Articles

CYCLISATION-ACETYLATION KINETIC OF (R)-(+)-CITRONELLAL BY ZN2+–NATURAL ZEOLITE AS SOLID SOLVENT CATALYST Cahyono, Edy; Muchalal, Muchalal; Triyono, Triyono; Pranowo, Harno Dwi
Indonesian Journal of Chemistry Vol 10, No 2 (2010)
Publisher : Universitas Gadjah Mada

Show Abstract | Download Original | Original Source | Check in Google Scholar | DOI: 10.22146/ijc.21459

Abstract

Kinetic in cyclisation-acetylation of (R)-(+)-citronellal with acetic anhydride was investigated over Zn2+-Natural zeolite (Zn2+-Natzeo) as a catalyst. (R)-(+)-citronellal has been isolated from citronella oil by fractional distillation under reducing pressure. Enantioselective capillary GC on a Supelco ?-DEX 225 column has been used for analysis the enantiomers ratio of citronellal. Catalyst Zn2+-Natzeo has prepared through acid activation of natural zeolite from Malang using HF 1% and HCl 6 M, followed by ion-exchange with 3 M NH4Cl and calcination at 450 °C for 1 h under nitrogen to obtained H-natural zeolite (H-Natzeo). H-Natzeo was modified to Zn2+-Natzeo by ion exchange with 0.1 M ZnCl2. Cyclisation-acetylation reaction was carried out by heating (R)-(+)-citronellal (CIT), acetic anhydride (AA), and 1 g catalyst in glass batch reactor with vigorous stirring at 80 °C. Molar ratio CIT/AA that used, i.e. 0.25; 0.5; 1.0; 1.2 and 1.5. As the reaction proceeded, 1 mL sample was taken off at 10; 20; 30; 60; 120; 180 min and extracted using n-hexane for every molar ratio. Structure analysis of product was conducted by GC-MS. Kinetic of the cyclisation-acetylation reaction was analyzed according to the Langmuir-Hinshelwood mechanism. Increasing molar ratio of CIT/AA will decrease the isopulegyl acetate (IPA) and neo-isopulegyl acetate (NIPA) formation. Rate constant of cyclisation-acetylation reaction catalyzed by Zn2+-Natzeo was 30.964-47.619 mmol(min. g cat)-1 at 80 °C, 30 min and the ratio  adsorption equilibrium constant KCIT/KAA was 7.09.
THEORETICAL STUDY OF THE EFFECT OF WATER MOLECULE ADDITION ON THE CONFORMATION OF SUBSTITUTED DIBENZO-18-CROWN-6 ETHER IN ITS COMPLEXATION WITH NA+ CATION USING SEMI EMPIRICAL METHOD MNDO/D Pranowo, Harno Dwi; Siregar, Tuti Hartati; Mudasir, Mudasir
Indonesian Journal of Chemistry Vol 3, No 2 (2003)
Publisher : Universitas Gadjah Mada

Show Abstract | Download Original | Original Source | Check in Google Scholar | DOI: 10.22146/ijc.21894

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The effect of water molecule addition into modeling structure of complex of substituted dibenzo-18-crown-6 ether with metal ion Na+ was studied. The aim of this research is to find information about geometrical conformation of substituted DB18C6 and its selectivity to complex/coordinate metal ion Na+ in the presence of water molecule. In this research semi empirical method was used for calculation. To find the best conformation, trial and error experiments were conducted using semi empirical method available in HyperChem 6.0, finally MNDO/d method was selected. The result of geometry optimization showed that addition of water molecule improve the stability of the conformation of substituted DB18C6 and increase the selectivity of this compound to complex metal ion Na+. The presence of electron-withdrawing substituents decreased the binding energy while that of electron-donating one increase the binding energy (value of DE more negative). Cavity radii of DB18C6 in the presence of water molecule extended from 2.3 Å to 2.6 Å. This figure is almost similar to that of experimental data.
SOLVATION STRUCTURE DETERMINATION OF NI2+ ION IN WATER BY MEANS OF MONTE CARLO METHOD Arindah, Tutik; Setiaji, Bambang; Pranowo, Harno Dwi
Indonesian Journal of Chemistry Vol 2, No 3 (2002)
Publisher : Universitas Gadjah Mada

Show Abstract | Download Original | Original Source | Check in Google Scholar | DOI: 10.22146/ijc.21915

Abstract

Determination of solvation structure of Ni2+ ion in water has been achieved using Monte Carlo method using canonic assemble (NVT constant). Simulation of a Ni2+ ion in 215 H2O molecules has been done under NVT condition (298.15 K). The results showed that number of H2O molecules surround Ni2+ ion were 8 molecules in first shell and 17 molecules in second shell, interaction energy of Ni2+-H2O in first shell was -68.7 kcal/mol and in second shell was -9.8 kcal/mol, and there were two angles of O-Ni2+-O, i.e. 74o and 142o. According to those results, the solvation structure of Ni2+ ion in water was cubic antisymetric.
THE PREFERENTIAL STRUCTURE OF CO2+ SOLVATION IN AQUEOUS AMMONIA SOLUTION DETERMINING BY MONTE CARLO SIMULATION Kusumawardani, Cahyorini; Purtadi, Sukisman; Partana, Crys Fajar; Pranowo, Harno Dwi; Mudasir, Mudasir
Indonesian Journal of Chemistry Vol 7, No 1 (2007)
Publisher : Universitas Gadjah Mada

Show Abstract | Download Original | Original Source | Check in Google Scholar | DOI: 10.22146/ijc.21710

Abstract

A Monte Carlo simulation was performed for Co2+ in 18.6 % aqueous ammonia solution at a temperature of 293.16 K, using ab initio pair potentials and three-body potentials for Co-H2O-H2O, Co-NH3-NH3 and Co-H2O-NH3 interactions. The first solvation shell consists average of 2.9 water and 3.2 ammonia molecules, and the second shell of 10.4 water and 11.2 ammonia molecules. The structure of the solvated ion is discussed in terms of radial distribution functions, angular distributions and coordination number.
CATALYTIC ACTIVITIES OF FE3+- AND ZN2+-NATURAL ZEOLITE ON THE DIRECT CYCLISATION-ACETYLATION OF (R)-(+)-CITRONELLAL Cahyono, Edy; Muchalal, Muchalal; Triyono, Triyono; Pranowo, Harno Dwi
Bulletin of Chemical Reaction Engineering & Catalysis 2014: BCREC Volume 9 Issue 2 Year 2014 (SCOPUS Indexed, August 2014)
Publisher : Department of Chemical Engineering - Diponegoro University

Show Abstract | Download Original | Original Source | Check in Google Scholar | Full PDF (541.477 KB) | DOI: 10.9767/bcrec.9.2.5936.128-135

Abstract

Characterisation and catalytic ativities investigation of modified natural zeolite on cyclisation acetylation reaction of (R)-(+)-citronellal was performed. The experimental work involved isolation of (R)-(+)-citronellal from Java Citronella oil (Cymbopogon winterianus) by vacuum fractional distillation, determination of its enantiomer, preparation and characterisation of different catalysts i.e. H-natural zeolite (H-Za), Fe3+-natural zeolite (Fe3+-Za), and Zn2+-natural zeolite (Zn2+-Za), followed by examination of catalytic activity and selectivity. Isolated citronellal contained 88.21% ee of (R)-(+)-citronellal. The main products of cyclisation-acetylation of (R)-(+)-citronellal was IPA (isopulegyl acetate) and NIPA (neo-isopulegyl acetate). Although the highest yield of IPA and NIPA was obtained by Fe3+-Za catalyst (78.69%) at 80oC and 120 min, the stereoselectivity of Fe3+-Za slightly lower than that of Zn2+-Za. Structure elucidation of citronellal and products was carried out by means of GC and GC-MS. Lewis acidity plays the role of acetyl ionic formation from acetic anhydride. The Activity and stereoselectivity of catalysts depended on Lewis acidity and cation distribution on the catalyst surface. © 2014 BCREC UNDIP. All rights reservedReceived: 18th December 2013; Revised: 9th April 2014; Accepted: 17th April 2014[ How to Cite: Cahyono, E., Muchalal, M., Triyono, T., Pranowo, H.D. (2014). Catalytic Activities of Fe3+- and Zn2+-Natural Zeolite on the Direct Cyclisation-Acetylation of (R)-(+)-Citronellal. Bulletin of Chemical Reaction Engineering & Catalysis, 9 (2): 128-135. (doi:10.9767/bcrec.9.2.5936.128-135) ][ Permalink/DOI: http://dx.doi.org/10.9767/bcrec.9.2.5936.128-135 ] 
THE KINETIC OF CYCLIZATION-ACETYLATION (R)-(+)-CITRONELLAL WITH ANHYDRIDE ACETIC ACID WHICH CATALYZED OF Zn2+-NATURAL ZEOLITE Cahyono, Edy; Muchalal, M.; Triyono, Triyono; Pranowo, Harno Dwi
Jurnal Zeolit Indonesia Vol 8, No 1 (2009)
Publisher : Jurnal Zeolit Indonesia

Show Abstract | Download Original | Original Source | Check in Google Scholar | Full PDF (131.024 KB)

Abstract

Reaction kinetic of acetylation-cyclization (R)- (+)-citronellal with acetic acid anhydride which catalyzed Zn2+-zeolite (Zn2+-Za) was analyzed by Langmuir- Hinshelwood Models. (R)-(+)-citronellal isolated from lemongrass oil with fractionation distillation reduced pressure and analyzed anantiomer ratio with GC chiral column β- DEX 225. Catalyst preparation of Zn2+-Za conducted by acid activation on natural zeolite Malang 100 mesh using 1% HF and 6 M HCl, then soaked on 0,1 M NH4Cl. Calcination was done at 450oC during 1 hour with N2 flow to achieved H-natural zeolite (HZa). Cation exchange H-Za with 0,1 M ZnCl2 conducted to obtain Zn2+-natural zeolit (Zn2+-Za). Reactions of Cyclization-acetylation (R )-(+)- citronellal using a catalyst of Zn2+-Za was done by varying molar ratio of (R )-(+)- citronellal with acetic acid anhydride, namely 0.25, 0.5, 1.0; 1 , 25; 1.5. During the reaction, into system, samples were taken each 1 mL of reaction with duration 10, 20, 30, 60, 120, 180 minutes. Reaction product was extracted with n-hexana. Structure elucidation was done by GC-MS, FTIR spectrophotometer, and 1H-NMR spectrometer. The result showed a greater molar ratio (R)-(+)-citronellal against quantity of acetic acid anhydride acetic, pulegil total was decline. Acetylation-cyclization catalyzed with Zn2+-Za on duration of 30 minutes and 80°C has k of 30.964 to 47.619 mmol (minute.gram catalyst)-1 and KSIT/KAA of 7.09.
The Keto-Enol Tautomerism of Curcumin and Some 4-substituted Curcumin Derivatives : A Theoretical Study Based on Computational Chemistry Approach Istyastono, Enade Perdana; Margono, Supardjan A.; Pranowo, Harno Dwi
INDONESIAN JOURNAL OF PHARMACY Vol 14 No 3, 2003
Publisher : Faculty of Pharmacy Universitas Gadjah Mada, Yogyakarta, Skip Utara, 55281, Indonesia

Show Abstract | Download Original | Original Source | Check in Google Scholar | Full PDF (277.263 KB) | DOI: 10.14499/indonesianjpharm0iss0pp107-113

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Heat formation (DHf) for the enol and diketo tautomers of curcumin and some 4-substituted curcumin derivatives has been studied using semiempirical AM1 quantum-chemical calculations. The calculations on curcumin, 4-methylcurcumin, 4-ethylcurcumin, 4-npropylcurcumin, 4-isopropyl-curcumin, 4-n-butylcurcumin, and 4-benzylcurcumin showed that the more steric hindrance resulted from the subtituents, the more stable they were in the form of diketo tautomers than enol tautomers. Whereas, calculations on 4-phenylcurcumin, 4-(o-methoxyphenyl)-curcumin, and 4-(p-methoxyphenyl) curcumin showed that though steric hindrance influenced the keto-enol tautomerism, they were found more stable in the form of enol tautomers. This phenomenon was estimated to be related with conjugation effect of the aromatic groups with the enol moiety of the main bone structure.Keywords : 4-Substituted curcumin, the keto-enol tautomerism, AM1, semiempirical calculations.
SYNTHESIS AND CYTOTOXIC ACTIVITY OF CHALCONE DERIVATIVES ON HUMAN BREAST CANCER CELL LINES Harmastuti, Nuraini; Herowati, Rina; Susilowati, Dyah; Pranowo, Harno Dwi; Mubarika, Sofia
Indonesian Journal of Chemistry Vol 12, No 3 (2012)
Publisher : Universitas Gadjah Mada

Show Abstract | Download Original | Original Source | Check in Google Scholar | Full PDF (302.71 KB) | DOI: 10.22146/ijc.21340

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Chalcone, an α,β-unsaturated ketone, has been shown have many biological activities such as anticancer and antifungi. This research was conducted to synthesize the chalcone derivatives and to obtain their cytotoxic activity on human cervix cancer cell lines. Synthesis of chalcone and its derivatives, 4II-methylchalcone, 4II-methoxychalcone, and 3II,4II-dichlorochalcone was carried out using starting materials of benzaldehide and acetofenon, p-methylacetophenone, p-methoxyacetophenone, as well as m,p-dichloroacetophenone through Claisen Schmidt condensation catalized by NaOH in ethanol at 15 °C. The purity of synthesized compounds were analyzed by thin layer chromatography, melting range, and gas chromatography. Structure elucidations were conducted by UV spectrophotometer, IR spectrometer, 1H-NMR spectrometer, as well as mass spectrometer. Cytotoxic activities were determined by 3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazolium bromide (MTT) microculture tetrazolium viability assay. The results showed that chalcone and derivatives compounds have been able to be synthesized and purified and had the same structure as a predicted structure. Chalcone had highest cytotoxic activity compared to that of its derivatives, with the IC50 values of chalcone, 4II-methylchalcone, 4II-methoxychalcone, and 3II,4II-dichlorochalcone were 9.49, 14.79, 11.48, and 24.26 µg/mL respectively. It was concluded that methyl, methoxy as well as chlorine substitution at 3 II and 4II position decrease the cytotoxic activity of chalcone.
Two Isophalerin Compounds from Ethyl Acetate of Leave and Fruit of Mahkota Dewa (Phaleria macrocarpa (Scheff.) Boerl.) and Its Antibacterial Activity Susilawati, Susilawati; Matsjeh, Sabirin; Pranowo, Harno Dwi; Anwar, Chairil
Indonesian Journal of Chemistry Vol 15, No 2 (2015)
Publisher : Universitas Gadjah Mada

Show Abstract | Download Original | Original Source | Check in Google Scholar | Full PDF (396.885 KB) | DOI: 10.22146/ijc.21212

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Mahkota dewa plant (Phaleria macrocarpa (Scheff.) Boerl.) which is belong to family of Thymelaeaceae is one of Indonesias traditional medicines. The aim of this research is to isolate secondary metabolites from ethyl acetate extract of leave and fruit of mahkota dewa and to determine the molecular structure of isolated compounds using spectroscopic method and to know the antibacterial activity of the isolated compound. Sample was extracted with methanol, concentrated then extracted by n-hexane, chloroform and ethyl acetate. The compounds were separated and purified with column chromatography. The compound 1 was isolated from ethyl acetate extract of leave as white needle amorphous solid as 45 mg. The compound was identified by spectroscopic as 4,6-dihydroxy-4’-methoxybenzophenon-2-O-β-D-glucopyranoside and named isophalerin B. From the test results of antibacterial activity showed that the compound 1 (10 mg/mL) in ethanol has a weak activity against the bacteria S. aureus and E. coli. The compound 2 was isolated from ethyl acetate extract of fruit as peach needle crystal as 10 mg. The compound was identified by spectroscopic as 4,6-dihydroxy-4’-methoxybenzophenon-2-O-α-D-glucopyranoside and named isophalerin A.
Theoretical Study on the Extraction of Alkaline Earth Salts by 18-Crown-6: Roles of Counterions, Solvent Types and Extraction Temperatures Hadisaputra, Saprizal; Canaval, Lorenz R; Pranowo, Harno Dwi; Armunanto, Ria
Indonesian Journal of Chemistry Vol 14, No 2 (2014)
Publisher : Universitas Gadjah Mada

Show Abstract | Download Original | Original Source | Check in Google Scholar | Full PDF (576.723 KB) | DOI: 10.22146/ijc.21259

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The roles of counterions, solvent types and extraction temperatures on the selectivity of 18-crown-6 (L) toward alkaline earth salts MX2 (M = Ca, Sr, Ba; X = Cl-, NO3-) have been studied by density functional method at B3LYP level of theory in gas and solvent phase. In gas phase, the chloride anion Cl- is the preference counterion than nitrate anion NO3-. This result is confirmed by the interaction energies, the second order interaction energies, charge transfers, energy difference between HOMO-LUMO and electrostatic potential maps. The presence of solvent reversed the gas phase trend. It is found that NO3- is the preference counterion in solvent phase. The calculated free energies demonstrate that the solvent types strongly change the strength of the complex formation. The free energies are exothermic in polar solvent while for the non polar solvent the free energies are endothermic. As the temperature changes the free energies also vary where the higher the temperatures the lower the free energy values. The calculated free energies are correlated well with the experimental stability constants. This theoretical study would have a strong contribution in planning the experimental conditions in terms of the preference counterions, solvent types and optimum extraction temperatures.