San Jose State University

From the SelectedWorks of Juana Vivó Acrivos

1955

Study of the Complex Products of Polymerizationof some Quinones by ESR SpectroscopyJuana Vivó Acrivos, San José State UniversityM S Blois

Available at: https://works.bepress.com/juana_acrivos/126/

srvtrt or ·r H ; COMl'L X O CT.; t)f }10L 0 8-0 {'UtlONi:S DY ma snx:: SCtll'Y

OUD · Tl OS PllGl>CC O P OLS . D 0-D TUBIR aa.A.TlON '\ • tua.J..

orlw•

I. l9\[94uetigpThe i.t.ction of t.be co r-1,11'ot i ea J1U& fiuecl b7 on1 • the

ft he ol1o1 e C lex" � i.be ne1·t.urally oc.ourriag phea la nd dil)hen.oh1 lead•

i.o ihe for· i1on t • aorre•po di , o-diqula�nea. eae in turn u.re t.he

U• in t.he ro t.ion o auo n�turl\l pol:,11era • elasain qd

io l ra di ra fo ed

in the ut.o 4 t.ioa of e p-benzoquiao i . .i line •ol tiou been

at.u t.S ,-2 a f MU ai,eot.roaoop7 • 'fbe following 1 t.udy of t •

free r die la pro uced lo. U1e e <AJfl)e OOl« • ut-o-oxi �ion of a, Lf -

�ihyci 01.1pho117l'-'lUi 1 •• 'l'b. pro r ie ot tt e i'U ''iOiQ.11:, prod ed.

alt1 iue re c WI' 1 •

11.

'PR a reflection c Tit7 coueot.ecl

t.o a icro n bl-id -e •1 d per t.e 1 t • 3 wo.e ua din tho

preae t. at.udy.

T ox reaaion of the rea nee tlol tor tbo llowed. � LUit\ tr�ui-

tioo• tro t, field lJrei

(a.1)

llere R0 i• t-ho oent.r t the a�ctrw.n (110 • h I.I/ f.I)l(1 ). Y-1 l•

aea.aure of th• "•pl.a deaaU,7° t t.he 1 1 atom in t.be ol�cule ,rbiob

poaa.ea.aee on-zero nuclear apin 11• ln the recent or Miic free

n.tlioala, we fin4 t.taat. '1le c-,oaeat, elemoa'8 '\Ji:t.b aoa-ae,o miolear

•aaeue momenta an 111 ad •14• Their res,eotAve aplu are 1 a 1/1

alUI I. fte mauaer in wbiob tdle epeot,ra o,ro int.erFet.ed was 4ieoused

elsewbero.8 Also, t.he rolo.Uve apia derwi'1 ot. t.ho anmt.io rio.g poaiUGB

pvu a mea.�ue ol 6be .--cUvltq oft.he given site•

111. Pol,mel'ieatioa pro4aeta of a,4 Dih7dros,pbeo,laaJne in ta&sio111,v.e .1 ,.

!be tree ndioal r.eactlon eobeme oouiderotl is f.he followlqo The bis ot Use ISB apeotrum or (ll) abou14 consist. ot 14(8 x a8) linaP-

tiao eomponenu duo t,o Use lat.eraot.ioaa of' Use uapt,ind eleewon vitb t.!KI

pro\ons ia t.be CB1 poop ol Wle Gllaim at._.ed t,o t-he riq at. position I ca4

t.hose �• t.be rlag po1Bi'1ou a, a, end a. la a t,uic eolutJ.oa of DGPA oao

oltsonee a_itmllt.;u1eoul7 tlte BSB s,eet.nm or thNe rdioala so trro.t. tho line

aseigament. is no, simple. file ER apect-rma of ll ia roaotJ.a a.1 ia ldoati•

lied by ,oo no eavemo ate of eigbt, liaes ot eq1!$l aat,enai•y olfflervecl. The

cnwr of �e speetftttm is coafuiDS t,eouee of tile &ppeanaoe of t.he et.Iler

t.wo r&dioala. fbe total spU. t,ttlas for Mlie lint, radical ia a.a oa. TJao �

olhea' two tree htll•o.la uve muoh mnaller tow eplitUasa of a.o oatl a 1.,oe.

see ftgraN (a.1). We lsoow .._, the liaaa obsoned belODS ·to at. leaat. tb"8

different speoua beoo.aee duo t.o e amall tlifleftllee ,a a-taewrs �he eeat.ars

of a,mmGvY do not. ooinoide and beta.use the relative liae ia'81lait.y rat4os

var, witeb t,tme MUI Uae va1 the solut.iona arre prepare4. la oner tte i4eat4fF

the tree radioale-preeeot., we wUl et.udy t.he &,& apootra of aome eabsftit.ut.84

&,G-dtb7dro3f'iadolca.

file d17 BOPA-eelQGf.a no eeputGt.ed from t.be eu;vme eatel,ze4 aoa\ral

aoluUou menUoned allove. Thie mteri@.l la also po.r�Uo. fbe

-a ..

eapl�a��a tor fthls is Ula' h'oe htieal faet.iou llo.vo beGII oaplured ie tbG

aolAcl awuotAlfo et t.he polymer.

fhe aaWftl molaralc .... as a\adiett ta �id iafl an4 moaae molW10tD4

-­

�s uot, eabU,it, oa ma o.bsorpt.ton ulta \ho tissue were it. la found le

dried la a van.um of a 18-8 mm. of Ila• Nevort.holess, lfheu t,he me1ania is

U.berat.ed from tu t.ieaao in an oqgon "tmospbere a ver, :owcmg rl1R &IJatH'pt.-. 8 ioa i.o .t(l,uwl fort.ho dried ,omter. Haeon baa �port.Gd" higher coat.ea, of

'1le "phenolose oomplex" eaa,me io tissues conid.t.lnlaa t1101Mta. At, ·tdte Ume

the ateltAaln iB ro18fMled ftroa, the t,iaaue so the acm,me uill be roleaacd. 'fhus,

it. will be trff t,o aot, on tho auuvat.e prctaent. t,httough a. tree rtlti.ioo.1 tSGOh­

Qllisa almllar h react.Aon a.1. It, u.ppeav0 t,ha, tibe ttoe h410G1 iAitermeiH.&.'88

hoame W4'ppcd la t,he 1�1.,1ce of tJhe melud.a polyme_. a.ad ere Uau skhillze4.

'llte int,oneit,y ot t,he 1'3 Quur-1•Uoa is not. \\ffectff by dy&lisle of the bleek

powcle••

There is• iaUCC\tlon that. t.be above free r"dtoe.le a.re t.ra.pped int.he

surfr.ee of .... polJ'llOV• The 1':SR tAbsorpt,ion iatensi t,y la tt91,endent, OD t&o

e«&uilihrium os.,1011 fNS@\Wao .. \lt.hough u. satunt.!en of all the liaee ehdied

lw.s bees ebael'V'Gd, ibo rolat,iw ;lat,easitJ.es of mm altsfJttpt.ion were reoordod

at, a micl'OV&ve ,over or �v o.s mw. 1 were no eaiwr&,lon !a observe.cl. Ao a

et,aodud, a stV&ple of Use tree n.eliO!i»l IIDPP.A.8

ffiiS used. At. &tmoapberio

os.,sen preestlNls t.be .tffll ah&or�tiea inMDS!t,y is a,prox:lai.\ely ball u etrroas

ea t,bo,4' o., oqdlilWiutD pressures of 10-G mm. of Bg. The proooso ie

oomplot.ely reversible e�d s. 5!!9!!oor1tlg of oxypa on t.ho aurt"co will

aoeoun\ rer the oeuvalia&t4oa of tho splns1

.. 4 -

(I.I).

la �ple1 tllis u.dio.'8s 1. ldmolenlor reanloa of we 4iffeNmt;

Mlooulee -.,.._fled ee 1'e utelma&a ••• tbwdon; Mae i'Oeot.loa eeeme· (I.I) ·

____ ·;·----� $a_�h.ui!!;�L ____ ..;_,_ __ _....._::.-, ·-_.:...... .. � -------------

Synthetic�hydro�Y p�polymers

Natural Melanin 3,4- 4.

A.

Dried in the absence of air

B.Releasedfrom tissueand dried 1

L

in air(�

�)c.s amples B

degassed at-6 10 mm. Hg.

D.D 1 . eco or1.-zing of free radical DPPH

Squid Ink1 ' 2

Small ESR absorption (pressumably due to poor vacuum)

Strong ESR absorption

.ESR absorption 2x that of B.

2 3 -i Dihydroxy'

I pheyl- 1-�inophenolMouse Melanoma , 1 .

�i a a.nine 1-·--

No ESR abxorp­

tion when dried at710-6 mm. Hg.

(+)ESR absorption

A. does not

B. does

I

I

1

I

Pol. with Auto-enzyme I OXide in ESR abs. basic soln.

ESR abs. > 2x .Jj

ESR abs.

ESR abs. "> 2x .6

does decolor-ize i>ffM

•

�-----------·-----... -------- - ---- -- ----·----

1. Comm.oner, B., Townsend, J. and Pake, G., Nature, 174, 689 (1954).

2. Vivo'- Acrivos, J. L. and Blois, M.S., Stanford University,Hansen-Biophysics Laboratories.

3. Harding .. Passey, Mouse m�a.noma..

4. Mason, H., Advances in Enzymology, ll, 105, (1955).

H H

HO,o

/CH2,�J /COOH HO,o

/CH2., I /COOH

I C -H

I C

I ENZYME_,,, I HO/'- NH

2OR AUTO- 0.; • NH

2

:0:

]I[

. OXIDATION

(I) (][)

(]I[)

(Tir)

Tn" -CO2 ..I.L -SLOW

--�- MELANIN POLYMER

(3.1)

2 H0,0

13-H • -H

AUTO- .., AUTO-OXIDATION Q �6 .#

4 OXIDATION5

o�

o 0� �

Ir+ m

DZ' + I[[

c n >

2H 0,1� • 3

s I � "°OH

( lY)

� .

H0

,0 '" -9' � '- � ,......oH

o I

HO/�

( Y)

HO'

O

� .

0� h'

0/

0H

HO'

O

'OH � I

HO/ ( 3ZI)

c m >

3."L