luận án tiến sữ háo lý nghiên cứu cấu trúc khả năng chống oxy hóa của polyphenol và dẫn xuất trên nền fullerene bằng phương pháp hóa tính toán

Đ I H C HU TR NGăĐ I H C KHOA H C NGUY NăMINHăTHỌNG NGHIểNăC U C UăTRỎC,ăKH NĔNGăCH NG OXYăHịAăC A M T S POLYPHENOLăVĨăD N XU TăTRểNăN N FULLERENE (C60) B NG PH NGăPHỄPăHịAăTệNHăTOỄN LU NăỄNăTI NăSƾăHịAăLụăTHUY TăVĨăHịAăLụă HU ,ăNĔMă2016 Đ I H C HU TR NGăĐ I H C KHOA H C NGUY NăMINHăTHỌNG NGHIểNăC U C UăTRỎC,ăKH NĔNGăCH NG OXYăHịAăC A M T S POLYPHENOLăVĨăD N XU TăTRểNăN N FULLERENE (C60) B NG PH NGăPHỄP HịAăTệNHăTOỄN ChuyênăngƠnh:ăHóaălỦăthuy tăvƠăHóaălỦ Mưăs : 62.44.01.19 LU NăỄNăTI NăSƾăHịAăLụăTHUY TăVĨăHịAăLụ Cánăb h ng d n khoa h c: PGS TS Ph m C m Nam PGS TS Tr năD ng Hu ,ănĕmă2016 L IăCAMăĐOANă TơiăcamăđoanăđơyălƠăcơngătrìnhănghiênăc u c aăriêngătơi.ăCácăk t qu nghiênă c uăvƠăcácăk t lu n lu năánănƠyălƠătrungăth c,ăđ căcácăđ ngătácăgi choăphépă s d ngăvƠăch aăt ngăcôngăb b t kỳ m tăcơngătrìnhănƠoăkhác.ăVi c tham kh o cácăngu nătƠiăli uăđưăđ cătríchăd năvƠăghiăngu nătƠiăli u tham kh oăđúngăquyăđ nh Tácăgi Nguy năMinhăThông i L I C Mă N Đ uătiên,ătơiăxinăchơnăthƠnhăbƠyăt lịngăbi tă năsơu s c t i PGS.TS Ph m C m NamăvƠăPGS TS Tr năD ng,ănh ngăng dƠnhănhi u th iăgianăvƠăcôngăs căh L i c mă năc aătơiăcũngăxinăđ i Th yăđưăt nătìnhăh ng d n,ăgiúpăđ , ng d năchoătôiăhoƠnăthƠnh lu năán c g iăđ năTS.ăĐƠoăDuyăQuang,ăTS.ăNgôăTh Chinh, TS Ph măLêăMinhăThơngă Đ i h căDuyăTơnăvƠăcácăanhăch trongănhómă nghiênăc uăđưădƠnhăth i gian th o lu n khoa h căvƠăđóngăgópăcácăỦăki năquỦăbáuăchoă tơiăhoƠnăthƠnhălu năán Tôiăxinăg i l i c mă năchơn thƠnh t iăquỦăCơ,ăTh yătrongăkhoaăHóa,ăphịngăĐƠoăă t o Sau đ i h c,ăTr ngăĐ i h c Khoa h c - Đ i h c Hu vƠăBanăGiámăđ căPhơnă hi uăĐ i h căĐƠăNẵng t iăKonăTumăđưăt o m iăđi u ki n thu n l iăđể tôiăth c hi n lu năánănƠy TôiăxinăchơnăthƠnhăc mă năQuỹ Phátătriển Khoa h căvƠăCôngăngh Vi t Nam (Vietnam National Foundationă foră Scienceă andă Technologyă Developmentă ứă Nafosted)ăđưăh tr m t ph năkinhăphíăth c hi n lu năán Xin c mă năt t c b năbè,ăđ ng nghi păđưăđ ngăviênăvƠăgiúpăđ tôiătrongăsu t th i gian th c hi n lu năán Nhơnăd pănƠy,ătơiămu nădƠnhănh ngătìnhăc m sơuăs c nh t,ătrơnătr ng nh tăđ n nh ngăng iăthơnătrongăgiaăđình:ăB Mẹ - nh ngăng iăđưăh tălịngăniăd yătơiăkhơnă l n,ălnăđ ngăviênăh tr tơiăv m i mặt,ăcácăanhăch emăđưăchiaăsẻ nh ngăkhóăkhĕn,ă thơngăc măvƠăgiúpăđ tơiătrongăcu c s ng Huế, tháng năm 2017 Tácăgi Nguy năMinhăThông ii M CL C DANH M CăCÁCăCH VI T T T vii DANH M CăCÁCăB NG ix DANH M C CÁCăHỊNH xi M Đ U .1 CH NGă1.ăT NG QUAN V H CH TăNGHIÊNăC U 1.1 T NG QUAN V H P CH TăPOLYPHENOLăCịăTÁCăD NG CH NG OXYăHịA .5 1.1.1 H p ch t polyphenol 1.1.2 M t s nguyênăli uăgiƠuăh p ch t polyphenol Vi t Nam .10 1.1.γ.ăC ăch ho tăđ ng c aăcácăh p ch t ch ngăoxyăhóaăpolyphenol 12 1.1.4.ăTìnhăhìnhă ng d ngăhóaăh cătínhătốnătrongănghiênăc u kh nĕngăch ng oxyăhóaăc a h p ch t polyphenol 13 1.2 T NG QUAN V H P CH Tă FULLERENEă VÀă D N XU T FULLERENE 15 1.2.1 L ch s phátăhi n fullerene 15 1.2.2 C uătrúcăvƠăliênăk t c a fullerene 15 1.β.γ.ăTínhăch t v tălỦ 17 1.β.4.ăĐặcăđiểmăelectronăvƠăkh nĕngăph n ng 19 1.β.5.ăTínhăth m 20 1.β.6.ăTínhăch tăhóaăh c 20 1.2.7 Tìnhăhìnhănghiênăc u fullerene vƠăd n xu t fulerene 22 CH NGăβ.ăN IăDUNGăVÀăPH NGăPHÁPăNGHIÊNăC U 23 2.1 N IăDUNGăNGHIÊNăC U 23 2.2 T NG QUAN V PH β.β.1.ăC ăs ph NGăPHÁPăTệNHăTỐN 23 ngăphápătínhătốnăhóaăl ng t .23 β.β.β.ăPh ngăphápăbánăth c nghi m (semi-empirical methods) 26 β.β.γ.ăPh ngăphápălỦăthuy t phi măhƠmăm tăđ (Density Functional Theory - DFT methods) 27 iii 2.2.4 Ph ngăphápăONIOM .28 β.γ.ăCÁCăPH N M MăTệNHăTOÁN 31 2.3.1 Ph n m m Gaussian 09W 31 2.3.2 Ph n m m Gaussview 31 β.4.ă HịAă H Că TệNHă TOÁNă NG D NGă CHOă NGHIÊNă C Uă CÁCă H P CH TăPOLYPHENOLăVÀăD N XU T FULLERENE 32 2.4.1 T iă uăhóaăc uătrúcă(geometryăoptimization) 32 β.4.β.ăXácăđ nh tr ngătháiăchuyển ti păvƠătínhăhƠngărƠoănĕngăl β.4.γ.ăNĕngăl β.4.4.ăCácăđ iăl ng 32 ngăđiểmăđ nă(singleăpointăenergy) 34 ng nhi tăđ ngăxácăđ nh kh nĕngăch ngăoxyăhóaăc a h p ch t polyphenol 35 β.4.5.ăMơăhìnhăhóaăcácăh phơnăt trongădungămơi 36 CH NGăγ.ăK T QU VÀăTH O LU N 40 3.1 KH OăSÁTăPH NGăPHÁPăTệNHăNĔNGăL NG PHÂNăLYăLIÊNăK T OứH .40 γ.1.1.ăCáchăch nămơăhìnhăONIOMăβăl p 40 γ.1.β.ăÁpăd ngăchoăcácăd n xu t c a phenol .42 γ.1.γ.ăÁpăd ngăchoăcácăh p ch t flavonoid .45 3.1.4 Nh năxét 50 3.2 KH OăSÁTăPH NGăPHÁPăTệNHăNĔNGăL NGăIONăHịA 50 3.2.1 Gi i thi u 50 γ.β.β.ăĐánhăgiáătínhăchínhăxácăc aăph ngăphápătínhăIEă m călỦăthuy t PM6 .51 3.2.3 Nh năxét 52 3.3 KH NĔNGăCH NGăOXYăHịAăC AăCÁCăH P CH T POLYPHENOL CịăNGU N G C T CÂYăSAăKÊă(ARTOCARPUS ALTILIS) 53 3.3.1 L a ch n m t s h p ch tăpolyphenolăcóăch aătrongăcơyăsaăkê 53 γ.γ.β.ă C ă ch chuyểnă nguyênă t hydro (HAT) - Nĕngă l ngă phơnă lyă liênă k t (BDE) 54 γ.γ.γ.ăC ăch chuyển electron chuyển proton (SET-PT) 57 iv 3.3.4 Nh năxét 60 3.4 KH NĔNGăCH NGăOXYăHịAăC AăCÁCăH P CH T POLYPHENOL CịăNGU N G C T V MĔNGăC T (GARCINIA MANGOSTANA) 61 γ.4.1.ăCácăh p ch tăpolyphenolăcóăch a v mĕngăc t .61 γ.4.β.ă C ă ch chuyểnă nguyênă t hydro (HAT) - Nĕngă l ngă phơnă lyă liênă k t (BDE) 62 γ.4.γ.ăC ăch chuyển electron chuyển proton (SET-PT) 66 γ.4.4.ăC ăch chuyển proton chuyển electron (SPLET) 68 3.4.5 Nh năxét 71 3.5 KH NĔNG D P T T G C T DO C A M T S H P CH T POLYPHENOL .71 3.5.1 Gi i thi u 71 γ.5.β.ăNĕngăl ngăphơnălyăliênăk tăvƠănĕngăl ngăionăhóaăc a m t s h p ch t polyphenol 72 3.5.3 Ph n ng d p t t g c t peroxyl (CH3OO•) c a m t s h p ch t polyphenol 74 3.5.4 Nh năxét 79 3.6 CH CăNĔNGăHịAăFULLERENEăB NGăCÁCăD N XU T MALONATE .80 3.6.1 Gi i thi u 80 3.6.2.ăC ăchê ph n ng Bingel - Hirsch 81 3.6.3 Ph n ngă đóngă vòngă gi aă fullereneă vƠă d n xu tă flavonoidă malonateă cóă ngu n g c t chalcone,ăflavoneăvƠăflavanone 85 3.6.4 Nh năxét 89 3.7 KH NĔNGă CH NG OXYă HịAă C Aă CÁCă D N CH Tă LAIă HịAă FULLERENEăVÀăCHALCONE,ăFLAVONE, FLAVANONE 89 3.7.1 Gi i thi u 89 3.7.2 Kh nĕngăch ngăoxyăhóaăc aăcácăd n ch tălaiăhóaăfullereneăvƠăchalcone,ă flavone, flavanone 90 3.7.3 Nh năxét 91 v 3.8 THI T K CÁCăH P CH T CH NGăOXYăHịAăCịăNGU N G C T CÂYăSAăKÊăVÀăMĔNGăC TăTRÊNăN N FULLERENE 91 3.8.1 Gi i thi u 91 3.8.2 Ch cănĕngăhóaăfullereneăv i h p ch tăaltilisinăJăvƠămangostinăcóăngu n g c t cơyăsaăkêăvƠ v mĕngăc t 93 3.8.3 Kh nĕngăch ngăoxyăhóaăc aăcácăd n xu t fullerene-altilisinăJăvƠăfullerenemangostin 96 3.8.4 Nh năxét 97 NH NG K T LU NăCHệNHăC A LU NăÁN .99 NH NGăĐ NHăH NGăNGHIÊNăC U TI P THEO 101 DANH M CăCÁCăCỌNGăTRỊNHăLIÊNăQUANăĐ N LU NăÁN .102 TÀIăLI U THAM KH O .104 vi DANHăM CăCỄCăCH ăVI TăT T AO Atomic Orbital:ăOrbitalănguyênăt BDE Bond Dissociation Enthalpy: Nĕngăl DFT DensityăFunctionalăTheory:ăLỦăthuy t phi măhƠmăm tăđ EA ElectronăAffinity:ăÁiăl c electron ETE ElectronăTransferăEnthalpy:ăNĕngăl FAB Fast Atom Bombardment: B năpháănhanhăb ngănguyênăt HAT Hydrogen Atomic Transfer: Chuyểnănguyênăt hydro HOMO HighestăOccupiedăMolecularăOrbital:ăOrbitalăphơnăt b chi m cao nh t IE IonizationăEnergy:ăNĕngăl IEFPCM Integral Equation FormalismăPolarizableăContinuumăModel:ăMơăhìnhă ngăphơnălyăliênăk t ng chuyển electron ngăionăhóa phơnăc c liên t c s d ng ph ngătrình tíchăphơn IRC Intrinsic Reaction Coordinate: T aăđ ph n ng n i LUMO LowestăUnoccupiedăMolecularăOrbital:ăOrbitalăphơnăt ch aăb chi m th p nh t MM MolecularăMechanics:ăC ăh căphơnăt MO MolecularăOrbital:ăOrbitalăphơnăt ONIOM Our own N-layered Integrated molecular Mechanics:ăPh molecular Orbital and ngăphápătíchăh păc ăh căphơnăt vƠăorbitală phơnăt v i N l p PA ProtonăAffinity:ăÁiăl c proton PCM PolarizedăContinuumăModel:ăăMơăhìnhăphơnăc c liênăt c PDE Proton DissociationăEnthalpy:ăNĕngăl PES Potential Energy Surface: B mặt th nĕng QM QuantumăMechanics:ăC ăh căl ROS ReactiveăOxygenăSpecies:ăTácănhơnăph n ng ch a oxy SCRF Self ConsistentăReactionăField:ăTr SD StandardăDeviation:ăĐ l ch chu n SETứPT Single Electron Transfer-Proton Transfer: Chuyển m t electron chuyển proton vii ngăphơnălyăproton ng t ng ph n ng t h p SPLET Sequential Proton Loss Electron Transfer: Chuyển proton m t electron TCE Thermal Correction to Enthalpy: Hi u ch nhănĕngăl ngădaoăđ ng nhi t đ i v i enthalpy TCGFE Thermal Correction to Gibbs Free Energy: Hi u ch nhănĕngăl 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TăNGHIÊNăC U 1.1 T NG QUAN V H P CH T? ?POLYPHENOL? ?CịăTÁCăD NG CH NG OXYăHịA .5 1.1.1 H p ch t polyphenol 1.1.2 M t s nguyênăli uăgiƠuăh p ch t polyphenol Vi t Nam .10 1.1.γ.ăC... NGăQUANăV ăH PăCH T? ?POLYPHENOL? ?CịăTỄCăD NGăCH NGă OXY HịA Polyphenol? ?lƠăcácăh p ch t cóăngu n g c t nhiênăvƠăt n t i th c v t đ c ch ngăminhălƠăcóăkh nĕngăch ngăoxyăhóaăvơăcùngăhi u qu Polyphenol? ?cóăthể... 52 3.3 KH NĔNGăCH NGăOXYăHịAăC AăCÁCăH P CH T POLYPHENOL CịăNGU N G C T CÂYăSAăKÊă(ARTOCARPUS ALTILIS) 53 3.3.1 L a ch n m t s h p ch t? ?polyphenol? ?cóăch aătrongăcơyăsaăkê 53 γ.γ.β.ă C