F. Peter

Publications

6 Structural Analysis of Lignins from Different Sources

Authors: F. Peter, I. F. Fiţigău, C. G. Boeriu

Abstract:

Five lignin samples were fractionated with Acetone/Water mixtures and the obtained fractions were subjected to extensive structural characterization, including Fourier Transform Infrared (FT-IR), Gel permeation Chromatography (GPC) and Phosphorus-31 NMR spectroscopy (31P-NMR). The results showed that for all studied lignins the solubility increases with the increment of the acetone concentration. Wheat straw lignin has the highest solubility in 90/10 (v/v) Acetone/Water mixture, 400 mg lignin being dissolved in 1 mL mixture. The weight average molecular weight of the obtained fractions increased with the increment of acetone concentration and thus with solubility. 31P-NMR analysis based on lignin modification by reactive phospholane into phosphitylated compounds was used to differentiate and quantify the different types of OH groups (aromatic, aliphatic, and carboxylic) found in the fractions obtained with 70/30 (v/v) Acetone/Water mixture.

Keywords: Fractionation, Lignin, GPC, FT-IR

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5 Ionic Liquid Pretreatment and Enzymatic Hydrolysis of Wood Biomass

Authors: F. Peter, M. Ungurean, F. Fitigau, C. Paul, A. Ursoiu

Abstract:

Pretreatment of lignocellulosic biomass materials from poplar, acacia, oak, and fir with different ionic liquids (ILs) containing 1-alkyl-3-methyl-imidazolium cations and various anions has been carried out. The dissolved cellulose from biomass was precipitated by adding anti-solvents into the solution and vigorous stirring. Commercial cellulases Celluclast 1.5L and Accelerase 1000 have been used for hydrolysis of untreated and pretreated lignocellulosic biomass. Among the tested ILs, [Emim]COOCH3 showed the best efficiency, resulting in highest amount of liberated reducing sugars. Pretreatment of lignocellulosic biomass using glycerol-ionic liquids combined pretreatment and dilute acid-ionic liquids combined pretreatment were evaluated and compared with glycerol pretreatment, ionic liquids pretreatment and dilute acid pretreatment.

Keywords: Pretreatment, Enzymatic Hydrolysis, cellulase, lignocellulosicbiomass

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4 Synthesis of Peptide Amides using Sol-Gel Immobilized Alcalase in Batch and Continuous Reaction System

Authors: F. Peter, C. G. Boeriu, L. N. Corîci, A. E. Frissen, D -J. Van Zoelen, I. F. Eggen, C. M. Davidescu

Abstract:

Two commercial proteases from Bacillus licheniformis (Alcalase 2.4 L FG and Alcalase 2.5 L, Type DX) were screened for the production of Z-Ala-Phe-NH2 in batch reaction. Alcalase 2.4 L FG was the most efficient enzyme for the C-terminal amidation of Z-Ala-Phe-OMe using ammonium carbamate as ammonium source. Immobilization of protease has been achieved by the sol-gel method, using dimethyldimethoxysilane (DMDMOS) and tetramethoxysilane (TMOS) as precursors (unpublished results). In batch production, about 95% of Z-Ala-Phe-NH2 was obtained at 30°C after 24 hours of incubation. Reproducibility of different batches of commercial Alcalase 2.4 L FG preparations was also investigated by evaluating the amidation activity and the entrapment yields in the case of immobilization. A packed-bed reactor (0.68 cm ID, 15.0 cm long) was operated successfully for the continuous synthesis of peptide amides. The immobilized enzyme retained the initial activity over 10 cycles of repeated use in continuous reactor at ambient temperature. At 0.75 mL/min flow rate of the substrate mixture, the total conversion of Z-Ala-Phe-OMe was achieved after 5 hours of substrate recycling. The product contained about 90% peptide amide and 10% hydrolysis byproduct.

Keywords: protease, packed-bed reactor, peptide amide, sol-gel immobilization

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3 Double Immobilized Lipase for the Kinetic Resolution of Secondary Alcohols

Authors: F. Peter, M. Ungurean, C. Paul, A. Ursoiu, C. Marcu

Abstract:

Sol-gel immobilization of enzymes, which can improve considerably their properties, is now one of the most used techniques. By deposition of the entrapped lipase on a solid support, a new and improved biocatalyst was obtained, which can be used with excellent results in acylation reactions. In this paper, lipase B from Candida antarctica was double immobilized on different adsorbents. These biocatalysts were employed in the kinetic resolution of several aliphatic secondary alcohols in organic medium. High total recovery yields of enzymatic activity, up to 560%, were obtained. For all the studied alcohols the enantiomeric ratios E were over 200. The influence of the reaction medium was studied for the kinetic resolution of 2-pentanol.

Keywords: lipase, enantioselectivity, Double immobilization, kineticresolution, racemates, sol-gel entrapment

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2 Lipase Catalyzed Synthesis of Aromatic Esters of Sugar Alcohols

Authors: R. Croitoru, F. Peter, C. G. Boeriu, A. E. Frissen, C. M. Davidescu, L. A. M. van den Broek

Abstract:

Commercially available lipases (Candida antarctica lipase B, Novozyme 435, Thermomyces lanuginosus lipase, and Lipozyme TL IM), as well as sol-gel immobilized lipases, have been screened for their ability to acylate regioselectively xylitol, sorbitol, and mannitol with a phenolic ester in a binary mixture of t-butanol and dimethylsulfoxide. HPLC and MALDI-TOF MS analysis revealed the exclusive formation of monoesters for all studied sugar alcohols. The lipases immobilized by the sol-gel entrapment method proved to be efficient catalysts, leading to high conversions (up to 60%) in the investigated acylation reactions. From a sequence of silane precursors with different nonhydrolyzable groups in their structure, the presence of octyl and i-butyl group was most beneficial for the catalytic activity of sol-gel entrapped lipases in the studied process.

Keywords: transesterification, specificity, lipase, phenolic ester, sugar alcohol

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1 Improvement of Lipase Catalytic Properties by Immobilization in Hybrid Matrices

Authors: C. Zarcula, R. Croitoru, L. Corîci, C. Csunderlik, F. Peter

Abstract:

Lipases are enzymes particularly amenable for immobilization by entrapment methods, as they can work equally well in aqueous or non-conventional media and long-time stability of enzyme activity and enantioselectivity is needed to elaborate more efficient bioprocesses. The improvement of Pseudomonas fluorescens (Amano AK) lipase characteristics was investigated by optimizing the immobilization procedure in hybrid organic-inorganic matrices using ionic liquids as additives. Ionic liquids containing a more hydrophobic alkyl group in the cationic moiety are beneficial for the activity of immobilized lipase. Silanes with alkyl- or aryl nonhydrolizable groups used as precursors in combination with tetramethoxysilane could generate composites with higher enantioselectivity compared to the native enzyme in acylation reactions of secondary alcohols. The optimal effect on both activity and enantioselectivity was achieved for the composite made from octyltrimethoxysilane and tetramethoxysilane at 1:1 molar ratio (60% increase of total activity following immobilization and enantiomeric ratio of 30). Ionic liquids also demonstrated valuable properties as reaction media for the studied reactions, comparable with the usual organic solvent, hexane.

Keywords: Ionic Liquids, lipase, enantioselectivity, sol-gelimmobilization

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