Luận văn Thiết kế, tổng hợp một số sensor huỳnh quang từ dẫn xuất của cyanine, coumarin để xác định biothiol và Hg(II)

Kết quả tính toán đã cho thấy, sự phát xạ huỳnh quang của AMC, AMC- Cys, AMC-Hcy và AMC-GSH đều xuất phát từ các trạng thái kích thích electron ở mức cao (S2, S4) về trạng thái cơ bản S0. Đây là một trường hợp ngoại lệ của quy tắc Kasha. OO O O AMC OO O O AMC- thiol S R Fluorophore Receptor + Thiol 131 NHỮNG KẾT LUẬN CHÍNH CỦA LUẬN ÁN 1. Đã kết hợp linh hoạt giữa tính toán hóa học lượng tử và nghiên cứu thực nghiệm để phát triển thành công hai sensor huỳnh quang mới là L và AMC. Sự kết hợp linh hoạt này đã giảm đáng kể khối lượng tính toán lý thuyết và điều tra thực nghiệm, tiết kiệm thời gian và chi phí hóa chất, tăng khả năng thành công, làm sáng tỏ được bản chất các quá trình, tạo cơ sở khoa học cho các nghiên cứu tiếp theo. Cụ thể:  Đối với sensor L, tính toán đã dự đoán và định hướng cho thực nghiệm trong giai đoạn thiết kế, tổng hợp và đặc trưng sensor L; nghiên cứu thực nghiệm sau đó đã kiểm chứng và khẳng định lại các kết quả tính toán. Đến phức tạo bởi L và ion Hg(II), thực nghiệm được khảo sát trước; tính toán lý thuyết sau đó để giải thích và làm sáng tỏ ứng dụng của sensor L trong phát hiện ion Hg(II). Tiếp đến, việc sử dụng phức Hg2L2 để xác định biothiol lại được dự đoán trước từ tính toán; điều tra thực nghiệm sau đó để kiểm chứng và khẳng định lại kết quả tính toán.  Đối với sensor AMC, tính toán đã dự đoán và định hướng cho thực nghiệm ở giai đoạn thiết kế, tổng hợp và phản ứng giữa sensor AMC với các biothiol. Các đặc tính và ứng dụng của sensor AMC được nghiên cứu từ thực nghiệm trước; tính toán lý thuyết sau đó đã giải thích và làm rõ bản chất các kết quả thực nghiệm. 2. Các phản ứng tổng hợp sensor L và sensor AMC đã được nghiên cứu dự đoán và định hướng từ tính toán; thực nghiệm sau đó đã kiểm chứng và khẳng định các kết quả tính toán. 3. Cấu trúc, đặc tính của sensor L và sensor AMC đã được xác định ở mức lý thuyết B3LYP/LanL2DZ với kết quả đáng tin cậy, thông qua kiểm tra, đối chiếu và khẳng định từ các kết quả thực nghiệm. 4. (a). Sensor L có thể phát hiện chọn lọc ion Hg(II) trong sự có mặt các ion kim loại khác, hoạt động theo kiểu bật-tắt huỳnh quang. Giới hạn phát hiện và giới hạn định lượng ion Hg(II) theo phương pháp trắc quang là 0,076 μM 132 và 0,25 μM; theo phương pháp huỳnh quang là 0,059 μM và 0,19 μM. Phức Hg2L2 có thể phát hiện chọn lọc Cys trong sự hiện diện các amino acids không có nhóm thiol, hoạt động theo kiểu tắt-bật huỳnh quang. Giới hạn phát hiện và giới hạn định lượng Cys tương ứng là 0,2 μM và 0,66 μM. Sensor L phát hiện ion Hg(II) và phức Hg2L2 phát hiện Cys dựa trên phản ứng trao đổi phức giữa ion trung tâm Hg(II) với hai phối tử là L và Cys. (b). Sensor AMC có thể phát hiện chọn lọc các biothiol (Cys, GSH, Hcy) trong sự hiện diện các amino acids không có nhóm thiol, hoạt động dựa trên sự biến đổi tỉ lệ cường độ huỳnh quang ở hai bước sóng. Giới hạn phát hiện và giới hạn định lượng Cys tương ứng là 0,5 μM và 1,65 μM. Sensor AMC phản ứng với các biothiol (Cys, GSH, Hcy) theo cơ chế phản ứng cộng Michael. (c). Các sensor huỳnh quang Hg2L2 và AMC đều có thể phát hiện Cys trong dung dịch với lượng nhỏ dung môi hữu cơ, thời gian của phản ứng xảy ra nhanh, có thể phát hiện được Cys với nồng độ thấp hơn trong nội bào và thấp hơn so với các sensor đã công bố. 5. Đã sử dụng phương pháp TD-DFT để nghiên cứu đặc tính huỳnh quang của các chất dựa trên hình học tối ưu tại trạng thái cơ bản và các trạng thái kích thích; kết hợp với sử dụng phương pháp phân tích NBO để xem xét sự biến đổi đặc tính huỳnh quang của các chất dựa trên nghiên cứu bản chất các liên kết. Kết quả tính toán cho thấy, ion Hg(II) gây nên phản ứng tạo phức với L dẫn đến làm giảm khoảng cách năng lượng giữa HOMO và LUMO, đồng thời làm thay đổi hệ liên hợp electron π, là nguyên nhân dẫn đến sự dập tắt huỳnh quang trong phức Hg2L2. Sự phát xạ huỳnh quang của AMC, AMC- Cys, AMC-Hcy và AMC-GSH đều xuất phát từ các trạng thái kích thích electron ở mức cao (S2, S4) về trạng thái cơ bản S0. Đây là một trường hợp ngoại lệ của quy tắc Kasha. 133 ĐỊNH HƯỚNG NGHIÊN CỨU TIẾP THEO Những kết quả đạt được trong luận án đã mở ra những định hướng nghiên cứu triển vọng có thể tiếp cận trong thời gian đến. Cụ thể: 1. Thiết lập một cơ sở cho việc phát triển của các phức giữa ion kim loại với các phối tử huỳnh quang mới, cũng như các phối tử huỳnh quang đã được công bố trước đây để phát hiện cysteine. 2. Nghiên cứu cơ chế thay đổi đặc tính hấp thụ, huỳnh quang của các sensor trước và sau khi tương tác với chất phân tích, nhằm xây dựng cơ sở để định hướng thiết kế các sensor mới, nhất là tăng độ nhạy, độ chọn lọc và độ tan của các sensor. Đặc biệt, nghiên cứu phát triển các sensor huỳnh quang phát xạ ở vùng bước sóng dài, hoặc các sensor hoạt động dựa trên sự biến đổi tỉ lệ huỳnh quang ở hai bước sóng, nhằm hạn chế các ảnh hưởng khi dùng các sensor để phát hiện các chất trong tế bào sống. 3. Phát triển, mở rộng việc sử dụng L để phân tích ion Hg(II) trong các đối tượng: - Nghiên cứu ứng dụng phân tích trong các mẫu nước ăn uống sinh hoạt, các mẫu nước thải công nghiệp, nước thải y tế (đặc biệt các phòng nha), các mẫu thực phẩm tươi sống (đặc biệt cá biển ăn thịt), các mẫu thực phẩm chế biến có sử dụng bao bì đóng gói bảo quản. - Nghiên cứu ứng dụng phân tích các ion kim loại Hg(II) trong các tế bào sống. 4. 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