Вплив іонів металів на структурні переходи ДНК у водних розчинах спиртів та сечовини: Автореф. дис… канд. фіз.-мат. наук / О.В. Хакл, Харк. держ. ун

I?I?NOA?NOAI INA?OE OE?A?IE

OA?E?ANUeEEE AeA?AEAAIEE OI?AA?NEOAO

OAEE Ieaia Aanee?aia

OAeE 577.323

AIEEA ?II?A IAOAE?A IA NO?OEOO?I? IA?AOIAeE aeie

O AIAeIEO ?IC*EIAO NIE?O?A OA NA*IAEIE

03.00.02 — a?io?ceea

Aaoi?aoa?ao aeena?oaoe?? ia caeiaoooy iaoeiaiai nooiaiy

eaiaeeaeaoa o?ceei-iaoaiaoe/ieo iaoe

Oa?e?a — 1999

Aeena?oaoe??th ? ?oeiien.

?iaioa aeeiiaia o a?aeae?e? iieaeoey?ii? a?io?ceee O?ceei-oaoi?/iiai
?inoeoooo iecueeeo oaiia?aoo? ?i. A. ?. A??e?ia IAI Oe?a?ie.

Iaoeiaee ea??aiee:

aeieoi? o?ceei(iaoaiaoe/ieo iaoe, i?ioani?,

AEAAIE TH??e Iaaeiae/,

O?ceei-oaoi?/iee ?inoeooo iecueeeo oaiia?aoo? ?i. A. ?. A??e?ia IAI
Oe?a?ie, caa?aeoaa/ a?aeae?eo iieaeoey?ii? a?io?ceee.

Io?oe?ei? iiiiaioe:

aeieoi? o?ceei-iaoaiaoe/ieo iaoe, i?ioani?, Aanaeeia Ieaen?e Ieeiiiae/,
Naaanoiiieuenueeee aea?aeaaiee oaoi?/iee oi?aa?neoao, aee?aeoi?
aeaia?oaiaioo o?ceee oa o?i??;

eaiaeeaeao o?ceei-iaoaiaoe/ieo iaoe, Aieueaoo Oii A?eoi?iae/, ?inoeooo
?aae?io?ceee oa aeaeo?ii?e? ?i. A.ss.On?eiaa IAI Oe?a?ie, noa?oee
iaoeiaee ni?a?ia?oiee a?aeae?eo a?io?ceee (i. Oa?e?a).

I?ia?aeia onoaiiaa:

?inoeooo o?ceee IAI Oe?a?ie, i. Ee?a.

Caoeno a?aeaoaeaoueny « 29 » ea?oiy 1999 pieo i 15
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 « 27 » 03 1999 ?.

A/aiee nae?aoa?

niaoe?ae?ciaaii? a/aii? ?aaee Aaoao
N. A.

1

CAAAEUeIA OA?AEOA?ENOEEA ?IAIOE

Aeooaeuei?noue oaie. Aea/aiiy aca?iiae?? AeIE c ?iiaie iaoae?a ia?
aaeeea cia/aiiy c oi/ee ci?o aaaeeeai? ?ie?, eio?o a?ae?a?athoue ?iie
iaoae?a a i?ioean? ooieoe?iioaaiiy aaiaoe/iiai aia?aoo in vivo. ?acii c
aiaeith, ?iie iaoae?a noaa?e?cothoue no?oeoo?e ioeea?iiaeo eeneio,
aecia/athoue ??aiiaaao i?ae ??cieie oi?iaie aoi?eiii? oa o?aoeiii?
no?oeoo?e. Cia/aiiy aeine?aeaeaiiy ae?? ?ii?a iaoae?a ia no?oeoo?o AeIE
iniaeeai c?inoa? o ca’yceo c aeieia?/iei oa ?aae?aoe?eiei caa?oaeiaiiyi
aeiae?eey. E??i oiai, eiiieaene AeIE c ?iiaie iaoae?a iiaeooue i?aaeoe
ca iiaeaeueio nenoaio i?e aea/aii? ae?? oe?eiai ?yaeo e?ea?nueeeo
?a/iaei, ui niieo/athoueny c ioeea?iiaeie eeneioaie ca eao?iiei
iaoai?ciii, ia no?oeoo?o AeIE.

A?aeiii, ui eiiiaeoecaoe?y AeIE ? iaa?ae’?iiith /anoeiith i?ioeano
ooieoe?iioaaiiy AeIE in vivo, oiio aea/aiiy i?ioeano eiiiaeoecaoe??
aeeeeea? aaeeeee ?ioa?an c iiaeyaeo ?ice?eooy o?ce/ieo iaoai?ci?a,
a?aeiia?aeaeueieo ca ooieoe?iioaaiiy a?ieia?/ieo iieaeoe. I?ioa
iayai?noue oa iaoai?ci eiiiaeoecaoe?? AeIE i?ae ae??th aeaiaaeaioieo
?ii?a iaoae?a o aiaeieo ?ic/eiao i?aeoe/ii ia aea/ai?. E??i oiai, in
vivo AeIE ciaoiaeeoueny a oiiaao cieaeaii? aeoeaiino? aiaee, ye? in
vitro iiaeooue iiaeaeth-aaoeny oeyoii aeiaeaaaiiy aei ?ic/eio AeIE iaio
iiey?ieo, i?ae aiaea, ?ic/eiiee?a. Oiio i?aaenoaaey?oueny oe?eaaei
aea/eoe no?oeoo?i? ia?aoiaee AeIE i?ae ae??th aeaiaaeaioieo ?ii?a
iaoae?a o ci?oaieo ?ic/eiao, ye? i?noyoue aeii?oee iaaeaeo?ie?o?a.

Ca’ycie ?iaioe c iaoeiaeie i?ia?aiaie, ieaiaie, oaiaie. Aeena?oaoe?y
aeeiioaaeanue o a?aeiia?aeiino? c ieaiii iaoeiai-aeine?aeieo ?ia?o
a?aeae?eo iieaeoey?ii? a?io?ceee O?ceei-oaoi?/iiai ?inoeoooo iecueeeo
oaiia?aoo? ?i. A.?.A??e?ia IAI Oe?a?ie ca oaiith «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).

Iaoa ? caaea/? aeine?aeaeaiiy. Iaoa ?iaioe — aea/aiiy no?oeoo?ieo
ia?aoiae?a AeIE, ye? a?aeaoaathoueny i?e aca?iiae?? c ?iiaie Cu2+ oa
Na2+ o ?ic/eiao, oa anoaiiaeaiiy aieeao iecee oaeoi??a (ae?aeaeo?e/ii?
i?iieeiino?, no?oeoo?e ?ic/eio, oaiia?aoo?e) ia no?oeoo?i? ia?aoiaee
AeIE.

O a?aeiia?aeiino? aei aeacaii? iaoe caaaeaiiyie aeine?aeaeaiiy aoee:

aea/eoe no?oeoo?i? ia?aoiaee AeIE, ui a?aeaoaathoueny i?e aca?iiae?? c
?iiaie iaoae?a ??cii? aaeaioiino? o aiaeiiio ?ic/ei?, iaoiaeii ?*
niaeo?ineii??;

i?iaanoe ii??aiyeueiee aiae?c aieeao ?a/iaei, ye? noaa?e?cothoue oa
?oeiothoue no?oeoo?o aiaee, ia Cu2+- oa Na2+-?iaeoeiaaio eiiiaeoecaoe?th
AeIE a oe?ieiio ?ioa?aae? eiioeaio?aoe?e iaaeaeo?ie?o?a oa aeaiaaeaioieo
?ii?a iaoae?a;

2

aeine?aeeoe aca?iiae?th iie?oinoao?a ye iiaeaeueii? nenoaie AeIE c
?iiaie Cu2+ oa Na2+ o aiaeiiio oa ci?oaieo ?ic/eiao, ui i?noyoue aoaiie,
1,2-i?iiaiae?ie oa ae?oea?ei;

i?iaanoe aiae?c io?eiaieo ?acoeueoao?a a ?aieao oai??e eiiaeainaoe??
i?ioe?ii?a oa ??aiiaaaeiiai ca’ycoaaiiy; ia?aoe iiaeaeue, ui a?eueo
aaeaeaaoii iieno? aca?iiae?th ?ii?a aeaiaaeaioieo iaoae?a c AeIE.

Iaoeiaa iiaecia iaea?aeaieo ?acoeueoao?a.

a ?iaio? aia?oa iieacaii, ui ia?ao?ae AeIE o eiiiaeoio oi?io iiaea
i?ecaiaeeoe aei neeueiiai ca?eueoaiiy ?ioaineaiinoae nioa iiaeeiaiiy o
?*-niaeo?? AeIE;

iieacaia iiaeeea?noue eiiiaeoecaoe?? aenieiiieaeoey?ii? AeIE i?ae ae??th
aeaiaaeaioieo ?ii?a iaoae?a (Cu2+ oa Na2+) o aiaeiiio ?ic/ei? i?e
e?iiaoi?e oaiia?aoo??. Cai?iiiiiaaia iiaeaeue eiiiaeoecaoe??, iaea?aeai?
ioe?iee eiinoaio ca’ycoaaiiy oa ia?aiao??a eiiia?aoeaiino?;

aia?oa i?iaaaeaii aea/aiiy aieeao ?yaeo iaaeaeo?ie?o?a (aoaiieo,
1,2-i?iiaiae?ieo, ae?oea?eio) oa oaiia?aoo?e ia eiiiaeoecaoe?th AeIE o
?ic/ei? i?ae ae??th ?ii?a Cu2+ oa Na2+ o oe?ieiio ?ioa?aae?
eiioeaio?aoe?e iaaeaeo?ie?o?a (0 ( 20 ia.%);

aia?oa aea/aii aieea na/iaeie ia eiiiaeoecaoe?th AeIE o ?ic/ei? i?ae
ae??th ?ii?a Cu2+;

aia?oa aeine?aeaeaii aieea aoaiieo, 1,2-i?iiaiae?ieo oa ae?oea?eio ia
no?oeoo?i? ia?aoiaee o iie?oinoaoao i?ae ae??th ?ii?a Na2+ o ci?oaieo
?ic/eiao a ?ioa?aae? eiioeaio?aoe?e iaaeaeo?ie?o?a 0 ( 15 ia.%.

I?aeoe/ia cia/aiiy iaea?aeaieo ?acoeueoao?a. Iaea?aeai? a ?iaio?
aenia?eiaioaeuei? aeai? i?i aieea neeaaeo ?ic/eiieea oa oaiia?aoo?e ia
no?oeoo?i? ia?aoiaee AeIE i?ae ae??th ?ii?a iaoae?a iiaeooue ciaeoe
canoinoaaiiy i?e ?ic?iaoe? oa aea/aii? aieeao e?ea?nueeeo ?a/iaei, ui
ciaoiaeyoueny o eao?iii?e oi?i?, ia AeIE. Aeai? i?i aieea ?ii?a iaoae?a
ia no?oeoo?i? ia?aoiaee AeIE o ?ic/eiao oaeeo e??ii?ioaeoi??a, ye
1,2-i?iiaiae?ie oa ae?oea?ei, ui oe?iei canoiniaothoueny, iiaeooue aooe
aeei?enoai? o e??ia?ieia?? i?e ?ic?iaoe? iaoiaeee caa??aaiiy aaiaoe/iiai
iaoa??aeo.

Iniaenoee aianie caeiaoaa/a. A ?iaioao 1,3-5,10-12: aiae?c ioae?eaoe?e
ca oaiith, io?eiaiiy aenia?eiaioaeueieo aeaieo oa ?o ia?iaea, ?ic?aooiee
eiinoaio ca’ycoaaiiy oa ia?aiao??a eiiia?aoeaiino?, o/anoue o
iaaiai?aii? ?acoeueoao?a oa oi?ioethaaii? aeniiae?a. A ?iaio? 2: o/anoue
o i?iaaaeaii? aei??thaaiue, o/anoue a ia?iaoe? oa aiae?c?
aenia?eiaioaeueieo aeaieo oa a iaaiai?aii? ?acoeueoao?a. A ?iaioao 6-9:
aanue ianya ?ia?o, iia’ycaiee c iinoaiiaeith caaea/?, aiae?cii
ioae?eaoe?e ca oaiith, io?eiaiiyi aenia?eiaioaeueieo aeaieo oa ?o
iaoaiaoe/iith ia?iaeith, oi?ioethaaiiyi aeniiae?a.

3

Ai?iaaoe?y ?acoeueoao?a aeena?oaoe??. ?acoeueoaoe ?iaioe ca oaiith
aeena?oaoe?? aeiiia?aeaeeny ? iaaiai?thaaeeny ia 2 iaoe?iiaeueieo oa 13
i?aeia?iaeieo eiioa?aioe?yo: XII oeiea-nai?ia? «Niaeo?ineiiiy iieaeoe oa
e?enoaeia» (I?aeei, 1995); II c’?cae oe?a?inueeiai a?io?ce/iiai
oiaa?enoaa (Oa?e?a, Oe?a?ia, 1998); NATO-ASI Conference «Cytotoxic,
Mutagenic and Carcinogenic Potential of Heavy metals Related to Human
Environment» (Poland, 1996); 3rd European Conference on Bio-inorganic
Chemistry (The Netherlands, 1996); XXIII European Congress on Molecular
Spectroscopy (Hungary, 1996); Second International Symposium «Algorithms
for Macromolecular Modelling» (Germany, 1997); 2nd European Biophysics
Congress (France, 1997); 16th Annual International Meeting of the
Molecular Graphics and Modelling society «Model(l)ing ’97» (Germany,
1997); 7th European Conference on Spectroscopy of Biological Molecules
(Spain, 1997); 6th International Summer School on Biophysics
«Supramolecular structure and function» (Croatia, 1997); 7th
International Symposium on Macromolecule-Metal Complexes MMC7 (The
Netherlands,1997); Summer School «Physics of molecular biology»
(Denmark, 1998); XXXIII International conference on coordination
chemistry «The Chemistry of Metal Ions in Everyday Life» (Italy, 1998);
Conference on Physics of Biological Systems (Ukraine, 1998); NATO-ASI
«Metal-Ligand Interactions in Chemistry, Physics and Biology» (Italy,
1998).

Ioae?eaoe??. ?acoeueoaoe aeena?oaoe?? iioae?eiaaii a 12 iaoeiaeo
i?aoeyo, o oiio /ene? a 9 noaooyo oa a 1 iaoa??aeao ? 2 oacao
eiioa?aioe?e.

No?oeoo?a e ianya aeena?oaoe??. Aeena?oaoe?y neeaaea?oueny c? anooio,
i’yoe ?icae?e?a, aeniiae?a ? nieneo aeei?enoaieo e?oa?aoo?ieo aeaea?ae
(238 iaeiaioaaiue). Iiaiee ianya aeena?oaoe?? neeaaea? 188 noi??iie, c
ieo nienie aeei?enoaieo e?oa?aoo?ieo aeaea?ae — 23 noi?., ?ethno?aoe??
— 34 noi?.

INIIAIEE CI?NO ?IAIOE

O anooi? iaa?oioiaaii aeooaeuei?noue ia?aii? oaie, noi?ioeueiaai? iaoa ?
caaea/? aeine?aeaeaiiy, aecia/aia iaoeiaa iiaecia ? i?aeoe/ia oe?ii?noue
iaea?aeaieo ?acoeueoao?a.

A ?icae?e? 1 iiaeaii e?oa?aoo?iee iaeyae, yeee ioiieth? aiae?c
oai?aoe/ieo oa aenia?eiaioaeueieo aeine?aeaeaiue, ui noinothoueny aieeao
?ii-a?ae?aoiiai ioi/aiiy ia no?oeoo?o oa eiioi?iaoe?ei? ia?aoiaee AeIE o
?ic/eiao, eiiaeainaoe?? AeIE, a oaeiae aeei?enoaiiy iaoiaeo
?*-niaeo?ineii?? aeey aea/aiiy no?oeoo?ieo ia?aoiae?a o ioeea?iiaeo
eeneioao.

A ?icae?e? 2 aeaii oa?aeoa?enoeeo ia’?eo?a oa iaoiae?a aeine?aeaeaiue.
Ia’?eoaie aeine?aeaeaiue aoee iaoeaia AeIE oeiona oaeyoe c iieaeoey?iith
aaaith 1.9*107 Da, AeIE «Serva» c iieaeoey?iith aaaith 2(106 Da oa
iie?oinoaoe Nan+2PnO3n+1 «Sigma» c na?aaeiueith aeiaaeeiith eaioethaa
65(5 P. I?aia?aoe AeIE oa iie?oinoao?a ?ic/eiyee a 10-3 aai 5(10-3 I

4

eaeiae?eaoiiio aooa??, ?I 7.0. E?ioeaaa eiioeaio?aoe?y AeIE noaiiaeea
(3.5(5.5)(10-2 I oinoi?o.

A ?iaio? aeei?enoiaoaaeenue: iaoiae ?*-niaeo?ineii??, yeee aeicaiey?
aea/aoe ooai?aiiy eiiieaen?a AeIE c ?iiaie iaoae?a o ?ic/ei? oa
no?oeoo?i? ia?aoiaee, ui iiaeooue a?aeaoaaoeny o iae?iiieaeoe? a
?acoeueoao? aca?iiae?? c ?iiaie iaoae?a; iaoiae na?oei?icn?thaaiiy, yeee
aeicaiey? ?a?no?oaaoe ooai?aiiy ?icn?thaaieo oeaio??a o ?ic/ei? oa
i?iaiaeeoe ioe?ieo ?o ?ici???a; iaoiae IA*-ae?aeaeo?iiao???, yeee aea?
?ioi?iaoe?th i?i ?ooeea?noue iieaeoe aiaee o ci?oaieo ?ic/eiao, ui
i?noyoue aeii?oee iaaeaeo?ie?o?a.

A ?icae?e? 3 i?aaenoaaeai? ?acoeueoaoe aeine?aeaeaiiy aca?iiae?? AeIE c
?iiaie iaoae?a ??cii? aaeaioiino? o aiaeiiio ?ic/ei? iaoiaeaie
?*-niaeo?ineii?? oa na?oei?icn?thaaiiy. Iieacaii, ui i?e aca?iiae?? AeIE
c ?iiaie Tb3+, Nu2+, Mn2+ oa Ca2+, aea ia c ?iiaie Na+ (aei 1.2 I), o
?ic/ei? a?aeaoaa?oueny ??cea ca?eueoaiiy ?ioaineaiino? nioa iiaeeiaiiy
(NI) ye oinoaoieo a?oi (iae. 1,2), oae ? acioenoeo iniia AeIE.
Ca’ycoaaiiy oeeo ?ii?a c AeIE a ie?aeao ia i?ecaiaeeoue aei cia/iiai
ca?eueoaiiy ?ioaineaiino? NI. O ?iaio? ?icaeyaeathoueny ??ci? iiaeeea?
i?e/eie c?inoaiiy ?ioaineaiino? nioa iiaeeiaiiy o ?* niaeo?ao eiiieaen?a
AeIE-Mt2+. Ia i?eeeaae? eiiieaen?a AeIE c ?iiaie Tb3+, ye? aeeeeeathoue
eiiiaeoecaoe?th AeIE (Tajmir-Riahi, 1993), iieacaii, ui i?e/eiith
c?inoaiiy ?ioaineaiino? nioa iiaeeiaiiy iiaea neoaeeoe ia?ao?ae AeIE o
eiiiaeoiee noai i?ae ae??th ?ii?a Mtn+, ine?eueee ci?ie a ?*-niaeo?ao
eiiieaen?a AeIE c ?iiaie Tb3+ o aiaeiiio ?ic/ei? aiaeia?/i? ci?iai, ui
a?aeaoaathoueny a ?*-niaeo?ao eiiieaen?a AeIE c aeine?aeaeaieie
aeaiaaeaioieie ?iiaie iaoae?a (iae. 1). Ooai?aiiy eiiiaeoieo
?icn?thaaieo /anoie o ?ic/ei? i?e aca?iiae?? AeIE c ?iiaie Mt2+ iieacaii
oaeiae iaoiaeii na?oei?icn?thaaiiy — a i??o ca?eueoaiiy eiioeaio?aoe??
?ii?a Nu2+ iioe/ia aonoeia ?ic/ei?a AeIE c ?iiaie Nu2+ a iaeano? 330-625
ii, a ye?e a?aenooi? nioae iiaeeiaiiy AeIE, c?inoa? (iae. 3), ui
na?ae/eoue i?i ooai?aiiy ?icn?thaaieo /anoie. A iaeano? eiioeaio?aoe?e
?ii?a Nu2+/? ( 0.2(0.8 a?aeaoaa?oueny ooai?aiiy eiiiaeoieo ?icn?thaaieo
/anoie AeIE c na?aaei?i ?aae?onii ( 40 ii; a oeueiio ?ioa?aae?
eiioeaio?aoe?e ?ii?a Nu2+ ?ici??e /anoie caeeoathoueny iino?eieie ?
ca?eueoaiiy ?icn?thaaiiy ?aea ca ?aooiie ?inoo e?eueeino? ?icn?thaaieo
oeaio??a. I?e Nu2+/? > 0.8-0.9 a?aeaoaa?oueny ceeiaiiy eiiiaeoieo /anoie
o aa?aaaoe c ?ici??aie ( 120-160 ii.

Iae. 1. ?* niaeo?e AeIE (1 oa 1’) oa eiiieaen?a AeIE c ?iiaie iaoae?a
o aiaeiiio ?ic/ei? a iaeano? iiaeeiaiiy oinoaoieo a?oi AeIE.
Eiioeaio?aoe?y ?ii?a Mtn+: 2 — 2.6(10-2, 3 — 3.4(10-2, 4 — 9.4(10-4, 5 —
1.7(10-3 M; eiioeaio?aoe?y AeIE — 1 — 0.05, 1’- 0.036 M oinoi?o.

Iae. 2. Caeaaeiino? a?aeiinii? ci?ie ?ioaineaiino? R nioae
iiaeeiaiiy (S a?ae iiaii? eiioeaio?aoe?? ?ii?a Mtn+ o ?ic/ei? aeey
eiiieaen?a AeIE c ?iiaie Mtn+ o aiaeiiio ?ic/ei?. Eiioeaio?aoe?y AeIE —
(3.6(5)(10-2 I, [Na+]=10-3 M, pH 7, oaiia?aoo?a 290N.

R = Di/D0, aea Di — iioe/ia aonoeia o iaeneioi? nioae iiaeeiaiiy
eiiieaeno AeIE c i-oith eiioeaio?aoe??th iaoaea, D0 — oa ae naia
aaee/eia aeey AeIE aac ?ii?a aeai- aai o?eaaeaioieo iaoae?a.

Iae. 3. Caeaaeiino? iioe/ii? aonoeie ?ic/eio AeIE c ?iiaie Cu2+ a?ae
oaeeueiaiai /enea. Eiioeaio?aoe?y AeIE — 3.2(10-3 I, eiioeaio?aoe?y
?ii?a Cu2+, I:

1 — 0, 3(10-5, 10-4; 2 — 10-3; 3 — 1.2(10-3; 4 —
2(10-3; 5 — 3(10-3; 6 — 4(10-3; 7 — 7(10-3; 8 — 10-2.

Oaeei /eiii, ca?eueoaiiy ?ioaineaiino? nioa iiaeeiaiiy i?e ca’ycoaaii?
AeIE c ?iiaie Nu2+ a

iaeano? eiioeaio?aoe?e Nu2+/? < 0.7(0.8 (iae. 2) iia’ycaii c eiiaeainaoe??th AeIE i?ae ae??th ?ii?a Nu2+, ciaiueoaiiy ?ioaineaiino? NI i?e i?aeaeuaii? eiioeaio?aoe?? ?ii?a iaoaeo iia’ycaia c aa?aaaoe??th eiiiaeoieo /anoie AeIE oa /anoeiaei inaaeaeoaaiiyi AeIE. Aoaeoeai?noue aeine?aeaeaieo ?ii?a a ?iaeooe?thaaii? eiiiaeoecaoe?? AeIE, ye a iaeano? iiaeeiaiiy oinoaoieo a?oi, oae ? acioenoeo iniia, c?inoa? c aaeaioi?noth ?ii?a ([Tb3+] >> [Cu2+] >> [Mn2+] > [Ca2+]) (iae.
2) oa ei?aeth? c eiinoaioaie ca’ycoaaiiy oeeo ?ii?a c acioenoeie
iniiaaie AeIE, a oie /an ye eiinoaioe ca’ycoaaiiy ?ii?a Ca2+, Mn2+ oa
Cu2+ c

6

oinoaoieie a?oiaie a oiiaao aenia?eiaioo ii??aiyii? (Aeaaie, 1991).
Oaeei /eiii, eiiiaeoecaoe?y AeIE iaoiiaeth?oueny aca?iiae??th ?ii?a Mt2+
c acioenoeie iniiaaie, a ?acoeueoao? yei? iiaeeeaa iacia/ia
aeanoaa?e?caoe?y AeIE.

C?inoaiiy ?ioaineaiino? nioa iiaeeiaiiy a?aeaoaa?oueny o aocueeiio
?ioa?aae? eiioeaio?aoe?e aeai- oa o?eaaeaioieo ?ii?a (iae. 2), ui
na?ae/eoue i?i aenieo iiceoeaio eiiia?aoeai?noue i?ioeano
eiiiaeoecaoe?? AeIE. I?e i?aeaeuaii? eiioeaio?aoe?? ?ii?a Na+ o ?ic/ei?
aei 0.2 aai 1 I eiiia?aoeai?noue ??cei cieaeo?oueny, ui iaoiiaeaii
eiieo?aioe??th ?ii?a Mt2+ oa Na+. Oaeei /eiii, iaoai?ci eiiiaeoecaoe??
AeIE i?ae ae??th ?ii?a Mt2+ aeeth/a? a oiio /ene? ? aeaeo?inoaoe/iee
iaoai?ci.

Iae. 4. Iiaeaeue i?ae- (A) oa aioo??oiuei-iieaeoey?ii? (A)
eiiiaeoecaoe?? AeIE i?ae ae??th aeaiaaeaioieo ?ii?a iaoae?a o ?ic/ei?; C
— ii/aoeiaa noaae?y ooai?aiiy oi?o i?e aca?iiae?? AeIE, ui
iiaeaeth?oueny eaioethaeeii a?eueii-c’?aeiaieo naaiaio?a, c
aeaiaaeaioieie ?iiaie iaoae?a o ?ic/ei?.

A ?iaio? cai?iiiiiaaia iiaeaeue eiiiaeoecaoe?? AeIE i?ae ae??th ?ii?a
Mtn+ (iae. 4).

(1),

(2),

(G0, (H0 oa (S0 — ci?ie a?eueii? aia?a??, aioaeuei?? oa aio?ii?? i?e
ooai?aii? iaoe?. Iecueea ae?ia?aei?noue oeueiai i?ioeano aecia/a?oueny
a?eueoei uiaei aaniethoii? aaee/eie cia/aiiyi (S0 ((S0<0 oa (H0<0), i?e oeueiio (T(S(~ ((H(, ((G0( iaea ? aaee/eia eiinoaioe E0 iaea. A i??o 7 . I?e ooai?aii? N - oiai ca’yceo , (3) c o?aooaaiiyi (2) iiaeia caienaoe o aeaeyae? (4), . Oaeei /eiii, aeiaeaoie aei a?eueii? aia?a?? ? i?iii?oe?eiei nooiaith eiiiaeoecaoe??. K0 - eiinoaioa, yea aecia/a? aaee/eio ii?iaiai? eiioeaio?aoe?? aeaiaaeaioieo ?ii?a iaoae?a, iaiao?aeii? aeey ii/aoeo eiiiaeoecaoe??, ( - ia?aiao? eiiia?aoeaiino?. I?e oeueiio ??aiyiiy ca’ycoaaiiy o oi?i? Neao/a?aea ia?aoai?th?oueny ia , P - iiey?ia eiioeaio?aoe?y AeIE, n - eiao?oe?aio, ui aecia/a? iaiao?aeio aeey ?iaeooe?thaaiiy eiiiaeoecaoe?? AeIE /anoeio i?noeue ca’ycoaaiiy, ye? caeiyee ?iie Mt2+. Aaee/eia r iiaea oa?aeoa?ecoaaoe nooi?iue ca’ycoaaiiy ?ii?a Mt2+ a i?ioean? 8 eiiiaeoecaoe?? AeIE (iaeiae eeoa oeo ?ii?a, ca’ycoaaiiy c yeeie aaciina?aaeiuei i?ecaiaeeoue aei eiiiaeoecaoe??). Iae. 5. Caeaaeiino? a?aeiinii? ci?ie ?ioaineaiino? R nioae iiaeeiaiiy (S a?ae iiaii? eiioeaio?aoe?? ?ii?a Cu2+ o ?ic/ei? aeey eiiieaen?a AeIE c ?iiaie Cu2+ o ci?oaieo ?ic/eiao, ye? i?noyoue : A - 1,2- IAe, A - ae?oea?ei. Oaiia?aoo?a - 290N. = q2/(TkBb). Ca?eueoaiiy ia’?iii? e?eueeino? aoaiieo oa 1,2-IAe o ?ic/ei? aaaea aei c?inoaiiy eiinoaio ca’ycoaaiiy E0 ? ia?aiao??a eiiia?aoeaiino? ( (iae. 7). I?e oeueiio ?cioa?ie ca’ycoaaiiy iaaoaathoue iaiiiioiiiee oa?aeoa? c iaoanoaa?eueieie ? ianoaa?eueieie ae?eyieaie, ui oa?aeoa?ecothoueny cai?ioiueith caeaaei?noth r a?ae Cf, ye? aeey noaa?eueiiai i?ioeano 9 Iae. 6. Caeaaeiino? ii?iaiai? eiioeaio?aoe?? Nii? ?ii?a Cu2+ (1-3, e?aa oeaea) ? Na2+ (4, i?aaa oeaea), iaiao?aeii? aeey eiiiaeoecaoe?? AeIE, a?ae ia’?iii? eiioeaio?aoe?? iaaeaeo?ie?oa aeey nioae iiaeeiaiiy (S aeey eiiieaen?a AeIE c ?iiaie Mt2+ o ci?oaieo ?ic/eiao, ui i?noyoue: 1,4 - aoaiie, 2 - 1,2-IAe. 3 - ae?oea?ei. Iae. 7. Caeaaeiino? nooiaiy ca’ycoaaiiy r a?ae a?eueii? eiioeaio?aoe?? ?ii?a Cu2+ o ?ic/ei? (Cf) aeey eiiieaen?a AeIE c ?iiaie Cu2+ o aiaeiiio (1) oa ci?oaieo ?ic/eiao, ye? i?noyoue 9 ia.% aoaiiea (2), 1,2-IAe (3) oa ae?oea?eia (4). E?aiee - aeai? aenia?eiaioo, e?i?? - oai?aoe/i? caeaaeiino?, ?ic?aoiaai? ca oi?ioeith (5); eiinoaioe ca’ycoaaiiy E0 oa ia?aiao?e eiiia?aoeaiino? ( aeacai? ia iaethieo. aeanoaa?e?coth/i? ae?? ae?oea?eio ia no?oeoo?o ?ic/eio a?ae eiai eiioeaio?aoe?? (Timasheff, 1993). Eiiia?aoeai?noue i?ioeano eiiiaeoecaoe?? AeIE o aiaeii-ae?oea?eiiaeo ?ic/eiao ciaioo?oueny (iae. 5, 7), ui iiaea aooe iaoiiaeaii ?icoii?yaeeiaaiith ae??th ae?oea?eio ia no?oeoo?o aiaee (a oiio /ene? a?ae?aoio). Iaiiiioiii?noue aieeao ae?oea?eio caa??aa?oueny ? i?e 450N. Ine?eueee ci?ie ae?aeaeo?e/ii? i?iieeiino? ?ic/eio a i??o c?inoaiiy eiioeaio?aoe?? ae?oea?eio iinyoue iiiioiiiee oa?aeoa?, iiaeia c?iaeoe aeniiaie i?i oa, ui a aeaiiio aeiaaeeo eiiiaeoecaoe?y 10 AeIE aecia/a?oueny ia o?eueee ae?aeaeo?e/iith i?iieei?noth aiaeiiai ?ic/eio iaaeaeo?ie?oa, ye oea aeieeaa? c oai??? eiiaeainaoe?? i?ioe?ii?a, aea e no?oeoo?ith ci?oaiiai ?ic/eio. I?e oaiia?aoo?? 450N ciaioo?oueny eiioeaio?aoe?y ?ii?a Cu2+, yea iaiao?aeia aeey eiiiaeoecaoe?? AeIE o aiaeiiio ?ic/ei?, ui iia’ycaii ?c cieaeaiiyi oaiia?aoo?e ieaaeaiiy AeIE a i?enooiino? ?ii?a i?ae?, ooai?aiiyi aeaiaoo?iaaieo ae?eyiie ia AeIE ? c?inoaiiyi eiinoaio ca’ycoaaiiy ?ii?a Cu2+ c oeeie ae?eyieaie (Ni?ie?i, 1987), a oaeiae c? ciaioaiiyi aio/ei? aei?noeino? AeIE. Aeine?aeaeai? iaaeaeo?ie?oe - aoaiie, 1,2-IAe, ae?oea?ei - i?e iaeeo ia’?iieo eiioeaio?aoe?yo o ?ic/ei? noaa?e?cothoue no?oeoo?o aiaee, oiio i?aaenoaaey?oueny oe?eaaei aea/eoe no?oeoo?i? ia?aoiaee AeIE i?ae ae??th ?ii?a Cu2+ o aiaeieo ?ic/eiao na/iaeie, yea ?oeio? no?oeoo?o aiaee. Ci?ie a ?* niaeo?ao eiiieaen?a AeIE c ?iiaie Cu2+ o ?ic/eiao, ye? i?noyoue na/iaeio, aiaeia?/i? ci?iai, ui a?aeaoaathoueny o aiaeiiio ?ic/ei?. ?ioaineai?noue nioa iiaeeiaiiy oinoaoieo a?oi AeIE i?e aca?iiae?? c ?iiaie Cu2+ c?inoa?, o./. a i?enooiino? na/iaeie AeIE i?ae ae??th ?ii?a Cu2+ ia?aoiaeeoue o eiiiaeoio oi?io. Aeey an?o aeine?aeaeaieo ?ic/ei?a caeaaeiino? R (C) iathoue aeaeyae e?eai? c iane/aiiyi, aiaeia?/iee caeaaeiino? aeey eiiieaen?a AeIE c ?iiaie Nu2+ o aiaeiiio ?ic/ei?. Oaeei /eiii a i?enooiino? na/iaeie caa??aa?oueny eiiia?aoeaiee oa?aeoa? i?ioeano eiiiaeoecaoe?? AeIE (iae. 8). A i??o c?inoaiiy eiioeaio?aoe?? na/iaeie eiiia?aoeai?noue ciaioo?oueny, ui iiaea aooe iia’ycaii c ii?ooaiiyi aii?yaeeiaaii? no?oeoo?e aiaee, o oiio /ene? oaei?, ui aoiaeeoue o a?ae?aoio iaieiieo AeIE. Oa?aeoa? caeaaeiino? N1/2 (C1/2 - eiioeaio?aoe?y ?ii?a Nu2+, i?e yeee R(N1/2)=Rmax/2) a?ae eiioeaio?aoe?? na/iaeie o ?ic/ei? (iae.9) iiaeia iiynieoe eiieo?aioe??th aeaio ??ciiiai?aaeaieo i?ioean?a: c iaeiiai aieo, i?e c?inoaii? ae?aeaeo?e/ii? i?iieeiino? ?ic/eio i?e aeiaeaaaii? na/iaeie ciaioo?oueny aeiey ca?yaeo ia oinoaoao, iaeo?ae?ciaaiiai ca ?aooiie ca’ycoaaiiy iie?aeaeo?ie?oo c i?ioe?iiaie, c ?ioiai aieo, aeaa?ae?aoaoe?y ?ii?a Na+ oa Nu2+ a i?enooiino? na/iaeie i?ecaiaeeoue aei a?eueo aoaeoeaii? ae?ai??iaoe? ca?yae?a ia oinoaoao, ui iineeth? aoaeo ?ii?a Nu2+. Iaaii, a iaeano? A ia?aaaaeathoue naia aoaeoe, iia’ycai? c aeaa?ae?aooth/ei aieeaii na/iaeie ia i?ioe?iie (Na+ oa Nu2+) oa naio iae?iiieaeoeo. A iaeanoyo A oa N na?aae iiaeeeaeo iaoai?ci?a aieeao na/iaeie ia Cu2+-?iaeoeiaaio eiiiaeoecaoe?th AeIE iiaeia a?aecia/eoe c?inoaiiy ( ?ic/eio i?e ca?eueoaii? eiioeaio?aoe?? na/iaeie, ui ia?aoeiaeaea? aeiaeaoeia?e eiiaeainaoe?? i?ioe?ii?a, a oaeiae eiieo?aioe?th iieaeoe na/iaeie oa ?ii?a Cu2+ ca i?noey ca’ycoaaiiy ia AeIE. Oaeei /eiii, a aeaiiio aeiaaeeo i?ioean ia?aoiaeo AeIE o eiiiaeoiee noai i?ae ae??th ?ii?a i?ae? aecia/a?oueny ia no?eueee aoaeoaie ci?ie ae?aeaeo?e/ii? i?iieeiino? ?ic/eio, ne?eueee aoaeoaie nieueaaoaoe??. Iae. 8. Caeaaeiino? a?aeiinii? ci?ie ?ioaineaiino? R nioae iiaeeiaiiy (S a?ae iiaii? eiioeaio?aoe?? ?ii?a Cu2+ o ?ic/ei? aeey eiiieaen?a AeIE c ?iiaie Cu2+ o aiaeieo ?ic/eiao na/iaeie c eiioeaio?aoe??th: 0 (1), 0.17 (2), 0.25 (3), 1 (4) e 3 (5) I. Iae. 9. Caeaaeiino? aaee/eie N1/2 a?ae eiioeaio?aoe?? na/iaeie o ?ic/ei? aeey nioa iiaeeiaiiy (S (1) oa (aS (2) aeey eiiieaen?a AeIE c ?iiaie Nu2+. A ?icae?e? 5 i?aaenoaaeai? ?acoeueoaoe aeine?aeaeaiiy aieeao aoaiieo, 1,2-i?iiaiae?ieo oa ae?oea?eio ia eiiaeainaoe?th AeIE i?ae ae??th ?ii?a Na2+ o ci?oaieo ?ic/eiao i?e oaiia?aoo?? 29 oa 450N a ?ioa?aae? eiioeaio?aoe?e iaaeaeo?ie?o?a 0(20 ia.%. Iieacaii, ui caeaaei?noue ii?iaiai? eiioeaio?aoe?? ?ii?a Na2+, iaiao?aeii? aeey eiiiaeoecaoe?? AeIE o ci?oaieo ?ic/eiao, a?ae ia’?iii? eiioeaio?aoe?? iaaeaeo?ie?o?a o ?ic/ei? ia? iaiiiioiiiee oa?aeoa?. I?e eiioeaio?aoe?yo aoaiiea, ye? noaa?e?cothoue no?oeoo?o aiaee, ii?iaiaa eiioeaio?aoe?y ?ii?a Na2+ c?inoa? (aeea. iae. 6, e?eaa 4). Ciaioaiiy iaiao?aeii? eiioeaio?aoe?? ?ii?a Na2+ i?e eiioeaio?aoe?? aoaiiea ( 15-25 ia.%, ye ? o aeiaaeeo eiiiaeoecaoe?? AeIE i?ae ae??th ?ii?a Cu2+, iiaeia iiynieoe c?inoaiiyi eiinoaio ca’ycoaaiiy i?ioe?ii?a c AeIE ? /anoee neiiiainiaaiiai ca?yaeo ia AeIE ca ?aooiie aeiaeaoeiai? eiiaeainaoe?? i?ioe?ii?a i?e cieaeaii? ( ?ic/eio, a oaeiae /anoeiaith aeanoaa?e?caoe??th no?oeoo?e AeIE. A iaeano? eiioeaio?aoe?e aoaiiea 5-10 ia.%, a ye?e a?aeaoaa?oueny c?inoaiiy ii?iaiai? eiioeaio?aoe?? ?ii?a Na2+ (iae.6), niinoa??aaeiny eiiia?aoeaia ciaioaiiy oa?aeoa?enoe/ii? a’yceino? AeIE o aiaeii-nie?oiaiio ?ic/ei? a ?acoeueoao? ci?i o o?aoeii?e no?oeoo?? AeIE, iaoiiaeaieo ciaioaiiyi nee aeaeaeiae?? a iae?iiieaeoe? (Aanaeeia, 1988). Oaeei /eiii, eiioi?iaoe?ei? ci?ie a iieaeoe? iaoeaii? AeIE, ui a?aeaoaathoueny aiane?aeie no?oeoo?ieo ia?aaoaeia o ci?oaiiio ?ic/eiieeo, iiaeooue i?ecaiaeeoe aei ci?ie eiioeaio?aoe?? ?ii?a Na2+, iaiao?aeii? aeey ia?aaiaeo AeIE o eiiiaeoiee noai. I?e noaa?e?caoe?? iieaeoee AeIE iaiao?aeia aeey eiiiaeoecaoe?? eiioeaio?aoe?y ?ii?a Na2+ c?inoa?, a i?e aeanoaa?e?caoe?? iae?iiieaeoee AeIE oey eiioeaio?aoe?y ciaioo?oueny. Ae?ia?aeii, aeanoaa?e?caoe?y iae?iiieaeoee AeIE iieaaoo? i?ioean eiiiaeoecaoe?? i?ae ae??th aeaiaaeaioieo ?ii?a iaoae?a. 12 Aeey ia?aaiaeo AeIE o eiiiaeoiee noai o aiaeiiio ?ic/ei? i?e 450N iio??aia a?eueoa eiioeaio?aoe?y ?ii?a Na2+, i?ae i?e 290N, ui iiaeia iiynieoe c?inoaiiyi a?ae?aoaoe?? i?ioe?ii?a i?e oe?e oaiia?aoo?? (Naiieeia, 1957) oa ineaaeaiiyi ?o ae?ai??oth/i? ae?? ia oinoaoi? a?oie AeIE. Oaeei /eiii, i?ioeann ia?aoiaeo AeIE o eiiiaeoiee noai caeaaeeoue a?ae a?ae?aoaoe?? i?ioe?ii?a. Iaoai?ci aieeao oaiia?aoo?e ia eiiiaeoecaoe?th AeIE a i?enooiino? ?ii?a Cu2+, ye? iathoue a?eueoo nii??aeiai?noue aei iniia AeIE, a?ae??ciy?oueny a?ae iaoai?cio aieeao oaiia?aoo?e ia Ca2+-?iaeoeiaaio eiiiae-oecaoe?th AeIE: o aeiaaeeo ?ii?a i?ae? ia?aaaaeathoue aoaeoe c?inoaiiy eiinoaio ca’yco-aaiiy ?ii?a Cu2+ c aeaiaoo?iaaieie naeoaie, ui ooai?eeeny, ia AeIE oa ciaioaiiy aei?noeino? iae?iiieaeoee, o aeiaaeeo ?ii?a eaeueoe?y - cieaeaiiy ae?ai??oth/i? ae?? i?ioe?ii?a i?e c?inoaii? ?o a?ae?aoaoe?? c oaiia?aoo?ith. Iaaaeee? aeii?oee 1,2-IAe oa ae?oea?eio (4 ia.%) ??cei cieaeothoue iaiao?aeio aeey eiiiaeoecaoe?? eiioeaio?aoe?th ?ii?a Ca2+ oa eiiia?aoeai?noue i?ioeano eiiiaeoecaoe??, ui iiaea aooe iia’ycaii c ?o aeanoaa?e?coth/ith ae??th ia no?oeoo?o ?ic/eiieea (i?e 450N) ? ia naio iae?iiieaeoeo. O i’yoiio ?icae?e? oaeiae i?aaenoaaeai? ?acoeueoaoe aeine?aeaeaiiy aca?iiae?? iie?oinoao?a (??) ye iiaeaeueii? nenoaie AeIE c ?iiaie Na2+ o aiaeiiio oa ci?oaieo ?ic/eiao, ui i?noyoue aoaiie, 1,2-i?iiaiae?ie oa ae?oea?ei (0(15 ia.%). I?e ca’ycoaaii? ?? c ?iiaie Na2+ o aiaeiiio ?ic/ei? a?aeaoaa?oueny c?inoaiiy ?ioaineaiino? nioae iiaeeiaiiy (S, ui na?ae/eoue i?i ooai?aiiy a?eueo aii?yaeeiaaieo eiiiaeoieo no?oeoo?. I?e ca?eueoaii? eiioeaio?aoe?? ?ii?a Na2+ niinoa??aa?oueny aa?aaaoe?y iie?oinoao?a, ui noi?iaiaeaeo?oueny ciaioaiiyi ?ioaineaiino? NI. I?ioean ooai?aiiy eiiaeainao?a ?? i?ae ae??th ?ii?a Na2+ ia? a?eueo eiiia?aoeaiee oa?aeoa?, i?ae i?ioean eiiiaeoecaoe?? aenieiiieaeoey?ii? AeIE ca ?aooiie iaioi? aei?noeino? eaioetha?a iie?oinoao?a. A i??o c?inoaiiy eiioeaio?aoe?? aoaiiea oa 1,2-IAe o ?ic/ei? iiiioiiii ciaioo?oueny eiioeaio?aoe?y ?ii?a Na2+, yea iaiao?aeia aeey ?iaeooeethaaiiy eiiaeainaoe?? iie?oinoao?a, ui iiaeia iiynieoe iineeaiiyi ae?ai??oth/i? ae?? i?ioe?ii?a ia ca?yaee oinoaoieo a?oi iie?oinoao?a a ?acoeueoao? c?inoaiiy eiinoaio ca’ycoaaiiy i?e ciaioaii? ( ?ic/eio. Ine?eueee aieea aoaiieo ia eiiiaeoecaoe?th AeIE i?ae ae??th ?ii?a Ca2+ iineoue iaiiiioiiiee oa?aeoa? (iae. 6), iiaeia i?eionoeoe, ui no?oeoo?a ?ic/eio neeuei?oa aieeaa? ia i?ioean eiiiaeoecaoe?? a?eueo aenieiiieaeoey?ii? no?oeoo?e - AeIE - /a?ac oa, ui a ?? iieaeoe? iayai? neeuei? a?ae?ioiai? aca?iiae??. Aieea ae?oea?eio ia iaiao?aeio aeey eiiaeainaoe?? ?? eiioeaio?aoe?th ?ii?a Na2+ iineoue iaiiiioiiiee oa?aeoa?. A i??o c?inoaiiy ia’?iii? eiioeaio?aoe?? iaaeaeo?ie?oo o ?ic/ei? ciaioo?oueny eiiia?aoeai?noue i?ioeano eiiaeainaoe?? iie?oinoao?a i?ae ae??th ?ii?a Na2+ a ?yaeo aoaiie > 1,2-IAe >
ae?oea?ei.

13

aeNIIAEE

I?e aca?iiae?? AeIE n ?iiaie Nu2+, In2+ oa Na2+ o aiaeiiio ?ic/ei? c
aenieith eiioeaio?aoe??th AeIE a?aeaoaa?oueny ia?ao?ae AeIE o eiiiaeoiee
noai. I?e eiiiaeoecaoe?? AeIE c?inoa? ?ioaineai?noue nioa iiaeeiaiiy
oinoaoieo a?oi oa acioieo iniia AeIE a ?* niaeo??. Iaea?aeaia ioe?iea
?ici???a eiiiaeoieo /anoie AeIE, ui ooai?ththoueny i?e Cu2+/P ( 0.7(0.8,
ye? nooo?ai iaio? ca ?ici??e aa?aaao?a AeIE, ye? ooai?ththoueny i?e
a?eueo aenie?e eiioeaio?aoe?? ?ii?a Cu2+.

Aoaeoeai?noue aeine?aeaeaieo ?ii?a a ?iaeooeethaaii? eiiiaeoecaoe?? AeIE
c?inoa? c ?o aaeaioi?noth oa ei?aeth? ?c nii??aeiaiinoth oeeo ?ii?a aei
acioenoeo iniia AeIE: Tb3+ >> Nu2+ >> In2+ > Na2+. Oaeei /eiii,
eiiiaeoecaoe?y AeIE i?ae ae??th ?ii?a Mt2+ o ?ic/ei? caeaaeeoue a?ae
ca’ycoaaiiy ?ii?a iaoae?a c acioenoeie iniiaaie AeIE oa iieaaoo?oueny
i?e /anoeia?e aeanoaa?e?caoe?? no?oeoo?e iae?iiieaeoee.

Ia?ao?ae AeIE o eiiiaeoiee noai ia? aenieo iiceoeaio eiiia?aoeai?noue,
yea caeaaeeoue a?ae no?oeoo?e ?ic/eio oa cieaeo?oueny a i?enooiino?
?a/iaei, ui ?oeiothoue no?oeoo?o aiaee.

Cai?iiiiiaaia iiaeaeue eiiiaeoecaoe?? AeIE i?ae ae??th ?ii?a Mt2+, yea
aeeth/a? ye aioo??oiueiiieaeoey?iee, oae ? i?aeiieaeoey?iee iaoai?cie.

A i??o c?inoaiiy ia’?iii? eiioeaio?aoe?? aoaiieo oa 1,2-IAe o ci?oaiiio
?ic/ei? iiiioiiii c?inoa? nooi?iue Nu2+-?iaeoeiaaii? eiiiaeoecaoe?? AeIE
oa ciaioo?oueny eiioeaio?aoe?y ?ii?a i?ae?, iaiao?aeia aeey ia?aaiaeo
AeIE o eiiiaeoiee noai, ye i?e oaiia?aoo?? 29, oae ? 450N. Caeaaei?noue
iaiao?aeii? aeey eiiiaeoecaoe?? AeIE eiioeaio?aoe?? ?ii?a Nu2+ a?ae
ai?noo ae?oea?eio o ?ic/ei? ia? iaiiiioiiiee oa?aeoa? ye i?e 29, oae ?
i?e 450N.

Eiiiaeoecaoe?y AeIE i?ae ae??th ?ii?a Nu2+ o ci?oaieo ?ic/eiao, ui
i?noyoue aoaiie, 1,2-IAe oa ae?oea?ei, caeaaeeoue ia o?eueee a?ae
ae?aeaeo?e/ii? i?iieeiino? ?ic/eio, aea e a?ae no?oeoo?e ?ic/eio, ui
ooai?th?oueny.

Caeaaei?noue Na2+-?iaeoeiaaii? eiiiaeoecaoe?? AeIE a?ae eiioeaio?aoe??
aoaiieo oa 1,2-i?iiaiae?ieo o ?ic/ei? iineoue iaiiiioiiiee oa?aeoa? ?
i?e eiioeaio?aoe?yo iaaeaeo?ie?o?a, ui noaa?e?cothoue no?oeoo?o aiaee,
iaiao?aeia aeey eiiiaeoecaoe?? AeIE eiioeaio?aoe?y ?ii?a Na2+
i?aeaeuo?oueny.

I?e ia?aoiae? AeIE o eiiiaeoio oi?io o aiaeiiio ?ic/ei? i?e 450N o
aeiaaeeo ae?? ?ii?a Cu2+, ye? iathoue a?eueoo nii??aeiai?noue aei iniia
AeIE oa cia/ii cieaeothoue oaiia?aoo?o ieaaeaiiy AeIE, aecia/aeueieie
oaeoi?aie ? c?inoaiiy eiinoaio ca’ycoaaiiy ?ii?a Cu2+ c aeaiaoo?iaaieie
ae?eyieaie, ui ooai?ththoueny, ia AeIE, oa ciaioaiiy aei?noeino?
iae?iiieaeoee, o aeiaaeeo ?ii?a Na2+ — cieaeaiiy ae?ai??oth/i? ae??
i?ioe?ii?a i?e c?inoaii? ?o a?ae?aoaoe?? c oaiia?aoo?ith.

Aoaeoeai?noue ?ii?a Nu2+ oa Na2+ a ?iaeooeethaaii? eiiiaeoecaoe?? AeIE
caeaaeeoue a?ae ?o

14

a?ae?aoaoe??: c?inoaiiy a?ae?aoaoe?? i?ecaiaeeoue aei c?inoaiiy
iaiao?aeii? aeey eiiiaeoecaoe?? AeIE eiioeaio?aoe?? ?ii?a Mt2+,
aeaa?ae?aoaoe?y ?ii?a cieaeo? iaiao?aeio eiioeaio?aoe?th ?ii?a. I?e
iaaaeeeeo ci?iao ae?aeaeo?e/ii? i?iieeiino? na?aaeiaeua aoaeoe
nieueaaoaoe?? iiaeooue ia?aaaaeaoe.

Oai??y eiiaeainaoe?? i?ioe?ii?a ia aaeaeaaoii iieno? ia?ao?ae AeIE o
eiiiaeoio oi?io o ci?oaieo ?ic/eiao, ine?eueee aiia ia a?aoiao? aieeao
no?oeoo?e ?ic/eio. Oai??y ??aiiaaaeiiai ca’ycoaaiiy caaeia?eueii iieno?
eiiiaeoecaoe?th AeIE.

I?e aca?iiae?? iie?oinoao?a c ?iiaie Ca2+ o aiaeiiio ?ic/ei?
a?aeaoaa?oueny ooai?aiiy aii?yaeeiaaieo no?oeoo?, iiae?aieo aei
eiiaeainao?a AeIE. Oeae i?ioean ia? ??cei eiiia?aoeaiee oa?aeoa?.
Aoaiie, 1,2-i?iiaiae?ie oa ae?oea?ei a eiioeaio?aoe?? aei 15 ia.%
ciaioothue eiioeaio?aoe?th ?ii?a Na2+, iaiao?aeio aeey eiiaeainaoe??
iie?oinoao?a; aieea ae?oea?eio, ia a?aei?io a?ae aoaiieo oa
1,2-i?iiaiae?ieo, iineoue iaiiiioiiiee oa?aeoa?. A i?enooiino?
iaaeaeo?ie?o?a eiiia?aoeai?noue eiiaeainaoe?? iie?oinoao?a ??cei
ciaioo?oueny a ?yaeo aoaiie > 1,2-i?iiaiae?ie > ae?oea?ei.

NIENIE IIOAE?EIAAIEO I?AOeUe CA OAIITH AeENA?OAOe??

Hackl E.V., Kornilova S.V., Kapinos L.E., et.al. Study of Ca2+, Mn2+,
Cu2+ ion binding to DNA in solutions by means of IR-spectroscopy // J.
Mol. Struct. — 1997. — v. 408/409. -?. 229-232.

Andrushchenko V.V., Kornilova S.V., Kapinos L.E., Hackl E.V., et.al.
IR-Spectroscopic studies of divalent metal ion effects on DNA hydration
// J. Mol. Struct. -1997. -v. 408/409. — P. 225-228.

Oaee A.A., Ei?ieeiaa N.A., Aeaaie TH.I. Eiiiaeoecaoeey AeIE a
i?enoonoaee eiiia Nu2+ a aiaeiii e aiaeii-nie?oiauo ?anoai?ao // Aanoiee
i?iaeai aeie. e iaae.- 1998.- ? 8.- N. 41-51.

Kornilova S.V., Hackl E.V., Kapinos L.E. et.al. DNA interaction with
biologicaly active metal ions. Cooperativity of metal ion binding at DNA
compactization // Acta Biochimica Polonia. — 1998. — v. 45, N 1. — P.
107-117.

Oaee A.A., Ei?ieeiaa N.A., Aeaaie TH.I. Eco/aiea aeeyiey eiiia Nu2+ ia
AeIE a aiaeiuo ?anoai?ao, niaea?aeaueo 1,2-i?iiaiaeeie e aeeoea?ei,
iaoiaeii EE-niaeo?ineiiee. // A?ni. OAeO. — 1998. — ? 410. A?io?ce/iee
a?ni. Aei.1. — N. 62-70.

Oaee A.A., Ei?ieeiaa N.A., Nieiaueaaa A.N., Cei/aiei A.A., Aeaaie TH.I.
Ia?aoiae AeIE a eiiiaeoiia ninoiyiea i?e naycuaaiee n eiiaie iaaee a
?anoai?ao e?eii?ioaeoi?ia // I?iaeaiu e?eiaeieiaee. -1998. — ? 3.- N.
67-69.

Hackl E.V., Kornilova S.V., Bezlepkina N.A., Blagoi Yu.P. Effect of
glycerol and temperature on DNA interaction with Cu2+ ions // Metal ions
in biol. and med. — 1998. — v. 5. — ?. 104-108.

15

Hackl E.V., Kornilova S.V., Blagoi Yu.P. Influence of water activity on
DNA interaction with divalent metal ions // Metal ions in biol. and med.
— 1998. — v. 5. — ?. 99-103.

Oaee A.A., Ei?ieeiaa N.A., Aeaaie TH.I. Aeeyiea ii/aaeieu ia
acaeiiaeaenoaea eiiia Cu2+ n AeIE a ?anoai?a // A?ni. OAeO. — 1998. — ?
422. A?io?ce/iee a?ni. Aei.2. — N. 62-70.

Hackl E.V., Kornilova S.V., Blagoi Yu.P. IR-spectroscopic study of Ca2+,
Mn2+ and Cu2+ ions interaction with DNA in solutions with different
water activity // ?.Carmona, R.Navarro and A.Hernanz (eds.) Spectroscopy
of biological molecules: modern trends.- Kluwer, The Netherlands.-
1997.- ?. 389-390.

Hackl A., Kornilova S., Blagoi Yu.. Ca2+, Mn2+ and Cu2+ ions interaction
with DNA and polyphosphates in solutions with different water activity
// Eur. Biophys. J.- 1997.- v. 26, ? 1. — ?. 50.

Hackl E., Kornilova S., Blagoi Yu. DNA nondensation at divalent metal
ion binding. Influence of temperature and water activity // Book of
Abstracts of the 25th Silver FEBS Meeting. — (Kopenhavn) Denmark. —
1998. — ?. 37.26.

AIIOAOe?ss

Oaee I.A. Aieea ?ii?a iaoae?a ia no?oeoo?i? ia?aoiaee AeIE o aiaeieo
?ic/eiao nie?o?a oa na/iaeie. — ?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, i.Oa?e?a,1999.

Iaoiaeaie ?*-niaeo?ineii?? oa na?oei?icn?thaaiiy aeine?aeaeai?
no?oeoo?i? ia?aoiaee AeIE i?ae ae??th ?ii?a Cu2+ oa Ca2+ o aiaeiiio oa
ci?oaieo ?ic/eiao, ui i?noyoue aoaiie, 1,2-i?iiaiae?ie, ae?oea?ei (0(20
ia.%) oa na/iaeio (0(5 I) i?e oaiia?aoo?? 29 oa 450N. Iieacaii, ui i?e
aca?iiae?? AeIE c ?iiaie Cu2+ oa Ca2+ o aiaeiiio oa ci?oaieo ?ic/eiao
AeIE ia?aoiaeeoue o eiiiaeoiee noai, yeee oa?aeoa?eco?oueny
aii?yaeeiaaiith ii?oieia??th; /anoeiaa aeanoaa?e?caoe?y no?oeoo?e AeIE
iieaaoo? eiiiaeoecaoe?th. Iaea?aeaia ioe?iea ?ici???a eiiiaeoieo /anoie,
cai?iiiiiaaia iiaeaeue eiiiaeoecaoe??. Iieacii, ui eiiiaeoecaoe?y AeIE
ia? aenieo iiceoeaio eiiia?aoeai?noue, yea caeaaeeoue a?ae no?oeoo?e
?ic/eio. Aeine?aeaeaia caeaaei?noue eiiiaeoecaoe?? AeIE a?ae aaeaioiino?
oa a?ae?aoaoe?? i?ioe?ii?a, oaiia?aoo?e, neeaaeo ?ic/eiieea.
Anoaiiaeaii, ui o ci?oaieo ?ic/eiao eiiiaeoecaoe?y AeIE caeaaeeoue ia
o?eueee a?ae ae?aeaeo?e/ii? i?iieeiino?, aea e a?ae no?oeoo?e ?ic/eio.

Iaea?aeai? ?acoeueoaoe iaaiai?ththoueny a iaaeao oai??e eiiaeainaoe??
i?ioe?ii?a (NNO) oa ??aiiaaaeiiai ca’ycoaaiiy. Iieacaii, ui oai??y
??aiiaaaeiiai ca’ycoaaiiy, ia a?aei?io a?ae NNO, caaeia?eueii iieno?
i?ioean eiiiaeoecaoe?? AeIE i?ae ae??th ?ii?a Mt2+.

16

Eeth/ia? neiaa: AeIE, ?iie iaoae?a, ?*-niaeo?ineii?y, ci?oai? ?ic/eie,
aoaiie, 1,2-i?iiaiae?ie, ae?oea?ei, na/iaeia, eiiiaeoecaoe?y,
oaiia?aoo?a.

AIIIOAOeEss

Oaee A.A. Aeeyiea eiiia iaoaeeia ia no?oeoo?iua ia?aoiaeu AeIE a aiaeiuo
?anoai?ao nie?oia e ii/aaeiu. — ?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, a. Oa?ueeia, 1999.

Iaoiaeaie EE-niaeo?ineiiee e naaoi?annayiey enneaaeiaaiu no?oeoo?iua
ia?aoiaeu AeIE iiae aeaenoaeai eiiia Cu2+ e Ca2+ a aiaeiii e niaoaiiuo
?anoai?ao, niaea?aeaueo yoaiie, 1,2-i?iiaiaeeie, aeeoea?ei (0(20 ia.%) e
ii/aaeio (0(5 I) i?e oaiia?aoo?a 29 e 450N. Iieacaii, /oi i?e
acaeiiaeaenoaee AeIE n eiiaie Cu2+ e Ca2+ a aiaeiii e niaoaiiuo
?anoai?ao AeIE ia?aoiaeeo a eiiiaeoioth oi?io, oa?aeoa?ecothuothny
oii?yaei/aiiie ii?oieiaeae; /anoe/iay aeanoaaeeecaoeey no?oeoo?u AeIE
iaeaa/aao eiiiaeoecaoeeth. Iieo/aia ioeaiea ?acia?ia eiiiaeoiuo /anoeoe,
i?aaeeiaeaia iiaeaeue eiiiaeoecaoeee. Iieacaii, /oi eiiiaeoecaoeey AeIE
eiaao aunieoth iieiaeeoaeueioth eiiia?aoeaiinoue, eioi?ay caaeneo io
no?oeoo?u ?anoai?a. Enneaaeiaaia caaeneiinoue eiiiaeoecaoeee AeIE io
aaeaioiinoe e aeae?aoaoeee i?ioeaieiiia, oaiia?aoo?u, ninoaaa
?anoai?eoaey. Onoaiiaeaii, /oi a niaoaiiuo ?anoai?ao eiiiaeoecaoeey AeIE
caaeneo ia oieueei io aeeyeaeo?e/aneie i?iieoeaaiinoe, ii e io no?oeoo?u
?anoai?a.

Iieo/aiiua ?acoeueoaou ianoaeaeathony a ?aieao oai?ee eiiaeainaoeee
i?ioeaieiiia (NNO) e ?aaiiaaniiai naycuaaiey. Iieacaii, /oi oai?ey
?aaiiaaniiai naycuaaiey, a ioee/ea io NNO, oaeiaeaoai?eoaeueii iienuaaao
i?ioeann eiiiaeoecaoeee AeIE iiae aeaenoaeai eiiia Mt2+.

Eeth/aaua neiaa: AeIE, eiiu iaoaeeia, EE-niaeo?ineiiey, niaoaiiua
?anoai?u, yoaiie, 1,2-i?iiaiaeeie, aeeoea?ei, ii/aaeia, eiiiaeoecaoeey,
oaiia?aoo?a.

SUMMARY

Hackl E.V. Metal ions effect on DNA structural transitions in aqueous
solutions containing alcohols and urea. — Manuscript.

Thesis for candidate’s degree by speciality 03.00.02 — biophysics. —
Kharkov State University, Kharkov, 1999.

Using methods of IR spectroscopy and light scattering, DNA structural
transitions are studied under the action of Cu2+ and Ca2+ ions in
aqueous and mixed solutions containing ethanol, 1,2-propanediol,
glycerol (0(20 v.%) and urea (0(5 I) at temperatures 29 and 450C. It is
shown that on its interaction with Cu2+ and Ca2+ ions in aqueous and
mixed solutions DNA transits into a compact form characterized with the
ordered morphology; at the same time the intensity of absorption bands
in IR spectra of DNA metal complexes increase sharply.

It is shown that the partial DNA destabilization facilitates its
compactisation. The measure of sizes of compact particles is obtained.
The compactisation model including inter- and intramolecular mechanisms
is proposed. It is shown that DNA compactisation is of high positive
cooperativity depending on the solution structure and decreases in the
presence of substances disrupting the water structure. DNA
compactisation dependencies on the counterions valence and hydration,
the Na+ ions content in solution, the temperature and content of
solvents are studied. It is shown that the efectiveness of the ions
studied inducing DNA compactisation increases with their valence and
correlates with the affinity of these ions for DNA nucleic bases: Nu2+
>> In2+ > Na2+, that evidence that DNA compactisation under the Mt2+
ions action in solution depends on the metal ion binding to DNA nucleic
bases. Efectiveness of Nu2+ and Na2+ ions inducing DNA compactisation
depends on their hydration: the increase of hydration results in the
rize of Mt2+ ion concentrations required for DNA compactisation and the
ion dehydration decreases the required ion concentration. At small
changes in the solution dielectric permeability solvation effects can
prevail.

It is shown that ethanol and 1,2-propanediol effects on Nu2+ ion —
induced DNA compactisation are of monotonous character both at 29, and
450N: with the increase of volume contents of these nonelectrolytes in
solution the degree of DNA compactisation increases and the copper ion
concentration required for the DNA transfer into the compact state
decreases. The glycerol effect is of nonmonotonous character both at 29
and 450N. It is stated that in mixed solutions DNA compactisation
depends not only on the solution dielectric permeability but on the
solution structure.

It is stated that ehtanol and 1,2-propanediol effects on DNA
compactisation induced by Na2+ ions are of nonmonotonous character and
at nonelectrolyte concentrations stabilizing the water structure the
Na2+ ion concentration required for DNA compactisation increases. It is
shown that the effect of the solution structure on DNA compactisation is
more pronounced in the case of Na2+ ion — induced compactisation than in
the case of Cu2+ ion — induced one. This can be conditioned by
differences in the ion binding sites. On the DNA transfer to the compact
state in aqueous solution at 450N under the action of Cu2+ ions with
the greater affinity for DNA bases, the determing factors are the
increase of binding constants on the Cu2+ ion interaction with the
formed denatured sites on DNA and, in the case of Na2+ ions, the
decrease of the screening action of counterions with temperature.

A binding equation was obtained permitting to calculate binding
constants of Mt2+ on DNA compactisation and parameters of cooperativity.
The results obtained are being discussed in the frameworks of theories
of counterion condensation (CCT) and equilibrium binding. Unlike CCT,
the theory of equilibrium binding is shown to describe satisfactorily
the DNA compactisation process under the Mt2+ ion action.

Key words: DNA, metal ions, IR-spectroscopy, mixed solutions, ethanol,
1,2-propanediol, glycerol, urea, compactisation, temperature.

I?aeienaii aei ae?oeo 17.03.1999 ?. Oi?iao 60×84 1/16.

Oiiai.ae?.e. 1.0 Oe?aae 100 i?ei. Caiiaeaiiy 15-99.

?ioai??io OO?IO ?i. A.?.A??e?ia IAI Oe?a?ie, Oa?e?a 310164, i?. Eai?ia
47,

oae. (0572) 30-03-64

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