Indonesian Journal of Chemical Research http://ojs3.unpatti.ac.id/index.php/ijcr Indo. J. Chem. Res., 8(3), 242-246, 2021 DOI: 10.30598//ijcr.2021.7-mif 242 Mesoporous Silica MCM-48 as Chloramphenicol Adsorbent Paulina Taba * , Miftahul Jannah, Yusafir Hala Chemistry Department, Mathematics and Natural Sciences, Hasanuddin University, Perints Kemerdekaan Street Km 10, Tamalanrea, Makassar * Corresponding Author: paulinataba@unhas.ac.id Received: November 2020 Received in revised: November 2020 Accepted: December 2020 Available online: January 2021 Abstract This study is aimed to determine the potential use of MCM-48 to adsorb chloramphenicol pollution. Chloramphenicol adsorption was conducted at various times contact and concentration. Adsorption isotherm was studied by comparing Langmuir and Freundlich adsorption isotherm. The results showed that chloramphenicol adsorption was suited to Freundlich isotherm with an optimum contact time of 80 minutes Keywords: MCM-48, antibiotic, chloramphencol, adsorption capacity INTRODUCTION Before people discover antibiotics, infectious diseases were very deadly for humans (da Chuha et al., 2019). After Flemming discovered penicillin in 1928, antibiotics were produced on a commercial scale then continued to expand. ANtibiotics is not only for medicinal purpose but also use in animal husbandry and the agricultural industry (cdc.gov, 2019). The widespread use of antibiotics is not without consequences. Bacteria that can be inhibited by certain antibiotics quickly adapt and develop immunity and become resistant to these antibiotics (Heinemann, 1999; Lee Ventola, 2015; Michael et al., 2014). The costs of antibiotic resistance (RA) are currently enormous. The World Health Organization (WHO) estimates that until 2017 there were 700,000 deaths due to antibiotic resistance worldwide and predicts that in 2050 there will be 10 million deaths per year (WHO.int, 2019). The increased risk of RA does not reduce global antibiotic consumption. The antibiotics production and consumption on a large scale can initiate the antibiotic release into the environment. The study found traces of antibiotic contamination in estuaries, surface freshwater even drinking water (Zheng et al., 2011; Danner et al., 2019; Ye and Weinberg, 2007). Therefore, the prevention of antibiotic contamination is needed. The adsorption method is an effective and inexpensive method that use to tackle pollutants in liquid waste. Researches methods for treating pharmaceutical waste, such as anaerobic processes (Chelliapan et al., 2011; Larsson et al., 2007), chemical oxidation, and physicochemical techniques have been carried done, but have not yielded satisfactory results (Oktem et al., 2008; Hey, 2013; Jiang and Zhou, 2013). The adsorption method with mesoporous silica is an alternative solution in treating liquid waste containing antibiotics. One type of mesoporous silica is MCM-48. The MCM-48 has a high surface area, regular pores with a narrow pore size distribution, high pore volume, and has high biocompatibility (Taba et al., 2017; Gau et al., 2017; Nairi et al., 2017; Taba et al., 2018). These properties make it possible to use it as an adsorbent for antibiotic molecules. One of the antibiotics often used is chloramphenicol. In this study, the adsorption of chloramphenicol compounds with MCM-48 was carried out to study the potential of MCM-48 as a potential antibiotic waste adsorbent. METHODOLOGY Materials and Instrumentals The tools used were an oven (Type Spini SOSFD), analytical balance (Ohauss), magnetic stirrer (Fisher Type 115), hotplate stirrer (Ikari Basic 1), vacuum pump (Type ME4C), UV-Vis spectrophotometer (Spektronik 20 D+), Prestige-21 FT-IR spectrophotometer, and X-ray diffractometer (Bruker D2 Phaser 2ndGen). The materials used in this study were obtained from Merck and Sigma- Aldrich with high purity. The ingredients are Ludox HS-40, Cetyltrimethylammonium Bromide (CTAB), Triton X-100, absolute ethanol (C2H5OH), sodium hydroxide (NaOH), acetic acid (CH3COOH), chloramphenicol (C11H12Cl2N2O5), and distilled water (H2O). Synthesis of MCM-48 The MCM-48 material was synthesized using the Ryoo (1999) method modified by Taba (2001). Paulina Taba, et al. Indo. J. Chem. Res., 8(3), 242-246, 2021 DOI: 10.30598//ijcr.2021.7-mif 243 MCM-48 was prepared by mixing a tetracilicate solution (14.3g Ludox HS-40 and 45.25 g of 1M NaOH solution) with a surfactant solution (6.12 g CTAB; 1.34 g Triton X-100; and 83.47 g distilled water) in in a propylene bottle then shake for 15 minutes. The mixture was heated at 100oC for 24 hours while shake then cooled to room temperature. The pH was adjusted to 10 by using 30% acetic acid. The mixture was then heated at 100 °C for 24 hours then cooled to room temperature. The MCM-48 formed was filtered, washed with distilled water, and then dried in an oven at a temperature of 120 °C. MCM-48 characterization The synthesized MCM-48 result was characterized by the FT-IR method to determine the functional groups. The X-Ray Diffraction was carried out to see the crystallinity. Chloramphenicol Adsorption The adsorption of chloramphenicol with MCM- 48 was carried out to determine the optimum concentration, time, and adsorption kinetics. In order to determine the optimum adsorption time, 0.2 g of product MCM-48 was used to adsorb chloramphenicol in a solution with a concentration of 20 ppm in the period of 5-120 minutes until the optimum adsorption time was obtained. In determining the optimum concentration of adsorption, 0.2 g of MCM-48 was used to absorb chloramphenicol in solution at several concentrations during the optimum time. The chloramphenicol concentrations before and after adsorption were measured using a UV-Vis spectrophotometer. RESULTS AND DISCUSSION Characterization using X-ray diffractogram (XRD) The X-ray diffraction pattern of MCM-48 in this study (Figure 1) shows that MCM-48 is amorphous. The pattern obtained is not optimal, because of the limited tools used. Figure 1. X-ray diffraction pattern of the synthesized MCM-48 The X-ray diffraction pattern of MCM-48 in this study was measured from 2θ =15⁰, while the typical MCM-48 pattern was at a small 2θ angle (below 10⁰). Fourier Transform Infra-Red Spectrometer The results of characterization by FT-IR (Figure 2) showed that MCM-48 contained -OH, -CH, and Si- O functional groups. The organic groups -CH range are symmetrical and asymmetrical at wavelengths 2852.72 and 2922.16 cm -1 . The -CH groups are bent at wave number 1355.96; 1415.75; and 1471.69 cm -1 are surfactant groups that are still present in the material. The observed wave numbers 1060.86 and 1226.73 cm -1 are the symmetrical and asymmetrical stretches of the silicate lattice of the material. The Si- O stretching vibration of Si-OH was observed at wave number 962.48 cm -1 . The data obtained is similar to the data in Sari et al's (2015) study, so this data can be confirmed that the material being synthesized is MCM-48 mesoporous silica. Figure 2. FTIR spectra of synthesized MCM-48 Surface Area Determination by BET Method Isothermal adsorption and desorption of N2 gas on MCM-48 before washing can be seen in Figure 3. The adsorption isotherm by MCM-48 without washing corresponds to the type IV isotherm. Capillary condensation occurs in the adsorption process indicated by the presence of hysteresis in the N2 gas adsorption-desorption curve. The surface area (BET) of MCM-48 is 851,797 m 2 /g. The pore surface distribution shows in Figure 4. The pore radius based on the BJH method on MCM-48 was 15.268 Å. These results indicate that the synthesized MCM-48 is a mesoporous material. Paulina Taba, et al. Indo. J. Chem. Res., 8(3), 242-246, 2021 DOI: 10.30598//ijcr.2021.7-mif 244 Figure 3. Isothermal N2 adsorption of MCM-48 before washing Figure 4. Pore size distribution of MCM-48 Chloramphenicol adsorption by MCM-48 The optimum time of chloramphenicol adsorption by MCM-48 The optimum adsorption of chloramphenicol with MCM-48 was at 80 minutes contact time. Figure 5 shows that the number of chloramphenicol molecules absorbed in MCM-48 tends to be the same at 10 to 45 minutes until finally reaching its peak at 80 minutes. After 120 minutes, the number of chloramphenicol molecules absorbed decreased, which indicates that the adsorbent surface was already saturated. Study of Chloramphenicol Adsorption Kinetics by MCM-48 By plotting the t/qe value against contact time (Figure 7), the R 2 value is 0.9998. Thus, chloramphenicol adsorption on MCM-48 is pseudo- second-order adsorption. Figure 5. The number of chloramphenicol molecules adsorbed (qe) by MCM-48 as a function of contact time Figure 6. Chloramphenicol adsorption order on MCM-48 Adsorption Capacity of chloramphenicol by Mesoporous Silica MCM-48 The absorption of chloramphenicol molecules tends to increase with increasing number of molecules in the same volume (Figure 7). Using this data, the adsorption capacity is determined based on the Langmuir and Freundlich isothermal model. Langmuir isothermal model was created by connecting the linear curve Ce/qe to Ce, while the Freundlich isothermal model was created by connecting the linear log qe curve to log Ce. The second isothermal model, both Langmuir and Freunlich is shown in Figures 8 and 9. Figure 7. Number of chloramphenicol adsorbed (qe) by MCM-48 at various concentrations (Ce) 2.7 2.8 2.9 3 3.1 3.2 3.3 5 10 20 30 45 80 120 Q e Contact times (minute) y = 0.3181x - 0.0562 R² = 0.9996 0 10 20 30 40 50 0 50 100 150 t/ q e Contact times (Minute) 0 2 4 6 8 10 12 14 0 20 40 60 Q e Ce Paulina Taba, et al. Indo. J. Chem. Res., 8(3), 242-246, 2021 DOI: 10.30598//ijcr.2021.7-mif 245 Figure 8. Graph of Langmuir isothermal model Figure 9. Graph of Freundlich's isothermal model From these curves, it can be observed that the R 2 value in the Freundlich isothermal model is greater than the R 2 value in the Langmuir isothermal model. Therefore, chloramphenicol adsorption using MCM- 48 tends to follow Freundlich's isotherm. The Freundlich equation assumes that adsorption occurs multi-layer on the surface of the adsorbent and adsorbent. Therefore, the adsorption of chloramphenicol with MCM-48 occurs physically. Figure 10. FTIR spectra (a) before adsorption and (b) after adsorption CONCLUSION Adsorption of chloramphenicol antibiotic compound with optimum MCM-48 at 80 minutes according to Freundlich's adsorption isotherm. The adsorption of these compounds occurs physically with pseudo-order II. CMM-48 has the potential to be applied as an absorbent material for chloramphenicol in waste. ACKNOWLEDGMENT The authors would like to give thank you for the Master's research obtained from the Minister of Research and Technology REFERENCES Chelliapan, S., Wilby, T., and Sallis P. J., 2011. Effect of hydraulic retention time on up-flow anaerobic stage reactor performance at constant loading in the presence of antibiotic Tylosin. Brazilian J. Chemical Engineering, 28(1), 51-61. da Cunha B R., Fonseca L P., and Calado C.R.C., 2019. Antibiotic Discovery: Where Have We Come from, Where Do We Go?, Antibiotics (Basel), 8(2), 45, 1-21. Danner, M., Robertson, A., Behrends, V., and Reiss, J., 2019. Antibiotic pollution in surface fresh waters: Occurrence and effects, Sci. of the Total Environment, 664, 793-804. Gau, A.A., Taba, P., and Budi, P., 2017. Modification of MCM-48 mesoporous silica with 3 aminopropyltrimethoxysilane (3-APTMS) and its adsorption test against Pb 2+ ion, Techno: J. Penelitian 4(02), 23-30. Heinemann, J. A., 1999. How antibiotics cause antibiotic resistance, Drug Discovery Today, 4(2), 72-79 Hey, G., 2013. Application of chemical oxidation processes for the removal of pharmaceuticals in biologically treated wastewater, Available at: http://lup.lub.lu.se/record/3412268/file/3412272. pdf. Jiang, J., and Zhou, Z., 2013. Correction: Removal of Pharmaceutical Residues by Ferrate(VI), PLoS ONE, 8(6), 1-11. Larsson, D.G.J., Pedro, C.d., and Paxeus, N., 2007. Effluent from drug manufactures contains extremely high levels of pharmaceuticals, J. Hazardous Materials, 148, 751-755 Lee Ventola, C., 2015. The Antibiotic Resistance CrisisPart 1: Causes and Threats, Pharmacy and Therapeutics, 40(4), 277-283. Michael, C A., Dominey-Howes, D., and Labatte, M., y = 0.0156x + 3.4605 R² = 0.989 3.5 3.6 3.7 3.8 3.9 4 4.1 4.2 0 10 20 30 40 50 C e /Q e Ce y = 0.9243x - 0.4822 R² = 0.9998 0 0.2 0.4 0.6 0.8 1 1.2 0 0.5 1 1.5 2 L o g Q e Log Ce Paulina Taba, et al. Indo. J. Chem. Res., 8(3), 242-246, 2021 DOI: 10.30598//ijcr.2021.7-mif 246 2014. The Antimicrobial Resistance Crisis: Causes, Consequencies and Management, Front Public Health, 2, 145, 1-8. Nairi, V., Medda, L., Monduzzi, M. and Salis, A., 2017, Adsorption and Release of Ampicillin Antibiotic from Ordered Mesoporous Silica, J. Colloid Interface Sci., 497, 217-225. Oktem, Y. A., Ince, O., Sallis, P., Donelly, T., and Ince, B. K., 2008. Anaerobic Treatment of A Chemical Synthesis-Based Pharmaceutical Wastewater in A Hybrid Upflow Anaerobic Sludge Blanket Reactor, Bioresource Technology, 99(5),1089-1096. Sari A.Y. P., Taba, P., and Prastawa, B., 2015. Synthesis and Characterization of MCM-48 and Modified –NH2 Groups, Indo. J. Chem. Res., 3, 249-253. Taba, P., Budi, P., and Sari, A.Y.P., 2017. Adsorption of Heavy Metals on Amine-Functionalized MCM-48, Proceeding International Symposium on Current Proggress in Functional Materials, July 26-27, Denpasar Bali. Taba, P., Mustafa, R.D.P., Ramang, L.M., and Kasim, A.H., 2018, Adsorption of Pb 2+ on Thiol- functionalized Mesoporous Silica, SH-MCM48, J. Physics, Conference Series, 979, 012058. WHO. 2020. Antimicrobial Resistance, World Health Organization. Ye, Z., and Weinberg, H. S., 2007. Trace Analysis of Trimethoprim and Sulfonamide,Macrolide, Quinolone, and Tetracycline Antibioticsin Chlorinated Drinking Water Using Liquid Chromatography Electrospray Tandem Mass Spectrometry, Anal. Chem., 79, 1135-1144. Zheng, S., Qiu, X., Chen, B., Yu, X., Liu, Z., Zhong , G., Li, H., Chen, M., Sun, G., Huang, H., Yu, W., and Freestone, D., 2011. Antibiotics pollution in Jiulong River estuary: Source, Distribution and Bacterial Resistance, Chemosphere, 84, 1677-1685.