Graphene
Vol.05 No.04(2016), Article ID:70999,11 pages
10.4236/graphene.2016.54013

Graphene Sheets with Modified Surface by Sodium Lauryl Sulfate Surfactant for Biomedical Applications

Zhypargul Abdullaeva1*, Zhazgul Kelgenbaeva1, Tsushida Masayuki1, Megumi Hirano2, Shoji Nagaoka3, Tomohiro Shirosaki3

1Department of Materials Science and Engineering, Kumamoto University, Kumamoto, Japan

2Applied Chemistry and Biochemistry Department, Kumamoto University, Kumamoto, Japan

3Materials Development Department, Kumamoto Industrial Research Institute, Kumamoto, Japan

Copyright © 2016 by authors and Scientific Research Publishing Inc.

This work is licensed under the Creative Commons Attribution International License (CC BY 4.0).

http://creativecommons.org/licenses/by/4.0/

Received: August 19, 2016; Accepted: September 26, 2016; Published: September 29, 2016

ABSTRACT

This work describes synthesis of graphene sheets with modified surface by sodium lauryl sulfate (SLS) surfactant using one-pot solvothermal reaction method. Effect of sodium lauryl sulfate surfactant amount on surface modification level of graphene sheets was investigated. Ether (-S-OR- at 762 cm−1 - 863 cm−1), thiocarbonyl (=C=S at 1050 cm−1 - 1176 cm−1) and sulfoxide (S-O, Vs and Vas at 1030 cm−1 - 1450 cm−1) functional groups released from sodium lauryl sulfate (SLS) surfactant during solvothermal reaction and attached on the surface of graphene sheets were detected by (attenuated total reflectance-fast Fourier infrared) ATR-FTIR spectroscopy. (Atomic force microscope) AFM observations revealed apparent surface of graphene sheets modified by surfactant molecules with an average multiple profile of graphene nanosheets ≈ 4.8 nm high. This synthesis way of surface modified graphene sheets can be considered as easy, one-step and cheap method for manufacturing of novel biosurface with graphene, as reinforcement for biopolymer coatings such as ultra-high molecular weight polypropylene (UHMWPE), metallic biomaterials (Ti and Ti alloys) and bioceramics as hydroxyapatite (HA).

Keywords:

Graphene, Synthesis, Surface Modification, Surfactant, Attenuated Total Reflection

1. Introduction

Graphene is one of allotropic modifications of carbon element with atomic number 6, located in the Periodic table of chemical elements, which was notable Nobel Prize in Physics by A. Geim and K. Novoselov [1] - [3] . Graphene’s structure is basically composed of monolayer carbon atoms hexagonal lattice, in which individual carbon atoms are connected by sp2 bonds, similar to those of nanotubes, fullerenes and carbon onions [4] [5] . Graphene is defining as two-dimensional (2D) material [6] [7] , due to its width and length characteristics. Recent progress has shown that the graphene-based materials can have a deep impact on electronic and optoelectronic devices, chemical sensors, nanocomposites and energy storage [8] . Fabrication of graphene was achieved by several methods: chemical reduction [9] , plasma let [10] , chemical vapor deposition [11] , and so on [12] .

Chemical modification of graphene dispersion by surfactants in the content of manufacturing and commercialization was reported [13] .

Sodium lauryl sulphate (SLS)-modified activated carbon from risk husk for waste lead (Pb) removal was synthesized by using of series of treatments, such as: carbonization, activation with H3PO4 and surface modification using sodium lauryl sulfate (SLS) [14] .

This work was aimed to synthesize graphene sheets with modified surface by sodium lauryl sulfate (SLS) surfactant, using the simple and one-pot solvothermal reaction method. Solvothermal method is based on a chemical reaction between initial substances, mainly, the solvent and dissolved substances in it. Solvothermal reaction is generated inside stainless steel autoclave, under temperature and pressure conditions, in definite duration of time. Surface functionalized graphene has a number of superior advantages for biomedical applications, in particular, manufacturing of attachments for polymer molecules, creating of novel biosurface with graphene, as reinforcement for biopolymer coatings such as ultra-high molecular weight polypropylene (UHMWPE), metallic biomaterials (Ti and Ti alloys) and bioceramics as hydroxyapatite (HA). For example, chemical functionalization of graphene enables this material to be processed by solvent assisted techniques, such as layer-by-layer assembly, spin-coating, and filtration [15] . Surface modification of graphene by SLS surfactant positively improves the attachment of polymer molecules for creating of novel biosurface with graphene [16] [17] . It is also known that surface modification of graphene reduces its toxicity in vitro and in vivo [18] . At the same time, synthesis and surface modification of graphene sheets by SLS surfactant using the one-step solvothermal method and characterizations of as-obtained graphene were described in this work.

2. Experimental Procedure

A schematics of solvothermal synthesis method is presented in the Figure 1. Stainless steel autoclave (capacity of 100 ml) fixed to the metal equipment body, and was connected with temperature controller. Initial substances (total volume 60 ml), composed of solvent (distilled water-ethanol mixture with 3:1 volume ratio), pure carbon powder 0.3 g (purity 99.9%, purchased from Kojundo Kagaku. Co.), sodium lauryl sulfate (SLS) surfactant (C12H25NaO4S, 5% solution, purchased from Kanto Chemical Co.) were placed inside the stainless steel autoclave and covered with lid. Solvothermal reaction temperature was set at 170˚C with further increase of inner-autoclave pressure to 1.4 MPa, and

Figure 1. Schematics of experimental setup: (a) Drawing of solvothermal synthesis equipment with labeled compartments: 1―vessel; 2―lid; 3―packing seal; 4―mount seal; 5―safety valve; 6―pressure gauge; 7―valve; 8―thermo well; 9―stirrer; 10―stirring blade; 11―stirrer cooling hose outlet; 12―wrench; 13―heater; 14―thermo sensor; 15―tempertaure controller; 16―rubber seal; 17―specimen pipe; 18―pressure safety branch compartment; (b) Figure of stainless steel autoclave containing initial reaction mixture; (c) Photograph of surface modified graphene sample obtained after solvothermal reaction.

reaction time lasted for 1 hour. Solvothermal synthesis experiment was conducted three times, with SLS surfactant amounts of: 1 ml, 3 ml and 5 ml, for determination of surfactant amount effect on the surface modification of graphene sheets. Graphene sheets with modified surface by SLS surfactant were characterized by high resolution transmission electron microscope (HRTEM) Technai F-20 S-Twin equipped with an Energy dispersive X-ray spectroscopy (EDX) detector for elemental analysis at 200 keV. The HRTEM samples were prepared by placing a drop of surface modified by SLS graphene sheets solution (in ethanol) on a holey carbon-coated copper grid. The excess solvent was evaporated and the specimen was dried in a vacuum overnight. X-ray photoelectron analysis was carried out on Thermo Scientific XPS spectrometer. Raman spectrum was collected on HORIBA Jobin Yvon HR800 spectrometer, with He-Ne laser at 516 nm. ATR-FTIR spectra were recorded using the JASCO FT/IR-6300 spectrometer. Atomic force microscopy analyses were conducted on 5500 AFM (N9410S) Keysight Technologies, Inc., with measurement mode: AAC (acoustic ac mode in air).

3. Results and Discussions

Multi layered graphene sheets formed after solvothermal reaction were detected by high resolution transmission electron microscope (HRTEM) and Raman spectroscopy analyses (Figure 2). HRTEM characterizations, which are proven to be an excellent tool for structure analysis [19] , gave us a lot of necessary information regarding the structure, shape location, morphology and sizes of observing materials. Solubilization of carbon powder in ethanol-water mixture at 170˚C during solvothermal reaction and further graphitization led to formation of graphene sheets. Sonication technique can be applied for synthesis of graphene and separation of graphene multi-layer sheets into single sheets [20] [21] , however, our focus was made on solvothermal synthesis and surface modification of graphene, rather than sonication and separation processes. Sonication technique can be applied for synthesis of graphene and separation of graphene multi-

Figure 2. (a) HRTEM photograph of multilayer graphene sheets synthesized by solvothermal reaction method; (b) Raman spectrum collected from graphene sheets synthesized by solvothermal method, by using He-Ne laser beam, inset corresponding to multilayer graphene, inset adapted from [28] by permission of Elsevier; (c) High resolution photograph of graphene at 1 nm scale, red square shows areas for revealed hexagonal honey-comb lattice structure of graphene, inset is enlarged area shown in red square in (c), corresponding to the inter-atomic distance of 0.142 nm between C-C covalent bonds; (d) FFT image taken parallel with HRTEM observation; (e) Peak profile showing inter-atomic distance between C-C bonds equal to 0.142 nm.

layer sheets into single sheets [22] [23] , however, our focus was made on solvothermal synthesis and surface modification of graphene, rather than sonication and separation processes. Similar to previously reported works [22] - [24] , solvothermally synthesized graphene exhibited analogical structures and dimensions. Inter-atomic distance between C-C bonds in solvothermally synthesized graphene are coincident with mechanically exfoliated graphene, were equal to 0.142 nm [25] [26] . Comparing to other works, solvothermally synthesized graphene was stable against oxidation, whereas surface modified graphene by various surfactants [27] [28] were undergo reduction and oxidation as well.

Raman spectroscopy was used to study the number of layers and structure of surface modified graphene sample synthesized by solvothermal method. Peaks for D band at 1327.29 cm−1, G band at 1572.5 cm−1 and second ordered 2D band at 2663.54 cm−1 are detected during Raman spectroscopy analysis. It can be seen that shape and intensity of Raman peaks can be different depending on laser and wavelength type used during analysis [29] . Also, D band in the Raman spectrum can be composed of more than one peak, such as D1 and D2, which is associated with scattering of electrons by mechanism of double resonance process [30] . Solvothermally synthesized graphene composed of multilayer, which can be explained by the intensity and shape of 2D band peak [31] [32] . The intensity of the G band increases with increased graphene layers, and the shape of 2D band evolves into four peaks of bilayer graphene [33] . The 2D peak in graphene is due to two phonons with opposite momentum in the highest optical branch near the K (symmetry at K) [34] .

Figure 3 shows XPS spectrum collected from surface modified graphene sheets by solvothermal method, inset is C-C line C1s peak detected at 284.7 eV binding energy. Oxidation of graphene was not occurred during solvothermal reaction, which can be seen from the general survey, as there is only carbon atom C1s was appeared, and no oxygen atom peak was detected. Further qualification of obtained data is referred to [35] [36] .

ATR-FTIR spectroscopy was applied to determine SLS (C12H25NaO4S) surfactant molecules attached on the surface of graphene sheets. Figure 4 shows ATR-FTIR spec-

Figure 3. XRS spectra collected from surface modified by SLS surfactant graphene sheets: (a) Scan plot showing single peak for carbon C1s atom at 284.7 eV binding energy; (b) General survey showing peak for C1s carbon atom, and no peak for oxygen.

Figure 4. ATR-FTIR spectra of surface modified by SLS surfactant graphene sheets synthesized by solvothermal reaction method. Detected functional groups were released from SLS (C12H25NaO4S) surfactant during solvothermal reaction synthesis.

tra for pure carbon powder, surface modified graphene sheets by 1 ml SLS, and surface modified graphene sheets by 5 ml SLS, respectively. Adding of 5 ml SLS surfactant to the reaction mixture, provided higher intensity and much more number of peaks belonging to the ether (-S-OR) at 700 - 900 cm−1, thiocarbonyl (=C=S) at 1050 - 1200 cm−1 and sulfone (=S=O) at 1030 - 1450 cm−1 functional groups, respectively, in contrast to 1 ml of SLS surfactant amount.

Also, symmetric C-H stretches (CH3) at 2875 cm−1, asymmetric C-H stretches (CH2) at 2919 cm−1 and asymmetric C-H stretches (CH3) at 2956 cm−1 were detected. Attachment of above functional groups followed by release of them from SLS (C12H25NaO4S) surfactant during solvothermal reaction.

In comparison with other reported methods for surface modification of graphene, solvothermal reaction method have several advantages, such as: use of low temperature energy (1˚C - 300˚C), short reaction time (1 hour is quite enough), one-step process (synthesis of graphene and its surface modification can be achieved at the same time).

Atomic Force Microscopy is measurement technique, which can provide information not only about physical dimensions, but also let to detect surface features on nanomaterials. Figure 5 presenting AFM images of surface modified by SLS surfactant graphene sheets synthesized by solvothermal synthesis. Figure 5(a) shows solvothermally synthesized graphene sample which was dissolved in ethanol, dropped onto mica substrate and dried prior to observation. As it was discussed earlier [37] , SLS surfactant molecules attached onto graphene surface by using of low energy solvothermal reaction method, were observed as protuberant areas on the surface of graphene flakes shown in the Figure 5(a) inside red square, with height profile indication of 4.8 nm. Figure 5(c) shows surface modified graphene sheets by SLS surfactant, when sample was subjected onto HOPG substrate for AFM observation. Line profile in panel (d) represents the average obtained within the yellow line in panel (c), and the virtual nanosheets ≈ 27 nm

Figure 5. AFM images of surface modified by SLS surfactant graphene sheets synthesized by solvothermal method: (a) AFM image taken by using the mica substrate, inset is enlarged area shown in small red square, arrows indicating surfactant molecules attached to the graphene surface; (b) Height profile projected within the yellow line and showing graphene sheets height equal to 4.8 nm; (c) AFM image of SLS surfactant modified graphene sheets taken using the HOPG as substrate; (d) Line profile obtained within the yellow line in panel (c), and shows graphene nanosheets height attached with surfactant, equal to 27 nm.

high (relative to HOPG substrate).

Table 1 presenting Antibacterial activity of surface modified by SLS surfactant graphene sheets, studied using 3 M Petrifilms for E. coli bacterial colonies. It was observed, that antibacterial activity was higher for graphene sheets utilized 5 ml of SLS for surface modification, comparing to samples utilized 3 ml and 1 ml of SLS surfactant. Following results were obtained after average E. coli bacteria colonies calculation: for case 136.6 μg/ml of surface modified by SLS graphene nanosheets, 660 counts for 1 ml of SLS utilization, 570 counts for 3 ml of SLS utilization, and 376 counts for 5 ml of SLS surfactant utilized for surface modification. Antibacterial activity can be initiated by inhibition of metabolic processes [38] in E. coli bacterium colonies.

Summary of graphene family materials discussed [39] , indicating slight and nearly no toxic effects of graphene, reduced graphene and oxidized graphene against E. coli bacterium colonies.

These obtained results are certainly supporting the biomedical applications of surface

Table 1. Antibacterial activity of surface modified by SLS surfactant graphene sheets synthesized by solvothermal reaction method.

modified by SLS surfactant graphene nanosheets. Graphene elicit toxic effects both in vitro and in vivo, whereas surface modifications can significantly reduce its toxic interactions with living systems [17] , which allows biomedical applications of surface modified by SLS graphene sheets, in particular as inner linings and as reinforcement for biopolymer coatings such as ultra-high molecular weight polypropylene (UHMWP), Ti and Ti alloys and hydroxyapatite (HA).

4. Conclusion

Synthesis of surface modified graphene sheets by SLS surfactant during solvothermal reaction was highlighted in this work. Atomic state and elemental composition of surface modified graphene were consisted of C-C bonds with inter atomic distance 0.124 nm, and associated with C1s XPS peak, excluding oxidation of synthesized graphene. Multilayer graphene sheets consisting of hexagonal honey-comb lattice were revealed by HRTEM, and structure was determined by Raman spectroscopy. Influence of SLS surfactant amount on surface modification and attached functional groups were determined by attenuated total reflection FTIR spectroscopy. Higher amount of surfactant resulted in much more surface modification areas with higher intensity peaks and quantities of functional groups. Antibacterial activity of surface modified by SLS surfactant graphene sheets is found to be higher in case of increased amount SLS surfactant used during surface modification. Obtained results are highlighting biomedical applications of surface modified by SLS graphene sheets, as biocompatible coating platform between polymer, metallic, ceramic type implants and the living tissue.

Acknowledgements

This work was funded by start-up research acceleration fund (Funding number: 535- 11535016) of the Kumamoto University.

Cite this paper

Abdullaeva, Z., Kelgenbaeva, Z., Masayuki, T., Hirano, M., Nagaoka, S. and Shirosaki, T. (2016) Graphene Sheets with Modified Surface by Sodium Lauryl Sulfate Surfactant for Biomedical Applications. Graphene, 5, 155-165. http://dx.doi.org/10.4236/graphene.2016.54013

References

  1. 1. Novoselov, K.S., Geim, A.K., Morozov, V., Jiang, D., Zhang, Y., Dubonos, S.V., Grigorieva, V. and Firsov, A.A. (2004) Electric Field Effect in Atomically Thin Carbon Films. Science, 306, 666-669. http://dx.doi.org/10.1126/science.1102896

  2. 2. Geim, A.K. and Kim, P. (2008) Carbon Wonderland. Scientific American, 298, 90-97. http://dx.doi.org/10.1038/scientificamerican0408-90

  3. 3. Geim, A.K. and Novoselov, K.S. (2007) The Rise of Graphene. Nature Materials, 6, 183-191. http://dx.doi.org/10.1038/nmat1849

  4. 4. Saito, R., Fujita, M., Dresselhaus, G. and Dresselhaus, M.S. (1992) Electronic Structure of Graphene Tubules Based on C60. Physical Review B, 46, 1804-1811. http://dx.doi.org/10.1103/PhysRevB.46.1804

  5. 5. Gogotsi, Y. (2015) Not Just Graphene: The Wonderful World of Carbon and Related Nanomaterials. MRS Bulletin, 40, 1110-1120. http://dx.doi.org/10.1557/mrs.2015.272

  6. 6. Katsnelson, M.I. (2007) Graphene: Carbon in Two Dimensions. Materials Today, 10, 20-27. http://dx.doi.org/10.1016/S1369-7021(06)71788-6

  7. 7. Katsnelson, M.I. and Novoselov, K.S. (2007) Graphene: New Bridge between Condensed Matter Physics and Quantum Electrodynamics. Solid State Communications, 143, 1-2, 3-13. http://dx.doi.org/10.1016/j.ssc.2007.02.043

  8. 8. Singh, V., Joung, D., Zhai, L., Das, S., Khondaker, S.I. and Seal, S. (2011) Graphene Based Materials: Past, Present and Future. Progress in Materials Science, 56, 1178-1271. http://dx.doi.org/10.1016/j.pmatsci.2011.03.003

  9. 9. Stankovich, S., Dikin, D.A., Piner, R.D., Kohlhaas, K.A., Kleinhammes, A., Jia, Y., et al. (2007) Synthesis of Graphene-Based Nanosheets via Chemical Reduction of Exfoliated Graphite Oxide. Carbon, 45, 1558-1565. http://dx.doi.org/10.1016/j.carbon.2007.02.034

  10. 10. Lee, M.W., Kim, H.Y., Yoon, H., Kim, H. and Suh, J.S. (2016) Fabrication of dispersible Graphene Flakes Using Thermal Plasma Jet and Their Thin Films for Solar Cells. Carbon, 106, 48e55. http://dx.doi.org/10.1016/j.carbon.2016.05.018

  11. 11. Avouris, P. and Dimitrakopoulos, C. (2012) Graphene: Synthesis and Applications. Materials Today, 15, 86-97. http://dx.doi.org/10.1016/S1369-7021(12)70044-5

  12. 12. Zhang, M., Bao, W.X., Liu, X.L., Yu, B.Z., Ren, Z.Y. and Bai, J.T. (2015) Large-Scale Synthesis of Porous Graphene through Nanoscale Carbothermal Reduction Etching. Journal of Materials Science, 50, 7875-7883. http://dx.doi.org/10.1007/s10853-015-9309-1

  13. 13. Johnson, D.W., Dobson, B.P. and Coleman, K.S. (2015) A Manufacturing Perspective on Graphene Dispersion. Current Opinion in Colloid & Interface Science, 20, 5-6, 367-382. http://dx.doi.org/10.1016/j.cocis.2015.11.004

  14. 14. Al-Latief, D.N., Arnelli, Y. and Astuti, Y. (2015) Synthesis of Sodium Lauryl Sulphate (SLS)-Modified Activated Carbon from Risk Husk for Waste Lead (Pb) Removal. AIP Conference Proceedings, 1699, Article ID: 060017. http://dx.doi.org/10.1063/1.4938371

  15. 15. Kuila, T., Bose, S., Mishra, A.K., Khanra, P., Kim, N.H. and Lee, J.H. (2012) Chemical Functionalization of Graphene and Its Applications. Progress in Materials Science, 57, 1061-1105. http://dx.doi.org/10.1016/j.pmatsci.2012.03.002

  16. 16. Zhou, K., Motamed, T., Thouas, G.A., Bernard, S.S., Li, D., Parkington, H.S., et al. (2016) Graphene Functionalized Scaffolds Reduce the Inflammatory and Supports Endogenous Neuroblast Migration When Implanted in the Adult Brain. PLoS ONE, 11, e0151589. http://dx.doi.org/10.1371/journal.pone.0151589

  17. 17. Guo, X. and Mei, N. (2014) Assessment of the Toxic Potential of Graphene Family Nanomaterials. Journal of Food and Drug Analysis, 22, 105-115. http://dx.doi.org/10.1016/j.jfda.2014.01.009

  18. 18. Shi, S., Chen, F., Ehlerding, E.B. and Cai, W. (2014) Surface Engineering of Graphene- Based Nanomaterials for Biomedical Applications. Bioconjugate Chemistry, 25, 1609-1619. http://dx.doi.org/10.1021/bc500332c

  19. 19. Plachinda, P., Rouvimov, S. and Solanki, R. (2011) Structure Analysis of CVD Graphene Films Based on HRTEM Contrast Simulations. 2011 11th IEEE Conference on Nanotechnology (IEEE-NANO), Portland, 15-18 August 2011, 764-769. http://dx.doi.org/10.1109/NANO.2011.6144403

  20. 20. Ciesielski, A. and Samorì, P. (2014) Graphene via Sonication Assisted Liquid-Phase Exfoliation. Chemical Society Reviews, 43, 381-398. http://dx.doi.org/10.1039/C3CS60217F

  21. 21. Sharma, V., Garg, A. and Sood, S.C. (2015) Graphene Synthesis via Exfoliation of Graphite by Ultrasonication. International Journal of Engineering Trends and Technology (IJETT), 26, 38-42. http://dx.doi.org/10.14445/22315381/IJETT-V26P208

  22. 22. Englert, J.M., Dotzer, C., Yang, G., Schmidt, M., Papp, C., Michael, J., et al. (2011) Covalentbulk Functionalization of Graphene. Nature Chemistry, 3, 279-286. http://dx.doi.org/10.1038/nchem.1010

  23. 23. Wang, G., Yang, J., Park, J., Gou, X., Wang, B., Liu, H. and Yao, J. (2008) Facile Synthesis and Characterization of Graphene Nanosheets. Physical Chemistry C, 112, 8192-8195. http://dx.doi.org/10.1021/jp710931h

  24. 24. Dong, P., Yang, Y., Guo, L., Liu, B., Xin, S., Zhang, J., et al. (2012) A Facile One-Step Solvothermal Synthesis of Graphene/Rod-Shaped TiO2 Nanocomposite and Its Improved Photocatalytic Activity. Nanoscale, 4, 4641-4649. http://dx.doi.org/10.1039/c2nr31231j

  25. 25. Park, S.Y., Joon, S.Y.J., Floresca, H.C. and Kim, M.J. (2009) HRTEM Observation of Mechanically Exfoliated Graphene from Natural Graphite and HOPG. ECS Transactions, 19, 81-85. http://dx.doi.org/10.1149/1.3119530

  26. 26. Heyrovska, R. (2016) The Coulombic Nature of the van der Waals Bond Connecting Conducting Graphene Layers in Graphite. Graphene, 5, 35-38. http://dx.doi.org/10.4236/graphene.2016.52004

  27. 27. Uddin, M.E., Kuila, T., Nayak, G.C., Kim, N.M., Ku, B.C. and Lee, J.H. (2013) Effects of Various Surfactants on the Dispersion Stability and Electrical Conductivity of Surface Modified Graphene. Journal of Alloys and Compounds, 562, 134-142. http://dx.doi.org/10.1016/j.jallcom.2013.01.127

  28. 28. Kuilla, T., Bhadrab, S., Yao, D., Kim, N.H., Bosed, S. and Lee, J.H. (2010) Recent Advances in Graphene Based Polymer Composites. Progress in Polymer Science, 35, 1350-1375. http://dx.doi.org/10.1016/j.progpolymsci.2010.07.005

  29. 29. Ferrari, A.C., Meyer, J.C., Scardaci, V., Casiraghi, C., Lazzeri, M. and Mauri, F. (2006) Raman Spectrum of Graphene and Graphene Layers. Physical Review Letters, 97, Article ID: 187401. http://dx.doi.org/10.1103/physrevlett.97.187401

  30. 30. Cancado, L.G., Pimenta, M.A., Saito, R., Jorio, A., Ladeira, L.O. and Grueneis, A. (2002) Stokes and Anti-Stokes Double Resonance Raman Scattering in Two-Dimensional Graphite. Physical Review B, 66, Article ID: 035415. http://dx.doi.org/10.1103/physrevb.66.035415

  31. 31. Lloyd-Hughes, J. and Jeon, T.I. (2012) A Review of the Terahertz Conductivity of Bulk and Nano-Materials. Journal of Infrared, Millimeter, and Terahertz Waves, 33, 871-925. http://dx.doi.org/10.1007/s10762-012-9905-y

  32. 32. Beams, R., Cancado, L.G. and Novotny, L. (2015) Raman Characterization of Defects and Do Pants in Graphene. Journal of Physics: Condensed Matter, 27, Article ID: 083002. http://dx.doi.org/10.1088/0953-8984/27/8/083002

  33. 33. Tang, B., Guoxin, H. and Gao, H. (2010) Raman Spectroscopic Characterization of Graphene. Applied Spectroscopy Reviews, 45, 369-407. http://dx.doi.org/10.1080/05704928.2010.483886

  34. 34. Ferrari, A.C. and Robertson, J. (2000) Interpretation of Raman Spectra of Disordered and Amor Phous Carbon. Physical Review B, 61, 14095. http://dx.doi.org/10.1103/PhysRevB.61.14095

  35. 35. Knieke, C., Berger, A., Voigt, M., Taylor, R.N.K., Ro, J. and Peukert, W. (2010) Scalable Production of Graphene Sheets by Mechanical Delamination. Carbon, 48, 3196-3204. http://dx.doi.org/10.1016/j.carbon.2010.05.003

  36. 36. Jun, S.C. (2015) Fundamental of Graphene. In: Rashid bin Mohd Yusoff, A., Ed., Graphene-Based Energy Devices, Wiley, Hoboken, 1-48. http://dx.doi.org/10.1002/9783527690312.ch1

  37. 37. Walch, N.J., Nabok, A., Davis, F. and Higson, S.P.J, (2016) Characterisation of Thin Films of Graphene-Surfactant Composites Produced through a Novel Semi-Automated Method. Beilstein Journal of Nanotechnology, 7, 209-219. http://dx.doi.org/10.3762/bjnano.7.19

  38. 38. Zou, X., Zhang, L., Wang, Z. and Luo, Y. (2016) Mechanisms of the Antimicrobial Activities of Graphene Materials. Journal of the American Chemical Society, 138, 2064-2077. http://dx.doi.org/10.1021/jacs.5b11411

  39. 39. Jastrz?bska, A.M., Kurtycz, P. and Olszyna, A.R. (2012) Recent Advances in Graphene Family Materials Toxicity Investigations. Journal of Nanoparticle Research, 14, 1320. http://dx.doi.org/10.1007/s11051-012-1320-8