MD4319C1 - Bis[(iminodiacetate)oxothiomolybdate(V)]tetraphenylphosphonium hydrate and process for cultivation of Spirulina platensis cyanobacterium with the use thereof - Google Patents
Bis[(iminodiacetate)oxothiomolybdate(V)]tetraphenylphosphonium hydrate and process for cultivation of Spirulina platensis cyanobacterium with the use thereof Download PDFInfo
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- MD4319C1 MD4319C1 MDA20130077A MD20130077A MD4319C1 MD 4319 C1 MD4319 C1 MD 4319C1 MD A20130077 A MDA20130077 A MD A20130077A MD 20130077 A MD20130077 A MD 20130077A MD 4319 C1 MD4319 C1 MD 4319C1
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- iminodiacetate
- tetraphenylphosphonium
- oxothiomolybdate
- cyanobacterium
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- 235000016425 Arthrospira platensis Nutrition 0.000 title claims abstract description 20
- 240000002900 Arthrospira platensis Species 0.000 title claims abstract description 20
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 241001464430 Cyanobacterium Species 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims abstract description 9
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 10
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000015097 nutrients Nutrition 0.000 claims abstract description 7
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims abstract description 5
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims abstract description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000001110 calcium chloride Substances 0.000 claims abstract description 5
- 235000011148 calcium chloride Nutrition 0.000 claims abstract description 5
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 5
- 229910052927 chalcanthite Inorganic materials 0.000 claims abstract description 5
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims abstract description 5
- 235000019797 dipotassium phosphate Nutrition 0.000 claims abstract description 5
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims abstract description 5
- 229910052564 epsomite Inorganic materials 0.000 claims abstract description 5
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 5
- 239000011565 manganese chloride Substances 0.000 claims abstract description 5
- 235000002867 manganese chloride Nutrition 0.000 claims abstract description 5
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims abstract description 5
- 229910052939 potassium sulfate Inorganic materials 0.000 claims abstract description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 5
- 239000011780 sodium chloride Substances 0.000 claims abstract description 5
- 235000010344 sodium nitrate Nutrition 0.000 claims abstract description 5
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims abstract description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 claims abstract description 5
- 239000011686 zinc sulphate Substances 0.000 claims abstract description 5
- 235000009529 zinc sulphate Nutrition 0.000 claims abstract description 5
- 238000005286 illumination Methods 0.000 claims abstract description 4
- 239000012153 distilled water Substances 0.000 claims abstract description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 10
- 239000011733 molybdenum Substances 0.000 claims description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims description 10
- 239000002028 Biomass Substances 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000003078 antioxidant effect Effects 0.000 abstract 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract 1
- 150000004676 glycans Chemical class 0.000 description 9
- 229920001282 polysaccharide Polymers 0.000 description 9
- 239000005017 polysaccharide Substances 0.000 description 9
- 230000002378 acidificating effect Effects 0.000 description 7
- 229940082787 spirulina Drugs 0.000 description 6
- 239000002609 medium Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000001720 carbohydrates Chemical class 0.000 description 4
- 235000014633 carbohydrates Nutrition 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910017299 Mo—O Inorganic materials 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 230000000975 bioactive effect Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 1
- 108091023020 Aldehyde Oxidase Proteins 0.000 description 1
- 102000048262 Aldehyde oxidases Human genes 0.000 description 1
- 229910017311 Mo—Mo Inorganic materials 0.000 description 1
- 108010027912 Sulfite Oxidase Proteins 0.000 description 1
- 102000043440 Sulfite oxidase Human genes 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 208000007502 anemia Diseases 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000002429 anti-coagulating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 208000006673 asthma Diseases 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000001483 mobilizing effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000013630 prepared media Substances 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- -1 tetraphenylphosphonium cations Chemical class 0.000 description 1
- WAGFXJQAIZNSEQ-UHFFFAOYSA-M tetraphenylphosphonium chloride Chemical compound [Cl-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 WAGFXJQAIZNSEQ-UHFFFAOYSA-M 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 210000004881 tumor cell Anatomy 0.000 description 1
Landscapes
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Peptides Or Proteins (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
Description
Invenţia se referă la chimie şi biotehnologie, în special la sinteza unui nou compus coordinativ din clasa polioxotiometalaţilor şi la un procedeu de cultivare a cianobacteriei Spirulina platensis cu utilizarea acestuia. The invention relates to chemistry and biotechnology, in particular to the synthesis of a new coordinating compound from the class of polyoxothiometalates and to a process for cultivating the cyanobacterium Spirulina platensis using it.
Molibdenul este un microelement esenţial pentru organismul uman. El joacă un rol cheie în formarea/activarea aldehidoxidazei, care contribuie la detoxifierea aldehidei acetice - o substanţă toxică care poate provoca cancerul. Molibdenul mai este cofactorul enzimei sulfitoxidazei. El este foarte important în tratarea bolnavilor cu astm şi alte afecţiuni respiratorii care sunt sensibili la sulfiţi. Molibdenul poate preveni anemia prin mobilizarea fierului şi majorarea nivelului lui în organism. Îmbogăţirea spirulinei cu molibden şi alte substanţe bioactive ar permite utilizarea ei ca remediu curativ în multe din afecţiunile sus-menţionate. De asemenea este cunoscut faptul că biomasa de spirulină conţine polizaharide cu activitate biologică pronunţată, în special polizaharide sulfatate. Ele posedă nu doar proprietăţi anticoagulante, dar sunt şi inhibitori ai unor tumori, afectând direct celulele tumorale. În afară de aceasta, ele s-au manifestat şi ca inhibitori ai virusului Hiv de tip 1 şi 2. De aceea, îmbogăţirea biomasei de spirulină cu molibden şi alte substanţe bioactive, cum sunt polizaharidele acide şi sulfatate, ar deschide noi perspective în vederea obţinerii spirulinei cu noi proprietăţi curative. Molybdenum is an essential trace element for the human body. It plays a key role in the formation/activation of aldehyde oxidase, which contributes to the detoxification of acetic aldehyde - a toxic substance that can cause cancer. Molybdenum is also the cofactor of the sulfite oxidase enzyme. It is very important in treating patients with asthma and other respiratory conditions that are sensitive to sulfites. Molybdenum can prevent anemia by mobilizing iron and increasing its level in the body. The enrichment of spirulina with molybdenum and other bioactive substances would allow its use as a curative remedy in many of the above-mentioned ailments. It is also known that spirulina biomass contains polysaccharides with pronounced biological activity, especially sulfated polysaccharides. They possess not only anticoagulant properties, but are also inhibitors of some tumors, directly affecting tumor cells. In addition, they have also been shown to be inhibitors of HIV type 1 and 2. Therefore, the enrichment of spirulina biomass with molybdenum and other bioactive substances, such as acidic and sulfated polysaccharides, would open new perspectives in order to obtain spirulina with new healing properties.
Dintre mediile de cultivare, descrise în literatură, care asigură creşterea cianobacteriei Spirulina platensis şi obţinerea biomasei cu un conţinut înalt de glucide (10…15%) este mediul Gromov, ce conţine în calitate de sursă de molibden MoO3 în concentraţie de 0,000015 g/L [1]. Among the cultivation media, described in the literature, which ensure the growth of the cyanobacterium Spirulina platensis and the obtaining of biomass with a high carbohydrate content (10...15%) is the Gromov medium, which contains as a source of molybdenum MoO3 in a concentration of 0.000015 g /L [1].
Este cunoscut un procedeu de obţinere a biomasei de Spirulina platensis cu un conţinut sporit de glucide, care include inocularea spirulinei pe un mediu nutritiv, ce conţine următoarele componente, g/L: NaHCO3 - 16,8; NaNO3 - 2,50; NaCl - 1,00; K2SO4 - 0,50; K2HPO4 - 0,50; CaCl2 - 0,04; MgSO4·7H2O - 0,20; H3BO3 - 0,00286; MnCl2 - 0,00181; ZnSO4·7H2O - 0,000022; CuSO4·5H2O - 0,00008; FeSO4 - 0,01; MoO3 - 0,000015; EDTA - 0,08 şi apă; cultivarea ei la iluminare de 15...24 mii erg/cm2 (sau 3021…5166,71 lx/cm2) şi temperatura de 35±1ºC. A process for obtaining Spirulina platensis biomass with an increased carbohydrate content is known, which includes the inoculation of spirulina on a nutrient medium, which contains the following components, g/L: NaHCO3 - 16.8; NaNO3 - 2.50; NaCl - 1.00; K2SO4 - 0.50; K2HPO4 - 0.50; CaCl2 - 0.04; MgSO4·7H2O - 0.20; H3BO3 - 0.00286; MnCl2 - 0.00181; ZnSO4·7H2O - 0.000022; CuSO4·5H2O - 0.00008; FeSO4 - 0.01; MoO3 - 0.000015; EDTA - 0.08 and water; its cultivation at illumination of 15...24 thousand erg/cm2 (or 3021...5166.71 lx/cm2) and temperature of 35±1ºC.
Dezavantajul procedeului de obţinere a biomasei de Spirulina platensis cunoscut constă în ponderea scăzută a polizaharidelor acide şi sulfatate din conţinutul total de glucide. Conţinutul de polizaharide acide şi sulfatate determinat în biomasă alcătuieşte: 0,88…1,38 şi 0,061…0,098%, respectiv. The disadvantage of the known Spirulina platensis biomass production process is the low percentage of acidic and sulfated polysaccharides in the total carbohydrate content. The content of acidic and sulfated polysaccharides determined in the biomass is: 0.88...1.38 and 0.061...0.098%, respectively.
Problema pe care o rezolvă prezenta invenţie constă în extinderea arsenalului de regulatori ai conţinutului de polizaharide acide şi sulfatate la cianobacteria Spirulina platensis şi elaborarea unui procedeu de cultivare a spirulinei. The problem that the present invention solves consists in expanding the arsenal of regulators of the content of acidic and sulfated polysaccharides in the cyanobacterium Spirulina platensis and developing a process for cultivating spirulina.
Esenţa invenţiei constă în faptul că se propune un compus coordinativ nou - hidrat de bis[(iminodiacetat)-oxotiomolibdat(V)] de tetrafenilfosfoniu cu formula: The essence of the invention consists in the fact that a new coordination compound is proposed - tetraphenylphosphonium bis[(iminodiacetate)-oxothiomolybdate(V)] hydrate with the formula:
şi utilizarea lui într-un procedeu de cultivare a cianobacteriei Spirulina platensis, care constă în aceea că se cultivă cianobacteria pe un mediu nutritiv ce conţine, g/L: NaHCO3 - 16,80; NaNO3 - 2,50; NaCl - 1,00; K2SO4 - 0,50; K2HPO4 - 0,50; CaCl2 - 0,04; MgSO4·7H2O - 0,20; H3BO3 - 0,00286; MnCl2 - 0,00181; ZnSO4·7H2O - 0,000022; CuSO4·5H2O - 0,00008; FeSO4 - 0,01; EDTA - 0,08; sursă de molibden şi apă distilată, la iluminarea de 3000…4800 lx/cm2 şi temperatura de 35±1°C, totodată în calitate de sursă de molibden se utilizează compusul menţionat hidrat de bis[(iminodiacetat)-oxotiomolibdat(V)] de tetrafenilfosfoniu, care se adaugă în mediul nutritiv în a 2-a zi de cultivare, în concentraţie de 0,02…0,03 g/L. and its use in a process for cultivating the cyanobacterium Spirulina platensis, which consists in cultivating the cyanobacterium on a nutrient medium containing, g/L: NaHCO3 - 16.80; NaNO3 - 2.50; NaCl - 1.00; K2SO4 - 0.50; K2HPO4 - 0.50; CaCl2 - 0.04; MgSO4·7H2O - 0.20; H3BO3 - 0.00286; MnCl2 - 0.00181; ZnSO4·7H2O - 0.000022; CuSO4·5H2O - 0.00008; FeSO4 - 0.01; EDTA - 0.08; source of molybdenum and distilled water, at the illumination of 3000...4800 lx/cm2 and the temperature of 35±1°C, at the same time as the source of molybdenum the mentioned compound bis[(iminodiacetate)-oxothiomolybdate(V)] hydrate is used tetraphenylphosphonium, which is added to the nutrient medium on the 2nd day of cultivation, in a concentration of 0.02...0.03 g/L.
Rezultatul tehnic obţinut constă în majorarea la Spirulina platensis a ponderii polizaharidelor acide şi sulfatate în fracţia de glucide totale de 1,38…1,43 şi, respectiv, 1,76…2 ori comparativ cu cea mai apropiată soluţie. The technical result obtained consists in the increase in Spirulina platensis of the share of acidic and sulfated polysaccharides in the fraction of total carbohydrates of 1.38...1.43 and, respectively, 1.76...2 times compared to the closest solution.
Rezultatul tehnic al invenţiei este condiţionat de faptul că pentru prima dată în calitate de regulator al conţinutului de polizaharide acide şi sulfatate la cianobacteria Spirulina platensis se propune hidratul de bis[(iminodiacetat)-oxotiomolibdat(V)] de tetrafenilfosfoniu. Analiza comparativă a compusului revendicat cu prototipul demonstrează că ei se deosebesc printr-o combinare nouă a tipurilor de legături chimice deja cunoscute, şi anume: sunt reprezentanţii diferitor clase de compuşi chimici. Datorită particularităţilor caracteristice compusului coordinativ declarat, se obţine un rezultat net superior în comparaţie cu prototipul. The technical result of the invention is conditioned by the fact that, for the first time, tetraphenylphosphonium bis[(iminodiacetate)-oxothiomolybdate(V)] hydrate is proposed as a regulator of the content of acidic and sulfated polysaccharides in the cyanobacterium Spirulina platensis. The comparative analysis of the claimed compound with the prototype demonstrates that they differ by a new combination of the types of chemical bonds already known, namely: they are representatives of different classes of chemical compounds. Due to the characteristic features of the declared coordinating compound, a net superior result is obtained in comparison with the prototype.
Compusul revendicat se obţine la interacţiunea soluţiilor etanolo-apoase fierbinţi (50…55°C) a [Mo10S10O10(OH)10(H2O)5] · 20H2O cu acid iminodiacetic (H2IDA) şi clorură de tetrafenilfosfoniu, luate în raport molar de 1 : 10 : 10. Reacţia decurge în 30…40 min conform următoarei scheme: The claimed compound is obtained by the interaction of hot ethanol-aqueous solutions (50...55°C) of [Mo10S10O10(OH)10(H2O)5] · 20H2O with iminodiacetic acid (H2IDA) and tetraphenylphosphonium chloride, taken in a molar ratio of 1: 10 : 10. The reaction proceeds in 30...40 min according to the following scheme:
Procedeul de obţinere a compusului revendicat este simplu în executare, substanţele iniţiale accesibile, randamentul constituie 38% faţă de cel teoretic calculat. Complexul este stabil în contact cu aerul, solubil în apă şi alcooli, bine solubil în dimetilformamidă şi dimetilsulfoxidă, practic insolubil în eter. The procedure for obtaining the claimed compound is simple in execution, the initial substances are accessible, the yield is 38% compared to the theoretically calculated one. The complex is stable in contact with air, soluble in water and alcohols, well soluble in dimethylformamide and dimethylsulfoxide, practically insoluble in ether.
Exemplu de obţinere a hidratului de bis[(iminodiacetat)-oxotiomolibdat(V)] de tetrafenilfosfoniu (PPh4)2[Mo2O2S2(IDA)2].2,8H2O, unde Example of obtaining tetraphenylphosphonium bis[(iminodiacetate)-oxothiomolybdate(V)] hydrate (PPh4)2[Mo2O2S2(IDA)2].2.8H2O, where
900 mg de precursor [Mo10O10S10(OH)10(H2O)5]·20H2O (Cadot E., Salignac B., Marrot J., Dolbecq A., Secheresse F. [Mo10O10S10(OH)10(H2O)5]·20H2O: a novel decameric molecular ring showing supramolecular properties // Chem. Commun., 2000, p. 261-262) (1,875 mmol Mo2) şi 500 mg de acid iminodiacetic H2IDA (3,75 mmol) au fost dizolvate în 1M HCl (10 mL) şi etanol (5 mL) cu formarea unei soluţii roşii, care a fost încălzită la 60°C timp de 15 minute. Mai apoi, pH-ul a fost ajustat la valoarea 7 cu soluţiile de 2M K2CO3 şi 1M KOH, iar amestecul rezultant a fost agitat timp de 45 minute. În final, s-a adăugat un mic exces de PPh4Cl (1,5 g, 4 mmol), ce a dus la precipitarea unui solid galben-portocaliu, izolat prin filtrare, spălat cu etanol şi acetonă şi uscat în aer (900 mg, randament 38%). Compusul a fost caracterizat prin ESI-MS, TGA şi analiză elementală. 900 mg precursor [Mo10O10S10(OH)10(H2O)5]·20H2O (Cadot E., Salignac B., Marrot J., Dolbecq A., Secheresse F. [Mo10O10S10(OH)10(H2O)5]·20H2O : a novel decameric molecular ring showing supramolecular properties // Chem. Commun., 2000, p. 261-262) (1.875 mmol Mo2) and 500 mg of iminodiacetic acid H2IDA (3.75 mmol) were dissolved in 1M HCl (10 mL) and ethanol (5 mL) with the formation of a red solution, which was heated at 60°C for 15 minutes. Then, the pH was adjusted to 7 with the solutions of 2M K2CO3 and 1M KOH, and the resulting mixture was stirred for 45 minutes. Finally, a small excess of PPh4Cl (1.5 g, 4 mmol) was added, resulting in the precipitation of a yellow-orange solid, which was isolated by filtration, washed with ethanol and acetone and dried in air (900 mg, yield 38 %). The compound was characterized by ESI-MS, TGA and elemental analysis.
Calculat (%) pentru (PPh4)2[Mo2O2S2(IDA)2].2,8H2O (MM = 1277,4 g/mol): C 52,65; H 4,23; N 2,19; S 5,02. Determinat: C 52,61; H 4,46 ; N 2,14; S 4,91. Calculated (%) for (PPh4)2[Mo2O2S2(IDA)2].2.8H2O (MM = 1277.4 g/mol): C 52.65; H 4.23; N 2.19; S 5.02. Determined: C 52.61; H 4.46; N 2.14; S 4.91.
ESI-MS (H2O/MeOH 1/1) (fig. 1): m/z = 275,12 (aşteptat: m/z = 275,10) corespunzând picului principal din spectrul ES-MS şi atribuit anionului [Mo2O2S2(IDA)2]2-(aşteptat: m/z = 275,10). ESI-MS (H2O/MeOH 1/1) (fig. 1): m/z = 275.12 (expected: m/z = 275.10) corresponding to the main peak in the ES-MS spectrum and attributed to the anion [Mo2O2S2(IDA )2]2-(expected: m/z = 275.10).
TGA (fig. 2): 3,8% scăderea de masă în intervalul 20…200°C corespunzând la 2,8 H2O (calculat 3,9 %). TGA (fig. 2): 3.8% mass loss in the range 20...200°C corresponding to 2.8 H2O (3.9% calculated).
Structura moleculară a complexului anionic [Mo2O2S2(IDA)2]2- a fost stabilită cu ajutorul analizei cu raze X şi este prezentată în fig. 3. Unitatea binucleară - Mo2O2S2 conţine doi liganzi iminodiacetat (IDA2-) coordinaţi la centrele de Mo(V), însă modul de coordinare al ambilor liganzi nu este echivalent, complexul fiind chiral. Cu toate acestea, s-a constatat că în fază solidă ambii enantiomeri se regăsesc în celula cristalină, generând un cristal racemic (fig. 4). În baza datelor din literatura de specialitate pentru clusterii de [Mo2O2S2] (Lemonnier J.-F., Duval S., Floquet S., Cadot E. A Decade of Oxothiomolybdenum Wheels : Synthesis, Behavior in Solution and Electrocatalytic Properties // Isr. J. Chem. 2011. v. 51, nr. 2, p. 290-302), distanţa Mo-Mo egală cu 2,84 ⊕ este tipică legăturii Mo(V)-Mo(V), distanţele Mo-O cu atomii de oxigen terminali au fost stabilite a fi în intervalul 1,68…1,69 ⊕, caraceristice legăturii Mo(V)=O, distanţele Mo-S cu ionii-punte de sulfură sunt de asemenea în limitele valorilor aşteptate (Mo-S = 2,31…2,32 ⊕). În ceea ce priveşte modul de coordinare a celor doi liganzi, fiecare din ei este coordinat prin grupa amină în poziţie ecuatorială (Mo-N = 2,25 ⊕) sau în cea axială (Mo-N = 2,38 ⊕), precum şi prin cele două funcţiuni carboxilat ecuatorială (Mo-O = 2,09…2,12 ⊕) şi axială (Mo-O = 2,24 ⊕). Liganzii sunt dublu deprotonaţi, formând complexul anionic [Mo2O2S2(IDA)2]2- prin combinare cu unitatea de [Mo2O2S2]2+. Această presupunere este confirmată prin faptul că cei doi cationi adiţionali de tetrafenilfosfoniu se regăsesc în structura moleculară, precum şi din spectrele IR, care nu indică prezenţa vibraţiilor în intervalul 1700…1750 cm-1, tipice grupelor carboxil protonate. The molecular structure of the anionic complex [Mo2O2S2(IDA)2]2- was established using X-ray analysis and is presented in fig. 3. The binuclear unit - Mo2O2S2 contains two iminodiacetate ligands (IDA2-) coordinated to the Mo(V) centers, but the coordination mode of both ligands is not equivalent, the complex being chiral. However, it was found that in the solid phase both enantiomers are found in the crystalline cell, generating a racemic crystal (fig. 4). Based on data from the specialized literature for [Mo2O2S2] clusters (Lemonnier J.-F., Duval S., Floquet S., Cadot E. A Decade of Oxothiomolybdenum Wheels : Synthesis, Behavior in Solution and Electrocatalytic Properties // Isr. J. Chem. 2011. v. 51, no. 2, p. 290-302), the Mo-Mo distance equal to 2.84 ⊕ is typical of the Mo(V)-Mo(V) bond, the Mo-O distances with atoms of terminal oxygen were determined to be in the range of 1.68...1.69 ⊕, characteristic of the Mo(V)=O bond, the Mo-S distances with the sulphide-bridge ions are also within the limits of the expected values (Mo-S = 2.31…2.32 ⊕). Regarding the way of coordination of the two ligands, each of them is coordinated by the amine group in the equatorial position (Mo-N = 2.25 ⊕) or in the axial position (Mo-N = 2.38 ⊕), as well as by the two equatorial (Mo-O = 2.09...2.12 ⊕) and axial (Mo-O = 2.24 ⊕) carboxylate functions. The ligands are doubly deprotonated, forming the anionic complex [Mo2O2S2(IDA)2]2- by combining with the [Mo2O2S2]2+ unit. This assumption is confirmed by the fact that the two additional tetraphenylphosphonium cations are found in the molecular structure, as well as from the IR spectra, which do not indicate the presence of vibrations in the range 1700...1750 cm-1, typical of protonated carboxyl groups.
Astfel, în baza rezultatelor analizei elementelor şi cercetărilor fizico-chimice, a fost stabilită compoziţia şi structura probabilă a compusului declarat. Thus, based on the results of elemental analysis and physico-chemical research, the composition and probable structure of the declared compound was established.
Exemple de utilizare a hidratului de bis[(iminodiacetat)-oxotiomolibdat(V)] de tetrafenilfosfoniu (PPh4)2[Mo2O2S2(IDA)2] . 2,8H2O în calitate de regulator al conţinutului de polizaharide acide şi sulfatate la cultivarea cianobacteriei Spirulina platensis. Examples of use of tetraphenylphosphonium bis[(iminodiacetate)-oxothiomolybdate(V)] hydrate (PPh4)2[Mo2O2S2(IDA)2]. 2,8H2O as a regulator of the content of acidic and sulfated polysaccharides in the cultivation of the cyanobacterium Spirulina platensis.
Exemplul 1Se prepară mediul nutritiv cu următoarea componenţă (g/L): NaHCO3 - 16,80; NaNO3 - 2,50; NaCl - 1,00; K2SO4 - 0,50; K2HPO4 - 0,50; CaCl2 - 0,04; MgSO4·7H2O - 0,20; H3BO3 - 0,00286; MnCl2 - 0,00181; ZnSO4·7H2O - 0,000022; CuSO4·5H2O - 0,00008; FeSO4 - 0,01; EDTA - 0,08 şi apă. La mediul preparat se adaugă suspensia de Spirulina platensis în cantitate de 0,40…0,45 g/L. Cultivarea se efectuează în baloane Erlenmayer a câte 250 mL în 100 mL suspensie la temperatura de 35± Example 1 The nutrient medium is prepared with the following composition (g/L): NaHCO3 - 16.80; NaNO3 - 2.50; NaCl - 1.00; K2SO4 - 0.50; K2HPO4 - 0.50; CaCl2 - 0.04; MgSO4·7H2O - 0.20; H3BO3 - 0.00286; MnCl2 - 0.00181; ZnSO4·7H2O - 0.000022; CuSO4·5H2O - 0.00008; FeSO4 - 0.01; EDTA - 0.08 and water. The Spirulina platensis suspension is added to the prepared medium in an amount of 0.40...0.45 g/L. Cultivation is carried out in Erlenmayer flasks of 250 mL each in 100 mL suspension at a temperature of 35±
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