule has been broken after argon plasma jet treatment. The new photoproducts have been considered as stretching peaks at 17C\\18S_14C and 17C_19O [23]. In addition, the various applications of plasma occur in the industrial process. Because, non-thermal plasmas are high removal efficiency, energy yields and good economy. Sensitivity to pain is a hard case that people have been struggling for centuries. No drug has been discovered yet that is effective against pain and has no side effects. Today, the most drug group studied is analgesics. The main goal in pain research is to develop nonsteroidal antiinflammatory (NSAI) drugs and non-opiate analgesics that are as effective as opiates because of the least side effects. Also, non-acidic NSAIs have fewer side effects than acidic NSAIs [24]. In this context, benzothiazolinone derivatives are one of the promising groups for having analgesic activity. Benzothiazolinone derivatives are analogous molecules that are reference of NSAI drugs and are considered to be one of the promising groups because of their analgesic activity. They have heterocyclic ring systems with a wide range of biological activities such as antibacterial, analgesic, diuretic, antihistaminic, anticonvulsant, antiarrhythmic, antiasthmatic and central nervous system depressant [25–29]. Various biological effects of benzothiazolinone derivative molecules including analgesic and anti-inflammatory activities have been studied [30,31]. Benzothiazolinone derivatives have been reported to exhibit strong anti-inflammatory activity by inhibiting prostaglandin synthesis. It is also reported in the literature that there are fewer side effects compared to analgesic and anti-inflammatory drugs currently on the market [32]. Taking into account this information, some benzothiazolinone derivatives and studies on them have produced compounds with significant analgesic and anti-inflammatory activity. Some biologically active substituted benzothiazole derivatives can also be used in the treatment of breast cancer [33–40]. The organization of this study is the following: First of all, the introduction part is presented in Section 1. After that, Sections 2 and 3 describe the experimental setup, and molecule. In Sections 4 and 5, the experimental data have been presented with the assignment of spectra.
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And then, the results of NMR spectra are analyzed in Section 6. Finally, the innovation and importance for results are concluded in conclusions. 2. Experimental setup In this study, the dielectric barrier discharge-like (DBD-like) at atmospheric pressure is used for the experimental studies (Fig. 1). When the discharge does not interact with metals at the out of the discharge tube, this system is defined as DBD-like discharge without extra dielectric material. The presented system has two electrodes, whose geometries are different from each other. The discharge tube is also used as the dielectric material. The geometry of the grounded electrode made of aluminum is circular. The high voltage electrode was made of tungsten wire. Tungsten wire diameter and thickness are 0.16 and 170 mm, and the thickness and diameter of the aluminum electrode are 4 and 40 mm, respectively. The discharge tube has been made from a cylindrical quartz and it has a length of 17.3 cm. The outer and inner diameters of discharge tube are 8 and 6 mm. The high voltage and grounded electrodes are placed inside and outside of the discharge tube, respectively. The high voltage AC power supply was connected to the electrode to provide energy for discharge. The working frequency and voltage for power supply are between 10–25 kHz and 4–20 kV, respectively. For this study, the voltage of AC power supply has been adjusted as 16 kV at the 24 kHz frequency. The pure Ar has been sent into the discharge tube, which was held perpendicular in the system. The flow rate is controlled by Mass Flowmeter. For this study, the flow rate has also been selected as 4 l/min. The temperature of the plasma plume from the jet has been measured with Fluke CNXT3000 K-Type Wireless Temperature Module in 38–42 °C range. Tektronix Oscilloscope 500 MHz and AC current probe have also been used to measure current values of Ar atmospheric pressure plasma jet. Peak-to-peak and RMS currents have been measured as 14.60 and 1.37 mA, respectively. In the presented study, the 6FPB molecule has been tried to be modified with DBD-like discharge system. For this purpose, the solutions for the 6FPB molecule were prepared in liquid phase about 5 × 10−4 M with using two different solvents, which are ethanol and methanol. Also, the atmospheric pressure discharge has been used to apply the samples from the distances 1 cm with 3 min duration. The changes of molecule structure have been evaluated with FTIR, UV–Vis and NMR spectra. Infrared spectrum was obtained in the range 4000 and 300 cm−1 on a Perkin-Elmer two FT-IR System. The KBr pellet technique was used via this spectrophotometer. The absorbance spectra were also recorded in the range 200–800 nm with Shimadzu UV–Vis spectrophotometer and CPS-100 apparatus were used to keep the sample temperature constant at 22 °C during the experiment. NMRs were considered for both before and after APPT to the 6FPB molecule dissolved separately in ethanol and methanol. JEOL ECZ 500R spectrometer was used for NMR measurements at room temperature. The operating frequencies for 1H nucleus were 500.13 MHz. Deuterium oxide was chosen as solvent. All spectra were collected via standard pulse as 90° and the scan number has been adjusted to 32. 3. The structure and properties of the 6FPB molecule The optimized structure and atomic number for the 6FPB molecule are shown in Fig. 2. The properties of the molecular structure and FT-IR spectrum of solid phase for the 6FPB molecule have been represented in Table 1 and Fig. 3, respectively. The 6FPB molecule, which is given in Table 1, is a new molecule obtained by synthesizing in the Turkish Scientific Council (TÜBİTAK) Research Project (No: 108T192-2008). The molecule was not used in any study. All properties will be included in the literature for the first time and will contribute to a new benzothiazolinone derivative.
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Fig. 1. Schematic diagram of the plasma system.
4. Analysis of vibrational spectra before and after APPJ FT-IR spectra of 6FPB molecule dissolved in different solvents before and after Ar APPTs are given in Figs. 4 and 5. Also, the changes of molecule structure have been evaluated. In addition to this, some vibration modes of ethanol and methanol solvents have been clearly known in the literature [41]. A. The vibration modes of 6FPB molecule dissolved in ethanol before APPT are listed below: CH2 asymmetric stretching as sharp and strong was noticed at wavenumber 2975.37 cm−1. CH3 asymmetric stretching as sharp and medium was considered at wavenumber 2928.64 cm−1. CH3 symmetric stretching as narrow and strong was existed at wavenumber 2888.89 cm−1. A sharp and strong C _ C stretching was seen at wavenumber 1455.36 cm−1. A sharp and strong C\\C\\S\\N\\C stretching was recognized at wavenumber 1417.93 cm−1. C \\ C \\ C \\ C \\ C stretching was noticed as sharp and strong at wavenumbers 1417.93 and 1381.06 cm−1.
C _ C stretching was existed as sharp and strong at wavenumber 1381.06 cm−1 and it was seen as narrow and strong at wavenumber 1275.14 cm−1. C\\C\\C\\C\\C stretching was recognized as narrow and strong at wavenumber 1275.14 cm−1. C\\N stretching was noticed as sharp and medium at wavenumber 1330.72 cm−1. C \\ H stretching was existed as sharp and strong at wavenumbers 1090.87 and 1049.54 cm−1. C \\ N stretching as sharp and strong was recognized at wavenumbers 881.34 and 584.04 cm−1. C \\ S was noticed as medium and sharp at wavenumber 804.09 cm−1. CH2 scissoring as sharp and strong was recognized at wavenumber 1455.36 cm−1. C \\ H in-plane-bending was existed as sharp and strong at wavenumber 1417.93 cm−1. C\\H\\C\\C\\C\\S\\C\\N in-plane-bending stretching was noticed as sharp and strong at wavenumber 1090.87 cm−1. A sharp and strong C \\ H \\ C \\ C \\ C \\ S \\ C \\ N in-planebending was recognized at wavenumbers 1381.06 and 1049.54 cm−1. A narrow and strong CH2 wagging was noticed at wavenumber 1275.14 cm−1.
Fig. 2. a) The optimized structure and b) the atomic number for the 6FPB molecule.
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CH2 wagging was existed as medium and sharp at wavenumber 1330.72 cm−1. A sharp and strong CH3 deformation was recognized at wavenumber 1090.87 cm−1. CH2 rocking was noticed as sharp and strong at wavenumber 1049.54 cm−1. A sharp and strong C\\C\\C\\C\\C deformation was noticed at wavenumber 1049.54 cm−1. C \\ H out-of-plane-bending was existed as sharp and strong at wavenumber 881.34 cm−1. C \\ H out-of-plane-bending was existed as medium and sharp at wavenumber 804.09 cm−1. A medium and strong C \\ C \\ C \\ C \\ C out of plane bending at wavenumber 665.80 cm−1 was noticed. C \\ C \\ S \\ C \\ N out of plane bending at wavenumber 665.80 cm−1 was existed as medium and strong. C\\H\\C\\C\\C\\C\\C was recognized as medium and strong at wavenumber 665.80 cm−1. A sharp and strong C\\C\\C\\C\\C out of plane bending was noticed at wavenumber 584.04 cm−1. C\\ C\\ S\\ C\\ N out of plane bending was existed as sharp and strong at wavenumber 584.04 cm−1. CH2 rocking was existed as sharp and strong at wavenumber 584.04 cm−1.
Table 1 The properties of the 6FPB molecule. QSAR and QSPR parameters and properties
6FPB molecule
Dot Group The weight of molecule Boiling point (K) Melting point (K) The formula of molecule The number of total electron The number for full molecular orbital The number for empty orbital The number for total molecular orbital Molecular polarizability Dipole moment (Debye) EHOMO (eV) ELUMO (eV) q− qH+ Vm (cm3/mol) Ionization potentials (eV) Electron affinity (eV) Electronegativity (eV) Hardness for molecule (eV) Softness for molecule (eV) Index for electrophilic Log P Molar refractivity (cm3/mol) Formation heat (298 K) (kcal/mol)
C1 413.47 1031.18 810.22 C21H20FN3O3S 216 108 371 479 274.507 7.1845 −6.005 −1.754 −0.502 0.214 274.316 6.005 1.754 −3.880 2.126 0.470 3.540 2.169 110.316 −162.960
Points Count
Data Spacing
7201
849.5 763
%T r ansmittance
584.5
755 802.5
1002
25
1234 1284.5 1295
1575 1590.5
30
964
1452
35
1140 1144 1154.5 1193.5
1311 1379
40
623.5 695.5
933
1096.5 1052.5
1505
45
495.5 511.5
917
414 437
1781 1853 1908 2015.5 2073.5
50
2799 2852.5
2931 2977
55
2750
60
3047.5 3098
3309
65
0.5000
2252.5 2382.5 2420.5 2456 2562.5 2617 2686
70
915
20
1672
1645.5
15 10 5 0 4000 No
cm-1
3000 %T
Intensity
No
cm-1
2000 Wavenumber (cm-1) %T
Intensity
No
cm-1
1000 %T
Intensity
Fig. 3. FT-IR spectrum of the 6FPB molecule in solid phase.
No
cm-1
%T
Intensity
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M. Tanışlı et al. / Journal of Molecular Liquids 277 (2019) 912–920
%T
107 100 95 90 85 80 75 70 65 60 55 50 46 108 105 100
2256.50cm-1, 102.12%T1925.66cm-1, 100.17%T
474.28cm-1, 100.94%T 506.74cm-1, 98.31%T
1660.54cm-1, 95.70%T
561.05cm-1, 92.46%T 521.48cm-1, 95.88%T 491.03cm-1, 99.16%T 458.92cm-1, 101.30%T
1330.72cm-1, 81.64%T 1417.93cm-1, 76.68%T 1455.36cm-1, 75.09%T 1381.06cm-1, 72.51%T 881.34cm-1, 63.23%T
2928.64cm-1, 60.97%T 3340.79cm-1, 47.91%T 2975.37cm-1, 49.49%T 2888.89cm-1, 58.63%T
1049.54cm-1, 49.45%T 1090.87cm-1, 55.19%T
1925.59cm-1, 102.88%T 2256.36cm-1, 104.05%T 1660.41cm-1, 99.74%T
95 90 %T
5 4 4 .0 7 c m -1 , 9 4 .0 6 % T
804.09cm-1, 89.88%T 584.04cm-1, 88.31%T 665.80cm-1, 84.66%T
1275.14cm-1, 87.00%T
459.47cm-1, 101.87%T 491.38cm-1, 99.74%T 521.75cm-1, 97.84%T 583.98cm-1, 92.63%T 659.86cm-1, 90.09%T 804.10cm-1, 94.70%T 506.74cm-1, 99.77%T
1275.15cm-1, 93.37%T
85
1330.39cm-1, 89.12%T 1455.46cm-1, 83.98%T 1380.98cm-1, 81.86%T 1423.82cm-1, 85.38%T
80 75 70
473.84cm-1, 100.83%T
881.34cm-1, 71.84%T
65 60 55 53 4000
2888.83cm-1, 68.56%T
3340.40cm-1, 54.01%T
2975.56cm-1, 56.93%T 2928.66cm-1, 70.90%T
3500
1049.63cm-1, 54.60%T 1090.94cm-1, 62.93%T
3000
2500
2000
cm-1
Name Description T3 ETH Sample 064 By Administrator Date Sunday, May 28 2017 T3 ETH AR Sample 065 By Administrator Date Sunday, May 28 2017
1500
1000
500450
Fig. 4. FT-IR spectra for interactions of plasma and 6FPB molecule dissolved in ethanol. The subfigures are combined into a whole one (The spectrum shown above in red indicates the state after argon plasma interaction.).
The wavenumber 544.07 cm−1 includes the N\\C_O stretching and CH2 rocking modes as sharp and weak. CH2 rocking was existed as sharp and weak at wavenumber 521.48 cm−1.
C\\ C\\ C\\ C\\ C out of plane bending was noticed as sharp and weak at wavenumber 561.04 cm−1. C \\ C \\ S \\ C \\ N out of plane bending was recognized as sharp and weak at wavenumber 561.04 cm−1.
485.51cm-1, 96.41%T
%T
102
2869.3
95 90 85 80 75 70 65 60 55 50
3706.86cm-1, 96.05%T 3681.22cm-1, 95.86%T
2525.63cm-1, 94.37%T
2917.1
2052.00cm-1, 95.95%T 1706.46cm-1, 97.16%T
1454.31cm-1, 84.56%T 2977.7
547.15cm-1, 93.24%T
669.22cm-1, 88.85%T
1347.9 2832.11cm-1, 71.14%T
3325.71cm-1, 65.67%T
2945.20cm-1, 66.37%T
516.36cm-1, 95.13%T
45 100
1414.8
95 2525.29cm-1, 96.77%T
90
2043.91cm-1, 97.50%T
1670.88cm-1, 96.53%T
1115.68cm-1, 91.86%T
85
%T
509.13cm-1, 94.74%T 1115.16cm-1, 88.88%T
1450.23cm-1, 87.82%T
669.15cm-1, 88.86%T
80 75 70
2 8 3 3 . 9 5 c m
- 1 ,
7 5 . 2 4 %
T
2946.35cm-1, 71.63%T
65 60
3338.11cm-1, 64.15%T
54 4000
3500
1031.53cm-1, 54.90%T
3000
Name Description T3 METH ARG Sample 077 By Administrator Date Sunday, May 28 2017 T3 METH Sample 076 By Administrator Date Sunday, May 28 2017
2500
cm-1
2000
1500
1000
500450
Fig. 5. FT-IR spectra for interactions of plasma and 6FPB molecule dissolved in methanol. The subfigures are combined into a whole one (The spectrum shown above in blue indicates the state after argon plasma interaction.).
M. Tanışlı et al. / Journal of Molecular Liquids 277 (2019) 912–920
917
A sharp and weak C \\ C \\ C \\ C \\ C out of plane bending mode was noticed at wavenumber 506.74 cm−1. The wavenumber 521.48 cm−1 includes the sharp and weak C \\ S stretching and C\\ C\\ C\\ C\\ C out of plane bending modes. B. The vibration modes of the 6FPB molecule dissolved in ethanol after Ar APPT are listed below: CH2 asymmetric stretching was existed as sharp and strong at wavenumber 2975.56 cm−1. A narrow and medium CH3 asymmetric stretching was noticed at wavenumber 2928.66 cm−1. A narrow and strong CH3 symmetric stretching was existed at wavenumber 2888.83 cm−1 and also CH3 symmetric stretching was recognized as narrow and weak at wavenumber 2256.36 cm−1. The wavenumber 1455.46 cm−1 includes the CH2 scissoring and C _ C stretching modes as medium and sharp. The wavenumber 1423.82 cm−1 includes the C\\C\\S\\C\\N\\ C stretching, C \\ C \\ C \\ C \\ C stretching, and C \\ H in-planebending modes as narrow and medium. The sharp and strong C\\C\\C\\C\\C stretching, C\\H\\C\\C \\C\\S\\C\\N in-plane-bending, and C _ C stretching modes were noticed at wavenumber 1380.98 cm−1. CH2 wagging, C _ C stretching, and C\\ C\\ C \\ C\\ C stretching modes as narrow and strong were existed at wavenumber 1275.15 cm−1. The sharp and strong C\\N stretching and CH2 wagging modes were existed at wavenumber 1330.39 cm−1. The sharp and strong C \\ H \\ C \\ C \\ C \\ S \\ C \\ N in-planebending stretching, CH3 deformation, and C\\H stretching modes were noticed at wavenumber 1090.94 cm−1. CH2 rocking, C\\H stretching, C\\H\\C\\C\\C\\C\\C in plane bending, and C \\ C \\ C \\ C \\ C deformation modes as sharp and strong were recognized at wavenumber 1049.63 cm−1. C \\ N stretching and C \\ H out-of-plane-bending modes as sharp and strong were seen at wavenumber 881.34 cm−1. The medium and sharp C \\ S stretching and C \\ H out-of-planebending modes at wavenumber 804.10 cm−1 were existed. C\\C\\C\\C\\C out of plane bending, C\\C\\S\\C\\N out of plane bending, and C\\H\\C\\C\\C\\C\\C modes were existed as strong and medium at wavenumber 659.86 cm−1. The wavenumber 583.98 cm−1 includes the C\\N stretching, C\\C \\ C \\ C \\ C out of plane bending, C \\ C \\ S \\ C \\ N out of plane bending, and CH2 rocking modes as wide and strong. CH2 rocking was seen as sharp and weak at wavenumber 521.75 cm−1.
Fig. 6. UV–Vis for the 6FPB molecule dissolved in methanol before APPT.
Fig. 7. UV–Vis for the 6FPB molecule dissolved in methanol after Ar APPT.
C\\ C\\ C\\ C\\ C out of plane bending was noticed as sharp and weak at wavenumber 506.74 cm−1. C\\S stretching and C\\C\\C\\C\\C out of plane bending modes as sharp and weak were noticed at wavenumber 491.38 cm−1. A sharp and weak CH2 rocking was recognized at wavenumber 473.84 cm−1. CH2 rocking was noticed as sharp and weak at wavenumber 459.86 cm−1. The experimental vibration spectra of the 6FPB molecule dissolved in ethanol before and after APPT are given in Fig. 4. It is obvious that there is no break in the 6FPB molecule dissolved in ethanol before and after Ar APPT. After Ar APPT, some shifts and changes were only observed in the vibrational peaks. C. The vibration modes of 6FPB molecule dissolved in methanol before APPT are listed below: CH2 asymmetric stretching was existed as sharp and strong at wavenumber 2946.35 cm−1. CH3 asymmetric stretching was noticed as sharp and strong at wavenumber 2833.95 cm−1. A medium and wide CH3 symmetric stretching was noticed at wavenumber 2525.29 cm−1. CH3 symmetric stretching was existed as medium and wide at wavenumber 2043.91 cm−1.
Fig. 8. UV–Vis for the 6FPB molecule dissolved in ethanol before APPT.
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C\\C\\C\\C\\C out of plane bending, C\\C\\S\\C\\N out of plane bending, and C\\H\\C\\C\\C\\C\\C modes were existed as wide and strong at wavenumber 669.15 cm−1. D. The vibration modes of the 6FPB molecule dissolved in methanol after Ar APPT are listed below:
Fig. 9. UV–Vis for the 6FPB molecule dissolved in ethanol after Ar APPT.
C\\C\\S\\C\\N\\C stretching, C\\C\\C\\C\\C stretching, and C _ C stretching modes were recognized as narrow and medium at wavenumber 1450.23 cm−1. The wavenumber 1115.68 cm−1 includes the C\\C\\S\\C\\N\\ C stretching and C\\C\\C\\C\\C in plane bending modes as narrow and medium. CH2 rocking, C\\H stretching, C\\H\\C\\C\\C\\C\\C in plane bending, and C\\ C\\ C\\ C\\ C deformation modes were noticed as sharp and strong at wavenumber 1031.53 cm−1.
O\\H symmetric stretching modes were considered as narrow and medium at wavenumbers 3681.22 and 3706.86 cm−1. CH2 asymmetric stretching was acquired as strong and medium at wavenumber 2945.20 cm−1. CH3 asymmetric stretching was realized as sharp and strong at wavenumber 2832.11 cm−1. S_C stretching modes were existed as medium and wide at wavenumber 2052.00 and 2525.63 cm−1. CH2 scissoring and C _ C stretching modes were noticed as sharp and strong at wavenumber 1454.31 cm−1. CH3 deformation and C \\ H stretching modes were considered as strong and medium at wavenumber 1115.16 cm−1. CH2 rocking, C\\H stretching, C\\H\\C\\C\\C\\C\\C in plane bending, and C\\C\\C\\C\\C deformation modes were recognized as sharp and strong at wavenumber 1031.53 cm−1. C\\C\\C\\C\\C out of plane bending, and C\\H\\C\\C\\C\\ C \\ C modes were existed as wide and strong at wavenumber 669.22 cm−1. C \\ N \\ C \\ C \\ N stretching was noticed as weak and sharp at wavenumber 516.36 cm−1. CH2 rocking was acquired as sharp and weak at wavenumber 547.15 cm−1.
Fig. 10. a) 1H NMR spectra of the 6FPB molecule dissolved in methanol, b) after Ar APPT.
M. Tanışlı et al. / Journal of Molecular Liquids 277 (2019) 912–920
C\\ C\\ C\\ C\\ C out of plane bending was existed as sharp and weak at wavenumber 509.13 cm−1. C \\ H \\ C \\ C \\ C \\ C \\ C out of plane bending was noticed as sharp and weak at wavenumber 485.51 cm−1. As seen in Fig. 5, the following situations have occurred for the 6FPB molecule dissolved in methanol after Ar APPT: A very sharp and strong bond as 7N\\8 C_10O was broken at wavenumber 881 cm−1. The 9S\\8C peak was disappeared at wavenumber 804 cm−1. The 7N\\8 C_10O peak was disappeared at wavenumber 881 cm−1. A new peak as 5C\\9S\\8 C_10O bond occurred at wavenumber 2525.63 cm−1. A new peak as 9S_8C bond was observed at wavenumber 2052 cm−1. A new peak as a very sharp and strong C \\ C \\ S \\ C \\ N bond was seen at wavenumber 1090.87 cm−1.
919
at wavelengths 275 and 320–325 nm for ethanol after Ar APPT are related with the electronic transition n-π*. The 6FPB molecule contains the fluorine (F) atom attached to the phenyl ring. The electronic transitions in the 6FPB molecule are π-π* transitions originating from the benzothiazole ring in the molecules. Transitions observed in the 6FPB molecule between the wavelengths 270 and 320 nm for ethanol are n-π* transitions originating from “lone-pair” electrons in carbonyl groups. It is more intense than the nπ* transitions observed for the 6FPB molecule. This is the F atom, which has weak electronegativity in the 6FPB molecule. However, the F atom does not have a significant effect on the absorption wavelength. As seen in figures, the electronic transitions as π-π* and n-π* occurred on the 6FPB molecule. 6. Analysis of NMR spectra
5. Assignment of UV–Visible spectra The absorbance spectra for the 6FPB molecule dissolved in ethanol and methanol before and after Ar APPTs are recorded in Figs. 6–9. As seen in Fig. 6, the first absorption bands of spectrum at wavelengths 235 and 325 nm and, the second absorption bands of spectrum at wavelengths 255 and 315 nm for methanol before Ar APPT are related with the electronic transition n-π*. As seen in Fig. 7, the first absorption bands of spectrum at wavelengths 240 and 325 nm and, in spectrum, the second absorption bands at wavelengths 255 and 315 nm for methanol after Ar APPT are related with the electronic transition n-π*. As seen in Fig. 8, the first absorption bands of spectrum at wavelengths 255 and 300 nm and, the second absorption bands of spectrum at wavelengths 270 and 320 nm for ethanol before APPT are related with the electronic transition n-π*. As seen in Fig. 9, the first absorption bands of spectrum at wavelengths 255 and 300 nm and, the second absorption bands of spectrum
Proton (1H) NMR spectra of the title molecule dissolved in the ethanol and methanol and 1H NMR spectra of the molecule in liquid phase after Ar APPT have been measured and presented in Figs. 10−11. As seen in Figs. 10–11, protons of phenyl ring bonded to carbonyl group were appeared at 8.06 and 7.21 ppm as doublets because of each other, respectively. Moreover, these peaks were appeared as multiplet due to fluorine atom. Protons of pyridine ring have been seen at 3.48 and 2.25 ppm. Peaks of these atoms were observed as triplet. Protons of methyl group bonded to piperazine ring and CH2 group bonded to carbonyl group have been observed at 2.18 and 4.52 ppm, respectively. After Ar discharge was applied to the title molecule, there were some changes in the NMR peaks. Especially, peaks of protons of piperazine ring were removed. The reason of this may be nitrogen atom, which is electronegative. Because of the one, Ar APPT may be more affected according to other atoms. On the other hand, protons of CH2 groups of pyridine ring near to methyl group were disappeared. Wherein said
Fig. 11. (a) 1H NMR spectra of the 6FPB molecule dissolved in ethanol, (b) after Ar APPT.
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nitrogen atom is the nitrogen atom in the title molecule. Because, nitrogen atom in the title molecule affects the chemical shift in the NMR spectrum. In plasma application, no nitrogen atom is attached to the molecule. However other CH2 group was not disappeared. Chemical shift was observed at protons of methyl group (Fig. 10). The APPJ of Ar was applied to the 6FPB molecule dissolved in ethanol, 1H NMR spectrum is represented in Fig. 11. According to the spectrum obtained, the chemical shifts were seen in almost all peaks. In contrast to sample dissolved in methanol, except for protons of piperazine ring, all of the proton peaks were not observed in the spectrum after applied Ar APPT. Another result to be extracted from here, it has also been observed that the APPT effect varies according to solvent. 7. Result and discussion It is well-known that there are some studies about the interactions of molecules and laboratory plasmas. The purpose of this study is to search for some effects on a new molecule. Here the peak shifts of molecular bonds, breakdowns, intensification of the peaks are looked, and how the more divergent changes of molecular bonds occur. As a result, the conditions for molecular dissociation will also be investigated. It is revealed under which conditions and plasma species will degrade the molecule. Thus, a new decompose method has emerged. The molecular structure was described in detail with the modes before discharge applied. Subsequently, the plasma interaction has been carried out and the same detailed examination has been carried out once again for the changes. In order to make sure of the results, three different spectra as FT-IR, UV–Vis and NMR were taken. According to the spectra, it can be seen that the 6FPB molecule varies under shifts for a given solvent. In this context, with this and similar studies, it will be given in an answer to the question which molecules interactions will arise in which energies. There was no break in the 6FPB molecule dissolved in ethanol before and after Ar APPT. However, some shifts and changes occurred in the peaks. Unlike, as seen in the related figures, the following situations have occurred for the 6FPB molecule dissolved in methanol after Ar APPT: The 7N\\8C_10O very strong sharp bond was broken at 881 cm−1. The 9S\\8C peak disappeared at wavenumber 804 cm−1. New peak as 5C\\9S\\8 C_10O occurred at wavenumber 2525.63 cm−1. New peak as 9S_8C was seen at wavenumber 2052 cm−1. New peak as very strong, sharp C\\C\\S\\C\\N was obtained at wavenumber 1090.87 cm−1. According to NMR spectra, protons of phenyl ring were more affected than other protons from Ar APPT and these protons are not observed after Ar APPT. Especially, protons of piperazine ring, methyl group and CH2 group bonded to carbonyl have not been affected from Ar APPT. It is clear that Ar APPT indicated different effects depending on the solvent. Acknowledgement We are grateful to Anadolu University via Research Project No: 1701F028, Turkish Scientific Council (TUBITAK) Research Fund Committee via the Research Project No: 108T192 (2008) and Eskişehir Osmangazi University Research Foundation via Research Project No: 2016-1089, 2017.
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