, N.S. Antara 1, I.M.M. Wijaya1, I.W. Arnata1 and I.W.W.P. Putra1

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HOME ABOUT US EDITORIAL BOARD SUBSCRIPTION ABSTRACTED CONTACT PUBLICATION PROCESS MANUSCRIPT SUBMISSION Rasayan J. Chem. ISSN: 0974-1496(Print) ISSN:

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RASAYAN means Chemical, which is an incredibly reactive and self explanatory term in itself. RASAYAN is an open access as well as print journal and widely covers all branches of Chemistry including : Organic, Inorganic, Physical, Analytical, Biological, Pharmaceutical, Industrial, Environmental, Agricultural & Soil, Petroleum, Polymers,Nanotechnology, Green Chemistry, Forensic, Phytochemistry, Synthetic Drugs, Computational, as well as Chemical Physics and Chemical Engineering. In online version of RASAYAN all figures and photographs are colored with printable clarity.

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HOME ABOUT US EDITORIAL BOARD SUBSCRIPTION ABSTRACTED CONTACT US PUBLICATION PROCESS MANUSCRIPT SUBMISSION Rasayan J. Chem.

ISSN: 0974-1496(Print) ISSN: 0976-0083(Online) CODEN: RJCABP

Frequency: March, June, September & December

Current Issue

Volume 13 Number 2, April - June (2020)

ACUTE TOXICITY TEST AND HISTOLOGICAL DESCRIPTION OF ORGANS AFTER GIVING NANO HERBAL ANDALIMAN (Zanthoxylum acanthopodium)

Putri C. Situmorang , Syafruddin Ilyas, Salomo Hutahaean , Rosidah and Risma D. Manurung Rasayan J. Chem, 13 (2), 780- 788 (2020)

Keywords:Acute Toxicity, Andaliman, Brine Shrimp Lethality, LD50, Nanoherbal

DOI:http://dx.doi.org/10.31788/RJC.2020.1325621

FORMULATION AND EVALUATION OF LOTION AND CREAM OF NANOSIZED CHITOSAN-MANGOSTEEN (Garcinia mangostana L.) PERICARP EXTRACT

N. M. Saptarini and G. Hadisoebroto Rasayan J. Chem, 13 (2), 789- 795 (2020)

Keywords:Formulation Stability, Irritancy Test, Preference Test, Garcinia mangostana L., Nanosized Particle.

CHEMICAL CONSTITUENTS AND ANTIOXIDANT ACTIVITY OF Salix tetrasperma ROXB F. Utari, A. Itam, Syafrizayanti, and M. Efdi

Rasayan J. Chem, 13 (2), 796- 802 (2020)

Keywords:Salix tetrasperma Roxb, NMR, Antioxidant Activity, DPPH Method

ONE-STEP SYNTHESIS OF THERMALLY STABLE SOLID MOLYBDENUM BLUE USING BORON PHOSPHATE P. Ratheshkumar , S. Induja , R. Ravishankar and P.S. Raghavan

Rasayan J. Chem, 13 (2), 803- 809 (2020)

Keywords:Molybdenum Blue, BPO4 Stabilized, Polymolybdates, Selective Sulfoxidation.

THE EFFECT OF MOLYBDENUM DISULFIDE NANOPARTICLES AND SODIUM DODECYL SULFATE ADDITION TOWARDS WEAR PROTECTION PROPERTIES FROM THE SAE 10W-30 STANDARD LUBRICANTS

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Susilawati, M. Hanifuddin and U. Saragih Rasayan J. Chem, 13 (2), 810- 816 (2020)

Keywords:Molybdenum Disulfide (MoS2) Nanoparticles, Sodium Dodecyl Sulphate (SDS), Four-ball Scar Diameter, High- Frequency Reciprocating Rig (HFRR).

CHARACTERIZATION OF NANOCURCUMINOID FROM ETHANOL EXTRACT OF Curcuma Xanthorrhiza RHIZOME LOADED BY CHITOSAN AND ALGINIC AND ITS ANTIOXIDANT ACTIVITY TEST

S. Atun, Y. Dewi and N. Aznam Rasayan J. Chem, 13 (2), 817- 825 (2020)

Keywords:Alginic Canocurcuminoid, Antioxidant, Chitosan Nanocurcuminoid, Curcuma xanthorrhiza

INHIBITORY ACTIVITY OF THE ACTIVE COMPOUND OF ETHYL ACETATE FRACTION OF TAMOENJU (Hibiscus surattensis L.) LEAVES AGAINST α-GLUCOSIDASE AND DIPEPTIDYL PEPTIDASE-4 ENZYMES

Yuliet, EY Sukandar , Krisyanti Budipramana, IK Adnyana Rasayan J. Chem, 13 (2), 826- 835 (2020)

Keywords:?-Glucosidase, Antidiabetic, Dipeptidyl peptidase-4, Kaempferol, Tamoenju, Hibiscus surattensis L.

A HIGHLY SELECTIVE AND SENSITIVE ANALYTICAL TECHNIQUE FOR THE DETERMINATION OF ISOMALTULOSE IN PRESENCE OF ITS PROCESS RELATED IMPURITIES BY CAPILLARY ELECTROPHORESIS Sri Rama Krishna Surapureddi, Kunta Ravindhranath, Krishnna Darnasi and Suhashini Ramen

Rasayan J. Chem, 13 (2), 836- 844 (2020)

Keywords:Isomaltulose /Palatinose, Capillary Electrophoresis Analysis, Disaccharide.

ADSORPTION OF THE ANIONIC DYE OF CONGO RED FROM AQUEOUS SOLUTION USING A MODIFIED NATURAL ZEOLITE WITH BENZALKONIUM CHLORIDE

D. W. Astuti, N. H. Aprilita and M. Mudasir Rasayan J. Chem, 13 (2), 845- 853 (2020)

Keywords:Adsorption, Surfactant-modified Zeolite, Benzalkonium Chloride, Congo Red

NbCl5-AgClO4 AS AN EFFECTIVE, SYNERGETIC CATALYTIC SYSTEM FOR THE SYNTHESIS OF FULLY SUBSTITUTED PYRAZOLES

Kailas R. Kadam , Narendra R. Kamble, and Vinod T. Kamble Rasayan J. Chem, 13 (2), 854- 859 (2020)

Keywords:Fully Substituted Pyrazoles, Niobium Pentachloride, Silver Perchlorate, Combined Catalytic System.

AN AMMONIA OPTICAL SENSOR SILCA MIROSPHERES DOPED WITH NICKEL(II) ION AND REFLECTANCE TRANSDUCTION

A. Ulianas, O. Andini , Mawardi , Ramli and T. Ling Ling Rasayan J. Chem, 13 (2), 860- 867 (2020)

Keywords:Optical Sensor, Silica Microsphere, Reflectance, Transduction, Sensor Response

Rasayan journal of chemistry http://rasayanjournal.co.in/current-issue.php

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OPTIMIZING PROCESS CONDITION FOR AMIDIFICATION OF STEARIC ACID AND UREA USING RESPONSE SURFACE METHODOLOGY

Z. Masyithah, M. Syukri , M.Ashari , N. Annis and A. Ginting Rasayan J. Chem, 13 (2), 868- 875 (2020)

Keywords:Stearamide, Zirconium Tetrachloride, Amidification, Response Surface Methodology.

THE BEHAVIOURAL ATTRIBUTES ABOUT A COMPRESSION IGNITION ENGINE POWERED WITH DIESEL AND Artocarpus heterophyllus METHYL ESTER BLENDS

T. Nambaya Charyulu, P. Naveenchandran , E. Raja and R. N. Babu Rasayan J. Chem, 13 (2), 876- 886 (2020)

Keywords:Artocarpus heterophyllus Seeds, Jackfruit Seeds, Artocarpus heterophyllus Methyl Ester, Transesterification, Thermophysical Properties

PROGRESS IN ELECTRICAL AND OPTICAL PROPERTIES OF VANADIUM IONS DOPED (PVA+ZnO) POLYMER FILMS

Ch. Rani, M. Hemalatha , S. Hima Bindu and Ch. Linga Raju Rasayan J. Chem, 13 (2), 887- 897 (2020)

Keywords:Magnetic Stirrer, Distilled Water, Polyvinyl Alcohol, Zinc Oxide, Vanadium Sulphate.

IDENTIFICATION AND ANALYSIS OF MAJOR ELEMENTS IN INDONESIAN HERBAL MEDICINE USING LASER- INDUCED PLASMA SPECTROSCOPY

A.Khumaeni , B.S. Hartadi, A.Y. Wardaya, H. Sugito and W.S. Budi Rasayan J. Chem, 13 (2), 898 - 902 (2020)

Keywords:Herbal Medicine, Laser-induced Breakdown Spectroscopy, Plasma Spectroscopy.

INVESTIGATION OF BIVALVE MOLLUSCAN SEASHELLS FOR THE REMOVAL OF CADMIUM, LEAD AND ZINC METAL IONS FROM WASTEWATER STREAMS

Ch. Mahendra , R.R. Sivakiran, K.A. Badrinarayana, Lakshmi Priya, Shivani Raj and M. Mamatha Rasayan J. Chem, 13 (2), 903- 914 (2020)

Keywords:Heavy Metal, Adsorption, Low-cost Materials

SILVER DOPING EFFECT ON ANTIBACTERIAL ACTIVITIES OF CADMIUM OXIDE NANOPARTICLES J. Christina Rhoda, M. Giruba , S. Chellammal, K. Ravichandran and C. Sivaraj

Rasayan J. Chem, 13 (2), 915 - 919 (2020)

Keywords:Cadmium Oxide, Antibacterial Effects, Zone of Inhibition, Silver, Well Diffusion Method.

A REVIEW ON PROCESS PARAMETERS OF VARIOUS PROCESS INTENSIFICATION TECHNIQUES FOR ETHYL ACETATE PRODUCTION

Ganesh N. Patil and Nirmala Gnanasundaram Rasayan J. Chem, 13 (2), 920- 933 (2020)

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Keywords:Ethyl acetate, Reactive Distillation, Reactive Dividing Wall Column, Process Intensification

IN-VITRO ANTICANCER ACTIVITY AND DNA CLEVAGE OF BIOLOGICALLY ACTIVE VO(II) COMPLEX WITH ETHYL-4-AMINOBENZOATE AND OXALATE ION

B. Sathiyamoorthy, K.Rajasekar , S. Balasubramaniyan, R. Selvarani and C. Veravel Rasayan J. Chem, 13 (2), 934- 939 (2020)

Keywords:Ethyl-4-aminobenzoate, Oxalate Ion, VO(II) Complex, S.aureus, Anticancer, DNA Cleavage

DETERMINATION OF IMPURITIES OF RISPERIDONE API BY ULTRA PERFORMANCE LIQUID CHROMATOGRAPHY (UPLC)

L.P. Magar , B. H. Zaware , C. J. Laheru , Dharmendra.Singh , S.J. Takate and M.K.Gupta Rasayan J. Chem, 13 (2), 940- 948 (2020)

Keywords:Impurity Profile, Risperidone, Ultra Performance Liquid Chromatography, Related Substances, Analytical Method.

DECOLOURIZATION OF YAMUNA WATER USING PEANUT HULL IN PACKED BED REACTOR Varsha Panchal , Arpita Ghosh , Pushpa C. Tomar and Shilpa S. Chapadgaonkar

Rasayan J. Chem, 13 (2), 949- 954 (2020)

Keywords:Contaminants, Decolourization, Packed Bed Reactor, Peanut Hull, Sustainability, Wastewater Treatment, Yamuna Water.

ANTIOXIDANT ACTIVITY, TANNIN CONTENT AND DIETARY FIBER FROM COFFEE HUSK EXTRACT AND POTENTIAL FOR NUTRACEUTICAL

Anton Restu Prihadi , Askal Maimulyanti , Bella Mellisani and Nurhasanah Rasayan J. Chem, 13 (2), 955- 959 (2020)

Keywords:Coffee Husk, Extract, Antioxidant, Tannin, Dietary Fiber

SYNTHESIS, CHARACTERIZATION AND CATALYTIC ACTIVITY OF MONONUCLEAR IRON(III) COMPLEXES TOWARDS HYDROCARBON OXIDATION AT ROOM TEMPERATURE

Uday Sankar Agarwalla

Rasayan J. Chem, 13 (2), 960- 967 (2020)

Keywords:Catalysis, Non-heme, Iron Complex, Hydrogen Peroxide, m-Chloroperbenzoic Acid, Hydrocarbon Oxidation.

QUANTIFICATION OF ISOORIENTININTHREE VARIETIES OF PASSION FRUIT PEEL ETHANOLIC EXTRACT BY HIGH PERFORMANCE LIQUID CHROMATOGRAPHY MASS SPECTROMETRY

E. D. L. Putra , N. Nazliniwaty , F. R. Harun and N. Nerdy Rasayan J. Chem, 13 (2), 968- 972 (2020)

Keywords:Isoorientin, Ethanolic Extract, Peel, Passion Fruit, Varieties.

INVESTIGATION OF PHYTOCHEMICAL CONSTITUENTS AND CARDIOPROTECTIVE ACTIVITY OF ETHANOL EXTRACT OF BEETROOT (Beta vulgaris. L) ON DOXORUBICIN INDUCED TOXICITY IN RAT

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S. E. Nugraha , Yuandani , E. S. Nasution and R.A. Syahputra Rasayan J. Chem, 13 (2), 973- 978 (2020)

Keywords:Doxorubicin, Beetroot, Cardioprotective, CK-MB, LDH, Hematology.

EFFICIENT REMOVAL OF METHYLENE BLUE FROM AQUEOUS SOLUTION BY ALMOND SHELL ACTIVATED CARBON: KINETICS AND EQUILIBRIUM STUDY

M. K. Rai, B.S. Giri , R. S. Singh and B. N. Rai Rasayan J. Chem, 13 (2), 979- 990 (2020)

Keywords:Methylene Blue, Activated Carbon, Almond Shell, Isotherm, Adsorption

NEW NATURAL DYES DEVELOPMENT: Caesalpinia Sappan L.-Curcuma Longa BLENDED DYES N. Kusumawati , Samik , A.B. Santoso and S. Muslim

Rasayan J. Chem, 13 (2), 991- 999 (2020)

Keywords:Natural Dyes, Caesalpinia Sappan L., Bark, Curcuma Longa, Bulb

COMPARATIVE PHYSICAL STUDY OF EVANS BLUE BY FE3O4@CF-R COATED COMBINATION OF DECORATED GO AND TIO2 MAGNETIC NANOCOMPOSITE

Usha Jinendra , B. Lakshmi , Sachin Bhat and B. Dinesh Rasayan J. Chem, 13 (2), 1000- 1007 (2020)

Keywords:Blue Dye, Magnetic Core-shell Nanocomposite, Physical Adsorption, Antibiological Studies

Cu(II) COMPLEXES WITH AN NNO FUNCTIONALIZED HYDRAZONE LIGAND: SYNTHESIS, CHARACTERIZATION AND BIOLOGICAL STUDIES

S. S. Kolate , G. P. Waghulde and C. J. Patil Rasayan J. Chem, 13 (2), 1008 - 1013 (2020)

Keywords:Hydrazone Ligand, Cu(II) Complexes, Biological and Antioxidant Activity

REMOVAL OF CATIONIC TEXTILE DYE METHYLENE BLUE (MB) USING STEEL SLAG COMPOSITE J. Baalamurugan , V. Ganesh Kumar , B. S. Naveen Prasad and K. Govindaraju

Rasayan J. Chem, 13 (2), 1014 - 1021 (2020)

Keywords:Steel Slag, Methylene Blue, Core-shell Formation, Dye Removal, Wastewater Treatment.

ENHANCED DELIGNIFICATION OF CORN STRAW WITH ALKALINE PRETREATMENT AT MILD TEMPERATURE I.B.W. Gunam, Y. Setiyo, N.S. Antara, I.M.M. Wijaya , I.W. Arnata and I.W.W.P. Putra

Rasayan J. Chem, 13 (2), 1022 - 1029 (2020)

Keywords:Corn Straw, Lignocellulose, Alkali Pretreatment, Sodium Hydroxide, Mild Temperature.

SPECTROSCOPIC STUDIES OF SOL-GEL SYNTHESIZED CdOFePO4 COMPOSITE NANOPOWDER

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SK. Khaja Muswareen and Sandhya Cole Rasayan J. Chem, 13 (2), 1030 - 1036 (2020)

Keywords:Composite Nanopowder, XRD, SEM, FTIR, Diffused Reflectance Spectroscopy

AN EASY, EFFICIENT PTC-MEDIATED SYNTHESIS OF 2- SUBSTITUTED-6-CHLOROQUINOXALINES AND ANTIBACTERIAL ACTIVITY

T. Siva Sankara Babu, N. Srinivasu, B. Saha and S. Venkat Reddy Rasayan J. Chem, 13 (2), 1037 - 1041 (2020)

Keywords:6-Chloroquinoxaline, Phase Transfer Catalysts, Thiols, Amine, Antibacterial Activity.

ANTI-CANCER DRUG DOXORUBICIN INDUCED CARDIOTOXICITY: UNDERSTANDING THE MECHANISMS INVOLVED IN ROS GENERATION RESULTING IN MITOCHONDRIAL DYSFUNCTION

Shishir Upadhayay, Nidhi Sharma, Anil K. Mantha and Monisha Dhiman Rasayan J. Chem, 13 (2), 1042 - 1053 (2020)

Keywords:Anthracyclines, Cardiotoxicity, Chemotherapy, Mitochondrial Dysfunction, Reactive Oxygen Species (ROS).

DESIGN AND SYNTHESIS OF 5-OXOPYRROLIDINE-3- CARBOXYLIC ACID DERIVATIVES AS POTENT ANTIINFLAMMATORY AGENTS

K. M. Pandya and P. S. Desai Rasayan J. Chem, 13 (2), 1054 - 1062 (2020)

Keywords:Synthesis, 5-Oxopyrrolidine-3-carboxylic Acid, Anti-inflammatory Activity.

SORPTION POTENTIAL OF TREATED PLANT RESIDUES VIZ. POTATO PEEL AND NEEM BARK FOR REMOVAL OF SYNTHETIC DYES FROM AQUEOUS SOLUTION

Neetu Sharma, D. P. Tiwari and S. K. Singh Rasayan J. Chem, 13 (2), 1063 - 1073 (2020)

Keywords:Formaldehyde treated Potato Peel (PP), Formaldehyde-treated Neem Bark (NB), Sulphuric Acid-treated Potato Peel (APP), Sulphuric Acid-treated Neem Bark (ANB), Synthetic Dyes, Sorption Potential.

FERTILIZER ENCAPSULATION TO IMPROVE THE NUTRIENTS USE EFFICIENCY OF PLANT THROUGH SLOW/CONTROLLED RELEASE TO ENSURE FOOD SECURITY

Jayanudin and R. S. D. Lestari Rasayan J. Chem, 13 (2), 1074 - 1082 (2020)

Keywords:Composite Materials, Encapsulation Methods, Environmental Health, Microcapsule

CHEMICAL TOXICITY AND MICROBIAL CONTAMINATION OF GROUND WATERS NEAR AGRICULTURAL AREAS D. Nageswara Rao, G.V. Krishna Mohan and P.V.S. Machiraju

Rasayan J. Chem, 13 (2), 1083 - 1095 (2020)

Keywords:Groundwater, Agriculture, Characterization, Quality, Toxicity.

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PHYTOCHEMICAL, ANTIBACTERIAL, ANTIOXIDANT AND ANTICANCER ACTIVITY STUDY OF M. candidum LEAF ACETONE EXTRACT

Tita Juwitaningsih, Iis Siti Jahro, Ida Dumariris, Elvira Hermawati and Yaya Rukayadi Rasayan J. Chem, 13 (2), 1096 - 1103 (2020)

Keywords:M. candidum, Antibacterial, Antioxidant, Anticancer, Phytochemical.

SYNTHESIS OF Pd/SILICA-ALUMINA MESOPOROUS CATALYST BY USING CATFISH GELATIN AS TEMPLATE FOR HYDROTREATMENT OF PYROLYZED α-CELLULOSE

Wiharti, W. Trisunaryanti, Triyono, and M. F. Marsuki Rasayan J. Chem, 13 (2), 1104 - 1111 (2020)

Keywords:Hydrotreatment, Silica, Alumina, Pd/MSA, Pyrolysis, Catalysts

POLYMER ELECTROLYTE MEMBRANE FUEL CELL FROM SULFONATED POLYSTYRENE AND MALEATED NATURAL RUBBER BLEND

Ahmad Nasir Pulungan, Basuki Wirjosentono, Eddiyanto, Kurniawan, Junifa Layla Sihombin and Sunit Hendrana

Rasayan J. Chem, 13 (2), 1112 - 1123 (2020)

Keywords:Proton Exchange Membranes, Sulfonated Polystyrene, Maleated Natural Rubber, Proton Conductivity.

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Vol. 13 | No. 2 |1022 - 1029| April - June | 2020 ISSN: 0974-1496 | e-ISSN: 0976-0083 | CODEN: RJCABP

http://www.rasayanjournal.com http://www.rasayanjournal.co.in

Rasayan J. Chem., 13(2), 1022-1029(2020) http://dx.doi.org/10.31788/RJC.2020.1325573

ENHANCED DELIGNIFICATION OF CORN STRAW WITH ALKALINE PRETREATMENT AT MILD TEMPERATURE

I.B.W. Gunam

^1,*

, Y. Setiyo

²

, N.S. Antara

¹

, I.M.M. Wijaya

¹

, I.W. Arnata

¹

and I.W.W.P. Putra

¹

1Department of Agroindustrial Technology, Faculty of Agricultural Technology, Udayana University, Badung, 80361 Bali, Indonesia

2Department of Agricultural Engineering, Faculty of Agricultural Technology, Udayana University, Badung, 80361 Bali, Indonesia

*E-mail: [email protected]

ABSTRACT

The lignocellulosic substrate bioconversion to produce fuel is very potential to be developed in the future.

Converting cellulose to simple sugars requires a suitable and inexpensive preliminary treatment. This study aimed to investigate the use of alkali materials as chemicals suitable to delignify corn straw powder. The research was conducted to choose the chemical type for delignification, namely: NaOH, Ca(OH)2, NH3 (NH4OH), and Hydrazine.

In the next step, the concentration of the delignification solution for corn straw powder was determined at material/chemical ratio of 1:10 (w/v) and soaked for 8 h at room temperature. The tested alkaline solution concentrations were varied from 0, 2, 4, 6, to 8% (w/v). The pre- and post pretreatments affected the yield of α- cellulose, relative degree crystallinity by an X-Ray Diffraction (XRD), functional groups using a Fourier Transform Infra-Red (FT-IR) and surface morphology using a Scanning Electron Microscopy (SEM). Corn straw substrate in the best treatment will applied in the production of cellulase enzymes. The results showed that NaOH is the best used as a delignifying agent with the highest level of cellulose and the lowest lignin, namely 61.45% and 1.09%, respectively. The NaOH solution at the concentration of 4% gives optimal results, with cellulose content 65.46%, hemicellulose 14.58%, and lignin 8.66%. Based on FTIR, XRD and SEM analysis showed that alkali pretreatment especially with NaOH solution gives the result in which the corn straw cellulose structure becomes swelling.

Keywords: Corn Straw, Lignocellulose, Alkali Pretreatment, Sodium Hydroxide, Mild Temperature.

INTRODUCTION

Manufacturing chemical commodities¹ and fuels with bioconversion of lignocellulosic biomass is considered as a prospective substitute to our current reliance on fossil fuels.² Corn straw, as the agricultural waste, has high cellulose content³, allowing to be used as a growth medium for microorganisms to produce cellulase enzymes. To this point, the concentration of corn straw substrate is required for optimal cellulase enzyme production made of microorganisms in fermentation by using media from corn straw powder is not known. Making cellulase enzymes from corn straw waste as a substrate by using microorganisms as enzyme producers is easily cultured, has high growth rates, and is easily controlled for growth.^4‒5

Delignification is a process of removing lignin from lignocellulose complex compounds. This process is important before the cellulose material hydrolysis, because lignin can inhibit the penetration of acids or enzymes before hydrolysis takes place. By giving delignification treatment to the substrate, natural cellulose is expected to change its structure to be more amorphous, so that it becomes more easily hydrolyzed by cellulase enzymes. A variety of physical, chemical, and biological methods has been appraised for their technical feasibility at pre-treatment of lignocellulosic residues. These comprised alkali or acid treatment⁶. According to Irawan et al. (2018)⁷, NaOH as one of the alkaline solutions effectively removes lignin from coconut coir. Arnata et al. (2019)⁸ also reported that delignification of sago frond with 10% NaOH solution for 2 h is very effective in reducing lignin levels. In addition, the

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ENHANCED DELIGNIFICATION OF CORN STRAW I.B.W. Gunam et al.

higher the concentration of NaOH solution is, the ability to dissolve lignin and damage the structure of cellulose will increase and result in cellulose fibers which will be looser so that it is more easily used by microorganisms both for growth and for the production of cellulase enzymes.^5,9

Delignification treatment of corn straw substrate by using NaOH 6% (w/v) and substrate concentration of 2% (w/v), can provide the highest enzyme endoglucanase activity. Besides that, if the substrate concentration is optimal, the enzyme activity will be high.¹⁰

EXPERIMENTAL Materials

Fresh corn straw was collected a few hours after corn harvest from a field in Sanur Bali Indonesia. The chemicals for the preliminary treatment were: NaOH, Ca(OH)2, NH3 (NH4OH), and Hydrazine.

Chemicals for analysis included: HCl, H2SO4, etc. All chemicals were laboratory grade without further purification.

Sample Preparation Reducing the Size

Lignocellulosic waste of corn straw was weighed and dried using an oven, up to 10% moisture content.

After drying, it was crushed by a grinding tool. The grinding powder was sieved with a standard filter (Fisher Brand, Fisher Scientific International, Inc., Hampton, NH) between 60 mesh, and was carried at room temperature (28–30^oC). The resulting corn straw powder was stored in a cooler (4^oC) until it was used¹¹.

Alkaline Pretreatment

This experiment was conducted under a completely randomized design with one factor, namely the chemical type, consisting of NaOH, Ca(OH)2, NH3 (aqueous ammonia), and Hydrazine. Each treatment was repeated 3 times to obtain 12 experimental units.

Corn straw powder was weighed 5 g each, and each treatment was weighed 3 times, then put into a beaker and given a solution of NaOH, Ca(OH)2, NH3, and Hydrazine each at a concentration of 4% (b/v) at a ratio of 1:10 (w/v), soaked for 8 h at 28-30ôC. After pretreatment, the treated corn straw powder was recovered by filtration and rinsed with deionized water to reach pH 7.0 and was dried in an oven at 60ôC¹². The obtained powder material was stored at 4ôC^7,13.

Analysis of Cellulose and Lignin of Corn Straw Powder

Prehydrolysates were centrifuged at 13,000 rpm at 4ôC for 10 mins. The accumulated supernatant was warmed at 60ôC in a water bath, and 20% H2SO4 was put with continuous stirring until pH 2. The sample was cooled down in an ice bath to get a fast pellet. After centrifugated, the supernatant was poured (used later for hemicellulose extraction) and acid-insoluble lignin pellets were cleansed numerous times with acidified water (pH 2). Lignin pellets were dried and the weight was determined gravimetrically. After lignin precipited, the supernatant markers were used for hemicellulose extraction. The supernatant was added with anhydrous ethanol while stirring. The volumetric ratio of ethanol/filtrate was 4. Hemicellulose was separated by centrifugation (4,000 rpm, 5 min) and cleansed with ethanol until the supernatant was colorless. Finally, isolated hemicellulose was dehydrated in a vacuum oven at 50ôC for 24 h and the weight was verified gravimetrically^14,15.

Analysis of Corn Straw Powder Structure Before and After Pretreatment

The structure of corn straw powder before and after pretreatment was analyzed, respectively, with the benchmark testing system of the National Renewable Energy Laboratory (NREL), namely: FT-IR, XRD, and SEM analysis.

Fourier Transform Infrared Spectroscopy (FT-IR)

FT-IR spectroscopy is a proper procedure for verifying disparities introduced by distinctive treatments on the chemical structure of the isolated samples^16-18. The structural components and chemical transformations in the samples of corn straw powder were probed with FT-IR¹⁴.

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X-ray Diffraction (XRD) Analysis

Cellulose crystallization of corn straw was analyzed with XRD¹⁹.

The sample of pretreatment corn straw powder was put into a sample bottle using X-ray Diffraction XRD 7000 maxima X (Shimadzu Ltd., Tokyo, Japan). X-pert pro diffractometer set at 40 KV, 30 mA; the radiation was Cu Kα (λ = 1.54 Å), and grade range between 10 (2θ) to 30^o (2θ) with a step size 0.03^o. Scanning Electron Microscopy (SEM)

The morphology of corn straw samples (delignification) was analyzed by SEM. SEM was conducted to analyze changes in microstructure and surface characteristics of corn straw samples¹⁵.

Statistical Analysis

It was carried out in triplicate and completed as a mean ± standard deviation (SD). Statistical data were acquired by ANOVA and Duncan's multiple range test and a p-value <0.01 was assumed as a very significant difference.

RESULTS AND DISCUSSION

Cellulose and Lignin Levels of Corn Straw Powder After Alkaline Pretreatment

The analysis of variance results showed the treatment of variations regarding the type of delignifying solution which had a very significant effect (p<0.01) on the levels of cellulose and lignin. The average values of cellulose and lignin (Table-1).

Table-1: Average Values of Cellulose and Lignin Levels of Corn Straw Powder

Different letters behind the mean values indicated very significant differences (p<0.01).

Table-1 showed that the highest cellulose content produced in the treatment with NaOH was 61.45%, while the lowest cellulose content in the treatment with Ca(OH)2 solution was 41.33%. The decrease in the highest lignin content was produced in the treatment with NaOH solution by 1.09%, while the decrease in the lowest lignin content in the treatment with Ammonia solution was 3.26%. The greater the level of lignin is, the lower the level of lignin will decrease due to the treatment of delignification solution. Cellulose content in high cell walls of plants is around 35-50% of the dry weight of plants²⁰. The test results of the cellulose content in samples after delignification were significantly increased, whereas lignin levels decreased significantly. The decrease in lignin content may be caused by the use of a base solution which can dissolve lignin so that it is released from the lignocellulose bundle¹⁰. NaOH gives the best results in removing lignin and changing the structure of cellulose compared with Ca(OH)2, Ammonia and Hydrazine. The results of this research are supported by the results of several researchers who have reported that the NaOH treatment is a very proficient method to degrade and liquefy non-cellulose compounds by cleaving the α- and β-aryl ether linkages between lignin and hemicellulose^21,22.

Functional Groups by FT-IR

FT-IR spectra of corn straw were presented in Fig.-1. There were differences in the wavenumber values of the absorption patterns within each functional group and the diversity in the merits of transmittance between the four treatments.

The vibrational absorption of compounds between wave numbers 2000 and 1000 cm^-1 was related to cellulose, hemicellulose and lignin, which were related to each functional group of macromolecules. It should be noted that this signal was modified due to alkali treatment. In Fig.-1, spectra with vibrational uptake at wave number 2000 cm^-1 in the spectrum of corn straw powder were associated with the stretching of aliphatic C-H bonds.

Pretreatment Cellulose (%) Lignin (%)

NaOH 61.45±0.717^a 1.09±0.006^d

Ca(OH)2 41.33±0.423^c 1.65±0.046^c

NH3 46.01±0.170^b 3.26±0.064^a

Hydrazine 47.45±0.532^b 2.50±0.108^b

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Fig.-1: FT-IR Spectra of Corn Straw Powder Delingnated with NaOH, Ca(OH)2, Ammonia (NH3), and Hydrazine for 8 h at Room Temperature. Chemical Concentration was 4% with a Ratio of Ingredients and Chemical Solution 1:

10 (w/v). Y-axis Corresponds to Absorbance in Arbitrary unit, and X-axis is Wavenumber.

The absolute and difference FTIR spectra of each sample treated with specific base and spectra of ammonia minus control, hydrazine minus control, NaOH minus control and Ca(OH)2 minus control. The result of alkalization process, OH bond deformation in the absorption area around 1518 cm^-1 indicated the water absorption by cellulose²³ and may also indicating the presence of vibration of the guasil and lignin ring²⁴. The acetyl and ester groups in the hemicellulose, or the carboxyl acid group in the ferulic, and p- coumeric groups in lignin shown in spectra should be around 1740 cm^-1, characterized by C=O (carboxyl lignin vibration) groups, where 1236 cm^-1 peak may indicate the presence of a siringil group in lignin²⁵. In addition, alkalization should also reduce vibrational uptake of the C=C lignin spectra. Absorption area around 1420 cm^-1 showed the existing -CH2 bond which was deformed in cellulose, where this region revealed crystalline part, and the uptake part was escalated²⁶. The reaction occuring in the alkalization process was NaOH solution which dissociated into Na⁺ and OH^- then reacting with lignin. The OH^-ion reacted with the H group of lignin to form H2O. This would caused the O group to become free and reactive radicals with C forming C-O-C. The C group already had four 'hands' so that a series of groups loosened to group O. The reaction could produce two separate benzene rings, each of which had a reactive O group. This reactive O group reacted with Na⁺ and dissolves in a basic solution so that lignin amount were reduced when rinsed. This reaction also produced H2O. Meanwhile, cellulose is hydrophilic, so H2O is bound by cellulose which causes the concentration of O-H bonds to increase, and the absorption area at 865.13 cm^-1 showed C-H vibrations indicating the absorption characteristics of β-glycosidic^27,28, where the original absorption area was derived from β-glycosidic which connected between glucose units in cellulose^29-30.

From the results of the alkaline pretreatment showed above, the NaOH is the best performing base which can be seen from the decrement of the total amount of cellulose absorbance in Fig.-1. From this result, the solution was developed to obtain the best concentration of NaOH. The following immersion data using NaOH concentrations of 0%, 2%, 4% and 6% were presented in Fig.-2 (characteristics of corn straw powder) and structure analysis using FT-IR (Fig.-3). The characteristics of corn straw powder before and after immersion with various concentrations of NaOH for 8 h at room temperature (28–30^oC) gave optimum results at 4% NaOH concentration, namely cellulose levels of corn straw powder 65.46%, hemicellulose 14.58%, lignin 8.66%, moisture content 6.51%, ash 6.14% and hot water soluble (HWS) 5.80.

From the FT-IR spectra in Fig.-3, it is appearing that 4% of NaOH concentration is the best concentration to be used seeing from the highest peak in the region between 1000 and 2000 cm^-1. The delignated absorbance spectra were decreasing in corresponding increment of NaOH concentration, however only

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minute difference of absorbance was could be seen from Fig.-3 (dotted blue line). This indicate that there was no significant difference of treatment between 4% and 6% of NaOH. Meanwhile the difference between 4% and 2% of NaOH gave significant difference in absorbance (red dotted line). This would indicate that 4% is the best concentration for delignification, where addition until 6% of NaOH will not improve the delignification significantly.

Fig.-2: The Characteristic Substrate of Corn Straw Powder after Soaking with 0, 2, 4, 6 and 8% NaOH for 8h at Room Temperature

Fig.-3: FT-IR Spectra of Delignated Corn Straw Powder with Soaking Treatment of 2%, 4% and 6% NaOH for 8 h at Room Temperature (28-30^oC). Y-axis Corresponds to Absorbance where each Division is 0.4 Absorbance Units,

and X-axis is Wavenumber Surface Morphology

The surface morphology of corn straw powder after delignification treatment with SEM were presented in Fig.-4. The research presented information on structural changes and surface properties which occur in corn straw after pretreatment with NaOH. The cuticle wax coating on cornstarch had very low permeability to cellulose decomposing enzymes and it is hoped that pretreatment with NaOH could eliminate the surface of the outer granular wax and allowed direct contact with cellulase enzymes³¹. This research focuses on removing cuticle granules from non-cellulose materials using various concentrations of NaOH solution. Structure and SEM analysis were carried out on corn straw powder which had been given a pretreatment with 0% NaOH solution (control), 2%, 4%, and 6% NaOH (w/v). The analysis showed that the surface of natural corn straw powder (without NaOH) looks flat, rough, and continuous.

NaOH pretreatment damage to the external cell structure, raised external surface area and increased exposure to the internal cell structure as observed in the 4% NaOH treatment. Pre-treated samples with

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NaOH were much softer and easier to digest by cellulase enzymes than natural samples (NaOH 0%), and the structure of lignocellulose wax layer was partially removed.

Delignified cracks could be seen on the surface of 4% NaOH pretreated straw. Cracks were instigated by the elimination of easily digested lignocellulose fractions (such as hemicellulose). The partial deduction of lignin in 4% NaOH resulted in swelling of biomass and disorder of lignin structure¹⁵.

0% NaOH 2% NaOH

4% NaOH 6% NaOH

Fig.-4: SEM Images of Corn Straw Powder without Delignification (0% NaOH), 2%, 4% and 6% NaOH Soaked for 8 h at Room Temperature (28–30^oC).

In Fig.-4, we can also see that the difference in a surface structure after treatment using 0%, 2%, 4% and 6% NaOH for 8 h could increase the physical surface area of corn straw powder. This worked to increase the reaction of enzymes with the substrate i.e. corn straw powder and increase glucose levels resulted from enzymatic hydrolysis of solid residues³¹.

Analysis with XRD

Based on the analysis results of corn straw powder with XRD as shown in Fig.-5, It shows that chemical treatment causes a change in the crystallinity degree of cellulose corn straw powder. Corn straw and cellulose³² have two main diffraction peaks, namely at 2θ = 16° and 2θ = 22° which are related to the crystalline planes of (110) and (200, respectively. In addition, low intensity peaks were observed at 2θ = 34°, which corresponded to the crystalline plane of (004). This diffraction pattern shows that corn straw cellulose has characteristics of natural cellulose structure or polymorph type cellulose I. This crystalline structure corresponded to the parallel arrangement between the linear chains of the glycosidic bonds of cellulose and had been referred to as polymorph cellulose with vaster mechanical endurance.

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Corn straw Costa et al. (2015)

Fig.-5: X-ray Diffraction (XRD) Patterns of Corn Straw Powder after Pretreatment with 4% NaOH (A) and XRD Patterns of Pure Cellulose, Corncobs and Nanoparticle Material (B)

The XRD pattern of the nanoparticles had sharp peak intensities at 2θ = 20.7° and low intensities at 2θ = 11.4° which corresponded to the crystalline and the remaining amorphous regions, respectively.

Therefore, the original crystalline structure of cellulose did not change after acid hydrolysis. Based on the results of the graph above, it can be seen that the crystallinity degree of cellulose and cellulose nanoparticles were affected by the chemical usage in corn straw.

CONCLUSION

The results show NaOH is the best chemical as the delignifying agent with the highest levels of cellulose and the lowest lignin, namely 61.45% and 1.09%, respectively. The NaOH solution at the concentration 4% gives optimal results, with cellulose content 65.46%, hemicellulose 14.58%, and lignin 8.66%. FT-IR, XRD analysis and SEM also show the alkali treatment, especially with NaOH solution giving the result that the cellulose structure becomes swelling.

ACKNOWLEDGEMENT

The authors would like to gratitude to the Ministry of Research, Technology and Higher Education for the granting the fund through the Higher Education Applied Research (PTUPT) scheme (171.117/UN14.4.A/LT/2018).

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[RJC-5573/2019]