' ' ' ' V • v ; - ' î ; • 2 2 -i: ■A prdâitôt/a brystaii^^ ièolàtc&i;
/We 'mqnohydfd^ be, t%e^$
. nb% the <K bÿ t W nlïAyaria-CO^métW
' AAA-VAV'/'A : :,.A -aAA : : a/^ ■ ■ .aA:'®';:- ,A ^
(
24
)%/' Füfthermoré the,;hydi*qly8até whensbÿ/papër: ehdweà zio: oqfrqqp^
: to bri^ tÿrpËiïiG#^ hdWeypÿ . :
... oofrosponâingv-to
m .tlilne -,ah& /0-D B P -tyro8im e'
A.Wro/fo'un&*.; /Xi'All 'the\!:0thef;:ajid:hp\'adi'ad:.^
,;%eha%qd#(.y': Thüë^ nd^'f g r d u p / po.oufd ; ffée ..
/tyfoqiaind j^,(thG basi^^ -
/group:, of (:prnl'tb . thë : phenoli^^^ , ( - -: :
group of tyrdbihe : ia ff be i n 'thë ihtbot pdptide#=: . :Theao f èbiiit8 arè - in àgreemeht / with, the ihadluhility
df '/tyrddid A ih' acueoua'. aoaiimy darbohatë and ltd
^'MÂAAAAÀAAAÀ;:/:,': ÀÀ;:A::- ;AA,A.:A V: AAaAVAVÀÀAy-A'. AA .
./ready.. aplxibility; i h Aaqiieous; -ë6dimi.;-hydrd%iêe:./ , /- ' ' ;
:{/ Oh-'-the\,W8i#'^ -'thl'b:. 0vi&ahdQ--;thedd'::wpr^^^ ./;.'
■ dOhoiuded /. that the mbieoüÎG muat bo dydlio; W d -V:-" \ • mÂ::Av'Ay%/.A:.rAAAv,^
pût fôrWard the, amihd- adld rëëidùo formula df:.-:,
/ AAA:A:.AAAVAVA;:<A;^ :
.• tyroci'dîiïë' A/as; (Pr^ghehÿlalahihê:)g(:hr?pbëhylalaûlne)f:
/y;AAAAVA/.:/A:a/r:,/;; ..V, . /
A;i]ÿ&aïihe);,:(.Bët3œos ilvIirBr.oIllnë)V,A,.';'- .; r
. (ïfS r ïïfth iiie i ji;(|EiAgï^^
. :- :./. t
' (ït^^aèpcifàgihé- d r 'li-d jste : '://(
: to th ë e m p ifio à i fo r m iïa 0/piiô,40.. ' X-x
■-'As ëhôwh p r e v io u s ly , attem ptB ,;to determ in e
.:A;A%"v.::'Av:'AÀ-ÀvlA;:ÀyVv:À#.'A^^
: .thé m o lecu la r w e ig h t. o f ty r o c id in e by d if f é r e n t :
r A f c V i ' : A
methods gavé v er y v a r ia b le v a lu e s probably, due tô
a : : . K : : ; : v v v A A A v V : : ' V vv
th é known ten d en cy o f t h i s type, o f su b sta n ce to
:VA,/A:VA.::AAVV'AA/:A/X;/^A.'-;;V
a s s o c iâ t é , ahd- a ls o t o h o ld s o lv e n t of c r y s t a l l i s a t i o n . :
':v:=:AA'/:/A;v<A. :À A.:À\vv.:A/jrAj AÀ:: A -A :-,; A:./
H ow ever,- fo llo w in g t h e ir w ork.on th e i s o l a t i o n and ..
' ' .. : A-/V , : : :A'A/-
: ■‘o h h r h b te risa tio h ; p f t ÿ f o o id in e./A , B a ttérsby. and % C raig (2 5 ,2 6 ) 'p ù t forw ard la niethod f o r th e d e t e r - >
':.:-..AÂA^X.VA AAXA.-I. AA
//"'.m ination o f .the,_moloçtfîar,'W ëlghtsX;qf ..pdlypeptideb.*/, "X/:/
T his i s based on p a r t ia l s u h s t it u t io h o f a p o ly - X f u h o t io n ^ m o lecu le fo llo w e d bÿ fr a o tid n a tio n , o f :X."
. / / : M . : ; A . A ' A : . I / - ' A : ' : : % : ? , A A - y A A '
A 'A /tiie/resultant- m ixture • b y 0 *0.1),, R egarding th e
Al'
p a r t it io n r a t i o (K) bb anv o v e r a ll b a la n cé o f th e
hydr^ h y d r o p h ilic p r o p e r tie s o f th e
/ ëübsta n c e it /d a n be s e e n :th a t any change a f f e c t in g
: . / : % A A , ; A - A . l ' A l / A A , ; / ' A A . / A \ . ^ Â '
a p o la r group xn a s o lu t e m o lecu le m i l have;' a .. . ' s t r ik in g e f f e c t on th e p a r t it io n r a t i o . /-p lf ; /■ /
s e v e r a l p o la r groups a re in v o lv e d , eaoh w i l l -X.- X-
AAAA-ASV:: : ,:/.A. A. .A/,.AAAA',iAÀ': / A ' / / / / A;V,yA A:/
produce i t s ; ovm c o n tr ib u tio n to th e changé inXK; : /
/ : t À . ; A . A ' ' . : A : ' : . A / ' . : A : A À / ' , ; ^
/ '■ A
&môledulé Should thus : be separable by 0#0*Dw -X
X':.%XXAX'X//XV:X^^
:-// . ,.,.:;lf-‘;a.xpartlai-;Siibstitxition /- _ /àblèd^u^é i s dàiT ' some,'of . ÿiië\\:àtafting
m aterial imchanged, v th e’ mono- • Xahd d.i^aubstituted\ :
; x XX'::/:Xv'':x:xx:x:=xX X?:X : : xx
produots ; wotildr be Expected to. boour* D la trib u tio n X:: X’ of : the p f bduct in a su ita b le .system would then, g iv e
\X':Xm:;:3" -X yX:
a hü&bêr o f ; bands# depending on the number o f : / - Axx;%xx":x::..':4 x ’:X^'\ xxXXxxX/X'xKXXX .'./iXX/CxxX-XX:-
fu h ctio h a l groups ab le to fe a o t w ith th e eu b a titu tin g reagent * With one group# -two hands would be expebted # -:/'XXXXX"\X::X,:X; ';TX^
name l y unbhhhge d htartihg^ : mat é f ihl'-xand ; ^ th e- mbnbf ; XX: ■ri/.X: su W titu ted ;dérlvatiye:i:; With twb groupa^# :fou r -.-X ';-”X:X;, bands in ' thé;, .patternx'af è;XpbàéibIeÿ;:XX -;/ / ; XX';
'.^\-
b b h tà ih ih g the d isu b stitu ted Xbfbiduot would' beX-.w - X vX -.. exjX/'-':XA'-.x:^^ x-'xxxxx:xxx:x::x/:/-.
fu r th e st removed from th a t obhtainlhg the AVer A: ^ hnoW nged m h té fià l* Two p o s s ib le ih te fm e d ià te mono sub â t i t u t ed
prod ucts would be ex p ected to have Xveryx s im ila r
pàft.it iq h - r ^ t iqs;:/and :;'-pq overlapping/Xb'^d ^ ,
u ^ e s s a v e r y h ig h numb e r ; <if it f a iié f era had been applied;* xThe m o h o su b stitu ted product would be exp ected to l i e n e x t \t o thq Xtudohh^ed mdt e f ia i # ; th e d is u b s titu te d product Xhext to th e m
A n ^ y s is f o r th e su b stith tin g i; group in /a p a r tic u la r
X- A\W-y:,
-gg:-.
ëM â -woaia then .glvë,.% ë im lècular weight,' siaeë; thé
aumber -of s a b s titü ^ ts i s .knoïëi ;from the positloaV of
the bfflîd ia the ài stributioh pattern,
One d iffic u lty
o f course i s that the mono sub s t l tu t ed m ateriel might: ^
' r e a c t much more r a p iily than - th e':sta rtin g m'ateriëië.and 'u n less sp eila l/'p reea u tio n s- are...taken% e fo^imer. ,
-m ight n o t be d etected in the. f in a l 'mixture.. A. 'The
r e s u lt s are th e r e fo r e norm ally eonfix'ffled by carrying
' : A . ' A ! A ; A
out a second p a r ti aL, réa ctio n U sing d iffe r e n t 'fu n ction al
groups in '(he im leoule .
--A v. i.'A A ; ' "A, ■' A. A - / - /■;, / i/A.;.'-- /•; -,A. Whm Bppll s i to tyro oi dine A, two parti al r çaotlon#
were used, namely m'ethgholysis,. and. treatm'ieirt with;:
Sangef; s . r ë a g m t , . i;ufluo ro ,4 -d in i trb.b'ms en ë ( g # B ).. ;
In the f ir s t o as .e, -'puf o tyfo.oi din e - A ; :%aS. t r ëatëd, ' Wi th '
methsholicA hydiëgen .elTloridë' and 'd lstr lb u tio h o f th é \
: .crystallinëApzoduët gave, two wëll;Aseparàted bshds,"
One proved to bë unohenged. tyro'ci'dine.A:"whilst the ,