Theoretical investigations on antioxidant activity of quercetin and the mechanism of quinone formation via HOO• radical neutralization
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Abstract
The antioxidant activity and HOO• radical scavenging mechanism of quercetin were investigated using Density Functional Theory (DFT) at the B3LYP/6-311++G(d,p) level. Frontier molecular orbital analyses, combined with calculations of molecular thermodynamic and kinetic parameters, indicate that quercetin exhibits strong antioxidant activity in both polar and non-polar environments. The formation of stable quinone through the hydrogen atom transfer (HAT) mechanism occurs in two steps. The first step involves the formation of an intermediate quercetin radical, which is more favorable both thermodynamically and kinetically in pentyl ethanoate compared to water. Conversely, the abstraction of the second hydrogen atom to form the quinone product is more favorable in water. Compared to the HAT mechanism, the single electron transfer (SET) mechanism is less favorable in terms of both thermodynamic and kinetic factors.
Tóm tắt
Hoạt tính kháng oxy hóa và cơ chế trung hòa gốc tự do HOO• của quercetin được nghiên cứu bằng lý thuyết phiếm hàm mật độ (DFT) ở mức lý thuyết B3LYP/6-311++G(d,p). Các phân tích orbital biên, kết hợp với tính toán tham số nhiệt động và động học phân tử cho thấy quercetin thể hiện hoạt tính kháng oxy hóa mạnh trong cả môi trường phân cực lẫn môi trường kém phân cực. Quá trình hình thành quinone bền thông qua phản ứng trung hòa gốc tự do theo cơ chế chuyển nguyên tử hydrogen (HAT) diễn ra theo hai bước. Bước đầu tiên là hình thành gốc tự do quercetin trung gian. Ở bước này, môi trường pentyl ethanoate diễn ra thuận lợi về cả mặt nhiệt động học lẫn động học hơn so với trong nước. Ngược lại, ở bước tách nguyên tử hydrogen lần thứ hai để tạo thành sản phẩm quinone, nước chiếm ưu thế hơn. So với cơ chế HAT, cơ chế chuyển điện tử đơn lẻ (SET) kém thuận lợi hơn về cả yếu tố nhiệt động học lẫn động học.
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