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Volume 5 (2012): Issue 1 (April 2012)

Journal Details
Format
Journal
eISSN
1339-3065
First Published
10 Dec 2012
Publication timeframe
2 times per year
Languages
English

Search

Volume 7 (2014): Issue 1 (April 2014)

Journal Details
Format
Journal
eISSN
1339-3065
First Published
10 Dec 2012
Publication timeframe
2 times per year
Languages
English

Search

11 Articles
Open Access

The photodegradation of model quinolone carboxylates in aqueous media

Published Online: 27 May 2014
Page range: 1 - 8

Abstract

Abstract

This work was focused on the study of photoinduced processes of quinolone carboxylates in the presence of titanium dioxide in an alkaline media. UVA irradiation without/with titanium dioxide caused the decomposition of molecules, with higher efficiency of degradation in the presence of titanium dioxide. EPR spin trapping experiments proved that investigated quinolone carboxylates behave as the efficient scavengers of hydroxyl radicals produced upon irradiation of aerated alkaline titanium dioxide systems.

Keywords

  • Quinolone carboxylate
  • Titanium dioxide
  • EPR spectroscopy
  • UV/vis spectroscopy
  • EPR spin trapping technique
Open Access

On the structure of [Al(DMSO2)3]3+

Published Online: 27 May 2014
Page range: 9 - 14

Abstract

Abstract

The most stable [Al(DMSO2)3]3+ complex cation in dimethyl sulfone (DMSO2, (CH3)2SO2) has D3 symmetry with twofold axes in Al-S lines coincident with the twofold rotation axes of mutually turned DMSO2 ligands by ca 60°. The central Al atom is hexacoordinated by six O atoms with nearly octahedral coordination. More than one electron is transferred to the Al central atom from DMSO2 ligands. Weaker and longer S-O, stronger and shorter S-C bonds, lower O-S-O bond angles and greater O-S-C and C-S-C ones in [Al(DMSO2)3]3+ than in free DMSO2 are implied by weak Al-O bonding.

Keywords

  • B3LYP
  • MP2
  • geometry optimization
  • electron structure
  • solvent effect
Open Access

Structure of cis-dichlorobis(1,10-phenanthroline)manganese(II) and cis-dichlorobis(2,2´-bipyridine)manganese(II)

Published Online: 27 May 2014
Page range: 15 - 19

Abstract

Abstract

The crystal structures of the title compounds, [Mn(phen)2Cl2] (I) and [Mn(bipy)2Cl2] (II), have been determined at 150 K. The manganese atoms in both compounds are coordinated by four pyridine nitrogen atoms from two 1,10-phenanthroline or 4,4´-bipyridine ligands and two chloride anions, resulting in a distorted cis-MnN4Cl2 octahedral geometry. Both complexes are connected through C-H・・・Cl hydrogen bonds into frameworks. The π-π stacking interactions are observed in crystal structure of both ones.

Keywords

  • manganese
  • X-ray
  • crystal structure
  • 1,10-phenanthroline
  • 2,2´-bipyridine
Open Access

Phase diagram of the system CaSO4—K2SO4—KNO3—Ca(NO3)2—H2O

Published Online: 27 May 2014
Page range: 20 - 24

Abstract

Abstract

Potassium nitrate as a fertilizer suitable for greenhouse and hydroponic applications can be prepared by the reaction of potassium sulphate with calcium nitrate. However, it may happen that simultaneously with the precipitation of gypsum (CaSO4·2H2O) also two other binary salts, viz. syngenite (K2SO4·CaSO4·H2O) and görgeyite (K2SO4·5CaSO4·H2O) can crystallize. This would lower the yield of KNO3. For minimization of potassium loss we have to determine the conditions under which syngenite and görgeyite crystallize. As a useful tool for the quantitative determination of specific hydrates, simultaneous DTA/TG technique appeared. Each hydrate decomposes at a certain temperature. The loss of water at dehydration can be used for a quantitative determination of the amount of the hydrate in the precipitating solid phase. Based on the experimental data several conclusions can be drawn: (i) excess of calcium cations lowers the concentration of sulphate ions in the liquid phase together with lowering of contents of syngenite and görgeyite in the solid phase; (ii) higher content of water results in a higher solubility of sulphate ions; (iii) joint crystallization of syngenite and gypsum occurs in the composition area interesting from the point of KNO3 production; (iv) area of the primary crystallization of görgeyite does not exist in the phase diagram at 80 °C. However, görgeyite crystallizes at the molar ratio Ca(NO3)2:K2SO4 = 1:1 by ternary crystallization; (v) area of crystallization of pure gypsum is shifted to lower ratio Ca(NO3)2:K2SO4 by the addition of water to the system.

Keywords

  • görgeyite
  • phase diagram
  • potassium nitrate
  • syngenite
Open Access

The DFT calculations of pKa values of the cationic acids of aniline and pyridine derivatives in common solvents

Published Online: 27 May 2014
Page range: 25 - 30

Abstract

Abstract

The theoretical pKa values of the derivatives of anilinium and pyridinium ions in 7 solvents are presented. For this purpose, the usage of isodesmic reaction scheme using the DFT/B3LYP approach with IEFPCM solvation was evaluated. We have shown that the suitable selection of reference species has the primary influence on the resulting data. For the studied anilinium ion derivatives the nonsubstituted anilinium ion seems to be a satisfactory reference system. The calculated values are in good accordance with the available experimental data with the RMS error of 1.00 and 0.99 pKa units in water and THF, respectively. The highest error in predicted pKa value is less than 2.0 pKa units in all cases. The chemical accuracy of the applied treatment is limited in the case of nitroaniline ions and the maximal therotetical uncertainty for derivatives of the pyridinium ion is within 2.1 pKa units. Our theoretical results enable us to predict the values of pKa for the solvents, where the experimental data are not completely available. Also the influence of the chemical structure on the accuracy of the applied method was discussed.

Keywords

  • pKa
  • acid dissociation constant
  • DFT
  • B3LYP
  • IEFPCM
  • anilinium ion
  • pyridinium ion
Open Access

Solvation enthalpies of the electron in polar and non-polar solvents: Theoretical study

Published Online: 27 May 2014
Page range: 31 - 33

Abstract

Abstract

Although the electron transfer is a part of many important processes in biosystems that occur in the solution-phase, there is still no systematic theoretical study of the electron solvation enthalpies. The solvation enthalpies of the electron in different solvents of various polarities: benzene, toluene, acetone, methanol, ethanol, DMSO and water, are investigated. All calculations were performed by B3LYP, BHLYP and PBE approaches with aug-cc-pVDZ, aug-cc-pVTZ and aug-cc-pVQZ basis sets, using the Integral Equation Formalism Polarized Continuum Model (IEF-PCM). The calculations show that the B3LYP and PBE functionals provide similar results. With the exception of benzene, toluene and DMSO, the differences in values for all solvents are lower than 6 kJ mol-1. The BHLYP solvation enthalpies are higher by 20-25 kJ mol-1 than the B3LYP ones.

Keywords

  • electron solvation enthalpy
  • solvent
  • DFT
  • IEF-PCM
Open Access

Crystal and molecular structure of (5S,8aS,9S)-9-hydroxy- 5-methyl- 4,6,7,8,8a,9-hexahydrothieno-[ 3,2-f] indolizin-5-ium iodide

Published Online: 27 May 2014
Page range: 34 - 37

Abstract

Abstract

The title compound, C11H16NOS・I, is chiral molecule with three stereogenic centres. The absolute configuration was assigned from the synthesis and confirmed by the structure determination. The central six-membered ring of the indolizine moiety adopts a half-chair conformation with atom displaced by 0.655 (2) A from the plane of the oder remaining five atoms. The pyrrolidine ring adopts an envelope conformation, with the greatest deviation from the mean plane of the ring being 0.646 (2) A for the bridgehead N atom. The crystal structure of the title compound is stabilized by O-H・・・I and C-H・・・O hydrogen bonds.

Keywords

  • conformation
  • crystal structure
  • hydrogen bonds
  • indolizine
  • single-crystal X-ray study
Open Access

Testing of selected probiotic properties of lactic acid bacteria isolated from vegetarians and meat-eaters faeces

Published Online: 27 May 2014
Page range: 38 - 43

Abstract

Abstract

The aim of this work was to evaluate presence and properties of lactic acid bacteria in the faeces of 240 volunteers with various nutrition habits (vegetarians versus meat-eaters). Lactic acid bacteria counts in all age groups were nearly 5 or 6 logarithmic orders. Significantly higher amounts were found in women. Subsequently, based on the age and dietary pattern of probands, four samples were selected for isolation of lactic acid bacteria and identification of isolates in order to assign them to bacterial species. About 80 lactic acid bacteria were isolated from the faeces of young (21-30 years) and older (51-60 years) vegetarians and meateaters. The identification of the isolates was based on their morphological and biochemical characteristics. Isolates belong to lactobacilli, bifidobacteria, enterococci and propionibacteria. Surprisingly, bifidobacteria were predominated in older age group. The following probiotic properties were determined: survival at low pH value, and bile salt hydrolase activity. All strains were negative in bile salt hydrolase activity, but their growth was not inhibited in the presence of bile. The results from the study of survival at low pH value showed considerable variability in both dietary groups regardless the age of probands. However, it can be concluded, that bacteria isolated from the samples of older probands were more sensitive to acid pH.

Keywords

  • gastrointestinal tract
  • lactic acid bacteria
  • meat-eaters
  • vegetarians
Open Access

Identification of biodegradation products of biphenyl and 2,3-dihydroxybiphenyl (2,3-DHB)

Published Online: 27 May 2014
Page range: 44 - 51

Abstract

Abstract

We investigated the degradation of biphenyl and identified main degradation products. Biphenyl and 2,3-dihydroxybiphenyl (2,3-DHB) was added to cultivation media to identify whole collection of degradation products of four bacterial strains isolated from long-term PCB contaminated soil (Alcaligenes xylosoxidans and Pseudomonas stutzeri) and long-term PCB contaminated sediment (Ochrobactrum anthropi and Pseudomonas veronii). Cultivation flasks were processed in different time after inoculation to determine biphenyl fission rate. Alcaligenes xylosoxidans was revealed as the most appropriate strain for bioremediation process with the highest biphenyl transformation rate. Biphenyl degradation led to the formation of benzoic acid. However, as the presence of 2-hydroxy-6-oxo-6-phenylhex-2,4-dienoic acid (HOPDA) was not confirmed, the transformation pathway common for many other bacteria is probably modified.

Keywords

  • bacteria
  • biodegradation
  • biphenyl
  • degradation products
  • 2,3-dihydroxybiphenyl
Open Access

Lectin detection of cell surface saccharides remodeling induced by development of P-glycoprotein mediated multidrug resistance phenotype in L1210 leukemia cells

Published Online: 27 May 2014
Page range: 52 - 56

Abstract

Abstract

P-glycoprotein is an ATP dependent drug efflux pump the expression of which is responsible for strong depression of cell sensitivities to large group of structurally unrelated substances in neoplastic cells. We found that the expression of this protein in mice leukemia cells L1210 is associated with massive remodeling of cell surface saccharides. This remodeling is consistent with the alteration of cellular contents of UDP-sugars, glycogen and glycoproteins when P-gp positive and P-gp negative L1210 cell variants were compared. The current paper is focused on bringing the state of art information about this topic.

Open Access

Production of pectin lyase from Geobacillus pallidus p26, purification, characterization and fruit juice application

Published Online: 27 May 2014
Page range: 57 - 63

Abstract

Abstract

A bacterial strain was isolated from Pasinler hot spring, Erzurum, Turkey. The purified thermophilic isolate was identified as Geobacillus pallidus P26 and used to produce extracellular pectin lyase (EC 4.2.2.10). Pectin lyase enzyme was purified 34 fold by using DEAE-cellulose anion exchange column chromatography and characterized. Molecular weight of the enzyme was determined as 56 kDa by using Sephadex G-100 gel filtration chromatography. Purification of enzyme was verified by SDS-PAGE. The pH- and temperature optima of enzyme were determined (pH 9.0 and 60°C, respectively). Pectin lyase was mostly stable at 50 oC for 24 hours. Its’ activity decreased to 50 % for 24 h at 60°C. KM and Vmax were calculated as 24.8 mg/mL and 2.28 μmol/L min, respectively. Purified pectin lyase was inhibited by Fe3+, Zn2+, Cu2+, Ca2+, Co2+ and Hg2+ but not by Mg2+. The purified pectin lyase enzyme was used for getting fruits juices. It was found that yields of fruits juices increased when they were compared with control.

Keywords

  • Pectin lyase
  • purification
  • characterization
  • Geobacillus pallidus P26
11 Articles
Open Access

The photodegradation of model quinolone carboxylates in aqueous media

Published Online: 27 May 2014
Page range: 1 - 8

Abstract

Abstract

This work was focused on the study of photoinduced processes of quinolone carboxylates in the presence of titanium dioxide in an alkaline media. UVA irradiation without/with titanium dioxide caused the decomposition of molecules, with higher efficiency of degradation in the presence of titanium dioxide. EPR spin trapping experiments proved that investigated quinolone carboxylates behave as the efficient scavengers of hydroxyl radicals produced upon irradiation of aerated alkaline titanium dioxide systems.

Keywords

  • Quinolone carboxylate
  • Titanium dioxide
  • EPR spectroscopy
  • UV/vis spectroscopy
  • EPR spin trapping technique
Open Access

On the structure of [Al(DMSO2)3]3+

Published Online: 27 May 2014
Page range: 9 - 14

Abstract

Abstract

The most stable [Al(DMSO2)3]3+ complex cation in dimethyl sulfone (DMSO2, (CH3)2SO2) has D3 symmetry with twofold axes in Al-S lines coincident with the twofold rotation axes of mutually turned DMSO2 ligands by ca 60°. The central Al atom is hexacoordinated by six O atoms with nearly octahedral coordination. More than one electron is transferred to the Al central atom from DMSO2 ligands. Weaker and longer S-O, stronger and shorter S-C bonds, lower O-S-O bond angles and greater O-S-C and C-S-C ones in [Al(DMSO2)3]3+ than in free DMSO2 are implied by weak Al-O bonding.

Keywords

  • B3LYP
  • MP2
  • geometry optimization
  • electron structure
  • solvent effect
Open Access

Structure of cis-dichlorobis(1,10-phenanthroline)manganese(II) and cis-dichlorobis(2,2´-bipyridine)manganese(II)

Published Online: 27 May 2014
Page range: 15 - 19

Abstract

Abstract

The crystal structures of the title compounds, [Mn(phen)2Cl2] (I) and [Mn(bipy)2Cl2] (II), have been determined at 150 K. The manganese atoms in both compounds are coordinated by four pyridine nitrogen atoms from two 1,10-phenanthroline or 4,4´-bipyridine ligands and two chloride anions, resulting in a distorted cis-MnN4Cl2 octahedral geometry. Both complexes are connected through C-H・・・Cl hydrogen bonds into frameworks. The π-π stacking interactions are observed in crystal structure of both ones.

Keywords

  • manganese
  • X-ray
  • crystal structure
  • 1,10-phenanthroline
  • 2,2´-bipyridine
Open Access

Phase diagram of the system CaSO4—K2SO4—KNO3—Ca(NO3)2—H2O

Published Online: 27 May 2014
Page range: 20 - 24

Abstract

Abstract

Potassium nitrate as a fertilizer suitable for greenhouse and hydroponic applications can be prepared by the reaction of potassium sulphate with calcium nitrate. However, it may happen that simultaneously with the precipitation of gypsum (CaSO4·2H2O) also two other binary salts, viz. syngenite (K2SO4·CaSO4·H2O) and görgeyite (K2SO4·5CaSO4·H2O) can crystallize. This would lower the yield of KNO3. For minimization of potassium loss we have to determine the conditions under which syngenite and görgeyite crystallize. As a useful tool for the quantitative determination of specific hydrates, simultaneous DTA/TG technique appeared. Each hydrate decomposes at a certain temperature. The loss of water at dehydration can be used for a quantitative determination of the amount of the hydrate in the precipitating solid phase. Based on the experimental data several conclusions can be drawn: (i) excess of calcium cations lowers the concentration of sulphate ions in the liquid phase together with lowering of contents of syngenite and görgeyite in the solid phase; (ii) higher content of water results in a higher solubility of sulphate ions; (iii) joint crystallization of syngenite and gypsum occurs in the composition area interesting from the point of KNO3 production; (iv) area of the primary crystallization of görgeyite does not exist in the phase diagram at 80 °C. However, görgeyite crystallizes at the molar ratio Ca(NO3)2:K2SO4 = 1:1 by ternary crystallization; (v) area of crystallization of pure gypsum is shifted to lower ratio Ca(NO3)2:K2SO4 by the addition of water to the system.

Keywords

  • görgeyite
  • phase diagram
  • potassium nitrate
  • syngenite
Open Access

The DFT calculations of pKa values of the cationic acids of aniline and pyridine derivatives in common solvents

Published Online: 27 May 2014
Page range: 25 - 30

Abstract

Abstract

The theoretical pKa values of the derivatives of anilinium and pyridinium ions in 7 solvents are presented. For this purpose, the usage of isodesmic reaction scheme using the DFT/B3LYP approach with IEFPCM solvation was evaluated. We have shown that the suitable selection of reference species has the primary influence on the resulting data. For the studied anilinium ion derivatives the nonsubstituted anilinium ion seems to be a satisfactory reference system. The calculated values are in good accordance with the available experimental data with the RMS error of 1.00 and 0.99 pKa units in water and THF, respectively. The highest error in predicted pKa value is less than 2.0 pKa units in all cases. The chemical accuracy of the applied treatment is limited in the case of nitroaniline ions and the maximal therotetical uncertainty for derivatives of the pyridinium ion is within 2.1 pKa units. Our theoretical results enable us to predict the values of pKa for the solvents, where the experimental data are not completely available. Also the influence of the chemical structure on the accuracy of the applied method was discussed.

Keywords

  • pKa
  • acid dissociation constant
  • DFT
  • B3LYP
  • IEFPCM
  • anilinium ion
  • pyridinium ion
Open Access

Solvation enthalpies of the electron in polar and non-polar solvents: Theoretical study

Published Online: 27 May 2014
Page range: 31 - 33

Abstract

Abstract

Although the electron transfer is a part of many important processes in biosystems that occur in the solution-phase, there is still no systematic theoretical study of the electron solvation enthalpies. The solvation enthalpies of the electron in different solvents of various polarities: benzene, toluene, acetone, methanol, ethanol, DMSO and water, are investigated. All calculations were performed by B3LYP, BHLYP and PBE approaches with aug-cc-pVDZ, aug-cc-pVTZ and aug-cc-pVQZ basis sets, using the Integral Equation Formalism Polarized Continuum Model (IEF-PCM). The calculations show that the B3LYP and PBE functionals provide similar results. With the exception of benzene, toluene and DMSO, the differences in values for all solvents are lower than 6 kJ mol-1. The BHLYP solvation enthalpies are higher by 20-25 kJ mol-1 than the B3LYP ones.

Keywords

  • electron solvation enthalpy
  • solvent
  • DFT
  • IEF-PCM
Open Access

Crystal and molecular structure of (5S,8aS,9S)-9-hydroxy- 5-methyl- 4,6,7,8,8a,9-hexahydrothieno-[ 3,2-f] indolizin-5-ium iodide

Published Online: 27 May 2014
Page range: 34 - 37

Abstract

Abstract

The title compound, C11H16NOS・I, is chiral molecule with three stereogenic centres. The absolute configuration was assigned from the synthesis and confirmed by the structure determination. The central six-membered ring of the indolizine moiety adopts a half-chair conformation with atom displaced by 0.655 (2) A from the plane of the oder remaining five atoms. The pyrrolidine ring adopts an envelope conformation, with the greatest deviation from the mean plane of the ring being 0.646 (2) A for the bridgehead N atom. The crystal structure of the title compound is stabilized by O-H・・・I and C-H・・・O hydrogen bonds.

Keywords

  • conformation
  • crystal structure
  • hydrogen bonds
  • indolizine
  • single-crystal X-ray study
Open Access

Testing of selected probiotic properties of lactic acid bacteria isolated from vegetarians and meat-eaters faeces

Published Online: 27 May 2014
Page range: 38 - 43

Abstract

Abstract

The aim of this work was to evaluate presence and properties of lactic acid bacteria in the faeces of 240 volunteers with various nutrition habits (vegetarians versus meat-eaters). Lactic acid bacteria counts in all age groups were nearly 5 or 6 logarithmic orders. Significantly higher amounts were found in women. Subsequently, based on the age and dietary pattern of probands, four samples were selected for isolation of lactic acid bacteria and identification of isolates in order to assign them to bacterial species. About 80 lactic acid bacteria were isolated from the faeces of young (21-30 years) and older (51-60 years) vegetarians and meateaters. The identification of the isolates was based on their morphological and biochemical characteristics. Isolates belong to lactobacilli, bifidobacteria, enterococci and propionibacteria. Surprisingly, bifidobacteria were predominated in older age group. The following probiotic properties were determined: survival at low pH value, and bile salt hydrolase activity. All strains were negative in bile salt hydrolase activity, but their growth was not inhibited in the presence of bile. The results from the study of survival at low pH value showed considerable variability in both dietary groups regardless the age of probands. However, it can be concluded, that bacteria isolated from the samples of older probands were more sensitive to acid pH.

Keywords

  • gastrointestinal tract
  • lactic acid bacteria
  • meat-eaters
  • vegetarians
Open Access

Identification of biodegradation products of biphenyl and 2,3-dihydroxybiphenyl (2,3-DHB)

Published Online: 27 May 2014
Page range: 44 - 51

Abstract

Abstract

We investigated the degradation of biphenyl and identified main degradation products. Biphenyl and 2,3-dihydroxybiphenyl (2,3-DHB) was added to cultivation media to identify whole collection of degradation products of four bacterial strains isolated from long-term PCB contaminated soil (Alcaligenes xylosoxidans and Pseudomonas stutzeri) and long-term PCB contaminated sediment (Ochrobactrum anthropi and Pseudomonas veronii). Cultivation flasks were processed in different time after inoculation to determine biphenyl fission rate. Alcaligenes xylosoxidans was revealed as the most appropriate strain for bioremediation process with the highest biphenyl transformation rate. Biphenyl degradation led to the formation of benzoic acid. However, as the presence of 2-hydroxy-6-oxo-6-phenylhex-2,4-dienoic acid (HOPDA) was not confirmed, the transformation pathway common for many other bacteria is probably modified.

Keywords

  • bacteria
  • biodegradation
  • biphenyl
  • degradation products
  • 2,3-dihydroxybiphenyl
Open Access

Lectin detection of cell surface saccharides remodeling induced by development of P-glycoprotein mediated multidrug resistance phenotype in L1210 leukemia cells

Published Online: 27 May 2014
Page range: 52 - 56

Abstract

Abstract

P-glycoprotein is an ATP dependent drug efflux pump the expression of which is responsible for strong depression of cell sensitivities to large group of structurally unrelated substances in neoplastic cells. We found that the expression of this protein in mice leukemia cells L1210 is associated with massive remodeling of cell surface saccharides. This remodeling is consistent with the alteration of cellular contents of UDP-sugars, glycogen and glycoproteins when P-gp positive and P-gp negative L1210 cell variants were compared. The current paper is focused on bringing the state of art information about this topic.

Open Access

Production of pectin lyase from Geobacillus pallidus p26, purification, characterization and fruit juice application

Published Online: 27 May 2014
Page range: 57 - 63

Abstract

Abstract

A bacterial strain was isolated from Pasinler hot spring, Erzurum, Turkey. The purified thermophilic isolate was identified as Geobacillus pallidus P26 and used to produce extracellular pectin lyase (EC 4.2.2.10). Pectin lyase enzyme was purified 34 fold by using DEAE-cellulose anion exchange column chromatography and characterized. Molecular weight of the enzyme was determined as 56 kDa by using Sephadex G-100 gel filtration chromatography. Purification of enzyme was verified by SDS-PAGE. The pH- and temperature optima of enzyme were determined (pH 9.0 and 60°C, respectively). Pectin lyase was mostly stable at 50 oC for 24 hours. Its’ activity decreased to 50 % for 24 h at 60°C. KM and Vmax were calculated as 24.8 mg/mL and 2.28 μmol/L min, respectively. Purified pectin lyase was inhibited by Fe3+, Zn2+, Cu2+, Ca2+, Co2+ and Hg2+ but not by Mg2+. The purified pectin lyase enzyme was used for getting fruits juices. It was found that yields of fruits juices increased when they were compared with control.

Keywords

  • Pectin lyase
  • purification
  • characterization
  • Geobacillus pallidus P26

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