Introduction to Enzyme and Coenzyme Chemistry - E-Library Home

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Radicals in Enzyme Catalysis 253 CH 3 + − O 2 C CO 2 − benzylsuccinate synthase Gly CO 2 − − O 2 C (4) Suggest a radical mechanism for the formation of the modiWed tyrosine cofactor of galactose oxidase, shown in Figure 11.16, from the native structures of Tyr-122 and Cys-228, employing the nearby copper centre. You can assume that the copper centre can access Cu(I) and Cu(II) oxidation states, and that air oxidation is involved. (5) Suggest a catalytic mechanism for the quinoprotein methanol dehydrogenase from Methylobacterium extorquens, which catalyses the oxidation of methanol to formaldehyde, involving formation of a covalent linkage with the pyrroloquinone (PQQ) cofactor. HO 2 C HN CO 2 H HO 2 C HN CO 2 H HO 2 C N O O CH 3 OH H 2 C=O (PQQ) ox HO 2 C N OH (PQQ) red OH Further reading Vitamin B 12 -dependent enzymes R.H. Abeles & D. Dolphin (1976) The vitamin B 12 cofactor. Acc. Chem. Res., 9, 114–20. R. Banerjee (2003) Radical carbon skeletal rearrangements: catalysis by coenzyme B 12 -dependent mutases. Chem. Rev., 103, 2083–94. W. Buckel & B.T. Golding (1996) Glutamate and 2-methyleneglutarate mutase: from microbial curiosities to paradigms for coenzyme B 12 -dependent enzymes. Chem. Soc. Rev., 26, 329–37. E.N.G. Marsh & C.L. Drennan (2001) Adenosylcobalamin-dependent isomerases: new insights into structure and mechanism. Curr. Opin. Chem. Biol., 5, 499–505. T. Toraya (2003) Radical catalysis in coenzyme B 12 -dependent isomerization (eliminating) reactions. Chem. Rev., 103, 2095–127.
254 Chapter 11 Protein Radicals J. Stubbe & W.A. van der Donk (1998) Protein radicals in enzyme catalysis. Chem. Rev., 98, 705–62. S-Adenosylmethionine-dependent radical processes M. Fontecave, E. Mulliez & S. Ollagnier de Choudens (2001) Adenosylmethionine as a source of 5 0 -deoxyadenosyl radicals. Curr. Opin. Chem. Biol., 5, 506–11. P.A. Frey & O.T. Magnusson (2003) S-adenosylmethionine: a wolf in sheep’s clothing, or a rich man’s adenosylcobalamin Chem. Rev., 103, 2129–48. A. Marquet (2001) Enzymology of carbon–sulfur bond formation. Curr. Opin. Chem. Biol., 5, 541–9. Quinoproteins C. Anthony (1996) Quinoprotein-catalysed reactions. Biochem. J., 320, 697–711.
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Introduction to Enzyme and Coenzyme
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Introduction to Enzyme and Coenzyme
Page 6 and 7:
Contents Preface Representation of
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Contents vii 8 Enzymatic Addition/E
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Representation of Protein Three-Dim
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2 Chapter 1 H 2 N O NH 2 + H 2 O Ja
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4 Chapter 1 Table 1.1 The vitamins.
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6 Chapter 1 has very diVerent biolo
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2 All Enzymes are Proteins 2.1 Intr
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10 Chapter 2 (Gln). There are three
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12 Chapter 2 AAA Lys ACA Thr AGA Ar
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14 Chapter 2 H N O H N O Figure 2.8
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16 Chapter 2 (a) (b) Figure 2.12 St
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18 Chapter 2 Figure 2.14 Structure
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20 Chapter 2 (a) X Y Enzyme + Subst
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22 Chapter 2 maintaining protein te
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24 Chapter 2 surface glycoprotein g
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26 Chapter 2 O-linked glycosylation
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28 Chapter 2 Metalloproteins I. Ber
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30 Chapter 3 O N H R CO 2 H acylase
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32 Chapter 3 (a) Free energy uncata
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34 Chapter 3 Ester k rel Effective
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36 Chapter 3 3.4 The importance of
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38 Chapter 3 pKa Tyrosine CH 2 O H
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40 Chapter 3 glycoside hydrolysis (
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42 Chapter 3 O O Glu 143 O − R H
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44 Chapter 3 the hydroxyl groups of
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46 Chapter 3 E + S E + S ES' ES ‘
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48 Chapter 3 Examination of protein
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50 Chapter 3 (Note: Similar results
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52 Chapter 4 (1) Direct UV (2) Radi
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54 Chapter 4 Figure 4.3 PuriWcation
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56 Chapter 4 The two kinetic consta
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58 Chapter 4 Lineweaver−Burk Plot
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60 Chapter 4 E + S K i EI+ I ES E +
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62 Chapter 4 (2) by treatment with
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64 Chapter 4 In general the stereoc
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H D T CO 2 H CO − 2 T HO D H −
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68 Chapter 4 4.5 The existence of i
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70 Chapter 4 18O 18O 18 O O P O −
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72 Chapter 4 If a reaction involves
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74 Chapter 4 O D H ketosteroid isom
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76 Chapter 4 Table 4.3 Group speciW
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78 Chapter 4 [S] (mM) Rate of produ
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80 Chapter 4 Enzyme kinetics I.H. S
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82 Chapter 5 O = C NHR peptidase H
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84 Chapter 5 non-speciWc protease c
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86 Chapter 5 His 57 His 57 Asp 102
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88 Chapter 5 Other serine proteases
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90 Chapter 5 Figure 5.8 Structure o
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92 Chapter 5 now predominate Perhap
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OH R O Zn 2+ O O O Ph Glu 270 H 2 N
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96 Chapter 5 CASE STUDY: HIV-1 prot
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98 Chapter 5 HO Transition state pe
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100 Chapter 5 The aminoacyl group o
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102 Chapter 5 5.5 Enzymatic phospho
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108 Chapter 5 Adenosine 5 0 -tripho
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110 Chapter 5 functional group. Gly
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112 Chapter 5 CH 2 OH O RO HO OH O
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114 Chapter 5 to these atoms that t
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116 Chapter 5 Problems (1) Using pa
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118 Chapter 5 (6) Retaining glycosi
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120 Chapter 5 J.R. Knowles (1980) E
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122 Chapter 6 +1.0 Redox potential
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Table 6.1 Classes of redox enzymes.
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126 Chapter 6 An important point is
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128 Chapter 6 O H − OH − O OH H
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130 Chapter 6 one-electron transfer
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132 Chapter 6 (a) R N H + N O R N H
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134 Chapter 6 Inactivation by trany
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138 Chapter 6 (a) (b) Figure 6.23 S
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140 Chapter 6 glutathione called tr
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142 Chapter 6 neither has a stable
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144 Chapter 6 of the haem cofactor
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146 Chapter 6 Figure 6.33 Active si
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148 Chapter 6 HO H N N O O H N prol
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150 Chapter 6 R R R O 2 , Fe 2+ O O
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152 Chapter 6 CoA. Explain these re
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154 Chapter 6 NADH models O. Almars
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7 Enzymatic Carbon-Carbon Bond Form
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158 Chapter 7 O H − OH O − O H
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162 Chapter 7 Figure 7.6 Active sit
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164 Chapter 7 7.3 Claisen enzymes I
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166 Chapter 7 CoAS O EnzB − H D T
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168 Chapter 7 onto the acetyl-thioe
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170 Chapter 7 In the case of erythr
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172 Chapter 7 O HO O − O ATP ADP
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174 Chapter 7 CO 2 − vitamin K-de
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176 Chapter 7 7.8 Thiamine pyrophos
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178 Chapter 7 HN N + N H NH S O OPP
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180 Chapter 7 O OH OH camphor geran
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182 Chapter 7 CH 3 * OPP (−)pinen
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186 Chapter 7 C C C C C O OCH 3 C H
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188 Chapter 7 AcO HO HO NHAc O OH +
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190 Chapter 7 (9) Usnic acid is a n
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192 Chapter 7 Radical couplings W.M
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194 Chapter 8 C-O cleavage H E1 H C
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196 Chapter 8 leads to the formatio
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198 Chapter 8 aconitase citrate cis
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200 Chapter 8 *H R H H CO 2 − NH
Page 213 and 214: 202 Chapter 8 EnzB − 2 H − O 2
Page 215 and 216: 204 Chapter 8 involves no change in
Page 217 and 218: 206 Chapter 8 Glyphosate H H N CO
Page 219 and 220: 208 Chapter 8 (5) Chorismic acid (s
Page 221 and 222: 9 Enzymatic Transformations of Amin
Page 223 and 224: CO − − 2 CO 2 H H CO 2 − N +
Page 225 and 226: 214 Chapter 9 - BEnz CO − 2 Cl H
Page 227 and 228: 216 Chapter 9 Arg 292 Arg 292 Lys 2
Page 229 and 230: 218 Chapter 9 Arg 292 Asp 292 HN H
Page 231 and 232: 220 Chapter 9 S − B 1 Enz H − C
Page 233 and 234: 222 Chapter 9 9.6 N-Pyruvoyl-depend
Page 235 and 236: 224 Chapter 9 The biosyntheses of n
Page 237 and 238: 226 Chapter 9 Further reading Gener
Page 239 and 240: 228 Chapter 10 B 1 - H + NH 3 CO
Page 241 and 242: 230 Chapter 10 ‘low-barrier’ +
Page 243 and 244: 232 Chapter 10 H S C 6 H 13 HN His
Page 245 and 246: 234 Chapter 10 O H NH 3 CO 2 − CO
Page 247 and 248: 236 Chapter 10 sub-units. Each sub-
Page 249 and 250: 238 Chapter 10 Further reading Gene
Page 251 and 252: 11 Radicals in Enzyme Catalysis 11.
Page 253 and 254: 242 Chapter 11 CH 2 Co III Ad H OH
Page 255 and 256: 244 Chapter 11 − O 2 C − O CO
Page 257 and 258: 246 Chapter 11 H N H O 734 H N H PF
Page 259 and 260: 248 Chapter 11 H H* + H + H 3 N CO
Page 261 and 262: 250 Chapter 11 O HN NH + H 3 N H 3
Page 263: 252 Chapter 11 cofactor is involved
Page 267 and 268: 256 Chapter 12 self-splicing reacti
Page 269 and 270: 258 Chapter 12 Figure 12.2 Structur
Page 271 and 272: 260 Chapter 12 antigen combining si
Page 273 and 274: 262 Chapter 12 R O OR' OH − R O
Page 275 and 276: 264 Chapter 12 CO 2 − − O 2 C O
Page 277 and 278: 266 Chapter 12 (1) Selective substr
Page 279 and 280: 268 Chapter 12 HO O HO OH HO OH O O
Page 281 and 282: 270 Chapter 12 Problems (1) How rev
Page 283 and 284: Appendix 1: Cahn-Ingold-Prelog Rule
Page 285 and 286: Appendix 2: Amino Acid Abbreviation
Page 287 and 288: 276 Appendix 3 Preparation of orang
Page 289 and 290: 278 Appendix 4 (2) Intramolecular a
Page 291 and 292: 280 Appendix 4 from water at a-posi
Page 293 and 294: 282 Appendix 4 Chapter 8 (1) Treat
Page 295 and 296: 284 Appendix 4 (b) Formation of rad
Page 297 and 298: 286 Index b-hydroxydecanoyl thioest
Page 299 and 300: 288 Index glycosylation 26-7 glysop
Page 301 and 302: 290 Index phenylalanine ammonia lya
Page 303: 292 Index transition states 31-2 an
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