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Kinetics and mechanism of formation of nickel(II)porphyrin and its interaction with DNA in aqueous medium.

ABSTRACT: Kinetics between 5,10,15,20-tetrakis(N-methylpyridium-4-yl)porphyrin and Ni²⁺ species were investigated in aqueous solution at 25 ±1 °C in I = 0.10 M (NaNO₃). Speciation of Ni²⁺ was done in I = 0.10 M (NaNO₃) for knowing distribution of Ni²⁺ species with solution pH. Experimental data were compared with speciation diagram constructed from the values of hydrolysis constants of Ni²⁺ ion. Speciation data showed that hexaaquanickel(II) ions took place in hydrolysis reactions through formation of [Ni(OH₂)_6-n(OH)_n]^2-n species with solution pH. According to speciation of Ni²⁺ and pH dependent rate constants, rate expression can be written as: d[Ni(TMPyP)⁴⁺]/dt = (k ₁[Ni²⁺ _(aq)] + k ₂[Ni(OH)⁺ _(aq)] + k ₃[Ni(OH)₂ ^o _(aq)] + k ₄[Ni(OH)₃ ^- _(aq)])[H₂TMPyP⁴⁺], where k ₁, k ₂, k ₃ and k ₄ were found to be k ₁ = (0.62 ± 0.22) × 10^-2; k ₂ = (3.60 ± 0.40) × 10^-2; k ₃ = (2.09 ± 0.52) × 10^-2, k ₄ = (0.53 ± 0.04) × 10^-2 M^-1s^-1 at 25 ±1 °C, respectively. Formation of hydrogen bonding between [Ni(H₂O)₅(OH)]⁺ and [H₂TMPyP]⁴⁺ causes enhanced reactivity. Rate of formation of [Ni(II)TMPyP]⁴⁺ complex was to be 3.99 × 10^-2 M^-1s^-1 in I = 0.10 M, NaNO₃ (25 ± 1 °C). UV-Vis and fluorescence data suggested that [Ni(II)TMPyP]⁴⁺ and [H₂(TMPyP)]⁴⁺ interact with DNA via outside binding with self-stacking and intercalation, respectively. SYNOPSIS.

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The online version contains supplementary material available at 10.1007/s12039-021-01945-y.

SUBMITTER: Habib A

PROVIDER: S-EPMC8329907 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:BackgroundAzo dyes are recalcitrant organic pollutants present in textile industry effluents. Conventional treatment methods to remove them come with a range of disadvantages. Nanoparticles and their nanocomposites offer more efficient, less expensive and easy to handle wastewater treatment alternative.MethodsIn this study, nanoparticles of nickel oxide (NiO-NPs), copper oxide (CuO-NPs) and their nanocomposite (NiO/CuO-NC) were synthesized using co-precipitation method. The functional groups present on the surface of synthesized nanomaterials were verified using Fourier-transform infrared spectroscopy (FTIR). Surface morphology was assessed using scanning electron microscopy (SEM) whereas purity, shape and size of the crystallite were determined using X-ray diffraction (XRD) technique. The potential of these nanomaterials to degrade three dyes i.e., Reactive Red-2 (RR-2), Reactive Black-5 (RB-5) and Orange II sodium salt (OII) azo dyes, was determined in an aqueous medium under visible light (photocatalysis). The photodegradation effectiveness of all nanomaterials was evaluated under different factors like nanomaterial dose (0.02-0.1 g 10 mL-1), concentration of dyes (20-100 mg L-1), and irradiation time (60-120 min). They were also assessed for their potential to adsorb RR-2 and OII dyes.ResultsResults revealed that at optimum concentration (60 mgL-1) of RR-2, RB-5, and OII dyes, NiO-NPs degraded 90, 82 and 83%, CuO-NPs degraded 49, 34, and 44%, whereas the nanocomposite NiO/CuO-NC degraded 92, 93, and 96% of the said dyes respectively. The nanomaterials were categorized as the efficient degraders of the dyes in the order: NiO/CuO-NC > NiO-NPs > CuO-NPs. The highest degradation potential shown by the nanocomposite was attributed to its large surface area, small particles size, and quick reactions which were proved by advance analytical techniques. The equilibrium and kinetic adsorption of RR-2 and OII on NiO-NPs, CuO-NPs, and NiO/CuO-NC were well explained with Langmuir and Pseudo second order model, respectively (R2 ≥ 0.96). The maximum RR-2 adsorption (103 mg/g) was obtained with NiO/CuO-NC. It is concluded that nanocomposites are more efficient and promising for the dyes degradation from industrial wastewater as compared with dyes adsorption onto individual NPs. Thus, the nanocomposite NiO/CuO-NC can be an excellent candidate for photodegradation as well as the adsorption of the dyes in aqueous media.

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Kinetics and mechanism of formation of nickel(II)porphyrin and its interaction with DNA in aqueous medium.

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