The Physiological Activities, Layout, Spectrum, and Electrochemical Properties of Fe(Ii), Zn(Ii), and Co(Ii) Compounds, Include Pyrazine.2-carboxylic Acid Ligand and 2,2'-bipyridine

doi:10.21203/rs.3.rs-4699722/v1

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The Physiological Activities, Layout, Spectrum, and Electrochemical Properties of Fe(Ii), Zn(Ii), and Co(Ii) Compounds, Include Pyrazine.2-carboxylic Acid Ligand and 2,2'-bipyridine

https://doi.org/10.21203/rs.3.rs-4699722/v1

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Elements analysis, UV-Vis, FT-IR, and cyclic voltammetry have been used to characterize a new Iron (II), Zinc (II), and Cobalt (II) complex [Fe(II), Zn(II), Co(II)] complexes that contain 2,2'-bipyridine and pyrazine-2-carboxylic acid ligand. The interaction of this Fe (II), Zn (II), and Co (II) complex with calf thymus DNA techniques employed in fluorescence spectroscopy was investigated by UV-visible absorption. UV-Vis absorption studies yielded intrinsic binding constants (Kb) for the complex with CT-DNA of 1.9 x 104 and 2.1 x 104M^− 1. Pseudomonas aeruginosa, Staphylococcus aureus, and Bacilli cereus pathogens were assessed for their antibacterial effectiveness against a range of microorganisms using nanosystems to determine the ligand and complex antibacterial activity.

Metal complexes

Drugs Delivery

Antibacterial activities DNA and BSA binding

Site-specific binding characteristics of metal ions, DNA binding with metal complexes provides an alternative to the most recent chemotherapeutic medications.[1] There aren't many transition metal compounds that involve DNA as of yet.

Numerous technological and industrial applications can be found for metal complexes. In metal complexes, the ligands can entirely change or adjust the complex's characteristics, while the metal ions themselves may play a variety of important roles. The chemistry of transition elements is significantly influenced by the chemistry of coordination molecules. The first explanation of the nature of bonding in complexes was Werner's coordination theory, which was proposed in 1893. [2] The nature of bonding in complexes is explained by the hypothesis. The theory states that the secondary valence of a metal is represented by the coordination number, which is the number of ligand atoms coordinated to the metal atom. The primary valence of a metal is represented by the number of charges on the complex ion. Both a substantial quantity of experimental research and a comprehensive theoretical treatment have been dedicated to the field of coordination chemistry. Following the development of the valence bond theory of metal-ligand bonding, a number of theoretical chemists employed the wholly electrostatic Crystal Field Theory (CFT) to interpret the transition metal complex spectra. On the other hand, molecular orbitals created by metal and ligand orbitals can be used to explain the metal-ligand interaction. Since Molecular Orbital Theory does not readily yield numerical findings, a modified form of CFT has been developed wherein specific parameters are numerically changed to account for covalence effects. It is common to refer to this modified CFT as Ligand Field Theory.

In biological systems, metal complexes have a variety of significant functions. The roles of vitamin B12, haemocyanin, carbonic anhydrase, xanthine oxidase, hemoglobin, and chlorophyll show how closely inorganic chemistry and biology are related. These types of metal complexes are currently being studied within the quickly expanding field of bio-inorganic chemistry. Metal complexes have intriguing uses outside of the fields of medicine and catalysis. Inorganic materials have been used in medicine since the time of Hippocrates. He proposed the therapeutic use of metallic salts. However, the rational underpinnings for understanding the role of inorganic species in medicine were not established until after the advances in the field of bio-inorganic chemistry. Therapeutic and diagnostic agents have been employed with metal complexes. Among the subjects of ongoing research in bio-inorganic chemistry right now are studies on metal-based anticancer medications and ant-arthritic medicines. Numerous metal complexes have been investigated with the goal of employing them as antibacterial and anticancer medications, particularly those involving Schiff bases. The Schiff bases, their metal complexes, and their general use are covered in this chapter. Schiff bases and the first row transition metal complexes they produce, like Fe(II), Zn(II), Cu(II), etc., are said to have 114 anti-tubercular, fungicidal, and bactericidal effects. Particularly, a great deal of study has been done on Fe(II) complexes with various medications. This is probably because of Fe(II)'s biological function and the medications' synergistic effects. Numerous harmful fungi and bacteria have been tested for the antifungal and antibacterial qualities of various Fe (II) complexes.

A trace of Fe(II) has long been thought to eliminate microbes, but more modern processes have led to activated oxygen on metal surfaces. Due to the low Zn(II) activity, Zn kills the microorganism. The last twenty years have seen a significant increase in interest in research on the interaction of transition metal complexes with nucleic acid [2–4]. These studies can aid in the development of new reagents for biotechnology and medicine. Many researchers are interested in the rational synthesis of new transition metal complexes that bind and cleave duplex DNA with high sequence and structural selectivity. It has been established that the creation of new transition metal-based DNA-interacting coordination molecules by multi-mode binding would have advantages in terms of administration, toxicity reduction, etc.

Synthesis of complexes [Fe(bpy) (prz)]

A methanol (10 ml) solution containing 2–2'-Bipyridine was mixed with NaOH (0.1 g, 1.2 mmol) and allowed to stand for 15 minutes. FeCl3 (0.30 g, 1.2 mmol) was added to the solution along with 10 ml of methanol. The reaction mixture was then stirred for three hours. DMF was used to dissolve the rose-colored precipitate that had developed. 46% yield; melting point 167°C (dec). 91% (0.0222 g) of the yield; m.p. 211°C (dec). 1648s, 1496s, 1061s, 557s, 538s, 481s, and 437s are the selected peaks in FT-IR (KBr, v, cm-1). (br, broad; s, sharp). The following UV-vis values in DMF are reported: 267 (2101), 275 (3046), 288 (1845), 315 (2535), 327 (1612), 345 (2535), 362 (1147), 376 (1080), 397 (956), and 537 (16).

[Fe(bpy)(prz)]2

A solution of 2,2'-Biplyridine in 10 milliliters of methanol was mixed for 15 minutes at room temperature after adding NaOH (0.1 grams, 1.2 millimoles) to it. The solution was supplemented with ZnCl2 (0.30 g, 1.2 mmol) in methanol (10 ml) and prz (0.13 g, 1.2 mmol) in methanol (10 ml). The reaction mixture was then stirred for three hours. DMF was used to dissolve the rose-colored precipitate that had developed. FT-IT (KBr, v, cm-1) selected peaks: 3391s, 1512s, 1121s, 1657s, 568s, 533s, 477s, and 436s; yield: 59 (%) (0.0202 g); m.p. 115°C (dec). λmax/nm (\max/mol^− 1 cm^− 1)] for UV-vis in DMF are as follows: 267 (2677), 278 (3691), 288 (2136), 315 (1128), 327 (2258), 345 (3408), 362 (1216), 376 (1066), 397 (956), and 598 (2).

[Co(bpy)(prz)]2

Upon adding 0.1g (1.2 mmol) of NaOH to a 10 ml methanol solution containing 2,2'-Bipyridine, the mixture was allowed to sit at room temperature for 15 minutes while being agitated. To the mixture, CoCl2 (0.30 g, 1.2 mmol) in 10 ml of methanol was added. Stir the reaction mixture for three hours after adding it. DMF was used to dissolve the rose-colored precipitate that had developed. M.p. 179°C (dec); yield: 72(%). Selected peaks in FT-IR (KBr, v, cm^− 1) include 3213 br, 3139 br, 2029 s, 1573s, 1515sm, and 1277s. λmax/nm (̐max/mol-1 cm-1)] for UV-vis in DMF: 263(889), 328(919), 378(666), 585(34), 688(11)

Figure.1. FT-IR spectra of complexes 1 & 3

FT-IR and UV-vis spectroscopy

Complex 2's v(NH) [4] is responsible for the strong band seen in the ligand's infrared spectra at 3391cm^− 1. Thus, at 1649 and 1657cm^− 1, the ligand's ν(C = N) band was seen. Additionally, the compounds showed faint bands that are ascribed to ν(M-N) between 532 and 559cm^− 1[5]. On the other hand, the ligand's spectrum revealed a prominent band at 1512 and 1497cm^− 1, which was identified as ν(C-O), which was observed at 1063 and 1121cm^− 1 in the free ligand's spectrum. Additionally, the complexes' spectra showed faint bands between 436 and 481cm^− 1, which are linked to the ν(M-O)[19]. (Fig. 1)

The complexes' electronic spectra (Fig. 2) shows modest peaks at 536 and 599 owing to the d-d transition 3A₂g→3T₂g for the Zn + 2 complex, and bands at 267–288 nm* transition and 315–397 nm due to the n→ℼ* transition of the complexes [6].

Figure.2. UV-vis is spectra of complexes 1

Electrochemical Studies

Using cyclic voltammetry, the electrochemical behavior of the cobalt (II) complexes in dimethyl formamide containing 10^− 1 M tetra (n-butyl) ammonium perchlorate has been investigated. The potential range of the voltammetry is 0 to -1.2 V. Figure 4 shows cyclic voltammograms for all Zinc (II) and complexes (scan rate 50 mV s^− 1). The quasi-reversible reduction wave for complexes 1 and 2 is located at -1.0901 and − 0.8778 V, respectively.

UV-Vis absorption spectral studies

Electronic absorption spectroscopy is a useful tool for evaluating the DNA binding mechanism of metal complexes. As CT DNA concentrations rose, the absorption spectra of Complexes 1–3 were recorded at constant free metal complex concentrations. Since DNA is the primary carrier of genetic information and most malignancies result from DNA damage, DNA binding is one of the most crucial processes for the action of many metal-based anticancer drugs [7–11]. One of the most effective experimental techniques for studying the interactions between metal ions and DNA is electron absorption spectroscopy. The metal complex's electronic absorption spectrum varies when the macromolecule binds to it. To ascertain the mechanism and binding strength of DNA binding with tiny compounds, electronic absorption spectroscopy is typically employed [12]. There are three main ways in which a range of tiny compounds bind reversibly with DNA: (i) binding interaction with the DNA double helix's grooves; (ii) electrostatic interaction; and (iii) interaction between the native DNA's stacked base pairs [13–15]. Figure 4 displays the UV-Vis spectra of the complex measured between 231 and 301 nm when CT-DNA was present and absent.

At a certain complex concentration (1.0x10-5M), hyper-chronicity is seen at roughly 276 (18%) nm for complex 1 and 277 (24%) nm for complex 2. Strong hyperchromism, a tiny blue shift (8 nm) for complex 1, and no significance seen for complex 2 all point to groove binding as the primary cause of the complex's strong interaction with CT-DNA [9–10]. The UV absorbance band's hyperchromicity is known to be caused by the double helix's unraveling, unshackling, and concomitant base exposure; however, red and blue shift raises the possibility that the complex may also have some effect on DNA [16]. The intrinsic binding constants Kb are obtained by monitoring changes in the absorbance of the complex as the DNA concentration rises. This makes it possible to compare the complex's binding strength to that of CT-DNA. The binding constant, Kb, has been obtained from the spectroscopic titration data using equation [17, 18]. [DNA/(̐εb- εf)] = DNA/(̐εa- εb) + 1/Kb(εb- εr), where \a is the observed extinction coefficient for the charge transfer absorption at a specific concentration, εf is the extinction coefficient of the complex in solution, εb is the extinction coefficient of the complex when fully bound to DNA, and Kbis is the slope-to-intercept ratio from the [DNA]/(εa- εb)vs [DNA] plots.Complex 1–3's Kb values are 1.75 x 105, 1.98 x 105, and 2.38 x 105 M-1. The complexes have the highest binding affinity of all of them, and their moderate binding strength is seen from the values of their binding constants.

Antibacterial Screening Test:

The antibacterial activity of (M - Metal) solution, 50 mg/µl of the dye solution loaded in the well, was investigated. After incubation at 37°C for 24 hours, the zone of inhibition was evaluated by averaging the zone obtained from the duplicate plates.

Antibacterial activity:

In this investigation, zinc (II) complexes showed antibacterial activity against all test microorganisms using three distinct bacterial pathogens to screen for potential antimicrobial activity.[19–25]Against the three bacterial pathogens, they exhibited strong antibacterial action. Pseudomonas aeruginosa, Staphylococcus aureus, and Bacilli's cereus pathogens were the three bacterial pathogens against which complexes shown greater effectiveness (Fig. 5.)

Figure.5.Antibacterial activity

Table-1.

Antibacterial activity [concentration on in µl]

Bacteria

Pseudomonas

aeruginosa(nm)

Staphylococcus

aureus

(mm)

Bacillus cereus

(mm)

Concentration

+ve

We synthesized and analyzed the Iron (II), Zinc (II), and Cobalt (II) complexes (1–3), which display two irreversible waves at -0.76 & -0.86 and − 0.26 & -0.38. Characteristics of DNA binding complexes. Complex 1 has a more effective DNA binding agent than Complexes 2 and 3. The complexes and ligands' antibacterial activity was evaluated using a sample of the subjects under research.

ACKNOWLEDGEMENT

The Kirnd Institute of Research and Development Developments PVT LTD is grateful for the financial support provided by the SDCAS/MINI PROJECT SCHEME/2020.

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The Physiological Activities, Layout, Spectrum, And Electrochemical Properties Of Fe(Ii), Zn(Ii), And Co(Ii) Compounds, Include Pyrazine.2-Carboxylic Acid Ligand And 2,2'-Bipyridine,

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Authors' contributions

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Conception and design of study
Acquisition of data

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You are reading this latest preprint version

The Physiological Activities, Layout, Spectrum, and Electrochemical Properties of Fe(Ii), Zn(Ii), and Co(Ii) Compounds, Include Pyrazine.2-carboxylic Acid Ligand and 2,2'-bipyridine

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Version 1

Abstract

Figures

INTRODUCTION

Synthesis of complexes [Fe(bpy) (prz)]

[Fe(bpy)(prz)]2

[Co(bpy)(prz)]2

RESULTS AND DISCUSSIONS

FT-IR and UV-vis spectroscopy

Electrochemical Studies

UV-Vis absorption spectral studies

Antibacterial Screening Test:

Antibacterial activity:

CONCLUSION

Declarations

References

Additional Declarations

Status:

Version 1