iu Call1.logage •

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Bibljolt\~ciuenatio....eteeuCari~c1a. Direction

iu Call1.logage •

'pivisiondestheses canaclia"n_nes,

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NiI.li:~at~i151:wy01,~anad.a

~:~II~~P~1~:::;~~VjSiDn

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Previously copyrighted materials(journal artl~es,. publishedteers, sic.}arenoJWme~ . ' •

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^.NOTICE

.

'-'~~:-~."

..'"The quality of.the-qualitya/1M origi nii l l hesis submitt

Ihi~~i:~~_ji(:he

^is

hB~;:;'de-nt

ed formlcrolUm-",

up~:' .~ ~u'a;ili

qualile deta^dethese-so umis! au^CIttB

~;~roii~he

^dependmicroJilmage.Noua

grand8m~nt

evons^de18..

^'I

Ing. Every ertcrthas beenmade10ensur athe highest:. tout lail pour assurerunequ alit e ecperteurede repro-

qU~!:;Yp:~~:~:::,u~:~:nn:~::::~t t he u nl v ers ftJ _~hlch -.dUC:~I~·me~que~~s·pa~~',~~:q~er a~e~ ~ "

--:--....::~~~~~l:le~eg~.~., . -,," .,J I'UniYerslt~qUI ~ COnl~regr8de.,· .,

-v-: . , :

'-t~e .~~;~:8~;;Il~at~~:v~~~~;s~i~~t:r~~~~siv~~:'~~:'

^'.

iaiss;~ .q~~i~ :r~~::'~?~iS:~sd~B~~s'~~~~n~I~~e~nr:~l

~bbO':'oriftheu.niv.er~itysentusa poorp'~otocopy. .... d8ct YIOgrlJPh lees8I '8Ide d'un.rUbanu seoU_slfurHva~te "

nous a fait parvanlrunapl'lotoc opiade maUVl 188qualile.

. . .-...,

.Les doqu m90lsqullontdejill'obleld'undl'olld'ai:i-'~

~~:r~~J~~es~~a

^revue,

exame~s

publi!b , etc,}ne

8~lI.lPaS !~

·

^.

La',eprod uctlon,meme'part ielle,d e'cemi croli!mesl i

·scumrsek reLolcan adiann9·surtedroitd'8uteu r ,SAC, .

i

1970,c.e-~O ,.·V~uiJ1e,Z)lren d reconnerseence des for- mulesd'auIOPsJlll on--qui eecompecnentcalleth e se.

~ THIS DISSERTATl O.N

H~.J'E.E.N_MICROFILMEO

"EXACTLY AS RECEIVED .,'>

\ .

·_ .' LA THESEAETE '.

"''-~ICROFILMEE

^{TELLE QUE} , ,-.N0 iJS L'AVONSRECUE·.

"~

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.ABSTRACT

. .. . . ^{b ·~ ~} . . . .

:Et~Ylen~b.~a_~ode~aY8tem,',COnta1nin8liP(l_~y~ena~e..

linol en s t e;Bulphiteand!:Ie-thlonal. The systemhad811 opcUnalpHof

~vo!.!£.-peroxy,radicals.

St udiesofollygen,upt a,ke by

a , LAiU'o/llulpliit~

^.

~y8tem

showed that

't~e

,..r

. .

-.

.

..

I;jdeac.td.hYdropero :ci d e .8~lPh~teandmet h:U:;nal. ,T h epHoptilllUlll.wa~. 5. 6•.re isthoughtU,:at.tw~speeteaweill.l'ellpon~lblefor ~oi\Ver tln8 the

?..

thl~naltoethylene,thehydroxylr~dlea1~.fOt'E(!d ,dul"ing,!u l phit e oxldatlQll.·and singletoxyge nwhic hpr~bablyarose froothe collision.of'

- : .

" , . ' . ' . ~

. . " , . .

7.8.':r r e e radiealll; fo rm ed"dUJ'i ng theiipoxygena8~-cata1y:Ad,oxi da tion

.... .'" , ' . " , . ," ", I..

of nuolensee.weretho uglittoin.i t a t e sulphiteox:ldation. IIydroxyl

"., '. ,

.' ^{_ . ,}

ra dic al s.f om eddur i ngsulphiteoxida;ionreacted.wl.t~nlatbional.

hydroxyl,r:,dicll1'wu.£o~:'durlng^{s';lphit e}.O~idll~ :lonand may bl'!achain .CS~rYl~8epec Lee," Becausebothhydroxyl,radicalsand methionalinhi~l~ed:

su"lPhit e,o~~dationin itiat e dbyLAHPO'it~ll^thought,thatIllethional,_i react ing withhyd r oxy l ' udlcalllin oui:system.,Becauselnhibitoz:.sof

:

'll~lphite ox1dat~on o~ly.

pBrt_iallY\inhibited

e-th1l_en~

^{formationi twaf}

• ,I . ' , ', " i

th?ughttha~anotherspecle~,not-fOrllledduringsulphit eoxidationcoul d",- aho

b~~rellP0J"sible

^{,f ar}.t'he convers ionof methional't oet:hylen;.

The: evide nceforsi ngletoxygen produc tionby l1nOI~~~acidbydro-' pero xide'andBulphitec'lIJI.ebollithr e etech~lquea-·t hinl';"yer enalyda

'o f. the

:produ~t~

_. ^ofdi Ph&J\"y'rluran oXidation_:~~, ._•'inhib :l t or

o t~i~s ~n: .d~-'

_{- b'}

~

^.,

phenylfuranoxldll tion udng.f,lu ore llc\nce8P~ctrophotOllletry andchemil um- \ il\escence. OiPhenYlfJaIlva~con~ertedbylino~.ej,cacid:dr~per~ide '.Ethylenewas oneof'the productsof,the repcdon.

,,~

/ .

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"\

^....

. . i

....

111

.,~.

"'~1

..itl 1

•

s .

~'.

',. _{s. '.} . .

10 10

·10

n

'\

12..

h

¹⁶

, . " I _J

,I

i

23'

,

: .

2>

i, . .

. ...

-:

:'.

" ^.

OFe<murs

, .

:

1oII-~.,.tc i:t~l~. ·'DnI&~~~ " . '. .

.Ca.)·

n.

lD"ol v _ot of'llydroxyllad ic. lI'._~~ "

':..:.~ct·t bdE'Source ~' ., ", ' -,.... .

~bJ~In;';olv'l liento~S:l.ng1et"oX"I'j,n'^inthll"

.' Con v . nioo o f Het h:l.Orlf. l to Et hy lenll

,.,1 . ' . ', ) _

."'. (c ) TileSo»1'ce of.the_S.i.ql.~~"Q

_

.~

.

~D.w.s~.K!TJI(IlI : ltla,l _ h'od~

OIrn:q·Upte.ke

: ::~:;~:: ~P:" .~·7:~·_ ' _

, ' E:: 2j: ' =:~ ~:?::~. ·;~f~~ ~ :f

. -Product .

.

. .

^-

' ^;._.

^:

.

~~::re--trlr. D.t~tU.

^{of lat e}

~f

^IIrr

LIS'l'atoUIBUY1UtC*S.

""IJn'alDlC'lO.

US'tIACr. ::IICIOI:M.I:DGDmrrS

",~I.ST'c.r~GUUS

LISTor'T~-

. ,~.

--1~ _.

: . ...., -..

-, ..~'

'.-'."

.

^~-.,:::'

~"

.'.;

: :,1' ''-'

it~

i~R~~~ION'

,,

,~thy~e~1 .~~

^•

r::~~,C~~eed '0< ~~Y p.laIU~tiB.SU.'~'~:. I,~~_~,~~ '.'

^....:':

~::.

^-.

"•tn~lved-t.ne·wide.va:1e~1of'"P~Y8~o~8tee~el fPi:t s.fn·e~~ tng., ~ •. :-.

· . ~ 8SB.~r.f:i3; f:$:;'·

Th~ l;h~~~el' U;'~dl~ ~8~?eiat~ ~~h.:;~tt, ~tPenil1~ .a;~: ~'it-

^.

enJ.O&of .the fruitfl eah',hydro l ytic.'conve r sio n of atorage .;'.; aDd

ebang~~

in pi gment lIud

'ti..~~f-$·' . l~· s~·e. f~i~,'.~,~ee; ~h~?gea

Decor ov ere

fe~ da,ya

^{buf':j.ncitrull' fru i t y}

th~.e cban;e~' may

^take

".mont hs , Thefrui tat.hs t·r1 pe'novera'.hort.·p:ar"todof.t ~·~llIa11Y·

:~:4' r::::.:

^f

,::::~n.;::::~:~:;. ': ; ;~:::.:;~:Z:::~::;

fruits:'The

s~Ow ;11l.~l\ini .f.rui~8 do ri~~ ex~lt1~ce , the. ~tIC' ~f

"'tbyl e ne

~t~uei:,ion

^orthe'

bur'~ o f, r~'P.i~at!l.~

^';

·~ '~re

knOWll··"8.,a noD-l:l:S..JMeteriefru1.tl . •

" ;S~~E~~Zf2}r1

^of'atbYI~e'did , Ethylenece..se e"l11Crelt"ed 'syn t hes i s of'u~y

:

eD~e: ~~Ch

^ate

re.pcti~lbie

^{for the}

ch"Dg~e ~~t occu~ :~

^..

r~·

^.

rl

P,en :lIl8.{l )f«,

"

.

^.

.

^{',' ,~ , "}

.'rhe.probl~tb 1~thea1.8

11.

c~n~etned,it~11 how:1;-etby~ene,

aynt.!te~l.ted

^7'the

p~e~ts~r

^'of

'e~b::ill!lle ':'''~, un~vn

^for

'~n~' y~'r

^••".'

t

\

,. ...

• 2

.

'-..~

,

· :'

-

- "," :~~~

Th e pO"'lib lepre curso rs proposedindudedaee~ate.l inolen icac~d·.

pr o pan a i ,~ethan.Ol. glu~o·ae-.a<;ry lic·acl d.

e

"'l~n~nli!.organ icacide '.and ,mathi e n'ine6);~~owthe ,;only'two' seriouslycon81de redsre

." .

' . ' " , .

, - '

/" linOleni~.a Cl.~ .andlIlet hl onine.a nd thereisevidence forbo t h hyp othes e s. •

,'.In19 6.4,.Lieb e =anan~ Ma~Bon^(4? ah~ed^thatethyleneC~ld befot1lled frompe roxldatedlinolenicacid andcuproull ion .'Gai1:'1ard'

• " • ." ' . I • . .

.!!.~(5}.la t e r showed that ethyleneeouid befOr1lloo from appleex -,

.

.

^-

.

tract,,'.incubatedwithli'nolenlcacid andascorbate. Whatwa s

· ,"obablY' oc:c~rl~8 wa~ 'th~tl1~OXygen~lIe w al'l OX~dls1n_g

^the'"11'nolenlc .ae14 tol:l.n.ole~lc:acid hy~.rop_erox ld ewhich WIIS the nbroken downto

Mhylene

~

the

cupt"ou'~ ·io~.

The

'~bility ~f

extra:tll.f t"otJI,applea at d,i"f h r"nl:-atj'''''ofth"it"~dev;loPlle~t'^to,produ.eeethy l en efrom linolunicaeWe~rr..lat~withthe ethyleneproduction by thewhole ,fruit{6~. ^{ThbProba b l y.}re fl e c t e the :ac.tthat li'poxyge nll_seac~

tfV:i~r,:i.I'I~':I..andh'-lh at.abo~t..the'$.lim,:, timeas,the(burs t"

ethylene produ c t i onwhi c h occursaf ttec.l.1m.octe):~c ~t.agll(7). Enzyma.t.icre?etione~ilte...between ~ompourkl.econtai n ing dtf f e r ;nt'ma a a 1Sot-dpes·.=.e'apeciallywhe ncarb~n dl~1de or blear-

..

^.

." .

ibonate111 a,rea c tant(8). Beea ulleofthi ~li pidainhighe r'plants hav.. a hi ghe r'pe r e e n t ag e of,I,2c'tha n doearboh~ratea^{orprote i na(9).'}

¥tieanaillIh owntha t .th e et hyl en e prOduced'by avocado':' at't hela te'

·

~i.iIIa~te~ic, "a~.d po.stclima~terit

^{IIU Sell'-}

h:~.

^{a,13 C/ 12C}

~'atio

^{typiea l}

o~

J'l&l'I~l4i1da^{andnot plan tea}r bohYdrateaot" pr o t e i n

(iCl)',

-ludicatins

.~a·'c~;ty'a~id:-~t".i81/for

^{. ,}

ethYlene~'

^{' " , .}

: .... .

^'

--

---- - - -- --- . a u

Ji6SM . ~.,,

" ,' , ' .

,-,'," .

^{" , :'} -:

:

..

It·i~;gene rally'believed,however thatIDcthlo~~e

',1s'

.t h e precurso rof

::e"thYl~n~ 1~ 'b1gh'~· . pi~~'~~;.· ' ~t"1:h~ ea~e :~1me

^{. ,}

, ~b"'Y ~ho~e~ l1n~i~~c

:~~i;'c~~1d a~t 'III ., etbyle.~~.p:reeurllor, Li~b~nna~ ~ n~'-'Ka;·~~ ·~hOWd .·t~lIt

.·.~thYl~ne: ~:U}d ·' ~.~

^be

f~~ed ' fi:;;": ~'~Qdel ~;'a'~em COII;~~;:~,~g cUPr1~ 'i~m,

m~tblonin"(4 ),.Me thionine, ~ a dellDl~ate,!'and dee:a r bo x y-_

.

^{, " , ', '.. '.} ~. .

e~~io~alby aS~reckerde8l"ada~:l.on(~1?..c,~ta~ysed.b Y cuprou\; brok end~ t~ et~ylen..., poui b1ybyhydr oxyl,'

'".-'; . ~. \ ."

PlAn t,'t.~a 8uefed' wi t h,lIIethioninepro.duced1II0ra.etby lenetNincon -

:~'rOla . (3)·. ~ate"'r"Liebennin ~'!!.

ahow"d tha t

l4C_~th~~nine ~~'ll

^{conver ted}

···i 4· ' . , ' ." ' ,. , /

to".C- et hy l ene.with·60%efficiency.by,apg lesl1cea.(12). WOl"klng with

:.. - -- - ::;---

' . "cauliflowerflorltt a Kapao n alldWa%d a1e (13) showed.thatet h yl en e fol",-

~ .·.-inatiO~~st~u~ated

^bythe

addt"t11~~':f meth10n1~e,

Ethylerie could'

also be fonnedfrOlllcell-freeextractsal t h ou gh1n th i s case-.oeth10nal

~II ,a\etter'~recursor, Investig~tign

^of

th~

^{cel l-he el!J\.tract}

.h~w~d

^.'

that.thecOlllponen~s^{of.t.h e.}ethy~ne..-prOd~cinB^{sYlltemwere·a'peroxi d e} 'Benerat~g^ayatem (.glUCO~eJl!ld.-gluCOaeoxid~e) .^IIpero~idaae.a,pbeno l , .aaulph inte ac1dand-either me th 10ia l orCI~ke~lrhl0butyr1c^acid

.' . .

and enacceptor keto ac1d)17).

~

^{,Yan g}

i~v~ ... ,t1g.~t';d

^a

1lI0d.el 'S~~tam"conta1ning, Pel",~xid,~ae.

^{'. :}

'. 'hyd rogenperoxi deormang~nou.B^!-ons"lIul ph i te,II pheno l'and~~an.i.l (18)•.:The pe r oxidasewailth~g~tfaox1t~ae.the phenoltot~e.~h~';:oxy

;ad ical.which-th enin1tiated~^{the-aerobicoxida tion!of' . I}

- t ~ -

:;.,.

.::

_:"

. ...

^{. " .,j'\. " ,.:,' :,.,.,.'.}

i .~

I

·:,"· :~

': !

~ .

:';;

,'-~.;';'.Llj

" ..' .

.. '

, '

!,Y8~~/~^..r",o~~ra~i~~,in p18n t .the~henol.,~1d,pr':'bilbl y,~av"e

;'~~te<;lsc~e. 8 fo,the.,llthyien ePr1~ein8~i.~~.,'-,·Ad.r~d~^{,Pheno h .} ~

.··WOUld.Pl'Obe,b~/.b~u~~ble,^toge_tto,"t ile",~i.t~.^of'ethyl e n:b~~tlles1.II., .

~i1t.~lY~her~,~~no,.~ot~tebtiOIl.~et,ween ~~~~~~O,fP"tox~~8e.in,. pea ~.adehe-.... oun tofethy len e produeedby differllDtpart:.of pcin~t.Blea'kin8.intothe'buffetBur~ouod1ng'the"tts·s':"e•.

:.- i > .s~~e~':l o~h~r _ _ ~i~ee.~

^'-,Of

~~~d~n~e'-·8~~8ee,t'. ^that: "t~~,~e1_~~~-t'~ '

,-. propo s ed byYang doe..not oper a tein_plant ll•. 'Methion al ,although.-

.it

_.

"

_.

_.~~

_{. -}ⁱ

_~oo~,

_"

~r~curEi~r'~f

_.:-'

ethyie~:':in-'';~l(free eX~~~~U·'~f·~:l.lli""

_{" ",.., I .'.. . .~,", .' I'.'}

..p:o~~rf~?'ret8an din Yang ' s modelay~telll18 ,ap.oor.precurB~r'in intac~,ti8su e,'(20). .a1Q1~111'ut.ilize d.'1 00

x

IlIqr e'effect1ve.l ;Y..th~n"

IIlethionine.'by the perox ida. e ilylllt l!lll, butClllJoIllA.i,.ut i l i,udby'apple

~', ••-:-,, ',~.' •• '." .' .'<;:S " \ ' :, , ', : ',; .'

.rind,c au li flower.:thllluew~th,abo~t't:.he....aDI~ef~~ci~ncyalii Illethionine

::. '( 17 : 20) . if,oKMBA'iB .,

int~rmedi~te 1~t;'e C:On~eniln ~f llIethion~~e

"-..' ',... '..,"', . '.: ' . . ": . '. '·,c.. .. . .'.,' .' •

.,t~Yl.ene_th~8 c~ldbe1nterpr~te~all,llIeaniOgt.h atthe,conveni~n,

of llIeth1o:nine toaKMRAoccur .II.'v e r y quickly1nplants"lIod . t h a t.the~.

' c~nve~B'10~ of '~ene ~~\:~~·e-l~1t1ng .':

^{' . ,}

:"In't h e;

, m otel

,8yilt em

·llIori~Ph;'~o.18 ·c"r ·~,..dip~,~nO~~J~?t~~t.hY~~De,'.

."pr odu ctio nbut1nint8~t^tililllu"e,thelile hAve00effec t onet hy l e o·.

pr~duetio~^(21)•.

This

h hard ly8ur pr 11i11nglIi~c~ .ft.the perox1d'.lle'

' .; . " , '., . I ..

... _ ...._ •.T". . , ~---

-" ~ '~lPh,L 8\lP~roxid~·'r~dical._

^P."

"di" " ,",h

(02 ":') or

t.,~ ~,

^..

!h~roper~Zy rad1e.':1 (H02~ )' ^{' h,} hYd,~,:, 1 ^{:•• =::;.} ";'~re ^{<h J}

c'boug h t.,t~r~c't^{wit h}~ethio~l'^to

p roduce

e~hyieile .'.I~we 8,^{though t .}

tha~' theBe:~eai~'~'~. '~~'ld

^'be'oc eu ; ;108

1n~1d~-,~he ~~ul1~lowe.r

'.';..•., .."".., '.- '",.•''; -:....:'-. '1·' -, -'.<"-'...- ".'.'-'.

floreta .',ijowev er Liebema nand KuoUOlii (19V c la imed thatet h y l e ne

.,

, . "., ' , ' . _ ' "

l1'p.,~,.g~~a.e·-':ctiv:1t-y intOlll~to~jj^(7)•.They &1.0sh~d~hat-

~t,hYl~ne ~O\1U,

^be

fO~~d':fr~m , '~ ~dal 8~.~,8Il' ~on'taining ~e,~~~'lda!iej

.'

"p:'b,-dr~~benz~ate.· ~enz~~e ."u~phiniC'"

^{acid •.}

upo ~~~~enase.11nolenate ':~~'~'.

andalOlllA:'o~methi~n~l~.i.ip~xygenane- waa ~86en.tia1

.\ .

l .~~:els ,~ell:,.~uri~'.r1~n~8'

of

.t~to'^{fr u i t.s}~~?e.~ethy~.e.rie·p~o,..:_

d",ctignincreased.'It must bel:emf!IIlbe r e d thatperoxidasehas

~eve :r&~ i~·~enzyme~. ':':~l,; ·.~e ~~·" t·i.~~~-COU1C/.b~ .resi~n'~Ql~.~io;'.

:::;:::,::~:o:::n,::,~:;·:.'::::;::T:::::t :: ~::~' ;f '

.".\, " .. '".: "..- ,.- .' ... 1., .",'-.' . '",

eVi~encesuggests'thatIIperoxidase,isnot"1nvo~vedinethy~_,;~e.'.

.. :}I~~:~:::~:: ^{· ::.::::::: · :7} .::;:~r~::::,:;,::;:;;~oo::::~··

"out a,s t udy in wh:l<:.hradio ac,tiv,!,lyr1abel1ed , li n olenicacidand

Illeth10ninew"ere.ie d'to appledisca. tOl!lsto,discs~ndcau1iflower

.

, ., ; . ',. .'

. . .

:....' -.

' .

"

, ': <....: . :':'

f~or.eu"at.differenl:,_a.~.ag~.~^{o fthei r}ldevel0pm_e~t.,.~bell:~ ^,:'.:' . . .~~thi~nin~,was.e.a~verted , t~le.be~l~~ethY~~~~Y

8 Jj..

fru~t!'....t..~l~:-'

~.

8tagelf,'of

·tJ~fr, deve1apDlent.

Whe.i"iabeiled\inoleQic;acid ':'•.1giv en

:' "",e,' " ~ ." ^{, .' ' .; :} ',, ' : :-.-.' " .':, ;0.'-.'.':',

-c. .- "" : "."" , :, ", '

'~'

. ';,

" the P:\1itsn~,18bell,edu,hylene~1':P~,Odueed.:Hovever'io'apple

.di~~~ .ua~ab~lled Hn~l~~t~, ~~cre,aB~~ '~he f~~,t~~ ',~/14~~~t~Yl~ne

f~om~~C~eth~oaine'.':It'W~8'~ugge8t~d~-th~tH~Ol~~t~m8y'p'lay s

j'.'

S~,~o?~ar~':rol~"i~ :e't'h;len.e,·p~~~ueu~n;~and·~h.a·t:'i~,~?~ge~.8~·was '.aliloia~olved.•

.Hap80a'aadwar d a l ethe n'show'edthe:,prellenc e'ofsoenz~ewith'

... ..

^'

",. ... I" ,. ,

.

.../:.

; .

. .

/~

,

^"

. ' ;

,~.

^{\" ,}

~~~

^•.AMD

~s ^{, . " ;, .':}

.;. >:-.~::{;::;:':~:,:::~::,";:':':.~::~:::;::~~; ... .

. ,:. '.(T~,..I}o:^...2'i~iPbeft'lfura.~.,^(Dpf',._e8U"Pl b~)'.I"~O~~"'i.C^{.. •}

. . . ::::::. ~~;:;1;~ -d:~::::::7.::~:'::.~'::.1::::;.{::';: ..

~dr\~b,:~,~i~al^caspany..~.Unola~C'.~Cl~,b~~o,P~roOX1~~:'{zr~~::.~aa ^.' pnpa-.:ed.by·the,m~ thod.o ~,O'Brien(2,.,,end ,,:,aaa''!lixtut8,o ft~(.9-,and'

· ~.j- P~ ~~'~~~+Dxi~e.l. , .') .. : ~-' .. ..,....; , ,..."

...

^,

. . . "' ','. :;

' " "

Ethyl eneProduc t i on

.',

; :.~;

^{... .: .};,Incu bations_roe

C4·rori~.

^out

^1..

^25:W11·Erlel'lll.e;-n'f1A!ki.),e.iled.wit'b.

I : ~bber^{aept": 'n e}ilJCub~ti~·.ixt~re f~r^tbe.ynth~.u^of.~thylenli,

./... · ;~·:r ..': eOll~iuned

i /J40'uo.iU/&l1lipox ,Sl'na...1eHlino l ....t. :4

~

^sulphite,':.

....!.tA. .~.'.,.

,

. \

\ -

\ ,

:':,.",

·l'~H.t b i onai aDd1eHEDTA'.:inl. i50~pbo_p~.n.^{buf h r}~H^7.8•.

~".",,.'" .' . : . ' ..

.

^{..... . "}

.

^~

'. -

.- ,The fl~ka'wo:ratDcu batadfor,30aiDa,at30oC~ '. ' ~.

A,noo-en &ya i c_, _t _vasaiao'fOWlodtop~ue.-sth,.lene:r ,Tbe

noD.-

~~yadc ,_,,..e~~.l~ed

¹

.WJ. ~. l ,~ ~p~i~e .a~

¹

~"~th1OD&1

^.

!it

1·al50'IIfIac~uubufre r'pH 5.0.··ThenOll_ nz,.d.Cr..et l OQv. .au~b

'. :' ;::';~:~~:: ..:'3::::. ·:·.:::,;::~:a~::~: ;::.'::::~:\::: i

· t:~: ~f~,e::"

^va'.

~t' a:'con~t~~. :~~~~tur~ ' (2~OC) ·.~nd that t~

^..

ct.~en.~8

of theflas kwere lIIuedtborou8hly. Thera a c t i on va.'started.by the

.' :''- ' .. :'"..' '. , ,,' , .. .'. ,. .- ', . ' ", '.1 ·' ····',·,

~ .."..~nj~~.t100.~f,lOfllof_1~0lit!.LA,~O,t~r~the••_pt~i~tot~eir e actio":.,.",

m~tui~.

JO\I!,

~cub.tt,onva aea",i~outioarapi d l yehakina",lCODa ta nt

·

~perature vat~r

^{b.tho .-.-. ,-,-.-.,}

~~ \

' ; -: ,T h e.<

P~~U~·t.8,·O~.DPIB P01l1d~tio,~~':"e~e';"'t~.•~te.~'w:I:.thehio~~f~~:

8:,? .'

';

'_" '-:>'~'I,-:.~~ett_~d·:O~ :~'ll~ca_·ie~ ·p~~e·ll ?ri~~r. ~,~ ' ,j~e' ~~di~10~11

^Ul!I8d,

fOr:' ,~h~~~~1,~~

^'.

.' I ficationof DPIBF. The pr:dduets of DPIBF oxi dati on e.ouldbe lIeenunder

, ,'jlc:: ~llg~ ,., ' . . ' .- ' . , " .

',. "/

Ch~;"iiu';i~~,e.eriee

. :"'.'

.,:,' ';.:',~ ~,'.Qf" ,s~,?~~b~~Phateb~~fer ';

^,.PH·

6:.0>~a; pl~.e'~d _,1~'

^II

.gia'~s

^...

".':~,_ ~':

-',"'-"'-c-: c-- :".

::::::':::O:V~,::: : h:",::::::::::::1::.:::::', '::~:::::::J :

";':'~"'-"-c'-~._: ·.", ".~ ^... ::::EB~:~:1:::~:¥.D:::·:~::~::::i:~;~:::::~:::,." '

< , Ox~~t10~:~f:' Diph~nY1f~r:"n .-~

id'euti Ucl/;t1:.n

ofPiod~et8

.

.;';

. .

,

.

. ....

',; :.,~.

. .

. . ,

....

~~TS" <

. :.'. '. ,_{.'.' ...j}

:

_"

.. . 1

':'.1

'-l. . ~.

.

:,'.

"" '..., :;: :':' t~·t~ .i:~r .theu.~_~buj.t,. 'to "~abib~t

^.t,he_

r"Clt1~,

^{•. ..}

-~~1t';l'~;';Plet.l" ",

^,',

;8;~ ~ .> .::.-;., :~cl;~bit~ :t~,.i"~8 ~t~u~tio~

^{bu t..}

·tha~l ·~h1~h\·.1;·

⁸ⁿ

~ttlCl~:';~ hydt~,.l,

^.•

;:'~

^{...'.. :}

F . '. •• ':; ···'~' , ·7<O~,::~!, :::<:::::::<!:·~~: :~::;::;:::Z ';~' d:L.Hi.'.;(> ;' • ... _;~

I. i,... .. ^{t. ':7it'7 '''- "' 7} .."" " ~ . ~~ ^{.-, "'-:..} '~ ^.

'. ":

..

^"

16

• .• " 0. ,- . . .•

otsul phite but . would notappear to bll! nec.sueryforth e Bynthe lliSof'.

"\ ' , .' ethY~,:e . ~. catrY~~e h.af~~i<a B~~~ ~~fB~~. '~~. e~hYlene·,~r~ductl0~. ^{-" .0}

. hydr~g en peroxld ~woul,dnot app ea l'topla y,IImajorrol eill.~tl)ylen:.e eyntheeiB.( _

1 " , -,. .... , . ' ")

Singlet'ox ygeneC8v:e';&ers~uch'88 2..5:-dl~hellylfura~(26) and adde

---'-'(li)",ere' ~laoinef f e ctive. B1U~bin^illII s'l ngle t'o xyg en,que nc h el: (32)

' . ~ , . -, " ', ' .

.

- :

',bu t'i 8'lIleo probAb lysfree:rad iealaeRveuger,andIt.1l inhib i toryaction

va'8'

proba~iy ~u

^{.. to}

~tll

fr aa ra d i cAL'IICAveng ing

Abill~Y, :C"f:.~chOl

^is

anot he :.

~ingl"'t'- ox~gen

^andf;ee

radl~i. lJCaVen8~~

^{(l l ?'}

~hieh ~a8

!igood inhib it.or of ethyi;;;;-prod~ctlon. Howe ver11;-19~iaoaninhibit or o'f ,.H~~xyge~Be

and

't hb maybe hoW it is ac tins.h,e~e.

. Re aorcinolwhichetim...lateB'theperOX'1<la'ae-eon~inin8^{et hy lene -}

;: " , '" --. ~ .'. '.-;::,~ . , . ' '..

~f1-nerati~gsyatem~fYa !18 didpo tbav~ItiliJDilaJ:effecton ouJ:"',syateEl.

Non- Enz:ym1cEthy len:. Formation

R~~1ac~'nt ~ l1n~lep1c ~id

^and'l1poxygenas e by ,",l'!DM

l1nol~'1c

ae'id 'h yd r operox 1d e~laoresuit ed·1n~thyrene·format io n•.Thereactionhad

d'ifferen~ c~a~acte,J:lIltic8 th~n

^{th e}

~nz'Yl"i~

react i on•.The

OPt'~l

^pH'waa

5.01nstead : ; ; : 8 .

;~~'- P,~

^depe nd enc e

~f

^{thereaetlonis}

a~~wnlin F~~~e

~

.

. occu r red wh';nthe"sulph :1teconcentrat1o~",a a"1lIlM:'~The .mount of ethy l e ne

. '. .

.

:.-,8Ynthe~1.~ed·incr .... nel~1ne~~·lyup to this poin tbutlifte~a8u l phlte

I conc~ntrat1o~~,Of,

^{1-:t-wa u.reae-h ed}.fu r the r

incr~uea

1n lIUlphito'l

concen~

tratione1tdnot.1pcr~ se7helUIIo~nt.ofethy~enefo~.

~

...

.'

.~

.

7.

'~.'.'

;" ,~

"

.

,

^.'

. -:.:

11

(

" ;

.

.

~•^'4~..

.. :

..:'

T

:.>

1- ._~

' .L .,

j '....

! ~ ~.

^{4. 0}

. .

ij .

2.0

:

...• --.

,.j

'. -

,.~~, ~

;: -:

S'·!·, ,.

"1

Ptod~etl(ln: ~eu'tted,'witb~'LAHPOeon'e~n'ti';"ti~n~f"{IIH~^.;The'~ea~~ion'~$^•

.. ,'~ "',~"

..

,."," '~," ". ' ,. .."' :"',: ,.'

mae-h'fas t e rthan the anzymicreaction,being cosap1e tec1,wlthintwoIllinute.s ';',''. ,'.,' '. ',. ' .' .,

. . ..

,

...

::':

':--. : ', ....

^{" ,',',}.. .:...

,iDs t e~dof.s ixty:.,Thetitle.couf~e 'of.the,tell c,t.l~-U"..hcvn in'F ig~ te5,.

~~" l~cub'~tlon t1m~ :was'~~~e~''to "." 'one

,

,ml~ute"

^'

·i.J.t;~~gh

': ' ,

th~

'"^{ethylene,wu':.-}

" j .

'! o'r:med'~t

a

.;roch,faster rate

bt'

thf!,:no~-en~ym1e~eaci:io~' l:h~··'~-6f.l'8mO,UlIt:

\' "" ',' '" '. ", .-c,.·, - '", ' , .' . ',' " , ,".

of,ethyl~neproduce~.s e s only.,a bou t"one-,t hir d t he~ntproducedbyji he

. • ~::::~::F:-::":=~:S::::::::::::~::;:l:~;'~:;~~::~,::: ~:~"

:.,'".::':::"It:,

: a8 :th~u~~,~ , t~,t :~8 n~~~~nzym~~<~~lt~'~~,~~ :b~:~~i~~ ,~o· ~~u~yi'."

.:li

l1C

^{e'~~,e.'ra~e~fe~h11~~e..}f~~t:i~D",o71dn~~,:~~:~ffected.~h~:chang~a.,:il'.,^.

. ':EvE~~::::~::::: :::6:::h=ri:2::t::~1t:::Jr::,~:.~ ^{., ;}

,

~~" ~~;'o·l~~Jt·'~;f Hid'~ciXYl '~lca1s .~.~~:;h~~~- s~~rc'e

. . . . '.' .H;d4t: .:_,::<~:; ::::~:;:: : :1:::::,:;::::. _:::::~: .':, :::: : ' . .

.• _{· ;~0~~} ~~:_~"~jC~ .

'> -',' ';" ,". ".. " ,. .." ,

.:~.',::

' .. ', ',- ',:' ..

',1 .."".::' ",:',', ,.:....

.~~~~~.U~le,Il~,r~~~do.I1::.(~~)

0 : :

',~e:,:u~er~i~~,^..rad~cal.c~uth~n.^{re act.},~t~·:·

•

••.

~

^'>c.

":~~~l,;e~,to ';~~uc,~ ^'SOi:' :··.~u~. a:~~.in,~e~ti~. ~.cura,:

^{". .,}

.I . . .

.'

."

. ....

'-

. _{. . ..}

...-:-0

;

....

f· ._.

--.---I • • - .'

.... .' .. _ , , : , : .. \.. ",:rT~. ~~'~).>. '~'. '

:. '.;'

";"

'-P1~;~ 5:"'t~~~ or ~~~i~~1oG! '-. . - ..

1._ " - , - .

-(

21

I

, . /

..

thoUght

. '

th af,otheT species

... . ..

su ch

..

asthe hydroxyl ra4:lClll can

. .. , L

also eal"ry

: ....

. o~:'~~e.-~~~in; .~·~~~t'~o,n -b.~:': ~ea.ct::~:.~~?' :M.~U~Phi:te,

^..

~I/prod.~~~ :.~~~:~!~l~

^{-: ',-}

.phi~eradical,(HS03')~",~Dsup.port-of,t.bi~,it-·i ,~~ndtha t~"t'tsu per-:

ox~e 'di8lll~t~~-e ~tl<! hid~oxjl ~.diea1 :'Bl:ave~g~i:"~'''ln4~t;1~'~yg'en~

^{upta ke}

by '

~I th~ .~OlBU~Phite·,SYBt~, .<~~e ~_a~b' ^?l•. ,_~~~~;~ db~t~~,e ~'~~iYlleS-"

^.

th e

d1~utat:lon

_{. .}^{of .}_-,-^{uperoxid e}_{-' -.}

~adleals'

_.

.eeordi~

_{'," ,}to .thefol lowi ng' .-equllt:lon_,

~

,°2 7

~ O:r+: 2.H:':· ---? '

112

°2

'+

.02_~~ ':'-' ~7'·.

·..

ca~~~aae· a1~o":,~.h?_bit8 "~~yge~ :~~~the,~(~u1~hi{~. ,8yft~.'

cOn~1ste~~ "'lt~:'~he h~pothe8~8 -t~t

^{:res etion'(v )}'l a::ths"so ui ee'of tile .

.' "

..

^{',' . .' , . ,. ' ' ." '. '." ' , '}

" , ~~roXyi'~~d~~£8:

.;

::';~I1~i~,t: ~g~~':.~~~nche,r~·: ~~~h.

⁸⁶

~,~':" ~.d·~~CO.·

^dll,.

~~~':~~ib~~ ~xig~~" ; '

uPtak~.:,in.fact th~y'enh~ti~e

:i.t:though: 'the.·

't"e~Bon:

for this

.1~ u~kn.m;;'

',' .

--"i'J;;

w.stidil1e~ ~e't~iOll~e<an~ '~~~~~\I:~~',~~~ s: ~ingl~~·,.~l[Y8~"'SC~V~~~·s.:

'~36{ b~~''~hifC:~' ~l8O r~~t ^;;'tth hY~~oxYl' ra~~ci;lS

^'(30)

'~:h~ro'8~

': '

~

...:: : .

~:,

' : " .' ...". . ", ,, : >- , ,;' ::-': "

"c':' ."'" .

perox1~ e."Thes eamino acidsprobsbly,'inblbi ~:,oxyge nuptake:bec.u~.eof,

.".' ,.. .. " " i · ' :.,. , .

,.th eir ab ili tyto scav eng e hyd roxyl'ra dio;ala\!Indhydrog en.peroxi d e.

" :.. ','. ." ', ".' , I,. . " , .'. ,. ,

.,The1IP.~1ox;id,811t8BaA,~d'lIDGA.~lso.inh1b ~ t'ox;yge u Ilpt.akabutonly

-tak~ '~~~l~iy" ~e~u8~ 'Of'1~8' h~d;o'xyi ~~'l~al '8e~~e~in8'ab~lit~ {34)'.

. '.-,

.

^'.

.,, "',

^{. ..: '.' ,':,- ,:",'. ,,-- .~.'}

.

,.Thedi Uare'conl i s tent withtbe bypoth e8i•.~ba t'theHsber -We:l88

r~;;;" n:(;,t.'t1= iv)i.t~n'~". of thehY';;"" "'1~;".

. , 'In

i97ri ':~ea~~lIIl~ '~~ F~~~~C~ ~28)' ~~~d ~

^{. ,}

Uperoi;~de,r.dleal

~-~n~~~~';~'~erD' : (l[~~thin'~ a~d ~n~~ine ~;dd~\~~') ~

^to

:ah~" tbat

^{hydr oxYl}

_. • ::;:;':r::::i::.::t;::b.:;:::O::r;: ;;~::.~:::::::::,:;.:r~Po.~d .

....!Eo!!.

(34 ):clnlfi nn,N.~bathyd,roxyl radi cal.·react edwHh lll,~t hiona.l.ver y

:," ',." ",:_'" '. ' ....,.,.'.:".< .',,, ," . " , ".".'" : ,:

and

IIlso·showed.'thatBuperoxldersdic al 8onlyre.et~slowly

..-. .. . ' / "'. ' . :

·· C::~--

.. ..:

!}.~~~~:,: D~C~,::h~C.~:.fO~,e.,.,a" ~~.~:~:'-tr;~Bf~r

^..

eomPleX ·~t,h.:1l1n&1~t

"' ", .:

:~

o,xrge n be1;l1lVes'~~ ~·6~UII ~,'~lIner. ',':."

"' :,' :.' . ,. :,

:" '/ .',. '-': . .. ', ' ;

. ' " ,'

.,':.:.," , .

" ; ;ot:~· :·· .~ ,. .h.!l" r· ·f .. 7;h:'.~ ..• _{~tn'· ~~~} . .. _{; t~:=1n _ ;} . . •

^{r<,..:.,.\.;.: •}

, "><: :" " : .~

....;.

. ' ...

^',

':-:',

:~8' ~en~.i.~_~\~:' ~;f.~r~., ~Ydr~.y~··,~'~t~~~·~,~~~~~~.~F.B·, ;~~~b,l~i.·~~~~bi':~: ^{;" " ,}

·etby lene·synt hesis •.Withbo thn~butanolandethanol_amaxt -inbiblt~o~·", w,ss.

~~'~~'D_~d ^.',' C:ta~~l~e: ~~BO:.ln~lb lt~~ '~~hYi'~n:e"-~;;he8·.i·~~:. :M._:hY~_~~_~.en·

.'peroxl iiest:l.a1ulated.11:.Howev~r:superox1de"diamuta ae.hednoeft"ec:.t.",

~· ·:·:.··.An~~·~.~~'~~ CO~d~~~?~: -l~!I~~i_~~- ~~~;l~ne ~i~yri~~_~S.·~8,:-~?%~"

f:",.'

r~~ge· ~,eBult.<8UgS~~.S·ted'·

^_:0:

u:~_.th~t::~o~~ ~:~eci~~ .fO~~d. dU~.lng, 8~.~~·.,~

^..,

;Ut~ :bJdd~tl~nrW~~/at _1~a8~ pa~t!.~lly_:reepo~8~~~e

^.:

the·:l;~~~f~io~~.:~~·, ',

-',' o{~'et~io~~ ' ~~':~;;h;l~~e. ':S~;e~~~~~:- ~Jl~~ll:'a~\~''' ;~n~·e~t,~a~ i~~8:,~i:', :.

· : ·~Yd·r~~~~ ~t~.~ie':l!;, :,~h~" hyd~OXY:l't~d':Lc~i~: ;p~r~~~~~'.~~n~~" ~onv;'~ t ~~ _'p .;~.:.;

^.

.~:. ~ ~qb... ~.~.~.'. " ^•• ~. '~~ , ":" ^{. . ,} ··~"::;··h

^'

Of,·o

^.

'.:·~ n ·;·e . ::,.t ,h .·,I.;

^v"

. '> t· .·h ':y~'~ "·. :.n ~. '~:'.;.~"': ^.

~18;34):'a~,

10

'p~okblY

: . th\!.

Iipeei~'8'tl!~P~'o"S'ib~;~he.r~~

. . ; _~!;.;::t= ::':::::"::::,::?;{:;:,:::,P:::~"'L:r;:'~~.:::j:.,·

'cOUlplet~l;'

^{.i1}.hib lt}

.S~l~h.i~'e

.

o:Xid:t.i~n.onlY pe~tlallY, :inhi~1i:~d,. ~thyi~.~.~;

b~~~rri~hes~'

^{,i t}

"wa~:,.th~8~~.

^tbir.,i::

'~~other. ~pe,c~~8 ,'ili~t'·'~Q,~ed"

^during'

.~,:,.l':',:'

~h,iteOJ:id.t1.Qn,~Y'bere,~~~ible

for

coilvet:ti~'ine.th1onal·toetli~i~n.e.'

: 'i;oiv'~~~t '~f" il~;e'{·OxYa·e'~ . :i~'

^the:

'c~nvei~i~:,~'f' ~~t~l'~'~~: ~o';·'·

. Ethylene . ('"

.":~id~'l~"~'

.,tn gl.et

~xyge~,q\l.~~ber' ~hl·C~.~ti~bl~'.,the';f~~ti~n:,?f

Ilthyle ner,,~.'Dethl~~i^(IiBS'T~~1e'·:'.4).;· "T~i8'c::"nno'tb~'d,~e',:to" ,~t" ~~tiori

. ''..'...,.'•"',"..~J.' '. .' ,. ". '.' .' ." ,.." .-:. ' ••

•OU_" 6U;lph~tB_{.. . . . ,},o:d~aUon_! }linCB_{_},It:a.t,~la,tell_{. --- .}oll:Y8et;l ,up~ak'7.by.an.;un~ow:n

,.

.>;;'

. :\.

...,.":". ',:' .;'.,: ;.',:"..,'.':""'".>,'.,: .'c....- . ..:. '. .',' :. •::... ','

.·;Et,hoxyqu ln ...11.the111081;'effec:t1v" an tiQ'ddant,l n:lnhib i t:1ngethy -'

..

~~e ~io~th~" '1a< '~"

^{"' .}

~~.

^{". '.' ..}

':'.~~ ",:"'~.:.:

^..

. ( e)

.;Th~··S~l"~" ;f···~h~^{'St ngb t}OX;:8~:.'

:~~\~to~baQ

^•..

Thil l~·, ~rObably· b~!",~e

^ihey

.~~

^react·'...

;th

both'·

-.:'-; :

.·~~l~~ ~18

^..

~.,(3S) ~~ hY~,~~~_ r~d~~l~. ~3~) .'-~··~~'~1d_~~ 'i~. aDO!=he r:

.':'-.r: - ; ~c:~ :h1ch ~~D,l"~c:t: _"lt~~~t~ ~t.;alet .~om,~. hydl"i~,:l"adl::

^{', '}

-.~. 'c:ala.,·,,"*:,ve l"'l t,i.aot·'.uch .pot:eat 1ahl ltlto rof.et hyle a ehio 'Flt bed ••.

~"The'. Qtl Qlllcl8DU.8BA...pfopyIPt1at.·~lmCA

.leo

Inhibitedethy:'

~e~ ~~~t~~'h a~ :~~IlD·tr~~io.:.:m~~h ~~~. ·~.ne~~.~;~:.~: ,~~it~g .:: . ',>.

.upta ke:

T~~, &IIt1~:i.d.ni:lI ·~~n.

^{rea ct·...I:th}

.ud.l~.le to~ '

^fro;.'

th~

^'fatty.".

'~~... .'~

. . . :; ::~:t:~ t::~;::~~:2;D::.::~; ;:':;:7:::::~~<::::, . ,. '

.":

_~.:.-.

:.: '

.'.

bx~~~.I~n.,.~<~!iB~: .::~ ~b~.' fOll~~·.:~p~e.\f~~ho·~cae~~~C:'~1, .~~. ^.,:"

:.... .:;::. '.::::.~ :>..: -.'

:'.;:'

.':; '. i.':' ''" ' .' ... >.:

.. ' ' f

. ·· l·

. .' ..

~

1,~

1

' i

· t ·'.

...

1

~.

j ~

.. ...

^:..

::;;. '

" .

-.,.-

,.'

'2": :'..

.:,.'

420Qlll.

oxidat~~ W;~\not,';,~~~'l~l~~~, by~ t~'" '~~,r~l ~~d~+l 'B~aV~g.t

^{. .. .}

~~'eOl,.

etha~i

^••

n:-p-rO~l!~Ol '~Ot ll~~tanol.

^The

8:lnSle~:',ox)'ge~ qti,e~eher

^{..'lIzid e}

~,~h~"ahig'l,e~cixyg~n':~raps.-d1nleC:h)'lf~~an:.tryptol'hllnand'II.';thton:We

,~i.'BO ~d· ~o:, e~fect·O~'.DP~~F-~~l~a~J.on

^{-. ','A s}

'~~Il't:lOlled·;J:,ev::l~.lY· tt~~ "·

t,ophanandmethl~ri~ri~;^als9reactW'1.th'hyd~o~enpllro~lde ~"th~refore

8pe'~;~eB ~ "a~:a~, ';rob8bl;:~~.~,'

-' .

~~oi~~d

' ,'

i~

~

'~;i~'" aXid~ti~~.'

" " ;, '

, :

-.

'; h,e',On1y. '~i

.. ..

'pf eoii'.pO':'~. ;W"~ii:b/e:-f'~e~ti~~.lY ~b:lb~ted ,DP'I~~ ,~:l~,': '

da·t~on·:;;"';r'et.he~,nt'i~id:"nt:B.:.ihe~~ W8re v.~y,effe~~ive"a~'lOw'~~e:.:.~

' ,4',.:

:~~~,t'~o~~,; . . ~,t: ~~,~·,~~'e~:,a~~~.~)',":::,Ua~<~!!

^{.. :,' ': ',"}, . " .

oradicalaean in1tlat!'!' DI'IBF,O1I:id~t1.0ll;',:~N,Ib ptobab1 ythe,re ac t ioo"

".;",.'

', :" "'.:.;:,

.~". .-'",' , ,. '," ,

',"

,~,.,':,'-~-:.':';'~

, oeeur r1.ns·'he,-re.'The!!£-p..rroxy,radical sl118.ya't1.sa.fr C)Dl ' :reaction(vi1.~).:

- . Ro,:;+ \tOO~ :~ .RQH--=" R~' "

Ant!ox::ldellte l.nhibl.t Dl'IBF oxUatioi:l byle a v ef\l ln a"ROO"o't",RO·(38)•.

.':

" ~~i:BF ~:idlt1~ ' ~ae·~.e.i" t,;.·~t:t:em~t·:: t~, d~o&t~~t~ ~~~ ·~~~lv~nt

. ..

. . . . ^{~ .}

:

' .

. . ' t¢~k>!U&iJit1AiU~J~.,:;;.o;S,; >t.:;;::C:Z%J2&tZJ,~}Wi\9Hh'"

30

1'.

. Oxyg enne;d~^{in't h eaqueQua}pha lle,would be 'toohigh(40)• .

terellt~g' '~o· n~t~ '~ha:~ ~la~~'ng

^a

b~ii~ng

chip"in the

ad':'till~tion ~ial

( ',' .: ", "', ".'

..

^' " ',' ' " :', ..'

.',' !lha nced th..ch emi l umin e..cenc a3-fold ~ po;aiblyby en cou ra gi ng thefor-,(

.. . ,

'. '" ';

lI.lI.t io uof _11'pxygs u'bubb l es.onita,SUTfllC.8. Thesingls t'oxygen

" " , ', :. '" , ' ,"

:hi$tidine all,inh ibite dthe ebf,milUlll inellc ence. DABCO had litt1.e effect.

It would. ,

~p~~ted

^{,:t o}

enh~nce ' ~be: ehEllli~umi~e

..ce;"ceby

SUbil~~i~g

the,s1):,gletoxy g en in,a chlll"ge- t l"ansfer'cOlEll?lex. The antioxidan ts'BRA

lind;'~RT

lil a o"i nh i bi t edth ech emiluminescence :.'The'

be~t 'inh1bitor ~f

, " ' ,," "

..

thechelllilUllli~~~_~e_n~,ewa,1lm,ethionalwh i ch:inh i b.1ted,call1pl e tely.at'O.~ oM,·

'.(Ui) The Convers ionof DPF to cis-DBE

."Oip~enYl!U~an

^(DPF)

~eacts

.,ii t h·..1ngletoxygen togiV ll'.5.!s- .

~i~eiu.oyiethYlene <£!!-~BE) '

^(26). _,Fig u r ejahowlltheies ultll

oLta~~d

, l?

exP6~1m~~~ 'f1 d;Si~ned

_.

t ~'

det e rf!li n e t_. he

prOduc~ . '~,f

^DPF

oxidatio~'

^{by .}

'.to;),' .~o^andIl\llph i te.",XnO~:f1il;lglet^oxygen.produd~g reactionscon.verte~

,ilPP_'; o'...'p roduct

~hieh.:ill p~e8Ull1~bly

£!!.- ilJlE. Ithall the,llllllleRf

~a1ue

~~ ~ut~en;ic

.5.!!.-DllE

U8~g th~:s8llle

^{aolven t}

-Sy~'t_

^{(26 ) . It iaalao',:,}

rI'· ' ' ' '. ''. , ~'. ''. , .-.

prese nt 66 anim.pu r lty oftr a,?s-DB,E,•.' Enoughc1B-DllEwa s.f or1!led to per -

~o~ 'an' ~p~~~";~i:~ ~1a:n:,i.t.~tive an:at3,Sia;~~

^{:;--pre ..}

e~ce ^of

^various'

,:,,:agent~ . ,T.bl~7 ghell~",t.:lma.tesof tbe amoun t of~-DBEfo~•

."'.ulde.,DAllCO·...ndmethio~ine'aliinib i t ed theconve -.:aiouof,,'DW·t:o

. ." ,

..

^{~ . ~ . .}

~-IlJl.E.indic ating.t.hutit,~,tli t!gl e t~X:Y8en~nd,~otf'l:ce rtldiea ltlwhlc~.

c~nv~r't'tlDPF~O'-~~lIE. Anr'i'o x,id,anu alsoinhibite d £!!.-DlIE·pr odu c tion.

"_{.H&nn i}; _tol"_{catalsa e}.._and'" _{SOD had no}, '..:'_{..ffe et .}, ,_{Acet Olie}

-

. ._.an effi cient inh i b ito r. ,:

. ,

^, v .^"

~, :";"'~'~t;,

su i phtt e

'oxidst~o,n ~d·'D.o ef~'~ct '~ .~let ~JtYgen' produc~ion;

^.

00' 7**444 ^{*> :}

. ..''~ -'-~F~~:':'-~; -;' ;.,:'

.

^~"

: ..

^-,.

.:-~ .v :

. _~ .. ,. ' . , <

"

^',-': .~^-

.... :: .. ^{" :}

^{,:':. '}

.': , ' . . .-Y~

'..I'> '.' ~

.Conv e rd.oaoJ DPF;to.s.1J..,DIl!. 111 the .Prellenc:. ofV.dn... 11l.~1b 1t or•

. :; '.

...

':.c. •

.:

.

.,ka.;

: . '

^{'. .}

:

u J~)l(+Mhaa ,.k i

".

IX ::;J&;;::.•

f··

- . '~f

opyo...truct1 0l:l_

:-." ^"'

..

,·' r

.}

r.,' -":..}

':

. . ::

"

~, ii~· I'~:~.e~.t~,:.·~:~V~.~al~:l~,~" ' Of:.~~~e~~e

^-.

~~~c.hI 8~ ·t1·t':ai·ng.l~~~

oxygen11be1na fOr'llledd.ur1ng·the,react10n betweenlAHPOand__sulph1te.

.'

'Jl'~~~~~·~lPhit. ~Z1d~~1~'~ ~~ ~be:"'~ib1tid."·~i~bout' \~1blt·i..~·<~~~ie·t·:~

~~.~~ ~~od':'C,~ic.'D:· ~~ :.~'~. ~f t~~' ~lb~'t~D'

^ofaiDglet

'oXy~~

^'pro.:',

"~,_ .: • ' . ' -...~,~.•., .': :.::.:.·r '. ' ,..'" '..' ,..~. ~',

d~~~10.n~~,l.:"'~~~nt.rat:1~n~-.of ant1ox1rnu.~t¹¹,tboul~~.tbatth. _.;1

. ::~~z:e.:.;~;:::::~

^f::o

~:h,::~:\:l:o:~::::o:,~::~~::l::

^--.,;,

·.th>:leD;~·~V:'~

^we'

dci.'~~~ ,~:~~ether: ~h·.: ·.~&~~t· ~I~ ~~ i.. ~.~iq

'.~, .'.

" ." "

wH.b_tb.1.o~1toprocl~~.etbyle neor....b••rhe':;th..·. 1n&btO"l"g~

b'"' '",'.

~'l

" :e~:~'8~~ f~r ~ti~ .~ner~~1~<i: ., O-: l)th~r· ~;'d:~ ~blCb' ~' ~~ert ' »: .,." ~

, >:' .:~ .':;- .;;~:; . ;'S;: '~'~:: IY ·.~~ y ·~ . · ~~~ .~':"::':: " '~~ B.~ .i).:~.:~: ", ^{' i}

.

•.

;~ .'.

,'(36).::.

ACl~rk:"l:YP'o'zYl en;~iec~rode'cDnt.1~1nl^SliMlIIethyb~

'blue

end' t-

' , ' ,;, '·~:':f . . ~~t~.1o~~i .~ i·~:9':·~'~" ~~:~( ~~~pJt~ ~Uff~~>';:H):O' ~~\~~~~~' '.:. _.~~:

... _{;~ ~ ~~t\~~~~~ ·l~~~t,} . ,.~. r~~~J o~~e~ ~;t~~~'.~ ... ~ba~rv~.L/~·.~~~.~,~f _ ,-:::'...-, _' _{:: ,~.}

0~8ea"upt.:keVa."-h.nc8d7~~oicr^{whe li}thepho.phet.~;..db801v~':1D.'" :'

.:_. :#

" \ .' '.i.,

^{" y . " '" .•..}

^{":; "1:: ':;;" ' " ' . "} '~_ . .::. . _~;J

:".

,

.

?" .

',J

'"

. .

' ,. :

i::n",~ . )~' ;;:: 'J:'

: ^.

^.

., ^.:

^.':~;'

r

^''.

·i: ·.:s; .

"o':f;'.'

. .~DISalSSION

and_thlonal~ Sulpbiteox~tlonva_h1tiatedb,~h_phano~:r,~~~l ..£o rmed..

b r .

theent ,... . InourlDoo.,el.ayat_.-.u lp~1t~oxida tion,i~th~lht . .. ,.:tobe'iniUated

by

^{free radical}

~;'~~e'U~t ea fo~ed

'dur1ng

~he ozida~ioD

. /

~f·~;inolet1t~ ~Y ·lipo~;'g~n

^e:

·:'i.i~·gena.e-~~~ '~leo·'cat:'lY~~·

^.

....,

~-, ox'~·~~ti.~n·,~e~~·~~?n~',

^..

Vh~~:~~:~I ~' :fo~, 'fr~e: ~~dic:~i~'~~~~rdhg'

.'.: ' -

;'foll owin8 mech:'nilllD~"

^{... .:". :}

, " . LH ~ ~ ~.~?~:

; .· :, ~':-:; : Ij:,\,' : X' \ ^{.. >< ; :} , . ~;0ftf'

.Bothour.lIIOdelaYIUIi.and.Tang'llllode1.ayat_ haVI .:n optt-lpB.o ( 7.8•.•... .

,

_..

:·~~''"''~';

_...

~ffi[::£~

_{. .} ....-<:;J'.^{. .7 •}

.;..,:.,r...;'.~~

... .

·~.;<

'

...

..

Sf ""i,~ "'" $1[ .... ,....;•

. .•

•;

...

,'. { ·

~ ^{.. . ": . .•.} ~::;~:::.::':::-::::,:~:~';":;.,:: :;::~:::::. ^{; ,,-} ',.,;~

, nllt

b'a

operaUtl gj.nplant l .·Inorganic llul phUa1."not u";'aUyfoundin

\ . . .Plant l. The :rlaule lul phiule le141

lJUeb .~s .e:rlt.lu.

-.ulph.1nie'ae id

o r :'

;.. ,,'::~i;{ f :: ::!~t::,:::/~::n:r ~::~~:;,,~::, .,

.~.,.. .... produeUouwhicheeee eedur tna the,cll_c~.rlC:·ltag. Qffrul t..ripen 1.Dg.'.'

-. ':". ": , ' . ..' .. :. ...'<' ... .. '.' .. :0<' '".'

';"~ ~. :

/:

;.;.

'

- , ;: :'/::'

^'

..

. '.:~7:k_e,n/?~" :t~, ~~hY-l.e,iia ~qd_. :th~~ '. P~.~~:c'~_~: }J: .

e.

':~1d~~~, ~:~_11:~~~: '~_~-' -",';":

pend ent:y oo.el1tn:l:aa t l on.-,---:r:c;"

> 1

' 1 i

.~

':}: J

. e . ,ud e eey . ·.. ~i .'" : "nv... ';e ;~ .~.;'h!.~1 . · '? «;y'ee.,,;oe1Y . : '~: Th . .e.. "' .'.1 r

. ~t~e~· ~roduc:t~

^.•Of.

met~lonal _~X1dll.tl.on ~eu .~ot, 1d;_tU~ed .-but

^_

.t_~e

^.ain .;'.; "'"

_;.~_

... ... ::::::.::~::;r~l:y:;.:::::,~e.,~e ~.jo<prod~f': 'OO') / . '.". ....• .t

'.\NoenzY!"Gorenl:}'1Ile

pathw~y

^.Ma y a!:.b een fou,ndwl!1.cb...ean dir e eUY· .

I :._;.:.~_' .

. :=;::~'::ht:~:e::;::::~::;v:::::::'W~':~P:~:::.::v::,::;; ^{.. . 1 11}

"·::j·:::~:e~~Z::·:, :~:~~:!t/:::1tp·:::~~:~·,·:::~:::::·~u~:tv:~:.··'~:-:: ·: ',~ ^{. ..••.. ·· J} r .. ¹

.:f't"l!G.ud1ealmed1afedr~'~t1on. r. :~ .:.:.;.~. __

....-.-.:

...

^,....... """"-'

/ •.' 'I~ ' -....i ''''":i~

'.'.'::'

: " :~)~~

/.

·· '=:~~~~~~:·~g~2.;Q": _.•. :::::~l::':;:::.:':;:~~":;::::::W:::.~:::::":::::.::::~;':~L

hYdr~:"Yl

.

~~di.cal eca~.ngen

..

inb,i~:it.ed , =;8.. 11 "'Pta~. :":';'d,,,.~b,:l.':''':a1 :1~'

•.

_~'.:

.'

~~wri.hY<tr'Olf.Yl-·r adical'·.C&v~Dg';'r·--it-wa~'"c';~cludedtha.t'methi o nalw&lI':

-. " ~<;::r~:~:':;;:L::::~:'<:.::.::;;:~,".".~", .. /.~ ~ . . ^{i 9.}

~~~ ~~r. i.~-~~_

^•.

·~~rnl ~~~~

^...

~~~r~x~d~ :_d~~.~a~e

^,.11:0'

~?~'.~i~h.i~i.t,_'~·t;:Yl~~~ ..

"", ." '. '.'. ,f o rlllAt :l.on..'Uth ia ,,,,••ul.t,101'''1'.8,10.0:beb~Ue~...:L:it.wou! d mean.tha t'the'..

. >;' _ ::tYl ~''';ol'' <0.10'0< po.~~lY ~,<.; ^{,; ..} '"; "'b~:'W~<~' ^...

^{i, ,;"}

.: ' "",

- ~. ' H'l~~ 't :~i ~·oi.'_+' mi-_.-~\/·~ · .~~-

^'·'M··

'..•. ~ _< , ^{• ..•.} _:::.', ^{. >. .} ~". ^c _". ^{,. •.} _": ^{. •..} _'>. ^{..• •. •} _::.., ^{... . ..,} _: ^. _\ ^{• ...•. • • .. ..} ,:~.: ^{, "} _.. ^.. :~u~e~_.;_~id~ r~d1~~,8 ^.. ~_~:~ ^.. u~_ed_ +~-:,th ^.. :,~~~~-~~,D .a~:·~re- ~l'll.~ ··~t.~~ll'~.a? ^'::

for:

,th~.'p~o<:luel;1.c",

^of.,

hydr~8_ p';.ro"'~

^....

:.,)~dF08en" ~e~lo.,,,~e :ls.n~~IIj,.4rY

^:

'. ;--.'~', . ':"~.::'

^"

' .:>'J \ ::".

^, ,~,^"

. .: >

^.

.:

. .. :

~';."

.:I! II.&. _ IIIiiii Illlii ...__

;O" _ _""''''·..ll'''_ _I ~,· '__'.~_<

'53

.'

: :'

' 0 .

, ..

·· ..f .

fo~

^'..

~ 'le.. t.~

^of,t...

tby1eD~ orynt·~e.~~ ·.i~.,. .t";l~ • • ~t~ •• i~

h

;.~hibitedbY!.Clo.t.~.e•.eftd.et.~t.t~,b.,.;~roaenp.r...~e.:._:.

-;.' ,;. Tb~Baber-Weu era.~t1ocr....fi1::8tpr"oPOfJ-..till1934byBaber-aDd.•

\I ::: ; :.~t:o:::~::::::::; :·~::-"::l':~:::':':: v:~ . .. ' .

:.. '·~~.t;;"';' ~o/h~';'"o;,: ·;e-;OXi,i.~uct£_ no~ invo1vl;~ ·.upe ~oXid~ ^{. .}

·.,i~.j·i~~_i. ~O'1l1~":'b~ deooO~.~ra~ed O!"" -~P~~~ibl.-' r~c~ion f~r th. i·~~t:.·t'~~~ -:

^;"1

.~

^l

'~of'hYdr~~lredic. I.could:b~ "

.' .:. ..' '.

". <.:' ., H~otl'_~:,~~i ~ ~ : OH~~>'· ~~/~-'~ :~~~:::.>

. ·c

' ., .

,:- . .

. :1.' ^...

^,,:

.:l.~" J

:

~

,' ,, ',".

. i t' ·,

. "

c.. . . ... \:

<,'>,

. ' .. \

":,., Ithas beenpro'posed (37) thstROO' tan

re~et

wi t h DPI// FrOIlf

the,

lex~,er~e~u whe,:~

DPIBF oxidati?D:wall

fo~lo:"ed

^spe;'.tro

loJomet ri call Y

';

1~. w:·~ . . ~O~Clu~ed_-.th.;~·.R~" ~~8 h~~ fo~~d .~~ ~r: 8Y8~~;

^{.\", '.}

Peroxy,radicals,ean arisl!by_another,pathway.(reactio (vi)aDd..' (Vii);"' .: .' - . ,':

l' , ' ". ' ." , \"

io-> ·s·8ti~,;~on )'·-; -:~ 'ClR! 1 ·~.. . : ... ; (~)

. ^{-'~ -} . . -· .:·. .. ^{' ;; ~ h~} . . ^{, :oo· I. .. .. . . '; (v l,)}

... Ho~m"h;. ,; 'P;1ma<y ;o<"y~.d,,,,. ;h."';'I. b~<w~,"

. ' .'. . .. . ... • ~'\~:::F~;::1:~:~:: . • ~:.t.::t::·h:::::::~::n ^{· :r·} i : • . ^{amol • . · •. ,'"}

efficientiDitiatorofin11phlteoxidation.thanl~,LAHPO. , vever a tpH.:

7'.~.:·~~~1~'~~~e8C~-e:·~8 ·~~~ei~d _~~r1~g

^{. ;}

reactio~ b'e~: ^- '~O:.~d '.:;.:"

.sulphite

but

:n~t

between'

eueeue hydroperoi!de:and'sulphite.

:,, "'

-' .

^{.' '}:," ;""" ':.,~,"' ," ",~," .;,,' . '

:

^{," ,' .}

a~,~Og~~,~~oDI,,~ke~,.-1t:~O~§~bh ~or:,t,ert.~,r.y;~~~o~~~s,~~int:e~~~t by'th~~u ll llell ~chan1811l.,. ;Tb~S1sjurt-hei'~id encethat,thes gl et

. oxfg:;:: ::::::',::~~::,:::l::i:'::i::: ~~P""r ^' <O""'C "" · " .:..

~~'

conversion,'of

~e~h~~nal' t~. B~hYl~8

^by

t~e'~'~l S;8t~

^:,,'

~>','," ^::'.:

~

^{of.'th e}'pr obi emll 8Il1l0Cia't'oo

'~1t~ lnhlb~tor',8tudiBs :l~ tJ~ i:'i~ '

^'

difficult'to

fi~

inhibit or s whic harespeciU:forone SP8c1esjASfar

I "

8S18known azide andOABCO only quenchai nglet oxygenand donot rea<:.t ... .. lIit hh;gOSYl ra4 i ce.1IiI:alkoxy

rad,!¢'l~

^{or hydrOperOXY},radicals.. The

~

lower alcoho l slIIethanol ,ethanol,propanoland butanol arethough tobe.,"

. .

^{~ .-}

' ,. ,' y

SP,~C~iC

^{hydroxy l}

~Sd.i~~l sc~~~ger,s

^.•,Theatl,tiOxid4nt a,

,B~. ~_ I'

^tIDGA

~ ':

:::::~r~,: i;~.~~g~i:' ~o ~r~~~i'_Wlt~,:~i;~~ 'pei:~Xy , ~a,d,ic~.l~::,:,:

.', ".",::',:,::,-',:'

':' ~~ , :::'

^::,::"':;"',

'.~

^{" ','} "'",,Az,ide

'~areiallY ~~~blt~,

the converdon

Of:,1II8t~,iO,~~ ,~O,',&:,:hy~e~e~ ," ',~

^..

~,:

i, ;,/n'; ~'\ ^{.•. .} in.hlbi' '~1;~T.·.:t~~i:;>:~~" 7~ht:'~.h.:."n" . .. _{~ \'I'~} ^.. _:':,;~f';~ ^{:.•.• . '.}

,:: :';; . : =• •: . .': ": --:':~'- ,

" " '" "i, '.; ::,;::'- ; "

, . .

_,1.f:,'"''

'4~?zi;giaiw£a:is -= = ^sii~~

· --:."

-

-.

.' . .

t~e pr~uct1.cinof';I n'g l e toxygenJ.frd l;'t he·bYdt~perO:dde;:'DABCO.beh~vell

. . ' . ,. . ' '. . " " .... ':

'

in a-8tml~ar lIUl.~ner .,_Thel:e.fo~~siogl e,t"oJtYgeJi ,,:eac ts..w,lth methi ODal.t~

:jlr'odu ceethyl~ne:^{bu t.bo o t'to tally}'responl1 blefor:ethyl~8a~th~s:b^•.

BHA, NDGAand pr"opyl gallAte a18'0'pa r tiallyinh,ib1t~ethylene f~rina.tion'^:

" ~OD~'lrmi~g ~~'LhyPo~hea1s th~i ~itigiet'~~~en ^does deriy~ frollht'~e··h~ro-.

·~~~~x~e. , ; ~thoxy~uin:_ l.S

^a

fa~ ~~tter ~~~bltcir 'o:f -e~h~'l~e fC?~tlori

" . ;~j,:':,::~:::.:h;:;::::~:a::;:::,r:o;:::::·::bi~::::·:a;:;:~':~ : , ;' '

.o t her:spe Cieslnd,!~ed,~8ul~IIHeoXldat1on.. .

""' ,

nKM~

and lllethional

~n

^b.oth'be

ui::l.1:l.zed'b~.Yang 's

^{Diodel srteIU.:} ,(Si) andour model

B~8tem

to produce'ethy lene.

Meth:fO,nJ.n~·'can

^be'con- .'vertedto aXHBA. euymically(7)

a~ 'it

^re

:~~S~~b1e t~~'-'~e~hionin~.c~id

.-.aiaobe ecnverced.to D!stlJiona1,enz'!Jlically ,.There

i~e

^aeveralother waysin";h i c h lIlethioninecouldbecODver~edto mettllonal.

.,

^' .' ".,.. "

It has J;ecentlybeensh own·tha t· lIIet h i onln e can,beconv ert edto

::, ,

.. . .

^{, .' . ", ' ."}

llIsth:l.cinalwhen lillffiower,oH'18'1?-eated ,b r i efl y to200°C.(s'4'):'.Thill traatille~t pr~vent&'fu rthet.'.autoxidadon

of .

thef~tty^{ae'ids :} Het:h{~nai':

vasshown to be the

~ent ac.t1n~ a~

^an

aPtioll;,id;nt ~ ~e~in8 ~e'th iOnine

.vit.h soyebea u'pr ot e i n'als~re s ulte1n';th e fotm8.tiOn,'of.m.eihional(55),

..: : ::0 '::;::~::~~:::' .:::::.:::' ,~::::~:f.::::': ;,:h::::~" '

ly z e.the.~~ction'

ImM

..a_t,he'Str~~ker~'degred~tlo:n(see Figure~Q),

'.

. ....

<.

's ubstr a t e' ,_NeitherhydrOXyl'ra1:!-cals"n~r"S1ngiet·oxYgen,ca nr~act';ftb .~:~

----

_..ll1et,h,io~ine^" ~,t o give ethylene^." .'The LAHPO,

..

sulphite. reacti~n

.

^{, ,'}cannot con,-

vert,methionineto'ethylenesopr e s umab l yROO~ a~d

ao-

'can~o~react with'

.methionine.to produceet hylene,

,Seve J:alc ompou nd sbave beell.;~~ested⁸⁸intermedi~t~si~^{th epa t h -}"".

way fr<!;""

methill~in~

toet h y l e n e:•

a.nmA waa~

cine

PJ:Opo8ed ,inte~e.dillte

and this

POS~ibi1,~ty

^wu

,discus~e~

^{in the}

intr~d~C~:l.on' Anoth~~

^suggcst.ed

'int e rme d iatewasS-a d e n os Ylme t h1on i ne. This was's\1ggested.b1Yang in

'.'

^.

.

^'.

.

1974(44). Ysng proposedthatS-a d e nos y lllie th 1o nin ewasbroken down by a pyridoxal

pho~phate dependent y"'~l1m1~~i:'1~n react1~~'~h1ch

^ale;

',r~-

q~1." OX"... · . t . . .

^<

.. ""-~•.•• ••4. ....J>...

Ther e a;etwo

P05~ible'~planitiOn~

whyL.AHroandsu.l ph i te

d id

'n ot

. •~..' .; ..;' '.. .'..:..',..'. ." ,-'.. • ', ' ,••1• , . '..

:· c,o.nv~rt. m~~hiooine,to .eth~lene. '.E,~~h~~~~ br~~o,'~id,DO~-, . lead toth'e·f o-m:at i·on.of

PtOd.uc:t~' Vith.the'ac~i'Ve g~oup ~t

^{.t h e}

lUtUo~ine

;,;8 ,.~~nv~rted,Ilain~y '~o: th'/8~i.P~Oxidt

^•

.Ii··simll~rreactions.occur when:,.et h yleoe'ia~einkf0r,medthe~·1.p1d

.'~er.oxtdes(preswnably,l oea t d.iri"theai~brane~)^{wil l firiit.}hQ~.^tobriak

d~

^{t'o the}

.·~~poundii ~o~taiidn~ '~he"~~~~p ~pabl~

^of

"C~~'s~;ziitg·s

^.

. . :.~t~'~~ke:~:'

^'d.

~~.~.~~t.~~n:,:.:.~The6e,:~~e~.~~~~:'WOU~~ ~: t !, ·.-~~ff~~~·.'i~ti. 'f~~ ' ~yt~.~

p~aslll, of.the'~~1l.wheret;h~ycclul d.catal~lI~th e.conversion

pf

Ulet hi o n ilie