MD4438C1 - Process for the production of [tetraoxoethylenediamine tetraacetatedimolibdenum V] bis-(tetraphenylphosphonium)di-hemihydrate compound and process for feeding bees with its use - Google Patents

Process for the production of [tetraoxoethylenediamine tetraacetatedimolibdenum V] bis-(tetraphenylphosphonium)di-hemihydrate compound and process for feeding bees with its use Download PDF

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MD4438C1
MD4438C1 MDA20150005A MD20150005A MD4438C1 MD 4438 C1 MD4438 C1 MD 4438C1 MD A20150005 A MDA20150005 A MD A20150005A MD 20150005 A MD20150005 A MD 20150005A MD 4438 C1 MD4438 C1 MD 4438C1
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bees
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Ион ТОДЕРАШ
Валентина ЧЕБОТАРЬ
Аурелиан ГУЛЯ
Ион БУЗУ
Себастьен ФЛОК
Эммануэль КАДО
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Институт Зоологии Академии Наук Молдовы
Университет Versailles St-Quentin-En-Yvelines
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Abstract

The invention relates to beekeeping, namely to a process for feeding bees using the [tetraoxoethylenediamine tetraacetatedimolibdenum V] bis-(tetraphenylphosphonium)di-hemihydrate compound and to a process for the production thereof.The process for the production of the compound comprises preparation of the [Mo2O4(H2O)6]2+ complex solution by addition to the Na2Mo4·2H2O hydrazine monohydrate in aqueous HCl solution, then to the [Mo2O4(H2O)6]2+ complex solution is added NaH2EDTA, the mixture is brought to pH 6, heated to 70°C, stirred until the production of a red solution, cooled to room temperature, then is added PPh4Cl and is maintained until the formation of orange needles, which are separated by filtration, washed and dried.The process for feeding bees comprises mixing of the aqueous solution of said compound with the concentration of 1 mg% with sugar syrup in a ratio of 2:100, respectively, and feeding of bees with this mixture in an amount of 100…300 mL per each interval of frames, once every two days, for three weeks.

Description

Invenţia se referă la apicultură, şi anume la un procedeu de hrănire a albinelor cu utilizarea compusului [tetraoxoetilendiaminotetraacetatdimolibden V] de bis-(tetrafenilfosfoniu) di-semihidratat, precum şi la un procedeu de obţinere a acestuia. The invention relates to beekeeping, namely to a method of feeding bees using the compound [tetraoxoethylenediaminotetraacetatdimolybdenum V] of bis-(tetraphenylphosphonium) di-semihydrate, as well as to a method of obtaining it.

După iernare, în perioada de primăvară, coloniile de albine se află, de regulă, în stare de convalescenţă ca rezultat al confruntării cu acţiunile negative ale diferitor intemperii. În organismul albinelor se constată o carenţă de substanţe nutritive bioactive, în special de microelemente, care au un rol catalizator în procesele fiziologice de activitate vitală a albinelor, îndeplinind în organismul albinei funcţii multiple la nivel celular, intrând în componenţa unor enzime şi hormoni cu rol hotărâtor în metabolism. Insuficienţa substanţelor biologic active, în special a microelementelor, conduce la diminuarea activităţii funcţiilor reproductive, slăbirea rezistenţei familiilor de albine la boli şi diminuarea productivităţii lor. After wintering, in the spring period, the bee colonies are, as a rule, in a state of convalescence as a result of confronting the negative actions of different weather conditions. In the body of bees, there is a lack of bioactive nutrients, especially microelements, which have a catalytic role in the physiological processes of bees' vital activity, performing multiple functions at the cellular level in the bee's body, entering into the composition of enzymes and hormones with a role decisive in metabolism. The insufficiency of biologically active substances, especially of microelements, leads to the reduction of the activity of reproductive functions, the weakening of the resistance of bee families to diseases and the reduction of their productivity.

Sursele principale naturale de aprovizionare a organismului albinelor cu microelemente sunt nectarul şi polenul, culese de la florile plantelor melifere. Potrivit informaţiilor ştiinţifice, în miere şi polen se găsesc peste 30 de micro şi macroelemente, inclusiv oligoelemente, care au un rol enorm în metabolismul fiziologic al organismelor vii. Printre acestea, molibdenul (Mo) se găseşte în cantităţi foarte mici, până la 14 µg% (după Kerkvliet, 1989, citat de Cristina Mateescu în cartea „Apicultura - manualul cursantului”, Ploieşti, LVS Crepuscul, 2012, p. 279-298), dar rolul acestui microelement în metabolismul substanţelor din corpul albinelor nu este suficient cunoscut. The main natural sources of supplying the bees' body with microelements are nectar and pollen, collected from the flowers of honey plants. According to scientific information, honey and pollen contain more than 30 micro and macro elements, including trace elements, which play an enormous role in the physiological metabolism of living organisms. Among them, molybdenum (Mo) is found in very small amounts, up to 14 µg% (according to Kerkvliet, 1989, cited by Cristina Mateescu in the book "Apiculture - manualul cursantului", Ploiesti, LVS Crepuscul, 2012, p. 279-298 ), but the role of this microelement in the metabolism of substances in the body of bees is not sufficiently known.

În legătură cu faptul că primăvara timpuriu (perioadă deficitară de cules în natură), majoritatea apicultorilor hrănesc familiile de albine cu sirop de zahăr, în componenţa căruia majoritatea microelementelor necesare lipsesc, identificarea surselor accesibile de oligoelemente pentru îmbogăţirea suplimentelor nutritive în raţia albinelor devine o problemă stringentă. In relation to the fact that in early spring (deficient harvesting period in nature), most beekeepers feed bee families with sugar syrup, in the composition of which most of the necessary microelements are missing, identifying accessible sources of trace elements to enrich the nutritional supplements in the bee ration becomes a problem stringency.

Este cunoscut un procedeu de hrănire a familiilor de albine cu surse de microelemente, şi anume cu un amestec cu sirop de zahăr, substituient de polen, set de aminoacizi şi vitamine, distribuit în stup o dată la 12 zile, timp de 36 de zile [1]. Dezavantajele acestui procedeu constau în faptul că este costisitor, componenţa amestecului nutritiv este prea complicată, procesele de preparare şi aplicare ale acestuia sunt îndelungate, iar microelementele introduse sub formă de săruri sunt greu digestibile pentru albine şi, fiind uşor oxidabile, provoacă dereglări ale tubului digestiv la albine. A method of feeding bee families with sources of microelements is known, namely with a mixture of sugar syrup, pollen substitute, set of amino acids and vitamins, distributed in the hive once every 12 days, for 36 days [ 1]. The disadvantages of this process consist in the fact that it is expensive, the composition of the nutrient mixture is too complicated, its preparation and application processes are long, and the microelements introduced in the form of salts are difficult for bees to digest and, being easily oxidizable, cause disturbances in the digestive tract to bees.

Cea mai apropiată soluţie, după esenţa tehnică şi rezultatul obţinut, este procedeul de hrănire a familiilor de albine Apis mellifera [2], ce include hrănirea albinelor primăvara cu un amestec din soluţie de 1% mas. de extract din biomasa tulpinii cianobacteriei Spirulina platensis CNM-CB-02 şi sirop de zahăr de 50% luate în raport de 1:500, respectiv, tulpina cianobacteriei Spirulina platensis fiind cultivată în prezenţa compusului coordinativ - sulfat cromat de potasiu dodecahidrat [KCr(SO4)2·12H2O](„Apispir+Cr”), iar hrănirea albinelor cu amestec se efectuează în cantitate de 100...130 ml la o ramă cu albine, la fiecare 2 zile, timp de două săptămâni. The closest solution, according to the technical essence and the result obtained, is the process of feeding Apis mellifera bee families [2], which includes feeding the bees in the spring with a mixture of 1% mass solution. of extract from the biomass of the strain of the cyanobacterium Spirulina platensis CNM-CB-02 and 50% sugar syrup taken in a ratio of 1:500, respectively, the strain of the cyanobacterium Spirulina platensis being cultivated in the presence of the coordinating compound - potassium chromate sulfate dodecahydrate [KCr(SO4 )2·12H2O]("Apispir+Cr"), and the bees are fed with the mixture in the amount of 100...130 ml per a frame with bees, every 2 days, for two weeks.

Dezavantajul acestui procedeu constă în faptul că tehnologia de obţinere a extractului din biomasa tulpinii cianobacteriei Spirulina platensis, cultivată în prezenţa compusului coordinativ sus-menţionat, este prea complicată şi costisitoare, iar eficienţa utilizării microelementelor din compusul coordinativ administrat în cantităţi relativ mari este scăzută. The disadvantage of this process lies in the fact that the technology for obtaining the extract from the biomass of the cyanobacterium Spirulina platensis strain, cultivated in the presence of the above-mentioned coordinating compound, is too complicated and expensive, and the efficiency of using microelements from the coordinating compound administered in relatively large quantities is low.

Problema pe care o rezolvă prezenta invenţie constă în elaborarea unui procedeu de obţinere a unui supliment nutritiv bioactiv pentru hrănirea albinelor şi a unui procedeu de hrănire a familiilor de albine în perioadele deficitare de cules în natură, care ar asigura necesităţile albinelor în microelementul Mo, ar activiza funcţiile reproductive ale reginei, ar spori cantitatea de puiet căpăcit în cuib şi puterea familiei de albine Apis mellifera, contribuind la creşterea productivităţii ei. The problem that the present invention solves consists in the development of a process for obtaining a bioactive nutritional supplement for feeding bees and a process for feeding bee families during periods of poor picking in nature, which would ensure the needs of bees in the trace element Mo, would activates the queen's reproductive functions, would increase the amount of brood in the nest and the strength of the Apis mellifera bee family, contributing to increasing its productivity.

Invenţa soluţionează problema prin aceea că se propune un procedeu de obţinere a compusului [tetraoxoetilendiaminotetraacetatdimolibden V] de bis-(tetrafenilfosfoniu) di-semihidrat, care include prepararea soluţiei complexului [Mo2O4(H2O)6]2+ cu concentraţia de 8,26·10-2 mol/L prin adăugarea la 0,23 ml/4,7 mmol de monohidrat de hidrazină a 4 g/16,5 mmol de Na2MoO4·2H2O în 100 ml de soluţie apoasă de HCl cu concentraţia de 3,2 mol/L, după care la 11 ml/0,909 mmol de soluţie a complexului [Mo2O4(H2O)6]2+ se adaugă 307 mg/0,909 mmol de Na2H2EDTA, amestecul se aduce până la pH 6 cu KOH de 4 mol/L, se încălzeşte până la 70°C timp de 30 min, se agită până la obţinerea unei soluţii de culoare roşie, se răceşte până la temperatura camerei, apoi se adaugă 1 g/2,7 mmol de PPh4Cl şi se menţine până la formarea unor ace oranj, care se separă prin filtrare, se spală cu apă rece şi se usucă. Compusul obţinut cu denumirea „AA20Mo” se utilizează în calitate de supliment nutritiv bioactiv pentru hrănirea albinelor. The invention solves the problem by proposing a process for obtaining the compound [tetraoxoethylenediaminotetraacetatedimolybdenum V] of bis-(tetraphenylphosphonium) di-semihydrate, which includes the preparation of the solution of the [Mo2O4(H2O)6]2+ complex with a concentration of 8.26·10 -2 mol/L by adding to 0.23 ml/4.7 mmol of hydrazine monohydrate 4 g/16.5 mmol of Na2MoO4·2H2O in 100 ml of 3.2 mol/L aqueous HCl solution , after which 307 mg/0.909 mmol of Na2H2EDTA is added to 11 ml/0.909 mmol of solution of the [Mo2O4(H2O)6]2+ complex, the mixture is brought to pH 6 with 4 mol/L KOH, heated to at 70°C for 30 min, stir until a red solution is obtained, cool to room temperature, then add 1 g/2.7 mmol of PPh4Cl and maintain until the formation of orange needles, which separate by filtration, wash with cold water and dry. The compound obtained with the name "AA20Mo" is used as a bioactive nutritional supplement for feeding bees.

Totodată, se propune un procedeu de hrănire a albinelor, care include amestecarea soluţiei apoase de 1 mg% de compusul obţinut menţionat cu sirop de zahăr de 50% în raport de 2:100, respectiv, şi hrănirea albinelor primăvara cu acest amestec în cantitate de 100…300 ml la fiecare interval de rame cu albine, o dată la două zile, timp de trei săptămâni. At the same time, a procedure for feeding bees is proposed, which includes mixing the aqueous solution of 1 mg% of the obtained compound mentioned with 50% sugar syrup in a ratio of 2:100, respectively, and feeding the bees in the spring with this mixture in an amount of 100...300 ml at each interval of frames with bees, once every two days, for three weeks.

Pentru verificarea eficienţei suplimentului nutritiv sus-menţionat şi a procedeului de hrănire a albinelor, în luna aprilie 2013, au fost desfăşurate experienţe de testare comparativă a acestuia pe trei loturi de familii de albine (vezi tabelul), câte 16 familii în fiecare lot, dintre care: lotul I - martor (albinele căruia au fost hranite doar cu sirop de zahăr de 50%), lotul II - cea mai apropiată soluţie (albinele căruia au avut ca hrană sirop de zahăr îmbogăţit cu suplimentul nutritiv „Apispir+Cr” (MD 476 Z 2012.09.30)) şi lotul III - invenţia propusă (albinele căruia au fost hrănite cu sirop de zahăr îmbogăţit cu suplimentul „AA20Mo”). In order to verify the effectiveness of the above-mentioned nutritional supplement and the bee feeding process, in April 2013, comparative testing experiments were carried out on three batches of bee families (see the table), 16 families in each batch, among which: group I - control (whose bees were fed only with 50% sugar syrup), group II - the closest solution (whose bees were fed sugar syrup enriched with the nutritional supplement "Apispir+Cr" (MD 476 Z 2012.09.30)) and lot III - the proposed invention (whose bees were fed with sugar syrup enriched with the "AA20Mo" supplement).

Tabel Table

Valoarea medie a caracterelor morfoproductive ale familiilor de albine The average value of the morphoproductive characters of bee families

din loturile experimentale from the experimental groups

Denumirea caracterelor Lotul I, martor (N* = 16) Lotul II, cea mai apropiată soluţie (N* = 16) Lotul III, invenţia propusă „AA20Mo” (N* = 16) Media caracterului % Media caracterului % faţă de lotul I Media caracterului % faţă de lotul I % faţă de lotul II Prolificitatea mătcii, ouă/24 ore 1590 ± 20 100 1673 ± 14 105,2 1757 ± 15 110,5 103,8 Cantitatea de puiet căpăcit în cuib, sute celule 190,8 ± 2,4 100 200,7 ± 1,6 105,2 210,8 ± 1,7 110,5 105,0 Puterea familiei, kg 3,20 ± 0,02 100 3,28 ± 0,04 102,5 3,58 ± 0,05 111,9 109,1 Cantitatea de miere la primul cules, kg 11,62 ± 0,40 100 13,24 ± 0,40 113,9 13,90 ± 0,36 119,6 105,0 Character designation Batch I, control (N* = 16) Batch II, closest solution (N* = 16) Batch III, proposed invention "AA20Mo" (N* = 16) Character mean % Character mean % compared to batch I Mean of the character % compared to batch I % compared to batch II Prolificity of the queen, eggs/24 hours 1590 ± 20 100 1673 ± 14 105.2 1757 ± 15 110.5 103.8 The amount of brood in the nest, hundreds of cells 190.8 ± 2.4 100 200.7 ± 1.6 105.2 210.8 ± 1.7 110.5 105.0 Family strength, kg 3.20 ± 0.02 100 3.28 ± 0.04 102.5 3 .58 ± 0.05 111.9 109.1 The amount of honey at the first harvest, kg 11.62 ± 0.40 100 13.24 ± 0.40 113.9 13.90 ± 0.36 119.6 105, 0

Remarcă: N* - efectivul familiilor de albine în lot Note: N* - the number of bee families in the batch

Datele obţinute în experimente au fost prelucrate conform statisticii biometrice variaţionale (Плохинский Н.А. Руководство по биометрии для зоотехников. Изд. Колос, Москва, 1969, 256 p.). The data obtained in the experiments were processed according to variational biometric statistics (Плохинский Н.А. Руководство по биометрии для зоотехников. Изд. Колос, Москва, 1969, 256 p.).

Rezultatele testării au demonstrat că hrănirea albinelor cu suplimentul nutritiv „AA20Mo”, primăvara în perioada deficitară de cules, a contribuit la creşterea semnificativă a valorilor principalelor caractere de reproducţie ale reginei şi de dezvoltare ale familiei de albine, evaluate conform Normei zootehnice privind bonitarea familiilor de albine, creşterea şi certificarea materialului genitor apicol (aprobate prin Hotărârea Guvernului Republicii Moldova nr. 306 din 28.04.2011). The test results demonstrated that feeding the bees with the nutrient supplement "AA20Mo", in the spring during the poor picking period, contributed to the significant increase in the values of the main reproductive characteristics of the queen and the development of the bee family, evaluated according to the Zootechnical Norm regarding the certification of bee families bees, breeding and certification of bee breeding material (approved by the Decision of the Government of the Republic of Moldova no. 306 of 28.04.2011).

S-a constatat că substanţele biologic active din suplimentul nutritiv „AA20Mo” au provocat indirect un impact stimulator asupra funcţiilor ovogeneze ale mătcii, contribuind la creşterea pontei şi a cantităţii de puiet căpăcit în cuib. Deoarece matca nu consumă în hrană suplimentul nutritiv administrat în cuib, ci este permanent hrănită de către albinele lucrătoare cu lăptişor de matcă, am ajuns la concluzia că substanţele biologic active din suplimentul nutritiv intră în componenţa acestui lăptişor, de unde provoacă impactul stimulator asupra funcţiilor reproductive ale reginei. Ca rezultat, prolificitatea mătcilor din familiile de albine din lotul III a crescut semnificativ, comparativ cu lotul I (martor) şi lotul II (cea mai apropiată soluţie), cu 167 şi 84 ouă/24 ore sau cu 10,5 şi 3,8% (td = 6,7 şi 4,1; P < 0,001), respectiv. It was found that the biologically active substances in the nutritional supplement "AA20Mo" indirectly caused a stimulatory impact on the ovogenic functions of the queen, contributing to the increase of the clutch and the amount of chicks placed in the nest. Since the queen does not consume the nutritional supplement administered in the nest, but is constantly fed by the worker bees with royal jelly, we came to the conclusion that the biologically active substances from the nutritional supplement are part of this royal jelly, from where they cause the stimulating impact on reproductive functions of the queen. As a result, the prolificacy of queens in bee families in batch III increased significantly, compared to batch I (control) and batch II (the closest solution), by 167 and 84 eggs/24 hours or by 10.5 and 3.8 % (td = 6.7 and 4.1; P < 0.001), respectively.

De asemenea, cantitatea de puiet căpăcit în familiile de albine din lotul III a fost semnificativ mai mare, comparativ cu lotul I (martor) şi lotul II (cea mai apropiată soluţie), cu 20,0 şi 10,1 sute de celule sau cu 10,5 şi 5,0% (td = 6,8 şi 2,1; P < 0,001 şi P < 0,05), respectiv. Also, the amount of brood hatched in bee families from group III was significantly higher, compared to group I (control) and group II (the closest solution), with 20.0 and 10.1 hundred cells or with 10.5 and 5.0% (td = 6.8 and 2.1; P < 0.001 and P < 0.05), respectively.

Creşterea prolificităţii mătcilor şi a cantităţii de puiet căpăcit a condus la creşterea esenţială a puterii familiilor de albine, exprimată prin cantitatea totală de albine populate în cuib. Astfel, puterea familiilor de albine din lotul III a fost semnificativ mai mare, comparativ cu lotul I (martor) şi lotul II (cea mai apropiată soluţie), cu 0,38 şi 0,30 kg de albine, sau cu 11,9 şi 9,1% (td = 7,1 şi 5,0; P < 0,001), respectiv. The increase in the prolificacy of the queens and the amount of hatched brood led to the essential increase in the power of the bee families, expressed by the total amount of bees populated in the nest. Thus, the power of bee families in group III was significantly higher, compared to group I (control) and group II (the closest solution), with 0.38 and 0.30 kg of bees, or with 11.9 and 9.1% (td = 7.1 and 5.0; P < 0.001), respectively.

Activizarea, de către substanţele biologic active ale suplimentului nutritiv „AA20Mo”, a funcţiilor ovogeneze ale mătcilor şi de dezvoltare reproductivă ale familiilor de albine a contribuit la creşterea substanţială a productivităţii lor. Astfel, familiile de albine din lotul III, la primul cules, au acumulat în cuib, comparativ cu lotul I şi lotul II, o cantitate mai mare de miere cu 2,32 şi 0,7 kg sau cu 19,6 şi 5,0% (td = 4,3 şi 1,8; P < 0,001 şi P < 0,1), respectiv. The activation, by the biologically active substances of the nutritional supplement "AA20Mo", of the ovogenic functions of the queens and reproductive development of the bee families contributed to the substantial increase of their productivity. Thus, bee families from batch III, at the first collection, accumulated in the nest, compared to batch I and batch II, a larger amount of honey by 2.32 and 0.7 kg or by 19.6 and 5.0 % (td = 4.3 and 1.8; P < 0.001 and P < 0.1), respectively.

Prin urmare, rezultatul tehnic al invenţiei constă în stimularea funcţiilor ovogeneze ale reginelor, creşterea cantităţii de puiet căpăcit, dezvoltarea cantitativă (puterea) a familiilor de albine şi sporirea productivităţii lor. Therefore, the technical result of the invention consists in stimulating the ovogenic functions of the queens, increasing the amount of hatched brood, the quantitative development (power) of bee families and increasing their productivity.

Rezultatul tehnic al invenţiei se datorează substanţelor biologic active din compusul organic coordinativ, în special oligoelementul Mo. Ionii de Mo(V), fiind parte componentă a tetraoxoetilendiaminotetraacetatului de molibden, au un rol catalizator în metabolismul substanţelor azotate la albinele lucrătoare, participă la sinteza unor enzime, acizi nucleici şi aminoacizi esenţiali, ameliorează componenţa calitativă a lăptişorului de matcă şi stimulează secreţia acestuia la albinele doici, cu influenţe indirecte (prin alimentaţia reginei cu lăptişor) asupra sistemului reproductiv al mătcii, activizând ovogeneza şi ponta. Toate acestea determină, în mare măsură, activitatea vitală a albinelor lucrătoare, prolificitatea mătcii, dezvoltarea larvelor şi a puietului din cuib, contribuind la creşterea puterii familiilor de albine şi a productivităţii lor în ansamblu. The technical result of the invention is due to the biologically active substances in the coordinating organic compound, especially the trace element Mo. Mo(V) ions, being a component of molybdenum tetraoxoethylenediaminetetraacetate, play a catalytic role in the metabolism of nitrogenous substances in worker bees, participate in the synthesis of enzymes, nucleic acids and essential amino acids, improve the quality of royal jelly and stimulate its secretion in nurse bees, with indirect influences (by feeding the queen with milk) on the reproductive system of the queen, activating oogenesis and oogenesis. All this determines, to a large extent, the vital activity of the worker bees, the prolificacy of the queen, the development of the larvae and the brood in the nest, contributing to the increase of the power of the bee families and their productivity as a whole.

Exemple de realizare a invenţiei Examples of realization of the invention

Exemplul 1 Example 1

Procedeul de obţinere a suplimentuluui nutritiv bioactiv pentru hrănirea albinelor include prepararea soluţiei complexului [Mo2O4(H2O)6]2+ cu concentraţia de 8,26·10-2 mol/L prin adăugarea la 0,23 ml/4,7 mmol de monohidrat de hidrazină a 4 g/16,5 mmol de Na2MoO4·2H2O în 100 ml de soluţie apoasă de HCl cu concentraţia de 3,2 mol/L, după care la 11 ml/0,909 mmol de soluţie a complexului [Mo2O4(H2O)6]2+ se adaugă 307 mg/0,909 mmol de Na2H2EDTA, amestecul se aduce până la pH 6 cu KOH de 4 mol/L, se încălzeşte până la 70°C timp de 30 min, se agită până la obţinerea unei soluţii de culoare roşie, se răceşte până la temperatura camerei, apoi se adaugă 1 g/2,7 mmol de PPh4Cl şi se menţine până la formarea unor ace oranj, care se separă prin filtrare, se spală cu apă rece şi se usucă, obţinându-se suplimentul nutritiv bioactiv [tetraoxoetilendiaminotetraacetatdimolibden(V)] de bis-(tetrafenilfosfoniu) di-semihidrat: (PPh4)2[Mo2O4(EDTA)]·2,5H2O, cu masa molară de 1267,9 g/mol. The process for obtaining the bioactive nutritional supplement for feeding bees includes the preparation of the [Mo2O4(H2O)6]2+ complex solution with a concentration of 8.26·10-2 mol/L by adding 0.23 ml/4.7 mmol of monohydrate of hydrazine to 4 g/16.5 mmol of Na2MoO4·2H2O in 100 ml of aqueous HCl solution with a concentration of 3.2 mol/L, then to 11 ml/0.909 mmol of a solution of the complex [Mo2O4(H2O)6 ]2+ add 307 mg/0.909 mmol of Na2H2EDTA, bring the mixture to pH 6 with 4 mol/L KOH, heat to 70°C for 30 min, stir until a red solution is obtained , cool to room temperature, then add 1 g/2.7 mmol of PPh4Cl and maintain until the formation of orange needles, which are separated by filtration, washed with cold water and dried, obtaining the nutritional supplement bioactive [tetraoxoethylenediaminotetraacetatedimolybdenum(V)] of bis-(tetraphenylphosphonium) di-semihydrate: (PPh4)2[Mo2O4(EDTA)]·2.5H2O, with a molar mass of 1267.9 g/mol.

Exemplul 2 Example 2

Procedeul de hrănire a familiilor de albine Apis mellifera se realizează în felul următor. The process of feeding Apis mellifera bee families is carried out in the following way.

Pentru obţinerea suplimentului bioactiv „AA20Mo” se dizolvă 10 mg de substanţă uscată a compusului organic coordinativ [tetraoxoetilendiaminotetraacetatdimolibden(V)] de bis-(tetrafenilfosfoniu) di-semihidrat: (PPh4)2[Mo2O4(EDTA)]·2,5H2O în 1000 ml de apă distilată. Soluţia apoasă de supliment se păstrează la răcoare (t° = +4 ... +16°C), în locuri întunecate. Ulterior, se amestecă suplimentul bioactiv cu siropul de zahăr de 50% încălzit la temperatura de 30 ... 35°C, în raport de 2:100, respectiv. Amestecul nutritiv se distribuie albinelor în hrănitorul stupului primăvara, în perioada deficitară de cules în natură, în cantitate de 100 ml pentru fiecare interval de rame populat cu albine, la fiecare 2 zile, timp de trei săptămâni. To obtain the bioactive supplement "AA20Mo", dissolve 10 mg of the dry substance of the coordinating organic compound [tetraoxoethylenediaminotetraacetatedimolybdenum(V)] of bis-(tetraphenylphosphonium) di-semihydrate: (PPh4)2[Mo2O4(EDTA)]·2.5H2O in 1000 ml of distilled water. The aqueous supplement solution is kept cool (t° = +4 ... +16°C), in dark places. Afterwards, mix the bioactive supplement with the 50% sugar syrup heated to a temperature of 30 ... 35°C, in a ratio of 2:100, respectively. The nutrient mixture is distributed to the bees in the beehive feeder in the spring, during the poor picking period in nature, in the amount of 100 ml for each frame interval populated with bees, every 2 days, for three weeks.

1. Еремич Н.Г. Повышение продуктивности пчелиных семей путем использования комплекса белково-витаминных подкормок. Автореферат диссертации кандидата сельско-хозяйственных наук. Москва, 1986, 16 р. 1. Еремич Н.Г. Increasing the productivity of bee families by using the protein-vitamin supplement complex. Автореферат дерессии накладита сельско-хозяйственных наук. Moscow, 1986, 16 p.

2. MD 476 Y 2012.02.29 2. MD 476 Y 2012.02.29

Claims (2)

1. Procedeu de obţinere a compusului [tetraoxoetilendiaminotetraacetatdimolibden V] de bis-(tetrafenilfosfoniu) di-semihidrat, care include prepararea soluţiei complexului [Mo2O4(H2O)6]2+ cu concentraţia de 8,26·10-2 mol/L prin adăugarea la 0,23 ml/4,7 mmol de monohidrat de hidrazină a 4 g/16,5 mmol de Na2MoO4·2H2O în 100 ml de soluţie apoasă de HCl cu concentraţia de 3,2 mol/L, după care la 11 ml/0,909 mmol de soluţie a complexului [Mo2O4(H2O)6]2+ se adaugă 307 mg/0,909 mmol de Na2H2EDTA, amestecul se aduce până la pH 6 cu KOH de 4 mol/L, se încălzeşte până la 70°C timp de 30 min, se agită până la obţinerea unei soluţii de culoare roşie, se răceşte până la temperatura camerei, apoi se adaugă 1 g/2,7 mmol de PPh4Cl şi se menţine până la formarea unor ace oranj, care se separă prin filtrare, se spală cu apă rece şi se usucă.1. Process for obtaining the compound [tetraoxoethylenediaminotetraacetatedimolybdenum V] of bis-(tetraphenylphosphonium) di-semihydrate, which includes the preparation of the solution of the [Mo2O4(H2O)6]2+ complex with a concentration of 8.26·10-2 mol/L by adding to 0.23 ml/4.7 mmol of hydrazine monohydrate of 4 g/16.5 mmol of Na2MoO4·2H2O in 100 ml of aqueous HCl solution with a concentration of 3.2 mol/L, then to 11 ml/ 0.909 mmol of solution of the complex [Mo2O4(H2O)6]2+ add 307 mg/0.909 mmol of Na2H2EDTA, the mixture is brought to pH 6 with 4 mol/L KOH, heated to 70°C for 30 min, stir until a red solution is obtained, cool to room temperature, then add 1 g/2.7 mmol of PPh4Cl and maintain until the formation of orange needles, which are separated by filtration, washed with cold water and dry. 2. Procedeu de hrănire a albinelor, care include amestecarea soluţiei apoase de 1 mg% de compusul obţinut prin procedeul definit în revendicarea 1, cu sirop de zahăr de 50% în raport de 2:100, respectiv, şi hrănirea albinelor primăvara cu acest amestec în cantitate de 100…300 ml la fiecare interval de rame cu albine, o dată la două zile, timp de trei săptămâni.2. Method of feeding bees, which includes mixing the aqueous solution of 1 mg% of the compound obtained by the method defined in claim 1, with 50% sugar syrup in a ratio of 2:100, respectively, and feeding the bees with this mixture in the spring in the amount of 100...300 ml at each interval of frames with bees, once every two days, for three weeks.
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