Subject Index

Cambridge University Press 0521462924 - Amino Acids and Peptides G. C. Barrett and D. T. Elmore Index More information

Subject index

acetamidomalonate synthesis 123–4 in fossil dating 15 S-adenosyl--methionine 11, 12, 174, 181 in geological samples 15 alanine, N-acetyl 9 in Nature 1 structure 4 IR spectrometry 36 alkaloids, biosynthesis from amino acids 16–17 isolation from proteins 121 alloisoleucine 6 mass spectra 61 allosteric change 178 metabolism, products of 187 allothreonine 6 metal-binding properties 34 Alzheimer’s disease 14 NMR 41 amidation at peptide C-terminus 57, 94, 181 physicochemical properties 32 amides, cis–trans isomerism 20 protein 3 N-acylation 72 PTC derivatives 87 N-alkylation 72 quaternary ammonium salts 50 hydrolysis 57 reactions of amino group 49, 51 O-trimethylsilylation 72 reactions of carboxy group 49, 53 reduction to -aminoalkanols 72 racemisation 56 amidocarbonylation in amino acid synthesis 125 routine spectrometry 35 amino acids, abbreviated names 7 Schöllkopf synthesis 127–8 acid–base properties 32 Schiff base formation 49 antimetabolites 200 sequence determination 97 et seq. as food additives 14 following selective chemical degradation 107 as neurotransmitters 17 following selective enzymic degradation 109 asymmetric synthesis 127 general strategy for 92 - 17–18 identification of C-terminus 106–7 biosynthesis 121 identification of N-terminus 94, 97 biosynthesis from, of creatinine 183 by solid-phase methodology 100 of nitric oxide 186 by stepwise chemical degradation 97 of porphyrins 185 by use of dipeptidyl aminopeptidase 105 of ribonucleotides 183 by stepwise enzymic degradation 105 of urea 185 racemisation during 103 biotechnological synthesis 121 of genetically abnormal proteins 112 circular dichroism 40 sources and roles 1 conjugation with other compounds 182 sources of information xiv–xv, 19 - 13–14 stereoselective synthesis 127 definitions 1 synthesis 120 derivatisation 58 Bucherer–Bergs 123–4 extra-terrestrial distribution 15 by carbonylation of alkylamides 123 - 17 from coded amino acids 122 Gabriel synthesis 125 from diethyl acetamidomalonate 124 GLC 85 from glycine derivatives 123

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Subject index

Strecker 123–4 structure 10 thin-layer chromatography 59 cysteine, structure 5 trivial names 4–6 unusual 11 dansylamino acids 58–9 UV spectrometry 37 dehydroalanine 8 UV fluorescence spectrometry 37 denaturing of peptides 29–30 -amino group protection 134 deoxyribonucleic acid, sequence determination of aminoisobutyric acid 120 116 aminoacylRNAs 3 depsipeptides, definition 3 aminoadipic acid 18 derivatisation of amino acids for analysis 58 aminolaevulinic acid 18 diethoxypiperazines 128 aminophosphonic acids 2 dimethylvaline in dolastatin 15, 67 aminosulphonic acids 2 dipeptides, conformations 21, 26 amphiphilic oligopeptides 28 disulphide bonds angiotensin II, mechanism of generation 203 determination of position of 112 angiotensin-converting enzyme (ACE) 203 exchange reactions of 112 antibodies, epitopes of 213 formation from cysteine 8 production of 213 methods of cleaving 96 anthrax spore, poly(-glutamic acid) content 3 methods for forming 170 arginine, structure 4 types in peptides and proteins 91 asparagine, structure 4 dityrosine 8 aspartic acid, N-methyl-- 14 DNA sequence determination 116 side-chain reactions 122–3 dolastatin 15, structure determination 67 structure 4 domain 27 azapeptides 211 -Dopa 12 azetidine-2-carboxylic acid 13 dopamine 12 azlactones (see also oxazolones) 53, 124 asymmetric hydrogenation 128 Edman sequencing 57, 70, 77, 97 enantiomeric analysis of amino acids 59 Barrett representation, -amino acid 4 enkephalins 2, 212 -bends and -turns 24 enniatins 3 bestatin 18 enzymes, quaternary structure 28 bradykinin 213 epidermal growth factor (EGF) 202 mass spectrum 73 essential amino acids 13 bradykinin analogue, conformation 26 extended conformation of peptide 21 Bucherer–Bergs synthesis of amino acids 123–4 fast atom bombardment MS 75 -carboxyglutamic acid 12, 124 Fischer projection, -amino acid 4, 9 -carboxy-group protection 135 fluoresceamine derivatives of amino acids 58–9 carboxylation of amino acid side-chain 8 Fmoc amino acids carnitine 18 in analysis 58–9 cell adhesion peptide 24, 27 in peptide synthesis 135 chemical ionisation MS 75 folic acid 200 Chou–Fasman rules for CD 41 cis-peptide bonds 21 GABA 17 citrulline 8 Gabriel synthesis of amino acids 125 coded amino acids 3 genetic code 175 combinatorial synthesis of peptides 215 globular proteins 28 conformations of peptides 20 glutamic acid transitions between 29 side-chain reactions 122–3 N-methyl peptides 25 structure 4 crosslinks in peptides and proteins (see also glutamine disulphide bonds) 92 side-chain methylation 8 crosslinking amino acids 8, 92 structure 4 Curtius rearrangement, in amino acid synthesis glutathione 2 123, 125 biosynthesis of 190 cyclic peptides in biosynthesis of leukotriene derivatives 192 homodetic 10, 26, 168 glycine heterodetic 170 in interstellar dust clouds 15 cyclosporin A 92 structure 4

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Subject index

glycosylated amino acids 8 methylvaline in dolastatin 15, 67 glycylglycine, formation 7 microcystins 18, 44 gramicidin S analogues, conformation 25 Miller–Urey amino acid synthesis 123 gramicidins, MS 75 Mitsunobu reaction with serine 122

helicogenic amino acids 22–3 N-blocked peptides, MS sequencing 70 -helix 24 N-methyl--aspartic acid 14 CD 36, 39 ninhydrin reaction of amino acids 52, 184 -helix-promoting amino acids, see helicogenic nerve-growth factor (NGF) 202 amino acids NMR 41 histidine, structure 5 nomenclature of amino acids and peptides 4–7 hydantoin synthesis 123–4 norleucine 13 hydantoinase in asymmetric synthesis, amino nylon(2) 3 acids 127 hydrophilicity 4 oligopeptide, definition 2 hydrophobicity 4 one-letter names for amino acids 4–5, 7–8 hydroxy acids 3 OPA derivatives of amino acids 58–9 hydroxyproline structure 8 organoboron amino acids 2 hydroxyvaline in dolastatin 15, 67 ornithine 8, 17 orthogonal group protection, in peptide synthesis imino acids 3–4 132 instrumentation for MS 75 oxazol-5(4H)-ones (see also azlactones) 124, 128 insulin 2, 10, 25, 178, 203 oxytocin 201 formation from proinsulin 11 structure 10 Parkinson’s disease 12 iodo--alanine 122 partial hydrolysis of peptides 57, 72 IR spectrometry 36 penicillins and cephalosporins, biosynthesis from isoleucine, structure 4 tripeptide 16, 192 isopeptides 2 pepstatin 205 isopenicillin N synthase (IPNS) 194 peptide antibiotics 217 IUPAC–IUB nomenclature rules 5 peptide bonds evidence for in peptides and proteins 91 kainic acid 12 formation using acid anhydrides 151 lanthionine 8 using acid chlorides and fluorides 151 leucine, structure 4 using acyl azides 150 lysine using carbodiimides 153 side-chain acylation 8 using phosphonium and isouronium side-chain methylation 8 derivatives 155 structure 5 using reactive esters 153 lysinoalanine 8 peptide hormones 201 lysozyme 28 azapeptide analogues of 211 biosynthesis of 212 Marfey’s reagent 44, 59 retropeptide analogues of 211 Maillard reaction 53 thionopeptide analogues of 210 mass spectra peptide synthesis, and genetic engineering 132 amino acids 61 enantiomerisation during, mechanisms of 146 peptides 62 methods of quantification 148 interpretation 65 principles and strategy 130 derivatised peptides 71 using enzymes for 164 MeBmt in cyclosporin 10 using solid-phase supports (SPPS) 156 melittin, MS 75–6 apparatus for 163 metastable peaks in mass spectra 68 linkers for 158 methionine using a soluble handle 163 S-oxidation 8 peptides S-alkylation 8 abbreviated names 7 structure 5 acid–base properties 32 methionyl bonds, selective cleavage of 107 circular dichroism 39–40 methotrexate 201 cyclic 10, 26, 168 methylDOPA 120 C-terminal esterification 71

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Subject index

definitions 2 role of amino acids 175 derivatisation for MS 71 role of messenger RNA (mRNA) 176 enzyme-linked immunosorbent assays role of transfer RNA (tRNA) 176 (ELISAs) for 88 protein, definition 2 fragmentation after electron impact 62 proteinases general sources of information xiv–xv, 19 inhibitors 204 IR spectrometry 36 mechanism of action 204 mass spectra 62 et seq. proteins, post-translational changes 11, 178 metal-binding properties 34 PTC amino acids in analysis 58 N-terminal acylation 71 PTH derivatives of amino acids 60 NMR 41–7 primary structure 27, 29, 91 et seq. radioimmunoassay methods for 87 quaternary structure 28 reactions of amino group 49, 51 quisqualic acid 12 reactions of carboxy group 49, 53 routine spectrometry 35 R/S convention 5 secondary structure 27 racemisation, amino acids in fossils 15–16 tertiary structure 27 racemisation kinetics, amino acids 15 UV spectrometry 37 racemisation of amino acids 15, 56 UV fluorescence spectrometry 37 random conformation, CD 39, 42 peptoids 3 renin 203 phenylalanine, structure 5 resolution of -amino acids 125 phosphate esters of amino acids 8 retropeptides 211 platelet-derived growth factor (PDGF) 202 poly(amide)s, definition 3 Schiff base alkylation in amino acid synthesis 123 poly(amino acid)s, definition 3 Schiff base formation from amino acids 50, 52 poly(glycine) 7 Schöllkopf synthesis of amino acids 127–8 poly(-glutamic acid) 3 secondary amino acids 7–8 poly(-glutamic acid) 39 secondary structure 27 polyamino-polyalcohols from peptides 72 sequenator 70 polypeptide nomenclature 7 serine proteinases polypeptide, definition 2 irreversible inhibitors 208 post-translational processing of peptides 8, 11 kcat (suicide) inhibitors 209 acetylation 180 mechanism of action 206 -carboxylation of glutamate residues 180 titrants for 208 location of 114 serine, structure 5 phosphorylation of serine and threonine -sheet 21–2 residues 178, 180 CD 40, 42 C-terminal amide group formation 57, 181 -sheet-promoting amino acids 3 prepropeptides 11 statine 18, 205 proinsulin 10–11 Strecker synthesis of amino acids 123 primary structure 27, 91 et seq. sulphate esters of amino acids 8 pro-drugs 216 sulphide formation from cysteine 8 proline, structure 5 sulphonamide drugs 200 propeptides 11 protecting groups taste of amino acids and peptides 14 for amide groups 145 taxol 18 for -amino groups 134 tertiary structure 27 for -amino groups 138 tertyrosine 8 for guanidino groups 141 thionopeptides 210 for hydroxy groups 140 three-letter names for amino acids 4, 7 for imidazole rings 142 threonine, structure 5 for indole rings 146 thyronine 202 for thioether groups 139 thyrotropin 202 for thiol groups 139 thyrotropin-releasing hormone (TRH) 202 removal 146 thyroxine 202 protein amino acids 3–5 torsion angles, peptide bond 21, 24 nomenclature 7 side-chain 24 protein biosynthesis, post-translational transition-state inhibitors 205 modification following 11, 178 trans-peptide bonds 21

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Subject index

tryptophan, structure 5 vaccines 213 tryptophan, toxic impurity 14 valine, structure 4 tryptophyl bonds, selective cleavage of 109 valinomycin 3 tyrosine, in sun-tan lotion 14 tyrosine, structure 5 X-ray crystallographic structures of proteins 35, tyrosyl bonds, selective cleavage of 108 41

Ugi four-component condensation 123

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