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In the present work, we reported a successful synthesis and high antioxidant activity of C-alkylcalix[4]resorcinarene and C-alkylcalix[4]pyrogallolarene derivatives. The C-alkylcalix[4]resorcinarenes were prepared from a cyclization reaction of resorcinol and either pentanaldehyde or octanaldehyde in acidic condition. Meanwhile, the C-alkylcalix[4]pyrogallolarenes were prepared from a cyclization reaction of pyrogallol with pentanaldehyde or octanaldehyde. Four synthesized products, i.e. nBu-CR, nHep-CR, nBu-CP, and nHep-CP, were successfully prepared in 92.4-96.4% yield. The chemical structure of these products was elucidated by Fourier transform infrared (FTIR), liquid chromatography-mass spectrometry (LC-MS), and proton nuclear magnetic resonance (1H-NMR) analysis. The antioxidant activity assay of these compounds was evaluated through an in vitro assay employing 2,2-diphenyl-1-picrylhydrazyl (DPPH) radicals. From the DPPH assay, it was found that the half-maximal inhibitory concentration (IC50) values of nBu-CR, nHep-CR, nBu-CP, and nHep-CP compounds were 25.1, 22.9, 11.5, and 21.9 µg mL-1, respectively. The IC50 value of the synthesized compounds was 2.0-4.3 times lower than the IC50 value of butylated hydroxytoluene (BHT) as the positive standard (49.9 µg mL-1), which is remarkable. This finding demonstrates that either C-alkylcalix[4]resorcinarenes or C-alkylcalix[4]pyrogallolarenes are better antioxidant agents than BHT. The nHep-CR compound was found as the best antioxidant agent from the other compounds due to weaker intramolecular and intermolecular hydrogen bonding as well as longer alkyl chain.

The 4-OH-chalcone was suspected to absorb and reduce ultraviolet radiation intensity that exposed to the skin. The 4-OH-chalcone was formulated as gel dosage form using combination of carbopol in content of 0.50-1.00% w/w; propylene glycol in content of 19-20% w/w; and CMC-Na in content of 0.50-1.00% w/w. This study’s purpose was to optimize the three gel bases, evaluate physical properties, physical stability, and activity of 4-OH-chalcone gel as sunscreen by in vitro method. Simplex Lattice Design (SLD) method was used to optimize gel base with Design Expert software version 10.0. Activity of 4-OH-chalcone gel as sunscreen was determined spectrophotometrically by determining Sun Protecting Factor (SPF) value, percent transmission of erythema (% TE), and percent transmission of pigmentation (% TP). Data were analyzed statistically with SPSS Statistic software. Optimum formula of 4-OH-chalcone gel with 0.50% w/w carbopol content, 0.50% w/w carboxymethylcellulose sodium content, and 20,0% w/w propylene glycol content has pH of 5.59, viscosity of 37.4 dPa.s, spreadability of 28.8 cm2, adhesive time of 1.28 seconds, SPF value of 28.65, %, TE value of 16.44%, %TP value of 0.24%, and relatively stable physical properties.

Coronavirus disease 2019 (COVID-19) is still as global pandemic. No officially drugs to treat COVID-19 are available until now. Increasing number of patients and deaths trigger new antiCOVID-19 discovery efforts. In this study, we have conducted in silico screening employing molecular docking for Indonesian phytochemicals. Docking process was performed by employing AutoDock4 software on crystal structure 6VSB. Based on molecular docking results, several compounds had potential as antiCOVID-19 drugs, such as β-carotene, veramiline, ecliptalbine, betulinic acid, and lupeol. β-carotene was the most potential compound to treat COVID-19.

Plasmodium falciparum (P. falciparum) is the most fatal among the other Plasmodium parasites that infect humans with the malaria disease. Currently, the resistance of P. falciparum against some antifolate drugs has become a severe problem. On the other hand, xanthone and thioxanthone derivatives have been reported to have remarkable antimalarial activity. However, molecular docking studies have not evaluated thioxanthone derivative compounds as antimalarial agents. Accordingly, this research investigated the binding pose and inhibition mechanism of several thioxanthone derivatives against P. falciparum proteins DHFR (PDB ID: 1J3K) and DHODH (PDB ID: 1TV5) through molecular docking study. The compound structures were geometrically optimized using Gaussian 09 software and docked to the receptors using AutoDock4 software. The results showed that the free binding energy of thioxanthone derivatives ranged between -6.77 to -7.50 and -8.45 to -9.55 kcal mol–1 against pfDHFR and pfDHODH, respectively, with RMSD values of less than 2 Å. Compound F (4-iodo-3,4-dihydroxy-thioxanthone) gave the most substantial free binding energy against both proteins. Furthermore, the hydrogen bond interaction of compound F was the same as the native ligands of pfDHFR and pfDHODH. These results suggested that compound F has a more robust interaction in pfDHFR and pfDHODH. Thus, it is promising to further evaluate the compound as a candidate for a new antimalarial agent.

Overexpression of mutant p53 in cancer cell inactivates the p53 pathways to execute apoptosis and cell cycle arrest. This study aimed to synthesize new kardiena derivative compound, 3-carbethoxy-4(3’-chloro-4’-hydroxy)phenyl-but-3-en-2-one, to reactivate the p53 pathways to execute apoptosis and cell cycle arrest. Characterization of the synthetic compound employing melting point, IR, EI-MS, 1H-NMR, and 13C-NMR spectra revealed 3-carbethoxy-4(3’-chloro-4’-hydroxy)phenyl-but-3-en-2-one was successfully synthesized from 3-chloro-4-hydroxybenzaldehyde and ethyl acetoacetate using dimethylamine as a catalyst. This compound had antiproliferative activity against the WiDr cells which carried mutant p53. Its antiproliferative activity was better than 5’-FU as a reference standard to treat colon cancer. Increasing WiDr cell accumulation in the G2-M phase, the active form of caspase-3, and inducing apoptosis demonstrated the ability of 3-carbethoxy-4(3’-chloro-4’-hydroxy)phenyl-but-3-en-2-one to reactivate p53 pathways to execute apoptosis and cell cycle arrest in cancer cells carrying mutant p53.

In this study, the microreactor system was investigated and compared with the batch-wise system as rapid and effective extractive Pb(II) separation over Fe(III), Cu(II) and Zn(II) with tetraacetic acid calix[4]arene. By using a microreactor system, the Pb(II) extraction percentages reached the maximum of 73, 89 and 100% in 8 sec residence time at equilibrium pH of 2.00, 2.25 and 2.50, respectively. The stripping percentage was 92% at 8 sec residence time by using a microreactor system with 2.0 M HNO3 as a stripping reagent. Complete separation of Pb(II) over Fe(III), Cu(II) and Zn(II) ions with the tetraacetic acid calix[4]arene in a competitive metal system was achieved at pH 2.00. However, the batch system required 24 h to reach the equilibrium for both extraction and stripping processes. The results suggested that the microreactor system enhanced the Pb(II) extraction and stripping rate up to 104 times faster than the batch-wise system.

Indonesia is rich with essential oils such as anise and clove leave oils. In respect to explore the potential utilization of these resources, it has been conducted the transformation of p-hydroxybenzaldehyde and vanillin (4-hydroxy-3-methoxy benzaldehyde) respectively derived from anise oil and clove leaves oil to a series of C-arylcalix[4]resorcinarenes and C-arylcalix[4]pyrogallolarene macrocycles. Treatment of these aldehydes with resorcinol in the presence of HCl in absolute ethanol at reflux for 8 h afforded C-4-hydroxyphenylcalix[4]resorcinarene (3a) and C-4-hydroxy-3-methoxy phenyl-calix[4]resorcinarene (3b) in good yields. When the aldehydes were treated with pyrogallol under the similar condition, the products were C-4-hydroxyphenyl calix[4]pyrogallolarene (3c) and C-4-hydroxy-3-methoxyphenylcalix[4]pyrogallolarene (3d) which were also obtained in excellent yields. Treatment of these calix[4]resorcinarenes and calix[4]pyrogallolarenes with cinnamoyl chloride and benzoyl chloride in pyridine afforded the corresponding cinnamate esters and benzoate esters in high yields. The resulted C-arylcalix-[4]resorcinarenes and C-arylcalix[4]pyrogallol arenes were subjected to antioxidant activity test using DPPH method and showed strong activity with IC50 values of 15–80 μg/mL. In terms of the synthesized calix cinnamates, the compounds showed UV-B absorption with SPF values of 15–30 at a concentration of 25 ppm which demonstrate their potential to be applied as a UV-B protector. Furthermore, these compounds were also tested for their photostability on the UV-B region and the results showed that the compounds were still unstable under irradiation for 30 min.

C-4-hydroxyphenylcalix[4] pyrogalolarene (Pg4OH) is a synthetic chemical compound that shows strong antioxidant activity. It is potential to be developed as UV skin protector. For topical admission, an acute skin irritation test is being prerequisite to be fulfill. This study was conducted to investigate the irritation effect of Pg4OH on the skin. In vivo study by quasi experiment with posttest only design was carried out by employing 3 adult male albino rabbits. The back hair was shaved at 24 h before the treatment. The Pg4OH was smeared on the bare shaved-skin and left naturally within 4 h. The observation began at 24, 48 and 72 h after exposure. The erythema and edema scores were measured. Calculation by using primary irritation index (PII) was applied. Calculation was categorized with globally harmonized system (GHS) and international organization for standardization (ISO) parameters. As a result, among three rabbits, only one animal shown erythema and edema with very small size (score: 1), on 3 sites, at 72 h. Both the control site and the sample sites gained same score. Two other rabbits were obtained 0 value at each observation location. According to the PII, the observed data was obtained score 0.0093 (very light or negligible). It can be concluded that the tetracyclic compound of Pg4OH does not irritate the skin.

A synthesis and kinetic study of the urea controlled-release composite material based on isolated Na-lignosulfonate, Na-alginate and tapioca was carried out. This experiment’s aims were to isolate Na-lignosulfonate from wood sawdust and to applicate this isolated Na-lignosulfonate, along with tapioca and Na-alginate as urea control release composite material. A kinetic study of urea released from the composite materials was also conducted. Na-lignosulfonate was isolated by Kraft lignin method to give a brown solid yield of 16.92% and was characterized by FT-IR spectrophotometer and SEM-EDX. The composite materials were synthesized by blending urea as the active compound with composite material as the carrier compound. Three types of material were prepared: complete material (A), low-concentration Na-lignosulfonate material (B) and material without tapioca (C). The composite material had a spherical form with 0.79 mm radius and 2.16 mm swollen radius. Urea content inside material was 40.425 mg urea/g material. The urea diffusivity coefficient for material A, B, and C were 7.27 x 10–6; 15.50 x 10–6 and 0.94 x 10–6 m2 h–1, respectively. Modelling analysis showed the experiment obeyed around only 15% of the Korsmeyer–Peppas model, but there was good correlation (80%) with the unsteady-state diffusion model.

The present study was aimed to synthesize and evaluate sunscreen activity of C-methylcalix[4]resorcinaryl octacinnamate and C-methylcalix[4]resorcinaryl octabenzoate. The target compounds were synthesized in 2 steps. They were a synthesis of C-methylcalix[4]-resorcinarene via acid catalyzed the condensation of resorcinol and acetaldehyde by using HCl catalyst, followed by esterification using cinnamoyl chloride and benzoyl chloride. The characterization of the target compounds was performed by IR, 1H-NMR, 13C-NMR, and LC-MS spectrometers. The sunscreen activity test was conducted by spectroscopic method and MTT-assay. Commercial sunscreen p-amino benzoic acid (PABA) was used as a comparator to the MTT assay. The sunscreen activity test used spectroscopic showed that C-methylcalix[4]resorcinaryl octacinnamate and C-methylcalix[4]resorcinaryl octabenzoate can absorb the ultraviolet radiation between 280 and 320 nm (UV-B) with the maximum absorption at 290 nm (ε = 31.535 M-1 cm-1) and 282 nm (ε = 42.217 M-1 cm-1), respectively. The results of MTT-assay indicated that the IC50 of C-methylcalix[4]resorcinaryl octacinnamate, C-methylcalix[4]resorcinaryl octabenzoate and PABA are 12.006, 20.568 and 12.564 ppm, respectively, it means that the order of sunscreen activity is C-methylcalix-[4]resorcinaryl octacinnamate, PABA and C-methylcalix[4]resorcinaryl octabenzoate.

A new upper rim-functionalized benzoyl C-phenylcalix[4]resorcinaryl octaacetate and cinnamoyl C-phenylcalix[4]resorcinarene have been synthesized and evaluated as the absorbers for ultraviolet radiation. The benzoyl C-phenylcalix[4]resorcinaryl octaacetate was synthesized in 3 steps. They were synthesis of C-phenilcalix[4]resorcinarene via acid-catalyzed-condensation of resorcinol and benzaldehyde, followed by O-acetylation and Friedel-Craft benzoylation. The cinnamoyl C-phenylcalix[4]resorcinarene was synthesized in 4 steps. They were synthesis of C-phenilcalix[4]resorcinarene via acid-catalyzed-condensation of resorcinol and benzaldehyde, followed by O-acetylation, Friedel-Craft cinnamoylation and hydrolysis. Spectroscopic analysis (UV) showed that the target molecule absorbed the ultraviolet radiation between 200 and 400 nm with the maximum absorption at 240.50 nm (ε = 10.135 M-1 cm-1) and 243.50 nm (ε = 12.135 M-1 cm-1).

The aims of this research is to synthesize Pb(II) imprinted polymers with carboxymethyl chitosan (CMC) as polymers and bisphenol A diglycidyl ether (BADGE) as cross-linker (Pb-IIP). Chitosan (CTS), non imprinted polymer (NIP) and Pb-IIP were characterized using infrared (IR) spectroscopy, X-ray diffraction (XRD), surface area analyzer (SAA), scanning electron microscopy (SEM), and energy dispersive X-ray (EDX) spectroscopy. The result showed that the adsorption was optimum at pH 5 and contact time of 250 min. Adsorption of Pb(II) ion with all of adsorbents followed pseudo-second order kinetic equation. Adsorption of Pb(II) ion on CTS followed Freundlich isotherm while that on NIP and Pb-IIP followed the Langmuir adsorption isotherm. The adsorbent of Pb-IIP give higher capacity than the NIP and CTS. Adsorption capacity of Pb-IIP, NIP and CTS were 167.1, 128.9 and 76.1 mg/g, respectively. NIP gave higher adsorption selectivity for Pb(II)/Ni(II) and Pb(II)/Cu(II), whereas Pb-IIP showed higher adsorption selectivity for Pb(II)/Cd(II).The hydrogen bonding dominated interaction between Pb(II) ion on NIP and Pb-IIP.

This research was conducted to evaluate the anticancer activity of new compounds of benzyl-1,10- phenanthroline derivatives and their selectivity. In vitro anticancer activity of 11 benzyl-1,10-phenanthroline derivatives were conducted on three human cancer cell lines, cervical cancer (HeLa), myeloma (NS-1), and breast cancer (MCF-7) using MTT-based cytotoxicity assay. The cytotoxicity of each compound was assessed to normal Vero cell line by the same method. The in vitro anticancer activity and cytotoxicity was expressed by the concentration inhibiting 50% of the cell growth (IC50), and the selectivity index (SI) was determined by calculating ratio of the IC50 on Vero cell line and the human cancer cell lines. The results showed that among the 11 compounds tested, the (1)-N-(4-butoxybenzyl)-1,10-phenanthrolinium bromide exhibited the best in vitro anticancer activity with an IC50 27.60 ± 2.76 µM on HeLa, 6.42 ± 5.53 µM on NS-1 and 9.44 ± 2.17 µM on MCF-7 cell lines. Its SI were 377.65 ± 39.97 on HeLa, 6158.72 ± 5306.34 on NS-1 and 1140.11 ± 261.85 on MCF-7 cell lines. This study demonstrated that (1)-N-(4-butoxybenzyl)-1,10-phenanthrolinium bromide possessed a potential in vitro anticancer activity on cancer cell lines with high selectivity

A research has been conducted to investigate the capability of a series of novel calix[6]arenes-based polymers: poly-monoallyloxycalix[6]arene (2a), poly-monoallyloxypenta-estercalix[6]arene (2b) and poly-monoallyloxypenta-acidcalix[6]arene (2c) for trapping of heavy metal cations such as Cd(II), Cu(II) and Cr(III). The existence of active hydroxy group (-OH) and with a tunnel-like structure of the polymers, caused the polymers can be used as adsorbents for heavy metals. The adsorption process was carried out in batch method in the variation of acidity (pH), contact time and initial concentration of metal ions. The results showed that the amount of adsorbed metal increased with the increasing of the pH of metal solution. For these three polymers, the amount of metal ions Cd(II), Cu(II) and Cr(III) adsorbed was optimum at pH 7, 6 and 5 respectively. The optimum contact time for Cd(II) and Cu(II) was 120 min, while that for Cr(III) was 60 min. Study of the adsorption kinetics showed that the adsorption of Cd(II), Cu(II) and Cr(III) using polymer 2a followed kinetics model of Ho. For adsorbent 2b and 2c, the adsorption kinetics of Cd(II) and Cr(III) also followed kinetics model of Ho while for the Cu(II) followed Lagergren kinetic models. Isothermal studies showed that the adsorption of metal ions on all adsorbents tend to follow the Langmuir isotherm. The adsorption energies of the three adsorbents were higher than 23 kJ/mole and polymer 2c has the largest adsorption capacity for Cr(III).

The aim research is application of poly-5-allyl-calix[4]arene tetra carboxylic acid as adsorbent of heavy metal cations. Adsorption was carried out towards Pb(II), Cd(II) and Cr(III) ions in batch system. Several variables including pH, contact time and initial concentration of metal ions were determined. The optimum adsorption conditions were achieved at pH 6.0 for Cd(II) and Cr(III), while at pH 5.5 for Pb(II) ions. In addition, the optimum contact time of Pb (II), Cd(II) and Cr(III) ion adsorption were 180 min. The adsorption kinetics of Pb(II), Cd(II) and Cr(III) ions using the calixarene polymer adsorbent followed a pseudo 2nd order kinetics model, with adsorption rate constants of 2x10-2; 5x10-3, and 3.1x10-2 g mole-1 min-1, respectively. Furthermore, the adsorption isotherm of Pb(II) and Cd(II) ions tends to follow the Freundlich isotherm, whereas the adsorption of Cr (III) tends to follow the Langmuir isotherm. The adsorption capacity of Pb(II), Cd(II) and Cr(III) metal ions were 104.04, 61.78 and 228.69 μmole/g, with adsorption energy of 24.87; 21.62 and 31.07 KJ/mole, respectively.

A research has been conducted to synthesize thiomethylated-C-4-methoxyphenylcalix[4]resorcinarene using fennel oil as a starting material. The synthesis was carried out in four steps i.e. (1) oxidation of anethole to yield p-anisaldehyde, (2) HCl-catalyzed condensation of p-anisaldehyde with resorcinol, (3) chloromethylation of C-4-methoxyphenylcalix[4]resorcinarene with paraformaldehyde and HCl in the presence of ZnCl2 to yield tetrakis-chloromethyl-C-4-methoxyphenylcalix[4]resorcinarene, and (4) reaction of tetrakis-chloromethyl-C-4-methoxyphenylcalix[4]resorcinarene with thiourea followed by hydrolysis with sodium hydroxide solution to yield tetrakis-thiomethyl-C-4-methoxyphenylcalix[4]resorcinarene. The prepared compounds were characterized based on melting point, FT-IR, and NMR spectrometers. According to the analysis of 1H-NMR spectrometer, C-4-methoxyphenylcalix[4]resorcinarene and tetrakis-chloromethyl-C-4-methoxyphenylcalix[4]resorcinarene were observed in the chair or flattened partial cone conformation, while tetrakis-thiomethyl-C-4-methoxyphenylcalix[4]resorcinarene tend to exist in the crown or cone conformation.

A study has been conducted to synthesize a novel polypropylcalix[6]arene polymer using p-t-butylphenol as a starting material. It was of interest to investigate the capability of the polymer with a tunnel-like structure, as adsorbent to trap the heavy metal cation such as Cr3+. The synthesis was carried out in several steps i.e (1) formation of p-t-butylcalix[6]arene from p-t-butylphenol as a starting material, (2) treatment of p-t-butylcalix[6]arene with 4.95 equivalents of allyl bromide under alkaline conditions to yield p-t-butyl-37,40-diallyloxy-38,39,41,42-tetra-hydroxy-calix[6]arene, and (3) polymerization of p-t-butyl-37,40-diallyloxy-38,39,41,42-tetrahydroxycalix[6]arene by treatment with concentrated sulfuric acid to yield polypropyl-calix[6]arene. The application of polypropylcalix[6]arene for trapping Cr(III) was investigated by stirring the suspension of calixarene under variation of pH, time, and adsorbent mass. IR and 1H NMR spectra, showed that two allyl groups had been incorporated to the lower rim of the p-t-butylcalix[6]arene and the polymer was obtained as brownish green crystals with the melting point of 108-110 °C. The study also showed that the polypropylcalix[6]arene was able to trap Cr(III) cation. The optimum adsorption conditions were achieved at pH 5, contact time 60 min and concentration 12 mg/l for every 0,008 g of polymer.

A research has been conducted to synthesize tetra-p-propenyltetraestercalix[4]arene and tetra-p-propenyltetracarboxylicacidcalix[4] arene using p-t-butylphenol as a starting material. The synthesis was carried out in following stages, i.e (1) synthesis of p-t-butylcalix[4]arene from p-t-butylphenol, (2) debutylation of p-t-butylcalix[4]arene, (3) tetraallilation of 25,26,27,28-tetrahydroxycalix[4]arene with NaH and allilbromida in dry tetrahydrofuran, (4) Claissen rearrangement of 25,26,27,28-tetrapropenyloxycalix[4]arene, (5) esterification of tetra-p-propenyltetrahydroxycalix[4]arene, (6) hydrolisis of tetra-p-propenyltetraestercalix[4]arene. The all structures of products were observed by means of melting point, FTIR, and 1H-NMR spectrometers. Tetra-p-propenyltetraestercalix[4]arene compound was obtained as yellow liquid product in 55.08% yield. Tetra-p-propenyltetracarboxylicacidcalix[4]arene compound was obtained as white solid product with the melting point 135-137 °C at decomposed and in 70.05% yield. Keywords: calix[4]arene, Claissen rearrangement, esterification, hydrolisis

The effects to the extractability forwards Cr3+, Cd2+, and Pb2+ ions of de-tert-butylation and functionalization with amine groups at the upper rim of p-tert-butylcalix[4]arene had been studied by applied the p-tert-butylcalix[4]arene (1), tetrahydroxycalix[4]arene (2), and p-(amino)butoxycalixarene (3) compounds as extractants for the heavy metals ions. The extraction involved optimise of three parameters, i.e. pH, time, and concentration of extractants. The extraction degrees of the heavy metals ions at optimum conditions were compared each other to decide the effects. Compound 1 showed high extractability to Cr3+ and Pb2+ ions over Cd2+ ion, but compound 2 as the debutylated product of compound 1 showed low extractability to the all of the heavy metals ions. Compound 3 as product of etherification with butyl groups of the lower rim followed functionalization with amine groups of the upper rim of compound 1 showed high extractability to Pb2+, but low to Cr3+ and Cd2+. Pursuant to the facts it was concluded that debutylation of compound 1 to compound 2 causing decrease drastically of extractability to the heavy metals ions; functionalization of the upper with amine groups as ionophore (compound 3) causing increase of the extractability to Pb2+ ion and decrease of the extractability to Cr3+ with increasing of separation factor value β(Pb2+/Cr3+) from 1.74 by compound 1 to 48.00 by compound 3. By slope analysis, the extracted species and mechanisms of the extractions have been confirmed. Keywords: p-tert-butylcalix[4]arene, debutylation, p-(amino)butoxycalix[4]arene, extractability, heavy metals, extraction mechanisms.

The research on transport of Cr3+, Cd2+, Pb2+, and Ag+ through bulk liquid membrane using p-tert-butylcalix[4]arene-tetracarboxylic acid as ions carrier has been conducted. The aims of this research were to determine optimum condition, efficiency, and selectivity of transport of the ions carriers to those ions. Both optimum condition and efficiency of transport were obtained by determination of transported ions concentration with pH variation of source phase, ionic carrier concentration, nature of stripping agent in target phase, and transport time. The transport selectivity of ions carrier was obtained from experiments of equimolar mixture ions transport competition. Amount of Cr3+, Pb2+, Cd2+, and Ag+ transported across liquid membrane were about 6, 80, 84 and 87 % respectively after being transported for 48 h. The ion carrier was selective for both Pb2+ ion (separation factors are 9.6 for Ag+ ion, 1.9 for Cd2+ ion and infinite for Cr3+ ion) and Ag+ ion (separation factors are 1.8 for Cd2+ and infinite for both Pb2+ and Cr3+ ions). This system represents a proton-coupled transport with flow of protons in the opposite direction. Keywords: transport, p-tert-butylcalix[4]arene-tetracarboxylic acid, efficiency, selectivity, bulk liquid membrane, heavy metals

The study on transport of Cr(III), Cd(II), Pb(II), and Ag(I) through bulk liquid membrane using p-tert-butylcalix[4]arene-tetraethylester as ions carrier has been conducted. The aims of this work are to determine the optimum condition, efficiency, and selectivity of transport of the carriers for those ions. Both optimum condition and efficiency of transport were obtained by determination of the concentration of transported ions with variation of source phase pH, ion carrier concentration, the nature of stripping agent in the target phase, and transport time. The ion transport selectivity of ion carrier was obtained from the ions transport competition experiments using equimolar mixtures. The amount of Cr(III), Pb(II), Cd(II), and Ag(I that was transported across liquid membrane was about 0, 10, 10 and 50 % respectively after 24 hours, except for Pb(II) (32 hours). The ion carrier is selective for Ag(I) where separation factor to Cd(II) was 16.0, that to Pb(II) was 42.8, and that to Cr(III) was infinite. Keywords: transport, calix[4]arene, efficiency, selectivity, bulk liquid membrane, heavy metals

Derivatization of 5,11,17,23-tetra-t-butyl-25,26,27,28-tetrahydroxycalix[4]-arene to 5,11,17,23-tetra-amino-25,26,27,28-tetrabutoxycalix[4]arene compound via etherification, ipso nitration, and reduction reactions, respectively has been conducted. The etherification reaction was carried out by refluxed the mixture of 5,11,17,23-tetra-t-butyl-25,26,27,28-tetrahydroxy-calix[4]arene, 1-bromobutane, NaI, and NaH in solvent mixture of THF-DMF (10:1 v/v) and nitrogen atmosphere for 4 hours to resulted 5,11,17,23-tetra-t-butyl-25,26,27,28-tetrabutoxycalix[4]-arene 84% in yield; ipso nitration reaction was carried out by stirred the mixture of 5,11,17,23-tetra-t-butyl-25,26,27,28-tetrabutoxycalix[4]arene and HNO3 100% in solvent mixture of dichloromethane-acetic acid glacial (1:1 v/v) for 2 hours and than refluxed for 1 hour to resulted 5,11,17,23-tetra-nitro-25,26,27,28-tetra-butoxycalix[4]arene 50% in yield; and reduction reaction was carried out by refluxed the mixture of 5,11,17,23-tetra-nitro-25,26,27,28-tetrabutoxycalix[4]arene and SnCl2/HCl reductor in ethanol solvent for 6 hours to resulted 5,11,17,23-tetra-amino-25,26,27,28-tetrabutoxycalix[4]arene 67% in yield. In the etherification reaction, the conformation of calix[4]arene compound was converted from cone to partial cone; but in the followed reactions, i.e. nitration and reduction reactions, the conformation of calix[4]arene compounds were remain in partial cone. Keywords: aminobutoxycalixarene, conformation, etherification, ipso nitration, reduction

C-Methyl 4,10,16,22-tetramethoxycalix[4]arene has been synthesized from phenol. The reaction performed consisted of methylation of phenol, acetylation of methyl phenyl ether, reduction of p-methoxyacetophenone, and cyclization of p-methoxy-(1-hydroxyethyl)benzene to form C-methyl-4,10,16,22-tetramethoxycalix[4]-arene using BF3-methanol as the acid catalyst. Methylation of phenol was done by reacting phenol with solution of NaOH to generate sodium phenoxide salt. This mixture was strirred at reflux for 0.5 hours. Dimethyl sulphate was added and the reflux was continued for 2,5 hours. The product obtained was methyl phenyl ether, which was found as a colorless liquid in 99.0% yield. Acetylation of methyl phenyl ether was carried out in chloroform using acetic anhydride as the acetylating agent and anhydrous aluminium chloride as the catalyst. The addition of acetic anhydride and anhydrous aluminium chloride was done in two portions. The first portion was 0.967 g of acetic anhydride and 1.4 g of anhydrous aluminium chloride. The second portion was 0.54 g of acetic anhydride and 0.6 g of anhydrous aluminium chloride. The product obtained was found as a reddish yellow liquid in 69.6% yield. Reduction of p-methoxyacetophenone as the acetylation product was done using NaBH4 in ethanol at reflux for 2.5 hours. From this reaction, p-methoxy-(1-hydroxyethyl)benzene was obtained as a brown viscous liquid in 44.9% yield. Cyclization of p-methoxy(1-hydroxyethyl)benzene was done using BF3-methanol as the acid catalyst for two days at room temperature. The product obtained from this cyclization was found as a brown very viscous liquid in 87.3% yield. Identification of reaction products were carried out using Infra Red (IR) Spectrophotometer, Proton Nuclear Magnetic Resonance (1H NMR) spectrometer and Gas Chromatography-Mass spectroscopy (GC-MS). Keywords: synthesis, calix[4]arene, cyclization, and catalyst.

Quantitative Structure-Activity Relationship (QSAR) analysis of 1,10-phenantroline analogs as antimalarial drug has been conducted using atomic net charges (q) as predictors of their activity. Data of predictors are obtained from computational chemistry method using semi-empirical molecular orbital AM1 calculation. Antimalarial activities are taken as the activity of the drugs against plasmodium falciparum (FcM29-Cameroun) strain and are presented as the value of ln(1/IC50) where IC50 is an effective concentration inhibiting 50 % of the parasite growth. The results show that there is correlation between antiplasmodial activity and electronic structure as represented by a linear function of activity versus atomic net charges of N1, C7, C10, C14 atoms on the 1,10-phenanthroline skeleton and is expressed by : log IC50 = -3,4398 - 14,9050 qN1 - 8,5589 qC10 - 14,7565 qC7 + 5,0457 qC11 The equation is significant at 95% level with statistical parameters : n = 13; r = 0,96275; r2 = 0,92689; SE = 0,61578 and F (4,8) = 25,3556. Keywords: antimalarial drug; 1,10-phenanthroline; QSAR; antiplasmodial activity.

The synthesis of 6-nitro veratryl alcohol and 6-nitro veratraldoxim from vanilin which was required as intermediates for the preparation of C-9154 antibiotic derivatives was carried out. C-9154 antibiotic is a sufficiently potent antibiotic, but so far this is produced only in low yields through microbiological processes. The reaction steps performed were (1) methylation of vanilin, (2) nitration of the methylation product, (3) reduction of the corresponding nitro compound and (4) reaction of the nitration product with HO-NH2.HCl. Methylation of vanilin was conducted using dimethylsulfate and NaOH at 60 oC for 2 hours. Nitration of the methylation product was performed in 2 methods, i.e. using neat HNO3 and using a mixture of HNO3 and H2SO4 both at 5 oC for 2 hours. Reduction of the nitration product was conducted using NaBH4 either at room temperature and at reflux. Reaction of the nitration product with HO-NH2.HCl was carried out in ethanol 95% at 50 oC for 2 hours. The products were analyzed by means of TLC, GC, IR, 1H NMR and GC-MS spectrometers. The methylation of vanilin gave 87.7% yield of veratraldehyde which was found as a white crystal (m.p 43 oC). The nitration of veratraldehyde produced 6-nitro veratraldehyde observed as a yellow crystal having of m.p. 130 oC. Nitration using neat HNO3 gave a smaller yield (50.35%) of 6-nitro veratraldehyde than nitration with a mixture of HNO3 and H2SO4 (93.63%). Reduction of 6-nitro veratraldehyde using NaBH4 at room temperature and at reflux afforded 6-nitro veratryl alcohol which was found as brown crystal (m.p 123-127 oC) respectively in 13.47% and 56.61%. This reduction also produced 6-amino veratryl alcohol and 3,4-dimethoxy benzoic zcid as by products. 6-Nitro veratraldehyde reacts with HO-NH2.HCl to give 6-nitro veratraldoxim in 48.27% yield. Keywords: antibiotics, veratril alcohol, veratraldoxim vanilin

Fe-Ionic Imprinted Polymer (IIP) from polyeugenol as base polymer and polyethylene glycol diglycidyl ether (PEGDE) as cross-linking agent had been synthesized to adsorb Fe(III) from aqueous media. The non-imprinting material (NIP) and polyeugenol were used in the adsorption study as control. Synthesis work included polymerization, template uploading, crosslinking and template removal, optimized for different template ion upload pH and concentrations. The polymers were characterized by FTIR spectroscopy, XRD and SEM-EDX, followed by adsorption test to study the adsorption kinetics and isotherms for all adsorbents. Selective adsorption study of IIP was carried out using binary mixtures of Fe(III) and Cr(III), Pb(II), Cd(II). Experimental results showed that the optimum conditions for the synthesis was template upload pH of 3, Fe/polyeugenol ratio of 1 mg/g, while the optimum adsorption pH was 3. The adsorption mechanism of Fe(III) on all adsorbents was dominated by hydrogen bond formation. The adsorption kinetics followed the pseudo-second-order model while the equilibrium data was best explained by the Langmuir isotherm model. The adsorption capacity of Fe(III) on the IIP was 12.73 mg/g, higher than that of the other adsorbents. Results also show that IIP-Fe was more selective toward Fe than NIP by 2.69 (Cd), 1.66 (Cr) and 1.6 (Pb) fold, respectively.

Studies on the synthesis of polyurethane/silica modified epoxy polymer using 1,3-propanediol has been conducted. Synthesis of polymers made by reaction of tolonate and 1,3-propanediol (ratio NCO/OH=2.5) as the building blocks of polyurethane with diglycidyl ether bisphenol A (DGEBA) epoxy and catalyst dibutyltin dilaurate (DBTL).The total weight of the polyurethane used was 20% (w/w) of the total epoxy. Based on Fourier Transform Infrared (FTIR) and 1H-Nuclear Magnetic Resonance (1H-NMR) spectra indicated the existence of a new bond that is formed from the reaction of isocyanate group and hydroxyl group, where the hydroxyl groups derived from epoxy and 1,3-propanediol. The addition of silica (5, 10, and 15% w/w to epoxy) into the epoxy-modified polyurethane has been carried out through sol-gel reaction of tetraethyl orthosilicate (TEOS). The isocyanate conversion rate for the addition of silica 5, 10, and 15% are 95.69; 100, and 100%, respectively. The morphology and element identification by Scanning Electron Microscopy/Energy Dispersive X-Ray Analysis (SEM/EDX), showed that Si element has been successfully added in the polymer. From the tensile strength and elongation analysis, also thermal stability analysis using Thermal Gravimetric Analyzer (TGA), the increase of silica amount into the polyurethane modified epoxy did not significantly affect to thermal properties, but decrease the tensile strength of the polymer.

The present study was aimed to synthesize and evaluate sunscreen activity of C-methylcalix[4]resorcinaryl octacinnamate and C-methylcalix[4]resorcinaryl octabenzoate. The target compounds were synthesized in 2 steps. They were a synthesis of C-methylcalix[4]-resorcinarene via acid catalyzed the condensation of resorcinol and acetaldehyde by using HCl catalyst, followed by esterification using cinnamoyl chloride and benzoyl chloride. The characterization of the target compounds was performed by IR, 1H-NMR, 13C-NMR, and LC-MS spectrometers. The sunscreen activity test was conducted by spectroscopic method and MTT-assay. Commercial sunscreen p-amino benzoic acid (PABA) was used as a comparator to the MTT assay. The sunscreen activity test used spectroscopic showed that C-methylcalix[4]resorcinaryl octacinnamate and C-methylcalix[4]resorcinaryl octabenzoate can absorb the ultraviolet radiation between 280 and 320 nm (UV-B) with the maximum absorption at 290 nm (ε = 31.535 M-1 cm-1) and 282 nm (ε = 42.217 M-1 cm-1), respectively. The results of MTT-assay indicated that the IC50 of C-methylcalix[4]resorcinaryl octacinnamate, C-methylcalix[4]resorcinaryl octabenzoate and PABA are 12.006, 20.568 and 12.564 ppm, respectively, it means that the order of sunscreen activity is C-methylcalix-[4]resorcinaryl octacinnamate, PABA and C-methylcalix[4]resorcinaryl octabenzoate.

A new phosphonate modified silica (PMS) has been investigated for adsorption of Co(II), Ni(II), Cu(II), and Zn(II) in aqueous solution. The adsorbent was modified of silica by immobilizing aminoethyl dihydrogen phosphate (AEPH2) on 1,4-dibromobutane grafted silica. The physicochemical of the adsorbent was investigated using Fourier Transform Infra-red (FTIR) spectroscopy, X-ray Fluorescence (XRF), and N2 gas adsorption/desorption. The adsorption study was carried out in a batch system by mixing solution of metal ions at various pHs, contact times, and initial metal ion concentrations. The unadsorbed metals were determined by Flame Atomic Absorption Spectrophotometry (FAAS). Result of characterization showed that PMS has been successfully prepared. The product contained 45.99% (w/w) silica and 1.33% (w/w) phosphorous with surface area, pore volume, and pore size of 115.3 m2g-1; 0.7578 mLg-1; and 131.44 Å, respectively. Adsorption of metal ions on PMS occurred quite fast, less than 30 min. Modification of phosphonate on silica increased the adsorption capability, up to 8 times higher than that of unmodified silica, depending on metal ion type and pH solution. The capacity order of the metals adsorption was Cu(II)>Co(II)>Ni(II)>Zn(II). Based on the adsorption characteristic, the adsorbent is promising to be applied as a material for solid phase extraction of transition metal ions.

The hydration of α-pinene has been studied in the presence of Y-zeolite (Si/Al = 2.89) as a solid acid catalyst. The reaction was performed in batch reactor in isopropyl alcohol at various temperature and reaction time with magnetic stirrer. The acid catalyst hydration reaction of a-pinene yields a complex mixture of monoterpenes, alcohols and hydrocarbons. The selectivity of α-terpineol (the monocyclic alcohol) as main product was 59.20% with a conversion of 83.83% and the non alcoholic as the isomerization co-product as 30% after 60 min at 65 °C. The conversion and selectivity to α-terpineol increase significantly with in increase in temperature and reaction times.

The synthesis of 5-nitro-1,10-phenanthroline hydrate 2 derivatives from 1,10-phenanthroline monohydrate as starting material has been carried out. The 5-nitro-1,10-phenanthroline hydrate 2 was obtained through nitration reaction using H2SO4 and HNO3 as catalyst and reagent, respectively. Synthesis of (1)-N-alkyl-6-nitro- and (1)-N-benzyl-6-nitro-1,10-phenanthrolinium have been prepared using dimethyl sulphate (DMS), diethyl sulphate (DES), benzyl chloride, benzyl bromine, and benzyl iodide. The reagents of benzyl bromine, and benzyl iodide were synthesized from benzyl chloride using NaBr in ethanol absolute and NaI in acetone, respectively. The five compounds of 5-nitro-1,10-phenanthroline hydrate 2 derivatives were conducted to evaluate the in vitro antiplasmodial activity. The in vitro antiplasmodial was evaluated on strains of Plasmodium falciparum FCR-3 resistant chloroquine and D10 sensitive chloroquine. The 50% inhibition concentration (IC50) of the five compounds ranged from 2.41±1.41 to 0.07±0.01 μM. The results showed that the (1)-N-benzyl-6-nitro-1,10-phenanthrolinium iodide had highest antiplasmodial activity.