Theoretical Study on The Investigation of Antioxidant Properties of Some 4-Benzylidenamino-4,5-dihydro-1H-1,2,4-triazol-5-one Derivatives

Öz

In this study, the antioxidant properties of some experimentally determined 4-benzylideneamino-4,5-dihydro-1H-1,2,4-triazol-5-one derivatives of antioxidant properties were compared by density functional theory method. Quantum chemical calculations based on density functional theory (DFT) were employed to study the relationship between 4-benzylideneamino-4,5-dihydro-1H-1,2,4-triazol-5-one derivatives (for 2a and 2g) having the highest and least antioxidant activity in experimental results. The solvation effects on the antioxidant activity were taken into account by using the conductor-like polarisable continuum model with different dielectric constants (ϵ= 2.25, C6H6; ϵ = 78.39, H2O). The three antioxidant action mechanisms, hydrogen atom transfer (HAT), single electron transfer-proton transfer (SET-PT) and sequential protonloss electron transfer (SPLET) were elucidated. The reaction enthalpies related to the steps in these mechanisms were computed in gas phase and solvents, the compatibility of the calculated results with experimental values ​​is discussed. The results showed that SPLET was the most favourable mechanism for describing the antioxidant activity of 2a and 2g in the aqueous phase, SPLET represented the most thermodynamically plausible reaction pathway. Calculations performed by using DFT method at the rB3LYP/6-311++G (2d,2p) level of theory for neutral molecules and anions in the gas and solvation phase, for radicals and cations, uB3LYP/ 6-311++G (2d,2p) basis set has been used.

Anahtar Kelimeler

• Antioxidant mechanism
• radical scavenging activity
• antioxidant descriptors
• density theory
• triazole

4-Benzilidenamino-4,5-dihidro-1H-1,2,4-triazol-5-on Türevlerinin Antioksidan Aktivitelerinin Teorik Olarak İncelenmesi

Öz

Bu çalışmada, antioksidan özellikleri deneysel olarak belirlenmiş bazı 4-benzilidenamino-4,5-dihidro-1H-1,2,4-triazol-5-on türevleri bileşiklerinin Yoğunluk Fonksiyonel Teorisi yöntemiyle antioksidan etkinliklerinin karşılaştırılması yapılmıştır. Yoğunluk fonksiyonel teorisine (DFT) dayanan kuantum kimyasal hesaplamalar, deneysel sonuçlarında en fazla ve en az antioksidan aktiviteye sahip 4-benzilidenamino-4,5-dihidro-1H-1,2,4-triazol-5-on türevlerinin (2a ve 2g için) arasındaki ilişkiyi incelemek için kullanılmıştır. Antioksidan aktivitesi üzerindeki solvasyon etkileri, farklı dielektrik sabitleri (ϵ = 2.25, C6H6; ϵ = 78.39, H2O) ile iletken benzeri polarize süreklilik modeli kullanılarak dikkate alınmıştır. Üç antioksidan reaksiyon mekanizması, hidrojen atom transferi (HAT), tek elektron transfer-proton transferi (SET-PT) ve ardışık proton kaybı elektron transferi (SPLET) açıklanmıştır. Bu mekanizmalardaki adımlarla ilgili reaksiyon entalpileri gaz fazında ve çözücülerde hesaplanmış, hesaplanan sonuçların deneysel değerlerle uyumluluğu tartışılmıştır. Sonuçlar, SPLET'in sulu fazda 2a ve 2g’nin antioksidan aktivitesini tanımlamak için en uygun mekanizma olduğunu göstermiştir, SPLET en termodinamik olarak makul reaksiyon yolunu temsil etmiştir. Hesaplamalar, DFT yöntemiyle nötral moleküller ve anyonlar için rB3LYP/ 6-311++G (2d,2p), radikaller ve katyonlar için uB3LYP/ 6-311++G (2d,2p) temel setleri kullanılarak yapılmıştır. 

Anahtar Kelimeler

• Antioksidan mekanizma
• radikal süpürme aktivitesi
• antioksidan tanımlayıcılar
• yoğunluk teorisi
• triazol

Kaynakça

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