SYNTHESIS OF COMPLEX COMPOUNDS OF DIVALENT COPPER WITH HISTIDINE AND ARGININE LIGANDS, INVESTIGATION OF THEIR PROPERTIES AND INFLUENCE ON PHYSIOLOGICAL PROCESSES OF WHEAT SPROUTS Текст научной статьи по специальности «Химические науки»

ХИМИЧЕСКИЕ НАУКИ

Gahramanova Sh.I.

PhD in Chemistry, Researcher, Institute of Catalysis and Inorganic chemistry named after academician M.F.Nagiyev, ANAS

Jalaladdinov F.F. leading researcher, associate professor Institute of Catalysis and Inorganic chemistry named after academician

M.F.Nagiyev, ANAS Azizov I. V. Doctor of Biological Sciences Institute of Molecular Biology and Bio technologies of, ANAS

Khudaverdiyev R.A. leading researcher, associate professor, Institute of Catalysis and Inorganic chemistry named after academician

M.F.Nagiyev, ANAS Mammedova Z.M.

Researcher,

Institute of Catalysis and Inorganic chemistry named after academician M.F.Nagiyev, ANAS

Pashayeva F.K. Researcher,

Institute of Catalysis and Inorganic chemistry named after academician

M.F.Nagiyev, ANAS Gahramanov T.O.

Associate professor, "Physical and Colloid" chemistry department

Baku State University Hajiyev A. Sh. Researcher,

Institute of Catalysis and Inorganic chemistry named after academician

M.F.Nagiyev, ANAS Кахраманова Ш.И. Кандидат химических наук, научный сотрудник, Институт Катализа и Неорганической химии им. акад. М. Нагиева НАНА.

Джалаладдинов Ф. Ф. Кандидат химических наук, доцент Институт Катализа и Неорганической химии им. акад. М. Нагиева НАНА.

Азизов И.В. Доктор биологических наук Институт молекулярной биологии и биотехнологий НАНА.

Худавердиев Р. А. Кандидат химических наук, доцент Институт Катализа и Неорганической химии им. акад. М. Нагиева НАНА.

Мамедова З.М. научный сотрудник,

Институт Катализа и Неорганической химии им. акад. М. Нагиева НАНА.

Пащаева Ф.К. научный сотрудник,

Институт Катализа и Неорганической химии им. акад. М. Нагиева НАНА

Гахраманов Т. О.

Докторант, Доцент кафедры «Физической и коллоидной» химии Бакинский Государственный Университет

Гаджиев А. Ш.

научный сотрудник,

Институт Катализа и Неорганической химии им. акад. М. Нагиева НАНА.

SYNTHESIS OF COMPLEX COMPOUNDS OF DIVALENT COPPER WITH HISTIDINE AND ARGININE LIGANDS, INVESTIGATION OF THEIR PROPERTIES AND INFLUENCE ON PHYSIOLOGICAL PROCESSES OF WHEAT SPROUTS

Summary: New complex copper compounds with ligands (histidine and arginine) with the composition [CuCkL (H2O)] H2O, [CuCl2L2], [CuC^L (H2O)] 3H2O were synthesized. It is shown that the composition of the

complexes obtained depends on the ratio of the initial components. The composition and structure of the complexes were studied by chemical analysis, IR spectroscopy, and thermogravimetry.

Key words: histidine, arginine, copper oxide, amine groups, complex compounds

Аннотация: Синтезированы новые комплексные соединения меди с лигандами (гистидин и аргинин) с составом [CuCl2L (H2O)] H2O, [CuCl2L2], [CuCl2L (H2O)] 3H2O. Показано, что состав полученных комплексов зависит от соотношения исходных компонентов. Состав и структура комплексов изучались химическим анализом, ИК-спектроскопией и термогравиметрией.

Ключевые слова: гистидин, аргинин, оксид меди, аминогруппы, комплексные соединения

INTRODUCTION

The chemistry of complex compounds of transition metals with multidentate ligands, which simultaneously contains several donor atoms, is not only theoretical but also of practical interest, since in addition to the unusual properties of such complexes, the structure and types of binding of multidentate ligands with different metals give a new impetus to the development coordination chemistry as a whole. Among the coordination compounds, the complexes obtained on the basis of biomaterials take a special place. This is due to the fact that they play an important role in many biochemical processes and therefore are widely used in plant growing, animal husbandry, and pharmacology. In turn, the study of the properties and structure of coordination compounds of metal ions with organic ligands containing various donor centers was an important factor in the development of new approaches to their physico-chemical research. [1-3]

On the other hand, complex compounds of many transition elements, including copper, can possess a wide range of useful properties, for which the chemistry of complex compounds has not yet been sufficiently studied [4-6].

In this paper, we present methods of synthesis and study of the properties of copper (II) complexes with ligands (histidine and arginine)

Physical measurements

The composition and chemical structure of the synthesis products obtained are studied by physical-chemical analysis methods: elemental analysis (iCP-MS); X-ray phase analysis (diffractometer (Germany) D-2 Phaser firm Bruker); IR spectroscopy ("Specord M-80" brand Carl Zeiss). The spectra of the reaction solutions in the IR and UV regions were recorded on the Nicolet IS10 spectrometer and the Evolution 60S spectrophotometer, manufactured by Thermo Scientific Spectronic (USA). Differential thermogravimetric analysis was performed on a derivative (NETZSCH STA 449F3 STA449FSA-0622-M).

Wheat seeds have been soaked in the solution of the complex within 24 hours. Control seed were soaked with water. Control and experimental seeds germinated on filter paper in Petri dishes at 20 ° C

incubation conditions. Germination rate and energy of germination were determined. The content of chlorophyll and the activity of the photosystems were determined according to the works (1,2).

EXPERIMENTAL PART

Synthesis -[CuCkL2]

A sample of 0.85 g (0.005 mole)-CuCl2 2H2O was dissolved in a two-necked flask under reflux in 30 ml of ethyl alcohol at a temperature of 60 ° C, and 1.55 g (0.01 mole) of ligand L-histidine - (in a molar ratio of 1: 2) previously dissolved in 20 ml of ethyl alcohol. The resulting mixture was heated for 2 hours, then cooled to room temperature, filtered and put on crystallization. The beige-colored crystals were filtered, washed several times with the mother liquor, then 10-15 ml with acetone and dried in a desiccator over sulfuric acid until a constant weight was established.

Synthesis -[CuCl2L2]2H2O

To a beige color solution obtained by dissolving 0.85 g (0.005 mole) -CuCl2 • 2H2O in 20 ml of ethyl alcohol, 1.55 g (0.01 mole) of ligand L- histidine dissolved in 30 ml of ethyl alcohol (in a molar ratio 1: 2). The solution was heated for 2-2.5 hours at a temperature of 60 ° C. Further, the synthesis process was carried out according to the above described procedure.

Synthesis -[CuCl2L(H2O)] 3H2O

According to the above procedures, 1.74 g (0.01 mol) of ligand L- arginine (molar ratio 1: 1), previously dissolved in 20 ml of ethyl alcohol, was added to 1.71 g (0.01 mole) -CuCl2 2H2O dissolved in 30 ml of ethyl alcohol, alcohol. The resulting mixture was heated for 2 hours, then cooled to room temperature, filtered, washed several times with the mother liquor, then 10-15 ml with acetone and dried in a desiccator over sulfuric acid until a constant weight was established.

Elemental analysis

The elemental analysis results for the synthesized complexes confirm the 1:1 , 1:2 ratio metal-ligand. The elemental analysis data of the metal-ligand complexes are pointed up in Table 1.

Table 1.

Elemental analysis results the complexes_

Symbolic Molecular %Cl %H %N %Metal

formula weight Calc. Meas. Calc. Meas. Calc. Meas. Calc. Meas.

[CuCl2L2] 445 15.95 15.01 4.04 3.12 9.44 9.21 14.37 14.18

[CuCl2L2]2H2O 571 12.43 12.21 3.85 3.21 7.36 7.11 11.21 11.01

[CuCl2L(H2O)] 3Н2О 3Н2О 381 18.63 18.16 5.71 5.01 14.69 14.17 16.79 16.29

RESULTS and CONCLUSION To determine the coordination character of the synthesized complex compounds formed between the ligand and the coupler, IR spectroscopic analysis was

tra of the covalent vibrations of the NH bond as a function of the spectra of co-ordination absorption oscillations Vnh = 3273.64 cm-1, 3139.56 cm-1 shift to the lower area and the intensity is weakened, and voh = 3447.72 cm-1 refers to the residues of the solvent,

carried out. In the primary amine, the absorption spec- alcohol

Fig.1. IR spectra of complex[CuCl2L2]2H2O ; L-arginin

When the IR spectra of the free ligand are aligned with the spectra of the complexes obtained, an obvious change is observed. The absorption bands due to the valence vibrations of the OH bond to the carboxyl group of the arginin 3300-3500 cm-1 in the mollusk disappear, and instead of the absorption bands vcoo = 1632.77 cm-1 ; 1352 cm-1 relating to the carboxylate ion.

To determine the composition and thermal stability of the synthesized two complexes [CuCl2L (H2o)] H2O, [CuCl2L2] 2H2O and [CuCl2L2] a thermal analysis was carried out and were determined. Complexes are stable up to a temperature of 170°C. The thermal

decomposition of [CuCl2L2]2 H2O begins at a temperature of 170°C, with a mass loss of 2.65%, in the second stage, a decrease in mass corresponds to (3.91%), and this refers to 1 mole of water. In the third stage, mass loss is 14.93% and this corresponds to 1 mole of ligand. At a high temperature, the destruction of complexes begins, which passes through several stages and in all cases of thermal processes the final product is CuO.

A solution of the complex [CuCl2L2] in a concentration of 0.01 m and ultraviolet absorption spectrum.

Fig. 2 a) the decrease of absorption of the wavelength range from 500 nm to 900 nm; b) the increase of absorption of the wavelength range from 400 nm to 900 nm.

Thermocouple analysis was carried out to determine the composition and thermal stability of the complexes under study. Despite the fact that the deri-vatograms of the complexes are identical, they differ substantially in the nature of the thermal decomposition. Results of thermogravimetric and X-ray phase studies have shown that the thermal decomposition of complexes occurs in three stages and in all cases the

third stage of thermolysis is accompanied by oxidation of copper oxide.

Biological activity of complexes The germination of seeds treated with copper chloride complex with amino acids identified in seven-day seedlings, content of chlorophyll and the activity of the photosystems were determined in two weeks seedlings (Table 2).

Table2.

Effect of Complexes CuCl2 -histidine and CuCl2 - arginine on seed germination, chlorophyll content and activity __of photosystems (PSI, PSII) in wheat leaves__

Variants Germination, % Chlorophyll a+b (mg/g leaf) Chlorophyll a/b Activity of PS II mkmol O2 / mg chl. hour Activity of PS I mkmol O2 / mg chl. hour

Control 85 6.75±0.2 2,5 72±2 125±4

CuCl2 -histidine 96 8,95±0.2 2,8 90±3 150±6

CuCl2 - arginine 92 7.25±0.3 2,6 85±2 135±3

As it is seen from the Table 1, the seeds treated with CuCl2 -histidine and CuCl2 - arginine have high germination rate and high activity of photosystems. These complexes also had a positive effect on the chlorophyll content, as well as the ratio of Chlorophyll a / Chlorophyll b.

The stimulating effect of low concentrations of copper chloride and manganese sulfate solution on germination energy, germination and seedling growth was noted by several authors (1-2). In these investigates has been indicated that low concentrations of copper chloride and manganese sulfate has a positive effect on the synthesis of chlorophyll and carotenoids, increased functional activity of chloroplasts.

Thus, the histidine and arginine complexes with copper chloride accelerated the germination of wheat seeds and increased the chlorophyll content in leaves, and also increased the activity of photosystems of chloroplasts.

References

1. Gahramanova Sh.I., Kuliyeva.E.A., Azizov. I.V. Influence of newly synthesized zinc complexes with amino acids on the morphophysiological characteristics of wheat seedlings. // Academic Journal

of West Sibiuryi. 2014. № 5. T.10. P. 94-95. [in Russian].

2. Gahramanova Sh. I., Guliyeva.E.A., Suleymanov G.Z., Azizov.I.V. Influence Newly Syntesized Manganese Complexes with Amino Asids on Morphophysiological Chracteristics Wheat Germ. American International Journal of Contemporary Research 2014. V.4. №12. P.58-60.

3.Mahmudov K. T., Sutradhar M., Martins L., Silva F. C, Ribera A., Nunes V. M.,Marchetti F., Pombeiroa A. L., Gahramanova Sh.I. Mn II and Cu II complexes with arylhydrazones of active methylene compounds as effective heterogeneous catalysts for solvent and additive-free microwave-assisted peroxi-dative oxidation of alcohols. // RSC Advances An international journal to further the chemical sciences. The Royal Society of Chemistry. 2015.V. 5. P. 25979-25987.

4. Gahramanova Sh. I., Kulyeva EA, Su-leimanov GZ, Kerimova UA, Askerova T. Ya. Interaction of manganese (II) with valine and B-alanine // International Youth Scientific and Practical Conference of Students, graduate students and young "Fundamental and applied research in the field of chemis-

try and ecology", 2015.(Kursk 23- 26.). P. 29-31. [In Russian].

5. Babayeva V.I, Kerimov U.A, Osmanov N.S. Synthesis and study of rhenium (IV) complexes with some amino acids. // Journal. Chemistry and chemical technology. 2011.V.54 №1, P.33-36. [in Russian].

6. Molodkin AK, Esina N.Ya., Gnatik E.N. Complex compounds of Pt (IV) with cytosine and threonine. Inorg. chemistry.1998.V.43.№7.P.1160-1166. [In Russian].

УДК 547.541.521

Масуд Абдо-Аллах, Шипидченко М.В., Исак А.Д., Попов Е.В.

Институт химических технологий Восточно-Украинского национального

университета им. В. Даля (г. Рубежное) Abdo-Allah M., Shypidchenko M., Isak А.,Popov Ye.

Institute of Chemical Technologies of the Volodymyr Dahl East Ukrainian National University (Rubizhne).

СИНТЕЗ N-APM-6- МЕТИЛУРАЦИЛ-5-СУЬФОНАИДОВ И ИХ БИОЛОГИЧЕСКАЯ

АКТИВНОСТЬ

SYNTHESIS OF N-ARIL-6-METHYLURACYL-5-SUBFONAIDS AND THEIR BIOLOGICAL ACTIVITY

Проведено исследование реакции взаимодействия ароматических первичных аминов с 6-метилурацил-5-сульфохлоридом (МУСХ). Показано, что удобней всего проводить взаимодействие 6-метилурацил-5-сульфохлорида с первичными ароматическими аминами в среде инертного органического растворителя. В качестве растворителей предложено использовать использовать четыреххлористый углерод, хлороформ, хлористый метилен, дихлорэтан,, уксусную кислоту в присутствии ацетата натрия, пиридин и другие. Предварительные исследования (использование программы PASS) показали, что среди полученных соединений имеются такие, которые проявляют антиоксидантные свойства и могут быть использованы в качестве цитостатиков.

Ключевые слова: 6-метилурацил, б-метилурацил-б-сульфохлорид, N-арилсульфонамиды, механизм реакции, биологически активные вещества

The interaction of aromatic primary amines with 6-methyluracil-5-sulfochloride (MUSH) was studied. It is shown that it is most convenient to conduct the reaction of 6-methyluracil-5-sulfochloride with primary aromatic amines in an inert organic solvent. As solvents, it was suggested to use carbon tetrachloride, chloroform, methylene chloride, dichloroethane, acetic acid in the presence of sodium acetate, pyridine and others. Preliminary studies (using the PASS program) showed that among the compounds obtained there are those that exhibit antioxidant properties and can be used as cytostatics.

Key words: 6-methyluracil, 6-methyluracil-6-sulfochloride, N-arylsulfonamides, reaction mechanism, biologically active substances.

Сульфамидные препараты обладают химио-терапевтической активностью при инфекциях, вызванных грамположительными и грамотрицатель-ными бактериями, некоторыми простейшими (возбудители малярии и токсоплазмоза), хламидиями при трахоме, паратрахоме) [1, 2]. Сульфамидные препараты обладают широким спектром антимикробного действия. Они оказывают бактериостати-ческий эффект в отношении стрептококков, стафилококков, менингококков, гонококков, кишечной палочки, палочек дизентерии, брюшного тифа, холерного вибриона и др. [3].

После того как сульфамид получил признание, начиная с 1930-х годов химики синтезировали тысячи родственных ему веществ, исследовали их эффективность в качестве бактериостатических

O

SO /Cl

O'X

агентов, т.е. веществ, способных прекращать распространение инфекций. Но медицинское применение нашли лишь 20 из них. Было установлено, что многие из этих соединений обладают данными свойствами и в настоящее время сульфамидные препараты прочно вошли в медицинскую практику. Обнаружено, что сульфапиридин является лечебным средством при пневмонии, вызываемой микроорганизмами пневмококками, а также при других пневмококковых заболеваниях и гонорее.

Среди амидов сульфоновых кислот найдены вещества с различной физиологической. Широкое применение для дезинфекции находят хлорамины Ти Б формулы

O

SC /С

Хлорамин Т

Na

O

Хлорамин Б

Na