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

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

AAEAOE* ?ai? Einoyioeiiae/

OAeE 577.3;621.384.8

AEA*AIIss OA?IIAeEIAI?*IEO OA?AEOA?ENOEE EIIIIIAIO?A A?EEIAI-IOEEA?IIAEO
EIIIEAEN?A

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 I?eiiiae/,
Naaanoiiieuenueeee aea?aeaaiee oaoi?/iee oi?aa?neoao I?i?noa?noaa ina?oe
Oe?a?ie, aee?aeoi? aeaia?oaiaioo o?ceee oa o?i??, (i. Naaanoiiieue);

aeieoi? o?ceei-iaoaiaoe/ieo iaoe, i?ioani?, AIAe?IIIA Aieiaeeie?
Ieoaeeiae/, Oa?e?anueeee aea?aeaaiee oi?aa?neoao I?i?noa?noaa ina?oe
Oe?a?ie, caa?aeoaa/ eaoaae?e aenia?eiaioaeueii? o?ceee, (i. Oa?e?a).

I?ia?aeia onoaiiaa:

Aeiiaoeueeee aea?aeaaiee oi?aa?neoao I?i?noa?noaa ina?oe Oe?a?ie,
eaoaae?a a?io?ceee, i. Aeiiaoeuee.

Caoeno a?aeaoaeaoueny « 19 » o?aaiy 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?uee?anueeiai aea?aeaaiiai oi?aa?neoaoo: 310077, i.Oa?e?a,
ie. Naiaiaee, 4.

Aaoi?aoa?ao ?ic?neaiee « 16 » ea?oiy 1999 ?ieo

A/aiee nae?aoa?

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

1

CAAAEUeIA OA?AEOA?ENOEEA ?IAIOE

Aeooaeuei?noue oaie. ?ieue aca?iiae?e i?ae a?eeaie oa ioeea?iiaeie
eeneioaie aeoaea aaeeea, ine?eueee on? ooieoe?? ioeea?iiaeo eeneio
cae?eniththoueny o eiiieaen? c a?eeaie. Aea/aiiy iniaeeainoae oa
iaoai?ci?a oaeeo aca?iiae?e iaeaaeeoue aei aeooaeueieo caaea/ no/anii?
a?io?ceee. Aei iei?oiueiai /ano aeine?aeaeaiiy a?eeiai-ioeea?iiaiai
ai?ciaaaiiy, aaaeeea? aeey ?icoi?iiy aaaaoueio a?ieia?/ieo i?ioean?a, ui
a?aeaoaathoueny ia iieaeoey?iiio ??ai?, i?iaiaeeeeny ??ciiiai?oieie
iaoiaeaie. ?aioaai?anueea e?enoaeia?ao?y oa ssI?-niaeo?ineii?y aeathoue
?ioi?iaoe?th i?i no?oeoo?e ai?ciath/eo a?eeiai-ioeea?iiaeo eiiieaen?a,
cie?aia i?i aoiii? a?oie, a?aeiia?aeaeuei? ca niaoeeo?/ia ai?ciaaaiiy.
?ioaa?aeuei? oa?iiaeeiai?/i? ia?aiao?e oaeeo eiiieaen?a, ui
aecia/athoueny, iai?eeeaae, eaei?eiao?e/ieie iaoiaeaie, noinothoueny aei
noia?ii? aca?iiae?? ia ??ai? iae?iiieaeoe, ui ia aea? iiaeeeaino?
aeae?eeoe aeeaae niaoeeo?/ieo aca?iiae?e o ai?ciath/eo oeaio?ao. Aeey
?ica’ycaiiy inoaiiuei? caaea/? aeei?enoiao?oueny i?aeo?ae iiaeaeueiiai
aeine?aeaeaiiy ai?ciath/eo nenoai ia ??ai? iiiiia??a aai o?aaiaio?a
a?ee?a oa ioeea?iiaeo eeneio, ui aeicaiey? aeae?eeoe oae? aca?iiae??,
aeyaeoe ?oith i?e?iaeo, aea??eia?noue oa ?ieue o caaaeueiiio i?ioean?
eiiieaeniooai?aiiy.

Ca?aeii aeayeei i?eeiyoei iiaeaeyi, ai?ciaaaiiy caniiaaia ia
niaoeeo?/ieo «oi/eiaeo» aca?iiae?yo io?eiiauo oa i???i?aeeiiauo iniia c
aieiaeie eaioethaaie ai?iieeneio. I?e oeueiio, aea??eia?noue oaeeo
iiiii??ieo aca?iiae?e caa??aa?oueny ? o a?eueo neeaaeieo
ioeeaii?ioa?aeieo nenoaiao. Oiio iiaeia aaaaeaoe, ui caeiiii??iino?,
aeyaeai? o i?inoeo iiaeaeueieo nenoaiao, a?ae?a?athoue /eiaeo ?ieue o
caaacia/aii? niaoeeo?/iinoe aca?iiae?e a?ee?a c ioeea?iiaeie eeneioaie
oa aaeaeaaoii a?aeaeaathoue i?ioean ai?ciaaaiiy oeeo aeiiie?ia??a.

Oaeei /eiii, aeine?aeaeaiiy, i?enay/ai? aecia/aiith aia?aaoe/ieo
ia?aiao??a ioeeaii?ioa?aeieo eiiieaen?a ia ??ai? iiiiia??a, a oaeiae,
iaea?eueo aea?aeieo ?oi?o no?oeoo?, ? nueiaiaei? aaeueie aeooaeueieie oa
aaaeeeaeie aeey ?icoi?iiy caaaeueieo i?eioeei?a oa iaoai?ci?a
a?eeiai-ioeea?iiaiai ai?ciaaaiiy.

Ca’ycie ?iaioe n 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 OO?IO IAI Oe?a?ie ii oai?
«Aeine?aeaeaiiy no?oeoo?ieo oa

2

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. Iaoith aeaii? ?iaioe aoei aecia/aiiy
oa?iiaeeiai?/ieo oa no?oeoo?ieo oa?aeoa?enoee aca?iiae?e iniia
ioeea?iiauo eeneio c ai?iieeneioaie a oiiaao aaeooio, aeyaeaiiy
niaoeeo?/iino? oaeeo aca?iiae?e oa aecia/aiiy iaea?eueo aea?aeieo
eiio?ao?aoe?e ooai?aiiy iiaeaeueiuo iiiii??ieo eiiieaen?a.

Aeey aeinyaiaiiy aeacaii? iaoe aoei iinoaaeaia oaei caaea/i:

1. Oaeineiiaeaiiy nenoaie iaioneo iieueiaiai aeaea?aea ?ii?a aeey
caaacia/aiiy iiaeeeaino? niinoa?aaeaiiy anioe?aoe?? ?a/iaei c ??ciith
eaoth/?noth o aaeooi? oa aecia/aiiy oa?iiaeeiai?/ieo oa?aeoa?enoee
iaea?aeoaaieo eiiieaen?a.

2. Aenia?eiaioaeueia aecia/aiiy a?aeiinieo eiinoaio anioe?aoe?? oa
aioaeuei?e ooai?aiiy aiaeiaai-ca’ycaieo eiiieaen?a iniia ioeea?iiaeo
eeneio c ae?eeai?aeii yeee iiaeaeth? aieia? a?oie ai?iieeneio ania?aaeio
oa aeooaieio. Iiaoaeiaa ?yaeo noaa?eueiino? aeey oaeeo eiiieaen?a ia
iniia? a?aeiinieo eiinoaio anioe?aoe?? oa aioaeuei?e ooai?aiiy
anioeeao?a.

3. Ia/eneaiiy eaaioiai-o?i?/ieie iaoiaeaie no?oeoo? eiiieaen?a oa
aia?a?e aca?iiae?? iniia ioeea?iiaeo eeneio c ae?eeai?aeii.

4. Aeyaeaiiy ?ie? ??cieo aoiiieo a?oi i?e ooai?aii? oi/eiaeo eiioaeo?a o
i?ioean? a?eeiai-ioeea?iiaiai ai?ciaaaiiy.

Iaoeiaa iiaecia iaea?aeaieo ?acoeueoaoia iieyaa? o oiio, ui aia?oa ca
aeiiiiiaith iaoiaeo ian-niaeo?iiao??? io?eiai? e?euee?ni? aeai? i?i
aca?iiae?? o niaoeeo?/ieo ai?ciath/eo eiiieaenao iniia ioeea?iiaeo
eeneio oa ae?eeai?aeo, iiaeaethth/iai ai?aeio a?oio ai?iieeneio ia ??ai?
iiiiia??a. Aecia/aii a?aeiini? eiinoaioe anioe?aoe?? oa aioaeuei??
ooai?thaaiiy oaeeo anioe?ao?a, oa ia ?o i?aenoaa? anoaiiaeaii ?yae
noaa?eueiinoe aeey eiiieaen?a ae?eeai?aeo c ??cieie iniiaaie.
Anoaiiaeaii, ui aca?iiae?y a?aeaoaa?oueny c ooai?aiiyi, ye i?aaeei,
aeaio aiaeiaaeo ca’yce?a.

?ic?aooieiaeie iaoiaeaie aia?oa aecia/aii oeaio?e aca?iiae?e oa
no?oeoo?e aeeia??a ae?eeai?aeo c iaoeeiio?aeieie iniia ioeea?iiaeo
eeneio. Ia i?aenoaa? aenia?eiaioaeueieo aeaieo oa oai?aoe/ieo
?ic?aooie?a aecia/aii iaea?eueo aea?aei? i?noey ca’ycoaaiiy aeey
eiiieaen?a acioenoeo iniia oa ae?eeai?aeo. Anoaiiaeaii, ui iaea?eueo
aia?aaoe/ii aea?aeiith ? aca?iiae?y ca aeiiiiiaith aiaeiaaeo ca’yce?a ii
aoiiiei a?oiai, ui aa?ooue o/anoue a ooai?aii? Oionii-E?eeianueeeo ia?.

3

I?aeoe/ia cia/aiiy iaea?aeaieo ?acoeueoao?a. Aeine?aeaeaiiy o aaeoc?
iieaeoey?iiai ai?ciaaaiiy iiaeooue iaoe i?aeoe/io oe?ii?noue aeey
iaaeeoeeie. Ciaiiy no?oeoo?e eiioaeoieo a?oi oa aoii?a, ii yeei
a?aeaoaa?oueny ai?ciaaaiiy, aeicaieeoue eiino?othaaoe iia? e?ea?nuee?
caniae — ?ia?a?oi?e, ui aeieothoue ai?ciath/? oeaio?e iaaieo oa?iaio?a.

Iaea?aeai? o ?iaio? aenia?eiaioaeuei? oa oai?aoe/i? ?acoeueoaoe
iiaeeaeththoue ?nioth/? oyaeaiiy i?i iaoai?ci ai?ciaaaiiy a?eeaie
ioeea?iiaeo eeneio ia ??ai? iiiiia??a oa iiaeooue aeei?enoiaoaaoeny aeey
ioe?iee eiia??iino? ai?ciaaaiiy aieiaeie a?oiaie ai?iieeneio ania?aaeio
oa aeooaieio aoiiieo a?oi iniia o aeiaaeeo iaeiieaioethaiaiai noaio
ioeea?iiai? eeneioe. Aeai? ii aioaeuei?yi ooai?aiiy anioe?ao?a
ae?eeai?aeo oa iniia iiaeooue aooe aeei?enoai? o iiaeaeueoeo
aeine?aeaeaiiyo a?eeiai-ioeea?iiaeo eiiieaen?a o ?aieao iiaeae? oi/eiaeo
eiioaeo?a, a oaeiae aeey a?aei?aoethaaiiy ia?aiao??a ?ic?aooie?a
aiaeia?/ieo iiaeaeueieo eiiieaen?a ??ciiiai?oieie eaaioiai-o?i?/ieie
iaoiaeaie, ui aeeiiothoueny o oae caaiiio «aaeooiiiio iaaeeaeaii?».

Iniaenoee aianie caeiaoaa/a. A iioaeieiaaieo c niiaaaoi?aie iaoeiaeo
i?aoeyo iniaenoee aianie caeiaoaa/a iieyaa?:

a ?iaioao [1-11], ui iioae?eoaaeeny ii oai? aeena?oaoe??, caeiaoaa/
i?eeiaa aeoeaio o/anoue o ?ic?iaoe? aenia?eiaioaeueieo i?aeoiae?a aeey
?ica’ycaiiy iinoaaeaieo caaea/; eiio iaeaaeeoue oaanue ianya ?ia?o ii
i?iaaaeaiith aenia?eiaioaeueieo aei??thaaiue, ia?iaoe? iaea?aeaieo
?acoeueoao?a;

a ?iaioao [4, 5, 11], i?e i?iaaaeaii? eaaioiai-o?i?/ieo ?ic?aooie?a,
aeena?oaio i?eeiaa o/anoue o ae?ia?oeo iinoaiiaee caaea/? oa aeai??
iiaeae? ?ic?aooie?a, i?iaaaeaii? ie?aieo aoai?a ?ic?aooie?a, oa
iaaiai?aii? io?eiaieo ?acoeueoao?a.

Ai?iaaoe?y ?acoeueoao?a aeena?oaoe??. Iaoa??aee ?iaioe ca oaiith
aeena?oaoe?? aeiiia?aeaeenue ? iaaiai?thaaeenue ia:

VII Ananithciie eiioa?aioeee ii niaeo?ineiiee aeiiieeia?ia.- Oa?ueeia.-
1991.

I c’?cae? Oe?a?inueeiai aeio?ce/iiai oiaa?enoaa, Ee?a, 1994.

13-th Intern. Mass Spectrometry Conference, Budapest, Hungary, 1994.

6th Intern. Beijing Conf. on Instrum. Analysis, Beijing, China, 1995.

International Conf. « Genome structure and Function», Marciana Marina,
Italy, 1996.

14th International Mass Spectrometry Conference, Tampere, Finland, 1997.

Intern. Conference «Biomolecular Recognition», Spetses, Greece, 1997.

4

II c’?cae? Oe?a?inueeiai a?io?ce/iiai oiaa?enoaa, Oa?e?a, 1998.

Conf. on Physics of biological Systems (PBS 98).- Kyiv, Ukraine, 1998.

Intern. Conf. «Energetics of stable molecules and intermediates»,
Castelo Branco, Portugal, 1998.

Ioae?eaoe??. ?acoeueoaoe aeena?oaoe?? iioae?eiaaii a 11 iaoeiaeo
i?aoeyo, o oiio /ene? a 5 noaooyo o iaoeiaeo aeo?iaeao oa a 5 oacao ? 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 (176 iaeiaioaaiue). Iiaiee ianya aeena?oaoe??
neeaaea? 201 noi??ieo, c ieo aeiaeaoie caeia? 26 noi?., nienie
aeei?enoaieo e?oa?aoo?ieo aeaea?ae — 18 noi?., ?iaioa i?noeoue 60
iaethie?a oa 35 oaaeeoeue. Iaethiee oa oaaeeoe?, ye? ?icoaoiaai? ia
ie?aieo noi??ieao, caeiathoue: iaethiee — 15 noi?., oaaeeoe? — 6 noi?.

INIIAIEE CI?NO ?IAIOE

O anooi? iaa?oioiaaii aeooaeuei?noue ia?aii? oaie, iaaaaeaii ??
i?aeoe/ia cia/aiiy oa iaoeiao iiaecio iaea?aeaieo ?acoeueoao?a,
noi?ioeueiaaii iaoo ? caaea/? aeine?aeaeaiiy, iaaaaeaii caaaeueio
oa?aeoa?enoeeo aeena?oaoe??.

?icaeie 1 iinoeoue iaeyae eioa?aoo?e, i?enay/aiee no/aniiio noaio
i?iaeaie aieeiai-ioeea?iiaiai aiiciaaaiiy. O ?icae?e? iienai? oa?aeoa?i?
iniaeeaino? iieaeoey?iiai ai?ciaaaiiy, a oaeiae caaaeuei? oyaeaiiy i?i
eiai iaoai?cie. Aeae? ioa?aeoa?eciaaii aenia?eiaioaeuei? oa? oai?aoe/i?
iaoiaee aeine?aeaeaiiy ai?ciaaaiiy a?eeaie ioeeaeiiauo eeneio oa
iaaaaeaii ?acoeueoaoe i?aoeue, i?enay/aieo aecia/aiith no?oeoo?e oa
iiaeeeaeo iaoai?ci?a ooai?aiiy ??cieo? a?eeiai-ioeeaeiiauo eiiieaen?a ia
??ai? a?iiie?ia??a. Iaaaaeaia no?oeoo?ia nenoaiaoeea a?eeiaeo aeiiai?a,
ui ca’ycothoueny c AeIE.

Aeyaeaii, ui ca?aeii no/aniei oyaeaiiyi, ai?ciaaaiiy caniiaaia ia
niaoeeo?/ieo aca?iiae?yo iniia ioeea?iiaeo eeneio c aieiaeie a?oiaie
ai?iieeneio. A?aecia/aii, ui caaaeath/e ia neeaaei?noue i?e?iaeieo
eiiieaen?a a?iiie?ia??a, aeey ?oiueiai aea/aiiy canoiniaothoueny
iiaeaeuei? i?aeoiaee, ui aeicaieythoue aea/aoe oae? aca?iiae?? ia ??ai?
iiiiia??a. O ca’yceo c oeei, iaaaaeai? ?acoeueoaoe no?oeoo?ieo
aeine?aeaeaiue iiaeaeueiuo a?eeiai-ioeea?iiaeo eiiieaen?a ia ??ai?
iiiiia??a.

Ia iniia? aaeeei? e?eueeinoe e?oa?aoo?ieo aeaieo aeyaeaii, ui
ai?iieeneioe ania?aaei oa aeooaiei ? iaeieie c iaea?eueo /anoi
i?eeiath/eo o/anoue o i?ioean? a?eeiai-ioeea?iiaiai ai?ciaaaiiy. O
aeaeyae? aeiaiaeo oeueiai, iaaaaeai? no?oeoo?e

5

a?eeiai-ioeea?iiauo eiiieaen?a, o yeeo ai?ciaaaiiy ?aae?co?oueny oeyoii
aca?iiae?? c oeeie ai?iieeneioaie. Iaeiae, aiae?c iayaieo aeaieo
iieaco?, ui iaa?oue iiaeaeuei? i?aeoiaee, ia aeathoue ?ioi?iaoe?th i?i
oa?iiaeeiai?/i? ia?aiao?e aca?iiae?e ia iiiiia?iiio ??ai?.
Aenia?eiaioaeueia aea/aiiy ia iiiiia?iiio ??ai? eiiiiiaio?a ai?ciath/eo
oeaio??a, aeeth/ath/eo iaaaeeea /enei ca’ycaieo oeyoii aiaeiaaeo
ca’yceca ooieoe?iiaeueieo aoiiieo a?oi, aea? iiaeeea?noue aeae?eeoe
aeeaae naia niaoeeo?/ieo aca?iiae?e o eiiieaeniooai?aiiy. Iaea?aeaoe
oaeo ?ioi?iaoe?th aeicaiey? iaoiae oaiia?aoo?ii-caeaaeii? iieueiai?
ian-niaeo?iiao???, yeee aea? ciiao aecia/aoe oa?iiaeeiai?/i?
oa?aeoa?enoeee (aioaeuei??) ooai?aiiy iiiiia?ieo eiiieaen?a a oiiaao
aaeooio. O o?niiio ca’yceo c aea/aiiyi oa?iiaeeiai?/ieo oa?aeoa?enoee
aca?iiae?? iiiiia?ieo eiiieaen?a a?ee?a oa ioeea?iiaeo eeneio
ciaoiaeeoueny caaea/a aecia/aiiy iaea?eueo aea?aeii? no?oeoo?e oaeeo
eiiieaen?a, yea iiaea aooe oni?oii ae??oaia ca aeiiiiiaith ?ic?aooieiaeo
eaaioiai-o?i?/ieo iaoiae?a.

A ?icaeiei 2 iiaeaii caaaeueio oa?aeoa?enoeeo iaoiaeia aeineiaeaeaiiy oa
aeei?enoaieo iaoa?iaeia. O iueiio ?icaeyiooi o?ce/i? iniiae iaoiaeo ian
niaeo?iiao??? c iieueiaith ?ii?caoe??th. Iienaia iiaaae?iea /anoie o
aacia?e oac? o cii? iiaeeco a?no?y yi?oa?a o aeaeo?e/iiio iie? aeniei?
iai?oaeaiino?. Iieacaii, ui aca?iiae?? a?aeaoaathoueny iii?ae
iaeo?aeueieie iieaeoeaie e ooai?aiiy ?ii?a o/aniee?a oa i?iaeoeo?a
?aaeoe?e o aacia?e oac? a?aeaoaa?oueny a oiiaao oa?iiaeeiai?/ii?
??aiiaaae. Iieacaii, ui caaaeyee i?aeaeuai?e eiioeaio?aoe?? iieaeoe o
cii? iiaeeco iiaa?oi? ai?oa?a, a oaeiae i’yeiio caniao ?ii?caoe?? ui
caaacia/o? iecueeee nooi?iue o?aaiaioaoe?? oa caa?aaeaiiy iiaeeeaino?
niinoa?aaeaiiy neaaeeo iaaaeaioieo aca?iiae?e i?ae iieaeoeaie, iieueiaa
ian-niaeo?iiao??y aeicaiey? aea/aoe i?ioeane anioe?aoe?? a?iiieaeoe, a
oiio /ene?, eiiiiiaio?a ioeeaeiiauo eeneio. Iaoiae aaco?oueny ia
aecia/aii? a?aeiinii? eiinoaioe anioe?aoe?? Ean iieaeoe o aacia?e oac?
ia i?aenoaa? ian-niaeo??a, iiaoaeia? aaio-Aiooianueeeo caeaaeiinoae,
oiaoi caeaaeiinoae Ean a?ae oaiia?aoo?e ?aaeoe?eii? ciie, oa
ciaoiaeaeaii? aioaeuei?e (I ooai?aiiy eiiieaen?a, ui niinoa??aathoueny.
A oiiaao iieueiai? ?ii?caoe?? aaee/eia ?iiiiai no?oio (?ioaineai?noue
e?i?e ian-niaeo?o) iia’ycaia c eiioeaio?aoe??th iaeo?aeueieo iieaeoe o
cii? ?ii?caoe?? ??aiyiiyi:

IA(F) = (A(F)(nA(F)
(1)

aea IA(F) — ?ioaineai?noue i?eo iieaeoee oeio A i?e iai?oaeaiino? iiey
F,

nA(F) — eiioeaio?aoe?y iaeo?aeueieo iieaeoe oeio A, (A(F) — eiao?oe??io
?ii?caoe??.

6

Aeey eiinoaioe anioe?aoe?? ?aaeoe?? oeio A+A (AA iiaeia caienaoe:

(2)

aea E(an — ?noeiia eiinoaioa ??aiiaaae, (((F) — aoaeoeaiee eiao?oe??io
?ii?caoe??, ui i?noeoue eiao?oe??ioe ?ii?caoe?? ia?a?nieo iieaeoe oa
eiiieaeno, ? caeaaeeoue a?ae aaee/eie iiey.

Yioaeuei?? ((I) ooai?aiiy aiaeiaai-ca’ycaieo eiiieaen?a ae?eeai?aeo c
??cieie iniiaaie iaea?aeoaaee c aaio-Aiooianueeeo oaiia?aoo?ieo
caeaaeiinoae a?aeiinieo eiinoaio anioe?aoe?? (Ean) o a?aeiia?aeiino? c
oi?ioeith:

(3)

aea R — oi?aa?naeueia aaciaa iino?eia, O — aaniethoia oaiia?aoo?a.

Aeae? iienaii aenia?eiaioaeueia iaeaaeiaiiy oa can?a, ui canoiniaoaaany
aeey aeaioiaeaiiy iieueiaeo aieooa??a. Aenia?eiaioe i?iaiaeeeeny ia
noaoe/iiio naeoi?iiio iaai?oiiio ian-niaeo?iiao?? IE 1201 (Oe?a?ia).
Ian-niaeo?iiao? aoei iaeaaeiaii niaoe?ae?ciaaiei eaai?aoi?iei iieueiaei
aeaea?aeii ?ii?a, aei eiino?oeoe?? yeiai aoee aianai? aeiaeaoeia?
oaeineiiaeaiiy, ui ni?eyee noai?aiith noaa?eueii? eiioeaio?aoe?? iieaeoe
o cii? iieueiaiai ai?oa?a. Aeey i?aeo?eiee oa aeiaeaoeiaiai ca?eueoaiiy
eiioeaio?aoe?? iieaeoe o ?aaeoe?ei?e cii? aoa ?ic?iaeaiee ooi?iieanoiaee
oeeeeiae?, ?icoaoiaaiee iaaeiei ai?ooa?o oa eiai oo?eioaa/a. Oea ni?eyei
ciaioaiith oaeaeeino? a?aeieeao iieaeoe, ui iaaeoiaeyoue aei ciie
ai?oa?a, a, ioaea, ca?eueoaiith ?oiuei? eiioeaio?aoe??, i?eaeecii ia
10%.

Aeey aea/aiiy a?eeiai-ioeea?iiaiai ai?ciaaaiiy ia ??ai? iiiiia??a
aeei?enoiaoaaeenue iiaeaeuei? niieoee. O aeaeyae? iiaeae? aieiaeo a?oi
ai?iieeneio ania?aaeio oa aeooaieio aeei?enoiaoaaany ae?eeai?ae. O
aeaeyae? iiaeaeae iiiiia??a ioeea?iiaeo eeneio aeei?enoiaoaaeenue
iaoeeiio?aei? i???i?ae?iiaeo oa io?eiiaeo iniia.

A caeeth/i?e /anoei? oeueiai ?icae?eo aeaii noeneee iaoaiaoe/iee iien
?ic?aooieiaeo iaoiae?a — oai??? ooieoeeiiaeo u?eueiino? (OOU) oa ab
initio ia ??ai?

7

Iaeea?-Ieannao -2 (I?2), a oaeiae iaoiaeeee ?ic?aooie?a, ui
aeei?enoiaoaaeany aeey ae??oaiiy iinoaaeaieo caaea/.

Iae.1 Iieueia? ian-niaeo?e ?aaeoe?eieo noi?oae ae?eeai?aeo (Ae?) n
iaoeeiio?aeieie ioeea?iiaeo iniia: a — m21,4Cyt (Oai=298E, Ua=+5eA); a —
m9Gua (Oai=310E, Ua=+5eA).

??aiiaaaei? a?aeiini? eiinoaioe anioe?aoe??, ui ia/eneththoueny c
ni?aa?aeiioaiiy ?ioaineaiinoae i?e?a iaea?aeaieo ian-niaeo??a,
i?iii?oe?ei? ?noeiiei eiinoaioai anioe?aoe?? (aeea. oi?ioee (1), (2)).
Eiao?oe??io i?iii?oe?eiino? a?aeiia?aea? aoaeoeaiiio eiao?oe??ioo
?ii?caoe??, ui aecia/a?oueny a?aeiioaiiyi eiao?oe??io?a ?ii?caoe??
iaeo?aeueieo o/aniee?a oa i?iaeoeo?a anioe?aoe??. Eiao?oe??io ?ii?caoe??
iiaea ci?ithaaoeny a?ae aenia?eiaioa aei aenia?eiaioo. Oiio, iiaeia
ii??aithaaoe eeoa a?aeiini? eiinoaioe anioe?aoe?? aeey na??? ?a/iaei,
iaea?aeai? o iaeieo aenia?eiaioaeueieo oiiaao. C oe??th iaoith aoee
i?iaaaeai? aenia?eiaioe o yeeo niinoa??aaeeny ii aeaa aiaeiaai-ca’ycaieo
aaoa?ianioe?aoa, ui ooai?thaaeeny i?e noi?niiio iaioneo o ?aaeoe?eio
ciio

8

aeaio ??cieo iniia oa ae?eeai?aeo. O eiaeiiio ianooiiiio aenia?eiaio?
iaeia c iniia, ui i?eeiaea o/anoue o iiia?aaeiueiio aeine?ae?,
aeei?enoiaoaaeany o aeaeyae? ?aia?a. O?aaiaioe aeaeieueeio ian-niaeo??a,
iaea?aeaieo a ?acoeueoao? iienaieo aeua aeine?ae?a, iaaaaeai? ia iae. 2.

Iae.2 Iieueia? ian-niaeo?e ?aaeoe?eieo noi?oae ae?eeai?aeo (Ae?) c
iaoeeiio?aeieie ioeea?iiaeo iniia: a — (m9Ade oa m1Ura), a — (m9Ade oa
m9Gua) (Oa=311E, Ua=+5eA).

C ni?aa?aeiioaiiy ?ioaineaiinoae i?e?a ian-niaeo??a aecia/aii a?aeiini?
eiinoaioe anioe?aoe??. Ia i?aenoaa? iaea?aeaieo aenia?eiaioaeueieo
cia/aiue a?aeiinieo eiinoaio anioe?aoe?? iiaoaeiaaii ?yae noaa?eueiino?
aeey eiiieaen?a ae?eeai?aeo c ??cieie iniiaaie:

m9Gua ( m21,4Cyt ( m1Cyt > m9Ade >m31,4,4Cyt > m1Ura > m21,3Thy
(4)

Aeey ciaoiaeaeaiiy cia/aiue Ean i?e ??cieo oaiia?aoo?ao o ?aaeoe?ei?e
cii? aoee io?eiai? oaiia?aoo?i? caeaaeiino? ?iiieo no?oi?a aeey on?o
?ii?a, ui niinoa??aaeeny. Ci?io oaiia?aoo?e ?aaeoe?eii? ciie i?iaiaeeee
oeyoii ?acenoeaiiai iaa??ao iieueiaiai yi?oa?a aeaeo?e/iei no?oiii ia.
Oaiia?aoo?i? caeaaeiino? lgI=f(ia) aeey on?o ?ii?a o ian-niaeo?ao
eiiieaen?a ae?eeai?aeo c iaoeeiio?aeieie io?eiiaeo oa ii?iiiaeiiiaeo
iniia a ?ioa?aae? oaiia?aoo? 280-420E iieacaii ia iae. 3. Iaea?aeai?
oaiia?aoo?i? caeaaeiino? ?iiieo no?oi?a i?aaenoaaeythoue ci?io ??aiiaaae
?aaeoe?e anioe?aoe?? o o?eniaaiiio ?ioa?aae? oaiia?aoo?, aea
eiao?oe??ioe ?ii?caoe?? aca?iiae?th/eo iieaeoe oaeoe/ii iaci?ii?. C iae.
3 aeaeii, ui o?ae oaiia?aoo?ieo caeaaeiinoae ?ioaineaiinoae ?iiieo
no?oi?a aeey on?o ?ii?a iiiiia??a oa aaoa?iaeeia??a on?o aea/aieo
eiiieaen?a aeyaey? iaeiaeia? oaiaeaioe??. ?c c?inoaiiyi oaiia?aoo?e

9

?ioaineaiino? i?e?a iiiiia??a, ye i?aaeei, c?inoathoue, a ?ioaineaiino?
i?e?a aaoa?iaeeia?ia iaaeathoue i?aeoe/ii aei ??aiy oiio.

Iae.3. Oeiia? caeaaeiino? ?iiieo no?oiia iiiiia?ia e aaoa?iaeeia?ia
ae?eeai?aeo oa ioeea?iiaeo iniia a?ae no?oia ?acenoeaiiai iaa??ao
iieueiaiai ai?oa?a: a — aeey m31,4,4Cyt (1 — Ae?eeai?ae, 2 — m31,4,4Cyt,
3 — eiiieaen ( Ae?eeai?ae +m31,4,4Cyt )), a — aeey m9Ade (1 —
Ae?eeai?ae, 2 — m9Ade, 3 — eiiieaen (Ae?eeai?ae+m9Ade)),

Aioaeuei?? ooai?aiiy anioe?ao?a ciaoiaeeee c iioeeo aaio-Aiooianeeo
caeaaeiinoae o a?aeiia?aeiino? c oi?ioeith (3). I?eeeaaee
aaio-Aiooianueeeo caeaaeiinoae aeey eiiieaen?a ae?eeai?aeo c
iaoeeiio?aeieie io?eiiauo oa i???i?ae?iiaeo iniia iieacaii ia iae.4.

Iae.4. Oaiia?aoo?i? caeaaeiino? Ean aeey eiiieaen?a ae?eeai?aeo c
??cieie iaoeeiio?aeieie oeeoiceio — (a), (1 — m1Cyt, 2 — m21,4Cyt, 3 —
m31,4,4Cyt ) oa c iaoeeiio?aeiei aaeai?io (m9Ade) -(a).

Iaea?aeai? cia/aiiy aioaeuei?e on?o aea/aieo eiiieaen?a i?aaenoaaeai? o
oaae. 1. Cia/aiiy iaaaaeaieo o oaae. 1 aioaeuei?e oa iia??oiinoae ?
?acoeueoao ona?aaeiaiiy aaee/ei o na??? aenia?eiaio?a. Iia??oi?noue
ia/eneaiiy aioaeuei?e o eiaeiiio

10

aenia?eiaio? aecia/aeany caniaii iaeiaioeo eaaae?ao?a. Caeaaeiino?
lnKan=f(1/T), ye aeaeii c iae. 4, a on?o aeiaaeeao e?i?ei?. Oea
na?ae/eoue i?i oa, ui o aenia?eiaioaeueiiio

Oaaeeoey 1

Aioaeuei?? ooai?aiiy eiiieaen?a ae?eeai?aeo c iaoeeiio?aeieie iniia
(eAeae/iieue)

Iniiaa m21,4Cyt m1Cyt m31,4,4Cyt m9Ade m9Gua m21,.3Thy m1Ura

Aioaeuei?y ((I) -58,7

(5,0 -57,0

(3,3 -45,7

(4,2 -52,0 (5,0 -59,5

(3,8 -28,5

(2,5 -40,6

(4,2

oaiia?aoo?iiio ?ioa?aae? (280 — 420E) aioaeuei?y ooai?aiiy eiiieaen?a
iino?eia oa ia caeaaeeoue a?ae oaiia?aoo?e. Ii??aiyiiy iaaeaieo o oaae.
1 aenia?eiaioaeueieo cia/aiue aioaeuei?e c ?yaeii noaa?eueiino?
eiiieaen?a (aeea. ?yae (4)), na?ae/eoue i?i iiaio a?aeiia?aei?noue ae?oa
ae?oao ?yae?a, iiaoaeiaaieo ia iniiai a?aeiinieo eiinoaio anioe?aoe?? oa
aioaeueiie aeey aea/aii? na??? iniia. Oea aeicaiey? c?iaeoe aeniiaie i?i
ia?aaaaeiee aioaeuei?eiee aianie aei a?eueii? aia?a?? ooai?aiiy
eiiieaen?a.

Oaeiae o oeueiio ?icaeiei i?iaaaeaii ia?aai?eo aieeao iiey ia
iaea?aeoaai? cia/aiiy aioaeuei?e anioe?aoe??. Aecia/aii aaee/eie
aioaeuei?e ooai?aiiy eiiieaen?a i?e ??cieo iioaioe?aeao ia yi?ooa??.
Ciaeaeaii, ui o aenia?eiaioaeueieo ?ioa?aaeao iai?oaeaiinoae iiey oa
oaiia?aoo? aeey on?o aea/aieo eiiieaen?a, ie??i eiiieaen?a ae?eeai?aeo c
oeeoiceiii, aieeaii iiey iiaeia ciaaaaeeoe, oiaoi o iaaeao iia??oiino?
aenia?eiaio?a aioaeuei?? ia caeaaeaoue a?ae aaee/eie ?ii?coth/iai iiey.
Aeyaeaia caeaaei?noue aeey eiiieaenia c oeeoiceiii coiiaeaia a?eueoith,
o ii??aiyii? c ?ioeie iniiaaie, aaee/eiith aeeiieueiiai iiiaioo, a
oaeiae, ae?ia?aeii, iaio ni?eyoeeaith a?aeiiniith i???ioaoe??th aeeiieae
o eiiieaen?.

*aoaa?oee ?icae?e i?enay/aii iiaoaeia? no?oeoo?ii-yia?aaoe/ieo noai
niaoeeo?/iiai ca’ycoaaiiy iniia ioeea?iiaeo eeneio c ae?eeai?aeii.
Iaoiae oaiia?aoo?ii-caeaaeii? ian-niaeo?iiao??? c iieueiaith
?ii?caoe??th aeicaiey? aecia/eoe aaee/eio aioaeueii? aca?iiae??, aea i?e
oeueiio ia aea? ?ioi?iaoe?th i?i eiie?aoi? no?oeoo?e eiiieaen?a. O
ca’yceo c oeei, aoei iaiaoiaeii canoinoaaoe oai?aoe/ii ?ic?aooieiai
iaoiaee aeey aecia/aiiy i?noeue ca’ycoaaiiy oa iaea?eueo aeaiaeieo
no?oeoo? eiiieaenia. O ?icaeiei i?aaenoaaeaii ?acoeueoaoe ?ic?aooieia
no?oeoo? oa aia?aie ooai?aiiy aeey eiiieaenia ae?eeai?aeo c
iaoeeiioiaeieie ?icieo iniia, i?iaaaeaieo iaaii???/ieie iaoiaeaie OOU oa
ab initio ia ?iaii I?2. Io?eiaii

11

cia/aiiy aia?a?e aca?iiae?? aeey iaeaieueo aeaiaeieo eiiieaenia
ae?eeai?aeo c m1Ura, m1Cyt oa m21,4Cyt i?aaenoaaeaii o oaae. 2.

Oaaeeoey 2

Aia?a?? eiiieaen?a ??cieo iniia c ae?eeai?aeii, io?eiai? iaoiaeaie
OOU/B3LYP/6-31++G** oa I?2/6-31+G*. On? aia?a?? io?eiai? aeey aaiiao??e
ae?ia??a, iioei?ciaaieo ia ??ai? OOU/B3LYP/6-31++G** (eAeae/iieue)

Iaoiae OOU

(m1Ura+ | m1Cyt+ |m1,4Cyt+

Ae?ee- | Ae?ee- | Ae?ee-

ai?ae) | ai?ae) | ai?ae ) Iaoiae I?2

(m1Ura+ | m1Cyt+ | m1,4Cyt+

Ae?ee- | Ae?ee- | Ae?ee-

ai?ae) | ai?ae) | ai?ae )

Aia?a?y aca?iiae??, -52,32 -65,81 -66,68 -62,04 -75,83 -80,62

Aia?a?y aca?iiae?? c o?aooaaiiyi noia?iiceoe?eii? iii?aaee,

-49,95

-63,26

-64,21

-48,68

-61,72

-65,04

Aia?a?y aca?iiae?? c o?aooaaiiyi noia?iiceoe?eii? iii?aaee oa iii?aaee
aei aia?- a?? ioeueiaeo eieeaaiue,

-52,70

-70,15

-70,93

-51,43

-68,61

-71,76

Ia ianooiiiio aoaii ca aeiiiiiaith iaaiii??/ieo ?ic?aooieiaeo iaoiaeia
OOU oa ab initio aecia/aii ??aiiaaaei? no?oeoo?e eiiieaen?a ae?eeai?aeo
c m1Ura, m1Cyt oa m21,4Cyt. Anoaiiaeaii, ui on? eiiieaene iniia
ioeea?iiaeo eeneio c ae?eeai?aeii iathoue ieaia?io no?oeoo?o, oa
noaaieiciaaii aeaiia aiaeiaaeie ca’yceaie, i?e/iio c aieo iniia o
eiiieaeniooai?aii? aa?ooue o/anoue aoiiii a?oie, ye? cae/aeii
i?eeiathoue o/anoue a oionii-e??eianueeiio ca’ycoaaii?.

Iieacaii, ui ?acoeueoaoe ?ic?aooie?a aeia?a ni?aa?aeiinyoueny i?ae
niaith oa c aenia?eiaioaeueieie aeaieie o iaaeao oi/iino? aenia?eiaio?a.
I?iaaaeaii iaaiai?aiiy oa ii??aiyiiy io?eiaieo ?acoeueoao?a c inioth/eie
eioa?aoo?ieie aeaieie. Aiii aeicaiey? i?eioneaoe, ui aeey
iaeiini??aeueii? AeIE aai ?? ?anieaoaieo ae?eueieoeue (ye ? aeey ie?aieo
iieaeoe iniia) niaoeeo?/ieie ? aca?iiae?? c

12

ai?iieeneioaie, ui ooai?ththoue aeaa aiaeiaaeo ca’ycee c o/anoth
ai?aeii? a?oie. I?e oeueiio aea?aei?noue aca?iiae?? c o??th aai ?ioith
iniiaith ioeea?iiaeo eeneio coiiaeaia, a iniiaiiio, aaoa?iaaii?noth
?oiueiai ca?yaeiaiai ?iciiae?eo oa ia? oi?aa?naeueiee oa?aeoa?, ui ia
caeaaeeoue a?ae ioi/aiiy. Aeey aeaioni??aeueii? AeIE, ii?yae c
a?aecia/aiith aeua, c’yaey?oueny aeiaeaoeiaa niaoeeo?/i?noue
ioeeaii?ioa?aeieo eiiieaen?a c aieo iniia, ui iiaei a i?iyaeyo?oueny o
iiaeeea?e aeanoaa?e?caoe?? A-O-aaaaoeo ae?eueieoeue AeIE o aaeeeiio
aeieia? i?e aca?iiae?? c aeooaieiii oa ania?aaeiii.

Aiae?c iaea?aeaieo aeaieo, ?oi? ii??aiyiiy c aeaieie ?ioeo aaoi??a
aeicaieythoue iiaoaeoaaoe no?oeoo?ii-aia?aaoe/i? noaie ca’ycoaaiiy,
a?aeiia?aei? iaea?eueo aea?aeiei eiio?ao?aoe?yi aiaeiaai-ca’ycaieo
eiiieaen?a ae?eeai?aeo c iaoeeiio?aeieie iniia ioeea?iiaeo eeneio.
Cai?iiiiiaaii noaie i?aaenoaaeaii ia iae. 5.

Aeiaeaoie ai?uo? oaaeeoe? ?ic?aooieiaeo aeaieo ii aeiaaeeiai ca’yce?a,
aaeaioiei oa oi?n?iiiei eooai, a oaeiae ca?yaeai ia aoiiao aeey
eiiieaen?a ae?eeai?aeo c iaoeeiio?aeieie aeayeeo iniia.

AENIIAEE

Iieacaia iiaeeea?noue ooai?aiiy o aaeooi? eiiieaen?a i?ae ai?aeiith
a?oiith ai?iieeneio oa on?ia iniiaaie ioeea?iiauo eeneio, iiaeaethth/eo
i?ioean a?eeiai-ioeea?iiaiai ai?ciaaaiiy ia ??ai? iiiiia??a.
Anoaiiaeaii, ui aca?iiae?y a?aeaoaa?oueny c ooai?aiiyi, ye i?aaeei,
aeaio aiaeiaaeo ca’yce?a. I?e oeueiio, iaea?eueo aia?aaoe/ii aea?aeiith
? aca?iiae?y oeyoii aiaeiaaeo ca’yce?a c aoiiieie a?oiaie, ui aa?ooue
o/anoue a ooai?aii? oionii-e?ee?anueeeo ia?.

Iaoiaeii oaiia?aoo?ii-caeaaeii? iieueiai? ian-niaeo?iiao??? aecia/aii
eiinoaioe anioe?aoe?? oa aioaeuei?? ooai?aiiy aiaeiaai-ca’ycaieo
eiiieaen?a ae?eeai?aeo c iaoeeiio?aeieie iniia ioeea?iiaeo eeneio o
aaeooi?. Ia i?aenoaa? iaea?aeaieo eiinoaio anioe?aoe?? oa aioaeuei?e
anoaiiaeaii ?yae noaa?eueiino? aeey eiiieaen?a ae?eeai?aeo c ??cieie
iniiaaie:

m9Gua ( m21,4Cyt ( m1Cyt > m9Ade >m31,4,4Cyt > m1Ura > m21,3Thy

Iiaoaeiaai? ia iniia? a?aeiinieo eiinoaio anioe?aoe?? oa aioaeuei?e
?yaee noaa?eueiino? eiiieaen?a oe?eeii a?aeiia?aeathoue iaeei iaeiiio.
Oea aeicaiey? c?iaeoe aeniiaie i?i ia?aaaaeiee aioaeuei?eiee aianie o
a?eueio aia?a?th ooai?aiiy eiiieaen?a.

13

Iae. 5. Noaie ooai?aiiy eiiieaen?a ae?eeai?aeo c ioeea?iiaeie iniiaaie o
aaeooi?.

a — c m1Ura, a — c m21,3Thy, a — c m9Ade, a — c m9Gua, ae — c m1Cyt, a —
c m21,4Cyt, ae — c m31,4,4Cyt. Aoiie N iiai?noth /i?i?, aoiie N
ia?ao?anii-caoo?eoiaai?, aoiie I n??? oa aoiie I — a?e? e?oae

3. Ca aeiiiiiaith iaaii???/ieo ?ic?aooieiaeo iaoiae?a OOU oa ab initio
aecia/aii ??aiiaaaei? no?oeoo?e eiiieaen?a ae?eeai?aeo c iaoeeiio?aeieie
??cieo iniia oa ?ic?aoiaaii aia?a?? aca?iiae?? aeey on?o io?eiaieo
??aiiaaaeieo no?oeoo?. Anoaiiaeaii, ui aeeia?e ae?eeai?ae-iniiaa
ieaia?i? oa noaa?e?ciaai? aiaeiaaeie ca’yceaie, ui iathoue iinoeeiao
no?oeoo?o.

14

4. Ia i?aenoaa? ii??aiyiiy aenia?eiaioaeueieo oa oai?aoe/ieo aeaieo,
iaea?aeaieo

iaoiaeii ian-niaeo?iiao??? oa oai?aoe/ieie iaoiaeaie OOU, I?2 ?
aoii-

aoiiieo iioaioe?eieo ooieoe?e, iiaoaeiaaii no?oeoo?ii-aia?aaoe/i?
noaie

ooai?aiiy eiiieaen?a iniia ioeea?iiaeo eeneio c ae?eeai?aeii ?c
cacia/aiiyi

iaea?eueo aea?aeieo i?noeue ca’ycoaaiiy aeey on?o annioe?ao?a.

5. Ia i?aenoaa? aenia?eiaioaeueieo oa ?ic?aooieiaeo aeaieo anoaiiaeaii,
ui aeey

iaeiini??aeueii? AeIE i?e aca?iiae?? iniia ioeea?iiaeo eeneio c
ai?iieeneioaie

niaoeeo?/ieie ? aca?iiae??, i?e yeeo ooai?ththoueny aeaa aiaeiaa?
ca’ycee ca o/anoth

ai?aeii? a?oie ai?iieeneio. I?e oeueiio, aea?aei?noue aca?iiae?? c
o??th aai ?ioith

iniiaith ioeea?iiaeo eeneio coiiaeaia, a iniiaiiio,
iaiaeii??aei?noth ca?yaeiaiai

?iciiae?eo o iieaeoeao iniia oa ia? oi?aa?naeueiee oa?aeoa?, ui ia
caeaaeeoue a?ae

ioi/aiiy. Aeey aeaioni??aeueii? AeIE ii/eia? i?iyaeyoeny
aeiaeaoeiaa niaoeeo?/i?noue

i?e ooai?aii? ioeeaii?ioa?aeieo eiiieaen?a c aieo iniia, ui
a?aeaeaa?oueny o

iiaeeeaino? aeanoaa?e?caoe?? A-O -aaaaoeo ae?eueieoeue AeIE i?e
aca?iiae?? c

ai?iieeneioaie aeooaieiii oa ania?aaeiii o aaeeeiio aeieia?.

6. Iieacaii, ui a?aooaaiiy noia?iiceoe?eii? iii?aaee oa iii?aaee aei
aia?a??

ioeueiaeo eieeaaiue i?e ?ic?aooieao no?oeoo? oa aia?a?e aca?iiae??
eiiieaen?a

ae?eeai?aeo c iaoeeiio?aeieie iniia ioeea?iiaeo eeneio o aaeooi?
iaoiaeaie ab

initio oa OOU cia/ii iie?auo? ocaiaeaeaiiy oai?aoe/ieo
?ic?aooieiaeo aeaieo c

aenia?eiaioaeueieie ?acoeueoaoaie, io?eiaieie o oe?e ?iaio?.

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

Oaieeoeeee A.A., Aaeaoe/ E.E., Nooiaeoa E.O.Yia?aaoeea ia?aciaaiey
eiiieaenia aieiieeneioa — iniiaaiea a aaeooia (aeooaiei, ania?aaei —
o?aoeee, oeiei) // Aeioeceea. — 1990. — O. 35, ? 5. — N. 709-710.

Poltev V.I., Shuljupina N.V., Bruskov V.I., Teplitsky A.B., Sukhodub
L.F., Galetich I.K. Experimental and theoretical study of energetics of
complex formation between nucleic acids bases and the bases with amide
group // J. Biomol. Struct. Dynam. — 1991. — V.9, ? 1. — P. 1O1-111.

Aaeaoe/ E.E., Oaeeianeee A.N., Einaae/ I.A., Aeaaie TH.I. Ii?aaeaeaiea
yia?aaoe/aneeo ia?aiao?ia iaaeiieaeoey?iuo acaeiiaeaenoaee a eiiieaenao
iaoeei?iecaiaeiuo oeeoiceia n ania?aaeiii e aeooaieiii // Aanoi. i?iaeai
aeie. e iaae. — 1998. — ?8.- N. 27-40.

15

4. Aaeaoe/ E.E., Noaiaiueyi N.A., Oaeeianeee A.N., Einaae/ I.A., Aeaaie
TH.I.,

Aaeaiiae/ E. Yenia?eiaioaeueiia e oai?aoe/aneia eco/aiea
iaaeiieaeoey?iuo

acaeiiaeaenoaee a ociathuai eiiieaena iaoeeo?aoeeea n ae?eeaieaeii
// A?ni.

Oa?e. oi-oo. — 1998. — ? 410. A?io?ce/iee a?ni. Aei. 1. — N. 57-61.

5. Galetich I.K., Shelkovsky V.S., Kosevich M.V., Blagoy Yu.P.,
Shulyupina N.V., Poltev

V.I. Mass-spectrometric and computational study of complex
formation of nucleic acid

bases with acrylamide as a surrogate for asparagine and glutamine
residues // Rapid

Commun. in Mass Spectrom. — 1998. — V. 12, ? 22. — P. 1761-1764.

6. Galetich I.K. Model Study of protein-nucleic acid base interactions
involving amide

group by means of field ionization mass spectrometry // Proc.
International 6th Beijing

Conf. on Instrum. Analysis.- Beijing (China). — 1995. — P. B87-B88.

7. Kosevich M.V., Galetich I.K., Shelkovsky V.S. Interpretation of some
field ionization

mass spectra applying the ideas of field polymerization // 13-th
International Mass

Spectrometry Conf. — Budapest (Hungary). — 1994. — P. 318.

8. Einaae/ I.A., , Iaoeinueea A.A., Aaeaoe/ I.E., Oaeeianueeee A.N.
Eiieo?aioi?

i?ioeane, ui noi?iaiaeaeothoue a?ae?aoaoe?th ai?aeii? a?oie
ai?iie?neio // Oace

aeiiia?aeae I C’?caeo Oe?. aiioic. oia. — Ee?a. — 1994.- N.
129-130.

9. Oaeeianeee A. N., Ai?ye I. A., Aaeaoe/ E. E., Einaae/ I. A. Eco/aiea

iieeia?ecaoeee aeieiae/anee aeoeaiuo niaaeeiaiee, eiaeooee?oaiie
oneiaeyie

iann-niaeo?iiao?e/aneiai yenia?eiaioa // Oacenu aeieeaaeia VII
Ananithc. eiio.

ii niaeo?ineiiee aeiiieeia?ia.- Oa?ueeia.- 1991. — N. 262-263.

10. Aaeaoe/ I.E., Oaeeianueeee A.N., Iaoeinueea A.A., Einaae/ I.A.,
Aeaaee TH.I.

Iiaeaethaaiiy iieaeoey?iiai ?iciiciaaaiiy a oiiaao
ian-niaeo?iiao?e/iiai

aenia?eiaioo // Oace. Aeiiiaiae. II C’?caeo Oe?. aiioic. oia.
(OAOO-98). — Oa?e?a.-

1998.- N. 35.

11. Aaeaoe/ ?.E., Oaeeianueeee A.N., No?iaiyi N.A., Einaae/ I.A., Aeaaee
TH.I.

Aenia?eiaioaeueia oa oai?aoe/ia aeine?aeaeaiiy aca?iiae?? i?ae
ae?eeai?aeii oa

iaoeeiio?aeieie o?aoeeeo oa oeeoiceio c oi/ee ci?o iieaeoey?iiai
ai?ciaaaiiy //

Conf. on Physics of biological Systems (PBS 98).- Kyiv (Ukraine).
— 1998.- P. 92.

AIIOAOe?ss

Aaeaoe/ ?.E. Aea/aiiy oa?iiaeeiai?/ieo oa?aeoa?enoee eiiiiiaio?a a?eeiai
— ioeea?iiaeo eiiieaen?a. — ?oeiien.

16

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.

Iaoiaeii oaiia?aoo?ii-caeaaeii? iieueiai? ian-niaeo?iiao??? aecia/ai?
eiinoaioe anioe?aoe?? oa aioaeuei?? ooai?aiiy aiaeiaai-ca’ycaieo
eiiieaen?a ae?eeai?aeo c iaoeeiio?aeieie iniia ioeea?iiaeo eeneio o
aaeooi?, iiaeaethth/eo i?ioean a?eeiai- ioeea?iiaiai ai?ciaaaiiy ia
??ai? iiiiia??a. Ia i?aenoaa? io?eiaieo eiinoaio anioe?aoe?? oa
aioaeuei?e anoaiiaeaii ?yae noaa?eueiinoe aeey eiiieaen?a ae?eeai?aeo c
??cieie iniiaaie. C?iaeaii aeniiaie i?i ia?aaaaei?noue aioaeuei?eiiai
aeeaaeo o naiaiaeio aia?a?th ooai?aiiy eiiieaen?a. Ca aeiiiiiaith
iaaii???/ieo ?ic?aooieiaeo iaoiae?a OOU oa ab initio aecia/aii
??aiiaaaei? no?oeoo?e eiiieaen?a ae?eeai?aeo c iaoeeiio?aeieie ??cieo
iniia oa ia/eneaii aia?a?? aca?iiae?e aeey on?o io?eiaieo ??aiiaaaeieo
no?oeoo?. Anoaiiaeaii, ui aeeia?e ae?eeai?ae-iniiaa ieaia?i? oa
noaa?e?ciaai?, ye i?aaeei, aeaiia aiaeiaaeie ca’yceaie, ye? iathoue
iinoeeiao no?oeoo?o. Ia iniia? aenia?eiaioaeueieo oa oai?aoe/ieo aeaieo
caoaeiaaii no?oeoo?ii-aia?aaoe/i? noaie ooai?aiiy eiiieaen?a iniia
ioeea?iiaeo eeneio c ae?eeai?aeii c cacia/aiiyi iaea?eueo aea?aeieo
i?noeue ca’ycoaaiiy aeey on?o anioe?ao?a.

Eeth/ia? neiaa: a?eeiai-ioeea?iiaa ai?ciaaaiiy, iieueiaa
ian-niaeo?iiao??y, aiaeiaai-ca’ycaiee eiiieaen, eiinoaioa anioe?aoe??,
aioaeuei?y.

AIIIOAOeEss

Aaeaoe/ E.E. Eco/aiea oa?iiaeeiaie/aneeo oa?aeoa?enoee eiiiiiaioia
aaeeiai — ioeeaeiiauo eiiieaenia.- ?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.

Iaoiaeii oaiia?aoo?ii-caaeneiie iieaaie iann-niaeo?iiao?ee ii?aaeaeaiu
eiinoaiou annioeeaoeee e yioaeueiee ia?aciaaiey aiaei?iaeii-naycaiiuo
eiiieaenia ae?eeaieaea n iaoeei?iecaiaeiuie iniiaaiee ioeeaeiiauo eeneio
a aaeooia, iiaeaee?othueo i?ioeann aaeeiai-ioeeaeiiaiai ociaaaiey ia
o?iaia iiiiia?ia. Ia iniiaaiee iieo/aiiuo eiinoaio annioeeaoeee e
yioaeueiee onoaiiaeai ?yae noaaeeueiinoe aeey eiiieaenia ae?eeaieaea n
?acee/iuie iniiaaieyie. Naeaeai auaiae i i?aeiouanoaaiiii yioaeueieeiii
aeeaaea a naiaiaeioth yia?aeth ia?aciaaiey eiiieaenia. Onoaiiaeaii, /oi
acaeiiaeaenoaea i?ienoiaeeo n ia?aciaaieai, eae i?aaeei, aeaoo
aiaei?iaeiuo naycae. N iiiiuueth iayiie?e/aneeo

17

?an/aoiuo iaoiaeia OOI e ab initio ii?aaeaeaiu ?aaiiaaniua no?oeoo?u
eiiieaenia ae?eeaieaea n iaoeei?iecaiaeiuie ?acee/iuo iniiaaiee e
?ann/eoaiu yia?aee acaeiiaeaenoaey aeey anao iieo/aiiuo ?aaiiaaniuo
no?oeoo?. Onoaiiaeaii, /oi aeeia?u ae?eeaieae — iniiaaiea ieaia?iu e
noaaeeece?iaaiu, eae i?aaeei, aeaoiy aiaei?iaeiuie naycyie, eiathueie
iinoeeiaoth no?oeoo?o. Ia iniiaaiee yenia?eiaioaeueiuo e oai?aoe/aneeo
aeaiiuo iino?iaiu no?oeoo?ii-yia?aaoe/aneea noaiu ia?aciaaiey eiiieaenia
iniiaaiee ioeeaeiiauo eeneio n ae?eeaieaeii n oeacaieai iaeaieaa
auaiaeiuo iano naycuaaiey aeey anao annioeeaoia.

Eeth/aaua neiaa: aaeeiai-ioeeaeiiaia ociaaaiea, iieaaay
iann-niaeo?iiao?ey, aiaei?iaeii-naycaiiue eiiieaen, eiinoaioa
annioeeaoeee, yioaeueiey.

SUMMARY

Galetich I.K. Investigation of the thermodynamic parameters
(characteristics) of the components of protein-nucleic acid complexes. —
Manuscript.

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

Interaction between proteins and nucleic acid bases occurs at all stages
of replication and expression of DNA and in many processes of
bio-regulation . Our knowledge about the mechanisms of such interactions
is, however, very limited, which is caused mainly by the complexity of
the system of large macromolecules. To simplify the study of such
complex systems model experiments are conducted, the main aim of which
is to establish the specificity of the recognition of nucleic acid bases
by the side chains of amino acids. Study of interactions between the
components of nucleic acids and proteins allows to estimate the yield of
different atomic groups in formation of protein-nucleic acid complexes
and to predict changes in their stability, caused by the changes in the
primary structure of the biopolymers.

A method of temperature-dependent field ionization (TD FI) mass
spetrometry provided to be efficient in experimental determination of
the energy of formation of pair and triple compexes of biomolecules in
vacuum. It should be stressed that this technique is nearly a single
method, which experimental data can be directly compared with the
theoretical data obtained by quantum chemical calculations of such
systems in the so-called «vacuum approximation». In the frames of the
problem of molecular recognition this work is aimed at the determination
of the thermodynamic and structural characteristics of interactions
between nucleic acid bases and amino acids in vacuum conditions, the

18

search of molecular specificity of these interactions and determination
of the most favourable configurations of the model complexes on monomer
level.

The interactions between the monomers of nucleic acids and proteins,
were studied on the systems (consisting of methylderivatives of nitrogen
bases Uracyl, Thymine, Cytosine, Adenine and Guanine and acrylamide)
which are good models of interactions, involving specific aminoacid side
chains of Glutamine and Asparagine. Thermodynamic parameters of
interactions were obtained using a method of TD FI mass spectrometry.
Under the mass spectrometric conditions the associates of molecules were
formed in the gas phase; variation of the temperature allowed to obtain
relative association constants and to calculate the enthalpies of
associates formation ((H) using Vant-Hoff plots. These data permits us
to construct the stability row for the complexes between the acrylamide
and methylderivatives of nitrogen bases. Enthalpies of formation of
nucleic acid base-acrylamide complexes, determined experimentally by
means of TD FI mass spectrometry, were in good agreement with the
interaction energies calculated theoretically using non-empirical
methods ab initio and DFT. As a result of combined experimental and
computational study, configurations of the most favourable complexes
corresponding to interaction energy minima were constructed. The most
favourable sites of interaction of acrylamide with the bases correspond
to its hydrogen bonding to the same base atoms involved in Watson-Crick
pairing.

Key words: protein-nucleic acid recognition, field ionization mass
spectrometry, hydrogen-bonded complex, association constant, enthalpy.

I?aeienaii aei ae?oeo 23.03.1999 ?. Oi?iao 60×84 1/16.

Oiiai.ae?.e. 1.0 Oe?aae 100 i?ei. Caiiaeaiiy 18-99.

__________________________________________________________________

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

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