1
G aphical abs ac
In his wo k he in luence o he inco po a ion o a oma ic subs i uen s a he end o he
hyd ophobic ail on he binding o ca ionic su ac an s o cyclodex ins was s udied.
2
HOST-GUEST INTERACTIONS BETWEEN CYCLODEXTRINS AND
SURFACTANTS WITH FUNCTIONAL GROUPS AT THE END OF THE
HYDROPHOBIC TAIL
Vic o ia Isabel Ma ín, F ancisco José Os os, Manuel Angulo1, An onio Má quez, Pila
López-Co nejo, Manuel López-López2, Ana Te esa Ca mona3 and Ma ía Luisa Moyá*
Depa men o Physical Chemis y, Uni e si y o Se ille, C/ P o eso Ga cía González 1,
41012 Se ille. Spain. Tl . 34954557175. E-mail:moy[email p o ec ed]
1NMR Se ice, Uni e si y o Se ille, Apa ado 1203, E-41071 Se ille, Spain
2Depa men o Chemical Enginee ing, Physical Chemis y and Ma e ials Science, Facul y o
Expe imen al Sciences, Campus de El Ca men, A da. de las Fue zas A madas s/n, 21071
Huel a. Spain
3Depa men o O ganic Chemis y, Uni e si y o Se ille, C/P o eso Ga cía González 1,
41012 Se ille. Spain
Key wo ds: Su ac an s, cyclodex ins, inclusion complexes, a oma ic subs i uen s,
conduc i i y, NMR.
*Au ho o whom all co espondence should be di ec ed
3
Abs ac
The aim o his wo k was o in es iga e he in luence o he inco po a ion o
subs i uen s a he end o he hyd ophobic ail on he binding o ca ionic su ac an s o α-, β-,
and -cyclodex ins. The equilib ium binding cons an s o he 1:1 inclusion complexes o med
ollow he end K1(α-CD)>K1(β-CD)>>K1(-CD), which can be explained by conside ing he
in luence o he CD ca i y olume on he hos -gues in e ac ions. F om he compa ison o he
K1 alues ob ained o dodecyl ie hylammonium b omide, DTEAB, o hose es ima ed o he
su ac an s wi h he subs i uen s, i was ound ha he inco po a ion o a phenoxy g oup a he
end o he hyd oca bon ail does no a ec K1, and he inclusion o a naph hoxy g oup has
some in luence on he associa ion p ocess, sligh ly diminishing K1. This makes e iden he
impo ance o he con ibu ion o hyd ophobic in e ac ions o he binding, he leng h o he
hyd ophobic chain being he key ac o de e mining K1. Howe e , he p esence o he
a oma ic ings does in luence he loca ion o he hos and he gues in he inclusion
complexes. The obse ed NOE in e ac ions be ween he a oma ic p o ons and he CD p o ons
indica e ha he a oma ic ings a e pa ially inse ed wi hin he hos ca i y, wi h he
cyclodex in emaining close o he a oma ic ings, which could be pa ially in e cala ed in he
hos ca i y. To he au ho s´ knowledge his is he i s s udy on he associa ion o
cyclodex ins wi h monome ic su ac an s inco po a ing subs i uen s a he end o he
hyd ophobic ail.
1. In oduc ion
Cyclodex ins, CD, a e cyclic oligosaccha ides o med h ough (1-4) e he linkages
o glucopy anoside uni s [1,2]. The mos common CDs, -, -, and -CD, a e composed o
six, se en and eigh glucose uni s, espec i ely. CDs a e shaped like a unca ed cone wi h
in e nal ca i ies anging om 5 o 8 Å. The hyd oxyl unc ions a e o ien ed o he ex e io o
he ca i y, wi h he seconda y hyd oxyl g oups loca ed on he wide edge, and he p ima y
4
ones on he na ow edge. The C-H bonds on he ing and he nonbonding elec on pai s o he
glycosidic oxygen b idges poin inwa d. As a esul o his spa ial a angemen o he
unc ional g oups, he ca i y shows a ela i ely hyd ophobic cha ac e while he ex e nal
su aces a e hyd ophilic. This is esponsible o bo h hei wa e solubili y and hei abili y o
o m inclusion complexes wi h molecula gues s o sui able size. This capaci y o o m
inclusion complexes wi h a wide a ie y o molecules, oge he wi h he non- oxici y owa ds
humans, has been he basis o he CDs la ge ange o applica ions [3-9].
The unde s anding o he d i ing o ces in ol ed in he CD inclusion complex
o ma ion is undamen ally impo an no only in CD chemis y, bu also o sup amolecula
chemis y as a whole. In a ecen e iew Valen e and Söde man [10] poin ed ou ha
su ac an s a e ideal gues s o undamen al s udies on he complexa ion wi h CDs since bo h
hyd ophobic and hyd ophilic egions o he su ac an molecules can be sys ema ically a ied.
These au ho s examined he e ec o di e en su ac an a chi ec u es on he o ma ion o
inclusion complexes by conside ing he esul s ob ained by se e al au ho s o single ailed,
double ailed, gemini and bola o m su ac an s, wi h special emphasis on ca ionic su ac an s.
Howe e , o he au ho s´ knowledge, he in luence o he inco po a ion o a unc ional g oup
a he end o he hyd ophobic su ac an ail on he su ac an :CD in e ac ions has no been
in es iga ed. Wi h his in mind, he su ac an s ie hyl(1-phenoxydodecyl)ammonium
b omide (Phenoxy12) and ie hyl(2-naph hoxydodecyl)ammonium b omide (Naph hoxy12)
we e p epa ed in his wo k and hei in e ac ions wi h -, -, and -cyclodex ins s udied. In
o de o help he discussion o he esul s, he o ma ion o hos :gues complexes be ween
dodecyl ie hylammonium b omide (DTEAB) and CDs was also in es iga ed. Since he e is
no much in o ma ion abou su ac an s wi h unc ional g oups a he end o he hyd ophobic
ail in he li e a u e, a b ie discussion o he physicochemical p ope ies o Phenoxy12 and
5
Naph hoxy12 aqueous solu ions was done be o e conside ing he o ma ion o he inclusion
complexes.
N
CH2-CH3
B
( )11
DTEAB Phenoxy12
ON
B H
Naph hoxy12
( )11 CH2-CH3
CH2-CH3
CH2-CH3
ON
( )11 CH2-CH3
CH2-CH3
CH2-CH3
B
CH3
CH3-CH2
CH3-CH2
Scheme 1.- S uc u e o he su ac an s used in his wo k.
The esul s ob ained in his wo k will con ibu e o he unde s anding o he
su ac an :cyclodex in in e ac ions. This is impo an in ela ion o he wide ange o
applica ions o bo h CDs and su ac an s, which can be inc eased by aking ad an age o he
CD-su ac an complex o ma ion.
2. Expe imen al sec ion
2.1. Ma e ials and chemicals
Dodecyl yme hylammonium b omide, DTAB, was om Sigma-Ald ich. -, -, and
-cyclodex ins o he highes pu i y a ailable we e also pu chased om Ald ich (>99%
pu i y, acco ding o he manu ac u e ) and we e kep unde acuum. DTEAB was p epa ed in
a p e ious wo k [11] and i s syn hesis is b ie ly desc ibed in he Supplemen a y Ma e ial. The
p epa a ion o Phenoxy12 and Naph hoxy12 is desc ibed below. The su ac an s we e
cha ac e ized by 1H NMR, 13C NMR and elemen al analysis (CITIUS, Uni e si y o Se ille).
D2O was supplied by Sigma. Wa e was MilliQ ( esis i i y >18 M cm).

6
2.2. P epa a ion o he su ac an s
2.2.1. P epa a ion o Phenoxy12
The syn hesis o Phenoxy12 was pe o med acco ding o Scheme 2. S a ing om
comme cial 1,12-dib omo-dodecane, he phenoxy g oup, PhO, was in oduced a he end o
he a y alkyl chain by nucleophilic subs i u ion eac ion wi h sodium phenoxide in ace one,
hus gi ing compound 1 (12-b omo-1-phenoxydodecane) in 29% yield. Finally, a nucleophilic
displacemen eac ion wi h ace oni ile and ie hylamine ga e he compound 2 ( ie hyl(1-
phenoxydodecyl) ammonium b omide) in 75% yield. I s 1H NMR spec um indica ed he
appea ance o a iple and a qua e signals in eg a ing o nine and six p o ons, espec i ely,
co esponding o he new h ee e hyl g oups. P ocedu es o he p epa a ion o he su ac an
and in e media es a e desc ibed in de ail in Supplemen a y Ma e ial.
B (CH2)10B +PhONa ace one B (CH2)10 OPh
N(CH)10 OPh
B
ie hylamine
CH3CN
1
2
Scheme 2.- Syn hesis o Phenoxy12
2.2.2. P epa a ion o Naph hoxy12
The syn hesis o Naph hoxy12 was simila o ha o Phenoxy12, as i is shown in
Scheme 3. In his scheme he naph hoxy g oup is ep esen ed by NaphO. Comme cial 1,12-
dib omo-dodecane and sodium naph hoxide we e used in he nucleophilic subs i u ion
eac ion o ende compound 3 (12-b omo-1-naph hoxydodecane), in 52% yield. Finally, he
nucleophilic displacemen eac ion wi h ace oni ile and ie hylamine ga e he compound 4
( ie hyl(1-naph hoxydodecyl) ammonium b omide) in 97% yield. Simila ly o Phenoxy12,
7
+NaphONa ace one
B
ie hylamine
CH3CN
3
4
B B
10 NaphO B
10
NNaphO 10
Scheme 3.- Syn hesis o Naph hoxy12
1H NMR spec um o Naph hoxy12 indica ed he appea ance o a iple and a qua e signals
in eg a ing o nine and six p o ons, espec i ely, co esponding o he new h ee e hyl g oups.
P ocedu es o he p epa a ion o he su ac an s and in e media es a e also desc ibed in de ail
in Supplemen a y Ma e ial.
2.3. Me hods
2.3.1. Conduc i i y measu emen s
Conduc i i y was measu ed wi h a C ison GLP31 conduc ime e calib a ed wi h KCl
solu ions o he app op ia e concen a ion ange. The conduc ime e was connec ed o an
ex e nal wa e ci cula o (He o) and he whole sys em was placed in a oom in which he
empe a u e was kep cons an wi hin ±0.5 K. Tempe a u e was main ained a 3030.01 K.
Solu ions we e used wi hin 5 h a e p epa a ion. In a ypical expe imen a su ac an solu ion
was placed in he he mos a ed conduc i i y cell; hen, aliquo s o he CD solu ion, in he
p esence o he same su ac an concen a ion, we e added in a s epwise manne using a
p og ammable dispense C ison Bu e e 1S (0.1 L). The speci ic conduc i i y o he
solu ion was measu ed 10 min a e each addi ion, a e checking ha he speci ic
conduc i i y emained cons an wi h ime. Each expe imen was epea ed a leas wice.
The c i ical micella concen a ions o Phenoxy12 and Naph hoxy12 we e es ima ed
by means o conduc i i y measu emen s as desc ibed in e . 12.
8
2.3.2. Su ace ension measu emen s
Su ace ension was measu ed by a du Noüy ing me hod using a KSV 703 digi al
ensiome e (Finland) as desc ibed in e . 12.
2.3.3. NMR measu emen s
The NMR spec a we e pe o med in CITIUS (Resea ch Gene al Se ices o he
Uni e si y o Se ille). NMR samples we e p epa ed by dissol ing he co esponding amoun
o he su ac an and/o he CD in D2O ollowed by a b ie sonica ion. The solu ions we e
kep he mos a ed a 303 K o a leas 5 hou s be o e ca ying ou he NMR expe imen s.
NMR expe imen s we e eco ded on a B uke A ance III 500 MHz spec ome e (500.2 MHz
o 1H) equipped wi h a 5 mm TCI c yop obe ope a ing a 303 K. All 1H chemical shi s a e
e e enced o he esidual HDO signal se o 4.71 ppm [13].
Two-dimensional, 2D, o a ing ame nuclea O e hause e ec expe imen s we e
pe o med using he B uke s anda d pulse sequence (EASY-ROESY e sion [14]). 2048 x
256 da a poin s we e acqui ed wi h 16 ansien s pe inc emen and a elaxa ion delay o 1.5 s.
A mixing ime o 250 ms was used. Da a p ocessing was pe o med on a 1024 x 1024 da a
ma ix. Cosine-squa ed window unc ions we e used along F1 and F2.
3. Resul s and discussion
3.1. Physicochemical p ope ies o he Phenoxy12 and Naph hoxy12 aqueous solu ions
The c i ical micella concen a ion, cmc, and he micella ioniza ion deg ee, , o
Phenoxy12 and Naph hoxy12 in aqueous solu ions we e de e mined using conduc i i y
measu emen s. Figu e S1 (Supplemen a y Ma e ial) shows he dependence o he speci ic
conduc i i y on Phenoxy12 and on Naph hoxy12 concen a ions a 303 K. The Ca pena
me hod [15] was used in o de o ob ain he cmc and α alues om he expe imen al esul s.
These da a a e summa ized in Table 1, oge he wi h ha co esponding o DTEAB. The
Gibbs ene gy o micelliza ion, GoM, can be calcula ed by using eq. 1 [16]:
9
GoM= RT(2-α) ln cmc (1)
whe e cmc is exp essed in mole ac ion and R and T ha e hei usual meaning. GoM alues
a e lis ed in Table 1. Compa ison o he GoM alues ob ained o he h ee su ac an s shows
Table 1.-C i ical micella concen a ion, cmc, micella
ioniza ion deg ee, , and Gibbs ene gy o micelliza ion,
GoM, o he ca ionic su ac an s s udied in his wo k, a
303 K.
Su ac an
Cmc/mM

GoM/kJ
mol-1
DTEABa
14.30.4
0.350.02
-34.31.8
Phenoxy12b
3.70.2
0.400.03
-38.81.7
Naph hoxy12b
0.6410.015
0.430.03
-45.01.9
aRe . 11; bThis wo k.
ha he in oduc ion o a phenoxy and a naph hoxy g oup a he end o he su ac an
hyd ophobic ail subs an ially a o s micelliza ion. The expe imen al obse a ions can be
explained by aking in o accoun he ans e Gibbs ene gy con ibu ion, Go ans , o he Gibbs
ene gy o micelliza ion, GoM. Go ans conside s he ans e o he hyd ophobic su ac an
chains om he aqueous phase o he micella in e io and i is he d i ing o ce o he sel -
associa ion p ocess o su ac an s [17]. The su ac an s lis ed in Table 1 ha e a dodecyl
hyd ophobic chain and he co esponding Go ans con ibu ion would be he same o all o
hem. The 4- old and a 22- old diminu ion in he cmc, wi h espec o ha o DTEAB, caused
by he inco po a ion o a phenoxy g oup, C6H5O-, and o a naph hoxy g oup, C12H7O-, a he
end o he hyd ophobic ail can be a ionalized by conside ing he addi ional hyd ophobic
con ibu ion o Go ans due o he ans e o he C6H5O- and C12H7O- g oups in o he
micelles. The la ge di e ence ound be ween he cmc´s o Phenoxy12 and Naph hoxy12
could be accoun ed o by he di e en hyd ophobici y o hese wo a oma ic subs i uen s. As
an example, he loga i hm o he oc anol/wa e pa i i ion coe icien , logP, is 1.46 and 2.70
o phenol and naph hol, espec i ely [18].
16
o ien a ion o he su ac an , wi h he a oma ic moie y loca ed close o he na owe im o he
cyclodex in.
In e ac ions be ween he CD p o ons and he a oma ic su ac an p o ons a e obse ed
o Phenoxy12 and Naph hoxy12. Conside ing he ROESY spec a o he Phenoxy12
su ac an , one can see NOE in e ac ions be ween he a oma ic H1' and H2' p o ons (s onge
o H1') o he su ac an and p o ons o he cyclodex ins o -, -, and -CD. Fo
Naph hoxy12 (see Figu e 4S, Supplemen a y Ma e ial) NOE in e ac ions be ween he p o ons
H1', H3´, H4´, and H8´ (s onge o H1´and H3´) and p o ons o he CDs a e obse ed. These
indings poin ou ha in he o med inclusion complexes he cyclodex in emains close o
he a oma ic ings, which could be pa ially in e cala ed in he hos ca i y. They also
show he dynamic cha ac e o he inclusion complex o ma ion, which associa es and
dissocia es wi h a equency ha would depend, o a gi en gues , on he CD na u e. This
dynamic cha ac e could explain he eally in e es ing ac ha he in e ac ion be ween he CD
p o ons and all he a oma ic p o ons o Phenoxy12 is only obse ed in he case o -CD. This
cyclodex in has he la ges ca i y olume o he h ee CDs, which would make he
dissocia ion easie han o - and -CD, inc easing he p obabili y o in e ac ions be ween
he CD and he a oma ic p o ons. The es ima ed equilib ium binding cons an s ob ained in his
wo k suppo his assump ion (see below).
3.3. S oichiome y
P io o he calcula ion o he equilib ium binding cons an s o he inclusion
complexes, he binding s oichiome y o he CD:Su ac an hos -gues complexes has o be
es ima ed. In o de o do so Job´s me hod was used [26]. I is obse ed ha when CDs a e
added o an aqueous ionic su ac an solu ion, a cons an su ac an concen a ion, an inc ease
in CD concen a ion could esul in a dec ease in he expe imen al speci ic conduc i i y. This
dec ease can be asc ibed o he o ma ion o CD:Su ac an , CDS, inclusion complexes, which

17
ha e conside ably smalle ionic equi alen conduc i i y han hose o su ac an monome s
[27]. Fo his eason, conduc i i y measu emen s can be used in o de o ge in o ma ion
abou ionic su ac an s/CD in e ac ions. Figu e 3 shows some o he Job´s plo s ob ained o
he di e en su ac an s and cyclodex ins in es iga ed, whe e he dependence o
(κobs)× [CDT] on he CD mola ac ion was shown, obs being he expe imen al speci ic
conduc i i y. In all cases only 1:1 complexes, CDS, a e o med unde he wo king condi ions.
0.0 0.2 0.4 0.6 0.8 1.0
0
2
4
6
8
10
XCD
DTEAB:-CD
Maximum a XCD=0.50
a)
103x(obs[CDT] (mol m-4)
0.0 0.2 0.4 0.6 0.8 1.0
0
2
4
6
8
10
12
XCD
Phenoxy12:-CD
Maximum a XCD=0.50
103x(obs[CDT] (mol m-4)
b)
0.0 0.2 0.4 0.6 0.8 1.0
0.0
0.5
1.0
1.5
2.0
Naph hoxy12:-CD
XCD
Maximum a XCD=0.50
c)
103x(obs[CDT] (mol m-4)
Fig. 3.-Job´s plo s a 303 K. a)DTEAB:-CD; b)Phenoxy12:-CD; c)Naph hoxy12:β-CD.
3.4. Fo ma ion equilib ium cons an s o he inclusion complexes
The associa ion p ocess be ween he su ac an s and he cyclodex ins has been s udied
by a ying he CD concen a ion, o a cons an su ac an concen a ion lowe han he cmc.
18
The s abili y o he inclusion complexes can be desc ibed in e ms o he equilib ium binding
cons an s, K1. Fo a 1:1 complex K1 can be de ined as:
CD + S  CDS K1=[CDS]
[CD ][S] (2)
F om he mass conse a ion law equa ions and aking in o accoun ha he expe imen al
speci ic conduc i i y is he sum o he con ibu ions coming om he su ac an ee ions, he
b omide coun e ions and he CDS inclusion complexes, he obse ed dec ease in he mola
conduc ance o he su ac an aqueous solu ions due o he addi ion o CD, obs, can be
exp essed as [28]:
ΔΛ𝑜𝑏𝑠 =Δ𝜆
2𝐾1[𝑆𝑇]{𝐾1([𝑆𝑇]+[𝐶𝐷𝑇])+
+1−((𝐾1 ([𝑆𝑇]+[𝐶𝐷𝑇])+1)2−4𝐾1
2 ([𝑆𝑇]+[𝐶𝐷𝑇]))1/2}
(3)
whe e,  is he di e ence in he ionic conduc i i ies o he unassocia ed, S, and associa ed,
CDS, su ac an ions, and [ST] and [CDT] a e he o al su ac an and cyclodex in
concen a ions in he solu ions. Figu e 4 shows some examples o he dependence o obs on
he o al cyclodex in concen a ion. Eq. 3 was i ed o he expe imen al da a using a non-
linea leas -squa e algo i hm. Solid lines in Figu e 4 show he esul o he i ings. One can
see ha he ag eemen be ween he expe imen al and heo e ical da a is good. The alues o
he binding equilib ium cons an s, K1, ob ained om he i ings a e summa ized in Table 2.
Expe imen s wi h di e en su ac an concen a ions we e ca ied ou and he esul s showed
ha [ST] does no in luence he es ima ed K1 alue. The me hod was also checked by
de e mining K1 o he 1:1 inclusion complex o med be ween dodecyl ime hylammonium
b omide, DTAB, and -cyclodex in a 298 K. The K1 alue ob ained o his inclusion
complex was 1.9104 M-1, in good ag eemen wi h li e a u e da a [10]. K1 alues summa ized
in Table 2 a e he a e age o a leas ou di e en expe imen s.
19
0 1 2 3 4 5 6 7
0
1
2
3
4
5
a)
103[-CDT]
104obs(-1 m2 mol-1)
[Phenoxy12T]=2.0710-3 M
0 1 2 3 4 5
0
1
2
3
4
5
6b)
103[-CDT]
104obs(-1 m2 mol-1)
[Phenoxy12T]=1.7410-3 M
0 2 4 6 8 10 12 14
0
1
2
3
4
103[-CDT]
104obs(-1 m2 mol-1)
c)
[Phenoxy12]=1.7010-3 M
0.0 0.5 1.0 1.5 2.0 2.5 3.0
0
1
2
3
4
5
6
103[-CDT]
104obs(-1 m2 mol-1)
[Naph hoxy12T]=4.8510-4 M
d)
Fig. 4.-Dependence o obs on he o al cyclodex in concen a ion o he su ac an s
in es iga ed a 303 K. Solid lines show he i ing o he expe imen al da a by using eq. 3.
Table 2.- Values o equilib ium binding cons an ,
K1, es ima ed om he i ings o he obse ed
mola conduc ance a ia ions o he aqueous
su ac an solu ions upon inc easing he o al CD
concen a ion, by using eq. 3. T= 303 K.
Su ac an :CD
K1 (M-1)
DTEAB:-CD
(2.40.5) 104
DTEAB:-CD
(1.60.4)104
DTEAB:-CD
(3.80.3)102
Phenoxy12:-CD
(2.20.5)104
Phenoxy12:-CD
(1.30.2)104
Phenoxy12:-CD
(6.90.5)102
Naph hoxy12--CD
(2.90.7)104
Naph hoxy12--CD
(8.20.8)103
Naph hoxy12--CD
(4.02.2)102
I is wo h no ing ha he es ima ion o he equilib ium binding cons an s o he
inclusion complexes Naph hoxy12:CDs was ca ied ou in he p esence o [su ac an ]510-4
20
M, due o he low cmc o his su ac an (cmc=6.710-4 M). As a consequence, he p ecision
o he es ima ed K1 alues is poo , pa icula ly o he Naph hoxy12:-CD sys em.
The o ma ion equilib ium cons an s o he inclusion complexes can also be es ima ed
by using 1H NMR measu emen s. The e ec o micelliza ion in he chemical shi s o he
su ac an esonances has been a oided using a ixed su ac an concen a ion below he cmc.
The concen a ion o cyclodex in was a ied o ob ain di e en mola a ios
[CD]/[Su ac an ]. Rep esen a i e esul s o he 1H NMR spec a o he CD/su ac an
mix u es a e shown in Figu e 5 o he sys em Phenoxy12:-CD. The 1H NMR spec a o α-,
Cx=C2, C3, C4, C5, and C6
Fig. 5.- 1H NMR spec a o Phenoxy12:-CD solu ions in D2O a 303 K, wi h
[Phenoxy12]=2.05x10-3 M. a) [β-CD]=0 M; b) [β-CD]= 4.0x10-4 M; c) [β-CD]=2.0x10-3 M; d)
[β-CD]=4 x10-3 M; Mo e β-CD concen a ions we e in es iga ed bu he spec a a e no
included in he igu e o he sake o cla i y. T=303 K.
8
2'
3'
1
2
3
7
4
6
5
1
a)
b)
c)
d)
Cx
C1
21
β-, and -CD a e shown in Figu e S5 (Supplemen a y Ma e ial). Assuming ha he condi ion
o as exchange on he NMR ime scale applies, he measu ed equency is a weigh ed
a e age o he equencies in each si e, and he chemical shi can be used o measu e he
ex en in which he equilib ium is displaced [28]. The obse ed chemical shi , o a 1:1
inclusion complex is [10]:
δobs = XS δS +XSCDδSCD =(1−XSCD)δS+XSCDδSCD (4)
whe e XS=[S]/[ST] and XSCD=[SCD]/[ST]. In his case:
∆𝛿𝑜𝑏𝑠 = 𝛿𝑜𝑏𝑠 −𝛿𝑆= 𝑋𝑆𝐶𝐷(𝛿𝑆𝐶𝐷 −𝛿𝑆)= 𝑋𝑆𝐶𝐷∆𝛿𝑜 (5)
Fo a 1:1 inclusion complex, one can w i e [10]:
K1=[SCD]
[S][CD]=[SC]
([ST]−[SCD])([CDT]−[SCD]) =
=XSCD
(1−XSCD)([CDT]−XSCD[ST]) (6)
A e some algeb aic manipula ion and simpli ica ion [10]:
Δ𝛿𝑜𝑏𝑠 =Δδ0
2𝐾1[𝑆𝑇](𝐾1([𝑆𝑇]+[𝐶𝐷𝑇])+1−
−((𝐾1([𝑆𝑇]+[𝐶𝐷𝑇])+1)2−4𝐾1
2[𝑆𝑇][𝐶𝐷𝑇])1/2) (7)
Eq. 7 was i ed o he expe imen al da a using a non-linea leas -squa e algo i hm. Figu e 6
shows wo examples o he dependence o obs on he o al cyclodex in concen a ion o
some nuclei. The expe imen s we e done a leas wice o each su ac an -cyclodex in
sys em. Since hese measu emen s we e done in o de o check he eliabili y o he
equilib ium cons an s alues lis ed in Table 2, only β-cyclodex in was used. The equilib ium
cons an o he Naph hoxy12:CD complexes could no be calcula ed om 1H NMR
expe imen s because o he la ge e o s due o he low su ac an concen a ion p esen in he
deu e a ed solu ions. The alues o he binding equilib ium cons an s, K1, ob ained om
NMR measu emen s a e summa ized in Table 3. One can see ha he K1 alues lis ed in
Tables 2 and 3 a e in good ag eemen .

22
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
-0.04
-0.03
-0.02
-0.01
0.00
obs/ppm
H(5)
103x[-CDT]/M
a)
DTEAB:-CD
0 1 2 3 4 5
0.000
0.010
0.020
0.030
0.040
0.050
0.060
obs/ppm
H(3)
103x[-CDT]
b)
Phenoxy12--CD
Fig. 6.- Dependence o he chemical shi obs=obs-S on o al -cyclodex in concen a ion
o selec ed p o ons o he su ac an s. Solid lines a e he bes i o eq. 14.
Table 3.- Values o equilib ium binding cons an , K1, es ima ed om he
i ings o he obse ed chemical shi a ia ions o su ac an p o ons
upon inc easing he o al CD concen a ion, by using eq. 14. T= 303 K.
Su ac an :CD
[Su ac an T](M)
K1 (M-1)
DTEAB:β-CD
1.9510-3
(1.60.5) 104
Phenoxy12:β-CD
2.0510-3
(1.40.4)104
N
B
6
5
4
3
21
23
The expe imen al esul s ha e shown ha inclusion complexes a e o med be ween he
CDs and he su ac an s in es iga ed. A his poin , i is in e es ing o conside how hey a e
o med. The su ac an s a e qua e na y ammonium de i a i es, wi h iden ical ca ionic head
g oups and a hyd oca bon ail wi h wel e ca bon a oms. The olume o he -N(C2H5)3+ head
g oup is la ge and, besides, i is cha ged and o push i h ough he ela i ely non pola ca i y
o he CDs will be ene ge ically expensi e. As a consequence, i would be expec ed ha he
in e cala ion o he su ac an ail in o he hos ca i y occu ed as is shown in Figu e 7. The
Fig. 7.-Fo ma ion o he inclusion complexes
wo k o Lyon e al. [29] suppo ed his hypo hesis. These au ho s in es iga ed he o ma ion
o inclusion complexes be ween he bola o m su ac an s [(CH3)3N(CH2)nN(CH3)3]B 2 (n=8,
10, 12) and ((CH3)2E N(CH2)10NE (CH3)2)B 2, and α-CD. They ound ha he eplacemen o
one me hyl by an e hyl in each o he end g oups on he ((CH3)3N(CH2)10N(CH3)3)2+
su ac an esul s in a s ong dec ease in he equilib ium binding cons an . Replacemen s o
wo o all o he me hyls by e hyls p e en he o ma ion o he inclusion complexes e en
a e p olonged hea ing.
The geome ies o he a oma ic subs i uen s we e op imized wi h a RHF wa e unc ion using
6-81g(d) basis se wi h he Gaussian 09 sui o p og ams [30] and hei olumes we e
calcula ed. As is shown in Figu e 8, he bulk o he wo a oma ic subs i uen s pe mi s he
inse ion o he hyd ophobic ail in o he hos ca i y o ei he -, - o -CD o o m he
inclusion complexes. Figu e 7 shows ha wo possible inclusion complexes could be o med
due o he unca ed cone shape o he CD molecule. Only in he case o he α-CD:Phenoxy12
24
sys em, he ROESY spec um sugges s ha he su ac an is p e e en ially o ien ed wi h he
a oma ic moie y loca ed close o he na owe im o he cyclodex in. The expe imen al da a
would gi e in o ma ion abou he a e age equilib ium binding cons an .
Fig. 8.- Some s uc u al in o ma ion abou he hos molecules and he wo a oma ic
subs i uen s.
The d i ing o ces leading o he o ma ion o CD:Su ac an inclusion complexes
include elec os a ic in e ac ions, an de Waals in e ac ions, hyd ophobic in e ac ions,
hyd ogen bonding, elease o con o ma ional s ain o he CD, exclusion o ca i y-bound
high-ene gy wa e om he CD ca i y and cha ge- ans e in e ac ions [31]. Tables 2 and 3
show ha he equilib ium binding cons an s ollow he end K1(α-CD)>K1(β-CD)>>K1(-
CD). These obse a ions can be explained by conside ing he olume o he cyclodex in
ca i y (α-CD(V=174 Å3 [32]), β-CD (V=270 Å3 [32]) and -CD(V=472 Å3 [32]), and aking
in o accoun ha he smalle he ca i y is, he s onge he su ac an -CD in e ac ions will be
[10, 33-36]. Due o en halpy-en opy compensa ion, elease o con o ma ional s ain and
exclusion o ca i y-bound high-ene gy wa e do no usually play an impo an ole in he
complex o ma ion. Van de Waals in e ac ions and hyd ophobic in e ac ions cons i u e he
majo d i ing o ces o cyclodex in complexa ion, oge he wi h elec os a ic in e ac ions
and hyd ogen bonding. This is in ag eemen wi h he no subs an ial e ec s o he subs i uen s
25
on K1. One can see ha he inco po a ion o a phenoxy g oup, C6H5-O-, a he end o he
dodecyl chain does no signi ican ly a ec he binding o he su ac an molecules o he h ee
CDs in es iga ed. On he o he hand, he p esence o a naph hoxy g oup, C10H7-O-, makes he
associa ion o he su ac an o he α-CD somewha s onge , whe eas he associa ion o he β-
CD is made a li le weake . The binding o Naph hoxy12 o -CD also seems o be weake ,
al hough he la ge expe imen al e o s do no pe mi o each any conclusion. This makes
clea ha he hyd oca bon chain leng h is he key s uc u al su ac an ea u e de e mining he
s abili y o he inclusion complexes in es iga ed, which can be aken as e idence o he
impo ance o he hyd ophobic in e ac ions con ibu ion o he binding [10, 31]. A simila
esul was ound by o he au ho s in he s udy o inclusion complexes o med be ween
anionic, ca ionic and non-ionic su ac an homologs and cyclodex ins [10, 37, 38]. The
p esence o he a oma ic ings a he end o he hyd ophobic ail does no subs an ially a ec
K1, howe e , i does in luence he loca ion o he hos and he gues in he inclusion
complexes. The obse ed NOE in e ac ions be ween he a oma ic p o ons and he CD p o ons
indica e ha he a oma ic ings a e pa ially inse ed wi hin he hos ca i y, wi h he
mac ocycle p e e en ially loca ed a he end o he hyd oca bon ail o he su ac an , in
con as wi h he s uc u e o he inclusion complexes o med wi h DTEAB. I was also ound
han in he case o he phenoxy subs i uen , he pa e n o in e molecula NOEs obse ed
sugges s a speci ic o ien a ion o he su ac an in he inclusion complex o med wi h α-CD,
wi h he a oma ic moie y loca ed close o he na owe im o he cyclodex in.
4. Conclusions
In he s udy o he complexa ion be ween cyclodex ins and su ac an s he in luence
o se e al ac o s in he s abili y o he hos -gues complexes has been in es iga ed. The
e ec s on he o ma ion o he inclusion complexes o changing he size o he hos ca i y
[10, 33-36, 39], he hyd ophobic chain leng h o he su ac an [10, 37, 38], he na u e o he
32
ension, calo ime y, and molecula dynamics o cyclodex ins wi h a non-ionic
su ac an . J. Phys. Chem. B 111 (2008) 4383-4392.
[36] S. M. Gho eishi, M. Behpou , M. Goles aneh, S udy o he inclusion complex
o ma ion be ween a ca ionic su ac an , wo cyclodex ins and a d ug. J. Incl.
Phenom. Mac ocycl. Chem. 62 (2008) 279-284.
[37] M. Benko, R. Tabajdi, Z. Ki aly 976The modynamics o o ma ion o b-cyclodex in
inclusion complexes wi h ou se ies o su ac an homologs. J. The m. Anal. Calo im.
112 (2013) 969-976.
[38] A. Pe ek, M. K ajnc, A. Pe ek S udy o hos -gues in e ac ion be ween -cyclodex in
and alkyl ime hylammonium b omides in wa e . J. Incl. Phenom. Ma ocycl. Chem.
86 (2016) 221-229.
[39] S. K. Meh a, K. K. Bhasin, S. Dham, M. L. Singla, Micella beha io o aqueous o
dodecyldime hyle hylammonium b omide, dodecyl ime hylammonium chlo ide and
e adecyl ime hylammonium chlo ide in he p esence o -, -, HP--, and -
cyclodex ins. J. Colloid In e ace Sci. 321 (2008) 442-451.
[40] X. Du, X. Chen, W. Lu, J. Hou, Spec socopic s udy on binding beha io s o di e en
s uc u al nonionic su ac an s o cyclodex ins. J. Colloid In e ace Sci. 274 (200)
645-651.
[41] D. Ondo, Calo ime ic s udy on he in e ac ion o didecyldime hylammonium and
decyl ime hylammonium ca ions wi h na i e cyclodex ins in wa e . J. Chem.
The modynamics 97 (2016) 235-243.
[42] E. Alami, S. A. Alami, J. Eas oe, I. G illo, R. K. Heenan, In e ac ions be ween a
nonionic gemini su ac an and cyclodex ins in es iga ed by small-angle neu on
sca e ing. J. Colloid In e ace Sci. 255 (2002) 346-356.

33
[43] Ch. Zhou, D. Wang, M. Cao, Y. Chen. Z. Liu, Ch. Wu, H. Xu, S. Wang, Y. Wang,
Sel -agg ega ion, an ibac e ial ac i i y, and mildness o cyclodex in/ca ionic ime ic
su ac an complexes. ACS Appl. Ma e . In e aces 8 (2016) 30811-30823.
[44] M. Qui oga, M. Pa ajó, P. Rod íguez-Da on e, L. ga cía-Río, Kine ic s udy o
[2]pseudo o axane o ma ion wi h an asyme ical ead. Langmui 32 (2016) 6367-
6375.
[45] V. I. Ma ín, B. Sa ión, M. López-López, P. López-Co nejo, I. Robina, M. L. Moyá,
Re e sibili y o he in e ac ions be ween a no el su ac an de i ed om lysine and
biomolecules. Colloids Su . B 135 (2015) 346-356.
[46] Gonzalez-Pe ez A, Dias RS, Nylande T, Lindman B. Cyclodex in–su ac an
complex: a new ou e in DNA decompac ion. Biomac omolecules 9 (2008) 772-775.
[47] Ca ls ed J, Gonzalez-Pe ez A, Ala o e-Meda M, Dias RS, Lindman B. Release o
DNA om su ac an complexes induced by 2-hyd oxyp opyl-be a-cyclodex in. In .
J. Biol. Mac omol. 46 (2010) 153–8.
[48] Gonzalez-Pe ez A, Ca ls ed J, Dias RS, Lindman B. Cyclodex ins in DNA
decompac ion. Colloid Su . B 76 (2010) 20–7.
[49] Ca ls ed J, Lundbe g D, Dias RS, Lindman B. Condensa ion and decondensa ion o
DNA by ca ionic su ac an , spe mine, o ca ionic su ac an –cyclodex inmix u es:
mac oscopic phase beha io , agg ega e p ope ies, and dissolu ion mechanisms.
Langmui 28 (2012) 7976–89.
[50] A. J. Ki by, P. Camille i, J. F. B. N Engbe s, M. C. Fei e s, R. J. M. Nol e, O.
Söde man, M. Be gsma, P. C. Bell, M. L. Fielden, C. L. Ga cía Rod íguez, P. Guda ,
A. K eme , C. McG ego , C. Pe in, G. Ronsin, M. C. P. an Eijk, Gemini su ac an s:
New syn he ic ec o s o gene ans ec ion. Angew. Chem. In . ed. 42 (2003) 1448-
1457.
34
Figu e cap ions
Figu e 1.- Concen a ion dependence o 1H NMR spec um o Phenoxy12, in D2O, on
su ac an concen a ion. a) [Phenoxy12]=2.00x10-3 M; b) [Phenoxy12]= 0.010M. T=303 K.
Figu e 2.- ROESY spec a o D2O solu ions con aining [Phenoxy12]=2.0510-3 M and
[CD]=2.0010-3 M a 303 K. a) α-CD; b)β-CD; c)-CD.
Figu e 3.-Job´s plo s a 303 K. a)DTEAB:-CD; b)Phenoxy12:-CD; c)Naph hoxy12:β-CD.
Figu e 4.-Dependence o obs on he o al cyclodex in concen a ion o he su ac an s
in es iga ed a 303 K. Solid lines show he i ing o he expe imen al da a by using eq. 3.
Figu e 5.- 1H NMR spec a o Phenoxy12:-CD solu ions in D2O a 303 K, wi h
[Phenoxy12]=2.05x10-3 M. a) [β-CD]=0 M; b) [β-CD]= 4.0x10-4 M; c) [β-CD]=2.0x10-3 M; d)
[β-CD]=4 x10-3 M; Mo e β-CD concen a ions we e in es iga ed bu he spec a a e no
included in he igu e o he sake o cla i y. T=303 K.
Figu e 6.- Dependence o he chemical shi obs=obs-S on o al -cyclodex in
concen a ion o selec ed p o ons o he su ac an s. Solid lines a e he bes i o eq. 14.
Figu e 7.-Fo ma ion o he inclusion complexes
Figu e 8.- Some s uc u al in o ma ion abou he hos molecules and he wo a oma ic
subs i uen s.
35
Tables
Table 1.-C i ical micella concen a ion, cmc, micella
ioniza ion deg ee, , and Gibbs ene gy o micelliza ion,
GoM, o he ca ionic su ac an s s udied in his wo k, a
303 K.
Su ac an
Cmc/mM

GoM/kJ
mol-1
DTEABa
14.30.4
0.350.02
-34.31.8
Phenoxy12b
3.70.2
0.400.03
-38.81.7
Naph hoxy12b
0.6410.015
0.430.03
-45.01.9
aRe . 11; bThis wo k.
Table 2.- Values o equilib ium binding cons an ,
K1, es ima ed om he i ings o he obse ed
mola conduc ance a ia ions o he aqueous
su ac an solu ions upon inc easing he o al CD
concen a ion, by using eq. 3. T= 303 K.
Su ac an :CD
K1 (M-1)
DTEAB:-CD
(2.40.5) 104
DTEAB:-CD
(1.60.4)104
DTEAB:-CD
(3.80.3)102
Phenoxy12:-CD
(2.20.5)104
Phenoxy12:-CD
(1.30.2)104
Phenoxy12:-CD
(6.90.5)102
Naph hoxy12--CD
(2.90.7)104
Naph hoxy12--CD
(8.20.8)103
Naph hoxy12--CD
(4.02.2)102
Table 3.- Values o equilib ium binding cons an , K1, es ima ed om he
i ings o he obse ed chemical shi a ia ions o su ac an p o ons
upon inc easing he o al CD concen a ion, by using eq. 14. T= 303 K.
Su ac an :CD
[Su ac an T](M)
K1 (M-1)
DTEAB:β-CD
1.9510-3
(1.60.5) 104
Phenoxy12:β-CD
2.0510-3
(1.40.4)104
36
SUPPLEMENTARY MATERIAL
HOST-GUEST INTERACTIONS BETWEEN CYCLODEXTRINS AND
SURFACTANTS WITH FUNCTIONAL GROUPS AT THE END OF THE
HYDROPHOBIC TAIL
Vic o ia Isabel Ma ín,a F ancisco José Os os, Manuel Angulo,b An onio Má quez,a
Pila López-Co nejo,a Manuel López-López,c Ana Te esa Ca mona,d and Ma ía Luisa
Moyáa*
aDepa men de Química Física, Uni e sidad de Se illa, C/ P o eso Ga cía González 1,
41012 Se illa. Spain. Tl . 34954557175 Fax: 34954557174 E-mail: [email protected]
bSe icio de RMN, Uni e sidad de Se illa, Apa ado 1203, E-41071 Se illa, Spain
cDepa men o Chemical Enginee ing, Physical Chemis y and Ma e ial Science, Facul y o
Expe imen al Sciences, Campus El Ca men, A da. De las Fue zas A madas s/n, 21071
Huel a,.Spain
dDepa men o O ganic Chemis y, Uni e si y o Se ille, C/P o eso Ga cía González 1,
41012 Se ille. Spain
*Au ho o whom all co espondence should be di ec ed.
37
P epa a ion o dodecyl ie hylammonium b omide, DTEAB
The DTEAB was p epa ed in a p e ious wo k ( e .11) ollowing he me hod o Guo e
al. (J. Polym. Sci. A 2009, 47, 434-449). B ie ly, s oichiome ic amoun s o 1-
b omododecane and ie ylamine we e hea ed, unde e lux, in ace one o 20 h a 75ºC. The
c ude p oduc was ec ys allized 5 imes om ace one and washed wi h e he . The p oduc
was ob ained as a whi e solid (26.7%). The pu i y o DTEAB was checked by NMR
measu emen s and mass spec ome y.
Expe imen al p ocedu es o ie hyl(1-phenoxydodecyl)ammonium b omide,
Phenoxy12 and ie hyl(2-naph hoxydodecyl)ammonium b omide, Naph hoxy12.
Gene al echniques. The cha ac e iza ion o he compound was pe o med by i s spec al
da a. 1H and 13C-NMR spec a we e ob ained o solu ions in D2O on a B uke A ance III 500
MHz spec ome e (500.2 MHz o 1H) equipped wi h a 5 mm TCI c yop obe ope a ing a
303 K. All 1H NMR chemical shi s a e e e enced o he esidual HDO signal se o 4.71
ppm; J alues a e gi en in Hz and δ in ppm. The NMR spec a o all compounds we e
pe o med in CITIUS (Resea ch Gene al Se ice o he Uni e si y o Se ille). The
comple ion o he eac ions we e moni o ed by TLC (silica gel HF254 (Me ck) hexane and
DCM:MeOH=3:1) wi h de ec ion by UV ligh and cha ing wi h Pancaldi. Elemen al analysis
o he su ac an was also ca ied ou .
12-B omo-1-phenoxydodecane (1)
A solu ion o 1,12-dib omo-dodecane (1g, 3.05 mmoles) and sodium phenola e (0.71g,
6.12 mmol) in d y ace one (70 mL), was s i ed unde A and hea ed a 62 °C o 30 min and
hen concen a ed o d yness a educed p essu e. The esidue was dissol ed in
dichlo ome hane and ex ac ed successi ely wi h wa e (4x15 mL). The o ganic phase was
d ied wi h Na2SO4 and concen a ed o d yness unde educed p essu e. The esidue was
pu i ied using column ch oma og aphy wi h silica gel and hexane. P oduc 1 was ob ained as
a whi e amo phous solid (0.3 g, 29%).
T ie hyl(1-phenoxydodecyl)ammonium b omide (2), Phenoxy12
A solu ion o 12-b omo-1-phenoxydodecane (0.246g, 0.79 mmol) and ie hylamine
(2.5mL, 17.9 mmol) in ace oni ile (19 mL), was s i ed unde A and hea ed a 90 °C o 1
day. The p og ess o he eac ion was con olled by TLC (DCM:MeOH=3:1). The eac ion
mix u e was hen concen a ed o d yness a educed p essu e. Subsequen ly, 10 ml o hexane
was added and he mix u e was s i ed o 15 min and hen il e ed unde acuum ( his

38
p ocedu e was epea ed h ee imes). P oduc 2 was ob ained as a whi e amo phous solid (0.24
g, 75%).
1H RMN (500 MHz, D2O): (ppm)=7.45 ( , 2H, Ph), 7.15-7.07 (m, 3H, Ph), 4.16 ( , 2H, Ph-
O-CH2-(CH2)11), 3.36-3.26 (m, 6H, N+(CH2)3(CH3)3), 3.21-3.13 (m, 2H, CH2-
N+(CH2)3(CH3)3), 1.88-1.79 (m, 2H, Ph-O-CH2-CH2), 1.76-1.66(m, 2H, CH2-CH2-
N+(CH2)3(CH3)3), 1.56-1.47 (m, 2H, Ph-O-(CH2)2-CH2), 1.47-1.34 (m, 14H, (CH2)7), 1.31 ( ,
9H, 3J = 7 Hz, N+(CH2)3(CH3)3).
13C RMN (75.4 MHz, CDCl3): δ (ppm) = 157.1, 129.24, 127.65, 123.63, 118.7, 106.7
(Ph), 67.9 (Ph-O-CH2-(CH2)11), 56.5 (CH2-N+(CH2)3(CH3)3), 52.7 (N+(CH2)3(CH3)3), 29.6,
26.4, (Ph-O-CH2-(CH2)9), 21.3(CH2-CH2-N+(CH2)3(CH3)3, N+(CH2)3(CH3)3)
12-B omo-1-naph hoxydodecane (3)
A solu ion o 1,12-dib omo-dodecane (2g, 6.10 mmoles) and sodium naph hola e
(2.03g, 12.19 mmol) in d y ace one (140 mL), was s i ed unde A and hea ed a 65 °C o 30
min and hen concen a ed o d yness a educed p essu e. The esidue was pu i ied using
column ch oma og aphy wi h silica gel and cyclohexane. P oduc 1 was ob ained as a whi e
amo phous solid (2.11 g, 52.26%).
T ie hyl(2-naph hoxydodecyl)ammonium b omide (4), Naph hoxy12
A solu ion o 12-b omo-1-naph hoxydodecane (0.640g, 1.64 mmol) and ie hylamine
(2.73mL, 19.62 mmol) in ace oni ile (50 mL), was s i ed unde A and hea ed a 90 °C o 1
day. The p og ess o he eac ion was con olled by TLC (DCM:MeOH=3:1). The eac ion
mix u e was hen concen a ed o d yness a educed p essu e. Subsequen ly, 10 ml o cold
cyclohexane was added and he mix u e was s i ed o 30 min and hen il e ed unde
acuum ( his p ocedu e was epea ed h ee imes). P oduc 2 was ob ained as a whi e
amo phous solid (0.624 g, 97.43%).
1H NMR (500 MHz, D2O, 303 K): (ppm)=7.38 (m, 2H, Naph), 7.05 (m, 1H, Naph), 7.02 (m,
2H, Naph), 4.09 ( , 2H, Naph-O-CH2-, 6.5 Hz), 3.23 (q, 6H, N+(CH2CH3)3, 7.3 Hz), 3.10 (m,
2H, -CH2-N+(CH2CH3)3), 1.76 (m, 2H, Naph-O-CH2-CH2-), 1.63 (m, 2H, -CH2-CH2-N+-),
1.44 (m, 2H, Naph-O-(CH2)2-CH2-), 1.38-1.26 (m, 14H, -(CH2)7-(CH2)2-N+-), 1.23 (b , 9H, -
N+(CH2CH3)3).
13C NMR (75.4 MHz, CDCl3): δ= 134.72 (C4’, C5’and C8’), 129.40-127.72 (C4’, C5’and
C8’), 126.79-126.41 (C6'), 123.58 (C7’), 119.12 (C1’ and C3’), 106.68 (C1’and C3’) 68.12
(C8), 57.74 (C3), 53.74 (C2), 29.59-29.25 (C7, C6 and C5), 26.60-26.19 (C6 and C5),
22.23(C4), 8.27 (C1).
39
0.0 0.5 1.0 1.5 2.0
0
20
40
60
80
100
120
cmc = 6.41x10-4 M
= 0.43
103x[Naph hoxy12]/M
/S cm-1
T=303 K
b)
Figu e S1.- Dependence o he speci ic conduc i i y, /S cm-1, on su ac an concen a ion.
a)Phenoxy12; b)Naph hoxy12. T=303 K. The solid lines co espond o he Ca pena i ings.
103x[Phenoxy12]/M
02468
0
100
200
300
400
500
/S cm-1
cmc=3.7x10-3 M
=0.40
T=303 K
a)
40
-8 -7 -6 -5 -4
44
48
52
56
60
exc=1.64x10-6 mol m-2
Amin=99x10-20 m2
ln([Phenoxy12]/M)
mN m-1
Figu e S2.- Dependence o he su ace ension, , on ln([Phenoxy12). T=303 K.
41
Figu e S3.- Concen a ion dependence o 1H NMR spec um o Naph hoxy12, in D2O, on
su ac an concen a ion. a) [Naph hoxy12]=5.00x10-4 M; b) [Naph hoxy12]=1.00x10-3 M.
T=303 K.
b)
a)