MD4366C1 - Bis[1-phenyl-3-methyl-6-(pyridinium-4-il)-4,5-diaza-hexa-1,3,5-triene-1-hydroxy-6-olato-O1,N4,O6]iron(II)sulphate tetrahydrate and process for cultivation of microalga Porphyridium cruentum with its use - Google Patents
Bis[1-phenyl-3-methyl-6-(pyridinium-4-il)-4,5-diaza-hexa-1,3,5-triene-1-hydroxy-6-olato-O1,N4,O6]iron(II)sulphate tetrahydrate and process for cultivation of microalga Porphyridium cruentum with its use Download PDFInfo
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- MD4366C1 MD4366C1 MDA20140069A MD20140069A MD4366C1 MD 4366 C1 MD4366 C1 MD 4366C1 MD A20140069 A MDA20140069 A MD A20140069A MD 20140069 A MD20140069 A MD 20140069A MD 4366 C1 MD4366 C1 MD 4366C1
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- iron
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- 238000000034 method Methods 0.000 title claims abstract description 19
- 241001494715 Porphyridium purpureum Species 0.000 title claims abstract description 17
- -1 iron(II)sulphate tetrahydrate Chemical class 0.000 title abstract description 6
- 239000002028 Biomass Substances 0.000 claims abstract description 34
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 12
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims abstract description 12
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 12
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910019501 NaVO3 Inorganic materials 0.000 claims abstract description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052927 chalcanthite Inorganic materials 0.000 claims abstract description 6
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims abstract description 6
- 235000019797 dipotassium phosphate Nutrition 0.000 claims abstract description 6
- 239000012153 distilled water Substances 0.000 claims abstract description 6
- 229910052564 epsomite Inorganic materials 0.000 claims abstract description 6
- 238000005286 illumination Methods 0.000 claims abstract description 6
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 claims abstract description 6
- 230000000737 periodic effect Effects 0.000 claims abstract description 6
- 239000011780 sodium chloride Substances 0.000 claims abstract description 6
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 235000010344 sodium nitrate Nutrition 0.000 claims abstract description 6
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229910000368 zinc sulfate Inorganic materials 0.000 claims abstract description 6
- 239000011686 zinc sulphate Substances 0.000 claims abstract description 6
- 235000009529 zinc sulphate Nutrition 0.000 claims abstract description 6
- 235000015097 nutrients Nutrition 0.000 claims abstract description 4
- 150000002989 phenols Chemical class 0.000 claims description 12
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 9
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 9
- 230000003078 antioxidant effect Effects 0.000 abstract description 9
- 239000003963 antioxidant agent Substances 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 235000013305 food Nutrition 0.000 abstract description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 238000013019 agitation Methods 0.000 abstract 1
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 14
- 241000206618 Porphyridium Species 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 229940074391 gallic acid Drugs 0.000 description 7
- 235000004515 gallic acid Nutrition 0.000 description 7
- 239000003446 ligand Substances 0.000 description 7
- 238000002329 infrared spectrum Methods 0.000 description 5
- 239000002609 medium Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- UQKCYIJPXBSQGJ-UHFFFAOYSA-L iron(2+);sulfate;tetrahydrate Chemical compound O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O UQKCYIJPXBSQGJ-UHFFFAOYSA-L 0.000 description 3
- 239000007003 mineral medium Substances 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 238000005115 demineralization Methods 0.000 description 2
- 230000002328 demineralizing effect Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 235000008935 nutritious Nutrition 0.000 description 2
- CVBUKMMMRLOKQR-UHFFFAOYSA-N 1-phenylbutane-1,3-dione Chemical compound CC(=O)CC(=O)C1=CC=CC=C1 CVBUKMMMRLOKQR-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000002225 anti-radical effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000004698 iron complex Chemical class 0.000 description 1
- QRXWMOHMRWLFEY-UHFFFAOYSA-N isoniazide Chemical group NNC(=O)C1=CC=NC=C1 QRXWMOHMRWLFEY-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
Landscapes
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Invenţia se referă la chimie şi biotehnologie, în special la sinteza unui nou compus coordinativ al fierului(II) care poate fi utilizat pentru obţinerea unei biomase cu un potenţial antioxidant sporit şi care poate fi utilizată în industria alimentară şi în medicină, şi la un procedeu de cultivare a microalgei Porphyridium cruentum cu utilizarea acestuia. The invention relates to chemistry and biotechnology, in particular to the synthesis of a new coordination compound of iron(II) that can be used to obtain a biomass with an increased antioxidant potential and that can be used in the food industry and in medicine, and to a process of the cultivation of the microalgae Porphyridium cruentum with its use.
Compusul coodinativ este propus spre aplicare în biotehnologiile de tip intensiv în scopul obţinerii de biomasă cu un potenţial antioxidant sporit. Biomasa obţinută este utilizată în calitate de materie primă pentru obţinerea produselor antioxidante, care pot fi utilizate în procesarea produselor alimentare şi în scopuri medicale în calitate de antioxidanţi (Rudic Valeriu ş.a. Ficobiotehnologie - cercetări fundamentale şi realizări practice. Tipografia "Elena V.I." SRL, Chişinău, 2007, 365 p.). The co-ordinative compound is proposed for application in intensive biotechnologies in order to obtain biomass with an increased antioxidant potential. The obtained biomass is used as a raw material for the production of antioxidant products, which can be used in the processing of food products and for medical purposes as antioxidants (Rudic Valeriu et al. Phycobiotechnology - fundamental research and practical achievements. Typografia "Elena V.I." SRL, Chisinau, 2007, 365 p.).
Este cunoscut procedeul de cultivare a microalgei Porphyridium cruentum pe mediul mineral nutritiv ce conţine, g/L: NaNO3 - 5,0; NaCl - 7,0; KCl -7,5; MgSO4·7H2O - 1,8; Ca(NO3)2·4H2O - 0,15; KBr - 0,05; KI - 0,05; K2HPO4 - 0,2; ZnSO4·5H2O - 0,00002; CuSO4·5H2O - 0,00005; MnSO4·5H2O - 0,0003; H3BO3 - 0,0006; MoO3 - 0,00002; NaVO3 - 0,00005 şi apă distilată până la 1 litru; având pH-ul 6,8…7,2, la temperatura de 23…25°C, iluminarea de 2000…3000 lx, cu agitare lentă periodică. În prima zi de cultivare mediul este suplimentat cu compusul [Fe3O(Gly)6(H2O)3](NO3)7·3,5H2O în concentraţia de 0,001 g/L. Conţinutul de fenoli în biomasa de Porphyridium constituie 10,6…11,8 echivalent mg acid galic/g biomasă [1]. The process of cultivating the microalga Porphyridium cruentum on the nutrient mineral medium containing, g/L: NaNO3 - 5.0 is known; NaCl - 7.0; KCl -7.5; MgSO4·7H2O - 1.8; Ca(NO3)2·4H2O - 0.15; KBr - 0.05; KI - 0.05; K2HPO4 - 0.2; ZnSO4·5H2O - 0.00002; CuSO4·5H2O - 0.00005; MnSO4·5H2O - 0.0003; H3BO3 - 0.0006; MoO3 - 0.00002; NaVO3 - 0.00005 and distilled water up to 1 liter; having a pH of 6.8...7.2, at a temperature of 23...25°C, illumination of 2000...3000 lx, with periodic slow stirring. On the first day of cultivation, the medium is supplemented with the compound [Fe3O(Gly)6(H2O)3](NO3)7·3.5H2O in a concentration of 0.001 g/L. The content of phenols in Porphyridium biomass is 10.6...11.8 mg gallic acid equivalent/g biomass [1].
Neajunsul compusului şi al procedeului cunoscut constă în conţinutul redus de fenoli în biomasa de Porphyridium. The shortcoming of the compound and the known process consists in the low content of phenols in the Porphyridium biomass.
Problema pe care o rezolvă prezenta invenţie constă în sinteza unui compus nou şi în elaborarea unui procedeu eficient şi reproductibil de sporire a conţinutului de fenoli în biomasa de Porphyridium cruentum CNMN-AR-01. The problem that the present invention solves consists in the synthesis of a new compound and in the development of an efficient and reproducible process for increasing the content of phenols in the biomass of Porphyridium cruentum CNMN-AR-01.
Esenţa invenţiei constă în faptul că se propune un compus coordinativ nou - bis[1-fenil-3-metil-6-(piridinium-4-il)-4,5-diaza-hexa-1,3,5-trien-1-hidroxi-6-olato-O1,N4,O6] fier(II) sulfat tetrahidrat, obţinut prin interacţiunea izonicotinoilhidrazonei 1-fenil-1,3-butandionei şi a sulfatului de fier(II) în raport molar de 2:1 ([Fe(L)2]SO4·4H2O). The essence of the invention consists in the fact that a new coordination compound is proposed - bis[1-phenyl-3-methyl-6-(pyridinium-4-yl)-4,5-diaza-hexa-1,3,5-trien-1 -hydroxy-6-olato-O1,N4,O6] iron(II) sulfate tetrahydrate, obtained by the interaction of isonicotinoylhydrazone 1-phenyl-1,3-butanedione and iron(II) sulfate in a molar ratio of 2:1 ([ Fe(L)2]SO4·4H2O).
De asemenea, se propune un procedeu de cultivare a microalgei Porphyridium cruentum, care constă în aceea că se cultivă microalga pe un mediu nutritiv ce conţine, g/L: NaNO3 - 5,0; NaCl - 7,0; KCl - 7,5; MgSO4·7H2O - 1,8; Ca(NO3)2·4H2O - 0,15; KBr - 0,05; KI - 0,05; K2HPO4 - 0,2; ZnSO4·5H2O - 0,00002; CuSO4·5H2O - 0,00005; MnSO4·5H2O - 0,0003; H3BO3 - 0,0006; MoO3 - 0,00002; NaVO3 - 0,00005, suplimentat cu compusul bis[1-fenil-3-metil-6-(piridinium-4-il)-4,5-diaza-hexa-1,3,5-trien-1-hidroxi-6-olato-O1,N4, O6]fier(II) sulfat tetrahidrat - 0,011…0,012 şi apă distilată până la 1 L; având pH-ul 6,8…7,2, la temperatura de 23…25°C, iluminarea de 2000…3000 lx/cm2, cu agitare lentă periodică. Also, a procedure for cultivating the microalgae Porphyridium cruentum is proposed, which consists in cultivating the microalgae on a nutrient medium containing, g/L: NaNO3 - 5.0; NaCl - 7.0; KCl - 7.5; MgSO4·7H2O - 1.8; Ca(NO3)2·4H2O - 0.15; KBr - 0.05; KI - 0.05; K2HPO4 - 0.2; ZnSO4·5H2O - 0.00002; CuSO4·5H2O - 0.00005; MnSO4·5H2O - 0.0003; H3BO3 - 0.0006; MoO3 - 0.00002; NaVO3 - 0.00005, supplemented with the compound bis[1-phenyl-3-methyl-6-(pyridinium-4-yl)-4,5-diaza-hexa-1,3,5-triene-1-hydroxy-6 -olato-O1,N4,O6]iron(II) sulfate tetrahydrate - 0.011...0.012 and distilled water up to 1 L; having a pH of 6.8...7.2, at a temperature of 23...25°C, illumination of 2000...3000 lx/cm2, with periodic slow stirring.
Conţinutul de fenoli, determinat prin metoda Folin-Ciocalteu, în biomasa de Porphyridium este de 13,6…13,8 echivalent mg acid galic /g biomasă. The content of phenols, determined by the Folin-Ciocalteu method, in Porphyridium biomass is 13.6...13.8 mg gallic acid equivalent /g biomass.
Compusul sus-menţionat, proprietăţile lui şi procedeul de obţinere nu sunt descrise în literatură. The above-mentioned compound, its properties and the method of obtaining it are not described in the literature.
Rezultatul tehnic al invenţiei constă în majorarea conţinutului de fenoli în biomasa microalgei Porphyridium cruentum cu 15…17% faţă de cea mai apropiată soluţie. Administrarea compusului din prima zi de cultivare stimulează acumularea componentelor fenolice în biomasa microalgei, care sporesc valoarea biomasei de Porphyridium în calitate de producător de antioxidanţi. The technical result of the invention consists in increasing the content of phenols in the biomass of the microalgae Porphyridium cruentum by 15...17% compared to the closest solution. Administration of the compound from the first day of cultivation stimulates the accumulation of phenolic components in the microalgae biomass, which increase the value of the Porphyridium biomass as an antioxidant producer.
Rezultatul invenţiei este condiţionat de aplicarea pentru prima dată a compusului bis[1-fenil-3-metil-6-(piridinium-4-il)-4,5-diaza-hexa-1,3,5-trien-1-hidroxi-6-olato-O1,N4,O6]fier(II) sulfat tetrahidrat în calitate de stimulator al biosintezei componentelor fenolice de către microalga Porphyridium cruentum. The result of the invention is conditioned by the application for the first time of the compound bis[1-phenyl-3-methyl-6-(pyridinium-4-yl)-4,5-diaza-hexa-1,3,5-triene-1-hydroxy -6-olato-O1,N4,O6]iron(II) sulfate tetrahydrate as a stimulator of the biosynthesis of phenolic components by the microalga Porphyridium cruentum.
Exemplu de realizare a invenţiei Example of realization of the invention
Metodă de obţinere a compusului revendicat Method of obtaining the claimed compound
În urma reacţiei dintre izonicotinoilhidrazona 1-fenil-1,3-butandionei şi sulfatul de fier(II) în raport molar de 2:1, la agitare în atmosferă inertă, se obţine combinaţia complexă sub formă de cristale de culoare verde, care decurge conform schemei: Following the reaction between 1-phenyl-1,3-butanedione isonicotinoylhydrazone and iron(II) sulfate in a molar ratio of 2:1, upon stirring in an inert atmosphere, the complex combination is obtained in the form of green crystals, which proceeds according to schemes:
Schema I. Obţinerea compusului [Fe(L)2]2SO4·4H2O Scheme I. Obtaining the compound [Fe(L)2]2SO4·4H2O
Structura ligandului necoordinat stabilită cu raze X este prezentată în figură, în care la împachetarea cristalină are loc formarea legăturilor de hidrogen cu participarea grupelor C=O şi NH. În spectrul IR al ligandului liber se manifestă benzile ν(NH)=3218 cm-1 şi ν(C=O)=1664 cm-1. The structure of the non-coordinated ligand established by X-rays is shown in the figure, where the formation of hydrogen bonds with the participation of C=O and NH groups takes place during the crystalline packing. The IR spectrum of the free ligand shows the bands ν(NH)=3218 cm-1 and ν(C=O)=1664 cm-1.
Compusul obţinut a fost apreciat prin analiza chimică elementală şi spectrele IR înregistrate în domeniul 4000…400 cm-1. The compound obtained was evaluated by elemental chemical analysis and IR spectra recorded in the range 4000...400 cm-1.
Spectrul în IR se caracterizează prin prezenţa a două benzi late în regiunea 3500…3200 cm-1, care pot fi atribuite ν(OH) asociate, absorbţie largă în regiunea 3100…3000 cm-1, care conţine câteva benzi ν(CH) ale inelelor benzenic şi heterociclic, 2930…2850 cm-1 ν(CH3), două benzi late de intensitate slabă la 2612 şi 2148 cm-1, care pot fi atribuite oscilaţiilor =NH+ (azotul heterociclic protonat) (Беллами Л. Инфракрасные спектры сложных молекул. Издательство иностранной литературы, Москва, 1963, 592 p., Накамото К. ИК спектры и спектры КР неорганических и координационных соединений. Москва, Мир, 1991, 536 p., Тарасевич Б. Н. ИК спектры основных классов органических соединений. Справочные материалы, Москва, 2012, 54 p.). The IR spectrum is characterized by the presence of two broad bands in the 3500…3200 cm-1 region, which can be attributed to associated ν(OH), broad absorption in the 3100…3000 cm-1 region, which contains several ν(CH) bands of benzene and heterocyclic rings, 2930...2850 cm-1 ν(CH3), two broad bands of weak intensity at 2612 and 2148 cm-1, which can be assigned to =NH+ (protonated heterocyclic nitrogen) oscillations (Беллами Л. . Издательство иностранной литературы, Moscow, 1963, 592 p., Nakamoto K. IR spectra and spectra of KR inorganic and coordination compounds. Moscow, Mir, 1991, 536 p., Tarasevich B. N. IR spectra of basic classes of organic compounds. Reference materials , Moscow, 2012, 54 p.).
Dispariţia benzii de absorbţie ν(C=O) a fragmentului hidrazidei acidului izonicotinic şi manifestarea unei benzi intensive la 1303 cm-1 confirmă faptul că ligandul coordinează la atomul de fier în formă enolică. Banda de intensitate medie la 1631 cm-1 este atribuită oscilaţiilor ν(C=N) şi ν(C=C). Oscilaţiile ν(N-N) se manifestă printr-o bandă de intensitate medie la 841cm-1. Prezenţa celei mai intensive benzi de absorbţie la 1079 cm-1 indică cu siguranţă prezenţa anionului SO4 2- în complex. The disappearance of the ν(C=O) absorption band of the isonicotinic acid hydrazide fragment and the appearance of an intensive band at 1303 cm-1 confirm that the ligand coordinates to the iron atom in enolic form. The medium intensity band at 1631 cm-1 is attributed to ν(C=N) and ν(C=C) oscillations. The ν(N-N) oscillations are manifested by a medium intensity band at 841cm-1. The presence of the most intensive absorption band at 1079 cm-1 certainly indicates the presence of the SO4 2- anion in the complex.
Conform datelor analizei elementale şi spectroscopiei IR pentru complexul dat se propune formula [Fe(L)2]SO4·4H2O. According to the elemental analysis and IR spectroscopy data, the formula [Fe(L)2]SO4·4H2O is proposed for the given complex.
Datele structurale ale ligandului necoordinat şi cele spectrale ale ligandului şi complexului fierului conduc la concluzia că ligandul coordinează la metal ca unul tridentat (setul de atomi ONO) şi nedeprotonat cu delocalizarea electronilor pe legăturile N-C-O ale fragmentului amidic şi migraţia protonului de la grupa N-H a acestui fragment la atomul de azot heterociclic, confirmând componenţa complexului [Fe(L)2]SO4·4H2O (Jin-Xiu Wang, Xiao-Zeng Li, Li-Na Zhu, Ji-Yao Wang, Hao Qu. Synthesis and Crystal Structure of a Fe(III) Complex with an Isonicotinyl Ligand, [Fe(N-Isonicotinamidosalicylaldimine)Cl2]. J. Chem. Crystallogr. (2010) 40: 726-730 DOI 10.1007/s10870-010-9726-6). The structural data of the uncoordinated ligand and the spectral data of the ligand and the iron complex lead to the conclusion that the ligand coordinates to the metal as a tridentate (ONO atom set) and non-protonated one with electron delocalization on the N-C-O bonds of the amide fragment and proton migration from the N-H group of this fragment at the heterocyclic nitrogen atom, confirming the composition of the complex [Fe(L)2]SO4·4H2O (Jin-Xiu Wang, Xiao-Zeng Li, Li-Na Zhu, Ji-Yao Wang, Hao Qu. Synthesis and Crystal Structure of a Fe(III) Complex with an Isonicotinyl Ligand, [Fe(N-Isonicotinamidosalicylaldimine)Cl2]. J. Chem. Crystallogr. (2010) 40: 726-730 DOI 10.1007/s10870-010-9726-6).
Metodă de obţinere a [Fe(L)2]SO4·4H2O Method for obtaining [Fe(L)2]SO4·4H2O
Reacţia are loc în atmosferă inertă, prin barbotare cu argon. The reaction takes place in an inert atmosphere, by bubbling with argon.
0,2 g de izonicotinoilhidrazona 1-fenil-1,3-butandionei se dizolvă în 10 ml metanol. La soluţia obţinută se adaugă soluţia formată din 0,1 g FeSO4 dizolvat în 5 ml de apă. Din soluţia obţinută de culoare neagră cad cristale mărunte de culoare cafenie, care se separă de soluţia-mamă prin filtrare, se spală cu metanol şi eter dietilic şi se usucă la aer. 0.2 g of 1-phenyl-1,3-butanedione isonicotinoylhydrazone is dissolved in 10 ml of methanol. To the obtained solution, add the solution consisting of 0.1 g of FeSO4 dissolved in 5 ml of water. Small brown crystals fall from the black solution obtained, which are separated from the mother solution by filtration, washed with methanol and diethyl ether and dried in air.
Se obţin 0,14 g (randamentul reacţiei este de 44,6%). 0.14 g is obtained (reaction yield is 44.6%).
Compusul este solubil în cloroform, dimetilformamidă, dimetilsulfoxidă, etanol, metanol şi insolubil în apă. The compound is soluble in chloroform, dimethylformamide, dimethylsulfoxide, ethanol, methanol and insoluble in water.
Rezultatele analizei elementale pentru [C32H30N6O4Fe]SO4·4H2O (M = 786 g): The results of the elemental analysis for [C32H30N6O4Fe]SO4·4H2O (M = 786 g):
găsit: C, 46,45; H, 4,64; N, 10,85; Fe, 8,00. found: C, 46.45; H, 4.64; N, 10.85; Fe, 8.00.
calculat: C, 48, 58; H, 4,83; N, 10,69; Fe, 7,13. calculated: C, 48, 58; H, 4.83; N, 10.69; Fe, 7,13.
Exemple de aplicare a compusului bis[1-fenil-3-metil-6-(piridinium-4-il)-4,5-diaza-hexa-1,3,5-trien-1-hidroxi-6-olato-O1,N4,O6]fier(II) sulfat tetrahidrat în calitate de stimulator al acumulării componentelor fenolice în biomasa microalgei Porphyridium cruentum. Examples of application of the compound bis[1-phenyl-3-methyl-6-(pyridinium-4-yl)-4,5-diaza-hexa-1,3,5-trien-1-hydroxy-6-olato-O1 ,N4,O6]iron(II) sulfate tetrahydrate as a stimulator of the accumulation of phenolic components in the biomass of the microalgae Porphyridium cruentum.
Exemplul 1 Example 1
Se prepară mediul mineral nutritiv cu următorul conţinut al componentelor (g/L): NaNO3 - 5,0; NaCl - 7,0; KCl -7,5; MgSO4·7H2O - 1,8; Ca(NO3)2·4H2O - 0,15; KBr - 0,05; KI - 0,05; K2HPO4 - 0,2; ZnSO4·5H2O - 0,00002; CuSO4·5H2O - 0,00005; MnSO4·5H2O - 0,0003; H3BO3 - 0,0006; MoO3 - 0,00002; NaVO3 - 0,00005 şi apă distilată până la 1litru. În prima zi de cultivare la suspensia de Porphyridium, în calitate de stimulator al biosintezei fenolilor, se adaugă compusul bis[1-fenil-3-metil-6-(piridinium-4-il)-4,5-diaza-hexa-1,3,5-trien-1-hidroxi-6-olato-O1,N4,O6] fier(II) - sulfat tetrahidrat în concentraţie de 0,011 g/L. Cultivarea se efectuează în baloane Erlenmayer a câte 1000 ml cu 500 ml suspensie în următoarele condiţii: pH-ul 6,8…7,2, temperatura de 23…25°C, iluminarea de 2000…3000 lx, agitare lentă periodică. La ziua a 10-a, biomasa de Porphyridium se separă de lichidul cultural, se supune demineralizării şi se standardizează după biomasă. În biomasa obţinută se determină conţinutul de fenoli cu aplicarea metodei Folin-Ciocalteu. Prepare the nutritious mineral medium with the following content of components (g/L): NaNO3 - 5.0; NaCl - 7.0; KCl -7.5; MgSO4·7H2O - 1.8; Ca(NO3)2·4H2O - 0.15; KBr - 0.05; KI - 0.05; K2HPO4 - 0.2; ZnSO4·5H2O - 0.00002; CuSO4·5H2O - 0.00005; MnSO4·5H2O - 0.0003; H3BO3 - 0.0006; MoO3 - 0.00002; NaVO3 - 0.00005 and distilled water up to 1 liter. On the first day of cultivation, the compound bis[1-phenyl-3-methyl-6-(pyridinium-4-yl)-4,5-diaza-hexa-1 is added to the Porphyridium suspension, as a stimulator of the biosynthesis of phenols ,3,5-trien-1-hydroxy-6-olato-O1,N4,O6] iron(II) - sulfate tetrahydrate in a concentration of 0.011 g/L. Cultivation is carried out in Erlenmayer flasks of 1000 ml with 500 ml of suspension under the following conditions: pH 6.8...7.2, temperature 23...25°C, illumination 2000...3000 lx, periodic slow stirring. On day 10, the Porphyridium biomass is separated from the culture liquid, subjected to demineralization and standardized by biomass. In the biomass obtained, the phenol content is determined by applying the Folin-Ciocalteu method.
Biomasa de Porphyridium conţine 13,6±0,06 (p<0,5) mg acid galic echivalent/g biomasă, faţă de 11,8 mg acid galic echivalent/g biomasă în cazul celei mai apropiate soluţii (vezi tabelul). Sporul conţinutului de fenoli este de 15%. Porphyridium biomass contains 13.6±0.06 (p<0.5) mg gallic acid equivalent/g biomass, compared to 11.8 mg gallic acid equivalent/g biomass in the case of the closest solution (see table). The increase in phenol content is 15%.
Exemplul 2 Example 2
Se prepară mediul mineral nutritiv cu următorul conţinut al componentelor (g/L): NaNO3 - 5,0; NaCl - 7,0; KCl -7,5; MgSO4·7H2O - 1,8; Ca(NO3)2·4H2O - 0,15; KBr - 0,05; KI - 0,05; K2HPO4 - 0,2; ZnSO4·5H2O - 0,00002; CuSO4·5H2O - 0,00005; MnSO4·5H2O - 0,0003; H3BO3 - 0,0006; MoO3 - 0,00002; NaVO3 - 0,00005 şi apă distilată până la 1 litru. În prima zi de cultivare la suspensia de Porphyridium, în calitate de stimulator al biosintezei fenolilor, se adaugă compusul bis[1-fenil-3-metil-6-(piridinium-4-il)-4,5-diaza-hexa-1,3,5-trien-1-hidroxi-6-olato-O1, N4, O6] fier(II) sulfat tetrahidrat în concentraţie de 0,012 g/L. Cultivarea se efectuează în baloane Erlenmayer a câte 1000 ml cu 500 ml suspensie în următoarele condiţii: pH-ul 6,8…7,2, temperatura de 23…25°C, iluminarea de 2000…3000 lx, agitare lentă periodică. La ziua a 10-a, biomasa de Porphyridium se separă de lichidul cultural, se supune demineralizării şi se standardizează după biomasă. În biomasa obţinută se determină conţinutul de fenoli cu aplicarea metodei Folin-Ciocalteu. Biomasa de Porphyridium conţine 13,8±0,04 (p<0,5) mg acid galic echivalent/g biomasă, faţă de 0,88 mg acid galic echivalent/g biomasă în cazul celei mai apropiate soluţii (vezi tabelul). Sporul conţinutului de fenoli este de 17%. Prepare the nutritious mineral medium with the following content of components (g/L): NaNO3 - 5.0; NaCl - 7.0; KCl -7.5; MgSO4·7H2O - 1.8; Ca(NO3)2·4H2O - 0.15; KBr - 0.05; KI - 0.05; K2HPO4 - 0.2; ZnSO4·5H2O - 0.00002; CuSO4·5H2O - 0.00005; MnSO4·5H2O - 0.0003; H3BO3 - 0.0006; MoO3 - 0.00002; NaVO3 - 0.00005 and distilled water up to 1 liter. On the first day of cultivation, the compound bis[1-phenyl-3-methyl-6-(pyridinium-4-yl)-4,5-diaza-hexa-1 is added to the Porphyridium suspension, as a stimulator of the biosynthesis of phenols ,3,5-trien-1-hydroxy-6-olato-O1, N4, O6] iron(II) sulfate tetrahydrate in a concentration of 0.012 g/L. Cultivation is carried out in Erlenmayer flasks of 1000 ml with 500 ml of suspension under the following conditions: pH 6.8...7.2, temperature 23...25°C, illumination 2000...3000 lx, periodic slow stirring. On day 10, the Porphyridium biomass is separated from the culture liquid, subjected to demineralization and standardized by biomass. In the biomass obtained, the phenol content is determined by applying the Folin-Ciocalteu method. Porphyridium biomass contains 13.8±0.04 (p<0.5) mg gallic acid equivalent/g biomass, compared to 0.88 mg gallic acid equivalent/g biomass in the case of the closest solution (see table). The increase in phenol content is 17%.
Tabel Table
Conţinutul de fenoli în biomasa de Porphyridium cruentum, obţinută la cultivare conform procedeului revendicat şi celei mai apropiate soluţii The content of phenols in the biomass of Porphyridium cruentum, obtained by cultivation according to the claimed process and the closest solution
Procedeul aplicat Concentraţia compusului, g/L Conţinutul de fenoli, echivalent mg acid galic /g biomasă Cea mai apropiată soluţie 0,01 10,6…11,8 Soluţia revendicată 0,011 13,6±0,06 0,012 13,8±0,04 The applied procedure Compound concentration, g/L Phenol content, equivalent mg gallic acid /g biomass The closest solution 0.01 10.6...11.8 The claimed solution 0.011 13.6±0.06 0.012 13.8±0, 04
Datele din tabel demonstrează o creştere a conţinutului de fenoli în biomasa de Porphyridium cruentum cu 15…17% conform procedeului revendicat, faţă de procedeul cel mai apropiat. Biomasa microalgei Porphyridium cruentum reprezintă o sursă modernă de substanţe antioxidante, iată de ce sporul conţinutului de fenoli este un factor al creşterii valorii porfiridiumului în calitate de producător de substanţe cu efect antioxidant. Proprietăţile compusului bis[1-fenil-3-metil-6-(piridinium-4-il)-4,5-diaza-hexa-1,3,5-trien-1-hidroxi-6-olato-O1,N4,O6]fier(II) sulfat tetrahidrat prezintă interes pentru biotehnologie în calitate de stimulator al producerii fenolilor, compuşi cu proprietăţi antioxidante, în biomasa microalgei Porphyridium cruentum. The data in the table demonstrate an increase in the content of phenols in the biomass of Porphyridium cruentum by 15...17% according to the claimed process, compared to the closest process. The biomass of the microalgae Porphyridium cruentum represents a modern source of antioxidant substances, this is why the increase in the content of phenols is a factor in increasing the value of porphyridium as a producer of substances with an antioxidant effect. The properties of the compound bis[1-phenyl-3-methyl-6-(pyridinium-4-yl)-4,5-diaza-hexa-1,3,5-triene-1-hydroxy-6-olato-O1,N4, O6]iron(II) sulfate tetrahydrate is of interest for biotechnology as a stimulator of the production of phenols, compounds with antioxidant properties, in the biomass of the microalgae Porphyridium cruentum.
1. Sadovnic D. Tehnologii de obţnere a preparatelor antioxidante şi antiradicalice din biomasa algei roşii Porphyridium cruentum CNM-AR-01. Teză de doctor în biologie, Chişinău, 2014 1. Sadovnic D. Technologies for obtaining antioxidant and antiradical preparations from the biomass of the red alga Porphyridium cruentum CNM-AR-01. PhD thesis in biology, Chisinau, 2014
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| MD4278B1 (en) * | 2013-04-30 | 2014-03-31 | Institutul De Chimie Al Academiei De Ştiinţe A Moldovei | Compound bis{bis(dimethylglyoximato)chloro}-µ-3-formylpiridineisonicotinoylhydrazone-di-cobalt(III) and process for cultivation of microalga Porphyridium cruentum with its use |
| CN203668407U (en) * | 2013-11-04 | 2014-06-25 | 许昌县四杰生物科技有限公司 | Induced cultivation system for microalgae |
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| Sadovnic D. Tehnologii de obţnere a preparatelor antioxidante şi antiradicalice din biomasa algei roşii Porphyridium cruentum CNM-AR-01. Teză de doctor în biologie, Chişinău, 2014 * |
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