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I?I?NOA?NOAI INA?OE OE?A?IE
OA?E?ANUeEEE AeA?AEAAIEE OI?AA?NEOAO
CENA ??eia Aanee?aia
OAeE 577.323
AEA*AIIss INIAEEAINOAE ACA?IIAe?? ?II?A IA?AO?AeIEO IAOAE?A C
IOEEA?IIAEIE EENEIOAIE, UI CIAOIAessOUeNss IA ??CIEO ??AIssO
NO?OEOO?II? I?AAI?CAOe??
03.00.02 – a?io?ceea
Aaoi?aoa?ao aeena?oaoe?? ia caeiaoooy iaoeiaiai nooiaiy
eaiaeeaeaoa o?ceei-iaoaiaoe/ieo iaoe
OA?E?A – 1999Aeena?oaoe??th ? ?oeiien.
?iaioa aeeiiaia o a?aeae?e? iieaeoey?ii? a?io?ceee O?ceei-oaoi?/iiai
?inoeoooo iecueeeo oaiia?aoo? ?i. A. ?. Aa?e?ia IAI Oe?a?ie.
Iaoeiaee ea??aiee:
aeieoi? o?ceeiiaoaiaoe/ieo iaoe, noa?oee iaoeiaee ni?a?ia?oiee, Ni?ie?i
A?eoi? Ieaenaiae?iae/, O?ceei-oaoi?/iee ?inoeooo iecueeeo oaiia?aoo? ?i.
A. ?. Aa?e?ia IAI Oe?a?ie, i?ia?aeiee iaoeiaee ni?a?ia?oiee.
Io?oe?ei? iiiiaioe:
aeieoi? o?ceei-iaoaiaoe/ieo iaoe, noa?oee iaoeiaee ni?a?ia?oiee,
Naiaiia Ieoaeei Ieaen?eiae/, ?inoeooo ?aae?io?ceee oa aeaeo?ii?ee ?i.
I.ss. On?eiaa IAI Oe?a?ie, i?ia?aeiee iaoeiaee ni?a?ia?oiee (i. Oa?e?a);
aeieoi? o?ceei-iaoaiaoe/ieo iaoe, noa?oee iaoeiaee ni?a?ia?oiee,
Oei?aaoia Ieaenaiae? Aai?a?eiae/, O?ceei-oaoi?/iee ?inoeooo iecueeeo
oaiia?aoo? ?i. A. ?. Aa?e?ia IAI Oe?a?ie, noa?oee iaoeiaee ni?a?ia?oiee
a?aeae?eo eaaioiai? oai??? ? iae?i?eii? aeeiai?ee iae?ineii?/ieo nenoai
(i. Oa?e?a).
I?ia?aeia onoaiiaa:
?inoeooo oai?aoe/ii? o?ceee ?i. I.I. Aiaiethaiaa IAI Oe?a?ie, i. Ee?a.
Caoeno a?aeaoaeaoueny “ 22 ” 04 1999 pieo i 15-00
aiaeei? ia can?aeaii? niaoe?ae?ciaaii? a/aii? ?aaee Ae 64.051.13 o
Oa?e?anueeiio aea?aeaaiiio oi?aa?neoao?, 310077, i.Oa?e?a, ie. Naiaiaee,
4, aoae. 7-4.
C aeena?oaoe??th iiaeia iciaeiieoeny o Oeaio?aeuei?e iaoeia?e
a?ae?ioaoe? Oa?e?anueeiai aea?aeaaiiai oi?aa?neoaoo: 310077, i. Oa?e?a,
ie. Naiaiaee, 4.
Aaoi?aoa?ao ?ic?neaiee “ 19 ” 03 1999 ?.
A/aiee nae?aoa?
niaoe?ae?ciaaii? a/aii? ?aaee Aaoao N.
A.
CAAAEUeIA OA?AEOA?ENOEEA ?IAIOE
Aeooaeuei?noue oaie. Iaei??th c iaeaaaeeea?oeo caaea/ a?io?ceee ?
o?ceee a?iiie?ia??a ? c’ynoaaiiy iieaeoey?ieo iaoai?ci?a, ui eaaeaoue
a iniia? ?o ooieoe?iioaaiiy. A ca’yceo c oeei anoaiiaeaiiy o?ce/ii?
i?e?iaee iniaeeainoae aca?iiae?? ?ii?a iaoae?a c ioeea?iiaeie eeneioaie
(IE) noaiiaeoue aaeeeee ?ioa?an. Oeae ?ioa?an coiiaeaiee, o anyeiio
?ac?, oaeeie iniiaieie a?ieia?/ieie aoaeoaie: o/anoth ?ii?a
aeaiaaeaioieo iaoae?a a a?ieia?/ieo i?ioeanao, ye? ooyaothoue IE
(iai?eeeaae, ia?aiin? aaiaoe/ii? ?ioi?iaoe??); iaaaoeaiei aieeaii ?ii?a
iaoae?a ia ooieoe?iioaaiiy aeeaeo i?aai?ci?a; aioeiooeeiiith aeoeai?noth
aeayeeo niieoe iaoae?a, ui ?ia?a??othoue neioac AeIE; aeei?enoaiiyi
iaoae?a ye ciiae?a aeey eii?aeeiaoe?eii? o?i?? ioeea?iiaeo eeneio.
Aeooaeuei?noue aea/aiiy iaoaeieiiieaen?a a inoaii?e /an ua a?eueoa
c?inea o ca’yceo c ??ceei iia??oaiiyi noaio iaaeieeoiueiai na?aaeiaeua,
aeeeeeaiei, cie?aia, caa?oaeiaiiyi aiaee, a?oioo, ?ineei, ?, ioaea,
i?iaeoeo?a oa?/oaaiiy nieyie ??cieo iaoae?a. Iniaeeai oea noino?oueny
?ii?a ia?ao?aeieo iaoae?a (II), cie?aia, ?ii?a Ni2+, Cd2+, Ag+, ye?
iathoue aaeee? eaioea?iaaiio oa iooaaaiio aeoeaiino?. Iacaaaeath/e ia
oa, ui ?nio? cia/ia e?euee?noue aenia?eiaioaeueieo oa oai?aoe/ieo ?ia?o,
i?enay/aieo iaoaeieiiieaenai IE, iieaeoey?i? iaoai?cie coiiaeaieo ?iiaie
a?ieia?/ieo i?ioean?a ana ua ia anoaiiaeai?, ui ?iaeoue iaiao?aeiei
aea/aiiy ac??iiae?? ?ii?a c IE, ye? ciaoiaeyoueny ia ??cieo ??aiyo
no?oeoo?ii? i?aai?caoe??.
Ca’ycie ?iaioe n iaoeiaeie i?ia?aiaie, ieaiaie, oaiaie. Aeena?oaoeey
aeeiioaaeanue o a?aeiia?aeiino? c ieaiii iaoeiai-aeine?aeieo ?ia?o
a?aeae?eo iieaeoey?ii? a?io?ceee OO?IO IAI Oe?a?ie ii oai?
“Aeine?aeaeaiiy no?oeoo?ieo oa o?ceei-o?i?/ieo aeanoeainoae eiiieaen?a
ioeea?iiaeo eeneio c a?eeaie oa a?ieia?/ii aeoeaieie ?a/iaeiaie” (oeo?
oaie 1.4.10.18.2), a oaeiae a ?aieao aeeiiaiiy i?iaeoo Aea?aeaaiiai
oiiaeo ooiaeaiaioaeueieo aeine?aeaeaiue “Eiiia?aoeai? yaeua,
eiioi?iaoe?ei? oa oacia? ia?aoiaee a iecueeiaei??ieo iae?iiieaeoeao
a?ieia?/iiai iioiaeaeaiiy” (iiia? i?iaeoo 2.2/159), i?iaeo?a
I?aeia?iaeiiai iaoeiaiai oiiaeo, a?aio U 23000-U 23200 “Divalent Metal
Ions Interaction with Nucleic Acids. Role of Water and Cooperative
Effects” ii i?ia?ai? “Long-Term Research Grants Program”.
Iaoa ? caaea/? aeine?aeaeaiiy. Iaoith aeaii? ?iaioe aoei anoaiiaeaiiy
i?e?iaee a?aei?iiinoae o ca’ycoaaii? ?ii?a ia?ao?aeieo iaoae?a c IE,
c’ynoaaiiy i?e/eie ??ciiai aieeao ?ii?a oeeo iaoae?a ia eiioi?iaoe?eiee
noai AeIE, a oaeiae aeyaeaiiy aieeao ??cieo ??aiae no?oeoo?ii?
i?aai?caoe?? IE ia ca’ycoaaiiy c ?iiaie ia?ao?aeieo iaoae?a.
A ca’yceo c aeacaiith aeua iaoith aoei iinoaaeaii oae? caaea/?:
1. Aecia/eoe aoiie, ye? eii?aeeiothoue ?iie Cu2+, Co2+ ? Zn2+ a GMP, a
oaeiae ?iie Ni2+, Cd2+ ? Ag+ a ??ai- ? aeaciene??aiioeeaioeaeao on?o
eaiii?/ieo iniia (r,dGMP; r,dAMP; r,dCMP; UMP ? dTMP) oa i?e?iaeii?
AeIE.
2. Aecia/eoe eiioi?iaoe?ei? ia?aoai?aiiy a i?e?iaei?e AeIE,
?iaeoeoiaai? oeeie ?iiaie.
3. ?ic?aooaaoe eiinoaioe ca’ycoaaiiy ?ii?a ia?ao?aeieo iaoae?a c
aeoeaieie oeaio?aie iniia AeIE, a oaeiae r- e d-ioeeaioeae?a.
4. C’ynoaaoe i?e?iaeo a?aei?iiinoae a ca’ycoaaii? ?ii?a, ye? iathoue
??cio aeaeo?iiio no?oeoo?o, c ioeeaioeaeaie ? AeIE.
Iaoeiaa iiaecia iaea?aeaieo ?acoeueoao?a. Aecia/ai? aaoa?iaoiie iniia
AeIE ? ie?aieo d- ? r-ioeeaioeae?a, ye? eii?aeeiothoue ?iie Ni2+, Cd2+ ?
Ag+, a oaeiae Cu2+, Co2+ ? Zn2+ (o?eueee c GMP) o aiaeieo ?ic/eiao,
ciaeaeai? ?ai?oa, a iniiaiiio, aeey nenoai ?c cieaeaiith aeoeai?noth
aiaee. Aeey d-ioeeaioeae?a oey ?ioi?iaoe?y iaea?aeaia aia?oa.
Iaea?aeai? cia/aiiy eiinoaio ca’ycoaaiiy oeeo ?ii?a c ioeeaioeaeaie ?
AeIE a oe?ieiio aeeaiacii? eiioeaio?aoe?e ?ii?a iaoae?a. Aeey eiiieaen?a
AeIE c ?iiaie Ni2+ ? Cd2+ , a oaeiae r- e d-ioeeaioeae?a c ?iiaie Ag+
oe? aeai? iaea?aeai? aia?oa.
Anoaiiaeaii, ui a?aei?iiino? a eiiieaeniooai?aii? aea/aieo ?ii?a c AeIE
aecia/athoueny a?aei?iiinoyie a ca’ycoaaii?, ui i?iyaeythoueny aaea ia
iiiiia?iiio ??ai?.
Iieacaii, ui a?aei?iiino? a a?euei?e aia?a?? ca’ycoaaiiy ?ii?a II c GMP
aecia/athoueny a?aei?ii?noth ?o ?iiieo ?aae?on?a.
A a?eueo oe?ieiio, i?ae ?ai?oa, ?ioa?aae? ai?noo ?ii?a iaoaeo iaea?aeai?
eiioeaio?aoe?ei? caeaaeiino? ci?ie oaiia?aoo?e ? ?ioa?aaeo ieaaeaiiy
AeIE a i?enooiino? ?ii?a Ag+, ui aeicaieeei aia?oa ca?a?no?oaaoe
iaoiaeii oa?i?/ii? aeaiaoo?aoe?? ooai?aiiy n??aeii aeaio ??cieo oei?a
eiiieaen?a.
Ia iniia? iaea?aeaieo aeaieo aia?oa cai?iiaiiaaii aeueoa?iaoeaio
?nioth/ei iiaeaeue “neaaeiai” eiiieaeno, yea i?eionea? ooai?aiiy
ooanoei?anueeeo GC-ia?.
I?aeoe/ia cia/aiiy iaea?aeaieo ?acoeueoao?a iieyaa? a oiio, ui
aenia?eiaioaeuei? aeai? i?i i?noey eii?aeeiaoe?? aea/aieo ?ii?a II ia
AeIE ? ?? iiiiia?ao, caeiiii??iino? a oa?aeoa?? ca’ycoaaiiy oeeo ?ii?a,
no?oeoo?i? ia?aoiaee, ?iaeoeoiaai? ieie a AeIE iiaeooue aooe aeei?enoai?
i?e c’ynoaaii? iieaeoey?ieo iaoai?ci?a ?aaoeyoi?ii? ?ie? ?ii?a o
ooieoe?iioaaii? (aai eiai ii?ooaii?) aaiaoe/iiai aia?aoo o i?i- ?
aoea??io?a.
Iaea?aeai? ?acoeueoaoe noaiiaeyoue ?ioa?an aeey ae??oaiiy caaea/,
iia’ycaieo c i?iaiicoaaiiyi aeieia?/ieo iane?aee?a ca?aaeaiiy
iaaeieeoiueiai na?aaeiaeua nieyie iaoae?a. Cie?aia, aeyaeaia aaeeea
cia/aiiy eiinoaio ca’ycoaaiiy ?ii?a II c iniiaaie AeIE iieaco?, ui
iiaeeo?eoth/a ae?y ?ii?a ia AeIE iiaea cae?enithaaoeny ieie i?e
eiioeaio?aoe?yo, a?aeiia?aeieo no/aniiio ??aith caa?oaeiaiiy
iaaeieeoiueiai na?aaeiaeua.
Aei??yi? a oe?e ?iaio? aeeoa?aioe?ei? OO-niaeo?e (AeOON)
iaoaeieiiieaen?a ??ciiai ioeeaioeaeiiai neeaaeo iiaeooue aooe
aeei?enoai? aeey aecia/aiiy oeaio??a ca’ycoaaiiy ?ioeo, ua ia aea/aieo
iaoae?a.
Iniaenoee aianie caeiaoaa/a. A iioae?eiaaieo c ni?aaaoi?aie iaoeiaeo
?iaioao iniaenoee aianie caeiaoaa/a iieyaa?:
a ?iaioao [1,2,4] – a o/ano? o iinoaiiaoe? caaea/? aenia?eiaioo,
iaea?aeaii? aenia?eiaioaeueieo AeOON AeIE, r- e d-ioeeaioeae?a a
i?enooiino? ?ii?a Ni2+, Cd2+ ? Ag+, ?o ia?iaoe? ? aiae?c?, ?ic?aooieo
eiinoaio ca’ycoaaiiy, a oaeiae ?ioa?i?aoaoe?? iaea?aeaieo aeaieo;
a ?iaioao [3,5,6,7] – a i?aeai??, ia?iaoe? ? aiae?c? e?oa?aoo?ieo
aeaieo, a oaeiae i?iaaaeaii? niaeo?ioioiiao?e/ieo aei??thaaiue. Aaoi?o
iaeaaeeoue aanue ia’?i ?ia?o, iia’ycaiee c /eneiaith ia?iaeith aeaieo ?
aiae?cii iaea?aeaieo ?acoeueoao?a.
Ai?iaaoe?y ?acoeueoao?a aeena?oaoe??. Iaoa??aee ?iaioe ii oai?
aeena?oaoe?? aeiiia?aeaeenue ? iaaiai?thaaeenue ia:
n 3rd European Conference on Bio-Inorganic Chemistry, Noordwijkerhout,
The Netherlands, August 4-10, 1996.
n XXIII European Congress on Molecular Spectroscopy, Balatonfured,
Hungary, August 25-30, 1996.
n VII European Conference on Spectroscopy of Biological Molecules, San
Lorenzo de El Escorial, Madrid, Spain, September 7-12, 1997.
n 7th Intern. Symp. on Macromolecule-Metal Complexes, Nordwijkerhout,
The Netherlands, October 6-10, 1997.
n II c’?cae? Oe?a?inueeiai aeio?ce/iiai oiaa?enoaa, Oa?e?a, 29 /a?aiy-3
eeiiy 1998.
n XXXIII International Conference on Coordination Chemistry, Florence,
Italy, 1998.
n XII Round Table “Nucleosides, Nucleotides and their Biological
Application”, Montpellier, France, September 6-10, 1998.
Ioae?eaoe??. ?acoeueoaoe aeena?oaoe?? iioae?eiaaii a 7 iaoeiaeo
?iaioao, a oiio /ene? a 3 noaooyo o iaoeiaeo aeo?iaeao ? a 3 oacao oa 1
o?oaeao eiioa?aioe?e.
No?oeoo?a e ianya aeena?oaoe??. Aeena?oaoe?y neeaaea?oueny ?c anooio,
/ioe?ueio ?icae?e?a, aeniiae?a, aeiaeaoeo ? nieneo aeei?enoaieo
e?oa?aoo?ieo aeaea?ae (155 iaeiaioaaiue). Iiaiee ianya aeena?oaoe??
neeaaea? 164 noi??iee, c ieo aeiaeaoie caeia? 4 noi?., nienie
aeei?enoaieo e?oa?aoo?ieo aeaea?ae – 17 noi?., ?ethno?aoe?? – 13 noi?.
INIIAIEE CI?NO ?IAIOE
O anooi? iaa?oioiaaii aeooaeuei?noue ia?aii? oaie, noi?ioeueiaaii iaoo
? caaea/? aeine?aeaeaiiy, iaaaaeaii caaaeueio oa?aeoa?enoeeo
aeena?oaoe??.
?icae?e 1 i?noeoue iaeyae e?oa?aoo?e, i?enay/aiee no/aniiio
oai?aoe/iiio ? aenia?eiaioaeueiiio aeine?aeaeaiith eiiieaen?a ?ii?a II c
ioeea?iiaeie eeneioaie ??ciiai ??aiy no?oeoo?ii? i?aai?caoe??.
Iaaiaeyoueny niiniae oai?aoe/iiai iieno aca?iiae?? ioeea?iiaeo eeneio c
iecueeiiieaeoey?ieie e?aaiaeaie, ye? a iiaeaeueoiio aeei?enoiaoaaeenue a
?iaio? i?e aecia/aii? ia?aiao??a ca’ycoaaiiy ?ii?a c AeIE ?
ioeeaioeaeaie, a oaeiae i?aeoiaee, ye? aeicaieythoue oai?aoe/ii
iienoaaoe aenia?eiaioaeuei? aeai? c ieaaeaiiy eiiieaen?a AeIE c ?iiaie
iaoae?a.
Aeaoaeueii i?iaiae?ciaaia ?nioth/a ?ioi?iaoe?y i?i i?noey eii?aeeiaoe??
eii?a II a ioeeaiceaeao, ioeeaioeaeao, aiiiiie?ioeeaioeaeao ? AeIE, i?i
aieea ?iiia oeeo iaoae?a ia ?? eiioi?iaoe?ei? ci?ie, a oaeiae aeai? i?i
oa?iiaeeiai?/i? oa?aeoa?enoeee eiiieaen?a ?ii?a iaoae?a n IE. Iieacaii,
ui iacaaaeath/e ia aaeeeo e?euee?noue aenia?eiaioaeueieo ?ia?o,
a?aei?ii?noue iauaeo?a aeine?aeaeaiiy, iaoiae?a ?, aieiaia, oiia
aei??thaaiue i?ecaaei aei oiai, ui iaa?oue a ?ac? ioeeaioeae?a ia ?nio?
iaeiicia/ii? ?ioi?iaoe?? i?i i?noey eii?aeeiaoe?? ?ii?a iaoae?a, oiae?
ye aiia eii/a iaiao?aeia i?e iiaoaeia? ?aaeueii? no?oeoo?e
iaoaeieiiieaen?a AeIE. Aieueo?noue iayaieo aeaieo iaea?aeaii a e?enoaeao
aai a nenoaiao, ye? i?noyoue ni?ic/eiieee, i?ioa o aiaeiiio ?ic/ei?
neooaoe?y iiaea aeyaeoeny ?ioith ? iio?aao? iiaeaeueoiai aea/aiiy.
A ?icae?e? 2 iiaeaii caaaeueio oa?aeoa?enoeeo iaoa??ae?a oa iaoiae?a
aeine?aeaeaiiy.
Ia’?eoii aeine?aeaeaiiy aoee 2’-aeacieneioeeaiceae-5’-oinoaoe
(NaadGMP, NaadTMP, dAMP, dCMP) oa ?o ??aiaiaeiae (NaaGMP, NaaUMP,
NaaAMP, NaaCMP), a oaeiae AeIE oeiona oaeyoe ([GC]41%) ? eae??aa n?eue
iie? C (“Serva”, I?ia//eia).
AeIE, ioeeaioeaee, AgNO3 ? oei?eaee Cu, Co, Zn, Ni, Cd ?ic/eiyee a
aoeaoaoiiio aooa?? (?I 6, [Na+] = 10-30,1 M). I?e aei??thaaii? AeOON
eiioeaio?aoe?y IE (?) noaiiaeea (10,1)10-4 I; a aenia?eiaioao ii
ieaaeaiith ? = (6,50,5)10-5 I. Iioeaea o aecia/aii? eiioeaio?aoe?? ? ?
?ii?a iaoae?a noaiiaeea 0,3 oa 0,5% a?aeiia?aeii.
Aenia?eiaioaeuei? iaoiaee: 1) aeeoa?aioe?eia oeueo?ao?ieaoiaa
niaeo?ineii?y (AeOON); 2) oa?i?/ia aeaiaoo?aoe?y. Iaoiae AeOON ia?
aenieo /ooeea?noue aei ci?ie iiaeeiaiiy (10-4 i.a./ii i?e aeei?enoaii?
niaeo?ioioiiao?a Specord M 40, Carl Zeiss Jena (I?ia//eia)), ui
aeicaiey? aeei?enoiaoaaoe ?icaaaeai? ?ic/eie, caiaey/e aei i?i?ioio
niioai?thth/o ae?th aa?aaaoe??, a oaeiae ca?eueoeoe ae?aiacii aea/a?ieo
eiioeaio?aoe?e ?ii?a. Oi?ia AeOON caeaaeeoue ia o?eueee a?ae i?e?iaee
ca’ycoth/i? iniiae, aea e i?e?iaee ca’ycoth/eo aoii?a. Iaoiae
?aeaioeo?eaoe?? ca’ycoth/eo oeaio??a caniiaaii ia ii??aiyii? oi?ie AeOON
iaoaeieiiieaen?a iiiiia??a c oi?iith aeeoa?aioe?eieo niaeo??a,
coiiaeaieo i?ioiioaaiiyi (Aeaaie, 1991), ine?eueee aeey i?ioii?a
?iieciaai? aoiie aecia/ai? c aenieei nooiaiai iaae?eiino?.
Aenia?eiaioaeuei? AeOON caienoaaee, aeei?enoiaoth/e /ioe?ueioethaaoio
noaio aei??thaaiiy. Iioeaea a aei??thaaii? iioe/ii? aonoeie
niaeo?ioioiiao?ii noaiiaeea 0,5%.
Ieaaeaiiy AeIE cae?enithaaee a aa?iaoe/ieo eaa?oeaaeo ethaaoao,
?ici?uaieo a 2 ?aeaioe/ieo i?aeieo aeieao, ?icoaoiaaieo a eaia??
niaeo?ioioiiao?a Specord UV VIS o??ie Carl Zeiss (I?ia//eia). Iaa??a
i?iaiaeeany c? oaeaee?noth 1 a?aae/oa. Aaniethoia iioeaea a aei??thaaii?
oaiia?aoo?e ciaoiaeeeanue a iaaeao 0,5N.
?icae?e 3 i?noeoue aenia?eiaioaeuei? AeOON eiiieaen?a ?ii?a II c
ie?aieie r- ? d-ioeeaioeaeaie, a oaeiae AeIE. Ia iae.1 ye i?eeeaae
iieacaii niaeo?e eiiieaen?a GMP+Cu2+. Oi/a ?ioaineai?noue AeOON
iaoaeieiiieaen?a nooo?ai iaioa, i?ae AeOON i?ioiioaaiiy, ?o oi?ia
i?aeoe/ii iaeiaeiaa o an?e iaeano? . Oey ianoaaeia aeicaiey? c?iaeoe
aeniiaie i?i oa, ui i?noeai eii?aeeiaoe?? ?ii?a oaeiae ? N7.
Ei?ioeioaeeueiaa ?ciaanoe/ia oi/ea ia AeOON, ?iaeoeoiaaieo ?iiaie
aea/aieo II, ci?uaia a /a?aiio noi?iio ii??aiyii c ?? iieiaeaiiyi ia
AeOON i?ioiioaaiiy N7 (iae.1, oaae.1). Oeae cnoa ? i?i?iaeueiei aeey
?ii?a Zn2+ ? iaeneiaeueiei aeey ?ii?a Ag+ ? Cu2+. I?e/eiith oaeiai
ci?uaiiy iiaea aooe aca?iiae?y ?ii?a c I6, yea aeeeeea? ia?ao?ae aoai?io
c eaoi- a ?iieueio oi?io. Ca?aeii c oai?aoe/ieie ?ic?aooieaie (Matsuoka,
1984), eaoi-?iieueiee ia?ao?ae aoaiiceio i?eaiaeeoue aei nooo?ai
a?eueoiai, i?ae i?ioiioaaiiy N7, aaoio?iiiiai cnoao ei?ioeioaeeueiai?
nioae iiaeeiaiiy.
wmetafile8? ??6D???i???????ue???????????-??
???u??????????”????-????????6y=y???`o???
????u5??????you‚p”l¦h?cE_U[eWuSOK’H5DBAO>[:
f7q52„/Uf*qO|I‡E’AOeeo?e a?ey e?eaeo – [Cu2+ ] x 105 M. Ioieoe?
– AeOON, coiiaeaiee i?ioiioaaiiyi N7 GMP (Aoaeianueeee, 1977). Eiai
?ioaineai?noue ciaioaii a 6 ?ac?a.
Oaaeeoey 1
??cieoe? a iieiaeaii? ei?ioeioaeeueiai? ?ciaanoe/ii? oi/ee ia AeOON
iaoaeieiiieaen?a ? i?ioiioaaiiy N7 GMP.
?iiCu2+Co2 +Ni2+Zn2+Ag+Cd2+, ni-12600210012003002600600
Aiaeia?/iei /eiii aoee aecia/ai? i?noey ca’ycoaaiiy ?ii?a c
ioeeaioeaeaie ??cii? i?e?iaee. Iaea?aeai? ?acoeueoaoe i?aenoiiaai? a
oaae. 2, ca?aeii c yeith: 1) ii?yae c neeueiei ca’ycoaaiiyi ?ii?a
iaoae?a c N7 io?ei?a ? N3 i??ei?aeei?a, yea ?ai?oa aoei ca?a?no?iaaii
aeey ie?aieo iiiiia??a, a iniiaiiio, a nenoaiao ?c cieaeaiith
aeoeai?noth aiaee, aeyaeaii neaaeo aca?iiae?th ?ii?a c ea?aii?eueieie
eeniyie. A ?ac? ?ii?a Cu2+, Ag+ ? Co2+ oey aca?iiae?y aeyaeyaoueny
iaea?eueo ae?acii (aeea. oaae.1). 2) ?iie Ni2+ ? Cd2+ i?aeoe/ii ia
ca’ycothoueny c N3N ia o?eueee ie?aieo iiiiia??a, aea e iie? N. 3)
eii?aeeioth/? ?iie aoiie a aeiaaeeo r- ? d-ioeeaioeae?a iaeiaeia?.
Oaaeeoey 2
Aaoa?iaoiie iniia, ye? eii?aeeiothoue ?iie iaoae?a a ioeeaioeaeao ?
AeIE, aecia/ai? ii aeaiei oe??? ?iaioe
Ni2+Cd2+Ag+Cu2+Zn2+Co2+r,dGMP
N7
(O6)r,dAMP (N7) (N7)N7,N1
(N3)r,dCMP
-neaai
N3N3
(O2)iie? N
I2I2N3
(O2)UMP–N3dTMP—AeIEN7G
N7AN7G
N7A 1) N7G
2)N7G-Ag-N3CAoiie, aecia/ai? ia iniia? ??cieoe? a AeOO-niaeo?ao
ioeeaioeae?a ? i?ioiioaaiiy, a?aecia/ai? aeoaeeaie.
AeOON, iaea?aeai? aeey ioeeaioeae?a, aeei?enoiaoaaeenue aeey aiae?co
no?oeoo?e eiiieaen?a ?ii?a Ni2+, Cd2+ ? Ag+ c AeIE. Aeey i?eeeaaeo ia
iae.2 cia?aaeaiee aeeoa?aioe?eiee niaeo? eiiieaeno AeIE+Ni2+.
Iacaaaeath/e ia iaeo ?ioaineai?noue, ia AeOON AeIE+Ni2+ a ae?aiacii?
510-610-3 I Ni2+ niinoa??aathoueny iniaeeaino?, iieiaeaiiy yeeo
ocaiaeaeo?oueny c iieiaeaiiyi iaeneioi?a ia AeOON ?ii?a Ni2+,
iaea?aeaieo aeey aeacieneioeeaioeae?a. Iaeneioi (a) e iea/a (a) iiaeooue
aooe i?eienai? aca?iiae?? Ni2+ a?aeiia?aeii c N7 dGMP ? N7 dAMP.
Ine?eueee iiaea?eia ni??aeue a i?enooiino? ?ii?a Ni2+ (? Cd2+)
caa??aa?oueny, iiaeia i?eionoeoe, ui iea/a (a) coiiaeaia aeieeath/ei a
?acoeueoao? aca?iiae?? c N7G ia?aiinii i?ioiio a?ae N1G aei N3C a
G-C-ia?ao. Iiae?aia oi?ia AeOON ? oa?aeoa?iith oaeiae aeey eiiieaen?a
AeIE c ?iiaie Cd2+ a ae?aiacii? 310-510-3 I oa ?iiaie Ag+ (a?eueo
?icieoa) a iaeano? r=[Ag+]/P0,1 (iae.3), ui na?ae/eoue i?i
?aeaioe/i?noue no?oeoo?e oeeo iaoaeieiiieaen?a a cacia/aiiiio ae?aiacii?
eiioeaio?aoe?e. I?e r>0,1 ?iie Ag+ ooai?ththoue eiiieaen ae?oaiai oeio
(“neaaeee” eiiieaen), ui noi?iaiaeaeo?oueny ia?aoiaeii AeIE a iiao
aeaioni??aeueio eiioi?iaoe?th. ?ai?oa i?eioneaeiny, ui “neaaeee”
eiiieaen yaey? niaith i?noie
wmetafile8? ??%%???i???????ue???????????-??
???u??????????”????-????????§?oey???1/4???
????u????????1 – 210-4 M Ni2+; 2 – dGMP+5,510-3 M Ni2+; 3 –
dAMP+2,510-4 M Ni2+; 4 – niaeo? i?ioiioaaiiy dCMP. Eiai ?ioaineai?noue
ciaioaii a 20 ?ac?a. 1 a?aeiineoueny aei e?ai? i?aeeiaoe, 2 – 4 -aei
i?aai?.
wmetafile8? ??>???i???????ue???????????-??
???u??????????”????-????????E?t???m+???
????u/???????WnS^NNJ>E/A =95oe 1e -Ue )N &A “? ° Y ? ’ ? 1 –
r = 0,03; 2 – 0,05; 3 – 0,075; 4 – 0,3; 5 – 0,4; 6 – 0,55; 7 – 0,75; a ?
a – AeOON yaeythoue niaith noio aeeaae?a ie?aieo iiiiia??a i?e ooai?aii?
i?noea N7G-Ag-N3C (ooanoei?anueea ia?a) ? N1G-Ag+-N3C
(oionii-e?ee?anueea ia?a).
oeio N1G-Ag+-N3C, i?ioa aeai? iae.3 iieacothoue, ui a?eueo ia?aaaaeiei ?
eiiieaen oeio N7G-Ag-N3C, yeee ooai?th?oueny a ?acoeueoao? ia?aoiaeo
aoaiiceio ?c aioe- a n?i-eiioi?iaoe?th. Iiai?io iaaeiei ae?eiceaeiiai
ca’yceo iiaea aooe oa?aeoa?iei ? aeey eiiieaen?a AeIE n ?iiaie Ni2+ ?
Cd2+, i?ioa ooai?aiiy “neaaeiai” eiiieaeno i?e oeueiio ia a?aeaoaa?oueny
?c-ca aeoaea neaaeiai ca’ycoaaiiy oeeo ?ii?a c N3 dCMP (aeea. oaae.2).
A oeueiio ?icae?e? iiaeai? oaeiae ?acoeueoaoe ?ic?aooieo eiinoaio
ca’ycoaaiiy (E) ?ii?a II c ioeeaioeaeaie ? AeIE (oaae.3). I?e oeueiio
aoei aeei?enoaii iiaeaeue ca’ycoaaiiy Neao/a?aea:
r/Af(n-r) = K
(1a)
aai
r/Af(n-r) = K exp(-wr) = K(r )
(1a)
aea r – a?aeiinia eiioeaio?aoe?y ca’ycaieo eaiie, Af – eiioeaio?aoe?y
a?eueieo ?ii?a, K – eiinoaioa ca’ycoaaiiy i?e r = 0, K(r ) – aoaeoeaia
eiinoaioa ca’ycoaaiiy, ui oa?aeoa?eco? ??aiiaaao i?e eiaeiiio cia/aii?
r, w – aia?a?y aca?iiae?? ?ii?a (a iaeeieoeyo eO).
Iaea?aeai? aeai? aeicaieeee c?iaeoe oae? aeniiaee 1) eiinoaioa
ca’ycoaaiiy ?ii?a c iio?aeieie aoai?io iaeneiaeueia, 2) i?e ia?aoiae?
a?ae ioeeaioeae?a aei aeaioni??aeueii? AeIE eiinoaioe ca’ycoaaiiy ?ii?a
c?inoathoue ia 1-2 ii?yaeee, ui coiiaeaii, iaaii, noia?iiceoe??th
neeiaeo iie?a a ?aaoey?i?e no?oeoo?? iie?ia?o. 3) ??aaiue no?oeoo?ii?
i?aai?caoe?? IE aieeaa? ia o?eueee ia aaee/eio E, aea e ia oa?aeoa?
ca’ycoaaiiy ?ii?a. sseui aca?iiae?y c ie?aieie ioeeaioeaeaie ?
iaeiiia?aoeaiith, oi ca’ycoaaiiy c AeIE iiaea iaoe ye iaaaoeaio, oae ?
iiceoeaio eiiia?aoeai?noue (iae.4). Ia?oa – coiiaeaia aeaeueiiae??th
eoeii?anueeiai a?aeooiaooaaiiy i?ae ?iiaie, ca’ycaieie c iie?ia?ii, oa
?iiaie, ye? aaeni?aothoueny iei ?c ?ic/eio. Iiceoeaia eiiia?aoeai?noue
ooai?aiiy neaaeiai eiiieaeno iia’ycaia c eiiia?aoeai?noth ia?aoiaeo AeIE
a IAeE, yeee aeeeeea?oueny n??aeii.
Oaaeeoey 3
Eiinoaioe ca’ycoaaiiy ?ii?a iaoae?a c aoiiaie iniia ioeeaioeae?a
(10-3 I Na+; pH 6; 214C) ? i?e?iaeii? AeIE (10-2 I Na+; pH 6; 262C).
GMPdGMPAMPdAMPCMPdCMPAeIE
Ni2+(3,50,5)103
[N7](1,30,3)104
[N7](4,70,3)102
[N7](1,50,5)103
[N7]9104
[N7]
C=0
Cd2+(41)103
[N7](3,51,5)103
[N7](4,30,3)102
[N7](1,60,2)103
[N7]
6,5104
[N7]
C=0
Ag+(1,30,1)104
[N7](1,30,1)104
[N7](30,2)102
[N3](5,40,5)102
[N7]
(2,60,2)102
[N3](1,40,1)103
[N3]
(1,00,3)103
[O2](8,00,5)102
[N3]
(9,00,5)102
[I2]
2105
[N3C-Ag-N7G]
C=0Co2+(1,40,2)103
[N7]Cu2+(1,50,2)104
[N7]Zn2+(1,50,2)103
[N7]A eaaae?aoieo aeoaeeao iiaeai? aaoa?iaoiie iniia, ca’ycoaaiiy c
yeeie a?aeiia?aea? iaea?aeaiei cia/aiiyi E; N – nooi?iue ca’ycoaaiiy.
Iaea?aeai? cia/aiiy eiinoaio ca’ycoaaiiy ?ii?a II c GMP a?aeiia?aeathoue
iine?aeiaiino? ??a?iaa-A?eueyina: Co2+
eiiieaen?a ?ii?a II c ?a/iaeiaie ??cii? i?e?iaee.
C iae.5 aeaeii, ui caeaaeiino? a?ae 1/R ? iiiioiiii c?inoath/eie
ooieoe?yie ia o?eueee aeey ?ii?a ia?ao?aeieo, aea e eoaeii-caiaeueieo
iaoae?a. I?e/iio ona?aaeai? ?yaeo oe? caeaaeiino? aeey GMP ? IMP a
iaaeao iioeaee ? oi?aa?naeueieie ooieoe?yie iaa?iaiiai ?aae?ono. Oea
aeicaieeei c?iaeoe aeniiaie i?i oa, ui ??cieoey a cia/aiiyo E ?ii?a
iaoae?a c oeeie ioeeaioeaeaie ana?aaeai? eiaeii? a?oie aecia/a?oueny ia
no?eueee aeaeo?iiiith no?oeoo?ith ?ii?a, ne?eueee ?o ?ici??aie, ?, ye
iane?aeie, iiaa?oiaaith aonoeiith ca?yaeo. Aeiaiaeii ia ei?enoue oeueiai
aeniiaeo ? oa ianoaaeia, ui aeey ia?aaaaeii? a?eueoino? iaoaeieiiieaen?a
i?e ia?aoiae? a?ae ?ii?a Cu2+ aei ?ii?a Zn2+ (aeea. oaae.3) eiinoaioa
ca’ycoaaiiy ciaioo?oueny oaeei /eiii, ui ?? aaee/eia noa? aeecueeith aei
cia/aiiy E aeey ?ii?a Ni2+. I/aaeaeii, ui i?e/eiith oeueiai ?
aeecuee?noue ?ici???a ?ii?a Ni2+ ? Cu2+ (iae.5).
wmetafile8? ??u???-????????ue???????????-??
???u??????????”????-????????fmy???„Iae.4. Caeaaei?noue
eiinoaio ca’ycoaaiiy ?ii?a Ni2+, Cd2+ ? Ag+ c AeIE (1-3) ? ?ii?a Ag+ c
ioeeaioeaeaie (4 – dCMP; 5 – dAMP) a?ae nooiaith ca’ycoaaiiy (N) .
wmetafile8? ??”???-????????ue???????????-??
???u??????????”????-????????ythu????]o???
????u??????
Iae.5. Caeaaei?noue a?eueii? aia?a?? ca’ycoaaiiy (G) ?ii?a iaoae?a a?ae
aaee/eie ?o e?enoaeia?ao?/iiai ?aae?ono. G0 -a?eueia aia?a?y ?ii?a Nu2+.
, – Sigel et al., 1994; + – Trimm, Patel, 1979.
A ?icae?e? 4 aeeeaaeaii ?acoeueoaoe aeine?aeaeaiiy ia?aoiaeo
ni??aeue-eeoaie AeIE a i?enooiino? ?ii?a Ag+.
Aea/aiiy aieeao ?ii?a n??aea ia ia?aiao?e ieaaeaiiy AeIE aeeiiaii a
?ioa?aae? r =01,5 i?e ?iii?e nee? 10-2 I Na+. Ii/aoeiaa i?aeaeuaiiy
oa?iinoaa?eueiino? (iae.6) a?aeaoaa?oueny a ?ioa?aae? r = 0-0,08. I?e
iiaeaeueoiio ca?eueoaii? eiioeaio?aoe?? ?ii?a aaee/eia Tm iaeaea ia
ci?ith?oueny. Ii/eiath/e c r = 0,12 a?aeaoaa?oueny iiaeaeueoa c?inoaiiy
oaiia?aoo?e ieaaeaiiy AeIE.
Eiioeaio?aoe?eia caeaaei?noue ci?ie ?ioa?aaeo ieaaeaiiy AeIE oaeiae
aeyaey? aea? nooo?ai ??cieo ae?eyiee (iae.6). A iaeano? iaeeo
eiioeaio?aoe?e n??aea niinoa??aa?oueny eiai ?icoe?aiiy, i?ioiaeaeaiiy
/a?ac iaeneioi ? iio?i ciaioaiiy aei cia/aiiy 7-8N, yea caa??aa?ouenya
?ioa?aae? r = 0,1-0,14. I?e r > 0,14 ?ioa?aae ieaaeaiiy ciia ii/eia?
c?inoaoe. Oaeo iiaaae?ieo ia?aiao??a ia?aoiaeo ni??aeue-eeoaie AeIE a
i?enooiino? ?ii?a Ag+ aeyaeaii aia?oa.
Oaeei /eiii, ca?aeii c aeaieie iae.3, iaea?aeai? ?acoeueoaoe c oa?i?/ii?
aeaiaoo?aoe?? oaeiae na?ae/aoue i?i iayai?noue aeaio oei?a ca’ycoaaiiy.
Nooo?ai, ui “neeueiee” eiiieaen ia? iaioo oa?iinoaa?euei?noue, i?ae
“neaaeee”. Iai?eeeaae, i?e r 0,75 e 1,5 aeaini??aeueia no?oeoo?a
caa??aa?oueny, o anyeiio ?ac?, aei 97N (iae.7).
wmetafile8? ?????i???????ue???????????-??
???u??????????”????-????????O?!????r???
????u>???????
Iaea?aeai? aenia?eiaioaeuei? aeai? ocaiaeaeothoueny c ia?aaeaa/aiiyie
oai???wmetafile8? ??O,???i???????ue???????????-??
???u??????????”????-????????µ?????”???
????u0???????1 -r = 0; 2 – 0,015; 3 – 0,031; 4 – 0,061; 5 – 0,1; 6 –
0,16; 7 – 0,315; 8 – 0,417; 9 – 0,75 ? 1,5.
“ne??iie” (O?aie-Eaiaiaoeueeee, 1968). Ca?aeii c oe??th oai???th aeey
aeiaaeeo“neeueiiai” ca’ycoaaiiy
(aiii ? oa?aeoa?iei aeey ?ii?a Ag+ i?e ooai?aii? “neeueiiai” eiiieaeno)
ci?ia ?ioa?aaeo ieaaeaiiy a 2 ?ace ia?aa?eueoo? ci?io oaiia?aoo?e
ia?aoiaeo ni??aeue-eeoaie. A?aeiia?aeia a?aeiioaiiy t/Tm
aeey ia?oeo o?ueio eiioeaio?aoe?e
Ag+ (iae.6) aei??aith? 2,30,1. Oaeei /eiii, iiaaae?iea oaiia?aoo?e ?
?ioa?aaeo ieaaeaiiy, a oaeiae neeueia aneiao??y e?eaeo ieaaeaiiy AeIE
(iae.7) aiaeano? ?nioaaiiy “neeueiiai” eiiieaeno (iae.6) coiiaeaia
ia?a?iciiae?eii ?ii?a c ?icieaoaieo ia ni??aeuei? ae?eyiee AeIE a
i?ioean? ia?aoiaeo ni??aeue-eeoaie.
Aeiaeaoee ai?uothoue iniiai? oi?ioee aeey ?ic?aooaaiiy eiinoaio
ca’ycoaaiiy ?ii?a iaoae?a c iniiaaie IE, a oaeiae e?eaeo oaciai?
??aiiaaae.
AENIIAEE
1. Ca?aeii c a?aeiieie aenia?eiaioaeueieie aeaieie, iaea?aeaieie
aieiaiei /eiii a nenoaiao ?c cieaeaiith aeoeai?noth aiaee, iniiaieie
aoiiaie iniia io?eiiaeo ioeeaioeae?a, ui eii?aeeiothoue aea/ai? ?iie o
aiaeieo ?ic/eiao, ? N7. E??i oiai, ia aeeoa?aioe?eieo niaeo?ao aeyaeaii
iniaeeaino?, ui aeicaieythoue i?eionoeoe aca?iiae?th ?ii?a c
ea?aii?eueieie eeniyie iio?aeieo aoai?io, yea iaea?eueo neeueii
aeyaey?oueny o ?ii?a Ag+ , Cu2+ oa Ni2+.
2. ?iie Ag+ eii?aeeiothoue c N3 ?, iiaeeeai, c I2 iio?aeieo oeeoiceio.
Iaaiaee, aca?iiae?y ?ii?a Ni2+ ? Cd2+ c N3C ? aeoaea neaaeith aai cian?i
a?aenooiy ia o?eueee ia iiiiia?iiio ??ai?, aea e o aeiaaeeo iie? N.
3. Iniiaiei ca’ycoth/ei aea/ai? ?iie aoiiii i?e?iaeii? AeIE ? N7G,
aca?iiae?y c yeei aeeeeea? ia?aiin i?ioiio a?ae N1G aei N3C a G-C-ia?ao.
I?e ooai?aii? oeueiai (“neeueiiai”) eiiieaeno eiioi?iaoe?y AeIE nooo?ai
ia ci?ith?oueny. ?iie Ag+ ooai?ththoue oaeiae “neaaeee” eiiieaen, a
eio?iio cai?noue i?noea N1G-Ag-N3C, ui i?eioneaany ?ai?oa, a?eueo
ia?aaaaeiei ? oaeao N7G-Ag-N3C, caeaoiee ooai?thaaoeny a ?acoeueoao?
ia?aoiaeo aoaiiceio ?c aioe- a n?i-eiioi?iaoe?th. A i?enooiino? ?ii?a
Ni2+ oa Cd2+ iiae?aiee eiiieaen ia ooai?th?oueny ?c-ca a?aenooiino?
ca’ycoaaiiy oeeo ?ii?a c N3C.
4. A?aei?ia o ca’ycoaaii? ?ii?a Ag+, Cd2+ ? Ni2+ c iniiaaie ??cii?
i?e?iaee aecia/a?oueny ??cieoeath aaee/eie iiaeoey iieaeoey?iiai
aeaeo?inoaoe/iiai iioaioe?aeo (IAI) ia a?aeiia?aeiiio aaoa?iaoii?.
5. ??cieoey a a?euei?e aia?a?? ca’ycoaaiiy ?ii?a ia?ao?aeieo iaoae?a
3d-a?oie c GMP a iniiaiiio aecia/a?oueny ??cieoeath ?iiieo ?aae?on?a e,
ye iane?aeie, iiaa?oiaai? aonoeie ca?yaeo ?ii?a.
6. Anoaiiaeaii aieea ??aiy no?oeoo?ii? i?aai?caoe?? ioeea?iiaeo eeneio
ia oa?aeoa? ?o ca’ycoaaiiy c ?iiaie Ni2+, Cd2+ ? Ag+:
a) i?e ia?aoiae? a?ae ioeeaioeaea aei aeaini??aeueii? AeIE eiinoaioa
ca’ycoaaiiy ?ii?a c?inoa? ia 1-2 ii?yaeee;
a) ia a?aei?io a?ae iaeiiia?aoeaii? aca?iiae?? ?ii?a c ioeeaioeaeaie, ?o
ca’ycoaaiiy c iniiaaie AeIE ia? iaaaoeaio aai iiceoeaio
eiiia?aoeai?noue. Ia?oa oa?aeoa?ia aeey ?ii?a Ni2+ oa Cd2+ ? coiiaeaia
aeaeueiiae??th eoeii?aneiai a?aeooiaooaaiiy i?ae ?iiaie, ye? ca’ycai? c
iie?ia?ii, oa ?iiaie, ye? aaeni?aothoueny iei ?c ?ic/eio. Iiceoeaia
eiiia?aoeai?noue ooai?aiiy ?iiaie Ag+ “neaaeiai” eiiieaeno –
eiiia?aoeai?noth ia?aoiaeo AeIE a iiao aeaini??aeueio eiioi?iaoe?th.
7. Aecia/ai? ia?aiao?e ia?aoiaeo ni??aeue-eeoaie AeIE a i?enooiino?
?ii?a Ag+. Aia?oa aeyaeaii aiiiaeueio oi?io eiioeaio?aoe?eii?
caeaaeiino? ?? oaiia?aoo?e ? ?ioa?aaeo ieaaeaiiy, yea i?aeoaa?aeaeo?
iayai?noue “neaaeiai” ? “neeueiiai” oei?a ca’ycoaaiiy n??aea c AeIE.
Ooai?aiiy inoaiiueiai iieno?oueny oai???th ne??iie. Iiaaae?iea
ia?aiao??a ia?aoiaeo ni??aeue-eeoaie AeIE aecia/a?oueny ia?a?iciiae?eii
?ii?a i?ae ni??aeueiith oa eeoaeiiiae?aiith oacaie AeIE a i?ioean?
ieaaeaiiy.
NIENIE IIOAE?EIAAIEO I?AOeUe CA OAIITH AeENA?OAOe??
1. Sorokin V.A., Valeev V.A., Gladchenko G.O., Sysa I.V., Blagoi Yu.P.,
Volchok I.V.. Interaction of bivalent Cu2+, Ni2+, Mn2+ ions with native
DNA and its monomers // J. Inorg. Biochem. – 1996. – V. 63, N 2. – P.
79-98.
2. Sorokin V.A., Sysa I.V., Valeev V.A., Gladchenko G.O., Degtyar M.V.
and Blagoi Yu.P.. Differential UV-Spectroscopic Studies of Transition
Metal Ion Interaction with DNA and Its Monomers // J. of Mol. Struct. –
1996. – N 408-409. – P. 233-236.
3. Ni?ieei A.A., Aaeaaa A.A., Aeaae/aiei A.I., Nuna E.A. Eco/aiea
acaeiiaeaenoaey eiiia aeaooaaeaioiiai eaaeiey n ioeeaioeaeaie e
i?e?iaeiie AeIE // Aeioeceea. – 1997. – T. 42, aui. 1. – N. 105-116.
4. V.A.Sorokin, V.A.Valeev, I.V.Sysa, G.O.Gladchenko, M.Degtyar,
Yu.P.Blagoi. Nature of differences in binding of transition metal ions
with bases of nucleic acids // Proc. of VII Eur. Conf. on Spectroscopy
of Biol. Mol.(ECSBM-7). – Madrid, Spain. – Publ. Kluwer, Ac. Press,
Dordrecht, Boston, London. – 1997. – P. 35-36.
5. Sysa I.V., Sorokin V.A., Valeev V.A., Gladchenko G.O., Degtyar M.V.
and Blagoi Yu.P. Cd2+ and Ag+ ion interaction with nucleotides and
natural DNA // Book of Abstr. of 7th Internat. Symp. On Macromol. Metal
Complexes (MMC-7). – Noordwijkerhout, The Netherlands. – 1997. – P100.
6. Nena ?.A., Ni?ie?i A.I., Aae??a A.I., Aeaae/aiei A.I., Aeaaoy? I.A.,
Aeaaie TH.I. Aca?iiae?y ?ii?a Ag+ c i?e?iaeiithAeIE ? ioeeaioeaeaie //
Oace aeiiia?aeae ?? c’?caeo Oe?. A?io. Oia. (OAOO-98). – Oa?e?a,
Oe?a?ia. – 1998. – N. 31.
7. Sysa I.V., Sorokin V.A., Valeev V.A., Gladchenko G.O., Degtyar M.V.,
Blagoi Yu.P. Effects of ionic radius on formation of coordination bonds
in metal complexes of GMP // Book of Abstr. of XXXIII Internat. Conf. On
Coordination Chemistry (ICCC XXXIII). – Florence, Italy. – 1998. – P.
651.
AIIOAOe?ss
Nena ?.A. Aea/aiiy iniaeeainoae aca?iiae?? ?ii?a ia?ao?aeieo iaoae?a c
ioeea?iiaeie eeneioaie, ui ciaoiaeyoueny ia ??cieo ??aiyo no?oeoo?ii?
i?aai?caoe??.- ?oeiien.
Aeena?oaoe?y ia caeiaoooy iaoeiaiai nooiaiy eaiaeeaeaoa
o?ceei-iaoaiaoe/ieo iaoe ca niaoe?aeuei?noth 03.00.02 – a?io?ceea.-
Oa?e?anueeee aea?aeaaiee oi?aa?neoao, Oa?e?a, 1999.
I?iaaaeaii aenia?eiaioaeueia aeine?aeaeaiiy eiiieaeniooai?aiiy ?ii?a
ia?ao?aeieo iaoae?a c ??ai- ? aeaciene??aiioeeaioeaeaie on?o eaiii?/ieo
iniia ? i?e?iaeii? AeIE o aiaeieo ?ic/eiao. Aei??yii aeeoa?aioe?ei?
OO-niaeo?e iaoaeieiiieaen?a, ui aeicaieeei aecia/eoe aaoa?iaoiie iniia,
ye? eii?aeeiothoue ?iie, a oaeiae ?ic?aooaaoe a?aeiia?aei? eiinoaioe
ca’ycoaaiiy. Anoaiiaeaii, ui a?aei?iiino? a eiiieaeniooai?aii? aea/aieo
?ii?a c AeIE aecia/athoueny a?aei?iiinoyie a ca’ycoaaii?, ui
i?iyaeythoueny aaea ia iiiiia?iiio ??ai?. ??cieoey o a?euei?e aia?a??
ca’ycoaaiiy ?ii?a ia?ao?aeieo iaoae?a c GMP aecia/a?oueny a?aei?ii?noth
?o ?iiieo ?aae?on?a. A oe?ieiio ?ioa?aae? ai?noo ?ii?a iaoaeo iaea?aeaii
eiioeaio?aoe?ei? caeaaeiino? ci?ie oaiia?aoo?e ? ?ioa?aaeo ieaaeaiiy
AeIE a i?enooiino? ?ii?a Ag+, ui aeicaieeei aia?oa ca?a?no?oaaoe
iaoiaeii oa?i?/ii? aeaiaoo?aoe?? ooai?aiiy n??aeii aeaio ??cieo oei?a
eiiieaen?a. Cai?iiaiiaaii aeueoa?iaoeaio ?nioth/ei iiaeaeue “neaaeiai”
eiiieaeno, yea i?eionea? ooai?aiiy ooanoei?anueeeo GC-ia?.
Eeth/ia? neiaa: ?iie ia?ao?aeieo iaoae?a, AeIE, ioeeaioeae,
iaoaeieiiieaen, aeeoa?aioe?iee OO-niaeo?, oa?i?/ia aeaiaoo?aoe?y.
AIIIOAOeEss
Nuna E.A. Enneaaeiaaiea iniaaiiinoae acaeiiaeaenoaey eiiia ia?aoiaeiuo
iaoaeeia n ioeeaeiiauie eeneioaie, iaoiaeyueieny ia ?acee/iuo o?iaiyo
no?oeoo?iie i?aaiecaoeee.- ?oeiienue.
Aeenna?oaoeey ia nieneaiea o/aiie noaiaie eaiaeeaeaoa
oeceei-iaoaiaoe/aneeo iaoe ii niaoeeaeueiinoe 03.00.02 – aeioeceea.-
Oa?ueeianeee ainoaea?noaaiiue oieaa?neoao, Oa?ueeia, 1999.
I?iaaaeaii yenia?eiaioaeueiia enneaaeiaaiea eiiieaeniia?aciaaiey eiiia
ia?aoiaeiuo iaoaeeia n ?eai- e aeaciene?eaiioeeaioeaeaie anao
eaiiie/aneeo iniiaaiee e i?e?iaeiie AeIE a aiaeiuo ?anoai?ao. Ecia?aiu
aeeooa?aioeeaeueiua OO-niaeo?u iaoaeeieiiieaenia, /oi iicaieeei
ii?aaeaeeoue aaoa?iaoiiu iniiaaiee, eii?aeeie?othuea eiiu, a oaeaea
?ann/eoaoue niioaaonoaothuea eiinoaiou naycuaaiey. ?acee/ey a
eiieaeniia?aciaaiee eco/aiiuo eiiia n AeIE ii?aaeaeythony ?acee/eyie a
naycuaaiee, i?iyaeythueieny oaea ia iiiiia?iii o?iaia. ?acee/ey a
naiaiaeiie yia?aee naycuaaiey eiiia ia?aoiaeiuo iaoaeeia n GMP
ii?aaeaeythony ?acee/eai eo eiiiuo ?aaeeonia. A oe?ieii eioa?aaea
niaea?aeaiey eiiia iaoaeea iieo/aiu eiioeaio?aoeeiiiua caaeneiinoe
eciaiaiey oaiia?aoo?u e eioa?aaea ieaaeaiey AeIE a i?enoonoaee eiiia
Ag+, /oi iicaieeei aia?aua ca?aaeno?e?iaaoue iaoiaeii oa?ie/aneie
aeaiaoo?aoeee ia?aciaaiea na?aa?ii aeaoo ?acee/iuo oeiia eiiieaenia.
I?aaeeiaeaia aeueoa?iaoeaiay nouanoaothuei iiaeaeue “neaaiai” eiiieaena,
i?aaeiieaaathuay ia?aciaaiea ooanoeiianeeo GC-ia?.
Eeth/aaua neiaa: eiiu ia?aoiaeiuo iaoaeeia, AeIE, ioeeaioeae,
iaoaeeieiiieaen, aeeoa?aioeeaeueiue OO-niaeo?, oa?ie/aneay
aeaiaoo?aoeey.
SUMMARY
Sysa I.V. Studies on peculiarities of transition metal ions interaction
with nucleic acids of different levels of structural organization. –
Manuscript.
Thesis for candidate’s degree by specialty 03.00.02 – biophysics. –
Kharkov State University, Kharkov, 1999.
The interest in metal complexes of nucleic acids is first of all
stimulated by the importance of metal ions to the functions of native
polynucleitides. For example these ions influence the synthesis rate and
accuracy of the nucleotide sequence in DNA- and RNA-polymerase system,
participate in the formation of protein-nucleotide complexes, and cause
mutagenesis and carcinogenesis. Molecular mechanisms of metal toxicity
affecting living organisms have recently become even more topical in
the context of general environmental contamination. Therefore, the basic
problem is to model real structure of metal complexes, and thus to find
the molecular mechanisms of the biological action of metal ions as well
as to assign the heteroatoms of nucleic acid bases which coordinate the
ions.
The information on this subject is ample, but in the case of aqueous
solutions, it is unambiguous only for complexes, including phosphates,
N7 of purines and N3 of cytosine. Weaker interactions are disputable
even at monomeric level. Interpretation of the experimental evidence
obtained for polynucleotides is naturally even more complex.
The present study is devoted to experimental investigation of transition
metal ion complexes formation with ribo- and deoxyribonucleotides of all
canonical bases and natural DNA in aqueous solutions. Differential UV
spectra were measured, the analysis of the shapes of which allowed us to
determine heteroatoms of the bases, coordinating ions, and to calculate
corresponding binding constants.
In accordance with known experimental data mainly obtained in systems
having lowered water activity, the main atom of purine nucleotide bases,
coordinating ions studied, in water solution is N7. Besides,
peculiarities in the difference spectra permit to assume ion
interaction with carbonilyc oxygens of guanine derivatives which more
distinct in the case of Ag+, Cu2+ and Co2+. Differences in the ions
complex formation with DNA determined by differences in binding showing
already in monomeric level. Differences in the free energy of transition
metal ions binding to GMP is caused by differences in their ion radii.
Concentration dependencies of change in temperature and interval of DNA
melting in the presence of Ag+ were obtained in wide range of the metal
ion content. This permitted to register first the formation of two
different silver complexes, by the thermal denaturation method. An
alternative model of a weak complex is proposed, supporting the
formation of Hoogsteen GC-pairs.
Key words: transition metal ions, DNA, nucleotide, differential UV
spectra, thermal denaturation.
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