p-Sulfonatocalix[6]arene-dodecyltrimethylammonium Supramolecular

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p-Sulfonatocalix[6]arene-Dodecyltrimethylammonium Supramolecular Amphiphilic System: Relationship Between Calixarene and Micelle Concentration Nuno Basílio, Borja Gómez-González, and Luis García-Río Langmuir, Just Accepted Manuscript • DOI: 10.1021/acs.langmuir.7b03084 • Publication Date (Web): 23 Oct 2017 Downloaded from http://pubs.acs.org on October 24, 2017

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p-Sulfonatocalix[6]arene-Dodecyltrimethylammonium Supramolecular

Amphiphilic

System:

Relationship

Between Calixarene and Micelle Concentration.

Nuno Basílio,†* Borja Gómez,‡ Luis García-Río‡*

†

LAQV-REQUIMTE, Departamento de Química, Faculdade de Ciências e

Tecnologia, Universidade NOVA de Lisboa, 2829-516 Caparica, Portugal. email: [email protected] ‡

Departamento de Química Física, Centro de Investigación en Química

Biológica y Materiales Moleculares (CIQUS), Universidad de Santiago de Compostela, 15782 Santiago de Compostela, Spain email: [email protected] ABSTRACT In this work the formation of supramolecular mixed micelles from a hexamethylated

p-sulfonatocalix[6]arene

(SC6HM)

derivative

and

a

conventional cationic surfactant (dodecyltrimethylammonium bromide, C12TAB) was investigated by surface tension and using pyrene as a micropolarity fluorescent probe to get insights into the role of the calixarene concentration on the aggregation behavior. The formation of micelles at concentration well below the critical micelle concentration of pure surfactant was observed in the presence of very low concentrations of SC6HM (below the µM range). 1 ACS Paragon Plus Environment

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Interestingly, the critical micelle concentration of the mixed system was show to be rather insensitive to the concentration of SC6HM. On the other hand, the concentration of mixed micellar aggregates was demonstrated to be highly dependent of the macrocycle concentration and less dependent of the C12TAB concentration in the range between the critical micelle concentrations of the mixed systems and pure surfactant.

INTRODUCTION Supramolecular amphiphiles are, by definition, non-covalent complexes formed from hydrophilic and hydrophobic molecules.12345 In practice, most of the reported examples of supramolecular amphiphiles are composed by an amphiphilic molecule that upon interaction with a second species forms a supramolecular complex with superior (or distinct) amphiphilic properties. Several strategies can be used to devise supramolecular amphiphiles including host-guest, hydrogen bonding, charge-transfer, π-stacking or coulombic interactions, to give some examples.6–25 p-Sulfonatocalix[n]arenes (SCn) are water-soluble macrocyclic host molecules formed from n 4-hydroxybenzenosulfonate units linked by methylene bridges in meta position. With π-rich hydrophobic cavities and an upper rim decorated with negatively charged sulfonate groups, these hosts display high affinity and selectivity for positively charged organic species.26,27 Beside of simple hostguest complexes, SCn were found to be very effective hosts for the construction of supramolecular amphiphiles owing to their special ability to induce the aggregation of suitable guest molecules.28–44 Self-assembled soft-materials based on SCn are particularly attractive for biological/biomedical applications

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due to their low toxicity, water solubility and straightforward synthesis in multigram scale .27,45,46 Owing to the high potential of these systems, deep knowledge of the selfassembly mechanisms is crucial for rational design and optimization. However, these topics remain largely unexplored. Exceptions include some work from our and other groups concerning systematic studies on the induced aggregation of surfactants and dyes.39,47–49 The SCn induced aggregation shows some parallelism with similar effects displayed by polyelectrolytes in the presence of oppositely charged amphiphilic compounds. As recognized by Guo and coworkers, the main differences between this two classes of compounds arise from the fact that SCn can form strong 1:1 host-guest complexes that predominate when the calixarene is in excess and therefore dissociate the aggregates.49 A mechanistic model accounting for this phenomena was previously proposed by our group allowing a quantitative analysis of these complex systems.39 While SCn with well-defined cavities and high binding affinities display evident differences from polyelectrolytes, methylated SCn derivatives are much more flexible and lack pre-organized cavities, displaying much lower tendency (weaker binding constants) to form discrete 1:1 complexes and therefore subtler differences from polyions. In previous works, the induced aggregation of the cationic surfactant dodecyltrimethylammonium

bromide

(C12TAB)

by

hexamethylated

p-

sulfonatocalix[6]arene (SC6HM) was investigated in detail (Scheme 1).28,47,48,50 Diffusion ordered NMR spectroscopy is a powerful technique to characterize the complex aggregation process (Figure 1).28,47 For concentrations of surfactant below ca. 0.2 mM, free species coexist with discrete 1:1 host-guest complexes.


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However, as SC6HM shifts the critical micelle concentration (CMC) from 14 mM to 0.2 mM, in concentration range between the CMC1 = 0.2 mM and 14 mM the formation of supramolecular micelles predominates (grey region if figure 1). Above 14 mM a second aggregation process occurs due to the self-assembly of free C12TAB monomers to form conventional micelles (yellow region in Figure 1) that reacts fast with supramolecular micelles and redistribute supramolecular amphiphile monomers as the total concentration of surfactant increases (yellow region in Figure 1). At low concentrations of SC6HM (e.g. 1x10-4 M) an interesting behavior can be observed in the supramolecular micelles concentration region (marked grey in Figure 1). Between the CMC1 and the charge neutralization point, the aggregation process is highly cooperative as can be observed by the sharp decrease in the observed diffusion coefficients; while above this point a change of aggregation regime is observed leading to an increase in the concentration of free C12TAB as the surfactant is continuously added to the solution. This is readily confirmed by the continuous increase of the diffusion coefficients after charge neutralization. Eventually, when the concentration of free C12TAB reaches the value of the CMC of pure surfactant, a second critical micelle concentration (CMC2) is observed. Noteworthy, the value of the CMC1 seems to be rather independent on the SC6HM concentration. In this work the effect of this parameter on the aggregation behavior of the C12TAB/SC6HM mixed system is analyzed in detail by surface tension and fluorescence measurements using pyrene probe.


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Scheme 1 – Structures of SC6HM and C12TAB.

6 x 10-6

4 x 10-6

supramolecular micelles

aggregation of free C12TAB

discrete H:G complexation

Dobs / cm2 s-1

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2 x 10-6

0 0.00001

0.0001

0.001 0.01 [C12TAB] / M

0.1

Figure 1. Concentration-dependent observed diffusion coefficients (Dobs) of C12TAB in the absence (crosses) and in the presence of 1x10-4 M (filled circles) and 5x10-3 M (white squares) of SC6HM. The graphic was constructed using previously reported diffusion data.

EXPERMENTAL SECTION 5 ACS Paragon Plus Environment

28,47

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Dodecyltrimethylammonium

bromide

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>98%

(C12TAB)

and

pyrene

are

commercially available products. Pyrene was used as received and C12TAB, which was re-crystallized up to six times from acetone to eliminate surface active impurities. p-Sulfonatocalix[6]arene (SC6) was available from previous studies.28 Surface tension was measured by the Wilhelmy plate method using a Kruss tensiometer at 25 ºC. The fluorescence spectra of pyrene (0.4 µM) were measured using a Cary Eclipse instrument with an excitation wavelength of 334 nm. RESULTS AND DISCUSSION

Figure

2

shows

the

equilibrium

air-water

surface

tension

of

dodecyltrimethylammonium bromide (C12TAB) at 1x10-4 M plotted against the concentration of hexamethylated p-sulfonatocalix[6]arene (SC6HM). Below 10-7 M of SC6HM, surface tension of C12TAB 1x10-4 M is similar to that measured for pure water (72 mN m-1) but decrease suddenly for higher concentration of calixarene approaching a plateau for submicromolar concentrations of SC6HM ca. [SC6HM] = 2x10-7 M showing powerful ability of this macrocycle to promote C12TAB adsorption at the air-water interface.


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γ / mN m-1

70

60

50

10-7

10-6

[SC6HM] / M -4

Figure 2. Equilibrium surface tension of C12TAB (1x10

M) represented against the

concentration of SC6HM.

80

80

γ / mN.m-1

γ / mN.m-1

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60

60

40

40

10-6

10-5

10-4

10-3

10-6

10-2

10-5

10-4

10-3

[C12TAB] / M

[C12TAB] / M

(a)

(b)

10-2

Figure 3. Equilibrium surface tension measured against the concentration of C12TAB in the presence of (a) [SC6HM] = 5x10-7 M and (b) [SC6HM] = 1x10-6 M .

Experiments complementary to that presented in Figure 2, show that in the presence of low SC6HM concentrations (0.5 and 1 µM) the surface tension of C12TAB levels off around 3 - 4x10-4 M (Figure 3). These values compare with 7 ACS Paragon Plus Environment

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CMC1 = 2 x10-4 M obtained for higher concentrations of SC6HM.28,47 If they represent the onset for the micelle formation (i.e. the CMC1), two important observations can be made: (1)

the critical micelle concentration of the

C12TAB/SC6HM supraamphiphilic

system

is

fairly independent

of

the

macrocycle concentration in a wide concentration range and (2) the critical concentration for the formation of micelles can be observed well above the charge neutralization, i.e., in the non-cooperative regime.47 Because in this concentration regime most of the added surfactant above the CMC1 does not micellize, leading to an increase in the concentration of free C12TAB, the concentration of micellar aggregates must be very low. It is worth noting that this behavior is contrary to what is assumed for conventional systems, where above the CMC the concentration of free surfactant can be assumed constant and equal to this critical concentration, i.e., above this all added surfactant leads to an increase in the number or size of the aggregates. The relative intensities of the first and third vibronic bands (I1/I3 ratio) in the emission spectrum of pyrene can be used to probe the micropolarity of micellar aggregates and identify the CMC. This method has the advantage of sensing the presence of micellar aggregates at very low concentrations where other methods such as conductivity, diffusiometry, etc may fail. Figure 4a shows a plot of the pyrene I1/I3 ratio as a function of the SC6HM concentration in presence of 2x10-4 M of C12TAB. As can be observed, for concentration of calixarene higher than ca. 10-7 M the I1/I3 ratio starts to decrease indicating the presence of apolar micellar aggregates that dissolve pyrene. This agrees with surface tension results of figure 2 showing that


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besides of the water:air interface saturation micellar aggregates are formed in solution at very low concentrations of calixarene.

1.8

1.8

I1/I3

I1/I3

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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1.6

1.4

1.6

1.4 10-8

10-7

10-6

10-5

10-4

10-5

10-4

[SC6HM] / M

10-3

10-2

10-1

[C12TAB] / M

(a)

(b)

Figure 4. I1/I3 ratio of pyrene emission spectrum plotted against (a) SC6HM concentration for a -4

constant concentration 2x10 M of C12TAB and (b) against the C12TAB concentrations in the presence of different concentrations of SC6HM (filled circles) 0 M, (open squares) 2x10-7 M, (filled triangles) 1x10-6 M, (filled squares) 2x10-6 M and (open circles) 5x10-4 M.

Figure 4b shows the complementary experiments of 3a. Now the concentration of SC6HM is kept constant and the influence of the C12TAB concentration on the I1/I3 ratio is investigated. As can be observed, the CMC1 (taken as the point where the I1/I3 reaches the plateau after the first decrease) seems to be rather insensitive to the SC6HM concentration, ranging between 2x10-4 M and 4x10-4 M. At higher concentrations of C12TAB a second CMC2 is observed and the I1/I3 values overlap with those observed in the absence of SC6HM in line with the formation of mixed micelles containing lower fraction of calixarene and properties similar to the ones observed for pure C12TAB aggregates, as discussed in previous works.28,47 The most interesting part of the data reported in figure 4b is that corresponding to the concentration range between the CMC1 and the CMC2. As can be 9 ACS Paragon Plus Environment

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observed as the concentration of SC6HM increases the I1/I3 values observed at the plateau (which are constant for this C12TAB concentration range) decrease. This can be only interpreted in two ways: in one hand, the polarity of the micelles decreases as the concentration of calixarene increases. The other explanation, more likely, is that for low concentration of SC6HM a small concentration of micelles is formed that is not enough to encapsulate (0.4 µM) all the pyrene in solution. If this is true, the small concentration of aggregates shall not vary significantly in this wide C12TAB concentration range in agreement with previous experiments that showed a large increase in the free concentration of free surfactant between the two CMC’s.47

0.12

Ie/I1

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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0.06

0 10-5

10-4

10-3

10-2

10-1

[C12TAB] / M Figure 5. Ie/I1 ratio of pyrene emission spectrum plotted against against the C12TAB concentrations in the presence of different concentrations of SC6HM (filled circles) 0 M, (open -6

-4

squares) 2x10 M and (closed triangles) 5x10 M.


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In addition to the I1/I3 ration obtained from the monomer emission spectra of pyrene, excimer emission showing a maximum around 500 nm can also be used to probe surfactant aggregation. Figure 5 shows the variations observed in the relative excimer emission intensity (Ie/I1, where I1 monomer emission intensity of the first vibronic band) as a function of the C12TAB concentration in the presence and absence of SC6HM. In the absence of calixarene, the Ie/I1 shows a sharp increase near the CMC followed by sharp decrease as the concentration of C12TAB increases. This behavior is readily interpreted as at the onset of micelle formation, just below the CMC, the concentration of micelles is low and then the aggregates are occupied by more than one pyrene molecule. This increase in the local concentration of dye facilitates the formation of excimers and thus the emission intensity of this species increases. As concentration of micelles increases the dye molecules are redistributed within the aggregates and the probability to find more than one pyrene molecule per micelle also decreases and consequently the excimer emission disappears. A similar behavior is observed in the presence 5x10-4 M of SC6HM but in this case the excimer emission appears and disappears at lower concentration of C12TAB due to the calixarene induced aggregation. For 2x10-6 M of SC6HM, the excimer emission also starts to be observed for ca. 1x10-4 M of surfactant but now it does not follow a sharp decrease as the concentration of C12TAB is augmented. For this SC6HM concentration, the excimer emission gradually increases from ca. 1x10-4 M to 1x10-2 of C12TAB supporting the presence of low micelle concentration in this wide range. Noteworthy, at 4x10-3 of C12TAB a second increase in the excimer emission is observed in agreement with the onset for the aggregation of free C12TAB


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monomers. This followed by a maximum at CMC2 that coincides with CMC of pure surfactant and a sudden decrease of the excimer emission due the dye redistribution as mentioned above. CONCLUSIONS The influence of the SC6HM concentration on the micellization of C12TAB was investigated by surface tension and using pyrene as a fluorescent probe. The results show that the induced aggregation of this cationic surfactant occurs even when SC6HM in present in concentrations below the µM range. The CMC1 of the mixed system shows a minor dependence on the concentration of calixarene while the concentration of mixed micellar aggregates is highly dependent on this parameter. Thus, results of this study show that in the concentration range between the CMC1 and the CMC of pure surfactant the concentration of micelles can be finely tuned by the concentration of calixarene. ACKNOWLEDGEMENTS The Spanish team acknowledge financial support from Ministerio de Economia y Competitividad of Spain (project CTQ2014-55208-P), Consellería de Cultura, Educación e Ordenación Universitaria (GR 2007/085; IN607C 2016/03 and Centro

singular

de

investigación

de

Galicia

accreditation

2016-2019,

ED431G/09) and the European Regional Development Fund (ERDF). The Portuguese team was supported by the Associated Laboratory for Sustainable Chemistry-Clean Processes and Technologies- LAQV. The latter is financed by national funds from FCT/MEC (UID/QUI/50006/2013) and co-financed by the ERDF under the PT2020 Partnership Agreement (POCI-01-0145-FEDER007265). N.B. gratefully acknowledges a postdoctoral grant from FCT/MEC (SFRH/BPD/84805/2012).


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p-Sulfonatocalix[6]arene-dodecyltrimethylammonium Supramolecular

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