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GAMMA RADIATION EFFECTS ON ORGANIC COMPOUND THIOUREA AND IONIC COMPOUND MACROCYCLIC BROMIDE F. Mohamed, B.Yatim, N.F. Khalid.

Universiti Kebangsaan Malaysia. Radiation Chemistry.

ABSTRACT One of the interesting characteristics of thiourea , an organic compound is to act as free radical scavenger. Macrocyclic bromide, an ionic compound acts as an important ligand in radiochemistry, particularly on irradiated chemical bonds. This study focused on gamma irradiation toward thiourea and macrocyclic bromide compounds in solid phase. The objective of this study was to observe the change in chemical bond conformation in solid thiourea and macrocyclic bromide compounds (powder forms) after irradiation. The second objective was to determine the effective absorbed dose value that caused the chemical change in irradiated thiourea and macrocyclic bromide in solid forms. The third objective was to compare the changes in chemical bonding conformation of thiourea and macrocyclic bromide structures before and after irradiation. Thiourea used was 1,2-bis-(4-methyl benzoyl thioureido) isopropane or S-13 and macrocyclic bromide used was 5,5,12,14,14-hexamethyl-1,4,8,11tetraazacyclotetradecana-4,11-dienium bromide. These two compounds were irradiated using gamma cell with doses 10, 20, 30, 40 and 50 kGy. Analysis was done using Fourier Transform Infrared Spectroscopy (FTIR). The change in chemical bonding conformation of thiourea and macrocyclic bromide samples was observed by looking at FTIR spectrum in terms of high intensity, missing, separation and overlapping of peaks between spectrums. The effective absorbed dose was not able to be determined on both compounds due to no breakage of chemical bonds of the main functional groups. There were missing main functional groups peaks in macrocyclic bromide. This showed that macrocyclic bromide was more sensitive towards gamma radiation than thiourea.

INTRODUCTION

Thiourea is an organic compounds consisting of carbon, nitrogen, sulphur and hydrogen with the formula that is CSN2H4. Thiourea is a white and sparkling crystal in structure. Thiourea is also has a planar molecular structure in which bond of carbon and sulphur is 1.600.1. The function of thiourea in aqueous solution is expected to be the protector from hydroxyl radicals, OHo attacked. When thiourea is radiated with X-rays, gamma rays or electrons, sulphur gas will be liberated (Dale, 1956). This reaction produces a high efficiency of the process and the functions of variables such as dose rate, oxygen depth, pH, concentration thiourea, temperature and so on. When it is in low concentrations, thiourea can also against the effects of indirect light rays thus be a protective for macro molecules. This is due to the nature of thiourea as radioprotector. K. Ziegler- Skylakakis (2003), lists the use of thiourea around the world in terms of production and modification of additional textile and dye auxiliaries, in the ore leaching, production of pharmaceuticals and pesticides. Besides that, thiourea also used as vulcanization accelerators and production photos.

Macrocyclic is the element that has a big ring structure with a number of donor atoms that can bind Lewis acids in the ring structure. Macrocyclic is from macromolecule which has a large molecules consisting of hundreds or thousands of repetitive structures. The specialty of Macrocyclic, it is very important as a ligand. According to Lindoy, L. F. (1989), macrocyclic can mimic biological ligands that have been built centuries ago by the environmental century. In addition, it states that the thermodynamic and kinetic stability of metal complexes with the ligand present.

OBJECTIVES This research has three main objectives. The first objective to be achieved is to determine the changes over the conformation of chemical bonds between thiourea and macrocyclic bromide in the solid state (powder). The conformation of each chemical bonds before and after irradiated can be seen by using Fourier Transform Infra Red (FTIR). The second objective is to determine the value of effective dose that can gave a chemical changes towards thiourea and macrocyclic bromide radiated in the solid state. When the value of the most effective dose is known, thus the chemical changes of radiated thiourea can be seen. The third objective is to compare the changes over the conformation of chemical bonds for thiourea and macrocylic bromide structure before and after radiated. This comparison is made to determine which of both samples is more sensitive to gamma radiation in the solid state.

RATIONAL Studies on thiourea has long studied since the 1950s. Much research on thiourea made primarily affect humans, animals and plants in terms of biology, chemistry and physics. In addition, studies on radiation protection found in thiourea is vital to modern radiobiologist, radiochemical aspects of ethnicity and genetic structure to protect against radiation imposed on the cells of organisms. Studies on macrocyclic also give a benefit and help to human living. According to Cheng et al. (1995), macrocyclic complex is connected covalently with antibody, for using as therapeutic treatment or diagnostic aim of cancer. Moreover, used as a temperature sensor in body tissue. In nuclear medicine said Troutner et al. (1986), he said that macrocyclic complex Technetium-99m was used as radionuclide imaging that very important for myocardial (heart) and lungs radiopharmaceutical. The virtues of this research is to see the effects of gamma radiation that can alter the compounds thiourea and macrocyclic bromide to get the most appropriate radiation dose for a change over the conformation of chemical bonds. Most probably happen is degradation. Thus, doses of radiation that can cause these changes can be determined within 10kGy, 20kGy, 30kGy, 40kGy and 50kGy according to Dale (1959).

METHOD Characterization method: Using Fourier Transform Infra Red (FTIR). It is an absorption peak method for each chemical bonding according to wavelength, cm-1. Materials: 1. Thiourea: 1,2-bis-(4-methyl benzoyl thioureido) isopropane or S-13 in solid state. 2. 4-Methyl Benzoyl Cloride, C8H7ClO. 3. Ammonium Thiocyanate, CH4N2S. 4. Aseton, C3H6O. 5. Ammonium Bromide, NH4Br. 6. Etylena diamine, C2H4(BH2)2. Apparatus: 1. Gamma cell- MDS Nordian GammaCell 220 Excel Model. 2. Fourier Transform Infra Red-Perkin Elmer Model Spectrum GX Model. 3. Hydraulic Press. 4. Pestle and mortar. Flow Chart: Sample Preparation

Irradiate all samples according to each dose 10,20,30,40,50 kGy

Sample analysis -FTIR

Data analysis

RESULTS FTIR results: Thiourea, FTIR (10,20,30,40,50) kGy


Control, 0kGy 10kGy

20kGy

30kGy

40kGy

50kGy

Macrocyclic Bromide, FTIR (0,10,20,30,40,50) kGy


Control, 0kGy 10kGy

20kGy

30kGy

40kGy

50kGy

For thiourea:

3500 3000 2500 2000 1500 1000 500 0

Comparison of each fuctional group in thiourea sample due to the doses

Wavelength, cm-1

Benzen-CH3 C=O N-H (primer) C=S N-H (sekunder) C-N C=S N-H (amida) Benzen=CH 0 10 20 30 40 50

Dose, kGy For macrocyclic bromide:

Comparison of each functional group in macrocyclic bromide sample due to the doses
3500 3000

Wavelength, cm-1

2500 2000 1500 1000 500 0 0 10 20 30 40 50 C-H C=N N-H C-H2

Dose , kGy DISCUSSION After what all have done in this research, we analyze through FTIR characterization method, it gives a spectrum of chemical bonds on thiourea and macrocyclic bromide between control and radiated. This gives an indication of the absorption spectrum of wave numbers that are very useful for identifying each functional group due to their frequency of vibration chemical bonding. Absorption intensity, % in FTIR graph does not provide a useful value in this analysis and it is not often recorded. It just stated the height of the arc spectrum according to the number and concentration of the sample. Through the observation in this analysis, there are changes occurs at certain functional group of chemical bonds. What are happen in the chemical bonds are spectrum lost, spectrum stretch and spectrum bend according to each vibration bonding. A new spectrum also exist at thiourea spectrum at dose 10,20,40 and 50kGy and at macrocyclic bromide spectrum at 20,30,40 and 50kGy dose when it compared with control samples respectively. CONCLUSION As a conclusion, thiourea and macrocyclic bromide showed a small change to over the conformation of chemical bonds in functional groups, especially when radiated with gamma radiation. The changes can be seen at the peak of the absorption spectrum occurs around spectral separation (split), overlap, high (high absorbance) and the wave number is lost (disappear) in a particular spectrum. In this research, the effective value of the absorbed dose cannot be trace for giving a chemical changes on thiourea and macrocyclic bromide. Gamma radiation cannot give a

significant impact to thiourea and macrocyclic bromide in solid state. This is because this research apply direct effect compared to indirect effect that indirect effect can give impact more clearly. Next, the comparison over the conformation of chemical bonds on the structure of thiourea and macrocyclic bromide proved that macrocyclic bromide is more sensitive than thiourea (refer to the result). Suggestion for future research as for the improvement is use thiourea and macrocyclic bromide in the liquid phase with an appropriate dilution according to solvents. In addition, adding other characterization method such as UV-Vis Spectroscopy using Fricke Dosimeter.

REFERENCES Cheng C. R., Fordyce W. A., Goeckleler W.F., Kruper W.J., Frank R.K., Garlich J.R, Kiefer G.E., MacMillan K., Simon J., Wilson D.A., Branghman S. 1995. Macrocyclic Conjugates and Their Use As Diagnostic And Therapeutic Agents. United States Patent. 5,434,990: 1-14.

Dale W.M. 1956. Irradation of Tiourea: Effect of Dose-rate upon The Chain Reaction. Journal of Nature 177: 531-531.

Lindoy, L. F. 1989. The Chemistry of Macrocyclic Ligand Complexes; Cambridge University Press: Cambridge.

Troutner D.E. & Volkert W.A. 1986. Macrocyclic complexes of Technetium-99m for use as diagnostic radionuclides. United States Patent. 4,615,876: 1-24.

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