SINTESIS POLI-5-ALLILKALIKS[4]ARENA DAN TURUNAN ESTER SERTA ASAM KARBOKSILATNYA SEBAGAI ADSORBEN DAN ANTIDOTUM KERACUNAN LOGAM BERAT

DESI SUCI HANDAYANI, Prof. Drs Jumina, Ph.D

2011 | Disertasi | S3 Ilmu Kimia

Telah dilakukan sintesis senyawa seri poli-5-allilkaliks[4]arena yang meliputi poli-5-allil-25,26,27,28-tetrahidroksikaliks[4]arena (PK[4]H), poli-5-allilkaliks[4]-arena tetra ester (PK[4]E) dan poli-5-allilkaliks[4]arena tetra asam asetat (PK[4]A). Apakah senyawa hasil sintesis dapat digunakan sebagai adsorben baik dalam bidang industri maupun sebagai antidotum dikaji dalam penelitian ini. Sintesis seri poli-5-allilkaliks[4]arena ini dilakukan melalui tahapan reaksi : (1) sintesis p-t-butilkaliks[4]arena, (2) debutilasi, (3) sintesis 25-alliloksi-,26,27,28- trihidroksikaliks[4]arena (kaliksarena 1), (4) sintesis 5-allil-25,26,27,28- tetrahidroksikaliks[4]arena (kaliksarena 2), (5) esterifikasi kaliksarena 2 sehingga diperoleh 5-allilkaliks[4] tetraester (kaliksarena 3), (6) hidrolisis kaliksarena 3 menghasilkan 5-allilkaliks[4]arena tetra asam asetat (kaliksarena 4), (7) polimerisasi kationik terhadap kaliksarena 2,3 dan 4. Uji adsorpsi PK[4]H, PK[4]E dan PK[4]A dilakukan menggunakan metode batch, sedangkan uji aktivitas antidotum dan keamanannya dilakukan secara in vivo. Sintesis kaliksarena 1, 2, 3 dan 4 menghasilkan produk dengan rendemen 88,36%; 78,33%, 44,33% dan 84,52%. Polimerisasi kaliksarena 2, 3 dan 4 menghasilkan produk PK[4]H, PK[4]E dan PK[4]A dengan titik leleh berturut-turut 292- 295, 298-300 dan 300-303 °C dan rendemen masing-masing 85, 70 dan 87,18%, serta berat molekul relatif berturut-turut 109.943; 84.510 dan 63.171 mol/g, dengan unit pengulang 273, 104 dan 91. Hasil uji adsorpsi menunjukkan bahwa pengaruh pH terhadap proses adsorpsi berbeda-beda untuk masing-masing spesies, tergantung dari jenis adsorben dan spesies logam yang akan diadsorpsi. Kajian kinetika adsorpsi menunjukkan bahwa adsorpsi ion logam Pb(II), Cd(II) dan Cr(III) menggunakan ketiga adsorben PK[4]H, PK[4]E dan PK[4]A, mengikuti model kinetika Ho, orde pseudo 2. Kapasitas maksimum adsorpsi menggunakan ketiga adsorben PK[4]H, PK[4]E dan PK[4]A mempunyai kapasitas terbesar pada adsorpsi dengan logam Cr(III) yaitu masing-masing sebesar 208,02; 197,25 dan 228,69 µmol/g, dengan energi adsorpsi berturut-turut 27,57; 27,15 dan 31,07 kJ/mol. Koefisien partisi PK[4]H pada pH 3,5 dan 7,4 berturut-turut 1,62 ± 0,1 dan 1,62 ± 0,07. Berdasarkan hasil uji in vitro penyerapan logam-logam essensial, maka dapat disimpulkan bahwa penggunaan PK[4]H sebagai antidotum keracunan logam Cd(II) harus disertai dengan pemberian suplemen yang mengandung Fe, Ca dan Zn. Uji toksisitas akut menunjukkan bahwa bahan uji mempunyai LD50 lebih besar dari 260 mg/kg BB mencit. Pemberian obat PK[4]H sebagai antidotum dapat menurunkan kandungan Cd dalam ginjal, hati dan darah. Uji aktivitas antidotum menunjukkan bahwa dosis efektif dari PK[4]H sebagai antidotum keracunan Cd adalah dosis 2 (0,65 mg/kg BB).

Series of poly-5-allylcalix[4]arenes had successfully been synthesized. These are poly-5-allyl-25,26,27,28-tetrahydroxycalix[4]arene (PK[4]H), poly-5-allylcalix[4]arene tetra ester (PK[4]E) and poly-5-allylcalix[4]arene tetra acetate acid (PK[4]A). Whether the compounds synthesized can be used as an adsorbent in industry and antidote were investigated in this study. Synthesis of poly-5-allylcalix[4]arene series was performed in several reactions: (1) synthesis of p-t-butylcalix[4]arene, (2) debutylation reaction of p-tbutylcalix[ 4]arene to give 25,26,27,28-tetrahydroxycalix[4]arene, (3) synthesis of 25- allyloxy-26,27,28-trihydroxycalix[4]arene (calixarene 1), (4) synthesis of 5-allyl25,26,27,28- tetrahydroxycalix[4]arene (calixarene 2), (5) esterification of calixarene 2 to produce calixarene 3, (6) hydrolysis of 5-allylcalix[4]arene tetra ester to yield calixarene 4, (7) cationic polymerization towards calixarene 2, 3 and 4. Adsorption of P[4]H, PK[4]E and PK[4]A conducted by batch method, whereas the activity test antidote and safety were carried outin vivo. The synthesis of calixarene 1, 2, 3 and 4 afforded products with yield 88.36%, 78.33%, 44.33% and 84.52%. Polymerization reaction towards calixarene 2, 3 and 4 gave PK[4]H, PK[4]E dan PK[4]A with m.p. of 292-295, 298-300 and 300-303 °C and yield percentage of 85, 70 and 87.18%, respectively. The relative molecular weight of PK[4]H, PK[4]E and PK[4]A respectively was 109,943; 84,509 and 63,171 mol/g with the repetition unit of 273, 104 and 91. Results of adsorption process showed that the effect of pH on the adsorption was different for Pb(II), Cd(II) and Cr(III). This depended on the type of adsorbent and adsorbate species. Study of adsorption kinetics showed that the adsorption of Pb(II), Cd(II) and Cr(III) metal ion using the adsorbents of PK[4]H, PK[4]E and PK[4]A followed the kinetic model of Ho, i.e. pseudo second order. Greatest adsorption capacity of adsorbent PK[4]H, PK[4]E and PK[4]A on metal adsorption by Cr(III) were 208.02; 197.25 and 228.69 mol/g, with the adsorption energies of 27.57; 27.15 and 31.07 kJ / mol, respectively. Partition coefficient of PK[4]H at pH of 3.5 and 7.4 was 1.62 ± 0.1 and 1.62 ± 0.07, respectively. According to the in vitro result of the essential metals adsorption, it could be concluded that the utilization of PK[4]H as antidote in Cd poisoning had to be coupled with the provision of supplements containing Fe, Ca and Zn. Acute toxicity test showed that until the highest dose (260 mg/kg body weight), there was no either male or female mice died, therefore, it could be stated that the test material had the LD50 higher than 260 mg/kg body weight of mice. Based on the result of activity test, it could be said that the effective dose of PK[4]H as antidote in Cd poisoning was dose 2 (0.65 mg/Kg body weight).

Kata Kunci : Logam berat, turunan ester