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ISSN 2522-1841 (Online) AZERBAIJAN CHEMICAL JOURNAL № 4 2022 ISSN 0005-2531 (Print)
UDC 535.33:543.4l
INFLUENCE OF IRON OXIDE NANOPARTICLES AND COMPLEXES OF BIOGENIC METALS WITH ORGANIC ACIDS ON PHYSIOLOGICAL AND BIOCHEMICAL CHARACTERISTICS OF WHEAT SEEDLINGS
1 2 3 1
G.H.Ismayilova , Sh.I.Gahramanova , I.V.Azizov , T.O.Gahramanov
1Baku State University Institute of Catalysis and Inorganic Chemistry, NAS of Azerbaijan 3Institute of Molecular Biology and Biotechnologies, NAS of Azerbaijan
sahnaz.gahramanova@gmail.com
Received 28.06.2022 Accepted 06.07.2022
In this study, complexes of manganese (II) and zinc(II) with ligands (salicylic acid and cysteine) [MnL2(H2O)2]2H2O, [ZnL2(H2O)2]2H2O have been synthesized. It is shown that the composition of the obtained complexes depends on the ratio of the initial components. The composition and structure of the complexes have been studied by elemental X-ray phase analysis, (DLS)method, UV-VIS spectroscopy, IR spectra1 and thermogravimetric analysis. The method of UV spectroscopy has show that the ligands in the composition of the metal (II) complexes enter the neutral form and coordinate with the complexing agent through the nitrogen atom. According to UV spectroscopy has d-d transition was observed in the complexes corresponding to the wavelength for Mn (II) 480-560 nm, for Zn (II) complex 238 nm. The results of thermogravimetric studies have shown that the final product of the thermal decomposition of all compounds is metal oxide, respectively. The complex compounds of manganese and zinc with the amino acids cysteine, methionine, glycine and salicylic acid and nanoparticles of Fe2 O3 have a positive effect on seed germination, the synthesis of photosynthetic pigments and activity of ascorbate peroxidase in wheat leaves.
Keywords: salicylic acid, cysteine, metal oxide, amine groups, IR spectroscopy, nanoparticles, thermogravimetry, germination, chlorophyll, carotenoids, ascorbate peroxidase.
doi.org/10.32 73 7/0005-2531-2022-4-53-59 Introduction
Over the past decades, the number of works aimed at studying the role of biogenic macro- and microelements in biochemical processes has significantly increased. It is noted that the role of these macro- and microelements are markedly enhanced when used in combination with amino acids [1-5]. Amino acids can play the role of metal-chelating ligands, which makes it possible to create, on this basis, drugs that combine amino acids with trace elements and ensure their efficient transport into the living environment [6-10]. Currently, an urgent scientific task is to elucidate the composition and structure of compositions based on macro-, microelements and amino acids at the molecular and supramolecular levels and their mechanism of action, to find ways to increase the effectiveness of these compositions.
The complexes of many metals with ami-noacids serve as a model of processes occurring in living organisms. Besides, many complexes
are widely used in medicine as medicine drugs [11-20].
The aim of this work was the synthesis of a complex of ligands (salicylic acid and cysteine with manganese (II) and zinc (II) chloride, the study of structures and their biological effects. The effect of iron oxide nanoparticles on the activity of antioxidant enzymes was also studied.
Materials and methods
Physical measurements
The composition and chemical structure of the synthesis products obtained have been studied by physical-chemical analysis methods: 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 UV regions were recorded on the Evolution 60S spectrophotometer manufactured by Thermo Scientific Spectronic (USA). Differential thermogravimetric analysis was performed on (NETZSCH STA 449F3 STA449FSA-0622-M).
Experimental part
Synthesis [ZnL2(H2O)2]2H2O, L - cysteine
A calculated amount of ligand (L-cys-teine) (0.01 mmol, 1.21 g) and the metal salt ZnSO4 2H2O (0.01 mmol, 1.97 g) were mixed in (1:1) molar ratio in 20 mL ethanol. 4-5 drops of dilute HCl were added to it and the mixture was continuously heated for 6 h. The resulting precipitate was filtered off, washed with ethanol and dried in a desiccator over sulfuric acid for one week.
Synthesis [MnL2(H2O)2]2H20, L - salicylic acid
The synthesis of a manganese (II) complex with salicylic-resorcinol alcohol was obtained by the method described above.
Results and conclusion
Infrared Spectroscopy
We have conducted infrared spectroscopy analysis to show the coordination characteristics of the analyzed and synthesized compounds generated between the given ligand and the Zinc. Accordingly, the Figure 1 illustrates the spectrum of ZnSO4 with cysteine. The spectrum of the obtained substance differs significantly from the spectrum of the ligand. Thus, in the spectrum of the cysteine molecule, the frequency bands associated with stretching vibrations of carboxyl and amine groups are visible in 1790 and 3374 cm-1 frequency range of the spectrum. These bands disappear in the spectrum of the complex and pass into the frequency range of 1563 and 3212 cm-1. Note that the absorption band corresponding to the stretching vibrations of the SH groups is visible in 2853 cm-1 frequency range of the ligand. This is due to the participation of the -SH group in intramolecular and intermolecular hydrogen bonds (Figure 1).
Differential Scanning Calorimetry
The thermographic analysis was carried out with the determination of the thermic stability and the composition of synthesized complexes [MnL2(H2O)2]2H2O (Figure 2).
The decomposition of the complexes was carried out in 2 stages in the range of 100-
500 C. Thermolysis of Mn complexes proceeds in two stages. The first stage is dehydration, the second stage is decomposition of anhydrous salt with simultaneous combustion of a carbon residue with formation of an oxide. Dehydration of the Mn complex occurs in the temperature range of 100-2000C. On the DTA curve this process corresponds to two endothermic effects. This corresponds to the fact that dehydration occurs in two stages. The first stage is the removal of a single molecule, the second stage removes two water molecules. The first endo-thermic effect (1100C) in the DTA curve has been detected in the temperature range of 90-1200C and is related to the removal of an outer-sphere one-molecule of water. In the second stage dehydration in the temperature range of 140-2000C is associated with the removal of two inner sphere water molecules. The high dehydration temperature apparently means that the water molecules are intraspheric. The anhydrous phase of the manganese complex decomposes in the temperature range of 220-6500C with the formation of metal oxide.
X-ray phase analysis
Figure 3 shows the result of X-ray phase analysis of the synthesis product. The interpretation of the obtained data also confirms the formation of the [ZnL2(H2O)2] 2(H2O) complex.
Since the parameters of the crystalline cell differ from each other, a complex coordination Zn-cysteine was established. Although cysteine peaks did not appear in Zn- cysteine, almost all complexes were created through analysis.
Figure 4 shows the result of X-ray phase analysis of the synthesis product. The interpretation of the obtained data also confirms the formation of the [MnL2(H2O)2]2 (H2O) complex.
The results of research have shown that in all cases the end product of thermal decomposition of complexes is a metal oxide. In the end, based on the results of modern physico-chemical methods used in the study, it has been determined that the composition and structure of the obtained complexes depend on the ratio of raw materials.
Wave number, cm-1 Fig. 1. IR spectra of complex [ZnL2(H2O)2]2H2O, L - cysteine.
100 200 300 400 300
Fig. 2. Thermogravigram complex [MnL2(H2O)2] H20, L- salicylic acid.
Fig. 3. Diffractogram of the complex [ZnL2(H2O)2]2(H2O), L- cysteine. AZERBAIJAN CHEMICAL JOURNAL № 4 2022
1 .0e+004 8.0e+003 6.0e+003 4.0e+003 2.0e+003 0.0e+000
10 - - 20 30 40 50 60 Manganese Chloride Hydrate, Mn Cl2 ( H2 O )2, 01-089-501i . 1 ll . 1 i I . , . . , . . .
- 1 1 . Salicylic acid, C6 H4 O H C O O H, 00-001-0558 1 I . . , . . .
• none, C13 H8 Cl2 C
Fig. 4. Diffractogram of the complex [MnL2(H2O)2 ]2(H2O),L- salicylic acid.
0 10 20 30 40 50
9-theta Crlen^
lOO.O Diameter (mil)
60
Median 5.8 (nm)
Diameter on % (2) 10.00% - 4.5 (nm)
(5) 50.00% - 5.8 (nm)
(9) 90.00 % - 7.2 (nm)
% on diameter
Mean 5.8 (nm)
Mode 6.0 (nm)
Span 0.4780
PI 7.3511E-2
Diffusion Coefficient 3.8160 E-11 (m2/s)
Fig. 5. According to the Dynamic light scattering (DLS) method, the distribution of particles in an aqueous solution of amino acid/MnCl2 complex at a temperature of 298 K.
Dynamic light scattering (DLS) method
The time-varying histograms of dynamic light scattering of the resulting supramolecular structures are given (Figure 5).
It was found that molecular complexes are hydrolyzed in an alkaline environment, and in the process of hydrolysis, aggregates that previously grew to 4-5 microns in size and in the later stages of the process, these aggregates precipitate to form a white disperse sediment consisting of Mn hydroxide-oxid
Elemental analysis, DLS method, IR and UV-VIS spectral and thermometric analyses have been conducted to study the thermal stability and composition of the complexes. Our studies showed that thermal decomposition of the
complexes in all cases leads to metal oxide in every case. Thus, it has been found that the composition and structure of the complexes obtained depend on the ratio of the given initial products according the results of the analysis.
Biological activity of complexes
The effect of the zinc-cysteine complex on the biosynthesis of photosynthetic pigments and morphological parameters of seedlings of irradiated wheat seeds has been studied (Table 1). Before irradiation, wheat seeds were treated with 0.1%; 0.01%, 0.001% solution of the complex and 0.001% Fe2O3 (The size of ferric oxide NPs is 20x40 nm (Skyspring Nanomaterials Inc, USA). At the next stage, the dried seeds were gamma irradiated with 300 Gy from a 60Co
source. Further, they were planted in the soil. Then germination, growth of seedlings, and the dynamics of the formation of photosynthetic pigments were studied. Initial experiments have showed that, when treated seeds with the (Zn-cysteine) complex, their resistance to gamma rays is increased. Germination of untreated seeds was low compared with treated seeds. The content of chlorophyll a, b, carotenoids and activity of ascorbate peroxidase were higher in the seedlings of the treated seeds than in the untreated ones.
Some researchers showed that at high concentrations of manganese, zinc, phosphorus and iron in the medium it is difficult zinc ab-
sorption by the root system of plants. However, the low concentrations of manganese, zinc and phosphorus enhance the growth and development of plants, increases the chlorophyll content in the leaves. It has concluded that the low concentrations of these elements provide the normal development of wheat plants (Table 2). In our experiments, 10-day-old seedlings of wheat were exposed to water stress. After a one-week period of drought began to pour water and followed the release of plants from stress situation. The output of the plant stress state was the following sequence: MnSO4-cysteine, MnSO4- methionine, MnSO4- glycine and control.
Table 1. Influence of Zn-cysteine complex with amino acids and nanoparticles Fe2O3 on content of chlorophylls, carot-enoids and activity of ascorbate peroxidase in leaves of wheat seedlings of irradiated with 300 Gy of gamma radiation
Variants Chlorophyll a, mg/g Chlorophyll b, mg/g Carotenoids, mg/g Activity of ascorbate peroxidase (nmolg-1min-1)
Control 9.2 ± 0.03 3.6 ± 0.04 3.2 ± 0.02 32.265±2.5
Zn-cisteine (0.001%) 6.8 ± 0.02 2.2 ± 0.03 2.5 ± 0.02 30.453±1.2
Irradiated 300 Gy
Control 5.6 ± 0.04 1.9 ± 0.05 1.8 ± 0.01 21.564±2.1
Zn-cisteine (0.1%) 6.2 ± 0.02 2.1 ± 0.01 2.0 ± 0.03 24.125±1.7
Zn-cisteine (0.01%) 6.8 ± 0.01 2.3 ± 0.04 2.5 ± 0.02 28.245±2.4
Zn-cisteine(0.001%) 7.3 ± 0.02 2.5 ± 0.01 2.7 ± 0.05 31.564±1.8
Fe2O3(nano) 9.5± 0.03 3.3± 0.06 3.4± 0.02 35.452±1.9
Table 2. Influence of MnSO4 - Amino acid Complex and nanoparticles Fe2O3 on seed germination and the Chlorophyll Content in Leaves of Wheat Seedlings (mg/g)_
Variants Germination energy, % Germination,% Chlorophill a+b Chlorophill a/b
Control (H2O) 30 65 6.75±0.02 2,5
MnSO4 -- H2O 29 63 5.54±0.04 2.2
MnSO4-cysteine 33 67 8.95±0.02 3,2
MnSO4 -methyonine 32 67 7.25±0.03 2.7
MnSO4-glycine 31 66 7.25±0.03 1.9
MnSO4 -salicylic acid 34 68 7.95±0.05 2.8
Fe2 O3(nano) 45 76 10,5±0.08 2,9
Conclusion
The complex compounds of zinc with cysteine and nanoparticles Fe2O3 remove the negative effect of gamma radiation on the synthesis of photosynthetic pigments and activity of ascorbate peroxidase in wheat leaves. Complexes of manganese with the amino acid cysteine, methionine, glycine and salicylic acid have a positive effect on seed germination and the synthesis of photosynthetic pigments in wheat leaves.
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DOMiR OKSÍD NANOZORROCiKLORiNiN VO BÍOGEN METALLARIN ÜZVÍ TUR§ULARLA KOMPLEKSLORiNiN BUGDA TOXUMLARININ FlZiOLOJi VO BlOKlMYOVi
XÜSUSlYYOTLORlNO TOSiRi
G.H.ismayilova, §.i.Q3hramanova, i.V.Ozizov, T.O.Qahramanov
Manqan (II) va sinkin (II) müxtalif liqandlarla (salisil tur§usu va sistein) [MnL2(H2O)2]2H2O, [ZnL2(H2O)2]2H2O komplekslari sintez edilmi§dir. Gostarilmi§dir ki, alinan komplekslarin tarkibi ilkin komponentlarin nisbatindan asilidir. Komplekslarin tarkibi va strukturu element, rentgen faza analizi, (ÍDS) üsulu, UB- spektroskopiyasi, ÍQ-spektral va termoqravimetrik analizlarla óyranilmiíjdir. ÍQ-spektroskopiya analizi üsulu ila müayyanla¡jdirilmi¡jdir ki, metal (II) komplekslarinin tarkibina liqandlar neytral formada daxil olur va kompleksla§dirici ila azot atomu vasitasila koordinasiya edir. UV spektroskopiyaya gora Mn (II) kompleksi ügün 480-560 nm, Zn (II) kompleksi ügün 238 nm dalga uzunluguna uygun olan d-d kegidi mü§ahida edilmi§dir.Termoqravimetrik tadqiqatlarin naticalari gostardi ki, bütün birla§malarin termiki pargalanmasinin son mahsulu müvafiq olaraq metal oksiddir. Manqan va sinkin sistein, metionin, qlisin va salisil tur§usu amin tur§ulari va Fe2O3 nanohissaciklari ila kompleks birla§malari toxumun cücarmasina, fotosintetik piqmentlarin sintezina, bugda yarpaqlarinda askorbat peroksidazamn aktivliyina faydali tasir gostarir.
Agar sozlar: salisil tur§usu, sistein, metal oksidi, amin tur§u, ÍQ spektroskopiyasi, nanohissaciklar, termoqravimetriya, сйсэгтэ, xlorofil, askorbatperoksidaza.
ВЛИЯНИЕ НАНОЧАСТИЦ ОКСИДА ЖЕЛЕЗА И КОМПЛЕКСОВ БИОГЕННЫХ МЕТАЛЛОВ С ОРГАНИЧЕСКИМИ КИСЛОТАМИ НА ФИЗИОЛОГИЧЕСКИЕ И БИОХИМИЧЕСКИЕ ХАРАКТЕРИСТИКИ ПРОРОСТКОВ ПШЕНИЦЫ
Г.Н.Исмайлова, Ш.И.Гахраманова, И.В.Азизов, Т.О.Гахраманов
Синтезированы комплексы марганца (II) и цинка(П) с лигандами (салициловая кислота и цистеин) [MnL2(H2O)2]2H2O,[ZnL2(H2O)2]2H2O. Показано, что состав полученных комплексов зависит от соотношения исходных компонентов. Состав и строение комплексов изучены методом элементного, рентгенофазового анализа, (DLS)-методом, УФ-ВИС спектроскопией, ИК-спектральным и термогравиметрическим анализом. Методом ИК-спектроскопии показано, что лиганды в составе комплексов металлов (II) переходят в нейтральную форму и координируются с комплексообразователем через атом азота. По данным УФ-спектроскопии в комплексах наблюдался d-d-переход, соответствующий длине волны для Mn(II) 480-560 нм, для Zn(II) комплекса 238 нм. Результаты термогравиметрических исследований показали, что конечным продуктом термического разложения всех соединений является оксид металла, соответственно. Комплексные соединения марганца и цинка с аминокислотами цистеином, метионином, глицином и салициловой кислотой и наночастицами Fe2O3 оказывают благоприятное влияние на прорастание семян, синтез фотосинтетических пигментов и активность аскорбатпероксидазы в листьях пшеницы.
Ключевые слова: салициловая кислота, цистеин, оксид металла, аминные группы, ИК-спектроскопия, наночастицы, термогравиметрия, прорастание, хлорофилл, каротиноиды, пероксидаза аскорбата.
