Advances in Enzymology and Related Areas of Molecular Biology, Volume 10

537 Pages·1950·18.155 MB·English

IN ENZYMOLOGY
ADVANCES
AND RELATED SUBJECTS OF
BIOCHEMISTRY
Volume X
CONTRIBUTORS TO VOLUME
X
TAGEA STRUP,C arlebergfonrleta Biologiake Znstitut, Copenhagen,
Denmark
THEODOBRE RBINU, niversitdtsstrasse 69,M arburg/Lahn, Germany
NOMANG . BRINKR, esearch Laboratories, Merck & Co., Inc.,
Rahway, New Jersey
M. DOUDOROFDFe,p artment of Bacteriology, University of Cali-
fornia, Berkeley 4, California
KARLF OLKEBBR, esearch Laboratories, Merck & Co., Znc.,
Rahway, New Jersey
WALTER G. FRANKENBURRGes,e arch Laboratory, General Cigar
Company, Inc., Lancaeter, Pennqilvania
FRANKC . HAPPOLDD,e partmat of Biochemistry, School of Medi-
cine, University of Leeds, England
W. HASSIDD, ivision of Plant Nutrition, University of California,
2.
Berkeley 4, California
F. LYNEN, Chemisches Uniumsitdta-Laboratium, Miinchen INW,
Germany
C. MARTIUS, Phyeiologisch-Chemisches Znatitut, Universitdt
Tt8binqenl Gmany
NGUYEN-VATNH OALI,a boratoire de Bwchimie ghntale et comparke,
Collage de France, Paris, France
JEANR OCHEL, aboratoire de Bwchimie gtnhale et comparbe, Col-
lage de France, Paris, France
CLAUDEE . ZOBELLS,c ripps Institution of Oceanography, Univer-
sity of California, La Jolla, California
ADVANCES IN ENZYMOLOGY
AND RELATED SUBJECTS OF BIOCHEMISTRY
Edited by F. F. NORD
FORDHAM UNIVERSITY, NEW YORK, N. Y.
VOLUME X
NEW YORK
INTERSCIENCE PUBLISHERS LTD., LONDON
Copyright, 1950, by
INTERS CI E NCE PUB LI SH E RS, I NC.
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CONTENTS
.
Blood Clotting and Related Processes By TAGE ASTRUP. Copenhagen.
........................................................
Denmark
1
I. Introduction ................................................. 1
I1 . Activation of Coagulation ..................................... 3
A. Thrombo lastin ......................................... 3
B . Plasma &omboplastin and Autocatalysis .................. 7
C . The Role of Calcium ..................................... 13
D . New Techniques ......................................... 15
E . Determination of Prothrombin ............................ 17
F. . Prothrombin and Thrombin ............................... 20
G Factor 5 or the Accelerator Factor ..........................
111. The Clotting Process ..........................................
A . Fibrinogen ..............................................
B . Clotting of Fibrinogen ....................................
IV . Inhibition of Coagulation ...................................... 33
A. Heparin ................................................ 34
B . Antithrombin and Heparin ............................... 35
V . Conclueion ............... ................................
References ................................................... 3389
.
.
T to hanase-Tryptophan Reaction By FRANK C HAPPOLD, Leeds,
YngiL. ......................................................... 51
I . Introduction ................................................. 51
I1 . Early Studies on Mode of Formation of Indole .................... 55
A . Introductory St.u dies on Mechanism ....................... 55
B . Nature of the Cell-Free Enzyme ...........................
C . Further Studies on Mechanism ............................ 6620
I11 . Preparation anci Properties of the Cell-Free Enzyme .............. 65
A. Michaelis Constant ...................................... 65
B . Effect of H ............................................ 66
c. Effect of Enzyme Concentration ........................... 66
.
D Heat of Activation of Tryptophan Indole Reaction in Pres-
tophanase ..........+... .................... 66
IV. Metal &%$s%%dole Production ........................... 6s
V. Inhibitors ................................................... 69
Effect of Various Cations .................................... 70
VI . Indole and the Synthesis Tryptophan ......................... 71
. of
VII Inhibition of Indole Production in Culture by Fermentable Carbo-
hydrate ................................................. 74
Specific Inhibition of Indole Production b Eecherichia coli in Pres-
ence of Phenslalanine or TvroRine and 6lucose in Simple Media . 77
References ..................................................... 81
.
Phos hatase Alcaline Par JEAN ROCHE et NGUYEN-VAN THOAI,
CoEbge de France. Paris ........................................... 83
I . Introduction GBn6rale ......................................... . 84
A . Existence de pH optima multiples des actions phosphatasiques
Signification .......................................... 84
B . Phosphatasm acides et phosphatases alcalines ............... 85
C . Sp6cificit6 de la phwphatase alcaline ....................... 86
V
vi CONTENTS
11. Identification, prbparation, et urification de la phosphatase alcaline
111. Ef...Af.....e.......c tI.enuhrisb diteio lna peht oinspahcta.it.va.as.et., .iao.b.n.a...l ..i ..n ..e. ... ... ... ... .... .. .. ,, .. .. .. .. .. .. .. .. .. .. . . . . .. .. .. .. .. .. 899944
B. Activation ............................................. 9.8-
C. SpBcificit6 d’organe et effecteurs.. .... , ................... 104
D. Effecteurs et activitB synthbtisante. .., ................... 105
Sur la constitution de la phosphatase alcaline.. ................. 107
A. Dissociation et reconstitution de la phosphatase alcalirie.. ... 106
B. RBactivation de la phosphatase alcaline au moyen d’effecteurs. 110
V. CoCCn..c lHHusyyioppnoostt hghbebnee6ss r ssauulerr s l.la a. constitution de la phosphatase alc.a.l.in.e.... ..... . 112
Bibliographie . . . . . . . . . .......... 117
118
Synthesis of Disaccharides with Bacterial Enzymes. By W. Z. HASSID
and M. DOUDOROFF, Berkeley, Calif ..............................
123
II.. I1nntrtorodduucctito.ino n..... .. .. .. .. .. .. .. ...................................... 123
11. Preparation of the Enzymic Extract from Pseudommas saccharophila
1I1V1.. SSypnecthifeisciisty o fo f SSuuccrorosese t hPrhoousgphh oMryelcahsea n.i.s.m.. o.f. .P.h..o.s.p.h.o..ro..ly..s.is..... ...... ... 11_2264_ .
129
V. Structure of Synthetic Disaccharidev.. ..........................
131
A. Synthetic Sucrose. ....................................................... .......
131
B. a-D-Glucopyranosyl-cksorbofuranoside. ...................
c. a-D-Ghcopyranosyl-,9-D-x loketofuranoside . . . . . . . . . . . . . . . . . 132
134
D. D-Glucosyl-~araboketos.i ~. , . . . . . . , . . ........... 135
E.
3-[a-~-G1~~0pyra110~yl]-~arabin0pyran0~ 136
VI. Formation of Sucrose and Other Disaccharide8 through Exchange of
Glycosidic Linkages. . . . . . . . . . . . . . , . . . . , . . . . . . . . . . . . . . . . . . . . . 138
VII. Relation of Sucrose Phosphorylase to Polysacoharide Synthesizing En-
Rezfyemre. n.c.e.s .. .. .. .. .. .. .. .. .. .. .. .......................................................................... . 140
142
Some Aspects of Streptomycin and Other Streptomyces Antibiotics. By
NORMAN G.B RINK and KARL FOLKERS, Rahzoay, N. J.. . . . . . . .
145
I. Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
11. Streptomycin. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
A. Isolation ............................................... 146
B. Nomenclature. . . . . . . . . . . . . . . . ...................... 146
C. Molecular Formula and Properties.. . . . . . . . . . . . . . . . 147
D. Streptidine. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
EF.. DNe-rMiveatthivyels- ~oGf lSutcreopstaombiionsea. m. .i n. e. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. 115419
G. Streptose.. . . . . . . . . . . . . . . . . . . . 152
H. Stereochemistry of Streptose.. . . 152
154
I. Structure of Streptobiosamine.. .
J. Linkage between Streptidine and Stroptobioaamine . . . . . . . . . . 154
K. The Maltol Rearrangement.. . . . . . . . . . . 155
L. Synthesis of N-Methyl-cGlucosamine. . . . . . . . . . . . . . . . . . . . . 156
157
M. Syntheses of Streptamine and Str
158
N. Relationship of Structure of Streptomycin to Antibiotic Activ-
111. Ma0n.n Aos iiSdtiyot.es .t or .ef . p .At .oc .mt .i o.yn .c .ion .f. .. S .. .t r ..e ..p ..t .. o ..m .. ..y ..c ..i n.. ... ... ... ... .,. ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... 116610
IV. Chloromycetin (Chloramphenicol) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
V. Aureomycin ...... . . . .. .. . . ... . . . . . . . . .. . .. .. .. . . . . .. . . . . . . .. . 1~ 6~~ 2
VI. Neomycin.. .. .. .. . . . . . . . . .... . . .. . . .. . . . . . . . . . . . . . . .. .. .. . . . 164
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . , . . . . . . . . . . . . . . . . . . . . . . 116644
CONTENTS vii
. .
Probleme des Citronenstturecyklus Von C MARTIUS. Tiibingen. und
F. LYNEN. Manchen ............................................. 167
I . Einleitung .............................................. 167
I1. Citronensaurecyklus und Acetatabbau in der Hefe ................ 169
A . Die Bildung von Citronensaure in Hefe .................... 169
.
B Versuche iiber den Abbau von Citronensaure und C4-Dicarbon-
sauren in Hefe ...................................... 173
fher den Abbau der Essigsliure im Tierkorper ............ 176
. Der Mechanismus der Kondensationsreaktion .................... 177
I11 A . Nachweis einer “Aktivierung” der Essigsaure ..... 177
.
BB. NNaacchhwweeiiss eeiinneess ““aakkttiivveenn”” B2Ce--FFrraaggmmeenntteess beim Pyruvatabbau
iinn ttiieerriisscchheemm GGeewweebbee ....................................... ...................... 180
CC. . CCiittrroonneennssaauurreebbiilldduunngg aauuss AAcccctte.e ssssiiggssaauurree uun d anderen &Keto-
ssaauurreenn .............................................................................................. 182
.
DD. DDiiee OOxxyyddaattiioonn ddeerr Fettsiiuren... ................................................ 186
E. Die Natur der “aktivierten” Essigsaurree .................. ........... ... 188
Aconitase ..................................................... ........... .. 190
A. Einleitung ............................................... .......... ... 190
B . Vorkommen, Eigenschaften und Beeinflussung des Fermentes . . 191
C . Substrate und Kinetik der Aconitase ....................... 192
.
D Dcr “unsymmetrische” Abbau dcr Citronensaure ............ 196
.
Oxalbernsteinsaure-Ochoa-Reaktion ........................... 199
V A . Darstellung und Icigenschaften der Oxalbernst.e insaure ....... 199
BR.. OOxxaallhbeerrnnsstt eeii nnssanuurrec--Cha+ro xyla.w . . . . . . . . . . . . . . . . . . . . . . . . . . . 202
.
VI . EEffFfCCec .kk tCCtooraare((rreOOnbhn occo ddhxhxeeooyyrraall ii-F-FceRRreeruuerermarannnkkggectt ni nivvototooenen nn) )dd ..eea a.,ss- - ..K(C ..: ci . tt .ro o.g n.l u.c tt.nn , rs.sa .iu i.uI ..r e.e c. y .Ak .Ul .u .0s. ..x . ..a ....l .t...) ..c.. .r... .n ... . s... t ....c ....i n. ... a.... i....i .u... .r... e.... 221038
Literatur .................................................... 217
Nachtrag bei der Korrektur .................................... 221
.
Die Phytochemie des Schwefels Von THEODOR BERSIN, Marburg/
Lahn, Germany .................................................. 223
Einleitunz ................................................... 223
.
I Elementarer Schwefel. Sulfate. und Polythionsauren .............. 229
I1. Schwefclwasserstoff. .............................. ........... ... 232
I11 . Schwefelsaureester. Sulfosauren. Sulfit. Thioather Sulfox.vdc. T hio-
aldehyde ................................................ 234
A . Schwefelsaureester ....................................... 234
B-. . Sulfonsaur.e- n- ...... ......................................................... ............. 236
c. Sulfit ...................................... .....
D. Thioather ............................................. ............. 238
EE .. SSttiicokkssttooffffrreeiiee aalliiccyycclliisscchhee DDiissuullffiiddcc uunndd SSuullffooxxyyddce ....
FF.. TThhiiooaallddeehhyyddee ............................................................ .
IV. TThhiioohhaarrnnsstt..ooffffee uunndd Senfiilee ................................................ ............ 260
.
..44 . TThhiioohhaarrnnssttooffff e. ...................................................... ............ 260
BB .. SSeennffoollee ............. ....................................................... ............ 262
V. Die schwefelhalt.i gen Aminosauren Methionin, Cystathionin, Cystein,
und Cystin .............................................. 268
VI. Schwefelhaltige Pept.i de und Prot.eine ........................... 284
A . Schwefelhaltige Polypeptide .............................. 288
.
B Schwefelhakige Proteine .................................. 297
VII. Am Schwefelstoffwechsel heteiligte Enzyme .. 306
A . Schwefelspesifische Redoxasen ............................. 306
B . Sulfatasen .............................................. 310
Literatur .................................................... 311
...
Vlll CONTENTS
. .
Chemical Changes in the Harvested Tobacco Leaf Par.t II Chemical and.
E n pC onversions during and Aging By WALTER G
FR NKENBURG. LancusteFre. rPmae .n.t.a.t.i.o.n. .......................... 325
I .. Chemical Changes Caused by Shed Curing ...................... 326
I1 Descri tion of the Fermentation and Aging Process.. ............. 327
A . 'Pypes of Processing ...................................... 327
B. External Symptom of the Fermentation ................... 333
1. Qualitative Changes ................................. 333
2 . Quantitative Effects ................................. 335
I11 . Chemical Changes in Tobacco Leaves Caused by Fermentation and
by A~in.g. .............................................. 357
A . Ana ytical Methods ...................................... 357
B. The Sweat of Cigar Leaf Tobaccos ......................... 358
..................
Techni ues of Cigar Leaf Fermenhtion 358
C . Analytica? Results ....................................... 361
1. of Wei ht ..................................... 301
23 .. LCInohssaosnl ugbeisl ioifa tkioonn -onfi trWogaetenro-Suos luLbelaef ComCpoonmepnotsn .e.n.ts. .......... 33.87..35
4 . Nitrogenous Com ounds ..........L.e.a.f. ............... 370
5 . Summary of the 8hemist of Cigar Fermentation . . 398
D . Aging of Flue-Cured Cigarette%obacco ..L..e.a.f. ............. 399
1. Compoeition Prior to Aging .......................... 399
2 . Technique of A . g .................................
3 . Analytical R e s g. ................................. 440001
.
IV Hypotheses Concerning the Causative Age& of Tobacco Fermenta-
tion ..................................................... 409
A. The Problem ............................................
B. The Development of Various Hypotheses ................... 440099
1. Firat Period: 1858-1900 ............................. 409
2. Second Period: 1901-1933 ........ 412
3 . Third Period: 1935 up to the Present ................. 415
C. The Present Picture ..................................... 425
1. Relationship between the Various Mechanism ......... 425
2 . Presumable Mechanism of Some Individual Conversions
Occurring in Fermentation and ............... 428
V . ERfeffeecrte nocf eFs e.r.m..e.n tation on Smoking PropertieAsg .i.n.g. ............... 443343
AAssZZssiiOOmmBBiillEaEattLLiiooLLnn,, LLooaf~f J,HH&I&, dd,rr oocCaccalaalirrifbbf ..oo..nn ..s.s. ...bb..yy.. .M..i.c.r.o.o.r.g.a.n.i.s.m..s.. ..B..y. .C..L.A..L.J.D..E. E. 443
II. . IInnttr,roodduucctitoiono ........... ........................................... 444
11. Ex rimentalMeth ods... ..................................... 445
Modification of Hydrocarbons., ...........................
445
B. Microbial Multiphcat.ion.. ............................... 446
C. Oxy enuptake.. .......................................... .............. 446
D. Metfylene Blue Reduction. .............................. 447
E. Carbon Dioxide Production ............................... 447
F. Nitrate and Sulfate Reduction ............................ 448
G . Methods of Dispersing H@rocarbons in Medium ............ 448
I11 . Occurrence of Hydrocarbon-Oxldizing Organism ................. 449
IV. Acti.o n of Hydrocarbons on Microorganism ...................... 4~~~ 51
A Antiseptic Hydrocarbons .......... 461
B . Selective Action of Hydrocarbons ... 452
C. Preservation of Cultures under Oil .... 453
V . Microbial Oxidation of Gaseous Hydrocar 454
.
VI Relative Oxidizability of Different Classes 456
A . Aliphatic vs. Aromatic Compounds . . 456
B . Effect of Chain Length Oxidizability of Hydrocarbons .... 457
C . Effect of Unsaturation oor nD ouble Bonds .................... 459
CONTENTS ix
D . Effect of Branching or Side Chains 460
E . Polycyclic Hydrocarbons ......... 461
VII . Action of Microorganisms on Hydrocarbon Derivatives .... 462
VIII . Products of Hydrocarbon 0xidat.ion. ................... 464
A . Cell Substance .......................................... 464
B. Carbon Dioxide ................. 465
C. Or anic Aci ........................................... 466
D . Alfehydea ..d.s. .......................................... 467
E. Alcohols and OxyphenoL. ................................. 467
F. Modified Hydrocarbom and Pigments ...................... 469
IX . MiAcr. o Rbiaatle M ofo dOixfiicdaattiioonn oof f POeitlr .o.le.u.m.. .a.n.d. .I.ts. Prod.u.c.t.s. ........................ 447701
B . Extent of Change .................. ................. 472
C . Petroleum Products ................. ................. 473
X . Microbial Decomposition of Rubber Hydrocarbons ............... 474
XI . Assimilation of Hydrocarbons by Animals ....................... 476
A . Paraffinic Hydrocarbons .................................. 476
B . Aromatic Hydrocarbons ..................... ..... 477
XI1 . Production of Hydrocarbons by Microorganisms .................. 478
XI11 . Summary and Conclusions ............ 479
References ................................................... 481
Author Index ...................................................... 487
Subject Index ...................................................... 515
Cumulative Index of Volumes 1.X .................................... 521
Advances in Enzymology and Related Areas of Molecular Biology, Volume I0
Edited by F. F. Nord
Copyright © 1950 by Interscience Publishers, Inc.
BLOOD CLOTTING AND RELATED
PROCESSES
By TAGE ASTRUP, Copenhagen, Denmark
CONTENTS
I. Introduction ..................................................... 1
Activatiou of Coagulation. ...................
A. Thrombo laatin ........................
B. Plasma dromboplastin and Autocatalysis
C. The Role of Calciuin.. ..................
D. New Techniques.. .....................
E. Determination of Prothrombin ...........
Prot,hromhin and Thrombill, ............
kG" . Factor 5 or the Accelerator Factor
111. The-Clottkg Process.. .........
A. Fibrinogen ...............
B. Clotting of Fibrinogen. ...
IV. Inhibition of Coagulation, ......
A. Heparin. ................
B. Antithrombin and Hcparin
V. Conclusion ....................
References.. ..................................................... 39
J. Introduction
The need in these series for a review on the processes related to blood coagula-
t,ion only a few years after Chargaff (52) published paper is a sign of the rapid
his
development of our knowledge in the field recent years. Part of this
during
work has been carried out in Europe during and after the last war, and has been
published in journals not rcadily available to all investigators. Emphasis
will
therefore be laid upon the presentation of such work. It is not the purpose to
give a comprehensive treatment of the whole field. The reader is referred here to
the appropriate Annual Reviews and abstracting journals, well as to a number of
aa
monographs (9,38,122,162,217,233,239,263,282,300c) overing various aspects of
the field.
It may be worth while first to look briefly on the development of our
understanding of the mechanism of blood clotting. Four periods may
be distinguished as such:
The first period of experimental work on blood clotting started in
1856 with the discovery of fibrinogen by Denis. After the investi-
gations of Alexander Schmidt, 0. Hammarsten, Arthus and Pages,
1