Synthesis, characterization of Novel β-diketone Ni, Fe, Cr Complexes and study of its Antifungal, Antibacterial, Antioxidant and Anti-Inflammatory Activity.

Introduction

d-block elements performs crucial part in the development of metal complexes in co-ordination chemistry.Enormous works are exist on the various applications of metal complexes. β-dike tone and their metal complexes perform crucial part in the aspect of co-ordination chemistry ¹. Important material in the thin film development which is used in optical device ², radio pharmaceuticals ³. β-dike tone perform as versatile reactant for different reactions of number of heterocycles ⁴ pharmacological importance of flavones ⁵, luminescence assets of pyrazolic ⁶,isoxazolyl ⁷, triazolic ⁸,pyrimidines ⁹.β-dike tone is utilizedas chelating agent ¹⁰,  toxic metal ions adsorbed on different resin ¹¹, protection from harmful radiation, toxins by cosmetics sun screen ¹², anti-HIV-1 drug design ¹³. photoluminescence and photoisomerization property ¹⁴. β-dike toneβ-dike tone complexes shows Lewis acidity, volatility,  idyllic molar enthalpy of formation, idyllic molar heat of sublimation,  catalytic property and vapor pressures ¹⁵.β-dike tone express medical property like anticancer and antibacterial ¹⁶ antimicrobial and antioxidant activity ¹⁷, anti-inflammatory activity ¹⁸. β-dike tone is useful for the treatment of anti-influenza ¹⁹. β-dike tone utilized in organic light emitting diodes (OLED)²⁰. β-dike tone express enol and keto tautomerization ²¹β-dike tone shows anti-spreading action such as lubricant oil on the surface of steel ²²β-dike tone shows anti-tumor property ²³ Since entirely mentioned assets, in current paper, involveβ-dike tone ligand and their different metal complexes. The prepared metal complexes are tested by different methods such as antioxidant, antifungal, and anti-inflammatory and antibacterial action.

Experimental

Merc AR grade chemicals are used in the current research task. Chemicals remain utilized without extra purification. The normal process utilized to purify solvents. For preparation  and recrystallization of metal complexes super dry distilled pure ethanol utilized.

Synthesis of β-diketone Ligand²²

Synthesis of metal complex metal complexes²²

Characterization

Melting points discovered by using capillary method. The elemental study performed via FLASH EA 1112 series Thermo Finnigan. FTIR scanned with the help of FTIR instrument made Bruker Optics  ALPHA-T.The complex is sited on ATR crystal. The Conductance is confirmed with help of Equip- Tronic conductivity meter. Magnetic susceptibility is reported through Guoy balance. The physical possessions of the metal complexes are studied. In metal complexes presence of coordinated water molecules due to this the probable geometry is octahedral.

Table 1: Metal complexes pH range of precipitation, colour, decomposition temperature and yield.

Sr. No.	Name of Complex	pH range of precipitation	Colour	Decomp. Temp./m.p. °C	Yeild (%)
1	Ni-complex	7.0-7.5	Light green	368°C	80
2	Fe-complex	7.0-7.5	Blackish brown	380°C	79
3	Cr-complex	7.0-7.5	Brown	376°C	85

Table 2: Elemental analysis of Metal complexes.

Name of Complex	Molecular Formula	% Found (Calculated)
		C	H	O	Metal
Ni-complex	C38H42NiO10	63.91 (63.62)	6.49 (5.90)	22.87 (22.30)	8.74 (8.18)
Fe-complex	C38H42FeO10	64.35 (63.87)	6.24 (5.92)	22.74 (22.39)	8.13 (7.81)
Cr-complex	C38H42CrO10	64.58 (64.22)	6.47 (5.96)	23.11 (22.51)	7.79 (7.32)

 

Magnetic susceptibility and Molar conductance of metal complexes

Ni-complex

Ni-complex molar conduction is estimated with the help of solvent DMSO at 10^-4 M concentration. Ni-complex molar conduction is 49.2 Ω^-1 cm² mol^-1 that shows Ni-complex nature is covalent and non-electrolyte.

Ni-complex magnetic moment is estimated at room temperature is 2.77 B.M. Ni-ion showing an octahedral geometry.

Fe-complex

Fe-complex molar conduction is estimated with the help of solvent DMSO at 10^-4 M concentration. Fe-complex molar conduction value is 64.5 Ω^-1 cm² mol^-1 shows that Fe-complex nature is covalent and non-electrolyte. Fe-complex magnetic moment is estimated at room temperature is 5.99 B.M are near to the required values for an octahedral geometry.

Cr-complex

Cr-complex molar conduction 26.7 Ω^-1 cm² mol^-1 shows Cr-complex is covalent and non-electrolyte. Cr-complex magnetic moment is estimated at room temperature is 3.78 B.M which is near to the required values for an octahedral geometry.

Table 3: Molar conductances and magnetic property of metal complexes:

Sr. No.	Name of complex	Molar conductance Ω-1 cm2 mol-1	μeff(B.M.)
1	Ni-complex	49.2	2.77
2	Fe-complex	64.5	5.99
3	Cr-complex	26.7	3.78

 

FT-IR of metal Complexes

Ni-complex

In the Ni-complex IR stretching vibration of carbonyl frequency 1606.1cm^-1 that is below IR stretching vibration of  ligand 1624.3 cm^-1[23]. This decreasing stretching vibration of complex display that ligand link with Ni. New-fangled stretching frequency at 633.7 cm^-1 is because of metal to oxygen bond in metal complex. It make sure that metal link with ligand via oxygen. Appearance of peaks at 2966.3 cm^-1 and 3391.2 cm^-1 shows presence of coordinated water in the complex ²⁴.

Fe-complex

In the Fe-complex IR stretching vibration of carbonyl frequency 1604.9 cm^-1 that is below stretching vibration of  ligand 1624.3 cm^-1. This decreasing stretching vibration of complex display that ligand linked with Fe. New-fangled stretching frequency at 633.2 cm^-1 is because of metal to oxygen bond in metal complex. It make sure that metal link with ligand via oxygen. Appearance of peaks at 2966.9 cm^-1 and 3436.4 cm^-1 shows presence of coordinated water in the complex.

Cr-complex

In the Cr-complex IR stretching vibration of carbonyl frequency 1603.5 cm^-1 that is below stretching vibration of  ligand 1624.3 cm^-1. This decreasing stretching vibration of complex display that ligand linked with Cr. New-fangled stretching frequency at 562.6 cm^-1 is because of metal to oxygen bond in metal complex. It make sure that metal linked with ligand via oxygen. Appearance of peaks at 2966.9 cm^-1 and 3432.7 cm^-1 shows presence of coordinated water in the complex.

The IR frequencies of the ligand and Cr-complex are equivalent with the exception of very slight minor changes in absoprtion frequency band created via metal ion.

Thermo gravimetric examination of metal complexes.

Ni Complex

Thermally decomposed of designated metal complex was performed at a hotness quantity of 10°C min^-1 with the help of N₂ environment between the thermal area 21.85°C to 1000°C. The Ni complex thermo gravimetric spectra expressions mass decrease between the temperature area 21.85°C to 200 °C that c express the appearance of co-ordinationated and lattice water molecules in Ni complex. The following mass decrease of obs. 5.02% , cal. 5.96%  correspond to the breakdown of the connect (H₄O₂) part of the synthesized ligand. ³³ The nickel complex offers breakdown from thermal area 200°C to 425°C, by obs. 77.94%, cal.  77.44% mass decrease because of removal of the (C₃₈H₃₈O₄) a portion of synthesized ligand, the exothermal method (T_DTA) peak at area for it. Again on  continueous heat to 968.97°C, the residual weight correlate to the nickel oxide (NiO). As mentioned in Fig.1. 

Figure 1: DTA/TGA Arcs of Ni-complex. Click here to View  figure

Fe Complex

Thermally decomposed of designated metal complex was performed at a hotness quantity of 10°C min^-1 with the help of N₂ environment between the thermal area 29.16°C to 1000°C. The Fe complex thermogravimetric spectra expressions mass decrease between the temperature area 29.16 °C to 200°C that  express the appearance of coordinationnated and lattice water molecules in Fe complex. The following mass decrease of obs. 5.04% , cal. 5.25%  correspond to the breakdown of the connect (H₄O₂) part of the synthesized ligand. The iron complex offers breakdown from thermal area 200°C to 510°C, byobs.  82.41%, cal.  82.07% mass decrease because of removal of the (C₃₈H₃₈O₆) a portion of synthesized ligand. Again on  continueous heatto 974.50°C, the residual weight correlate to iron oxide (FeO). [35] As mentioned in Fig. 2.

Figure 2: DTA/TGA Arcs of Fe-complex. Click here to View figure

Cr Complex

Thermally decomposed of designated metal complex was performed at a hotness quantity of 10°C min^-1 with the help of N₂ environment between the thermal area 28°C to 1000°C. The Cr complex thermogravimetric spectra expressions mass decrease between the temperature area 28°C to 200°C that express the appearance of coordinated and lattice water molecules in Cr complex. The following mass decrease of obs. 5.07% , cal. 4.49%  correspond to the breakdown of the connect (H₄O₂) portion of the synthesized ligand. The chromium complex offers disintegration from thermal area 200°C to 518°C, by obs.  78.61%, cal.  78.73% mass decrease because of removal of the (C₃₈H₃₈O₄) a portion of synthesized ligand. Again on  continueous heatto 974.84°C, the residual weight correlate to iron oxide (CrO). As mentioned in Fig. 3.

Figure 3: DTA/TGA Arcs of Cr-complex. Click here to View figure

Antibacterial Property

The optimistic regulator is taken streptomycin drug and express area of standby of 10mm and 16mm in against of E.coli and B. subtilis correspondingly. Adverse regulator include DMSO doesn’t express any antibacterial action.

Ni-complex and Cr-complex complexes shows antibacterial activity against both bacteria E.Coli and B. subtilis. Fe-complex doesn’t express any activity contrary to E.Coli and B. subtilis.

Antifungal Property

Optimistic regulator for antifungal action is clotrimazole drug and express area of shyness of 6mm against A. niger. Adverse control held DMSO doesn’t express any antifungal action. Cr-complex complex shows antifungal activity against A. niger. Ni-complex and Fe-complex doesn’t express any antifungal action contrary to A. niger.

Table 4: Antimicrobial Action of Ni-complex, Fe-complex and Cr-complex.

S. N.	Compounds	Antibacterial action		Antifungal action
		Zone of progress (mm)		Zone of progress (mm)
		E.coli	B.subtilis	A.niger
1	Ni-complex	7	11	̶
2	Fe-complex	̶	̶	̶
3.	Cr-complex	9	15	2
4.	Streptomycin	10	16	̶
5.	Clotrimazole	̶	̶	6

 

Antioxidant activity

Antioxidant activity of Ni-complex, Fe-complex and Cr-complextested contrary to the reference as ascorbic acid. 

Table 5: %  inhibition and IC₅₀values .

Sample/Standard	% inhibition at Concentration(µg/ml)					IC50 µg/ml
	200	400	600	800	1000
Ni-complex	14.21	27.55	37.12	45.93	54.82	882.61
Fe-complex	37.91	48.52	56.35	67.14	75.98	448.27
Cr-complex	9.8	15.82	22.41	28.65	32.21	1580.45
Ascorbic acid	52.55	65.41	76.32	86.95	95.25	126.84

 

Antioxidant activity in terms of percent inhibition of free radical is 75.98% for Fe-complex at concentration of 1000 µg/ml which is 19.27 % less than that of standard Ascorbic Acid 95.25% at same concentration. The IC50 value for Fe complex is 448.27 µg/ml and that of reference Ascorbic acid is 126.84 µg/ml. Thus Fe-complex has significant antioxidant activity similar to standard ascorbic acid. Least activity was shown by Cr-complex (32.21%) at 1000 µg/ml. Ni-complex shows intermediate antioxidant activity of 54.82% at concentration 1000 µg/ml.

Figure 4: antioxidant activity of Ni complex at various concentration. Click here to View figure

Figure 5: antioxidant activity of Fe complex at various concentration. Click here to View figure

Figure 6: antioxidant activity of Cr complex at various concentration. Click here to View figure

Anti-inflammatory action

The anti-inflammatory action of complexes was find out by using HRBC membrane stabilization technique.

Observation and Result

Table 6: Absorbance at 560 nm

Sr.No.	Concentration (µg/ml)	Absorbance at 560nm
		Diclofenac	Ni-complex	Fe-complex	Cr-complex
1	0 (Control)	0.925	0.925	0.925	0.925
2	100	0.731	0.899	0.756	0.911
3	200	0.703	0.856	0.725	0.902
4	300	0.678	0.812	0.699	0.889
5	400	0.645	0.765	0.668	0.875
6	500	0.611	0.733	0.639	0.852

 

Table 7: % Protection.

Sr.No.	Concentration (µg/ml)	% Protection
		Diclofenac	Ni-complex	Fe-complex	Cr-complex
1	0 (Control)	0.00	0	0	0
2	100	20.97	2.81	18.27	1.51
3	200	24.00	7.46	21.62	2.49
4	300	26.70	12.22	24.43	3.89
5	400	30.27	17.30	27.78	5.41
6	500	33.94	20.76	30.92	7.89

The percent protection of Fe-complex is higher than Ni-complex and Cr-complex complex. At highest concentration of 500 µg/ml its anti-inflammatory activity in terms of percent protection is 30.92% which is only 3.02% less than standard diclofenac (33.94%). On the other hand Cr-complex shows negligible anti-inflammatory action of 7.89% at highest concentration of 500 µg/ml. Ni-complex shows intermediate anti-inflammatory action of 20.76% at concentration of 500 µg/ml.

Figure 7: Dose dependent anti-inflammatory activity of Ni complex. Click here to View figure

Figure 8: Dose dependent anti-inflammatory activity of Fe complex. Click here to View figure

Figure 9: Dose dependent anti-inflammatory activity of Cr complex. Click here to View figure

Conclusion

Ni-complex,Fe-complex and Cr-complex are investigated for antioxidant action,anti-inflammatory action, antibacterial action and antifungal action.Ni-complex and Cr-complex shows antibacterial action, Cr- complex shows antifungal action opposite to various fungi form and bacteriological species. Ni-complex,Fe-complex and Cr-complex express antioxidant action and anti-inflammatory property.

Conflicts of interest

No conflict of interest.

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