Harno Dwi Pranowo
Faculty of Mathematics and Natural Sciences, University Gadjah Mada, Yogyakarta

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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 (71.575 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

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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.
Metilasi Asam Galat Menggunakan Agen Metilasi Dimetil Sulfat (DMS) atau Dimetil Karbonat (DMC) Yulinda, Lolita Ramya; Wahyuningsih, Tutik Dwi; Pranowo, Harno Dwi
Berkala Ilmiah MIPA Vol 23, No 2 (2013)
Publisher : FMIPA UGM

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Abstract

Methylation of gallic acid has been conducted by the use of dimethyl sulfate (DMS) or dimethyl carbonate (DMC)  as methylating agents. Methylation of gallic acid using DMS was carried out by various methods, i.e. mild condition at ambient temperature, reflux and sonication. The best method was achieved by methylation under reflux yielded 48.9% efficiency of 3,4,5-trimethoxybenzoic acid.            Methylation of gallic acid with DMC was performed with several variations on the type and amount of base and phase transfer catalyst (PTC). In addition, green methods sonochemistry and microwave irradiation have also been done. Unfortunately, the methylation of gallic acid failed to give 3,4,5-trimethoxybenzoic acid. Methylation of gallic acid using green reagent DMC gave high yield at mole ratio of gallic acid : DMC : K2CO3 : KI : PTC of tetrabuthyl ammonium bromide (TBAB) = 5 : 320 : 20 : 5 : 8 under reflux for 10 hours and produced 75.96% of methyl 3,4,5-trimethoxybenzoate. Atom economy of gallic acid methylation method using DMC is 37.95%, which is not very different from that of DMS method (30.47%). However, the methylation method using DMC produced by products, which  have the lower toxicity compared to that of methylation using DMS.
PEMANFAATAN GLISEROL DARI PRODUK SAMPING BIODIESEL UNTUK SINTESIS SENYAWA 2,3-DIBROMO PROPANOL Megawati, Dewi Sinta; Jumina, Jumina; Pranowo, Harno Dwi
Islamic Journal of Pharmacy Vol 1, No 2 (2015): Jurnal Farma Sains Vol. 1 (2) Juli 2015
Publisher : Islamic Journal of Pharmacy

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Telah dilakukan sintesis senyawa 2,3-dibromo propanol menggunakan bahan awal gliserol hasil isolasi produk samping pembuatan biodiesel. Peningkatan yang cepat dalam produksi biodiesel diperkirakan akan mengakibatkan surplus gliserol. Penggunaan gliserol sebagai bahan awal bertujuan meningkatkan nilai ekonomis dari gliserol itu sendiri. Gliserol dengan  rendemen 88,7 % telah diisolasi dari produk samping pembuatan biodiesel melalui reaksi transesterifikasi trigliserida dalam minyak sawit menggunakan katalis basa KOH. Selanjutnya, gliserol didehidrasi dengan asam format untuk mendapatkan senyawa alil alkohol melalui metode destilasi pada 195-260 0C. Sintesis senyawa 2,3-dibromo propanol dicapai melalui brominasi alil alkohol pada -2-0 0C menggunakan pelarut khloroform. Karakterisasi struktur dilakukan menggunakan spektrometer IR, 1H-NMR, dan GC-MS. Pada penelitian ini, alil alkohol yang diperoleh melalui metode destilasi memiliki rendemen sebesar 44,78 % dan reaksi brominai alil alkohol menghasilkan senyawa  2,3-dibromo propanol dengan rendemen 80,3 % yield.
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

Abstract

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

Abstract

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.
EXTRACTION OF STRONTIUM(II) BY CROWN ETHER: INSIGHTS FROM DENSITY FUNCTIONAL CALCULATION Hadisaputra, Saprizal; Pranowo, Harno Dwi; Armunanto, Ria
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 (740.602 KB) | DOI: 10.22146/ijc.21332

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The structures, energetic and thermodynamic parameters of crown ethers with different cavity size, electron donating/withdrawing substituent groups and donor atoms have been determined with density functional method at B3LYP level of theory in gas and solvent phase. Small core quasi-relativistic effective core potentials was used together with the accompanying SDD basis set for Sr2+ and DZP basis set was used for crown ether atoms. Natural bond orbital (NBO) analysis was evaluated to characterize the distribution of electrons on the complexes. The interaction energy is well correlated with the values of Strontium charge after complexation, the second order interaction energies (E2) and HOMO-LUMO energy gab (∆Egab). The interaction energy and thermodynamics parameters in gas phase are reduced in solvent phase as the solvent molecules weaken the metal-crown ether interaction. The thermodynamic parameters indicated that less feasibility to extract Sr2+ ion directly from pure water without presence of organic solvent. The theoretical values of extraction energy for Sr(NO3)2 salt from aqueous solution in different organic solvent is validated by the experimental trend. This study would have strong contribution in planning the experiments to the design of specific host ligand and screening of solvent for extraction of metal ion.
Structure and Dynamics of Zr4+ in Aqueous Solution: An Ab Initio QM/MM Molecular Dynamics Study Suwardi, Suwardi; Pranowo, Harno Dwi; Armunanto, Ria
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 (443.324 KB) | DOI: 10.22146/ijc.21209

Abstract

A QM/MM molecular dynamics (MD) simulation has been carried out using three-body corrected pair potential to investigate the structural and dynamical properties of Zr4+ in dilute aqueous solution. Structural data in the form of radial distribution function, coordination number distribution, and angular distribution function were obtained. The results indicate eight water molecules coordinate to zirconium ion and have two angles of O-Zr4+-O, i.e. 72.0° and 140.0° with a Zr4+-O distance of 2.34 Å. According to these results, the hydration structure of Zr4+ ion in water was more or less well-defined square antiprismatic geometry. The dynamical properties have been characterized by the ligand’s mean residence time (MRT) and Zr4+-O stretching frequencies. The inclusion of the three-body correction was important for the description of the hydrated Zr4+ ion, and the results indicated in good agreement with experimental values.