Int. J. Bio-Inorg. Hybr. Nanomater., 4(4): 197-202, Winter 2015
Graphene-manganase oxide nanocomposite as a hydrogen peroxidase sensor M. Ramezani; Kh. Eskandari*; M. Kamali Nanobiotecnology Research Center, Baqiyatallah University of Medical Science, Tehran, Iran
Received: 16 July 2015; Accepted: 20 September 2015
ABSTRACT: A feasible and fast method to fabricate hydrogen peroxide sensor was investigated by graphene-manganase nanocomposite carbone paste electrode. In the present work, in first step, the graphene was synthesized by chemical method and in second step, manganese oxide nanoparticle was doped on graphene. graphene-manganase nanocomposite was characterized by FTIR and SEM. The nanocomposite shows a high conductive and sensitivity for hydrogen peroxide determination as shown by electrochemical impedance spectroscopy. Graphene-manganase nanocomposite carbone paste electrode was used for sensing of hydrogen peroxide by choronoamperometry with a potential of 250 mV (Ag/AgCl), in 0.1 M phosphate buffer solution at pH= 7. The linear concentration rang of sensor is 8.8-263.3 ÂľM, and with detection limit of 1.04 ÂľM. Also, the life time of sensor is infinite. Keywords: Electrochemistry; Graphene; Hydrogen peroxide; Manganese oxide nanoparticle; Sensor
INTRODUCTION In the recent years, graphene has great interest in the fields of materials science, physics, chemistry and biology. This allotrope of carbon comprises layers of sixatom rings in a hexagonal configuration with atoms bonded by sp2 bonds (Chen, et al., 2012). As a basic building block of other carbon allotropes, graphite can be wrapped to generate 0D fullerenes, rolled up to form 1D carbon nanotubes, and stacked to produce 3D graphite (Wang, et al., 2011). Nowadays, Graphene can be produced relatively easy by mechanical exfoliation of graphite, or by heating SiC, or by the reduction of graphene oxide (Gasni* Corresponding Author - e-mail: kheskandari@alumni.ut.ac.ir
er, et al., 2013). Graphene has unique properties, such as high surface area, high electrical conductivity wide potential windows, fairly inert electrochemistry and good electrocatalytic activity for many redox reactions, low cost and strong mechanical strength. Also, in comparison with CNTs, graphene has many advantages, as follows: i) no metallic impurity, ii) cheap and easy production (Ting, et al., 2011). These properties have caused that, the graphene to be ideal candidates for electrochemistry investigation and chemical sensors and biosensors fabrication. Recently, much attention was reported for protein immobilization on graphene and hybrid of graphene (Wu, et al., 2009) was reported. Recent years have witnessed the establishment of vari-
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ous synthetic routes for graphene, including chemically derived graphene from graphite oxide (graphene oxide, GO), chemical vapor deposition (CVD) of graphene on transition metal films, and epitaxial growth of graphene resulted from the high temperature reduction of silicon carbide. Nanocomposites have attracted great attention because of their unique and novel properties as structural or functional materials. With appropriate designs, nanocomposites can exploit the superlative properties of parent constituents, producing a desired material with improved performance. In this context, intensive efforts have been made to elaborating organic–inorganic nanocomposites for different implementations such as optoelectronics, sensors, biology. Catalysis, Organic components mainly include synthetic polymers and biomacromolecules, while inorganic components typically include nanoparticles, nanotubes, and layered inorganic materials (Kang, et al., 2009). Hydrogen peroxide is an integral part of invironmental chemistry and biological systems. In the atmosphere, H2O2 is produced from the combination of hydroperoxyl radicals and their hydrated form it is an oxidant that. In biological systems, H2O2 is produced in reactions catalyzed by numerous bio-enzymes (Gregory, et al., 2011). different methods have been developed for H2O2 detection, such as Colorimetric, electrochemistry, biosensor and so on (Keihan, et al., 2013). In this study, graphene-manganase nanocomposite, recently synthesized in our laboratories, was used as a substrate modifier for hydrogen peroxide detection. Manganese nanoparticles is sensitive and selective substrate for hydrogen peroxide detection, and the other hand, graphene is very conductive for electron transferring of hydrogen peroxide. Therefore, we prepared graphene-manganase nanocomposite as a high conductive substrate and selective hydrogen peroxide sensor.
dipotassium hydrogen phosphate (K2HPO4) were purchased from Merck. A 0.1 M phosphate buffer solution pH 7.4 was employed as supporting electrolyte. Ultrapure water from a Millipore-MilliQ system was used for preparing all solutions. All the reagents were used as received, without further purification and all experiments were carried out at room temperature (25±2°C). Apparatus and measurements Electrochemical experiments were performed with an Autolab potentiostat (PGSTAT 101). A working glassy carbon electrode with a diameter of 3 mm, a silver/silver chloride (Ag/AgCl) reference electrode, containing 3 M, KCl and a platinum rod auxiliary electrode were used from metrohm. Electrochemical studies were performed using a single-compartment conventional three-electrode cell (volume 300 μL). A carbon paste electrod was used as working electrode. Saturated silver/silver chloride (Ag/AgCl) reference electrode, containing 3 M KCl and a platinum rod auxiliary electrode were used. All potentials were measured and reported versus the Ag/AgCl reference electrode. Cyclic voltammetry experiments were performed at 0.1 V/s. The amperometric experiments were carried out by applying the desired potential and allowing the transient current to reach the steady-state value prior to the addition of the analyte and the subsequent current monitoring. The morphology of the synthesized nanocomposite was obtained using a SEM Model LEO 440i, UK. The electrochemical behavior of nanocomposite and detection of hydrogen peroxide was carried out in an air-saturated solution for similarity of in vivo usage by Autolab potentiostat (PGSTAT 101). Graphene synthesis Graphene oxide (GrO) was synthesized from graphite using the Hummers method (Tang, et al., 2009) and reduction graphene (RGr) was obtained by reduction of GrO with K2S2O8. Briefly, graphite, sodium nitrate and potassium permanganate were added to concentrated sulfuric acid. After heating at 35°C for 30 min, the reacted mixture turned greenish and pasty. Then, the reaction was carefully quenched by the slow addition of water. The paste was kept at 100°C for 15 min
EXPERIMENTAL DETAILS Reagents Graphite powder was purchased from Fisher (Chemical Scientific grade #38). Paraffin oil, NaBH4, hydrogen peroxide, dihydrogen phosphate (KH2PO4) and 198
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and turned brownish. After further dilution with water it was allowed to cool to 30°C for 30 min, during which it turned yellow. Hydrogen peroxide was carefully added to form colorless soluble manganese sulfate. The resulting GrO was isolated while still warm by filtration and the yellow-brown filter cake was washed with warm 5% diluted hydrochloric acid and finally with water. The resulting stable and brownish GrO aqueous solution was reduced by 1:1 Gr/NaBH4 mass ratio, at room temperature, overnight. The graphene black precipitate was filtrated, washed with water. The different steps of the synthesis were evaluated by FT-IR spectroscopy.
Fig. 1: SEM image of graphene-manganase nanocomposite
Graphene-manganase nanocomposite preparation The recognized graphene was homogenized with potassium permanganate, then 0.1% of hydrogen peroxide was added by droppwish on the mixture until to change color to brownwish. Then, graphene-manganase nanocomposite centrifuge in 10000 rpm and wash three times by ultrapure water. Electrode preparation In the first step, 200 mg of graphite was mixed by 10 mg of graphene-manganase nanocomposite, and it was added to 10 µL of paraffin oil. The mixture of nanocomposite was fixed on syringe electrode and washed with the PBS three times. Finally, the prepared electrode was stored at 4°C before use.
Fig. 2: HRTEM image of graphene-manganase nanocomposite.
oxide show bands attributed to oxygen containing groups, which confirmed the successful oxidation of graphite. These bands are assigned to (O-H) stretching vibration mode of intercalated water (3400 cm-1); (C-O) stretching (1730 cm-1); (CO epoxy) stretching (1170 cm-1); and (CO alkoxy) stretching vibration (1014 cm-1) (Wan, et al. 2011). It is obvious that, the intensity of the absorption peaks for reducing graphene were decreased. This figure proves that, the
RESULTS AND DISCUSSION Graphene-manganase nanocomposite characterization Characterization of graphene-manganase nanocomposite is presented in Fig. 1. It shows that, manganese nanoparticles was synthesized successfully on graphene and graphene-manganase nanocomposite was made. The size of manganese nanoparticles are approximately 82 nm. FT-IR Spectroscopic characterization of Graphene Fig. 3 displays the spectroscopic FT-IR characterization of GrO and RGr. The IR spectrum of graphene
Fig. 3: FTIR spectra of graphene oxide (---) graphene (—).
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Fig. 6: Calibration curve of Cp electrode in different Hydrogen peroxide concentrations in PBS solution (pH= 7.4).
Fig. 4: EIS of Cp electrode in 3 M K3[Fe(CN)6] in PBS solution (pH= 7.4).
layer referred to attend of graphene-manganase nanocomposite on surface and concerned to its conductivity nature (Fig. 4) (Gao, et al., 2012). The graphit plot showed the maximum semicircle radius related to maximum charge transfer resistance and minimum conductivity (Fig. 5).
GrO was successfully reduced to RGr. The investigation of conductivity by electrochemical impedance spectroscopy (EIS) The electrochemical study results are presented as Nyquist plots in Figs. 4 and 5. According to the Figs. 4 and 5 it is evident that all the Nyquist plots showed a simple semicircle that revealed a deposited layer on electrode surfaces. The nanocomposite plot showed the minimum radius related to low charge transfer resistance and high conductivity of the electrode surface
Determination of hydrogen peroxide by nanocmposite Fig. 5 displays the chronoamperometric response of the sensor to different concentrations of hydrogen peroxide for Cp electrode (Fig. 6) and graphene-man-
Fig. 5: EIS of graphene-manganase nanocomposite elec-
Fig. 7: Calibration curve of graphene-manganase nanocom-
trode in different ratio, 1:10 (….), 1:1 (—), 10:1 (----)
posite electrode in different Hydrogen peroxide concentra-
nanoparticle to graphene as same condition of Fig. 4.
tions in same condition of Fig. 5.
Table. 1: Comparison of the analytical parameters obtained in the present work with those reported in the literature. Sensing materials Hb/Au@Fe3O4 HRP-nano-Au
L. R. (M) 3.4×10-6~4.0×10-3 1.2×10−5~1.1×10-3
D. L. (M) 6.7×10-7 6.1×10−6
Ref. (Yu, et al., 2009) (Lie, et al., 2004)
HRP/AuNPs
8.0×10−6~3.0×10−3
2.0×10−6
(Wang, et al., 2009)
Gr/Mn
8.8×10−6~2.6×10−4
1.0×10−6
This work
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ganase nanocomposite Cp electrode (Fig. 7). Subsequent addition of H2O2 to the solution resulted in an apparent increase in the reduction current. The linear concentration range of sensor for Cp electrode is 0.65.7 mM with detection limit of 0.06 mM (A) and the linear concentration rang of graphene-manganase nanocomposite Cp electrode (B) is 8.8-263.3 µM, and with detection limit of 1.04 µM. Present work is caparable with other Hydrogen peroxide sensors (Table 1).
Wang, Y., Li, Z., Wang, J., Li, J., Lin, Y., (2011). Graphene and graphene oxide: biofunctionalization and applications in biotechnology. Trends Biotech., 29; 205-212. Gasnier, A., Pedano, M.L., Rubianes, M.D., Rivas, G.A., (2013). Graphene paste electrode: electrochemical behavior and analytical applications for the quantification of NADH. Sens. Actuat. B, 176; 921-926. Ting, S.W., Periasamy, A.P., Chen, S.M., Saraswathi, R., (2011). Direct electrochemistry of catalase immobilized at electrochemically reduced graphene oxide modified electrode for amperometric H2O2 biosensor. Int. J. Electrochem. Sci., 6; 4438-4453. Wu, J.F., Xu, M.Q., Zhao, G.C., (2010). Graphenebased modified electrode for the direct electron transfer of cytochrome c and biosensing. Electrochem. Communications, 12; 175-177. Kang, X., Wang, J., Wu, H., Aksay, I.A., Liu J., Lin Y., (2009). Glucose biosensor based on immobilization of glucose oxidase in platinum nanoparticles/ graphene/chitosan nanocomposite film. Biosen. Bioelectron., 25; 901-905. Su, G., Wei, Y., Guo M., (2011). Direct Colorimetric Detection of Hydrogen Peroxide Using 4-Nitrophenyl Boronic Acid or Its Pinacol Ester. Amer. J. Anal. Chem., 2; 879-884. Keihan, A.H., Sajjadi, S., (2013). Improvement of the electrochemical and electrocatalytic behavior of Prussian blue/carbon nanotubes composite via ionic liquid treatment. Electrochimica Acta, 113; 803-809. Tang, L., Wang, Y., Li, Y., Feng, H., Lu, J., Li, J., (2009). Preparation, structure, and electrochemical properties of reduced graphene sheet films. Adv. Funct. Mater., 19; 2782-2789. Wan, L., Song, Y., Zhu, H., Wang, Y., Wang, L., (2011). Electron transfer of co-immobilized cytochrome c and horseradish peroxidase in chitosangraphene oxide modified electrode. Inter. J. Electrochem. Sci., 10; 4700–4713. Gao, Z., Liu, N., Wu D., Tao, W., Xu, F., Jiang, K., (2012). Graphene–CdS composite, synthesis and enhanced photocatalytic activity. Appl. Surf. Sci., 258; 2473-2478.
CONCLUSIONS Nowadays, the use of nanomaterial with having of biomimetic effect is extentive. Because they are cheep, simple to synthesize, high abundance and high life time. Therefore, We synthesize graphene-manganase nanocomposite as a peroxides biomimetice for hydrogen oxide detection. The graphene-manganase nanocomposite carbone paste electrode is a fast, easy and renewable electrochemical sensor. The proposed sensor have good characteristics such as; low detection limit of 1.04 µM, wide concentration range from (8.8-263.3 µM), infinite life time, fast response time and good selectivity coefficient. In this nanocomposit manganese oxide nanoparticle is a good catalyst for hydrogen peroxide. On the other hand, graphene is very conductive for electron transferring of chemical reaction. Thus, this synergetic effect caused that, the linear concentration rang of biosensor to be low.
ACKNOWLEDGMENT Financial supports provided by the Research Council of the Baqiatallah University of Medical Science are gratefully appreciated.
REFERENCES Chen, L., Hernandez, Y., Feng, X., Mullen, K., (2012). From Nanographene and Graphene Nanoribbons to Graphene Sheets: Chemical Synthesis. Angew. Chem. Int. Ed., 51; 7640-7654. 201
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Yu ,CM., Guo, JW., Gu, HY., (2009) Direct electrochemical behavior of hemoglobin at surface of Au@Fe3O4 magnetic nanoparticles. Microchim Acta. 166; 215-220. Lei, C.X., Hu, SQ., Gao, N., Shen, G.L., Yu, R.Q., (2004). An amperometric hydrogen peroxide biosensor based on immobilizing horseradish peroxidase to a nano-Au monolayer supported by
sol–gel derived carbon ceramic electrode. Bioelectrochemistry, 65; 33–39. Wang, J.W., Wang, L.P., Di, J.W., Tu, Y.F., (2009). Electrodeposition of gold nanoparticles on indium/tin oxide electrode for fabrication of a disposable hydrogen peroxide biosensor. Talanta, 77; 1454-1459.
AUTHOR (S) BIOSKETCHES Manizheh Ramezani, M.Sc., Nanobiotecnology Research Center, Baqiyatallah University of Medical Science, Tehran, Iran Khadijeh Eskandari, Assistant Professor, Nanobiotecnology Research Center, Baqiyatallah University of Medical Science, Tehran, Iran, E-mail: kheskandari@alumni.ut.ac.ir Mehdi Kamali, Assistant Professor, Nanobiotecnology Research Center, Baqiyatallah University of Medical Science, Tehran, Iran
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Linkage of doxycycline onto functionalized multi-walled carbon nanotube and morphological characterization S. Sedaghat*; M. Nasiri Department of Chemistry, Faculty of Science, Shahr-e-Qods Branch, Islamic Azad University, Tehran, Iran
Received: 28 July 2015; Accepted: 1 October 2015
ABSTRACT: In this paper functionalized multiwall carbon nanotubes (FMWCNT) were modified using doxycycline, containing reactable nitrogen, which can attach chemically to functionalized MWCNT. The synthesized nano compounds were characterized by Fourier transform infrared spectroscopy (FT-IR) and Raman spectroscopy. These spectrums proved the existence of nitrogen atoms of amide functional groups. The morphology was also determined by scanning electron microscopy (SEM) and Transmission electron microscopy (TEM). Also the SEM and TEM images confirmed the uniformly attachment of doxycycline, onto functionalized MWCNTs. Keywords: Doxycycline; Modification; Morphology; Multi-walled carbon nanotubes; Nanotechnology
INTRODUCTION Nanotechnology is one of the fastest developing fields in science which have found technological interest to many researchers. Carbon nanotubes (CNTs) which were discovered in 1991 by Sumio Iijima in Japan, caused a revolution in nanotechnology in various fields such as electronic, mechanic, environment, chemistry and pharmacology (Pandurangappa and Kempegowda, 2011). The physical properties, such as porous structures and facile surface functionalization have made the application of the CNTs more attractive as drug delivery vehicles. The poor solubility of carbon nanotubes in organic solvents restricts them to be used as a drug delivery agent into living systems in drug therapy. Hence many modification approaches such as physi(*) Corresponding Author - e-mail: sajjadsedaghat@yahoo.com
cal, chemical or combined methods have been used for the homogeneous dispersion in common solvents to improve their solubility (Kopaieemalek, et al., 2011). Carbon nanotubes have very wide surface, which is a good position for the functionalization, compared with its length scale in diameter, which is capable of adding different functional groups. The antimicrobial activity of antibiotics such as doxycycline against microbes is severely limited by poor membrane transport ability. Thus there is a need of delivery vehicles like CNTs that allow localizing and controlling delivery of antibiotics for preventing microbial infections (Ahangari, et al., 2013, Kim and Jones, 2004, Dini, et al., 2003). Multi-walled carbon nanotubes (MWCNTs) have potential roles in delivering pharmacologic agents. (MWCNTs) are more attrac-
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tive than single walled carbon nanotubes because of their relatively low production costs and availability in large quantities. Biomedical applications for MWNTs are being investigated actively because of their useful combination of size and physicochemical properties (Bianco, et al., 2005, Sedaghat and Mehraji, 2013). The aim of this study is the linkage of doxycycline as a drug containing amino group with functionalized multi-walled carbon nanotubes (FMWCNTs) for the synthesis of nano drug as illustrated in Figs. 1 and 2:
fluka. Deionized water was also used. Fourier transform infra red (FT-IR) spectrum was recorded using KBr tablets on a Perkin Elmer Spectrum-100 FT-IR spectrometer. Raman spectra recorded on Bruker Sentrra-2009 spectrometer. Scanning electron microscope (SEM) was used to study the morphology of the MWCNTs. SEM measurement was carried out on the Hitachi 4160 Electron Microscope. Surface functionalization of MWCNTs MWCNTs were refluxed in a mixture of H2SO4/ HNO3 for 30 minutes. Then were filtered with millipore membrane, and were washed by double distilled water. The synthesized MWCNTCOOH were dried and collected as black solid. In another step, carboxylated MWCNTs were stirred in 30 mL of a 20:1 mixture of thionyl chloride (SOCl2) and dimethyl formamide (DMF) at 70°C for 24 hours under reflux conditions. The resulting materials were decanted and the super-
MATERIALS AND METHODS Materials Multi-wall carbon nanotube (95% purity, 20-30 nm) were purchased from nanocarbon Co. Thionyl chloride (SOCl2), THF and DMF were purchased from
OH
O
O
OH
OH
H2N O (H3C)2N
OH
OH
Fig. 1: The structure of doxycycline.
H3C
CH3
Fig. 2: Strategy for the linkage of doxycycline onto functionalized multi-walled carbon nanotube.
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Fig. 4: Raman spectra of MWCNT-COCl and MWCNT-Doxy. Fig. 3: FT-IR spectra of: MWCNT-COOH, MWCNT-COCl and MWCNT-Doxy.
RESULTS AND DISCUSSION
natant were removed. Dry THF was then added and the mixture and then centrifuged. This operation was repeated for 5 times. The solid was then filtered on a millipore membrane and washed several times with ethyl alcohol and THF. Subsequently, the black solid was dried at room temperature for 6 hours under vacuum condition as described in our previous work (Sedaghat, 2014). Linkage of doxycycline onto functionalized multiwalled carbon nanotube 80 mg of previously synthesized MWNT-COCl were mixed with 200 mg of doxycycline and 25 mL of DMF and the reaction mixture were stirred for 72 hours under reflux conditions. The synthesized nano compound was washed thoroughly with ethyl alcohol and THF. Subsequently the black solid was dried at room temperature for 8 hours under vacuum condition (Chen and Hamom, 1998). The synthesized nano compound collected for future evaluations.
Fig. 3 shows the FT-IR spectra of MWCNTCOOH, MWCNTCOCl and synthesized nano drug respectively. The stretching frequency of OH, C=O and C-O are shown at 3416, 1715 and 1217 cm-1. The peaks who are related to C=O and C-O stretching frequencies are shifted to 1723 and 1221 cm-1 because of the negative inductive effect of chlorine atoms and the peak at 614 cm-1 can be assigned to the C-CL stretching frequency of COCl groups in MWCNTCOCl. C=O and C-O stretching frequencies are shifted to 1685 and 1205 cm-1 due to the formation of amide bond in nono drug and the peak at 1182 cm-1 is related to C-N stretching of amide groups, while the peak at 3400 cm-1 can be assigned to the N-H stretching frequency for the synthesized nano compound (Tahermansouri, et al., 2013). Raman spectra of functionalized MWCNTs and nano compound are shown in Fig. 4. As can be seen,
Fig. 5: SEM images of FMWCNT and FMWCNT-doxycycline
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Linkage of doxycycline onto functionalized multi-walled carbon nanotube
FMWCNTs-Doxy
FMWCNTs
Fig. 6: TEM image of MWCNT-COCl and MWCNT-Doxy.
CONCLUSIONS
the functional reactions slightly influence the "D band” and the "G band” of the samples. The characteristic peaks of MWNT tangential modes, namely the D band at around 1330-1350 cm-1 and the G band at around 1560-1580 cm-1 are slightly changed because of the strong negative inductive effect, the chlorine atoms are acting as electron withdrawing groups with respect to the nanotubes. However replacing chlorine atoms by amino functional groups can cause the opposite charge transfer from the lone pair of nitrogen to the nanotubes. These results are obvious evidences for the chemical functionalization and formation of nano compound (FMWCNTs-Doxy). In Fig. 5, SEM images of the functionalized MWCNTs and nano compound are shown. In the SEM images of MWNT-COOH, it seems that the uniform surfaces of nanotubes are relatively smooth. After functionalization with doxycycline the diameters of the modified MWNTs are slightly increased as compared to that of MWCNT-COOH, the changes in the morphology are clearly shown (Tahermansouri, et al., 2014). The transmission electron microscopy (TEM) images of the functionalized MWCNTs which are shown in Fig. 6 are the most powerful tool for structure and morphology of MWCNTs. The coating on the nanotubes surface could be observed which might be logically attributed to the doxycycline derivatives functionalities which results the formation of short tubular particles (Entezari, et al., 2013).
The linkage of doxycycline to the FMWCNTs surface by chemical functionalization is successfully carried out. The modified functionalized MWCNTs obtained were evaluated, using FT-IR, SEM and Raman spectroscopy. SEM and TEM images showed the formation of the FMWCNT-doxycycline and presence of the chemical bonding the matrix. FT-IR results showed the formation of amide in the products. The most important advantage of this method is to optimize the drug delivery.
ACKNOWLEDGMENT The authors are grateful to the Islamic Azad University, Shahr-e-Qods branch for their help in this research.
REFERENCES Pandurangappa, M., Kempegowda, R.; (2011), Chemically Modified Carbon nanotubes: derivatization and their applications. J. Intech., 65: 499-526. Kopaieemalek S., Yusof A.M., Abdul Rashid N.A Abbasi M.J., Kopaiee Malek T.; (2011). Study of stability and dispersibility of oxidized multiwall carbon nanotube and characterization with analytical methods for bioapplication. J. Chem. Health Risk, 17-22. 206
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Ahangari, A., Salouti, M, Heidari Z., Kazemzadeh, A.R., Safari, A.; (2013).Development of gentamicin-gold nanospheres for antimicrobial drug delivery to staphylococcal infected foci. J. Drug Deliv., 20: 34-39. Kim, HJ. Jones, M.N.; (2004). The delivery of benzyl penicillin to Staphylococcus aureus biofilms by use of liposomes. J. Liposome Res., 14: 123-39. Dini, E., Alexandridou, S., Kiparissides, C.; (2003). Synthesis and characterization of cross-linked chitosan microspheres for drug delivery applications. J. Microencapsul., 3: 375-85. Bianco, A., Kostarelos, K., Prato, M.; (2005). Applications of carbon nanotubes in drug delivery, Curr. Opin. Chem. Biol., 9: 674–679. Sedaghat, S., Mehraji, M.; (2013). Novel hybrid of Silver nono particles deposited on to the different carbon substrates and evaluation of antibacterial effects. Tech J Engin & App Sci., 3: 219-223. Sedaghat, S.; (2014). Synthesis and modification of
carboxylated multi wall nanotubes with atenolol. Soft Nanosci. Lett., 4: 75-81. Chen, J., Hamom, A.; (1998). Solution properties of single-walled carbon nanotubes. Science, 282: 0036–8075. Tahermansouri, H., Arianfar, Y., Biazar, E.; (2013). Synthesis characterization and influence of functionalized multi walled nanotubes with creatinine and 2-Aminobenzophenone on the gastric cancer cells. J. Bull Korean Chem., 34: 149-153. Thahermansouri, H., Aghaei, M., Azadfar, M.; (2014). The chemical functionalization of multi wall nanotubes with Methyl 2-(amino-4-oxo thiazol-5(4H) ylidene) acetate and phenylhydrazine. J. Orient. J. chem., 27: 1325-1329. Entezari, M., Hekmat, M., Tabatabaei, Z., Hekmat, SH.; (2013). Modification carboxylated multi wall nanotubes with aromatic amines and anti gastric cancer study. J. Trends mod. Chem., 5: 11-14.
AUTHOR (S) BIOSKETCHES Sajjad Sedaghat, Associate Professor, Department of Chemistry, Faculty of Science, Shahr-e-Qods Branch, Islamic Azad University, Tehran, Iran, E-mail: sajjadsedaghat@yahoo.com Maryam Nasiri, M.Sc., Department of Chemistry, Faculty of Science, Shahr-e-Qods Branch, Islamic Azad University, Tehran, Iran
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Cobalt(II) macrocycle complexes based synthesis of Co3O4 nanoparticles: structural and spectral characterization A. Dehno Khalaji1,2*; R. Rahdari1 Department of Chemistry, Faculty of Science, Golestan University, Gorgan, Iran 2 Cubane Chemistry of Hircan (CCH) Co, Gorgan, Iran
1
Received: 8 August 2015; Accepted: 11 October 2015
ABSTRACT: In this paper, macrocyclic cobalt(II) complexes [CoL1](NO3)2.4H2O (1) and [CoL2] (NO3)2.2H2O (2) have been synthesized from the reaction of dialdehydes 1,2-bis(2-formylphenyl)ethane and 1,3-bis(2-formylphenyl)propane, Co(NO3)2.6H2O and 1,2-cyclohexanediamine with molar ration 1:1:1 in methanole and characterized by elemental analyses and FT-IR spectroscopy. Then used as precursors for preparation of Co3O4 nanoparticles via solid-state thermal decomposition without the need a catalyst, employing toxic solvent, template or surfactant and complicated equipment, which makes it efficient, one-step, simple and environment-friendly. The structure and morphology of the Co3O4 products were characterized by FT-IR spectroscopy, XRD and TEM. The XRD result shows that the Co3O4 products are pure, single phase and crystalline. The TEM result shows Co3O4 nanoparticles with the size between <100 nm. On the basis of the above results, other transition metal macrocyclic Schiff base complexes are therefore potentially capable of forming other transition metal oxide nanoparticles. Keywords: Co3O4; Cobalt(II) complexes; Characterized; Metal oxide; Nanoparticles; Thermal decomposition
INTRODUCTION The interest in exploring new macrocyclic Schiff base compounds containing nitrogen and oxygen donor atoms has been increasing (Borisova, et al., 2007), because they play key role in the coordination chemistry of transition metals (Khandar, et al., 2010, Ilhan, et al., 2007a,b,c, Singh, et al., 2011). Also, macrocyclic complexes have been received much attention because of their antibacterial properties (Keypour, et al, 2013, Khanmohammadi, et al., 2009). Recently, Ilhan, et al. synthesized and characterized transition metal complexes with different size, number and donor atoms of (*) Corresponding Author - e-mail: alidkhalaji@yahoo.com
macrocyclic Schiff base (Ilhan, et al., 2007a,b,c, 2010, Ilhan, 2008). Spinel Co3O4 is an important magnetic p-type semiconductor with a normal spinel structure, is an active metal oxides with wide applications and properties, such as catalytic oxidation of CO (Lv, et al., 2013) and lithium ion batteries (Xu, et al., 2009). Recently, several groups used cobalt complexes as new precursor for preparation of cobalt oxide nanoparticles by various methods (Hosseinian, et al., 2012, Khalaji, et al., 2014, Farhadi and Pourzare, 2012). Although considerable effort has been dedicated to control the shape- and
A. Dehno Khalaji & R. Rahdari
size-controlled synthesized by different methods such as hydrothermal synthesis (Li, et al., 2012, Teng, et al., 2010), microwave (Kumar Meher and Rao, 2011, Chen et al., 2013), chemical precipitation (Makhlouf, et al., 2013) and the solid-state thermal decomposition (Farhadi, et al., 2014a,b, Farhadi and Safabakhsh, 2012) methods. Among various techniques for preparation of cobalt oxide nanoparticles, solid-state thermal decomposition of transition metal complexes is one of the best method to preparation of Co3O4 (Hosseinian, et al., 2012, Khalaji, et al., 2014, Farhadi and Pourzare, 2012, Farhadi, et al., 2014a,b, Farhadi and Safabakhsh, 2012), because it is inexpensive (economical) and doesn’t use toxic solvent (pollution free) and surfactant route and is much faster where as process conditions, particle size and purity can be easily controlled. Up to now, many efforts have been made to develop a simple, economical and large scale synthetic method for the preparation of Co3O4 nanoparticles with different morphologies (Lv, et al., 2013, Khalaji, et al., 2015, Li, et al., 2012). Recently, we have been fascinated in the synthesis of Co3O4, utilizing new precursors (Khalaji, et al., 2014 and 2015). Herein, we report the synthesis and characterization of Co3O4 nanoparticles by solidstate thermal decomposition of macrocyclic cobalt(II) complexes [CoL1](NO3)2.4H2O (1) and [CoL2] (NO3)2.2H2O (2) (Scheme 1).
carried out using a Heraeus CHN-O-Rapid analyzer, and results agreed with calculated values. X-ray powder diffraction (XRD) pattern of the complex was recorded on a Bruker AXS diffractometer D8 ADVANCE with Cu-Kα radiation with nickel beta filter in the range 2θ = 100°–70°. Fourier Transform Infrared spectra were recorded as a KBr disk on a FT-IR Perkin–Elmer spectrophotometer. The transmission electron microscopy (TEM) images were obtained from a JEOL JEM 1400 transmission electron microscope with an accelerating voltage of 120 kV. Preparation of Co(II) complexes The macrocyclic cobalt(II) complexes 1 and 2 used in the paper were prepared according to the literature (Yilmaz, et al., 2009). Anal. calcd for C22H24N4CoO8.4H2O (1): C, 43.78; H, 5.34; N, 9.28%; Found C, 43.89; H, 5.52; N, 9.57%. FT-IR (KBr, cm-1): 1631 (C=N), 1384 (NO3). Anal. calcd for C23H26N4CoO8.2H2O: C, 47.51; H, 5.16; N, 9.63%; Found C, 47.66; H, 5.27; N, 9.51%. FT-IR (KBr, cm-1): 1627 (C=N), 1383 (NO3).
RESULTS AND DISCUSSION Complexes The macrocyclic cobalt(II) complexes (1) and (2) are insoluble in most common organic solvents such as methanol, chloroform, ethanol and acetonitrile. Then, the suitable crystals of the complexes could not be obtained for single-crystal X-ray structure determination. In the FT-IR spectra of the complexes a sharp band appear at 1631 and 1627 cm-1, respectively, are corresponding to the frequency vibrations of C=N group of macrocyclic ligand indicating coordination
EXPERIMENTAL Materials and characterization All reagents and solvents for synthesis and analysis were commercially available and used as received without further purifications. Elemental analyses were
Scheme 1: The chemical structures of a) (1) and b) (2).
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Int. J. Bio-Inorg. Hybr. Nanomater., 4(4): 209-213, Winter 2015
Fig. 1: FT-IR spectra of the Co3O4 nanoparticles prepared from a) (1) and b) (2).
of the azomethine nitrogen to cobalt ion. The stretching frequencies at 1384 and 1383 cm-1, respectively, are corresponding to NO3 counter ion (Yilmaz et al., 2009).
Fig. 3: TEM images of the Co3O4 nanoparticles prepared from a) 1 and b) 2.
Co3O4 nanoparticles The Co3O4 nanoparticles were obtained by calcinations of complexes in an air atmosphere at 600°C for 3 h. The FT-IR spectra of the as-prepared Co3O4 nanoparticles are represented in Fig. 1 and shows two absorption bands at about 664 and 570 cm-1, that are assigned to the CoIII-O and CoII-O vibration in octahedral and tetrahedral sites of Co3O4 lattice, respectively (Hosseinian, et al., 2012, Farhadi and Pourzare, 2012).
The XRD patterns of Co3O4 nanoparticles prepared from 1 and 2 are shown in Fig. 2. The XRD patterns reveals diffraction peaks with 2 theta values of 19, 31, 37, 38, 45, 56, 59 and 65 that are assigned to the 111, 220, 311, 222, 400, 422, 511 and 440 crystal planes of the crystalline phase of Co3O4, respectively. All of the diffraction peaks are in good agreement with the cubic Co3O4 phase (Makhlouf, et al., 2013), confirms that the macrocyclic cobalt(II) complexes 1 and 2 are decomposed completely into the cubic Co3O4 phase and is in good agreement with the FT-IR results. The crystal sizes of the Co3O4 nanoparticles based on the FWHM of the all diffraction peaks are in the range of 20 to 40 nm. The morphology of the Co3O4 products was investigated by TEM (Fig. 3). The TEM samples were prepared by dispersing the powder in ethanol by ultrasonic vibration. From the TEM images, it was observed that the nanoparticles were approximately similar shapes and uniform sizes with weak agglomeration.
Fig. 2: XRD patterns of the Co3O4 nanoparticles prepared from a) 1 and b) 2.
211
Cobalt(II) macrocycle complexes based synthesis of Co3O4 nanoparÂticles
CONCLUSIONS
Temperature Synthetic Route of Co3O4 Nanoparticles. J. All. Compd., 515: 180-185. Hosseinian, A.; Jabbari, S.; Rahinipour, H.; Mahjoub, A.R.; (2012). Synthesis and Characterization of Nano-Scale of a New Azido Co(II) Complex as Single and Nano-Scale Crystals: Bithiazole Precursor for the Preparation of Co3O4 Nano-Structures. J. Mol. Struct., 1028: 215-221. Ilhan, S.; (2008). Synthesis and spectral Characterization of Pb(II) Perchlorate Complexes. Ind. J. Chem., 47A: 374-377. Ilhan, S.; Temel, H.; Pasa, S.; Tegin, I.; (2010). Synthesis and Spectral Studies of Macrocyclic Pb(II), Zn(II), Cd(II) and La(III) Complexes by Template Reaction of 1,2-Bis(2-Formylphenyl)ethane with Metal Nitrate and Various Diamine. Russ. J. Inorg. Chem., 55(9): 1402-1409. Ilhan, S.; Temel, H.; Kilic, A.; Tas, E.; (2007a). Synthesis and Spectral Characterization of Macrocyclic NiII Complexes Derived from Various Diamines, NiII Perchlorate and 1,4-bis(2-carboxyaldehydephenoxy)butane. Trans. Met. Chem., 32: 1012-1017. Ilhan, S.; Temel, H.; Yilmaz, I.; Sekerci, M.; (2007b). Synthesis, Structural Characterization and Electrochemical Studies of New Macrocyclic Schiff Base Containing Pyridine Head and Its Metal Complexes. J. Organomet. Chem., 692: 38553865. Ilhan, S.; Temel, H.; Ziyadanogullari, R.; Sekerci, M.; (2007c). Synthesis and Spectral Characterization of Macrocyclic Schiff Base by Reaction of 2,6-Diaminopyridine and 1,4-bis(2-Carboxyaldehydephenoxy)butane and Its CuII, NiII, PbII, CoIII and LaIII Complexes. Trans. Met. Chem., 32: 584-590. Keypour, H.; Shayesteh, M.; Rezaeivala, M.; Chalabian, F.; Valencia, L.; (2013). Synthesis and Characterization of a Series of Transition Metal Complexes with a New Symmetrical Polyoxaaza Macrocyclic Schiff Base Ligand: X-ray Crystal Structure of Cobalt(II) and Nickel(II) Complexes and Their Antibacterial Properties. Spectrochim. Acta A101:59-66. Khalaji, A.D.; Nikookar, M.; Fejfarova, K.; Dusek, M.; (2014). Synthesis of New Cobalt(III) Schiff
In this work, it was demonstrated that Co3O4 nanoparticles can be obtained by a simple solid-state thermal decomposition route of cobalt(II) macrocyclic Schiff base complexes, [CoL1](NO3)2.4H2O (1) and [CoL2] (NO3)2.2H2O (2), as new precursors for the first time in air at 600ÂşC for 3 h. The synthesis method is simple, mild and can also be extended to other transition metal oxides.
ACKNOWLEDGMENT The financial support from the Golestan University and CCH are gratefully acknowledged.
REFERENCES Borisova, N.E.; Reshetova, M.D.; Ustynyuk, Y.A.; (2007). Metal-Free Method in the Synthesis of Macrocyclic Schiff bases. Chem. Rev., 107: 4679. Chen, G.; Fu, E.; Zhou, M.; Xy, Y.; Fei, L.; Deng, S.; Chaitanya, V.; Wang, Y.; Luo, H.; (2013). A Facile Microwave-Assisted Route to Co(OH)2 and Co3O4 Nanosheet for Li-ion Battery. J. All. Compd., 578: 349-354. Farhadi, S.; Pourzare, K.; (2012). Simple and LowTemperature Preparation of Co3O4 Sphere-Like Nanoparticles via Solid-State Thermolysis of the [Co(NH3)6](NO3)3 Complex. Mater. Res. Bull., 47: 1550-1556. Farhadi, S.; Pourzare, K.; Bazgir, S.; (2014). Co3O4 Nanoplates: Synthesis, Characterization and Study of Optical and Magnetic Properties. J. All. Compd., 587:632-637. Farhadi, S.; Pourzare, K.; Sadeghinejad, S.; (2014). Synthesis and Characterization of Co3O4 Nanoplates by Simple Thermolysis of the [Co(NH3)6]2(C2O4)3.4H2O Complex. Polyhedron, 67: 104-110. Farhadi, S.; Safabakhsh, J.; (2012). Solid-State Thermal Decomposition of the [Co(NH3)5CO3] NO30.5H2O Complex: A Simple, Rapid and Low212
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Base Complex. A New Precursor for Preparation Co3O4 Nanoparticles via Solid-State Thermal Decomposition. J. Mol. Struct. 1071:6-10. Khalaji, A.D.; Rahdari, R.; Gharib, F.; Matalobos, J.S.; Das, D.; (2015). Preparation and Characterization of Co3O4 Nanoparticles by Solid State Thermal Decomposition of Cobalt(II) Macrocyclic Schiff Base Complexes. J. Cer. Process. Res., 16: 486-489. Khandar, A.A.; Hosseini-Yazdi, S.A.; Khatamian, M.; Zarei, S.A.; (2010). Synthesis, Characterization, Electrochemical Behaviour and X-ray Crystal Structures of Nickel(II) Complexes with a N2O2 Donor Set Macrocyclic Schiff Base Ligand. Polyhedron, 29: 995-1000. Khanmohammadi, H.; Keypour, H.; Salehei Fard, M.; Abnosi, M.H.; (2009). Synthesis and Biological Activity of Magnesium(II) Complexes of heptaaza Schiff Base Macrocyclic Ligands; 1H and 13C Chemical Shifts Computed by the GIAO-DFT and GSGT-DFT Methodologies. J. Incl. Phenom. Macrocycl. Chem., 63: 97-108. Kumar Meher, S.; Rao, G.R.; (2011). Effect of Microwave on the Nanowire Morphology, Optical, Magnetic, and Pseudocapacitance Behavior of Co3O4. J. Phys. Chem. C115:25543-25556. Li, D.; Wu, X.; Xiao, T.; Tao, W.; Yuan, M.; Hu, X.; Yang, P.; Tang, Y.; (2012). Hydrothermal Synthesis of Mesoporous Co3O4 Nanobelts by Means of
a Compound Precursor. J. Phys. Chem. Solids, 73: 169-175. Lv, Y.; Li, Y.; Shen, W.; (2013). Synthesis of Co3O4 Nanotubes and Their Catalytic Application in Co Oxidation. Catal. Commun., 42: 116-120. Makhlouf, S.A.; Bakr, Z.H.; Aly, K.I.; Moustafa, M.S.; (2013). Structural, Electrical and Optical Properties of Co3O4 Nanoparticles. Superlatt. Microstruct., 64: 107-117. Singh, D.; Grover, V.; Kumar, K.; Jain, K.; (2011). Synthesis and Characterization of Divalent Metal Complexes of the Macrocyclic Ligand Derived from Isatin and 1,2-Diaminoethane. J. Serb. Chem. Soc., 46(3): 385-393. Teng, Y.; Yamamoto, S.; Kusano, Y.; Azuma, M.; Shimakawa, Y.; (2010). One-pot Hydrothermal Synthesis of Uniformly Cubic Co3O4 Nanocrystals. Mater. Lett., 64: 239-242. Yilmaz, I.; Ilhan, S.; Temel, H.; Kilic, A.; (2009). Synthesis, Characterization and Electro-Spectrochemical Studies of Four Macrocyclic Schiff-base Co(II) Complexes Having N2O2 Set of Donor Atoms. J. Incl. Phenom. Macrocycl. Chem., 63: 163169. Xu, R.; Wang, J.; Li, Q.; Sun, G.; Wang, E.; Li, S.; Gu, J.; Ju, M.; (2009). Porous Cobalt Oxide (Co3O4) Nanorods: Facile Syntheses, Optical Property and Application in Lithium-Ion Batteries. J. Solid state Chem., 182: 3177-3182.
AUTHOR (S) BIOSKETCHES Aliakbar Dehno Khalaji, Ph.D., Assistant Professor, Department of Chemistry, Faculty of Science, Golestan University, Gorgan, Iran & Cubane Chemistry of Hircan (CCH) Co, Gorgan, Iran, E-mail: alidkhalaji@yahoo.com Raziyeh Rahdar, B.Sc., Department of Chemistry, Faculty of Science, Golestan University, Gorgan, Iran
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Int. J. Bio-Inorg. Hybr. Nanomater., 4(4): 215-223, Winter 2015
Investigation of non-bonded interaction between C10H8 and B12N12 nano ring: NBO and NMR studies M. Khaleghian1*; F. Azarakhshi2; Gh. Ghashami3 Department of Chemistry, Islamshahr Branch, Islamic Azad University, Tehran, Iran Department of Chemistry, Varamin-Pishva Branch, Islamic Azad University, Varamin, Iran 3 Department of Engineering, Islamshahr Branch, Islamic Azad University, Islamshahr, Iran 1
2
Received: 24 August 2015; Accepted: 27 October 2015
ABSTRACT: To determine the non-bonded interaction energies between Naphthalene and B12N12 Nano ring in different orientations and distances, geometry of molecules with B3LYP method and 6-31g* basis set optimized. Also reactivity and stability of Naphthalene alone and in the presence B12N12 Nano ring checked. Then calculated the NBO, NMR, FREQ, NICS and muliken charge of Naphthalene atoms alone and in the presence B12N12 done. The results of any order to reduce the reactivity and increase stability of Naphthalene in the presence B12N12 Nano ring tells. The Gaussian quantum chemistry package is used for all calculations. Keywords: Ab initio; DFT; Nano ring; Naphthalene -B12N12; NBO; NICS; NMR
INTRODUCTION Polycyclic Aromatic Hydrocarbons (PAHs) occur naturally in coal, Crude oil and gasoline. PAHs compounds are also products made from fossil fuels, asphalt and pitch. By converting coal to natural gas and the incomplete combustion of fossil fuels and garbage, PAHs compounds are released into the air. Which is much more incomplete combustion process more compounds released. PAHs compounds in the environment, water, soil and air are found and the months and years will remain in these areas. The amount of these compounds in urban air is 10 times higher than non-urban air. Subject carcinogenic poly nuclear aromatic compounds are still requires (*) Corresponding Author - e-mail: mehr_khaleghian@iiau.ac.ir
further study. The carcinogenic effects of a number of compounds of this group, in laboratory animals has been proven, but it is not known whether humans as a result of exposure to these compounds is cancer or not. In this study, changes in the properties one of these compounds in the presence of nanostructures reviewed. After the discovery of C60 (Kroto, et al., 1985), carbon nano structures such as fullerene clusters, nanotubes, nano-capsules, cones and cubes have been reported (Kroto, et al., 1985, Iijima, 1991, Oku, et al., 2000, Oku, et al., 2001). Boron nitride Nanostructure has a band gap energy of about 6 eV it is expected that different electronic, optical and magnetic properties reveal (Oku, et al., 2001). Therefore, many studies on BN nanomaterials such as BN nanotubes (Oku, et al.,
M. Khaleghian et al.
2001, Mickelson, et al., 2003), BN nanocapsules4, BN clusters (Oku, et al., 2000, Oku, et al., 2001) and BN nanoparticles (Oku, et al., 2003, Oku, et al., 2003) have been reported, it is expected that these compounds to be useful for the electronics, semiconductor with high thermal stability and nanowires. The number of BN clusters (Jensen and Toflund, 1993, Zandler, et al., 1996, Seifert, et al., 1997, Slanina, et al., 1997, Zhu, et al., 1997, Alexandre, et al., 1999, Fowler, et al., 1999, Pokropivny, et al., 2000, Strout, 2000, Will and Perkins, 2001, Alexandre, et al., 2002) and BN nano-rings (Monajjemi, et al., 2010, Monajjemi, 2011, Monajjemi and Boggs, 2013, Monajjemi and Khaleghian, 2011) have been studied using theoretical methods. Also absorption of benzene and polycyclic hydrocarbons on carbon nanotubes and graphene sheets studied by theoretical methods (Tran-Duc and Thamwattana, 2011, Mishra and Yadav, 2012, Kuc and Heine, 2010). In this study, the Naphthalene aromaticity properties as a known carcinogen combination, in interaction with B12N12 nanoring theoretically studied. The aim of this study, the electronic structure, structural stability or reduction in reactivity of Naphthalene in the presence B12N12 Nano ring by using theoretical methods.
Table 1: The values of the energy of Naphthalene and B12N12 molecules at different angles Naphthalene -B12N12 Angle of rotation
Energy /Hartree
-180
-1341.5632079
-160
-1341.5632372
-140
-1341.5632390
-120
-1341.5632263
-100
-1341.5632556
-80
-1341.5632761
-60
-1341.5632942
-40
-1341.5633148
-20
-1341.5633197
0
-1341.5632904
20
-1341.5633112
40
-1341.5633055
60
-1341.5632782
80
-1341.5632862
100
-1341.5632412
120
-1341.5632466
140
-1341.5632521
160
-1341.5632410
180
-1341.5632079
using ab initio gaussian quantum chemical package. The main purpose of this study was to evaluate changes of reactivity of aromatic compound in Nano ring field. Thus the energy of interaction between two molecules in different orientations and distances are calculated. The energy values are given in Tables 1 and 2. The table data shows that the best angle and
COMPUTATIONAL METHODS Geometric structure of Naphthalene molecule and B12N12 Nano ring with B3LYP method (Becke, 1993, Lee, et al., 1988) and 6-31g* basis set is optimized by
ring 2
ring 1
(a) ring 2
ring 2
ring 3 ring 1
ring 1 ring 4
(b)
Scheme 1: a) Optimized structure of Naphthalene b) optimized structure of Naphthalene -B12N12 Nano ring.
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Int. J. Bio-Inorg. Hybr. Nanomater., 4(4): 215-223, Winter 2015 Table 2: The values of the absorbed energy of Naphthalene and B12N12 molecules at different distances. E adsorption
Energy /Hartree
Distance
Naphthalene
/KCal/Mol
/Å
Naphthalene -B12N12
B12N12
1.6
-1341.532299
19.22243576
2
-1341.556045
4.321783428
2.4
-1341.562025
0.569464871
2.8
-1341.56326
-0.205823116
2.9
-1341.563347
3
-1341.563393
3.1
-1341.563411
-0.300263296
3.2
-1341.563406
-0.297000246
3.3
-1341.563382
-0.282316524
3.4
-1341.563347
-0.260416443
3.5
-1341.563304
-0.232994277
-385.8926484
-955.6702839
-0.260165439 -0.289281879
Table 3: Relative thermochemical parameters of Naphthalene, B12N12 and Naphthalene - B12N12. ∆G
∆H
E (Thermal)
S
/(Hartree/Particle)
/(Hartree/Particle)
/KCal/Mol
/Cal/Mol-Kelvin
Naphthalene
- 0.116
- 0.155
97.230
82.200
B12N12
- 0.069
- 0.131141
81.700
130.38
Naphthalene -B12N12
- 0.208
- 0.284
146.600
149.343
Compounds
distance values for the two adsorbed molecules equal to the -20.0° and 3.1 Å, respectively. Optimized structure shown in Scheme 1 and adsorption energy for optimized structure of Naphthalene -B12N12 equal to -0.30026 kcal/mol. So other calculations related to NBO, NMR and Freq for optimum structure at the level of B3LYP/6-31g* was used.
ergy (∆G), standard enthalpies (∆H), entropies (S), thermal energy (T) that is dependent on transfer, vibration and rotation movements of particles and sum of electronic and zero-point Energies (E+ZPE), sum of electronic and thermal Energies (E+T), sum of electronic and thermal Enthalpies (E+H) and sum of electronic and thermal Free Energies (E+G) values of Naphthalene, B12N12 and Naphthalene -B12N12 at B3LYP method with 6-31g* basis set have been calculated. The energy values are given in Tables 3 and 4. When Naphthalene is in non-bonded interaction with the Nano ring, Gibbs and enthalpy energies values
RESULT AND DISCUSSION Thermodynamic Analysis Thermodynamic quantities such as the gibbs free en-
Table 4: Sum of thermochemical parameters of Naphthalene, B12N12 and Naphthalene - B12N12 Compounds
E+ZPE / (Hartree/Particle)
E+T /Hartree
E+H /Hartree
E+G /Hartree
Naphthalene
-385.744
-385.737
-385.736
-385.775
B12N12
-955.560
-955.543
-955.542
-955.604
Naphthalene -B12N12
-1341.302
-1341.280
-1341.279
-1341.354
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Investigation of non-bonded interaction between C10H8 and B12N12 nano ring
decreases. Energy values reflect the reduced reactivity and increase stability of Naphthalene molecule in presence Nano ring field.
Table 5: Mulliken atomic charges (NBO charges) of Naphthalene and Naphthalene -B12N12. Mulliken atomic charges/e Naphthalene
NBO Analysis Density functional theory (DFT) calculations with B3LYP method for studying the effects of B12N12 Nano ring field on aromaticity and stability of the Naphthalene is done. Naphthalene and B12N12 structures by B3LYP/6-31g* can be optimized, and calculations NBO analysis done for these compounds. NBO analysis results are reported in Table 5 and 6. Distribution charge to carbon atoms of Naphthalene in the absence of Nano ring field and in the presence of Nano ring field by NBO method specified. The Mulliken atomic charges given in Table 5. Mulliken charges are obtained theoretically by partitioning of electron density distribution employing the Mulliken approximation (Mulliken, 1955). Table data specifies that the distribution of charge on the (1,4), (2,3), (5,10), (6,9) and (7,8) carbon atoms of Naphthalene is similar in the absence of Nano ring field, But when Naphthalene is in the presence of the Nano ring field, 31, 32 and 33 carbon atoms of Naphthalene that are closer to the nano ring, greater share of charge to allocated in comparison with 7, 8 and 9 carbon atoms. Which represents the electron transfer is from the Nano ring to Naphthalene and this is due to the non-bonded interaction between Naphthalene and nano ring (Atomic label is according to Scheme 1). Mulliken atomic charge values in Table 5 shows that the total atomic charge of carbon atoms of Naphthalene alone and in the presence of Nano ring equal to -1.031 and -1.048 respectively. And 31, 32 and 33 carbon atoms in the Naphthalene that are closer to the Nano ring receive the additional contribution of atom-
Naphthalene -B12N12
1 C
-0.1907
25 C
-0.19051
2 C
-0.13455
26 C
-0.13458
3 C
-0.13455
27 C
-0.13444
4 C
-0.19069
28 C
-0.19094
5 C
0.134754
29 C
0.135392
6 C
-0.19068
30 C
-0.19085
7 C
-0.13456
31 C
-0.13752
8 C
-0.13456
32 C
-0.14505
9 C
-0.19069
33 C
-0.19441
10 C
0.134777
34 C
0.135343
Sum of Mulliken charges
Sum of Mulliken charges
-1.03146
-1.04756
ic charges that due to the non-bonded interactions and electron transfer from Nano ring is to Naphthalene. Electronic properties such as Ionization energy (I), Electron affinity (A), energy gap (Eg), electronic chemical potential (μ), chemical hardness (η), electro philicity index (ω), global hardness (s) and electron transfer (Δn) can be obtained using NBO analysis. According to the data of Table 6 can be understood the energy gap for Naphthalene, B12N12 and Naphthalene -B12N12 Nano ring are 4.84 eV, 4.37 eV and 2.59 eV respectively. By comparing these values, we find that the presence of Nano ring with Naphthalene is a factor for Naphthalene is more stable and less reactive. Electron transfer to Naphthalene -B12N12 Nano ring is 2.83 that this represents the flow of electrons from the Nano ring to the Naphthalene, and electron transfer can be seen in the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) Orbitals diagram (Fig. 1). So that
Table 6: Electronic properties of Naphthalene and B12N12- Naphthalene at B3LYP/6-31g*. NBO data at B3LYP/6-31g* Compounds
LUMO
HOMO
(eV)
(eV)
Naphthalene
-0.945
Naphthalene-B12N12 B12N12
I(eV)
A(eV)
Eg(eV)
μ (eV)
η(eV)
ω(eV)
s(eV-1)
Δn(eV)
-5.790
5.790
0.945
4.845
-3.368
2.422
2.341
0.206
1.390
-3.222
-5.809
5.809
3.222
2.587
-4.516
1.294
7.882
0.387
3.491
-3.176
-7.547
7.547
3.176
4.371
-5.361
2.185
6.577
0.228
2.453
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Int. J. Bio-Inorg. Hybr. Nanomater., 4(4): 215-223, Winter 2015
Fig. 1: a) LUMO and HOMO molecular orbitals of Naphthalene and Naphthalene -Nano ring, b) DOS diagrams of Naphthalene and Naphthalene -nano ring.
HOMO orbitals matches the Naphthalene and LUMO orbitals matches the nano ring.
rameters are calculated using the ab initio method, an important role in studying the molecular structure of compounds is applied. There are different methods to determine NMR parameters such as Gauge-Including atomic orbitals (GIAO), Individual gauge for localized orbitals (IGLO), Localized orbitals local origin (LORG) and Continuous set of gauge transformations (CSGT). In this study GIAO method for the measurement NMR parameters of Naphthalene and Naphthalene -B12N12 Nano ring used. The results are report-
NMR Analysis Nuclear magnetic resonance (NMR) spectroscopy with the interactions between nuclear and magnetic fields involved. NMR spectroscopy is a powerful technique to study structural and dynamic properties of molecules in different physical states. Theoretical Studies of nuclear magnetic properties is based on advanced methods of quantum mechanics. NMR pa-
Fig. 3: GIAO magnetic shielding of Naphthalene -B12N12 Fig. 2: GIAO magnetic shielding of Naphthalene.
Nano ring.
219
M. Khaleghian et al. Table 7: NMR parameters of Naphthalene and Naphthalene -B12N12 Nano ring at B3LYP/6-31g*. compounds Naphthalene1C 2C 3C 4C 5C 6C 7C 8C 9C 10 C NaphthaleneB12N12 25 C 26 C 27 C 28 C 29 C 30 C 31 C 32 C 33 C 34 C
NMR parameters/ppm σ iso 68.207 71.012 71.012 68.204 64.108 68.205 71.012 71.013 68.208 64.113
σ aniso 145.783 161.834 161.835 145.786 199.777 145.784 161.833 161.832 145.781 199.775
σ11 -21.584 -24.278 -24.280 -21.590 -3.873 -21.588 -24.279 -24.277 -21.582 -3.867
σ22 60.810 58.414 58.414 60.807 -1.096 60.808 58.415 58.414 60.811 -1.092
σ33 165.396 178.902 178.902 165.394 197.293 165.394 178.901 178.901 165.396 197.296
Δσ 145.783 161.834 161.835 145.786 199.777 145.784 161.833 161.832 145.781 199.775
δ 97.189 107.889 107.890 97.191 133.185 97.189 107.889 107.888 97.188 133.183
η 0.848 0.766 0.766 0.848 0.021 0.848 0.766 0.766 0.848 0.021
Ω 186.980 203.180 203.182 186.985 201.166 186.982 203.180 203.178 186.978 201.162
κ -0.119 -0.186 -0.186 -0.119 -0.972 -0.119 -0.186 -0.186 -0.119 -0.972
σ iso
σ aniso
σ11
σ22
σ33
Δσ
δ
η
Ω
κ
68.190 70.945 70.957 68.190 64.097 68.146 71.293 70.932 68.259 64.124
145.456 161.628 161.721 145.498 199.449 145.450 160.676 160.790 145.101 199.368
-21.842 -24.299 -24.029 -21.532 -4.022 -21.762 -24.555 -22.081 -21.740 -4.154
61.251 58.437 58.129 60.913 -0.750 61.088 60.024 56.751 61.522 -0.510
165.160 178.697 178.771 165.189 197.063 165.113 178.411 178.125 164.993 197.037
145.456 161.628 161.721 145.498 199.449 145.450 160.676 160.790 145.102 199.369
96.970 107.752 107.814 96.999 132.966 96.967 107.117 107.193 96.734 132.912
0.857 0.768 0.762 0.850 0.025 0.854 0.790 0.735 0.861 0.027
187.002 202.996 202.800 186.721 201.085 186.875 202.966 200.206 186.732 201.190
-0.111 -0.185 -0.190 -0.117 -0.967 -0.113 -0.167 -0.212 -0.108 -0.964
atoms in s=71.012 ppm. 5 and 10 carbon atoms that are common aromatic rings appears in the lowest chemical shift. When Naphthalene is located adjacent to B12N12 Nano ring, 34 and 29 carbon atoms in a similar position to ratio of 5 and 10 carbon atoms of alone Naphthalene appears in the lowest chemical shift, that is s=64.097 ppm. When the Naphthalene is located adjacent to B12N12 nano ring, most chemical shift related to 31 carbon atom and appeared at s=71.293 ppm that due to being in the center of the magnetic field of Ring 1 of Nano ring. The magnetic field causes dishield and 31 carbon atom of the Naphthalene appear in the higher σ iso than the other carbon atoms of Naphthalene. But 32 carbon atom is located
Table 8: Nucleus-Independent Chemical Shifts of Naphthalene and Naphthalene -B12N12 Nucleus-Independent Chemical Compounds
Shifts Values / (ppm)
Naphthalene
ring 1 -4.1050
ring 2 -4.1074
Naphthalene-B12N12
-3.3538
-3.8838
ed in Table 7. According to the data of the table it is clear that Naphthalene has three types of carbon that in carbon NMR spectra appears as follows: (5,10) carbon atoms in s=64.112 ppm, (1,4) and (6,9) carbon atoms in s=68.203 ppm, (2,3) and (7,8) carbon
Fig. 5: IR spectrum of Naphthalene -B12N12 Nano ring.
Fig. 4: IR spectrum of Naphthalene.
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adjacent to the 4 nitrogen atom of Nano ring (with the effect of electron-induced attraction) causes dishieldings 32 carbon atom and appear in s=70.93 ppm. 33 carbon atom with the lowest chemical shift and the highest shieldings will appear in the s=68.258 ppm. Because 33 carbon atom is located in front of the 3 boron atom that is electropositive atom (Figs. 2, 3). Nucleus-Independent Chemical Shifts (NICS) calculations is done for Naphthalene and NaphthaleneB12N12. NICS Values are given in Table 8. In the presence of B12N12 Nano ring field, aromaticity of the both of Naphthalene rings reduced and ring 1 that is closer to Nano ring due to greater non bonded interaction with B12N12, shows aromaticity reduction greater than ring 2.
matic rings alone and in the presence of Nano ring can be found that the presence of Nano ring on the side aromatic compounds can cause dishield carbon atoms are close to the Nano ring and this leads to a change in chemical shift toward higher values is. Also results of HOMO and LUMO molecular orbitals the justification for the electron transfer of the Nano ring to the Naphthalene aromatic rings. So molecular orbitals diagram related to Naphthalene and Naphthalene -B12N12 shows HOMO orbitals based on Naphthalene aromatic rings and LUMO orbitals based on the Nano ring and as well as the results of the carbon NMR spectra justified. All of calculations shows reduce the reactivity and increase stability of naphthalene in the presence B12N12 Nano ring.
IR Spectroscopy By observing the IR spectra of Naphthalene (Fig. 4) we find that peak of C-H aromatic bond stretching vibration (C=C-H) at a frequency of qC=C-H=3220 cm-1 and in Naphthalene –Nano ring (Fig. 5) the peak appear in the frequency of qC=C-H=3218 cm-1. And the peak related to stretching vibration of C=C double bonds of the Naphthalene aromatic rings and Naphthalene –Nano ring appears in qC=C-H=1570 cm-1 and qC=C-H=1679 cm-1 respectively. Also Peak related to bending vibrations of aromatic C-H bonds (C = C-H) of the Naphthalene aromatic rings and Naphthalene –Nano ring appears in qC=C-H=678 cm-1 and qC=C-H=793 cm-1 respectively. For Naphthalene –Nano ring compound peak appeared at a frequency of qC=C-H=1861 cm-1 related to nitrogen atoms top of each loop and sharp peak appeared at a frequency of qB=N=1822 cm-1 related to other boron –nitrogen bonds in Nano ring. Stretching vibration related to Non-bonded interactions of C and N atoms appears at a frequency of qC=N=1218 cm-1 and qC=N=1245 cm-1 which marks the transition of the electron cloud between the Naphthalene aromatic rings and Nano ring. And for the Naphthalene -Nano ring compound C-C stretching vibration peaks appears at qC-C=1177 cm-1 and qC-C=1192 cm-1.
ACKNOWLEDGMENT This work was supported by Islamic Azad University, Islamshahr Branch. The authors thank Islamshahr Branch for financial supports.
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CONCLUSIONS Compare Carbon NMR spectra of Naphthalene aro221
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and cubic boron nitride prepared by chemical vapor deposition method, Diamond Relat. Mater., 12: 1138–1145. Oku, T.; Hiraga, K.; Matsuda, T.; Hirai, T.; Hirabayashi, M.; (2003). Formation and structures of multiply-twinned nanoparticles with fivefold symmetry in chemical vapor deposited boron nitride, Diamond Relat. Mater., 12: 1918–1926. Jensen, F.; Toflund, H.; (1993). Structure and stability of C24 and B12N12 isomers, Chem. Phys. Lett., 201: 89–96. Zandler, M.E.; Behrman, E.C.; Arrasmith, M.B.; Myers, J.R.; Smith, T.V.; (1996). Semiempirical molecular orbital calculation of geometric, electronic, and vibrational structures of metal oxide, metal sulfide, and other inorganic fullerene spheroids, J. Mol. Struct. (Theochem), 362: 215–224. Seifert, G.; Fowler, P.W.; Mitchell, D.; Porezag, D.; Frauenheim, Th.; (1997). Boron-nitrogen analogues of the fullerenes: electronic and structural properties, Chem. Phys. Lett., 268: 352–358. Slanina, Z.; Sun, M.L.; Lee, S.L.; (1997). Computations of boron and boron nitride cages, Nanostruc. Mater., 8: 623–635. Zhu, H.Y.; Schmalz, T.G.; Klein, D.J.; (1997). Alternant boron nitride cages: a theoretical study, Int. J. Quantum Chem., 63: 393– 401. Alexandre, S.S.; Mazzoni, M.S.C.; Chacham, H.; (1999). Stability, geometry, and electronic structure of the boron nitride B36N36 fullerene, Appl. Phys. Lett., 75: 61–63. Fowler, P.W.; Rogers, K.M.; Seifert, G.; Terrones, M.; Terrones, H.; (1999). Pentagonal rings and nitrogen excess in fullerene-based BN cages and nanotube caps, Chem. Phys. Lett., 299: 359–367. Pokropivny, V.V.; Skorokhod, V.V.; Oleinik, G.S.; Kurdyumov, A.V.; Bartnitskaya, T.S.; Pokropivny, A.V.; Sisonyuk, A.G.; Sheichenko, D.M.; (2000). Boron nitride analogs of fullerenes (the fulborenes), nanotubes, and fullerites (the fulborenites), J. Solid State Chem., 154: 214–222. Strout, D.L.; (2000). Structure and stability of boron nitrides: isomers of B12N12, J. Phys. Chem. A., 104: 3364–3366. Will, G.; Perkins, P.G.; (2001). Is there a new form
of boron nitride with extreme hardness?, Diamond Relat. Mater., 10: 2010–2017. Alexandre, S.S.; Nunes, R.W.; Chacham, H.; (2002). Energetics of the formation of dimers and solids of boron nitride fullerenes, Phys. Rev. B, 66: 085406-1-5. Monajjemi, M.; Lee, V.S.; Khaleghian, M.; Honarparvar, B.; Mollaamin, F.; (2010). Theoretical description of electromagnetic nonbonded interactions of radical, cationic, and anionic NH2BHNBHNH2 inside of the B18N18 nanoring, J. Phys. Chem. C, 114: 15315-15330. Monajjemi, M.; (2011). Quantum investigation of non-bonded interaction between the B15N15 ring and BH2NBH2 (radical, cation, anion) systems: A nano molecularmotor, Struct. Chem., 23: 551-580. Monajjemi, M.; Boggs, J.E.; (2013). A new generation of BnNn rings as a supplement to boron nitride tubes and cages, J. Phys. Chem. A, 117: 16701684. Monajjemi, M.; Khaleghian, M.; (2011). EPR Study of Electronic Structure of [CoF6]3- and B18N18 Nano Ring Field Effects on Octahedral Complex, J. Cluster Sci., 22: 673–692. Tran-Duc, T.; Thamwattana, N.; (2011). Modeling carbon nanostructures for filtering and absorbing polycyclic aromatic hydrocarbons, J. Comput. Theor. Nano.Sci., 8: 2072-2077. Mishra, P.C.; Yadav, A.; (2012). Polycyclic aromatic hydrocarbons as finite size models of graphene and grapheme nanoribbons: Enhanced electron density edge effect, Chem. Phys., 402: 56-68. Kuc, A.; Heine, T.; (2010). Graphene nanoflakesstructural and electronic properties, Phys. Rev. B., 81: 085430-085447. Becke, A.D.; (1993). Density-functional thermochemistry. iii. The role of exact exchange, J. Chem. Phys., 98: 5648–5652. Lee, C.; Yang, W.; Parr, R.G.; (1988). Development of the Colle-Salvetti correlation-energy for formula into a functional of the electron density, Phys. Rev. B, 37: 785-789. Mulliken, R.S.; (1955). Electronic Population Analysis on LCAOMO Molecular Wave Functions, J. Chem. Phys., 23; 1833-1840.
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AUTHOR (S) BIOSKETCHES Mehrnoosh Khaleghian, Assistant Professor, Department of Chemistry, Islamshahr Branch, Islamic Azad University, Tehran, Iran, E-mail: mehr_khaleghian@yahoo.com, mehr_khaleghian@iiau.ac.ir Fatemeh Azarakhshi, Assistant Professor, Department of Chemistry, Varamin-Pishva Branch, Islamic Azad University, Varamin, Iran Gholamreza Ghashami, Instructor, Department of Engineering, Islamshahr Branch, Islamic Azad University, Islamshahr, Iran
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CdS nanoparticles: An efficient, clean and reusable heterogeneous catalyst for one-pot procedure for synthesis of 3,4-Dihydropyrimidin-2(1H)-ones in solvent-free conditions Kh. Pourshamsian Department of Chemistry, Tonekabon Branch, Islamic Azad University, Tonekabon, Iran
Received: 6 September 2015; Accepted: 9 November 2015
ABSTRACT: 3,4-Dihydropyrimidinones and their derivatives are synthesized via Biginelli routes involving an aromatic aldehydes, ethylacetoacetates and urea in one-pot procedure by using CdS nanoparticles as efficient heterogeneous catalyst in solvent-free conditions. Compared with classical Biginelli reaction reported in 1893, this new method provides much improved modification in terms of simplicity. The present methodology offers several advantages such as a simple procedure with an easy work-up, short reaction times and excellent yields. Excellent yields and mild reaction conditions as well as the environmentally friendly character of CdS make it an important alternative to the classic acid catalyzed Biginelli's reactions. The catalysts could be recycled and reused for five times, without substantial reduction in their catalytic activities. The results are shown that electron-releasing group on aromatic ring causes reduced rate of reaction and electron with drawing group's causes increased the rate of reactions. The structure of products has been characterized by IR and 1HNMR spectra. Keywords: CdS nanoparticles; 3,4-Dihydropyrimidinones; Heterogeneous catalyst; One-pot reactions; Solvent-free conditions
INTRODUCTION In recent years, notable attention has been focused on solid acid reagent in organic synthesis. Many of them are reusable easy to separation from liquid products, high stability, grater selectivity and less harm to environment (Keneva, et al., 2010). The efficiency of heterogeneous catalysis has been improved by employing nano-sized catalyst, because of their extremely small size, high surface area and non-toxicity (Xia, et al., 2003). Currently the study of multicomponent reactions by heterogeneous nano-sized catalysts has become an active part of ongoing research due to several (*) Corresponding Author - e-mail: kshams49@gmail.com
advantages associated with the heterogeneous catalysts over homogeneous counterpart such as high atom efficiency, simplified isolation, easy of recovery, recyclability, non-toxicity of catalysts and minimization of metal trace in products after isolation etc. (MartinezCastanon, et al., 2005). In the past decade, dihydropyrimidinones (DHPMS) have exhibited important pharmacolo -gical and biological properties (Aly, 2008, Pinna, et al., 2005, Reznik, et al., 2004, Sondhi, et al., 2005, Bruno, et al., 2001, Gangjcc, et al., 2001, Banjanac, et al., 2009, Mangalagiu, et al., 2001, Wamhoff, et al., 1992, Kappe, 1993,
Kh. Pourshamsian
Kappe, 2000). So the synthesis of DHPMS has been revalued. The classical synthesis of dihydropyrimidinone was the Biginelli reaction of aldehyde, ethylacetoacetate, and urea or thiourea under acidic conditions (Biginelli, 1893). The method, however, requires harsh conditions leading often to low yields despite long reaction times. In order to circumvent these drawbacks many improvements and modifications have been developed, including microwave promotion (Li and Bao, 2003, Jain, et al., 2011, Pasunooti, 2011), ultrasound irradiation (Yadav and Reddy, 2001, Li, et al., 2003), ionic liquids (Peng and Deng, 2001; Abbaspour-Oliaded, et al., 2014, Niralwad, et al., 2010, Azimi and Hariri, 2016, Zhang, et al., 2015), tetrabutylammonium bromide (TBAB) (Slimi, et al., 2013), Bi(NO3)3 (Slimi, et al., 2011) , Al-MCM-41 (Oskooei, et al., 2011), NH4Cl (Shaabani, et al., 2003), nafion-H (Lin, et al., 2007), Cu(ClO4)2.6H2O (Lei, et al., 2011), trichloro acetic acid (Yu, et al., 2011), Fe(OTs)3 (Starcevich, et al., 2013), Zn((L)-proline)2 (Siddiqui, 2013), MnO2MWCNT (Safari and Gandomi-Ravandi, 2013), nanomagnetic-supported sulfonic acid (Kolvari, et al., 2014), SiO2-CuCl2 (Kour, et al., 2014), Fe3O3 NP (Zamani and Izadi, 2014), boehmite nanoparticle (Keivanloo, et al., 2014), L-proline nitrate (Bahekar, et al., 2015), L-ascorbic acid (Kodape, et al., 2015), MoO2Cl2 (Guggilapu, et al., 2015). Chiral DHPMS via Biginelli condensation reaction have been realized (wang, et al., 2011, Isambert, et al., 2011, Alshammari, et al., 2013). A variety of substituents including N-substituted urea (Ryabukhin, et al., 2010) and Nacylpyruvates (Ryabukhin, et al., 2010) in the components have been investigated to produce differently substituted DHPMS for however most of these procedures have significant drawbacks such as high temperature, long reaction times, and low yields of products,
harsh reaction conditions and difficult workup.
EXPERIMENTAL All known compounds were identified by comparison of their melting points and 1HNMR data with those reported in the literature. All reagents were prepared from analytical grade chemicals and purchased from Merck Company. Melting points were determined by using an Electrothermal 9100s apparatus in an open capillary tube and are uncorrected. FT-IR spectra were recorded in FT-IR Shimadzu IR-470 spectrophotometer in KBr matrix in the range of 4000-400 cm-1. The 1 HNMR was run on a Bruker Avance DRX-400 MHz spectrometer, using TMS as the internal standard and CDCl3 as solvent.
RESULTS AND DISCUSSION In this research we report CdS-nanoparticles as efficient and reusable catalyst for synthesis of 3,4-dihydropyrimidin-2-(1H)-ones derivatives in mild, onepot and three component procedure in solvent-free conditions. In order to determine the most appropriate reaction conditions and evaluate the catalytic activity of CdS-nanoparticles, initially, a model reaction was carried out with the aim of 3,4-dihydropyrimidin2-(1H)-ones derivatives by the condensation of urea (1.5 mmol), ethyl acetoacetate (1 mmol) and benzaldehyde (1 mmol) using different amounts of CdS-NP's in solvent-free conditions (Scheme 1). In the absence of catalyst, the yield of reaction was trace (Table 1, entry 1), after addition of a catalytic amount of CdS-NP's the yield of reaction increased. In order to optimize the amount of catalyst, the model O
O ArCHO
+
1
O
O OEt 2
+
NH2
H2N 3
CdS-NPs Solvent-free / 100 oC
Ar
EtO Me
NH N H
O
4 a-j
Scheme1: Synthesis of 3,4-dihydropyrimidin-2-(1H)-ones derivatives in mild, one-pot and three component procedure in solvent-free conditions
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reaction was repeated under different amount of catalyst. The experimental results were shown 20 mol% catalyst in 100°C after 30 min, are ideal conditions for this reaction (Table 1, entry 6). The increase in the amount of catalyst did not improve the yield of reaction (Table 1, entry 7, 8). The model reaction carried out in different solvents. The results indicate that different solvents affected the efficiency of the reaction. The results summarized in Table 3. Thus, using 20 mol% of CdS-NP's in solvent-free conditions at 100 °C was selected as the optimized condition for the synthesis of 4a. To show the ability of catalyst, different aromatic aldehydes were reacted with urea and ethyl acetoacetates under optimized conditions. In all cases the 4a-j compounds were obtained in excellent yields. The results summarized in Table 2. The recyclability of catalyst was investigated. To investigate these properties, the reaction of urea, benzaldehyde and ethyl acetoacetate was selected as the model. After completion the reaction, the catalyst was collected, washed with acetone and after drying, we reused in the next similar procedure. The results showed that the catalyst can be reused up to six runs without any significant loss in its activity.
1596 (arom. C=C Str.); 1HNMR (400 MHz CDCl3) δ (ppm): 1.06 (3H, t, J = 7.1 Hz, CH3); 2.24 (3H, s, CH3); 3.95 (2H, dq, CH2); 5.27 (H, d, J = 1.93 Hz, CH); 6.55 (H, s, NH); 7.13-7.25 (5H, m, Ar-H); 8.67 (H, s, NH). 5-(Ethoxycarbonyl)-4-(4-nitrophenyl)-6-methyl-3,4dihydropyrimidin-2(1H)-one (4d). White powder; Yield: 92%; mp: 209-211°C; IR (νmax/ cm-1) (KBr): 3228, 3120 (NH Str.); 3010 (arom. CH Str.); 1731 (ester, C=O Str.); 1704 (amid, C=O Str.); 1643 (arom. C=C Str.); 1519, 1350 (NO2 Str.); 1 HNMR (400 MHz CDCl3) δ (ppm): 0.97 (3H, t, J = 6.7 Hz, CH3); 2.14 (3H, s, CH3); 3.86 (2H, dq, CH2); 5.24 (H, d, J = 1.9 Hz, CH); 7.11 (H, s, NH); 7.32 (2H, d, J = 8.0 Hz, Ar-H); 7.94 (2H, d, J = 7.9 Hz, Ar-H); 8.80 (H, s, NH). 5-(Ethoxycarbonyl)-4-(2-Chloro phenyl)-6-methyl-3, 4-dihydro pyrimidin-2(1H)-one (4f). White powder; Yield: 89%; mp: 219-220°C; IR (νmax/ cm-1) (KBr): 3352, 3228 (NH Str.); 3112 (arom. CH Str.); 1702 (ester, C=O Str.); 1650 (amid, C=O Str.); 1586 (arom. C=C Str.); 1HNMR (400 MHz CDCl3) δ (ppm): 0.94 (3H, t, J = 7.1 Hz, CH3); 2.29 (3H, s, CH3); 3.86 (2H, dq, CH2); 5.71 (H, d, J = 2.6 Hz, CH); 6.23 (H, s, NH); 7.06-7.23 (4H, m, Ar-H); 8.97 (H, s, NH).
General procedure for synthesis of 3,4-dihydropyrimidin-2(1H)-ones (4a-j) A mixture of different aromatic aldehydes (1 mmol), ethyl acetoacetate (1 mmol), urea (1.4 mmol) and CdS-NP's (0.2 mmol) as catalyst were poured into a test tube in solvent-free conditions were stirred for an appropriate time. The progress of reaction was monitored by TLC. After completion of the reaction, the hot EtOH was added to the mixture and the heterogeneous insoluble CdS-NP's catalyst was separated by filtration. The residue solution was evaporated in vacuum condition, the collected impure solids were recrystallized with ethanol: water (1:1) and the pure products were obtained. Selected spectral data for some products:
5-(Ethoxycarbonyl)-4-(4-dimethylamino-phenyl)6-methyl-3,4-dihydropyrimidin-2(1H)-one (4h). Yellow powder; Yield: 80%; mp: 253-254°C; IR (νmax/ cm-1) (KBr): 3249, 3115 (NH Str.); 3012 (arom. CH Str.); 1700 (ester, C=O Str.); 1647 (amid, C=O Str.); 1614 (arom. C=C Str.); 1HNMR (400 MHz CDCl3) δ (ppm): 1.08 (3H, t, J = 4.3 Hz, CH3); 2.22 (3H, s, CH3); 2.85 (6H, s, N(CH3)2); 3.95 (2H, dq, CH2); 5.18 (H, d, J = 1.9 Hz, CH); 6.21 (H, s, NH); 7.04 (2H, d, J = 7.0 Hz, Ar-H); 7.12 (2H, d, J = 6.8 Hz, Ar-H); 8.43 (H, s, NH).
5-(Ethoxycarbonyl)-6-methyl-4-phenyl-3,4-dihydropyrimidin-2(1H)-one (4a). White powder; Yield: 88%; mp: 205-207°C; IR (νmax/ cm-1) (KBr): 3244, 3116 (NH Str.); 3010 (arom. CH Str.); 1704 (ester, C=O Str.); 1647 (amid, C=O Str.);
5-(Ethoxycarbonyl)-4-(4-methylphenyl)-6-methyl-3,4-dihydropyrimidin-2(1H)-one (4i). White powder; Yield: 89%; mp: 212-214°C; IR (νmax/ cm-1) (KBr): 3244, 3116 (NH Str.); 3010 (arom. CH Str.); 1704 (ester, C=O Str.); 1650 (amid, C=O Str.); 227
CdS nanoparticles: An efficient, clean and reusable heterogeneous catalyst Table 1: Effect of CdS-NP's catalyst amount on the model reaction a Entry
Catalyst (mol%)
T (°C)
Time (min)
Yield (%)b
1
None
80
150
trace
2
10
80
100
30
3
15
90
80
55
4
20
90
60
68
5
20
90
35
72
6 7 8
20 20 25
100 110 100
30 40 50
88 87 86
9
30
100
50
85
Reaction condition: Benzaldehyde (1 mmol), ethylacetoacetate (1 mmol), urea (1.4 mmol) and CdS-NP's (different amount) under solvent-free conditions at different temperature; (b) Isolated yields (a)
Table 2: Synthesis of 3,4-dihydropyrimidin-2(1H)-ones-2(1H)-ones 4a-j a Product
Yield (%)b
Mp°C Reported [Ref]
Entry
Aromatic aldehyde
1
C6H5CHO
4a
88
205-207
207 (Wamhoff, et al., 1992)
2
4-ClC6H4CHO
4b
92
210-211
212 (Mangalagiu, et al., 2001)
3
4-MeOC6H4CHO
4c
84
205-206
202 (Mangalagiu, et al., 2001)
4
4-NO2C6H4CHO
4d
92
209-211
207 (Pinna, et al., 2005)
5
3- NO2C6H4CHO
4e
90
222-224
226-228 (Pinna, et al., 2005)
6
2- ClC6H4CHO
4f
89
219-220
222-223 (Reznik, et al., 2004)
7 8
3-MeOC6H4CHO 4-(CH3)2NC6H4CHO
4g 4h
84 80
200-201 253-254
203-204 (Reznik, et al., 2004) 256-258 (Reznik, et al., 2004)
9
4-MeC6H4CHO
4i
89
212-214
215-216 (Reznik, et al., 2004)
10
Salicylaldehyde
4j
85
205-207
201-203 (Reznik, et al., 2004)
Found c
Reaction condition: Aromatic aldehyde (1mmol), ethylacetoacetate (1 mmol), urea (1.4 mmol) and CdS-NP's (0.2 mmol) under solvent-free conditions at 100°C; (b) Isolated yields; (c) Uncorrected (a)
1461 (arom. C=C Str.); 1HNMR (400 MHz CDCl3) δ (ppm): 1.19 (3H, t, J = 7.1 Hz, CH3); 2.33 (3H, s, CH3); 2.36 (3H, s, CH3); 4.04 (2H, dq, CH2); 5.39 (H, d, J = 1.7 Hz, CH); 6.17 (H, s, NH); 7.13 (2H, J = 7.6 Hz, Ar-H); 7.22 (2H, d, J = 7.8 Hz, Ar-H); 8.11 (H, s, NH).
Table 3: The effect of solvent on model reaction at refluxing conditions a Entry
Solvent
T (min)
Yield b
1
CH2Cl2
180
trace
2
CHCl3
150
trace
3
CH3OH
100
76
4
CH3CH2OH
100
70
5
CH3CN
80
68
6
THF
100
70
7
Toluene
80
72
8
H 2O
120
35
50
88
8
Solvent-free
CONCLUSIONS In summary we have introduced CdS-NP's as a new highly efficient, reusable and green catalyst for the one-pot, three component synthesis of 3,4-dihydropyrimidin-2(1H)-ones under solvent-free conditions.
Reaction condition: Benzaldehyde (1mmol), ethylacetoacetate (1 mmol), urea (1.4 mmol) and CdS-NP's (0.2 mmol); (b) Isolated yields (a)
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The promising points for the presented methodology are the high efficiencies, generality, short reaction times, clean method, environmentally compatibility, easiness of isolation of product and excellent reusability of the catalyst. The present method gave the products good yields at reduced reaction time, which might be due to the increased reactivity of the reactions on high surface area of CdS-NP's.
Press. Banjanac, M.; Tatic, I.; Ivezic, Z.; Tomic, S.; Dumic, J.; (2009). Pyrimidopyrimidines: a novel class of dihydrofolate reductase inhibitors. Food Technol Biotechnol., 47(3): 236-45. Biginelli, P.; (1893). Aldehyde−urea derivatives of aceto- and oxaloacetic acids. Gazz. Chim. Ital., 23: 360–413. Bruno, O.; Brullo, C.; Ranise, A.; Schenone, S.; Bondavalli, F.; Barocelli, E. et al.; (2001). Synthesis and pharmacological evaluation of 2,5-cycloamino-5H-[1]benzopyrano[4,3-d] pyrimidines endowed with in vitro antiplatelet activity. Bioorg. Med. Chem. Lett., 11(11): 11397-400. Gangjcc, A.; Vidwans, A.; Elzcin, E.; Mc Cuire, J.J.; Quccncr, S.F.; Kisliuk, R.L.; (2001). Synthesis, antifolate, and antitumor activities of classical and nonclassical 2-amino-4-oxo-5substituted pyrrolo [2,3-d] pyrimidines. J. Med. Chem., 44(12): 19932003. Guggilapu, S.D.; Prajapti, S.K.; Nagarsenkar, A.; Lalita, G.; Naidu Vegi, G.M.; Babu, B.N.; (2015). MoO2Cl2 catalyzed efficient synthesis of functionalized 3,4-dihydropyrimidin-2(1H)-ones/thiones and polyhydroquino lines: recyclability, fluorescence and biological studies. New J. Chem., View Article Online. Isambert, N.; Duque, M.M.S.; Plaquevent, J.C.; Genisson, Y.; Rodriguez, J.; Constantieux, T.; (2011). Multicomponent reactions and ionic liquids: a perfect synergy for eco-compatible heterocyclic synthesis. Chem. Soc. Rev., 40: 1347–1357. Jain, K.S.; Chaudhari, S.K.; More, N.S.; More, K.D.; Wakedkar, S.A.; Kathiravan, M.K.; (2011). A facile synthesis of 2-amino-5-cyano-4,6-disubstituted pyrimidines under MWI. Int. J. Org. Chem., 1: 51-56. Kaneva, N.V.; Yordanov, G.G.; Dushikin, C. D.; (2010). Manufacluring of patterned CdS films with application for photo initiated decolorization of malachite green in aqueous solutions. Bull Master. Sci., 33: 111-117 Kappe, C.O.; (1993). 100 Years of Biginelli dihydropyrimidine synthesis. Tetrahedron, 49: 6937– 6963. Kappe, C.O.; (2000). Recent advances in the Biginelli
ACKNOWLEDGMENT We appreciate Islamic Azad University (Tonekabon Branch) research and technology council for the financial support of this work.
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AUTHOR (S) BIOSKETCHES Khalil Pourshamsian, Associate Professor, Department of Chemistry, Tonekabon branch, Islamic Azad University, Tonekabon, Iran, E-mail: kshams49@gmail.com
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Hydrolysis of semi mustard (S.M) by MnCo2O4 (MnO-Co2O3) nanocomposite as a binary oxide catalyst: kinetics reactions study M. Sadeghi1*; S. Yekta2; E. Babanezhad3 Young Researchers and Elite Club, Ahvaz Branch, Islamic Azad University, Ahvaz, Iran 2 Department of Chemistry, Faculty of Basic Sciences, Islamic Azad University, Qaemshahr Branch, Qaemshahr, Iran 3 Department of Applied Chemistry, Faculty of Pharmaceutical Chemistry, Pharmaceutical Sciences Branch, Islamic Azad University, Tehran, Iran 1
Received: 23 September 2015; Accepted: 25 November 2015
ABSTRACT: MnCo2O4 (MnO-Co2O3) nanocomposite as a binary oxide has been successfully prepared by precipitation method using cobalt nitrate and manganese nitrate as the precursors and then characterized by scanning electron microscopy-energy dispersive micro-analysis (SEM-EDX) and X-ray diffraction (XRD) techniques. In this work, we report the hydrolysis kinetics reactions of semi mustard (chloroethyl ethyl sulfide (CEES)/S.M), a mimic of bis (chloroethyl) sulfide (i.e. sulfur mustard) that were carried out on the surface of MnCo2O4 nanocomposite as a destructive sorbent catalyst and were performed using GC-FID and GC-MS instruments. The effect of different parameters including solvent type and reaction time on the reaction efficiency were investigated. GC-FID analysis results emphasized that the maximum hydrolysis of CEES was related to n-hexane nonpolar solvent after the elapse of the reaction (12 h) at room temperature (25±1°C) with a 95% yield. On the other hand, minimum hydrolysis was reported for methanol polar solvent under similar conditions. The rate constant and half-life (t1/2) have been calculated 6.91×10-6 s-1 and 6.98×10-5 s-1, and 105 s and 9.9×103 s for methanol and n-hexane solvents, respectively. Also, Data explore the role of the hydrolysis product, i.e. hydroxyl ethyl ethyl sulfide (HEES) in the reaction of CEES with MnCo2O4 nanocomposite and GC-MS analysis was applied to identify and quantify semi mustard destruction product. Keywords: Binary oxide; Chloroethyl ethyl sulfide (CEES); Hydrolysis; Hydroxyl ethyl ethyl sulfide (HEES); Kinetic; MnCo2O4 nanocomposite
1. INTRODUCTION With the arrival of the new century, the fading use of chemical warfare agents (CWAs) as threats to the worldwide community has emerged again which posed renewed concerns in the very recent years. While vexing reports from Middle East and Syria during the last year have shown the crisis of CWAs such as sul(*) Corresponding Author - e-mail: meysamsadeghi45@yahoo.com
fur mustard used by terrorist organizations as they are cheap and easy to manufacture, devastating effects manifested in case of military actions, large worldwide stock of ammunition and certainly on the specter of terrorist attack (Ahmed, et al., 2012, Wellert, et al., 2008) have added research interests for the catalytic decontamination of CWA upon identifying new highly
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sis (Sun, et al., 2009), solvo-thermal synthesis (Rumplecker, et al., 2007), hydrothermal method (Yang, et al., 2004), mechano-chemical method (Tao, et al., 2004) and chemical combustion synthesis (Rusu, et al., 2000). Nevertheless, nearly all of these methods need specific instrumentation and harsh conditions. Martinde-Vidales, et al., 1993, prepared Co3O4 nanoparticles and MnCo2O4 nanocomposite by sol-gel method. They reported that using this route, size, and morphology and crystal structure of the products could be easily controlled. In the present study, the characterization of MnCo2O4 (MnO-Co2O3) nanocomposite as a binary oxide (manganese-cobalt oxide) synthesized by precipitation method at 400°C is investigated. MnCo2O4 nanocomposite were then evaluated as solid catalyst for the hydrolysis of semi mustard or chloroethyl ethyl sulfide (CEES) on their surface MnCo2O4 nanocomposite at room temperature (RT(25±1°C)) in different solvents such as methanol and n-hexane and kinetics of reactions were studied using GC-FID.
reactive decontaminants. Over time, adsorption of the toxic agents and subsequently degradation and neutralization strategies have been emerged in the spotlight of researchers, necessarily for research in countering terrorism and military defense units. One of the most known CWA is sulfur mustard (bis(chloroethyl) sulfide) with the molecular formula of (ClCH2CH2)2S, commonly abbreviated as H for munition grade and D for distilled). Less toxic analogues (agent simulants) such as semi mustard (S.M) or chloroethyl ethyl sulfide (CEES) with physicochemical properties similar to those of the agent could be generally subjected for the research studies due to extreme toxicity of HD. One of the main challenges for the decontamination of HD and its analogues is their permanency which makes them extremely hazardous. When a person exposed with these compounds blistering of the skin and mucous membranes is very common. Hence, they are so-called vesicants or blistering agents (Munro, et al., 1999). A lot of attentions have been paid toward improving the reactivity of metal oxides as solid adsorptive catalysts to replace the traditional liquid decontamination of HD and its simulants (Joseph, et al., 1999, Ozgr, et al., 2004, Ohtomo and Tsukazaki 2005, Schmidt, et al., 2003, Wang, et al., 2009). The investigations have proved metal oxide nanostructures as potential adsorbents for the catalytic decontamination of HD and its simulants (Prasad 2010, Prasad 2009, Sadeghi, et al., 2013, Sadeghi and Husseini 2012, Sadeghi and Husseini 2013). Recent investigations have explored the promising decomposition applications of the nano-sized metal oxides such as AP-MgO, AP-CuO, AP-Fe2O3 and APAl2O3 (Mirzaei, et al., 2006, Luisetto, et al., 2008, Rios, et al., 2010, Shinde, et al., 2006, Ahmed, et al., 2008, Sun, et al., 2009). In recent years, cobalt oxide (Co3O4) and manganese-cobalt oxide (MnCo2O4) spinel nanocomposite (Rios, et al., 2010) has been extensively studied owing to their potential uses in many fields including solar energy cells as photoelectric energy conversion materials (Wagner, et al., 1999, Wagner, et al., 2000). A variety of methods has been reported for the preparation of Co3O4 and MnCo2O4 nanocomposite including chemical spray pyrolysis (Shinde, et al., 2006), chemical vapor deposition (CVD) (Ahmed, et al., 2008), micro-emulsion synthe-
EXPERIMENTAL DETAILS Materials and reagents Co(NO3)2.6H2O, Mn(NO3)2.4H2O, KOH, toluene, methanol and n-hexane were purchased from Merck (Merck, Darmstadt, Germany). Chloroethyl ethyl sulfide (CEES) was obtained commercially from SigmaAldrich Co. (USA). All the chemicals were used as received and were of chemical grade. Instrumentation The morphology and approximate size of the prepared catalysts were studied via SEM images using a scanning electron microscope coupled with energy dispersive X-ray spectrometer (SEM-EDX, HITACHI S-300N). The powder X-ray diffraction pattern (XRD, Philips PW 1800) study was carried out on an X-ray diffractometer using CuKα radiation (30 mA and 20 kV and λ= 1.54056 Å). The analyses were conducted at 2° min-1 in the range of 2θ= 10-80°. A Varian Star 3400CX series gas chromatograph equipped with flame ionization detector (FID) and an OV-101CWHP 80/100 silica capillary column (30 m×0.25 mm inner diameter (i.d.), 0.25 μm film thickness) was used 234
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to monitor the hydrolysis reactions of the semi mustard, CEES. The extracted products were analyzed by a HP-Agilent gas chromatograph-mass spectrometer equipped with a fused-silica capillary column (DB 1701, 30 m×0.25 mm inner diameter (i.d.), 0.25 μm film thickness). The GC conditions used were as follows: the column temperature was initially hold at 60°C for 6 min and programmed at 20°C min-1 to 200°C to reach the final temperature which was then held for 13 min. The injector, MS quad and source temperatures were fixed at 60°C, 200°C and 230°C, respectively. Helium (99.999% purity) was selected as the carrier gas with the flow rate of 1 mL.min-1.
Co(NO3)2.6H2O/Mn(NO3)2.4H2O, deionized water, KOH
Mix
Co3O4 and MnCo2O4
Select
MnCo2O4
Preparation of Co3O4 and MnCo2O4 Prior to the reaction, Co3O4 nanoparticles and MnCo2O4 nanocomposite were synthesized by precipitation method as previously reported (Martin-de-Vidales, et al., 1993). For this purpose, 2 g of Co(NO3)2.6H2O as the source of Co2+ ions was dissolved in 100 mL of deionized water. Then, 100 mL of 3.2 M KOH aqueous solution was added drop-wise to the precursor solution. Pink precipitate appeared immediately which was oxidized Co(OH)3 easily by air and low heat or by weak oxidizing agents. As a result, a dark brown precipitate was produced which was separated and washed with deionized water, then dried in an oven at 60°C for 30 min. Reactions of Co(OH)3 production are as follows (1-3): Co(NO3)2.6H2O+KOH→Co(OH)NO3+ KNO3
(1)
Co(OH)NO3 + KOH → Co(OH)2 + KNO3
(2)
4 Co(OH)2+O2 + 2H2O → 4 Co(OH)3
(3)
Hydrolysis of CEES Product
Hydroxyl ethyl ethyl sulfide (HEES)
Scheme 1: The diagram for the synthesis of MnCo2O4 nanocomposite and its hydrolysis product with semi mustard (CEES).
Hydrolysis procedure of the CEES by MnCo2O4 nanocomposite as binary oxide catalyst The CEES molecule was hydrolyzed on the surface of MnCo2O4 nanocomposite according to the following procedure: First, 15 μL of toluene as internal standard and 15 μL of a 5:1 (v/v) ratio of CEES/H2O were added to 15 mL of each solvent (methanol and n-hexane) representing the optimizing work solutions, in a 20 mL Erlenmeyer flask which was sealed to prevent the vaporization of the solvents. All samples were vortexes for 1 min to give blank samples. 0.3 g of MnCo2O4 nanocomposite powder was then added to above solutions. No efforts were made to control ambient light or humidity. To achieve a perfect adsorption and a complete reaction between MnCo2O4 nanocomposite and semi mustard, all samples were shaken at periodic intervals until 12 h on a wrist-action shaker to study kinetics hydrolysis. After agitation of solution samples, they left until the precipitation process fulfilled. Finally, 10 μL of upper solution of each samples brought out via a micro-syringe and injected to columns of GC-FID and GC-MS instruments for studying the kinetics of hydrolysis of CEES. In scheme 1,
For the preparation of cobaltic-cobaltous oxide (Co3O4), the dark brown cobaltic hydroxide was calcined at 400°C for 5 h. On the other hand, to synthesize the MnCo2O4 nanocomposite, 1 g of Mn(NO3)2.4H2O and 2 g of Co(NO3)2.6H2O were dissolved in 100 mL of deionized water. While stirring vigorously, KOH was added until a homogeneous mixture was observed which then was dried at 60°C for 30 min. Finally, the calcination of this powder was also carried out at 400°C for 5 h. 235
Hydrolysis of semi mustard (S.M) by MnCo2O4 (MnO-Co2O3) nanocomposite
Fig. 1: SEM images of: (a) Co3O4 nanoparticles and (b) MnCo2O4 nanocomposite.
the diagram for the synthesis of MnCo2O4 nanocomposite and its hydrolysis product with CEES is shown.
size was determined from full width at half maximum (FWHM) parameter with the most intense peak obtained in XRD patterns. The average particle size of Co3O4 nanoparticles and MnCo2O4 nanocomposite were calculated from line broadening of the peak at 2θ= 10-80° using Debye-Scherrer formula (4) (Radwan, et al., 2007):
RESULT AND DISCUSSION SEM analysis The SEM images of cobalt oxide (Co3O4) nanoparticles and manganese-cobalt oxide spinel (MnCo2O4) nanocomposite for the investigation of the morphology and structure at 400°C are shown in Figs. 1a and 1b, respectively. Analyzing the morphology aspect of nanocomposite indicates that the sample consists of quasi-cubic particles. The results have also emphasized that both two catalysts have nano-sized particles (less than 100 nm). EDX analysis The energy dispersive X-ray (EDX) microanalysis was performed to confirm the presence of cobalt, manganese and oxygen elements in the catalyst samples. As indicated in Figs. 2a and 2b, there was no unidentified peak observed in the EDX spectra (only C element has been revealed which was corresponded to adsorbed atmospheric CO2). This fact clearly confirms the prepared purity and composition of Co3O4 nanoparticles and MnCo2O4 nanocomposite.
(a)
X-ray diffraction (XRD) patterns In Fig. 3, the structures of the nano-structured samples have been assayed by X-ray diffraction patterns of each sample at 400°C as shown. The crystalline
(b) Fig. 2: EDX analysis of: (a) Co3O4 nanoparticles and (b) MnCo2O4 nanocomposite.
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d=
0.94λ β cos θ
and MnCo2O4 nanocomposite with (JCPDS 23-1237), respectively. The β of the XRD peaks may also contain contributions from lattice microstrain. The average microstrain (ε) of the Co3O4 nanoparticles and MnCo2O4 nanocomposite were calculated using the Stocks-Wlison equation (5) (Shakur 2011):
(4)
Where d is the crystalline size, λ is the wavelength of X-ray Cu Kα source (λ= 1.54056 Å), β is the full width at half maximum (FWHM) of the most predominant peak at 100% intensity and θ is Bragg diffraction angle at which the peak is recorded. There were no characteristic peaks corresponded to of impurity were found, confirming that high-purity products be obtained. In two of the XRD patterns, seven peaks were revealed at approximately 2θ= 23.11°, 28.45°, 37.36°, 45.55°, 55.52°, 58.68°, and 63.74°, which correspond to the Bragg's reflection plane (111), (220), (311), (400), (422), (511) and (440) for cobalt oxide and four peaks at 2θ = 16.36°, 33.38°, 43.19° and 76.73°, related to the Bragg's reflection plane (110), (310), (300) and (421) for manganese oxide (Mn-O) nanoparticles, respectively. Using this formula, the smaller average particle sizes were estimated to be 27.29 nm and 22.19 nm for Co3O4 nanoparticles with (JCPDS 74-2120)
ε = β / 4 tan θ
(5)
Using this equation, the average microstrain was calculated about 0.25 and 0.31, respectively. The sizes obtained from XRD measurement are consistent with the results from the SEM study. Kinetics reaction study and GC-FID analysis The hydrolysis Kinetics reaction of semi mustard (CEES) on the MnCo2O4 nanocomposite surface was evaluated at room temperature (RT, 25±1°C) and those progresses were studied by GC-FID analysis. Effects of influencing parameters including polarity of the media and the choice of solvent type and reaction time
(a)
(b)
Fig. 3: XRD patterns of: (a) Co3O4 nanoparticles and (b) MnCo2O4 nanocomposite.
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have been explored through utilizing methanol and nhexane as the polar and nonpolar solvents and a 2 to 12 h range as shaking time of the reaction, respectively. The GC-FID chromatograms, the area under curve (AUC) data results under above parameters have been summarized in Figs. 4-7. The parameters of a, b, c, d, e, f and g are related to time intervals of 0, 2, 4, 6, 8, 10 and 12 h, respectively (Figs. 4 and 5). It can be showed from the GC-FID chromatograms that CEES eluted at about 10.3 min. To calculate the amounts of hydrolysis reaction, the integrated AUC data of two samples, CEES and toluene as internal standard for all variables were measured and its ratio (integrated AUC of CEES/integrated AUC of toluene) was determined. The results are shown in Fig. 6. Results have illustrated that with decrease in polarity along with increasing the time, the intensity of the AUC data of CEES were declined respect to that of toluene and higher amounts of this molecule were hydrolyzed which are illustrated by new peak at retention times of 14.4 min referring to the product respectively. Eventually, the experiments clearly noted that the perfect hydrolysis occurred in n-hexane after 12 h. Generally base sites present on the surface of MnCo2O4 nanocomposite whether the surface is acidic. Not withstanding the transition state must be involved in the polar reaction, polar solvent hinders the reaction's progress. It could be construed from GC-FID analysis that polar solvent can cover the reactive sites presented on the surface of MnCo2O4 nanocomposite including Lewis sites. Although the presence of high polarity poisons the adsorption sites, directly adding slight amount of H2O into the surface of MnCo2O4 nanocomposite would activate the acid sites and accelerate the hydrolysis of CEES. Positive water effect was also observed for the hydrolysis of semi mustard in literature (Ahmed, et al., 2008). In particular, despite of a large number of strong Lewis acid sites originated from high surface area MnCo2O4 nanocomposite, the blocking of these adsorptive sites would hinder the coordination of CEES. Since methanol is considered as such a strong hindrance to the reaction, this tends to lend further support to the idea that methanol simply blocks access to the surface of the catalyst. Thus, further reactions were investigated in n-hexane solvent. Surveying the reaction between MnCo2O4 nanocomposite and CEES through GC
analysis showed that if one allows for enough time, high destructive catalysis would readily occur. Surveying the reaction between MnCo2O4 nanocomposite and CEES through GC-FID analysis showed that if one allows for enough time, maximum destructive catalysis would readily occur. In fact, 95% of CEES was hydrolyzed by this catalyst after 12 h. Diagrams illustrating the amount of hydrolyzed and -Ln(a-x)/a versus time in Fig. 7 point out to the fact that reaction times induce a kinetic effect in which the number and vicinity of reactive sites with CEES molecules making them adsorb and destruct, access to these sites and their catalytic capacity increase with time. In Fig. 7, the parameter (a) refers to the state when the amount of CEES is virgin unreacted with MnCo2O4 nanocomposite and the parameter (x) related to the beginning of CEES reaction with MnCo2O4 nanocomposite till the end of reaction in which the CEES is hydrolyzed and decontaminated about 95%. Fig.7 has been drawn according to the data which has obtained from Fig. 6. In Fig. 6, decontaminated CEES% was utilized for the calculation of –Ln (a-x)/a versus reaction time which has mentioned in Fig. 7. The linearity in Ln diagrams 7 elucidates that the kinetics of the reaction have a first order steady state behavior. The formula (6) in below is used for calculation of half-life (t1/2) of the hydrolysis reaction. In this formula, parameter (k) is defined as diagram slope of –Ln (a-x)/a versus 1/h which equals to rate constant. t1/2 = 0.693 / k (6)
The average rate constant and reaction half -life using slope of the diagram were measured as 6.91×10-6 s-1 and 6.98×10-5 s-1, and 105 s and 9.9×103 s for methanol and n-hexane solvents, respectively. GC-MS analysis To understand the hydrolysis product of semi mustard with MnCo2O4 nanocomposite gas chromatography coupled with mass spectrometry (GC-MS) analysis was used. The mass spectra of semi mustard (chloroethyl ethyl sulfide (CEES)) and hydroxyl ethyl ethyl sulfide (HEES) were shown in Fig. 8. The detector was set to scan a mass range of 28, 43, 61, 75, 91, 109 and 123 m/z and 28, 43, 61, 75, 91 and 106 m/z for CEES 238
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Fig. 6: The curves of decontamination% versus time for CEES/MnCo2O4 nanocomposite sample in different solvents.
tamination reactions through cobalt and manganese species (Co3+ and Mn2+) species have been reviewed. It is worth-noting that one of the proposed pathways is possible and may proceed simultaneously. In this pathway, adsorption reaction of semi mustard occur through nucleophillic attack of the Bronsted (isolated hydroxyl groups (Co-OH and Mn-OH)) acid sites presented on the MnCo2O4 of the external surface of the nanocomposite to C-Cl bond of CEES molecule (initially, cyclic sulfonium ion seems to be formed as an intermediate which is in the nonvolatile form of the related compound so that could not be extracted out and detected by GC-FID instrument). In conclusion, the chlorine atom of CEES will be removed through the dehalogenation reaction. In continuation, in the presence and absence of water molecule, different reactions may proceed and hydrolysis product on the surfaces of Co3+ and Mn2+ as Lewis acid sites will be illustrated. The hydrolysis reaction of CEES has a single destruction product, namely hy-
Fig. 4: GC-FID chromatograms for CEES/MnCo2O4 nanocomposite sample at different times, a) 0, b) 2, c) 4, d) 6, e) 8, f) 10 and g) 12 h, in methanol solvent
and HEES, respectively. This observation emphasizes role of hydrolysis reaction of CEES to HEES. Mechanism of the hydrolysis procedure According to the above results, a proposed mechanism of hydrolysis of this reaction will provide in Scheme 2. The mechanism scheme reflecting the reaction steps of the semi mustard adsorption on the MnCo2O4 nanocomposite along with the formation of hydrolysis product are proposed (Scheme 2) in which the decon-
Fig. 5: GC-FID chromatograms for CEES/MnCo2O4 nanocomposite sample at different times, a) 0, b) 2, c) 4, d) 6, e)
Fig. 7: The diagrams of â&#x20AC;&#x201C;Ln (a-x)/a versus time for CEES/
8, f) 10 and g) 12 h, in n-hexane solvent.
MnCo2O4 nanocomposite sample in different solvents.
239
Hydrolysis of semi mustard (S.M) by MnCo2O4 (MnO-Co2O3) nanocomÂposite
Fig. 8: GC-MS of CEES and hydrolysis product of MnCo2O4 nanocomposite reaction with CEES: a) chloroethyl ethyl sulfide and b) hydroxyl ethyl ethyl sulfide.
..
MnCo2O4
S
Cl
S
COCLUSIONS SULFONIUM ION
In summary, MnCo2O4 nanocomposite has been synthesized by the hydrothermal method. The synthesized samples were characterized via SEM-EDX and XRD techniques. The unique property of synthesized MnCo2O4 nanocomposite catalyst for the hydrolysis of CEES was investigated by consideration of different parameters namely solvent type and reaction time at room temperature. Based on the observations obtained by GC-FID analysis, the utilized adsorbent catalyst possesses such a high performance and potential for the hydrolysis of the mentioned CEES. The obtained results revealed that the above semi mustard was hydrolyzed on the surface of MnCo2O4 nanocomposite in n-hexane solvent after 12 h at room temperature with a 95% yield and followed via first order steady state behavior. On the other hand, GCMS analysis has provided valuable information about the single hydrolysis reaction product of semi mustard, namely hydroxyl ethyl ethyl sulfide (HEES).
Cl
H
H O
O
S+ Cl
O
H
H
O M M M M M M M O O O O O M M M M M M M M O O O O O OHO O OH M M M M M M M M M M O O O O O O M M M M M M M MO O O O O O O M M M M M M M M O O O O O
M
O M
O
M
O M O
O M M
O
-HCl
S
S
OH
+H2O
O O
H
H
O M M M M M M M O O O O O M M M M M M O O OHO O O OHO O M M M M M M M M M O O O O O O M M M M M M M M O O O O O O M M M M M M M O O O O O
M M
O M M
M
O
O M O
O M M
ACKNOWLEDGMENT
O
Scheme 2: Reaction mechanism pathway for the hydrolysis of CEES on the surface of the MCo2O4 nanocomposite cata-
The authors gratefully acknowledge the financial supports of Young Researchers and Elite Club, Ahvaz Branch, Islamic Azad University, Ahvaz, Iran
lyst (M=Mn or/and Co).
droxyl ethyl ethyl sulfide (HEES). Similar results for the hydrolysis and destruction product were also observed by other researchers in several studies (Prasad 2010; Sadeghi and Yekta 2014, Mahato, et al., 2010, Kanyi, et al., 2009).
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van, R.; (2012). N,N′-dichloro-bis[2,4,6trichlorophenyl]urea (CC2) and Suspending Agents Used for the Preparation of Decontamination Formulation Against Chemical Warfare Agents A study of Compatibility by Thermoanalytical Techniques. J. Therm. Anal. Calorim., 107 (1): 141-147. Ahmed, J.; Ahmad, T.; Ramanujachary, K.V.; Lofland, S.E.; Ganguli, A.K.; (2008). Development of a Microemulsion-Based Process for Synthesis of Cobalt (Co) and Cobalt Oxide (Co3O4) Nanoparticles from Submicrometer Rods of Cobalt Oxalate. J. Colloid. Interf. Sci., 321(2): 434–441. Joseph, M.; Tabata, H.; Kawai, T.; (1999). p-Type Electrical Conduction in ZnO Thin Films by Ga and N Codoping. J. Appl. Phys., 38 (2): 12051207. Kanyi, C.W.; Doetschman, D.C.; Schulte, J.T.; (2009). Nucleophilic Chemistry of X-type Faujasite Zeolites with 2-Chloroethyl Ethyl Sulfide (CEES), a Simulant of Common Mustard Gas. Micropor. Mesopor. Mater., 124 (1-3): 232–235. Luisetto, I.; Pepe, F.; Bemporad, E.; (2008). Preparation and Characterization of Nano Cobalt Oxide. J. Nanopart. Res., 10 (1): 59-67. Mahato, T.H.; Prasad, G.K.; Singh, B.; Batra, K.; Ganesan K.; (2010). Mesoporous Manganese Oxide Nanobelts for Decontamination of Sarin, Sulphur Mustard and Chloro Ethyl Ethyl Sulphide. Micropor. Mesopor. Mater., 132(1-2): 15-21. Martin-de-Vidales, J.L.; O Garcfa-Martinez.; Vila E.; Rojas R.M.; Torralvo M.J.; (1993). Low Temperature Preparation of Manganese Cobaltite Spinels [MnxCo3−xO4 (0≤x≤ 1)]. Mat. Res. Bull., 28 (11): 1135-1143. Mirzaei, A.A; Feyzi, M.; Habibpour, R.; (2006). Effect of Preparation Conditions on the Catalytic Performance of Cobalt Manganese Oxide Catalysts for Conversion of Synthesis Gas to Light Olefins. Appl. Catal. A., 306 (1): 98-107. Munro, N.B.; Talmage, S.S.; Griffin, G.D.; Waters, L.C; Watson, A.P.; King, J.F.; Hauschild, V.; (1999). The Sources, Fate, and Toxicity of Chemical Warfare Agent Degradation Products. Environ. Health. Perspec., 107(12): 933-974. Ohtomo, A.; Tsukazaki, A.; (2005). Pulsed Laser De-
position of Thin Films and Superlattices Based on ZnO Semicond. Sci. Technol., 20 (4): 1-12. Ozgr, U.; Alivov, Y.I.; Liu, C.; Teke, A.; Reshchikov, M.A.; Avrutin, V.; Cho, S.J.; Mork, H.; (2004). A Comprehensive Review of ZnO Materials and Devices. J. Appl. Phys., 98(4): 041301. Prasad, G.K.; (2010). Decontamination of 2 chloro ethyl phenyl sulphide using mixed metal oxide nanocrystals. J. sci. Ind. Res., 69 (11): 835-840. Prasad G.K.; (2009). Silver Ion Exchanged Titania Nanotubes for Decontamination of 2-Chloro Ethyl Phenyl Sulphide and Dimethyl Methyl Mhosphonate. J. Sci. Ind. Res., 68 (05): 379-384. Radwan, N.R.E.; El-Shallb, M.S.; Hassan, H.M.A.; (2007). Synthesis and Characterization of Nanoparticle Co3O4, CuO and NiO Catalysts Prepared by Physical and Chemical Methods to Minimize Air Pollution. Appl. Catal. A., 331 (1): 8–18. Rios, E.; Lara, P.; Serafini, D.; Restovic, A.; Gautier, J.; (2010). Synthesis and Characterization of Manganese- Cobalt Solid Solutions Prepared at Low Temperature. J. Chil. Chem. Soc., 55(2): 261-265. Rumplecker, A.; Kleitz, F.; Salabas, E.L.; Schüth, F.; (2007). Hard Templating Pathways for the Synthesis of Nanostructured Porous Co3O4. Chem. Mater., 19 (3): 485–496. Rusu, C.N.; Yates, J.T. Jr.; (2000). Adsorption and Decomposition of Dimethyl Methylphosphonate on TiO2. J. Phys. Chem. B, 104 (51): 12292–12298. Sadeghi, M.; Husseini, M.; Tafi, H.; (2013). Synthesis and Characterization of ZnCaO2 Nanocomposite Catalyst and the Evaluation of its Adsorption/Destruction Reactions with 2-CEES and DMMP. Int. J. Bio-Inorg. Hybd. Nanomat., 2(1): 281-293. Sadeghi, M.; Husseini, M.; (2012). Nucleophilic Chemistry of the Synthesized Magnesium Oxide (Magnesia) Nanoparticles via Microwave@solgel Process for Removal of Sulfurous Pollutant. Int. J. Bio-Inorg. Hybd. Nanomat., 1(3): 175-182. Sadeghi, M.; Husseini, M.; (2013). A Novel Method for the Synthesis of CaO Nanoparticle for the Decomposition of Sulfurous Pollutant. J. Appl. Chem. Res., 7 (4): 39-49. Sadeghi, M.; Yekta, S.; (2014). Significance of Chemical Decomposition of Chloroethyl Phenyl Sulfide (CEPS) using Zinc-Cadmium Oxide (ZnO-CdO) 241
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Nanocomposite. Int. J. Bio-Inorg. Hybd. Nanomat., 3 (4): 219-229. Schmidt, R.; Rheinlnder, B.; Schubert, M.; Spemann, D.; Butz, T.; Lenzner, J.; Kaidashev, M.E.; Lorenz, M.; Rahm, A.; Semmelhack, H.C.; Grundmann, M.; (2003). High Electron Mobility of Epitaxial ZnO Thin Films on c-plane Sapphire Grown by Multistep Pulsed-laser Deposition. Appl. Phys. Lett., 82 (22): 3901. Shakur, H.R.; (2011). A Detailed Study of Physical Properties of ZnS Quantum Dots Synthesized by Reverse Micelle Method. Physica E, 44 (3): 641– 646. Shinde, V.R.; Mahadik, S.B.; Gujar, T.P.; Lokhande, C.D.; (2006). Supercapacitive Cobalt Oxide (Co3O4) Thin Films by Spray Pyrolysis. Appl. Surf. Sci., 252 (20): 7487–7492. Sun, L.; Li, H.; Ren, L.; Hu, C.; (2009). Synthesis of Co3O4 Nanostructures Using a Solvothermal Approach. Solid state Sci., 11 (1): 108-112. Tao, L.; Shao-Guang, Y.; Li-Sheng, H.; Ben-Xi, G.; You-Wei, D.; (2004). Formation of Co3O4 Nanotubes and the Magnetic Behaviour at Low Tem-
perature. Chinese Phys. Lett., 21(5): 966-969. Wagner, G.W.; Bartam, P.W.; Koper, O.; Klabunde, K.J.; (1999). Reactions of VX, GD, and HD with Nanosize MgO. J. Phys. Chem. B., 103 (16): 3225–3228. Wagner, G.W.; Koper, O.B.; LucasE.; Decker, S.; Klabunde, K.J.; (2000). Reactions of VX, GD, and HD with Nanosize CaO: Autocatalytic Dehydrohalogenation of HD. J. Phys. Chem., 104 (21): 5118–5123. Wang, F.; Liu, B.; Zhang, Z.; Yuan, S.; (2009). Synthesis and Properties of Cd-doped ZnO Nanotubes. Physica E, 41 (5): 879-882. Wellert, S.; Imhof, H.; Dolle, M.; Altmann, H.J.; Richardt, A.; Hellweg, T.; (2008). Decontamination of Chemical Warfare Agents Using Perchloroethylene-Marlowet IHF-H2O-based Microemulsions: Wetting and Extraction Properties on Realistic Surfaces. Colloid. Polym. Sci., 286 (4): 417-426. Yang, H.; Hu, Y.; Zhang, X.; Qiu, G.; (2004). Echanochemical Synthesis of Cobalt Oxide Nanoparticles. Mate. Lett., 58 (3-4): 387–389.
AUTHOR (S) BIOSKETCHES Meysam Sadeghi, M.Sc., Young Researchers and Elite Club, Ahvaz Branch, Islamic Azad University, Ahvaz, Iran, E-mail: meysamsadeghi45@yahoo.com Sina Yekta, M.Sc., Department of Chemistry, Faculty of Basic Sciences, Islamic Azad University, Qaemshahr Branch, Qaemshahr, Iran Esmaeil Babanezhad, Ph.D., Department of Applied Chemistry, Faculty of Pharmaceutical Chemistry, Pharmaceutical Sciences Branch, Islamic Azad University, Tehran, Iran
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Simple synthesis of new nano-sized pore structure vanadium pantoxide (V2O5) M. Farahmandjou*; N. Abaeiyan Department of Physics, Varamin Pishva Branch, Islamis Azad University, Varamin, Iran
Received: 3 October 2015; Accepted: 5 December 2015
ABSTRACT: New forms of vanadium oxide Nanoporous were fabricated using a simple chemical synthesis method. Vanadium pentoxide (V2O5) Nanoporous were synthesized by sodium metavanadate as precursor and ethylene glycol as surfactant. The samples were characterized by high resolution transmission electron microscopy (HRTEM), field effect scanning electron microscopy (FESEM) and X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and UV-Vis spectrophotometer. Structures of the nanoparticles were characterized by XRD technique to identify α-vanadium and γ-vanadium. The smallest particle size of sponge-like as-prepared sample was around 20 nm in diameter and for annealed sample was around 25 nm as estimated by XRD technique and direct HRTEM observation. The surface morphological studies from SEM depicted increasing dimension of sponge-like shaped structure by increasing ratio of the EG surfactant from 25 nm to 30 nm. The sharp peaks in FTIR spectrum determined the purity of V2O5 nanoparticles. Keywords: Ethylene glycol (EG); Nano-porous; Surfactant; Synthesis; Vanadium pentoxide
INTRODUCTION Vanadium oxide a strongly correlated oxide with its first-order metal-insulator transition a little above room temperature, has been well-studied over the last fifty years. Divanadium pentoxide (V2O5), the most stable form in the V-O system, has been at the front position of applied research due to its unique physio-chemical properties. The layered crystal structure of vanadium oxide nanos-tructures are currently drawn attention for the application of super capacitors and chemical sensors (Reddy, et al., 2006, Liu, et al., 2005), electrical and optical properties, has led to wide potential applications including rechargeable lithium batteries (*) Corresponding Author - e-mail: farahamndjou@iauvaramin.ac.ir
(Lampe-Onnerud, et al., 1995) and optical data storage media (Balberb, et al., 1975, Cam, et al., 2006). Vanadium pentoxide exhibits a number of polymorphs, including α-V2O5 (orthorhombic) (Singh, et al., 2008), β-V2O5 (monoclinic or tetragonal) and γ-V2O5 (orthorhombic) (Su, et al., 2009). The α-V2O5 phase is the most stable phase and the other two phases can be converted from the α-V2O5 phase under high temperature and high pressure (Balog, et al., 2007). Vanadium oxide based catalysts are widely used in a variety of chemical reactions like reduction of NOx or partial oxidation of alkanes (Yang, et al., 2008). Synthesis of a wide range of nanostructures predominantly, high or-
M. Farahmandjou & N. Abaeiyan
der nanomaterials with well-defined geometries such as nanorods, nanobelts, nanotubes and nanowires have attracted fabulous interest due to their novel chemical and physical properties and their prospective applications in fabricating electronic, magnetic, optical, electrochemical devices (Mai, et al., 2008, Lions, et al., 2009). Vanadium in V2O3 is formally +3 with two 3d electrons per V atom. There is another phase transition in V2O3 at about 520K, above which the conductivity is again lower than in the metallic phase. VO has the sodium chloride crystal structure and vanadium is formally +2. Bulk vanadium monoxide has many intriguing properties that are closely related to the issue of stoichiometry (Mousavi, et al., 2013, Vijaykumar, et al., 2012, Dinh, et al., 2010). Comparing with the other microstructure, nano-porous structure may be the most controllable, and its structure could significantly improve the battery life and increase Li+ diffusion rate and optical data storage media. In this paper, novel vanadium oxide nanoparticles are fabricated by using sol-gel method. Structural, optical and surface morphological properties are discussed by XRD, HRTEM, FESEM and FTIR analyses.
5 min, 2 mL ethylene glycol (EG) was added to the solution as complex agent and synthesis temperature was increased to 85°C. The color of solution changed from bright color to yellow color by adding EG. The Ph was fixed to 2 by adding sulfuric acid (1mL) drop by drop to the solution and the color changed to the orange yellow color. After one hour, during the process, the color of solution changed to obscure color. The product were evaporated for 2 hours, cooled to room temperature and finally calcined at 600°C for 4 hours. All analyses were done for samples without any washing and more purification. The specification of the size, structure and surface morphological properties of the as-synthesis and annealed vanadium oxide nanoparticles were carried out. X-ray diffractometer (XRD) was used to identify the crystalline phase and to estimate the crystalline size. The XRD pattern were recorded with 2θ in the range of 4-85° with type XPert Pro MPD, Cu-Kα: λ = 1.54 Å. The morphology was characterized by field emission scanning electron microscopy (SEM) with type KYKY-EM3200, 25 kV and transmission electron microscopy (TEM) with type Zeiss EM-900, 80 kV. All the measurements were carried out at room temperature.
EXPERIMENTAL DETAIL
RESULTS AND DISCUSSION
Vanadium oxide nanoparticles were synthesized by a simple synthesis according to the following manner. Firstly, 0.3 g sodium metavanadate was completely dissolved in 50 mL pure water with stirring at room temperature. Ammonium chloride (0.5 g) was then added to the solution until dissolve completely. After
X-ray diffraction (XRD) at 40Kv was used to identify crystalline phases and to estimate the crystalline sizes. Fig. 2(a) shows the XRD pattern of vanadium oxide before annealing. Fig. 2(b) shows the X-ray diffraction patterns of the powder after heat treatment at 600°C for 4 hours. The XRD patterns showed this sample have sharp peaks 2θ angle at the peak position at 25.2°, 32°, 33.5°, 37.5°, 45° and 51° with (101), (400), (011) , (301), (411) and (002) diffraction planes, respectively are in accordance rhombohedral structure of the V2O5 phase. The mean size of the ordered α-V2O5 nanoparticles has been estimated from full width at half maximum (FWHM) and Debye-Sherrer formula according to equation the following: D=
Fig. 1: Schematic structure of V2O5.
0.89λ Bcos θ
(1)
where, 0.89 is the shape factor, λ is the X-ray wave244
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Fig. 2: XRD pattern of vanadium pentoxide (a) as-synthesixed and (b) at 600°C.
length, B is the line broadening at half the maximum intensity (FWHM) in radians, and θ is the Bragg angle. The mean size annealed V2O5 nanoparticles was around 20 nm from this Debye-Sherrer equation. SEM analysis was used for the morphological study of nanoparticles of V2O5 samples. These analyses show high porosity structure emerged in the samples surface by increasing annealing temperature. With increasing temperature the morphology of the particles changes to the sponge-like shaped. Fig. 3(a) shows the SEM image of the as-prepared V2O5 nanoparticles with formation of clusters. Fig. 3(b) shows the SEM image of the annealed sponge-like shaped nanoporus V2O5 at 600°C for 4 hours. The smallest dimension of V2O5 nanoporous formed was about 25 nm. The effect of EG surfactant on the size of nanoporus were investigated and the results showed that with increasing the ratio of the surfactant from 2 mL (Fig. 3b) to 4 mL (Fig. 3c) the dimension of nanoporus increase from
(a)
(b)
(c)
Fig. 3: SEM images of the V2O5 nanoporus (a) as-prepared sample (b) annealed at 600°C with 2 mL EG and (c) anFig. 4: TEM images of the as-prepared V2O5 nanoporus.
nealed at 600°C with 4 mL EG.
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Simple synthesis of new nano-sized pore structure vanadium pantoxide
Fig. 5: FTIR spectrum of V2O5 sample.
25 to 30 nm. TEM analysis was carried out to confirm the actual size of the particles, their growth pattern and the distribution of the crystallites. Fig. 4 shows the as-synthesized TEM image of as-synthesized V2O5 particles prepared by chemical route. The vanadium oxide nanoparticles were formed with size of about 20 nm for smallest one. According to Fig. 5, the infrared spectrum (FTIR) of the synthesized V2O5 nanoparticles was in the range of 400-4000 cm-1 wavenumber which identify the chemical bonds as well as functional groups in the compound. The large broad band at 3135 cm-1 and 3037 are ascribed to the O-H and C-H groups. The absorption picks around 1401 cm-1 is due to the bending vibration of C=C vibration. FTIR spectra of V2O5 nanoparticles exhibited three characteristic vibration modes: V=O vibrations at 967 cm-1, the V-O-V symmetric stretch around 531 cm-1 and the V-O-V asymmetric stretch at 730 cm-1. As clearly seen, the bands appearing, between 950 and 1020 cm-1 were assigned to a vanadly stretching modes (δ V-O). Bands between 700 and 900 cm-1 were ascribed to the bridging V-O-V stretching.
is clear that with increasing temperature the morphology of the particles changes to sponge-like shaped. The effect of EG surfactant on the size of nanoporus were studied and the results showed that with increasing the ratio of the surfactant from 2 mL to 4 mL the dimension of nanoporus increase from 25 to 30 nm. TEM image exhibits that the uniform as-synthesized V2O5 nanoporous prepared by chemical route with an average diameter about 20 nm. From the FTIR data, it is shown the presence of V-O and V-O-V stretching mode of V2O5.
ACKNOWLEDGMENT The authors are thankful for the financial support of Varamin Pishva Branch at Islamic Azad University for analysis and the discussions on the results.
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CONCLUSIONS Novel nano-porous vanadium pentoxide particles were successfully prepared using sodium metavanadate as precursor and ethylene glycol as surfactant. XRD spectrum shows rhombohedral (hexagonal) structure of α-V2O5 annealed at 1000°C. From SEM images, it 246
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AUTHOR (S) BIOSKETCHES Majid Farahmandjou, Associate Professor, Department of Physics, Varamin Pishva Branch, Islamis Azad University, Varamin, Iran, E-mail: farahamndjou@iauvaramin.ac.ir Nilofar Abaeiyan, M.Sc., Department of Physics, Varamin Pishva Branch, Islamis Azad University, Varamin, Iran
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Investigation of fullerene (C60) effects on chemical properties of Metoprolol: A DFT study R. Ahmadi*; S. Pourkarim Young Researchers and Elite Clube, Yadegar-e-Imam Khomeini (RAH) Shahre-rey Branch, Islamic Azad University, Tehran, Iran
Received: 11 October 2015; Accepted: 14 December 2015
ABSTRACT: In this research at the first Metoprolol drug and its fullerene derivative were optimized. Natural bond orbital (NBO), nuclear Indepndent chemical shift (NICS) and finally IR calculations, for these compounds were carried out at the B3LYP/6-31G* quantum chemistry level. Different parameters such as energy levels, the amount of chemical shift in different atoms, the amount of HOMO/LUMO, chemical potential (¾), chemical hardness (Ρ), Thermodynamic properties were determined. Metoprolol is the generic form of the brand-name drug Lopressor, prescribed to treat high blood pressure. In this study we used fullerenes, as nano drug carriers, and Fulleren drevatives of Metoprolol drug were studied. The data in Tables and graphs and shapes were compared and discussed. Keywords: Chemical potential; Density functional theory (DFT); Fullerenes; Metoprolol; Nano drug carriers.
INTRODUCTION Nanostructures can be categorized into following forms according to their structures: diamonds with sp3 hybridization, Graphite with sp2 hybridization, Hexagonal diamonds with sp3 hybridization, fullerenes with SP2 hybridization, Nanoparticles, Graphene, single-layer and multi-layer nanotubes, Crystal Nanostructures (Xing, et al., 2014). All these forms of nanostructures produce unique Pharmaceutical and electronic properties. Graphenes have a two-dimensional structure of a single layer of carbon like chicken wire (Rastegar, et al., 2013). Metoprolol is a beta-blocker that affects the heart and circulation (blood flow through arteries and veins). (*) Corresponding Author - e-mail: roya.ahmadi.chem@hotmail.com
Metoprolol is used to treat angina (chest pain) and hypertension (high blood pressure) (Veloutsou, et al., 2014). It is also used to treat or prevent heart attack. Metoprolol may also be used for other purposes not listed in this medication guide. Metoprolol is used alone or in combination with other medications to treat high blood pressure. It is also used to prevent angina (chest pain) and to improve survival after a heart attack (Fleet, et al., 2014). Extended-release (long-acting) metoprolol is also used in combination with other medications to treat heart failure. Metoprolol is in a class of medications called beta blockers. It works by relaxing blood vessels and slowing heart rate to improve blood flow and decrease blood pressure (Wong, et al., 2014). To-
R. Ahmadi & S. Pourkarim
lol (Beheshtian, et al., 2012).
COMPUTATIONAL DETAILES Fig. 1: (RS)-1-(Isopropyl amino)-3-[4-(2-methoxyethyl) phe-
All structure relating to structure of Metoprolol and nano Fullerene- Metoprolol were designed primarily with use of Gauss view 5.0.8. In order to do final optimization, Gaussian 98 program of package DFT method were used. However, for this purpose, 6-31G* basis set was used. Computations were done in gas phase (Beheshtian, et al., 2013). In this study, Metoprolol drug and its 3 fullerene derivatives investigated (Fig. 2).
noxy]propan-2-ol.
day considerable advances have been accomplished in applications of nano- particles specifically in medical sciences. Fullerene is one of the other artificial forms of carbon element. Long life cycle of medicines in the human body is a successful factor in delivery of medicine to the specific place. Lots of nano-particles are being developed in this field. In this study, the metoprolol linked on fullerene (C60), and then the drug and its fullerene derivatives were optimized (Ung, et al., 2013). Then NBO (Regiec, et al., 2014) and NICS calculations (Elhage, et al., 2013) for compounds were performed in B3LYP/6-31G*. Studies of NICS (σ iso) were performed for all conditions and changes in chemical shift (δ) of the desired compound were considered. The chemical potential (μ) and chemical hardness (η) of the compound were studied. This drug is classified as a drug therapy as an adjuvant in the treatment of hypertension and congestive heart failure (CHF). The aim of present study was to evaluate the effect of fullerene on chemical properties of Metopro-
RESULT AND DISCUSSION Table (1) values of energies of the frontier molecular orbitals (EHOMO and ELUMO, eV), Electronic chemical potential, μ (eV), Chemical hardness, h (eV), calculated at the B3LYP/6-31G* level of theory. The results showed that the calculated energy gap is typically much higher of the Metoprolol than Metoprolol attached to Fullerene in each three connection on the other hand the amount of that in each four Metoprolol binds to Fullerene to connection forms is different and mostly the same compared with the ac-
Fig. 2: View of Metoprolol alone and Metoprolol derivatives have been obtained from carbon connection of Metoprolol C28 to Fullerene and shown briefly FMT (1), C14 to Fullerene and shown briefly FMT (2) and C11 to Fullerene and shown briefly FMT (3)
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Int. J. Bio-Inorg. Hybr. Nanomater., 4(4): 249-254, Winter 2015 Table 1: Values of energies of the frontier molecular orbitals (EHOMO and ELUMO, eV), Electronic chemical potential, Îź (eV), Chemical hardness, h (eV). Indices
Temperature = 298.15 K, Pressure = 1 atm C60
MT
FMT(1)
FMT(2)
FMT(3)
EHOMO (eV)
-9.83
-6.46
-9.29
-9.34
-9.15
ELUMO (eV)
-2.57
7.4
-2.84
-2.45
-2.31
Dipole Moment (debye)
0.00
3.18
3.6
5.74
7.68
HLG=ELUMO-EHOMO (eV)
7.26
13.86
6.45
6.89
6.84
DNMAX=-m/h
0.0111
-0.0768
0.0129
0.0123
0.0128
w=-m2/2 h (Ev)
0.0030
0.9804
0.0027
0.0031
0.0033
m =1/2(ELUMO-EHOMO) (eV)
-0.0403
0.5319
-0.0412
-0.0424
-0.044
h =(ELUMO-EHOMO)/2 (eV)
3.63
6.93
3.225
3.445
3.42
is higher than the other combinations. So we expect that when FMT (3) arrived our body, it is more soluble than other four combinations in water that is a polar solvent dissolved and has more solubility (Fig. 4). Chemical hardness indicate amount of the electron transfer from HOMO to LUMO, as much as chemical hardness is more, electron transfer from HOMO to LUMO is harder and consequently system reactivity decrease. In comparison with chemical hardness among Metoprolol and three combination of Nano-drug, we resulted like energy gap that chemical hardness of MT is more than three other combination (Fig. 5). Negative chemical potential is a symbol of system stability. The calculated results showed that the chemical potential Nano-drugs 1,2,3 and that is the same and the lowest and then is a chemical potential, the calculated highest value of the chemical potential allocate to Nano-drug 2 the more chemical potential the more reaction molecular or in the other words that type is more reactive (Fig. 6).
Fig. 3: Results of the survey molecular orbital energy levels of the drug and three Fullerene derivative in B3LYP/6-31G*
curacy of thousands (Fig. 3). MT > FMT (2) > FMT (3) > FMT (1) Since most of the weight of human blood is composed of water and it is a polar solvent, so the amount and the process of the change in dipole moment in Nanodrugs and Metoprolol in free mode are also important. Minimum value of dipole moment in order is first related to MT. In total the dipole moment FMT (3) alone
Fig. 5: Result obtained from chemical hardness in MT, FMT Fig. 4: The amount of dipole moment in FM, FMT (1), FMT
(1), FMT (2), and FMT (3) is calculated in B3LYP/6-31G*
(2), and FMT (3) is calculated in B3LYP/6-31G* level
level
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Investigation of fullerene (C60) effects on chemical properties of Metoprolol
eters between Metoprolol alone and Nano-fullereneMetoprolol. The value obtained of Thermodynamics indicate that preparation of Nano - drug reaction is a reaction heat retention and is not spontaneously and we need to changing conditions and precise control (Table 3).
CONCLUSIONS
Fig. 6: The result of the chemical potential of Metoprolol and its Fullerene derivatives
Computational Quantum Mechanics at the theory level of B3LYP/6-31G* on the structure of Metoprolol drug and its fullerene derivative and the results of this computation can be classified as follows: - The investigation of all the parameters show that the attachment of Fluoxetine structure to Fullerene structure will influence the energy levels and dipole moment changes and these changes are able to be investigated in the electrical and chemical parameters of Fullerene Derivatives structure. - The results showed that energy gap of MT is the highest and FMT (1) is the lowest. It should be noted that Derivatives of Metoprolol drug was done separately and only when the structure of Metoprolol was attached to conductivity of FMT (1) is the highest and MT is the lowest. - Chemical potential of MT is more than FMT (2) and
Current ring creates a magnetic field perpendicular to the ring and the effect of H ring outside circle caused more chemical shift for H, consequently reduce the amount of covering factor. Survey results of the calculations show that among derivatives Fullerene Metoprolol the most negative value of NICS is related to FMT (1) so the Hydrogen of ring 1 in FMT (1) has more chemical shift then this Hydrogen are better than others that participate in electrophilic substitution reaction (Table 2). Survey of the Thermodynamics In this work Metoprolol was linked to the fullerene, Metoprolol drug and its 3 fullerene derivatives investigated. Then compare Enthalpy (∆H), Entropy (∆S), Gibbs free energy (∆G), (∆E) Internal energy param-
Table 2: Amount of NICS (ppm). NICS
0
0.5
1
1.5
2
Metoprolol
12.039
-8.5596
-11.885
-9.7672
-5.2085
FMT(1)
-9.6915
-11.922
-12.148
-8.6999
-5.3517
FMT(2)
-9.5456
-11.725
-11.965
-8.4618
-5.0464
FMT(3)
-9.2291
-11.387
-11.573
-8.1687
-4.9494
Table 3: Thermodynamics properties. Temperature = 298.15 K, pressure = 1 atm FMT(1)
FMT(2)
FMT(3)
DH° (kJ/mol)
166.2825
153.1895
151.034
DS° (J/mol.K)
-108.296
-111.559
-109.829
DG° (kJ/mol)
198.771
186.657
183.983
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Int. J. Bio-Inorg. Hybr. Nanomater., 4(4): 249-254, Winter 2015
the following is FMT (3) and FMT (1). - Chemical hardness of MT is the highest and the lowest value is related to FMT (1). - Dipole moment of FMT (3) is highest. - The investigation of all the parameters show that the attachment of Metoprolol structure to Fullerene structure will influence the Enthalpy (∆H), Entropy (∆S), Gibbs free energy (∆G) changes are able to be investigated in the electrical and chemical parameters of Fullerene Derivatives structure. -The calculation of the values in the Table 3 shows this trend, for Fullerene derivatives (∆H>0), (∆S<0) and (∆G>0). -Represents the energy, Enthalpy (∆H), and the results show the reaction is endothermic, the results show this trend: FMT (1) > FMT (2) > FMT (3). -Entropy (∆S) represent irregularity and the results show a decrease in the amount of irregularities, the results show this trend: FMT (3) > FMT (2) > FMT (1). -Gibbs free energy (∆G) is the amount of energy available to a process and when it is positive (∆G>0) is show non-spontaneous reaction, so the results show that, reactions are non-spontaneous, the results show this trend: FMT (1) > FMT (2) > FMT (3).
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ACKNOWLEDGMENT We are appreciating and thanking Islamic Azad University of Yeager-e-Imam Khomeini (Rah) Share Rey.
REFERENCES Xing, M., Wang, R. & YU, J. (2014). Application of fullerene C60 nano-oil for performance enhancement of domestic refrigerator compressors. Int. J. Refrig., 40: 398-403.
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AUTHOR (S) BIOSKETCHES Roya Ahmadi, Associate Professor, Young Researchers and Elite Clube, Yadegar-e-Imam Khomeini (RAH) Shahre-rey Branch, Islamic Azad University, Tehran, Iran, E-mail: roya.ahmadi.chem@hotmail. com Somayeh Pourkarim, M.Sc., Young Researchers and Elite Clube, Yadegar-e-Imam Khomeini (RAH) Shahre-rey Branch, Islamic Azad University, Tehran, Iran
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