#TITLE_ALTERNATIVE#

• Main Author: PRATIWI (NIM: 30715009), RIMADANI
• Format: Dissertations
• Language: Indonesia
• Online Access: https://digilib.itb.ac.id/gdl/view/23995
• Institution: Institut Teknologi Bandung

Heavy metals are an element that is widespread distributed in the environment and <br /> <br /> <br /> <br /> <br /> <br /> a few of these metals are essential to life. However, abnormal level of them has <br /> <br /> <br /> <br /> <br /> <br /> been associated with the toxicity for a human being. Lead (Pb), cadmium (Cd), <br /> <br /> <br /> <br /> <br /> <br /> mercury (Hg), tin (Sn), arsenic (As), and copper (Cu) are several heavy metals <br /> <br /> <br /> <br /> <br /> <br /> which can contaminate food and drinking water. As the result, they have a <br /> <br /> <br /> <br /> <br /> <br /> maximum allowable level in food and drinking water. Numerous analytical <br /> <br /> <br /> <br /> <br /> <br /> methods have been developed for their detection with atomic absorption <br /> <br /> <br /> <br /> <br /> <br /> spectroscopy (AAS) and inductively coupled plasma mass spectrometry (ICPMS) <br /> <br /> <br /> <br /> <br /> <br /> being the most common. While AAS and ICPMS are sensitive and selective, they <br /> <br /> <br /> <br /> <br /> <br /> require expensive instrumentation, highly trained personnel and cannot be used for <br /> <br /> <br /> <br /> <br /> <br /> on-site analysis. Therefore, analytical methods for metals analysis that are simple, <br /> <br /> <br /> <br /> <br /> <br /> portable, and reliable are still needed. <br /> <br /> <br /> <br /> <br /> <br /> Colorimetric methods for metal detections have shown great potential in this field. <br /> <br /> <br /> <br /> <br /> <br /> This method can simply, conveniently and most importantly can observe by the <br /> <br /> <br /> <br /> <br /> <br /> naked eye. Porphyrin derivative compound has been widely used in analytical <br /> <br /> <br /> <br /> <br /> <br /> chemistry as chromogenic reagents for metal ion detection. Recently, porphyrin <br /> <br /> <br /> <br /> <br /> <br /> derivative compounds have been developed as optical sensors for metal detections. <br /> <br /> <br /> <br /> <br /> <br /> One of the most common detection motif used in &#956;PADs is a colorimetric method <br /> <br /> <br /> <br /> <br /> <br /> using specific reagents to identify and quantify analytes in the sample. In this work, <br /> <br /> <br /> <br /> <br /> <br /> a distance-based &#956;PADs has been developed using porphyrin derivative as the <br /> <br /> <br /> <br /> <br /> <br /> colorimetric reagent for metal detection. <br /> <br /> <br /> <br /> <br /> <br /> As preliminary study, interaction of three cationic porphyrins: meso-tetrakis(Nmethylpyridinium- <br /> <br /> <br /> <br /> <br /> <br /> 4-yl)porphyrin (TMPyP), meso-tetrakis(1,3- <br /> <br /> <br /> <br /> <br /> <br /> dimethylimidazolium-2-yl)porphyrin (TDMImP), and meso-tetrakis(1,2- <br /> <br /> <br /> <br /> <br /> <br /> dimethylpyrazolium-4-yl)porphyrin (TDMPzP) with metals ion (Pb, Cd, Hg, Sn, <br /> <br /> <br /> <br /> <br /> <br /> As, dan Cu) have been performed computationally using DFT method. DFT global <br /> <br /> <br /> <br /> <br /> <br /> chemical reactivity descriptors were calculated and used to predict their relative <br /> <br /> <br /> <br /> <br /> <br /> stability and reactivity. The result shows that M-TDMPzP has the highest chemical <br /> <br /> <br /> <br /> <br /> <br /> hardness and the lowest electrophilicity compare to M-TMPyP and M-TDMImP, <br /> <br /> <br /> <br /> <br /> <br /> iv <br /> <br /> <br /> <br /> <br /> <br /> indicating reaction of TDMPzP with metals will form a more stable complex. <br /> <br /> <br /> <br /> <br /> <br /> TDMPzP was continued to synthesized. <br /> <br /> <br /> <br /> <br /> <br /> TDMPzP was synthesized using Adler method in a salt form. A pure deep purple <br /> <br /> <br /> <br /> <br /> <br /> microcrystalline solid with yield 96,8% was obtained. This compound is soluble in <br /> <br /> <br /> <br /> <br /> <br /> water and analysis using UV-Vis spectrophotometry, NMR, and elemental analysis <br /> <br /> <br /> <br /> <br /> <br /> was performed for characterization. <br /> <br /> <br /> <br /> <br /> <br /> The characterization of the interaction of TDMPzP with metal ions was investigated <br /> <br /> <br /> <br /> <br /> <br /> by adding various kind of metals ion to the TDMPzP solution at different pH values. <br /> <br /> <br /> <br /> <br /> <br /> The colorimetric sensing ability of TDMPzP indicates that it was selective for Cu2+ <br /> <br /> <br /> <br /> <br /> <br /> detection in pH 2-4. Job’s Plot analysis suggest that a stoichiometry of TDMPzPCu <br /> <br /> <br /> <br /> <br /> <br /> complex is 1:1 with binding constant 4,15 x 105 M-1. <br /> <br /> <br /> <br /> <br /> <br /> The selectivity of TDMPzP for Cu2+ in acidic solution makes it a good candidate to <br /> <br /> <br /> <br /> <br /> <br /> be applied in developing a distance-based &#956;PADs for Cu2+. The lower measurable <br /> <br /> <br /> <br /> <br /> <br /> limit for this distance-based measurement for Cu2+ detection was at 1 mg L-1 which <br /> <br /> <br /> <br /> <br /> <br /> is in accordance with the regulation by US EPA and WHO guidelines for drinking <br /> <br /> <br /> <br /> <br /> <br /> water quality. The interference study results indicate the selectivity of &#956;PADs to <br /> <br /> <br /> <br /> <br /> <br /> Cu2+ over other metal ions. Application of this system for real drinking water <br /> <br /> <br /> <br /> <br /> <br /> sample showed a good agreement between distance-based &#956;PADs with ICP-MS. <br /> <br /> <br /> <br /> <br /> <br /> The recoveries were obtained with relative standard deviations of less than 10% <br /> <br /> <br /> <br /> <br /> <br /> All of these results suggest that TDMPzP as a colorimetric reagent was successfully <br /> <br /> <br /> <br /> <br /> <br /> applied on distance-based &#956;PADs for determination of Cu2+ in drinking water <br /> <br /> <br /> <br /> <br /> <br /> samples. This method is simple, rapid, cost-effective, instrument-free, and selective <br /> <br /> <br /> <br /> <br /> <br /> for on-site Cu2+ analysis in aqueous medium