SCIENTIFIC ABSTRACT YEVSTIGNEYEV, V. B. - YEVSTIGNEYEV, YE. I.

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• Content Type: SCIENTIFIC ABSTRACT

IVY
20-5-4/60
AUTHOR YEVSTIGNEYEV V.B. and GAVRILCVA '.V,A
0 a ~iai;;~e4e, Pri Phr tor~ducq
TITZE mar3 0 d Form of
Chlorophyll and its Analoguos.
(0 prirode pervichnoy fotovosstanovlennoy formy khlorofilla
i yego analogov.r Russian)
PZRIODZCIL Doklady Akademil Nauk SSSR 19571 Vol 1141 lir 5,,
pp 1066-1069 (U.S.S.R.)
ABSTRACT In laboratory wo:& (sea "A-0 belovO it was shown that
on illumin4tion of solutions of chlorophyll and its
analogues which contain a reducing substance the potential
of an inert metal electrode,shifts in negative direction
when immerged in the solution. This is connected with the
occurrence in the solution,of a labile, electrode-aotive,
primary reduced form of.pigpent. In the case of the pheophy-
tins, In which this form proved to be more stable than In
others of the pigments inveistigated-the absorption spectrum
of this form could successfully be recorded at low tempera-
ture. It posseases a flat absorption maximum within the
range of 470-500 Prs, It was deaonetrated -that the seast-
tivation roaotions of the oeries of oxidioing-reduaing
reactions through chloroph;r1l. or its analogues Vasa a
CARD 1/4

20-5-41/60
On the Nature of the Primary Photoreduced 7orm of
Chlorophyll and its Analogues.
stage of formation of the primary reduced forms It is
ionized. The nature of this form and its relationship with
the secondary reduced red form of the same pigments has not
been fully.explained. In order to obtain experimental
material on this problem a number of experiments with
ap ligation of spectral and,oleatrometrio methods was per-
forriod. Pig.1 shows the altarations of potex)~;kal of the
platinum electrode in a solution of chloraphy',' and
-oheophytin iii. p:rri(line- -on illumination of the.' aolution in
60uum..In boO oases the potential rises-a-g-ain after an-
initial deor4ase. Within a:few minutes it attains a level
of equilibriuln which is deltermined by the content of the
primdry reduced form, In siritching off the ligth the poteatp'-
al decrease to the Initialilevel or farther. The explana-
tidn has to be sought in t'he further alteration of the
primary form or In its conversion to the secondaty one
which possesses no electrode-sotivityl or in the decrease
in activity of the primary form itself as a consequence of
e.g. interaotiou with the solvent or reducing agent. Both
factors may exert influenoe here. The conclusion on the
change of the primary foratt as shown in fig.29 is correct.
EARM The position of the minimum of the curve depends on

20-5-41/60
On the Nature of the Primary Photoreduced Form of
Chlorophyll and its Analogues.
chlorophyll concentrations As it Is Impossible to cite
all test results here,~the authors only point out that
the electrometric measurements under different conditions
agree with the above-mentioned assumptions. The absence
of elootrode-activity In the secondary reduced form in
directly confirmed by tote in vacuum by youring phaeophy-
tine solution to the electrode. Fig-3 shows the tegst
results on the influenoe of low temperatures (-10.0 ) on
the-formatior.,apeed of the-primary photoreduced form of phae.
speed- Of L- tj
ophyt, Thal -progress- staye the
reduction
aame at -1 OOi-, -60 and 2Q C,'Irurther the speed_of the In-
verse reaction wais examined.at-the same temparatures and lis
darkness. In the case of phaeophytine at -20 0 the tuvqrse
reaotio7a prooeeds so alowly that the course of the curve
cannot be influenced during the short duration of the
test. Therefore the resiotion speed-le fully determined by
the apead of the direct reaction. This evidently proyea
that the formation of the primarily photoreduced form
CARD 3/4

20-5,41/60
On the Nature of.the Primary Photoreduced Form of
Chlorophyll and its Analogues.
represents a mer,e photoahemloal procedure - transition of
an electron from the donor (reduction substance) to the
pigment molecule activated by light. The primary form is
very capable of reaction, electrode-aotival possesses a
high reducing potential and a molecule charge. All this
indicated.that It is probably a compound of the type of
an ionized free radical - the semiquinones The red photo
reduced form apparenttr is a further alteration product
of the primary form by addition of a proton. Whether this
takes place directly by addition of the ionized semiquinono
or by dismutation is still uncertain.
(3 fig-, 11 Slavic reforen6es)
ASSOCIATION: "An.H. BAM" Institute for biochemistry of the Academy of
Soiencesof the USSR,
(Institut biQkhomii im.A.Y. Bakha Akademii nauk SSSR)
PRMZI(71;D BY: Axa(. TERMrIfft member of the Academy.
SVWiITTSD.- 20.12-56
AVAILABLE: Library of Congress.
CM 4/4

Vj L/ /3.
20-3-30/59
.AUTHORS Yevatigrneyevf Y.B., Gavrilova, T.A.
-TITLE __T_he-_N_a_tu-rt__of -the -Primary Light Reduced Form of Chlorophyll and it-S
Analbgueetas Investigated by the Use of D20.
(Issledovaniye prirody perviohnoy fotovosstanoylennoy formy khloro-
fills, i yego analogoy s primeneniyen D O.-Ruasian)
PERIODICAL Doklady Akademii 11auk SSSR,1957ty0l Ili ,Hr 3,pp 53o-533 (U.S.S.R.)
ABSTRACT The data given in former reports prove that the primary light re-
duoed form of chlorophyll and its analogues discovered by the au-
thor which are the first light reduced stago of these pigments ara
according to their nature a free radical,i.e. an ionized semiquinote.
It is formed by electron transfer from the reducing substance to
the long-lived excited biradioal pigment form.The question whether
the formation of the primary reduced form is really only the result
of the electron transfer to the pigment or whether a proton is also
taking part here,can,however,not be considered as definitely solved.
By simplifying the system the following 2 reaction series can be
realized on the occasion of the light reduction of clorophyll and
bits analogues.They contain the formation of the primary reduction
product with properties which were discovered in former investiga-
V
Chl + RH2 Chl +RH2 _----~.ChlH + Ra,
ChlV + RH2 ----- ) Ohl-+ RH ------ ~ ChlN2 + R.
Chl -chlorophyll in the biradical state,HH2-the reducing substance,
.Card 1 3 and Ohl -the primary and secondary forms.For the purpose of a do-

The Mature'of t~e.Frimary Light Reduced Form of. 59,
Chlorophyll and itB Analoguestas Investigated by the Use of D20'
finite solution of the question as to which series of these reac-
tions has to be preferred in every-case with reference to the form-
ation of the primary reduced foralthe authors decided to use the
well-known kinetic method which is based upon the substitution of
the unstable hydrogen (H) by deuterium(D). Illustration I shows the
in.fluence of the substitution of H by D in ascorbic acid on the Ye-
______l4_city of formation of the primary and secondary reduced pheophy-
tin -a- forms.The me-nt io-ne-d-siubs t_ituV16Vdoo,j-not--e low-down- this--
.21 reac *on,on 't a contrary i --, al -In
t t ightl rates the reaction.,.
y;:aqce A
contra.0 to that the substitution of HpO by D20-81dwo'dOwn-the ve-
locity-';'^of the appearance of the red reduced form to a griAt extent.
The.transition of the primary reduced pheophytin product was pro-
ved by the direct experiment, (fig.2).Thua the results of the use
Of D20 are absolutely against participation of the proton in the
formation of the primary reduced form,in-contrast to the formation
of thelsecondary reduced form.The latter-is formed by the primary
photo-ohemioal electron transfer from thLi reducing substance to the
pigme4t which is in the long-lived excit.-ad, stat a_.The electron con-
neotion. obviously takes part at an.,arbitrary- place of the system of:
conjugated bindings~whioh considerably ohange8'the abcorption spec-
trum of the pigment and makes it indistinct.Thc secorCary reduced
Card 2/3 form is obyiously a result of a further proton connection.The absoxpl-

20-3-30/59
the Nature of the Primary Light Reduced form of Chloro-
phyll and its Ana,logues,as Investigated by the Use of D20.
tion SDectrum becomes more discrete though it differs from the spec-
trum, oi the initial pigmeni. The use of D20 permitted the repeated
confirmation that the red-violet reduced compound which develops on
the occasion Of the light reduction of phtaloyanine. Inspite of its
instability represents the secondary reduced formpsince its veloci.-
ty of formation,espeoially that of the regressive reaction#deoreas-
es in the case of the substitution of H by D in the reduoting sub-
stance. There are 3 illustrations and 8 Slavic references.
LSSOCIATION Institute for Biochemistry "A.H.Bakh"of the A.M. of theU.S.S.R.
(Institut biokhimii im.A.N.Bakha Akademii Nauk SSSR)
FRESENTSD By TereninpA.H. Member of the Academyj, K=ch 2,, 1957
SUBMITTED February 22,1957
AVAILABLE Library of Congress.
Card 3/3

YNYSTIGNOW. V.B..,. GAVRIWYA, V.A., RnAW, ff.D.
Changes in the -oxidation-reduction potential off leef ho=cgenates
(ngreen suspension") Induced by light [with au=ary In Fingliehle
Blokhlmila 23 no~6sfth_834 N-D 158 (MIRA 11:12)
1. Inatitut biokhimii imeni A.N& Bakha AN SSSR, Koakwao'
(PLOTS, BMCT OF LIGHT CH)
(OXIDATICY-MUGTION REACTION)
(CHLOROPHYLL)

AUTHOR: Yevstigneyev. 76-32-5-1/47
TITLE: The Mechmnism of'the Photoreduction of Chlorophyll and Its
Sensitizing Effect-(Mekhanizm fotovosstanovIeniya khlorofilla
i yego sensibiliziruyushchego deystviya)
PERIODICAL: Zhurnal fizicheskoy khimii, 1958, Vol~ 32, Nr 5, pp. 969-980
-(USSR)
ABSTRACT i The investigations by A~ A,, Kraenovskiy based on a work by
K. A~ Timiryazov (Ref 4),and carried out at the Laboratory
of Photochemistry under the direction of A. 11. Terenin,
Member, Academy of Sciences, USSR, showed that chlorophyll
in solution cenbe reversibly photoreduced by ascorbic acid
and other dienol compounds; on this occasion a relatively
stable reduced red form of this pigment is formed which has
a higher reduction poteniial and in the dark reconverts into
its initial form especially on,the addition of an oxidizing
agent. In further works by A. A. Krasnovskiy a similar reacj.-
fLon was observed in the case of compounds of an analogous
structure of the ohloropbyll, as, howeTert the investiga,-
tLon results are incomplete, the present work carried out viih !he
collaborat1o_n_by-V.--A-.-- Gavrilova is-devoted- to the darif
Card 1/4 jion of the reaction mechanism as well as to the investigatioa

The Mechanism of the Photoreduction of Chlorophyll and Its 76-32-5-1/47
SeAsitizing Effect
Card 2/4
of perhaps occurring intermediate products. The spectropho-
tometric investigations carriod out showed that the photo-
chemical velocity of reduction of chlorophylls and pheophyt-
'ines in pyridin with ascorbio acid, and in toluene with phen-
Ylhydrazine increases steadily with the concentration of the
reducing agent, which fact points at a dependence on the pro-
bability of collision of the reaction molecules. A temperature
drop to -400. effected a practical otandstill of the formation
reaction of the red modification, while an exchange of hydro-
en by deuterium in the reduct:Lnglagent showed. that the fQrma,.-
g
on of the red reduced form of chlorophyll as well as of pheo-
phyti ne.is no pitre photochemical reaction but a stage of the
prdon transfer in the darks Continuing the worksby Timiryazer
(Ref 4) it was found that the reduction process in the dark
with zinc and-the photochemical onein the light lead to the
same products. Corresponding to the experimental results of
the pbtentiometria-experiments it is assumed that-a primary
form of the photoreduction develops before the formation of
the red modification and that it produced a remarkable re-
action on the electrode, this intermediate product having
been more stable with analcgw3containing no magnesium than

The Meohanism of the Photoreduction of-chlorop4rl! and its 76-32-5-1/47
Sansitizing Effect
with magnesium -containing ones; -it -was also found that its
formation can be espedally well observed at low temperatures.
On heating, thia forin converts partly to chlorophyll and part-
ly to the red reduction foria, while an addition of hydrogen
acceptors also-in the case of lo)w temperatures causes a re-forma-
the initiel pigment, whi,ah fact distinguishes this
form fiom the-secondary-re u 'a-form -,jua+,as_well_as_.thq
observation that-in the case of_t,hydrogen-deu terfum exchange
no change takesplace; and that there is proof that hydrogen
does not take part i*he formation reaction, Conductomettic
measurements showed that this pr,imary reduction form is an
ionized one and that it has a chaxge which fact also di-
stinguishes it from the secondar;r form and leads to the as-
~sumption-that it-is a free radical of the type of an ionized
semiquinone~ Ascheme of-the reversible photoreduction of
chlorophyll and its analcgics is given as well as explanations
concerning the'me-chanism of the ~hotosensibilization of chlo-
rophyll in redo= reactions in solutions serving as experimen-
tal basis for investigations of 'the effect in the living leaf,
Card 3/4 and where the electrochemical methods used for the first time

The Mechanism ofthe Photoreduction of Chlorophyll and Its 76-32-5-1/47
Aiensitizing Sffect..
__oAn also -be-- applied -successfully inAnveatigations of.:photo-
chemical reactions of other d7es. Pinally the author thanks
-A ' N Terenin, Member, Aoademy_of~Soiencest USSR,,and Profes,,:-
.5or A. A. Krasnovskiy for their interest in this work.
There--are 9 figures and 29 referenoes,-28 of which are
Soviet.
ASSOCIATION: A-kademiya nauk SSSR IInstitut biokhimii im,, A. N. Bakha
(Institute of -Biochedstry imeni A. N. Bakh )AS USSI-t)
SUBMITTIRD: February 3, 1956
2
Chlorophylls--Photochemical reactions Chlorophylls-
Photosensitivity 3. Ch-loropttylls-Test reaults
4. Spectrogrkphi-c analysis
0 ard

AUTHO',RS: Yevstigneyevj V. B.j Gavrilova, V. A. 2()_U8_,6.27/43
--------------------
TITIE: On the Original Reduced Form of Some Cozpox:ds aellatoeed to
Chlorophyll
(0 pervichnoy vosstanovlennoy forma nekatorykh rodstvennykh
khlorofillugoyedineniy)
PERIODICAL: Doklady Akademii Mauk SSSR, 1958, Vol. 118, Mr 6,
pp- 1146-1149 (USSR).,.
Y
ABSTRACT. The photochemical reduction of chlorophyll and pheophytin
taking place in 2 stages was proved in previous elaborate
investigations:by the authors (references la to 3), The first
stage leads to the original reduced form of the pigment. It has
the properties of a free radical, Viz. of semiquinone. This is
---achieved by-the--photochamical-trALnsfer--6f -an-electron- from the
reducer to the pigment-Frotopheophytin, bacteriopheophy-ti -n-afid_
haematoporphyrin which are capable of reversible reduction at
room_temperature~ were investigated in this report (references
3,4). The authors selected magnesiumfree compounds for spectro=.
graphical investigations, because they hoped the reduced fOr-Mu-
Card 1/4 would be-:-more.stable (references 2s1 v). The previously described

On the Original Reduced Form of Some Compounds Related 20-13B-6-27/43
to Chlorophyll
method (reference 1,2) wad applied for the determination of
the unstable reduced form, viz. spectrophotometry at low tem-
peratures, A more complete spectrum of absorption of the oriz
ginal reduced pheophytin-form a.-than given in reference 1 v,
isi given in figure 1. A comparison of these two spectra is gi=
ven. The yellow-greenish initial coloring changes rapidly to a
red coloring b y the illumination of an evacuated protopbeophytin-
solution containing ascorbic acid in pyridine, at - 4ooc. The
product of the reduction has a rather characteristic spectrum
of absorption (figure 2) with a small maximum at 64o m6A, two
maxima within the range of 55o - 555 and 520 m 6t , a pronounced
maximum at 46o m && and a flat maximum at 4oo m 6A_ The product
oc.
is apparently rather stable under anaerobic conditions at - 4o
When air is let in, and the, product is, shake~L) the spectrum
returns instantly-to the initial state, but it preserves reversi4-
btlity very well. It reacts as quickly with safranine, riboflavin
and several other dyes. The photoreduced solution becomes. greenivh-
yellow by heating up to room-temperature. It is seen from the spec=
trum that the red product passes, aver partly into the initial pifr,=
Card 2/4 meInt (figure,2). From these properties it may be concluded that

On the original Reduced Form of Some Compounds Related to
Chlorophyll
20-118-6-27/43
the red product represents a previously un)mown form of proto-
pheophytin. Bacteriopheophytin was (very) rapidly reduced at low
temperature and led usually to yellow, relatively' dtable,prcauats
of a deep-going reduction of apparently partly destructive characr-
ter, An unstable intermediate product was observed more clearly
when,,phenylhydrazine was used al reducers The spectrum could be
plotted only'approximately4 A maximum of absorption at 64o m 6&
,exists there#' In;the dirkness it passes already at low temperature
.partly over Into the Lnitial pigment, partly into the secondary
yellowish reduced product without'visible maxima. Also the exi=
c,tence of the'unstable original reduced form of haematoporphyrine
was proved. Due to a white illumination of the'pyridin-solution
in the presence of ascorbic*acid, the pink coloring changed rapidly
into orangei-yelloir at -4olDc.'The ~maxima of the initial pigment
decreasing due to the photoreduction- aria the increasing absorp-
tion 'within the range &f about 46o m 6~'~are given in figure 3.
An illumination lasting morE_ than 3o seconds had no further
effect since a state of equilibriun was apparently attained. The
admission of air or the addition of other electron-acceptors.
Card 3/4 shows the same effect as'with pheophytin. Also beating shows the,

On the OH47,inal Reduced Form of Some Compounds Related
to Ohlorophyll
ASSOCIATION:
TMEN=.*
SUBMITTEM:
Card 4/4
20-118..6-27/43
same effects. It may.be assumed that the unstabLe product, is
semi4hinone.'The conception that the electron-connection takes-
place initiallyat,the place ot the-inain system of the conjugated
compounds~and that it.destroys.this:system (reference 3), is
confiimed,by the results-'of-this' elaborate investigation. The
lacking or the presence of metal in the center of the molecule
.is 'O-f great importance for the kinetics of reduction. The replace-
ment of )ikdrogen-by magne6ium'increases the instability of the
initial reduced form of pigment*and consequently, the capability
of the initial pigment for.rapid cyclic oxidational reductive cone
,versions.
There are 3 figures, and 5 references., 4 of which are Slavic.
Institute for Biochemistry imeniA.N.Bakl-~ Ad USSR
I .(Ins~titut tiokhimii im. Ao'N.-Bakha Akademii nauk SSSR)
~iovember'4, 1957, by.A. N.-Terenins Academician.
November 1. 1957.

11JTHOESs Yevstigneyev, V. B., Gavrilova, V. A. 20-119-1-34/52
TITIZo An Investigation of Some Problems Concerning the Mechanism of
Sensitization of Red*oi Reactions by Chlorophyll and Its.

Analogues With the;
-Use of D20,(Issledovaniye nekotorykh
voprosov mekhanizma sensibilizataii okislitellno-
vosetanoviieVnikh reaktaiy khlorofillom i yego analogami, a,
primeneniyem %0)
PERIODICALs Doklady Akademli Nauk SSSRq 1958,'Vol.
119, Nr
1,
.
.
pp. 125-128 (USSR)
ABSTRACT s In papers (references 1-4, 8b) it was proved that the
sensitization mentioned in the title in solutions includes a
stage of the formation of a labile pro-reduced form of the
sensitizer-pigment which is'followed.by a reaction of this
form with an oxidizer. According to the existing data-
(keferenoev:M) an original (primary) photoreduosd form
which a0cording to its nature is an ionized somiquinone
(references -5,6) servps as this reduced intermediate product.
A high reactivity of-this latter form makes assume that the
secondary protonfo-torm (references 1,4) of the pigment does
Ca:rd .1/ 5 oh'Ahis occasion not find time for formation - in any case

An. jave stAgation. of Some Problems Concerning the Mechanism of 20-119-1-34/52
Sensitization of-Redox: Reactions by Chlorophyll and Its
AWLlOgUeQ. With the Use of D20
not in quantities which can play a part;worth mentioning. A
simple scheme of the possible-5-partial chemical reactions
..in the above-mentioned sensitization is given. The oxidized
reducer can form by the series of reactions 1,20, or IP4,5*
This reaction mainly takes place according to reactions'1,2,3*
Wfien:'reactions 4 and 5 p~&y a part 'at all, then it is i
minor one..In view of the fundamental importance of the
mechaniA, under., -review. the authors wanted to obtain additional
experimental material on it. In this paper they investigate
the influence' of the substitution of the labile hydrogen in
the reducer by deuterium,upon the velocity of the photo-
reduction of the azo dye in pyri 'dine which waa sensitized
by chlorophyll or its analogues. As was proved earlier (ref..7)
such a substitution of H by D,does not act upon the-formation,
velocity of the primary photoreduced pigment'form. But the
formation of the reduced protori-form (references TO) is
strongly slowed down (twice or more). It could therefore be
hoped that the use of D 0 would help to obtain valuable-
2
material with regard to the-mechaniam of sensitization.
dard -2/ 5 a + b- and a, b- chlorophyll-solutions, a-pheophytine- amd-

An Investigation of Some Problems Concerning the Mechanism of 20-119-1-34/~2
Sensitization of Redox Reactions by Chlorophyll and Its
Analogues With the Use of D20
,magnesium-phthalocyanate in pyridine (about io-5 Mol/liter)
were
used. Ascorbic acid and hydrochloric pheny1hydrazine
2
(lo- - 1o-3 Mol/liter) were used as reducer. Methyl red was
used as hydrogen-electron-acceptor. The velocities of the
sensitized reduction of the acceptor under illumination (with
the exclusion of oxygen) by light that is only absorbed by
the sensitizer-dye (light filter Rg-5) were compared, where
10% H 0 ot D 0 was added to pyridine. Figure 1 shows the
2
resuli of an
experiment in diagram form. The difference of the
reaction velocity in the presence Of H20 and D20 was smAll.
The chief material is given in table 1. No dependence of the
experimental results on the change of.the quantity of the
reducer (ascorbic acid-or pheny1hydrazine) or on the
intensity and time of illumination could hitherto be
determined. From the figures of the last lirie of table I
clearly follows that such a retardation of the read-cion which
takes place in the.case of a substitution of H by D in the
reducer during the formation reaction of the secondary
Carl 3/5 reduced form (40-50%) (references 7,8) does not take place

An Investigati on of Some Prohlems Concerning the Mechanism of,20-119-1-34/52
Sensitization of Redox Reactions by Chlorophyll and Its
-Analogues Wit"r, the Use of D20
in this case. Either the velocity of the sensitized reaction
is only slightly slowed down or even markedly accelerated.
Thereby it is confirmed that the formation of the reduced
protonic-form of the sensitizer does not represent an
obligatory stage of the sensitized reduction. Therefore the
sensitization actually predominantly, if not exclusively,
takes place by the formation of the primary, reduced
electronic form of the sensitizer with an immediate reaction
of this forip with the acceptor-oxidizer. The addition of a
proton and the formation of the leuco form of the reducible
dye apparently takes place on the way of further reactions
of the primary (electronic) reduced form (of the ionized
oemiquinone) of the acceptor (reaction 3). Similar 'investi-'
gations with acetone-solutions of dyes fully confirmed the
above-given results.
There are 1 figuref 1 table, and 10 references, 9 of which
..are Soviet.
ASSOCIATION: Institut biokhimii im. A. No Bakha Akademii nauk SSSR
Card 4/5 (Institute for Biechemistry imeni A. N. Bakh AS USSR)

-An Investigation of Some Problems Concerning the Mechanism of 20-119-1-34/52
'Sensitization of Redox Reactions by Chlorophyll and Its
Analoguea With the Use of D 0
2
PRESENTEDs b1lovember 4 P1957, by A. N. Terenint Member, Academy of
Elciances, 1JSSR
SUBMITTEDt 11ovember 1, 1957
Card -5/5

Nature of alementar7 photoreactions of chloron~n [vith
ffm"lar7
in Igniliahl. Biof izika 4 no.l: 124-218 Ja 159. (HIRA 12:1)
.1. Institut biokhimli im. A.H. Bakha AN SSSR, Hookwa.
(CHMOMMD
basic photoreactions (Rua))

:24 (7)
3011/ -8.;;;23
-4 5/36~
AUTHOR: YevatiLmeyev, V. B.
'
T the Fluorescence of
'
TITLE:.: O~i`i t h e"Activation" of/Chl6r.ophyll and Its Analogues (Ob-
-fluorest sent bi i khl-Prof illa i:yego analogov)
PERIODICAL: Izvestiya Akademii nauk-SSSR. Seriya fizichoukaya, 19599
Vol 23, Nr 1, PP 74 - 77 (USSR)

ABSTRACT:
ries
in the present paper the author discusees the dincove
made at the Laboratory of Photobiochemistry of the Inetitut
biokhimii im. A. If. Bakha Akademii nauk SSSR (Institute
of Biochemistry imeni A. ff. Bakh of the Academy of Sciorces,
USSR) under'the supervision of Terenin as well as
those made by Livin.-ston (Ref 3) and his collaborators (Us")
on their own part. These detections refer to the properti.-as
of chlorophyll in sucha polar solvents as benzene, toluene,
Ccl and other substances, the change offluorescence in-
4 1:1
tensity with simultaneous change of the absorption as de-
pendant on the absence or presence of minute quantities
of a pblar compound in the solution. In the precedin:- pa-per
..Tard 1/2 (Ref 2) the author detected a similar phenomenon in Zhe

On the "Activation" of the Fluordiieeme of Chlotiolft1l
and Its Analogues .
synthetic-comp-ound magnesium'-phthalocyanine -in- toluene.
The fluorescence intensity of chlorophyll ii i purest
toluene$ for instance# is greatly inareaead alroa4y by a
-small addition of water that flows over it in the form
of--humid- -air _(aa_tivation.__by__ polar- solvents)_(Figa- 1,2)-.
According to observations made in this field and additional
data on the influence of temperature (Fig 3) the author
arrived at the following conclusions: In apolar solvents,
the chlorophyll molecules and their analogues with Mg
represent non-fluorescent dimera. Tho whole phenomenon is
lacking in the analogues of chlorophyll without maeneoium
since the bond of two molecules is produced by way of
the magnesium atom. By adding a polar solvent, the dimers
are split into monomers due to affiliation of the polar
compound to the pigment. The author emphasizes the fact
that luminescence in present only with molecularly
distributed chlorophyll molecules and can be produced only
in that molecular distribution into,which the ag-loregates
of the molecule are transferred by the "activators", i.e.
polar compounds. There are-3 figures and 6 references, 3
Card 2/2- of which are Soviet.

170) SOV/20-124-3-57167

AtITILORSt: inal
Yevatignoyevo V. B. 1:, Gavrilova, V. A,# 5aV4 1. Ge
TITLE: -On the Photoreductio~):n of Bilirubin and Protoporphyrin in Connection
-With the Study of the Photoreduction of Chlorophyll (0 f0tovosstamov-
lenii bilirubina i-protoporfirina V avyazi a izuehaniyam foto-
vosstanovleniya khlorofilla)
PERIODICAL: Doklady Akademii nauk SSSR, 1959, Vol 124, fir 3, pp 6.91-694 (USSR)
A.BSTRACT. The chemical mechanism of the reaction, mentioned in the title, of
chlorophyll and its analogues (discovered and studied at the labors-
toriya fotobiokhimii = Laboratory of Photo-Biochemistry of the In-
stitute mentioned in the.Association) (refs 1,2) so far remains.
--unclarifie-d. The authors quote the findings hitherto made with re-
gard-to this problem-(Refsl~-10). Yor- the -purpose of obtaining
further data, bilirubin (Ref 12) was tested with regard to its
photoreductibility, Bilirubin contains the same 4 pyrrole rings,
connected by methine-bridges, as the porphyrins, the bond chain,
however, remaining open. Therefore, there is a bilizubin absorption
maximum in organic solvents in the. short wave range of the spectrum,
at about 450 mit. Solutions of reactive bilirubin in pyridine and
alcohol were investigated. They contained ascorbic acid or phenyl
Card 1/4 hydrazine. In vacuum tubes, the evacuated solutions were illuminated

SOV/20-124-3-57/67
On the Photoreduction of Bi2irubin and Protoporphyrin in Conneaticn Wrfith~ the
Study of the Photoreduction of Chlorophyll
through a light,filter BU-8 which cuts off the ultraviolet spectrum
re;nge below 370 and.-subjected to spoctrophot,ometry. The tests-
MJL
showed.that the bilirubin maximum decreaaed.only slowly and irre-
versibly, whereas the absorption Maxima of chlorophyll and other
porphyrin pigments (with or without magnesium in the molecule center)
-changed significantly and reversibly (Rafe 1,2). The counter-
reaction did not occur on the addition of air. These findings were
by the oleo trome trical measuring method of the redox
potentials-of photored-ta-cible-solu tions-,~-- The - to st- re sul ts - with-b-il i_-
rubin directly substantiate the assumption that a closed system of
conjugate double bonds plays the most important role in the-photo-
reduction of pigments. The results of the tests with the photo-
reduction of protoporphyrin, as carried omt by the authors, also
point to this fact (see diagram; Ref 12). Figure I shows the changes
of the absorption spectrum of an evacuated protoporphyrin solution
in pyridine-that containu ascorbi,; acid. They occurred with illumi-
nation and with the counter-reaction of the reduced product at
Toom temperature and at -400. From the analogy with the. primary
Card 2/4 processes that take place in the photoreduction of the pheophytins

SOV/20-124-3-57/67
or., the Photoreduction of Billrabin and FrotoporphYkin in Connection With the
Stu4Y of-the Photoreduction of Chlorophyll
---roto-~phddpby4g,-and-hematoporphyrin'I the,
a'and b, of-P -(Refs-2,3),
authorsAssums,-that--the now formed, highly.unstable reduced product
(absorbed~in_the 470-475 mprange) constitutes the primary photo-
reduced form of protoporphyiia; i.e. a free radical of the type of
an icnized ssaiquinone (Ref 4). Althoughthe lateral substituting
groups are not of fundamental importance for the photoreductibility
of the pigment, they may-neVertheleas affect the kinetics of partial
reactions, and consequently the result of the reaction in general
(Refs 2,3). The capacity of protoporphyrin to form the primary
electrode-active form is confirmed by alectrometrical measurings
of the redox potentials (Fig 2).. The above results prove the fact
that the photoreduction of protoporphyrin - which does no'. contain
a cyclopentanone-ring - yet occurs on the same pattern as in the
case of chlorophyll. These results re-confirmed the fact that this
very-ring system of conjugate double bonds is the localizing point
photochemical reduction process of the pigment. The absorbed
-light quanta by acting upon.-.-the TI-electrons of the system of said
bondsi-induce thelsystem-(due,-apparently, to a conversion into a
state in waich it is capable of receiving
a.surplus eie-iction. The if ---- & LaWe-r- (-if -:it-- occurs- at -a4 -
Card '3/4 localizingo --t e~

7 -_7
'On-the PhiDtoreduction-of Bilirubin and Protoporphyrin-in Connection-With-the
-Study of the Photoreduction. of Chlorophyll
still-remains unknown. In conclusion approaches of the solution
of this problem are indicated.- There are 1 figure and 16 refer-
ences, 13 of which are Soviet.
ASSOCIATION: Institut biokhimii im. A. N. Bakhe Akademii nauk SSSR
-(Ins'titate of Biochemistry imeni A. H. Bakh of the Academy of
Sciences, USSR)
-PBI:SMTEDs September 17, 19589 by A. N. Terenin, Academician
SUINITTEDI September 15, 1958
Cald 4/4

AUTHOIRSt SM/20-1 2-51164
Tevatigneyev, V. B.j Gavrilova, v. A. 126-
-TITLE:, Photosensitization of Redox Reactions by Chlorophyll Under
Heterogeneous Conditions (Ebtosensibilizatdiya okislitellno-
vosstanovitel9nykh reaktsiy khlorofillom v geterogennykh usloviyakh)
PMdODrCAL: DokladY Akademii nauk SSSR, 1059, Vol 126, Nr 2g PP 410-413 (USSR1
ABSTRACT: There are facts which indicate the ability of chlorop,.hyll, mentioned
in the title; however, they do not prove it directly (Refs 8,91.
Above all such a proof is missing for the aggregated state at, an
apparently existing separation maoro-surfacot pigmen~-medium. The
latter system is the subject of the present paper. The medium was
an aqueouB one-- both ay the electron source and bY.-the electron
receiver rare solved. In case a) ascorbic acid and in case b) azo
dyes vrere used-- methylred, acidic blue and acidic orange, which
supply irreversible reproduction products. As heterogeneous
sensitizing systems suspensions of chlorophyll, phcollydn and
magnesium phthalooyan:Ene were used. There were difficulties in
obtaining huspensiorsof the two former pigments which were overcome
by recording absorption curves without dye. The photoreaction took
place in vacuum vessels (Hof lOY while boiling the soluti;)n, Table
Card V3 I shows the sensitizing effect of the pigments in experiments

PhotosensitizAtion of Redox Reactions by.ChlorophyU Under S07/2G-126-2-51/64
Heterogeneous, Conditions
carried out by filtering off the pigment particles. A comparison of
the absorptiou ~B=tity in the maxima. of the dyev after illumination
and after a - storing -without - Miami nation _undoubt,6dly indicates a
photosensitizing eff6o't of.the.pigment-suspension. Further the
authors found o~t that the courso of the aenuitized-reaotion can
also be followed up without filtering off the pigment, For this
reason the extinction of the mixture has to be measured 20 - 30
seconds after shaking (Table 2, Fig 1). The sensitizing effect of
the pigment is due -to the surmounting of the activation energy of
the reaction between the two raa-peeLive components. The rate of +Aie
sensitizing reaction increases at illumination with Aght which is
absorbed by the'pigment only (Fig 2AJO and also in the case of
density increase of the sensitizei suspension (Fig a B),~ within
certain limits. The concentration of the reducing oubstance
exercises a strong effect at low concentrations and vice versa, The
sensitizing reaction takes place better in an acid medium. The presetme
or absence of air in heterogeneous systems in an SquMs medium is
without great importance for the reaction rate. Xn conclusion
various hypotheses are expressed concerning the photosensitizing
Card IV3 mechanism and papers are discussed (Refs 4# 5t 9 - 18). The

Photasensitization of Redox Reactions by Chlorophyll Under SOV120-126-2-51164
ffetemgeneous Conditions
simplified mechanism, described is by all means possible in-the
case -of ohloroplast~granuli# Vaere am 2 figures, 2 tables, and
18. references, 15 of wUoh an Soviet.
ASSCMATIM. rnsti-tut, biokbindi im._A. N.-Bakha Akademii nauk WSR (Ths:W e
for Biochemistry Imeni A. N. Bakh of the Academy of Saiencest USSR)
MIMED.- januuy 19 t. 1959. by A. N. Terenin, Academician
SUENITTED: Ndembbr~ 215i 1958
Card 3/3

ATIT1110431'' Yevatigneyev, -V,, B Gavrj'.Iovf---V 3 --7/20-127-1-5 /65
T."ITLE: An Investigation of the Mechanism of Photosensibilization of
Oxidation-reduction Reactions by Chlorophyll in Solutions by
Measuring Their Electroconductivity (Izuoheniye mekhanizma
fotosensibilizatsii okielitellno-vosstanovitelinykh reaktsiy
kh1orofillom v rastvorakh putom izmaroniya aloktroprovodnonti)
F-BRIODICAL: Deklady Akademii nauk SSSR, 1959, Vol 127, Nr 1, pp 198-201
(USSR)
13STRACT: A scheme is given initially according to which, in all
probability, the sensibiliz%tion mentioned in the title pr;;ceeds.
(Refs 1, 2)4' ChI7 is a primary reduced form of pigment, that is
a free zadical of the semiquinone. type (Ref 3) which is
produced by the electron addition to the pigment molecule
One of the symptoms of the occurrence of
ChI7__�_n the-solutibn ~(Widdr -dertain
-dally-ir.
-one tions,
pyridine, n the presence of phenyl~hydrazine) is the change of
the electroconductivity of the- Isolution when it is illuminate-d
(Ref 4). The character o'fthis change and the reduction of the
Card 1/3 electroconductivity when the light is switched off differs with

An Investig*ation of the Mechanism of Photosensibilization SOV/20-127-1-55/6,
-of Oxidation-reduction Reactions by Chlorophyll in Solutions by Measuring
Their Zlootroconductivit~
various dyes, and is datemined by tho experimontal conditions
-and-the _properties of the primary form reduced by light as voll
-of -the --tranuformation-of--o.the
as by t a prodt,,6- 6 r reaction
compon n Ure.Which resu ts--~ -------
0 to. Fizu ,-I shors a Aypical .-pic t
~oflight::andd -' neae in an evacuated
f rOM d- qUiCk BU0000 On ark
-chlokophyll-4 :i,0lu#"6r'i in.pyiidine~~ ontaiking phan -1
y
hydrdii'ne'). Probeedii'-~-` h h'
tig,f-rm t is..meo anism'-it. can belexpected
th' t: the: equilibri
a um-Vii-,ttii-T of:.Chr n the~,,presence of an:
-capa, 0~;~Oj- 'T eraction, with Chl*7
~~,electron acceptor lil "t quick Int
'kn
h rduri'~
-ill b mue ~- smalle' mixiation~ This ought,to.
W
an* '~~;e eo oc ndue
Influence1he-ch ge.-of th I I ~i o iivitY (Refelt 5)
It is --to be- 6xpectel~- specially in the--base of the chlorophyll a
e p Al
that the introduction of the chlorophyll will considerably
reduce and even stop ~he.changes shown in figure 1. Such an
effect would 'prove the correctness of the said mechanism. The
influence oE the presence of some dyes the reduction by light
of which can be sensibilized by chlorophyll a on the changes of
the elactroconductivity was investigated: methyl red (Ilef 6),
safranin T (Refs 6, 7), adide blue (Ref 8) and finally carotuene
Card 2/3 (Refs 9, 10, 124 16). Table 1 shovs quite obviously that the

65
An Investigation of the-mirechanism of Photosensibilization SOV/20-127-1-55/5
Cior --lorophyll in 1 Y aslari -
of 0.71dation-reducl L Reactions, by Ch So utions b,;~ Me
Their;,Eleotroconductivity
said electroconductivity changes cease completely in the
presence of the acceptor, but beain again according to tne
reduction -by' lig%-h' . of the acceptor., Figure 2 sho,.7s the resuilts
of experiments mith safranin. Its introduction into the
solution increases the eleptroconductivity rapidly. This is the
consequence of the ionization of the dye in pyridine.
Fluctuations of these chanjes take place, but stop after several
illumination periods. Thus the participation of the ionized
form reduced by light of pigment in the se4sibilization i.e.
the correctness of the initially mentioned'scheme was proved.
In pheophytin a similar phenomenon is observedo but its
picture is not so clear. Table 2 shovs the influonce of carotene.
There are 2 figures# 2 tables, and 16 references# 11 of rhich
are Soviet.
ASSOCIAT1011: Institut biol-.himii im. A. IT# Dakha Akadomii nauk SSSR(Institutu
of Biochemistry inani Ao N., Bakh of the Academy of Sciences, USSR)
PRESENT:Ot March,16, 1959, by A. N. Terenin, Academician
SUBMITT2.D: March 14, 1959
Card

MUNI~M I#
YUSTIGNEIV9, V.Be; GARIIDVA9 V.A~
j','he abillity of adsorbed c4lorophy-411 to photagened ti axidationn-
reduction reactions. Blqfizika 5 no. 5:399-608 160*
(MMA 13;10)
lustitut biokhimii imeni A.N. Bakha AN SSSRP Moskva.
(CHL6ROPIMU) (OXIDATIOll-REDUCTION REACTION)

I vq, 1v zj s7 uj
a
Ila
4

V A
lqxamination of the Ir"hotoreduction and Photosensitizing'
Ability of Chlorophyll bxV Measurement of Electrocoiductivity."
Report prevented at the 5th International Biochemistry Congress,
Mosc-ow, 10-16 August 1961

SOMNSM. p Abram Levkovichl -IISTIMMW~ V*B*# doktor takhh. naakp
speti;.: red.; mmusmus 0.!-.prGT.-j-SOKOLOVAq I,Ao# tekbn* red,
[phyllicoOdmical fdundAtid~d of the carawl Indiustryl Flziko-
khim.labaskie oanovy-proimodstva kax=eli. Izd. 2., perer dop.
Moskiray Fishchapromizdate 1961, 131 (MM 417)
(Carama4l.

UVST]:GVZYF.Vp- V.B.; SAVKIU&o I.G.
Studying. photoreduction of cblorophy.U. and its analogues In
variots solvents by measuring its electric conductivity.
Biofi2,ika 6 no. 1:30-39 161. (HIRA 14:2)
1. Ingititut biokhimii-im. A.N. Bakha, AN SSSR# Mosk7a.
(CHWROPHYLL) (OXIDATION-rdMUCTION REACTION)
(PHOTOCHEMISTRY) (ELECMIC COIMUCTIVITY)

UVST,'EGIGYEV:j V,B,; GAVRIIDVA) V.A.
Ability of an artificial lipoprotein complex of chloropbyll
to serisIbize oxidation-reduction reactions. Biofizika 6
no."Oi:563-571 161. (11M 15:3)
1. Institut biokhimii imeni A6B. Bakha All SSSR, Moskva.
(CHWROMU) (LIPOFROTEIIS)
(OXIDATION-REDUCTION REAcTION)

SAVIMLt I.Go; YEVSTI^ull= V.B.
Comparing.the photosewitizing activity of chloropbVis a end b in
Solutlon. Dokl.AN SSSR 138 no,4:958-961 Je f6l. Ofm 14-- 5)
1. Institut biokhimii,imeni A.N.Sakba AN SSSR. Predstavleno
akademikom A.H.Tereninyme;

-30712
Ll 6,0 S/1020/61/141/002/026/027
AUTHOR3 t YevsiARn~y!!v, V. B., and Gavrilova, V. A.
TITM Oompmrison of reduction poten'ials of chlorophyll and
bacterial pigments exposed to light
PERIODICALs Akademiya nauk SSSR. Doklady, v. 141, no. 2, 1961, 477-480
TEM For comparison of the reduction potentials of chlorophyll (Cp)
obtainod from nettle by ohromato graphic separation, of the baoterio
chlorophyll (Bap),of Rhobopseudomonas pal-as"tris and of the bacterioviridine
(Bv) of' Chlorobium lamicula, mixtures of the pigments were exposed to the
--ligh-t of-th'41 absorption maximum of-Cp and the absorption-maxirium-of the
bacterial pigments The bacterial pigments were prepared by Ye. V.
Pakshina, a collaborator in the authors) laboratory. The followin
mixtures were examineds chlorophyll a + b and bacterioohlorophyll fi);
chlorophyll a and bacteriochlorophyll (II); chlorophyll7b and
bacte'riochlorophyll (iir)j bacteriochlorophyll and baoterioviridine (IV);
chlorophyll a and bacterioviridine (V). 1he examination was carried out
in vacuum tubes by means of a Beokmann;DU apectrophotometer or an
Card 1/$

30712
S/02o 61/.141/002/026/027
Com arison of reduotion-potentials of B101%110
Cf-4 (EIP-4 ap eotr6pho tome ter. The band absorbed by Bap was obtained by
meana of a light-filter combination (5mm) from QC-11 (SZS-11)+kC-19 (KS-19)
which did not permit penetration of