Chemistry andPhy~icsO[£:iPid¢! 9 ( 1 9 7 7 ) I ~ V ! 4 9 - , ~ .... :-.--~. ,. ~ :: ~!.!: © Elsevier/North-Holland Scientific Publishes, Ltd~
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H. FRISCHLEDER,S...GLEICHMANNand.R;~KRAHL .-..:/: - : i- -.
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Received August 23rd, 1976,
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Sektion Physik der Kad,Marx.:U:~v~t~t,Arbeitsgruppe Mo!ekfil.NMR,Letpzig, -
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acceptedNovember2$ih, 1:976
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The binding of water to the dimethylphosphate anion (DMP'~) was ca!¢.tflat~ u s ~ : t h e : PCILO method. We found binding energies of 25.9~1 kcad' moI--~.~:/the.O ! ~ P : 0 3 i ~ ~g.ing the anionic oxygen atOmS.~ 19;3. kcal. r o o f -for the o ~ te.:~timlOC.:!:~Wa~ ::.:.::molecule to an anionk.- oxyMn atom of DMIP'. :~this:zanlp O n e ' ~ ! m o ~ ~ / d e d to :..
vMv- m the o1:... 03.b ged
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than water m o l ~ added. Aoother:..bi~nll stir. The/total ~ e a e t l W : o f $~.WM mO!o' cules to DMP-is 92 kcal .toOl : , a quantity which Is about 10%.!euthan l h e i ~ . : o f the binding energies of the cottespondln8 monohydzltm. " ""
1. Introduction
The phosphate group of phospholipids participates in intermolecular interactions with cations, positively charged groupsand water, 0fspe~alinterest is the interaction with water because ofthe-comple~/phase~vi'our:of phos~01ipi'd--water systems in relation to temperature and Water.¢O~tratiOn; ~ ~ y , a t low~water concentration [1,2], and theinfluence Of water on the ii~tetaCfioh:with cations, From experimental~investigations Of phos~lipidsWekJtoW:Out :iwater.can be readily evaporated from aque0us dispersionsofphmp~p~d0~/t0t~monohydrated state [3]. High:resolution proton ~ e t i c reso~¢einv~esttsatt~ ofthe line width and the chemicalshfft of theHzO peak in D l ~ ( d i ~ t 0 y l ~ p h 0 ~ i choline)-CsD6"H2.O dispersions demo~rate[4;5 ] t ~ t Water.is ~ ~ e d W-t lie/ phosphate group in.several hydratiori shells,..~: Water~.mole~Ie~ a hi~y~..re.--.- ~ duced mobility inits phosphate.bond:state wl~h indicates a very s t r ~ : ~ i n ~ g t o •
this group. Three to .five more.water molecules.hareasmaI!eg interagUon..~, t ~ . .
phospholipid phosphate ~o~pl.i~/icO~hto~:th,: ~ s t / ~ t e r : / m ~ i ! ~ : ! ! ~ , i
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• Pullmanetal, [/6-9].~¢ulated::t~:..~Arid~g~.:0fWate.t-::~~!.:t~-~ilt~!~i~~!/~. :phosphate anion(DM~ ) by an.:iabii~tio~F s~:3:G:pr~dU~ ~ i ~ ~ i m : i . ~ : GAUSS1AN 70.. For them0n0~a.¢¢:: they ~ d : : : t n 6 m b e t ~ o f : ¢ ~ ~ y ! i ~ ~ i
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"~
:
" . . .
.'~
• . . .
-
.
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...
, . . -
.
.
..
"
~--,
H. FRISCHLEDER,S...GLEICHMANNand.R;~KRAHL .-..:/: - : i- -.
.
.
.
.
.
-
,.-
.
,?."
_"
-
:
/
;
.:-
. . . .
. :.;.
,
.
..
::/::-~i ~ G D R :
' "
. .. •
.
-
Received August 23rd, 1976,
~
-
ii!i:ii:i::ii}
Sektion Physik der Kad,Marx.:U:~v~t~t,Arbeitsgruppe Mo!ekfil.NMR,Letpzig, -
. -
.....:::,. : , ,:. . :.-,:..: ~_~,:.... " : :.
..--
..
:
' . : . . -
:::;.~::i.:::::::':i:"-~.i./:i: !::::;.~:..:::.'i/:"-:::..{.::-"-.!.:.i:..""::!-..:"...:-:.::.:}:::.i::":. .:
.--,.
•
. -
. :
QUAN~M~~CALAN~U~i:i::!/!!.:I! DIMETHY~HOSP~~.~ONi
: "
-. .....
-:
~
"
,
...
acceptedNovember2$ih, 1:976
. •
. ..
•
-.
, . .
,
.
.
•
.
-•.,..
The binding of water to the dimethylphosphate anion (DMP'~) was ca!¢.tflat~ u s ~ : t h e : PCILO method. We found binding energies of 25.9~1 kcad' moI--~.~:/the.O ! ~ P : 0 3 i ~ ~g.ing the anionic oxygen atOmS.~ 19;3. kcal. r o o f -for the o ~ te.:~timlOC.:!:~Wa~ ::.:.::molecule to an anionk.- oxyMn atom of DMIP'. :~this:zanlp O n e ' ~ ! m o ~ ~ / d e d to :..
vMv- m the o1:... 03.b ged
o
eonhu,
:VMr-
than water m o l ~ added. Aoother:..bi~nll stir. The/total ~ e a e t l W : o f $~.WM mO!o' cules to DMP-is 92 kcal .toOl : , a quantity which Is about 10%.!euthan l h e i ~ . : o f the binding energies of the cottespondln8 monohydzltm. " ""
1. Introduction
The phosphate group of phospholipids participates in intermolecular interactions with cations, positively charged groupsand water, 0fspe~alinterest is the interaction with water because ofthe-comple~/phase~vi'our:of phos~01ipi'd--water systems in relation to temperature and Water.¢O~tratiOn; ~ ~ y , a t low~water concentration [1,2], and theinfluence Of water on the ii~tetaCfioh:with cations, From experimental~investigations Of phos~lipidsWekJtoW:Out :iwater.can be readily evaporated from aque0us dispersionsofphmp~p~d0~/t0t~monohydrated state [3]. High:resolution proton ~ e t i c reso~¢einv~esttsatt~ ofthe line width and the chemicalshfft of theHzO peak in D l ~ ( d i ~ t 0 y l ~ p h 0 ~ i choline)-CsD6"H2.O dispersions demo~rate[4;5 ] t ~ t Water.is ~ ~ e d W-t lie/ phosphate group in.several hydratiori shells,..~: Water~.mole~Ie~ a hi~y~..re.--.- ~ duced mobility inits phosphate.bond:state wl~h indicates a very s t r ~ : ~ i n ~ g t o •
this group. Three to .five more.water molecules.hareasmaI!eg interagUon..~, t ~ . .
phospholipid phosphate ~o~pl.i~/icO~hto~:th,: ~ s t / ~ t e r : / m ~ i ! ~ : ! ! ~ , i
':
• Pullmanetal, [/6-9].~¢ulated::t~:..~Arid~g~.:0fWate.t-::~~!.:t~-~ilt~!~i~~!/~. :phosphate anion(DM~ ) by an.:iabii~tio~F s~:3:G:pr~dU~ ~ i ~ ~ i m : i . ~ : GAUSS1AN 70.. For them0n0~a.¢¢:: they ~ d : : : t n 6 m b e t ~ o f : ¢ ~ ~ y ! i ~ ~ i
