| Dedication | 第1-6页 |
| Acknowledgement | 第6-7页 |
| 摘要 | 第7-9页 |
| Abstract | 第9-28页 |
| Chapter1:Introduction | 第28-32页 |
| ·Goal | 第28-29页 |
| ·Text framework and guide | 第29-30页 |
| ·Nomenclature | 第30页 |
| ·Reference | 第30-32页 |
| Chapter2:Prebiotic formation of N-phosphoryl amino acids via cyclic acylphosphoramidate (CAPA) | 第32-64页 |
| ·Introduction | 第32-36页 |
| ·Prebiotic formation of amino acids and polyphosphates | 第32-35页 |
| ·Reaction of amino acids with trimetaphosphate (P3m) | 第35页 |
| ·Significance of cyclic acylphosphoramidate (CAPA) | 第35-36页 |
| ·Results and Discussion | 第36-50页 |
| ·Bi-Electrophilicity of CAPAs towards H_2~(18)O—pathway to prebiotic formation of NPAAs | 第37-40页 |
| ·Bi-Electrophilicity of CAPAs towards amino group | 第40-43页 |
| ·Electrophilicity of CAPAs towards phosphate and methanol—pathway to prebiotic formation of N-(mono-substituted)phosphoryl amino acids | 第43-46页 |
| ·CAPAs vs. NCAs | 第46-50页 |
| ·Bi-electrophilicity | 第48-49页 |
| ·Peptide formation, phosphate activation and phosphorylation | 第49-50页 |
| ·Summary and perspective | 第50-51页 |
| ·Experimental section | 第51-57页 |
| ·Reference | 第57-64页 |
| Chapter 3: Preparation of N-phosphono-amino acids (NPAAs) and their analogues | 第64-85页 |
| ·Introduction | 第64-66页 |
| ·Results and Discussion | 第66-74页 |
| ·N-phosphorylation of alpha-amino acids by trimetaphosphate (P3m) | 第66-70页 |
| ·General procedure | 第66-69页 |
| ·Recycling of polyphosphates | 第69页 |
| ·Purification and Purity determination | 第69页 |
| ·pH dependence of synthesis of NPAA | 第69-70页 |
| ·N-phosphorylation of amines without containing a alpha carboxyl group by P_3m/CaO | 第70-74页 |
| ·Phosphorylation of NH_3, isopropyl amine and pyrrolidine | 第70-72页 |
| ·N-Phosphorylation of β-alanine, γ-amino-butyric acids and lysine | 第72-73页 |
| ·N-Phosphorylation of ethanol amine and propanol amine | 第73-74页 |
| ·Summary and perspective | 第74-75页 |
| ·Experimental section | 第75-82页 |
| ·Reference | 第82-85页 |
| Chapter 4: NMR Titration of NPAAs | 第85-106页 |
| ·Introduction | 第85-87页 |
| ·Results | 第87-92页 |
| ·~(31)P NMR-pH titration of simple phosphoramidates | 第88-89页 |
| ·~(31)P NMR-pH titration ofphosphoramidic acid, N-isopropylphosphoramidic acid,2-hydroxyethylphosphoramidic acid and 3-hydroxypropyl phosphoramidic acid | 第88页 |
| ·~(31)P NMR-pH titration of N~ε-phosphono-lysine | 第88-89页 |
| ·~(31)P NMR-pH titration of NPAAs | 第89-92页 |
| ·Full-pH ~(31)P NMR titration of N-phosphono-proline | 第89-90页 |
| ·~(31)P NMR-pH titration of N-phospho-amino acids with primary amino group | 第90-92页 |
| ·Discussion | 第92-101页 |
| ·pK_a of phosphoramidate nitrogen | 第92-94页 |
| ·pK_a of phosphoryl oxygen in phosphoramidates | 第94-95页 |
| ·pK_as of α-NPAAs | 第95-97页 |
| ·Implications to pK_a match and intramolecular strong H-bond between phosphate and carboxylate in α-NPAAs | 第97-101页 |
| ·pK_a match in α-NPAAs | 第97-98页 |
| ·Intramolecular H-bond in α-NPAAs | 第98-100页 |
| ·Conformational analysis of α-NPAAs | 第100-101页 |
| ·Summary and perspective | 第101-102页 |
| ·Experimental section | 第102-104页 |
| ·Reference | 第104-106页 |
| Chapter 5: Reactivity of NPAAs | 第106-132页 |
| ·Introduction | 第106-109页 |
| ·Results and Discussion | 第109-125页 |
| ·Hydrolysis of NPAAs and related analogues | 第109-117页 |
| ·Comparison of hydrolysis rates of species HL and H_2L in N~ε-P-Lys due to successive protonations | 第111-112页 |
| ·Rate enhancement contributed from vicinal carboxyl group in NPAAs | 第112-116页 |
| ·Rate enhancement contributed from vicinal hydroxyl group in phosphoramidates | 第116-117页 |
| ·Intermolecular N→O phosphate transfer mediated by N-P-Pro | 第117-119页 |
| ·N→Nphosphate transfer mediated by N-P-Pro | 第119-122页 |
| ·Reactivity of NPAAs in gas phase | 第122-125页 |
| ·Fragmentation pathways of NPAA monoainon [H2L]~- and [NaHL]~- in negative ESI MS | 第122-123页 |
| ·Fragmentation pathways of NPAA monocation [Na_3HL]~+and [Na_2H_2L]~+ in positive ESI MS | 第123-125页 |
| ·Summary and perspective | 第125-126页 |
| ·Experimental section | 第126-130页 |
| ·Reference | 第130-132页 |
| Chapter 6: Peptide Formation and Phosphate Transfer Mediated by NPAAs---Prebiotic Roles of NPAAs | 第132-147页 |
| ·Introduction | 第132-135页 |
| ·Results and Disscution | 第135-138页 |
| ·Summary and perspective | 第138-139页 |
| ·Experimental section | 第139-143页 |
| ·Reference | 第143-147页 |
| Chapter 7: Implications to biological phosphate transfer | 第147-156页 |
| ·Introduction | 第147-150页 |
| ·Reactivity of NPAAs provides implications to the biological phosphate transfer mechanism | 第150-153页 |
| ·Knowledge on model compounds NPAAs | 第150-152页 |
| ·Novel enzymatic phosphate transfer mechanisms with N-phospholysine as intermediate | 第152-153页 |
| ·Reference | 第153-156页 |
| Supporting information | 第156-182页 |
| NMR spectra | 第182-224页 |
| Academic communications during Ph.D study | 第224页 |
