Surfactants Based on Bis-Galactobenzimidazolones - Springer Link

J Surfact Deterg (2011) 14:487–495 DOI 10.1007/s11743-011-1262-7

ORIGINAL ARTICLE

Surfactants Based on Bis-Galactobenzimidazolones: Synthesis, Self-Assembly and Ion Sensing Properties L. Lakhrissi • N. Hassan • B. Lakhrissi • M. Massoui • E. M. Essassi • J. M. Ruso C. Solans • C. Rodriguez- Abreu

•

Received: 1 December 2010 / Accepted: 22 February 2011 / Published online: 15 March 2011 Ó AOCS 2011

Abstract A series of new non-ionic amphiphiles based on bis-galactobenzimidazolones have been synthesized by grafting alkyl bis-benzimidazolone units as hydrophobic tails on hydroxypropyloxygalacto-pyranose moieties as hydrophilic heads. Their surface and self-aggregation properties in water were evaluated. The compounds show very low critical micellar concentrations (CMCs) that decrease with increasing chain length; values for the minimal area per molecule at the interface (Amin) follow the same trend. The synthesized compounds also form

Electronic supplementary material The online version of this article (doi:10.1007/s11743-011-1262-7) contains supplementary material, which is available to authorized users. L. Lakhrissi B. Lakhrissi Laboratoire d’Agroressources et Geńie des Proce´de´s, Faculte´ des Sciences, Universite´ Ibn Tofaı¨l, Keńitra, Morocco L. Lakhrissi M. Massoui E. M. Essassi Laboratoire de Chimie He´te´rocyclique, Faculte´ des Sciences, Universite´ Mohamed V, Rabat, Morocco N. Hassan J. M. Ruso Soft Matter and Molecular Biophysics Group, Department of Applied Physics, University of Santiago de Compostela, 15782 Santiago de Compostela, Spain C. Solans C. Rodriguez- Abreu Institut de Quı´mica Avançada de Catalunya (IQAC), Consejo Superior de Investigaciones Cientı´ficas (CSIC), Jordi Girona, 18-26, 08034 Barcelona, Spain C. Rodriguez- Abreu (&) International Iberian Nanotechnology Laboratory, Av. Mestre Jose´ Veiga, 4715-310 Braga, Portugal e-mail: [email protected]

hexagonal liquid crystals in water for a certain range of hydrophobic tail lengths. On the other hand, the new amphiphiles show characteristic UV–Vis absorption and fluorescence emission bands associated with the benzimidazolone moiety. The fluorescence emission is quenched with a certain degree of selectivity by cations, due to their strong affinity towards the benzimidazolone group, which shows ion complexation properties. Hence, the reported new amphiphiles are candidates as self-assembling chemosensors. The quenching efficiency and also ion sensing sensitivity is higher in the monomeric state as compared to the micellar state. The fluorescence emission intensity is higher for compounds with a shorter alkyl chain. Keywords Bis-benzimidazolones D-Galactose Surfactant synthesis Non-ionic surfactants Surface properties Fluorescence probe spectroscopy

Introduction Sugar-based surfactants, with their low toxicity and excellent biodegradability, i.e. reduced environmental impact, offer an attractive alternative to more conventional non-ionic surfactants such as poly(ethyleneoxide) alkyl ethers[1]. Moreover, they show performance properties which are exploited in microbiology and biotechnology [2–4], and have potential pharmaceutical and biomedical applications [5–7]. Sugar surfactants are made from renewable resources and are increasingly used in washing agents [8], cosmetics [9, 10], and drug carriers [11, 12]. The influence of structural changes on the physical properties of this family of surfactants has been studied in several reports [1, 13–15].

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On the other hand, benzimidazolones are important heterocyclic components of various products with pharmaceutical and biological importance [16–19]. They also present chelating and complexation properties [20], and show a characteristic UV absorption band and fluorescence emission [21, 22]. Hence, they can act as intrinsic chemosensor molecules in which the donor atoms for substrate complexation are a part of the fluorophore [23, 24]; the interaction between the bound substrate and the fluorophore leads directly to the modification of its emission properties. However, the low solubility in water is a drawback, therefore designing benzimidazolone-based hydrosoluble chemosensors is an interesting goal [25]. They could attract an additional interest if they would have amphiphilic nature and therefore form self assemblies in solution or on substrates [23]. In a continuation of our previous work in this area [26–29], we have synthesized a series of new non-ionic amphiphiles based on bis-galactobenzimidazolone (see Fig. 1a), which was prepared by grafting the 6-O-[2,3-epoxypropyl]-1,2:3,4-di-O-isopropylidene-a–galactopyranose group on the N-3 nitrogen atom of two benzimidazolone units that are linked by an alkyloxypropylene group in the same conditions as described earlier [29], following by the deprotection of diacetonide galactopyranose moiety [28–31]. The new synthesis route is easier and involves fewer steps than the previously reported one [29]. Additionally, we evaluated surface and self-aggregation properties in water by several techniques such as surface tension, fluorescent probe spectroscopy, and polarized optical microscopy. The ion complexing properties of the synthesized compounds were studied by UV–Vis and fluorescence spectroscopy.

Fig. 1 Structures of (I) N,N0 -1,3-bis-[N-3-(6(20 -hydroxypropyloxy)D-galactopyranos-6-yl)2-oxobenzimidazol-1-yl)]2-alkyloxypropanes (4a-c) and (II) N,N- 1,3-Bis-[N-3(6-deoxy-3-O-methyl-Dglucopyranos-6-yl)-2oxobenzimidazol-1-yl)]2-dodecyloxypropane (compound LBC12)

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J Surfact Deterg (2011) 14:487–495

Experimental Chemical Analysis Thin-layer chromatography (TLC) was performed on Silica Gel 60 F254 (E. Merck) plates with visualization by UV light (254 nm) and/or charring with the vanillin–H2SO4 reagent. Column chromatography was performed using 230–400 mesh E Merck silica gel. Melting points were determined on an automatic electrothermal IA 9200 digital melting point apparatus in capillary tubes and are uncorrected. Optical rotations, for solutions in chloroform or methanol, were measured with a digital polarimeter JASCO model DIP-370, using a sodium lamp at 25 °C. 1 H-NMR spectra were recorded on a Bruker 300 WB spectrometer at 300 MHz, and 13C-NMR spectra were recorded at 75 MHz for solutions in CDCl3 or Me2SO-d6. Chemical shifts are given as d values with reference to tetramethylsilane (TMS) as internal standard. Analytical TLC was performed on Merck aluminium backed silica gel (Silica Gel F254); spots were visualized in UV light. Column chromatography was performed on silica gel (60 mesh, Matrix) by elution with hexane–acetone or acetone–methanol mixtures. Synthesis All chemicals were purchased from Aldrich or Acros (France). All solvents were distilled before use. The compound N,N0 -1,3-Bis-[N-3-(6-deoxy-3-O-methyl-D-glucopyranose-6-yl)-2-oxo-benzimidazole-1-yl)]-2-dodecyloxy propane, abbreviated as LBC12, was synthesized as reported in a previous paper [29].


1,3-N,N0 -bis-[2-oxobenzimidazol-1-yl]-2-alkyloxypropanes 1a-c were synthesized in three steps. The first one is the condensation of N-isopropenylbenzimidazolone [20] with epichlorohydrin in a toluene-DMSO mixture in the presence of potassium carbonate. The second step is the alkylation of the free OH group by n-bromoalkanes in a toluene-DMSO mixture and potassium hydroxide [29]. Subsequent N-3 deprotection in a cold acid medium [20] afforded the corresponding compounds 1a–c. 6-O-[2,3-epoxypropyl]-1,2:3,4-di-O-isopropylidene-aD-galactopyranose 2 was synthesized by adopting the modified Ko¨ll’s method [32] which consists of the reaction of 1,2:3,4-di-O-isopropylidene-a-D-galactopyranose [33] with epichlorohydrin in the presence of sodium hydroxide and in Toluene-DMSO mixture as solvent. N,N0 -1,3-Bis-[N-3-(6-(20 -hydroxypropyloxy)-1,2:3,4-diO-isopropylidene-a-D-galactopyranos-6-yl)-2-oxobenzimid azol-1-yl)]-2-alkyloxypropanes 3a–c were synthesized following Scheme 1, by condensing the 1,3-N,N0 -bis-[2oxobenzimidazol-1-yl]-2-alkyloxypropanes 1a–c [29] units with activate galactopyranose 2 in the presence of potassium carbonate and in pure DMSO as solvent [28, 29]. In order to give a hydrophilic character to the molecules obtained 3a–c, they were treated with a mixture of trifluoroacetic acid–water (9:1, v/v) at room temperature [29–31]. The precipitates obtained were purified by chromatography with a mixture of acetone-methanol (1:1, v/v) to give N,N0 -1,3-bis-[N-3-(6-(20 -hydroxypropyloxy)-D-galactopyranos-6-yl)-2-oxobenzimidazol-1-yl)]-2-alkyloxypropanes 4a–c as white solids. Physical constants are given in Tables 1 and 2 as a function of n, which is the number of carbon atoms in the n-alkyl chain. Surface and Self-Aggregation Properties The surface tension of surfactant solutions was measured by the Wilhelmy plate method with a Kru¨ss K12

489 Table 1 Physicochemical constants of compounds 4a–c and their precursors 3a–c Product

Yield Mp ( °C) Molecular (%) formula Molecular weight

3a (n = 10) 88.0

68–70

a/b ½a26 D ðc ¼ 1:0Þ

C57H84N4O17 -60.2°a

–

1097.29 3b (n = 12) 84.4

62–64

C59H88N4O17 -60.3°a

–

1125.35 3c (n = 14)

79.1

58–60

C61H92N4O17 -59.6°a

–

1153.40 4a (n = 10) 90.1

120–122

C51H76N4O17

20.4°b

3/4

1017.16 4b (n = 12) 88.0 4c (n = 14)

86.1

116–118

C53H80N4O17

20.2°b

5/6

96–98

1045.22 C55H84N4O17

20.8°b

3/4

1073.27 a

In CHCl3

b

In CH3OH

tensiometer at 25 °C. The samples were left to rest for several hours to reach equilibrium. Consecutive measurements were performed until surface tension data was constant with time. From the graphical plots of surface tension against logarithm of surfactant concentration the values of critical micelle concentration (CMC) were obtained. UV–Vis and Fluorescence Spectroscopy UV–Vis spectra at 25 °C were measured using a Varian Cary UV–Visible spectrophotometer whereas steady state fluorescence was measured at 25 °C using a Varian Cary Eclipse spectrophotometer. Both instruments were equipped with a temperature-controlled sample holder. Samples were placed in 1-cm path length quartz cuvettes. Pyrene was excited at a wavelength of 335 nm and the emission

Scheme 1 Synthesis method

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Table 2 NMR spectroscopic data of compounds 3a in CDCl3 and 4a in DMSO-d6 Compound 3a (n = 10)

3a (n = 10)

4a (n = 10)

Galactosyl moiety H1: 5.45 (d, 2H, J1,2 = 5.00) H2: 4.32 (dd, 2H, J2,3 = 2.40) H3: 4.60 (dd, 2H, J3,4 = 8.00) H4: 4.24 (dd, 2H, J4,5 = 1.70) H5: 3.96 (m, 2H, J5,6a = 6.60) H6a : 3.68 (dd, 4H, J6,6 = 10.10) H6b: 3.54(dd, 4H, J5,6b = 4.20) CH3iso: 1.24 -1.46 (4s, 12H) OH: 2.12 (s, 2H) C1: 96.2 C2: 70.4 C3: 70.6 C4: 71.1 C5: 66.7;66.7 C6: 71.4 (CH3)2: 26.2;26.5 Ciso: 111.7 C1α : 92.7 C1β: 97.4 C2, C3, C4, C5 : 68.4 − 83.1 C-6 : 70.1

Oxo-benzimidazolyl moiety Harom : 7.00-7.28 (m, 8H)

Alkyl chain moiety CH3ω : 0.87(t, 3H) CH2ω−1 : 1.03(sext, 2H) 7CH2 : 1.05-1.55(m,14H) OCH2α : 3.35 (t, 2H)

Propyloxy moiety

Hydroxypropyl moiety

OCH: 4.10 (m ,1H) OCH2: 3.44 (m,2H) NCH2: 3.95 (m, 4H) CHOH: 4.25 (m,2H) NCH2: 3.95(dd, 1H) J1,2 = 5.5 4.30 (dd, 1H)

Jω,ω−1 = 7.2 Jα,β = 6.4 C2=O: 155.1 C4,C7:108.4;108.5; 108.6;109.3 C5,C6:121.3;121.5 C8,C9:129.5;129.8

CH3ω: 14.1 CH2ω−1: 22.6 5CH2 : 29.3-31.8 CH2γ : 25.7 CH2β : 29.6 ΟCH2α : 71.3

NCH2: 43.6 OCH: 76.5

OCH2: 72.3;72.5 CHOH: 69.0;69.2 NCH2: 44.3;44.4

C2α=O: 153.8 C2β=O: 153.9 C4,C7:108.2;108.5 C5,C6:120.6;120.8 C8,C9:129.4;129.5 129.7;129.8

CH3ω: 13.9 CH2ω−1: 22.1 5CH2: 28.6 - 31.2 CH2γ : 25.0 CH2β: 29.2 ΟCH2α : 70.8

NCH2: 43.1 OCH: 76.1

OCH2: 72.8;72.9 CHOH:69.2;69;3 NCH2: 44.3;44.4

intensity from 350 to 600 nm was recorded. On the other hand, fluorescence emission spectra of synthesized compounds (without pyrene) were collected using an excitation wavelength of 280 nm. Aqueous solutions of copper, magnesium and sodium nitrate were used during spectrophotometric titrations. For experiments with copper nitrate, the pH remained between 5.2 and 6 in the experiments. Microscopy

which is a typical behavior for surfactants and evidences their capacity to decrease the surface tension as well as to form micellar aggregates in aqueous media. The Critical Micellar Concentrations (CMC) values derived from those breaks are very low and the surface tension values at the CMC, namely, the effectiveness of surface tension reduction, are around, 40 mN/m (see Table 3). As in the case of other amphiphiles [34], experimental points for CMC follow approximately an equation of the form log CMC = a - bn; a and b be are constants and n is the alkyl chain length. For the present series of compounds,

Samples placed in glass slides were observed at 25 °C under a polarized light microscope (Leica Reichert Polyvar 2) equipped with a hot stage (Mettler FP82HT) and a CCD camera.

Results and Discussion Surface and Self-Aggregation Properties The synthesized bis-galactobenzimidazolones 4a–c are soluble in water. The plot of surface tension versus logarithm of surfactant concentration of compound 4b (alkyl chain length n = 12) is presented in Fig. 2. Plots corresponding to compounds 4a and 4c (n = 10 and n = 14, respectively) showed the same features, with clear breaks in the data trends (see supplementary information, Fig. S1),

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Fig. 2 Surface tension (squares) and ratio of intensities of first and third peaks in pyrene fluorescence spectrum (I1/I3, circles) as a function of surfactant concentration (25 °C) for compound 4b (n = 12). The lines serve to indicate the break for each set of data


491

Table 3 Physicochemical parameters of compounds 4a–c Product

Chain length, n

CMC from surface tension (mM)

CMC from fluorescence (mM)

cCMC (mN/m)

Cmax 9 1010 (mol/cm2)

˚ 2) Amin (A

4a

10

0.0025

0.0024

38

2.7 (3 and 2.3)

60 (55 and 70)

4b

12

0.0016

0.0016

44

2.9 (3.2 and 2.5)

57 (52 and 66)

4c

14

0.0014

0.0013

41

3.4 (3.7 and 3.4)

48 (45 and 48)

Values of Cmax and Amin for alcohol ethoxylates with an average number of ethylene oxide units of 6 and 8 and the same alkyl chain length of compounds 4a–c are shown between brackets and in italics (data taken from Refs. [34, 35])

Fig. 3 Images of optical polarized microscopy (25 °C) for compounds 4a–c (a) n = 10 (b) n = 12 (c) n = 14. The compounds were put in contact with water (black region in the image) for the observation

b (&0.06) is quite small when compared to other surfactants [34], indicating that the effect of increasing the hydrophobic chain length on the aggregation tendency is less marked. The surface excess concentration (Cmax) corresponding to the maximum concentration of surfactant adsorbed at the saturated liquid/air interface, in mol/cm2, is obtained from the Gibbs equation for non-ionic surfactants, Cmax = -(dc/dlnC)/(RT), where (dc/dlnC) is the slope of the submicellar region of the plot of surface tension against logarithm of surfactant concentration, R = 8.31 J.mol-1. K-1 and T is the temperature in K. From the surface excess values, the area occupied per molecule of surfactant ˚ 2, adsorbed at the air/liquid interface (Amin), expressed in A 16 is obtained according to Amin = 10 /NA Cmax where NA is the Avogadro’s number and Cmax is the surface excess concentration. The Cmax and Amin values obtained (Table 3) are of the same order as those of alcohol ethoxylates with an average number of ethylene oxide units of 6–8 [34, 35], and very close to LBC12 homologue series (see Fig. 1) with alkyl chain lengths in the range n = 10–14 [29]. The values of effective surface area per molecule at the interface (Amin) follow the typical decreasing trend with increasing hydrophobic tail length. Pyrene is a fluorescent probe sensitive to the polarity of the microenvironment, which is proportional to the ratio of the first and third peaks in the probe emission spectrum (I1/I3). As a result, it has been widely used for the determination of the CMC. Figure 2 shows the results on

fluorescence probe spectroscopy for compound 4b (alkyl chain length n = 12). Plots corresponding to compounds 4a and 4c (n = 10 and n = 14, respectively) exhibited the same features (see supplementary information, Fig. S2), with clear breaks signalling a change in the microenvironment surrounding pyrene at the onset of aggregate formation. As can be seen in Table 3, the values of CMC derived from the breaks in I1/I3 data are in agreement with those derived from surface tension measurements. Amphiphilic compounds usually form lyotropic liquid crystals in water. The small amount of surfactant available from the synthesis reported here made it difficult to prepare well mixed, concentrated samples in water with a precise surfactant concentration. In such a case it is common to use the water penetration method to detect qualitatively the liquid crystal formation. Samples of the compounds 4a–c were examined by means of polarized optical microscopy. As it can be seen in Fig. 3, when putting the synthesized compounds in contact with water, they form liquid crystals with hexagonal grainy optical texture for alkyl chain lengths of 10 and 12 carbons. For 14 carbons, clear liquid crystal optical textures could not be observed; birefringence seems to be produced by crystals of insoluble solid. The compound LBC12, with a similar structure, also forms hexagonal liquid crystals in water, as reported in a previous article [29]. Ion Complexation We tried first to characterize the ion complexation properties of the synthesized compounds by UV–Vis

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492


spectrometry. UV spectra can be found in the supplementary information (Figs. S3 and S4). In the absence of Cu2?, the spectra of 4b and LBC12 compounds show a single absorption band with a maximum at 282 nm; compounds 4a and 4c show the same spectral features. The position of the characteristic band is almost the same as that of benzimidazolone in organic polar solvents such as ethanol and acetonitrile [21]. Upon addition of Cu2?, Mg2? or Na?, a slight bathochromic (red) shift was observed for the 282 nm band, and a new (overlapped) band seems to develop; from deconvolution of the spectra, the maximum of this band is estimated to be around 300–302 nm, almost in the same position of that found for neat cation (nitrate) solutions. The band remained even after subtraction of cation background, but results are not conclusive concerning the effect of ion complexation on UV–Vis spectra, particularly because the 302 nm band could not be detected at cation concentrations within the same order of magnitude of that of the synthesized compounds in the experiments. Fluorescence spectroscopy is known to be an analysis technique much more sensitive than UV–Vis spectrometry. Fluorescence emission spectra of compounds 4b upon titration with Cu2? are shown in Fig. 4. Neat 4a–c aqueous solutions (0.005 mM) show a single emission band at 312 nm, similar to benzimidazolone in organic polar solvents such as ethanol and acetonitrile [21]; this spectral feature is not changed by Cu2? addition, but the fluorescence intensity at the maximum decreases, i.e. there is a cation-induced quenching. Cation affinity of the imidazole group is determined by its complexing properties. The quenching process is induced by coordination of cations either directly to donor atoms of the fluorophore or to chelating groups covalently attached to the latter [36]. Particularly, Cu2? has a high thermodynamic affinity for

I (A.U.)

0 mM

6 mM

280

300

320

340

360

380

400

Wavelength (nm) Fig. 4 Fluorescence spectra (25 °C) for different Cu2? concentrations in aqueous solutions of compound 4b. The surfactant concentration is kept at 0.005 mM. Cu2? concentrations are varied from 0 to 6 mM in 1 mM steps

123

Fig. 5 Stern-Volmer plot for surfactants LBC12 and 4b (both with the same alkyl chain length) with Cu2? as quencher (25 °C). Io and I are the fluorescence intensities in the absence and in the presence of quencher, respectively. The surfactant concentration is fixed at 0.005 mM. The position of fluorescence maxima remains constant at 312 nm

typical N,O-chelate ligands and fast metal-to-ligand binding kinetics [37]. As can be observed in Fig. 5, fluorescence intensity quenching follows the Stern–Volmer relationship [38, 39], Io/I = 1 ? KSV [Q], where Io and I are the fluorescence intensities in the absence and in the presence of quencher, respectively, [Q] is the quencher concentration and KSV is the Stern–Volmer quenching constant (other Stern–Volmer plots can be found in the supplementary information, Figs. S5 and S6); K is a measure of the quenching efficiency. Results points to a diffusion-controlled quenching process. KSV values for 4b and LBC12 (both with the same alkyl chain length) decrease in the order Mg2?[Cu2?[Na? (see Table 4). Ionic radii of Mg2? and Cu2? are very similar and both are lower than that of Na?, hence, the relationship between ionic radius and KSV is not straightforward. KSV values for Cu2? as quencher are higher for LBC12 when compared to 4b, the latter having a bulkier group surrounding the benzimidazolone moiety. Therefore, steric effects might be playing a role. It should be mentioned here that other cations, such as Ca2? and Pb2? were also found to induce fluorescence quenching of the compound 4b. Concerning the effect of amphiphile concentration, KSV for Cu2? increases from 0.1532 to 1.0141 mM-1 when 4b concentration is decreased from 0.005 mM (micellar state) Table 4 Values for of Stern–Volmer constants (KSV) in mM-1 for different cations as quenchers (25 °C) Surfactant

Mg2?

Cu2?

Na?

4b

0.1922

0.1532

0.1098

LBC12

0.3106

0.2762

0.2510

The surfactant concentration is fixed at 0.005 mM


to 0.0005 mM (monomer state); hence, the quenching efficiency and also ion sensitivity is improved at low amphiphile concentration. This tendency has been reported before for associating polymers [40], and was attributed not only to stoichiometry but also to aggregation-related effects [40]. On the other hand, the alkyl chain length has practically no effect on KSV for Cu2? as quencher. Nevertheless, there are differences in the fluorescence intensity as a function of 4a–c concentration in neat solutions (no cation added): the shorter the alkyl chain, the stronger the emission intensity. This effect was found for certain alkyl substituted fluorophores [41], and was attributed to changes in chain conformation that affect fluorescent properties. The fluorescence intensity in the absence of cations (see supplementary information, Fig. S7) increased linearly with concentration of compounds 4a–c with no apparent discontinuity or steplike fluorescence enhancement in the vicinity of the CMC, contrary to that observed for another fluorescent amphiphile [42]. The position of the fluorescence intensity maximum also remained invariable below and above the CMC. This fact might be attributed to the location of the fluorescent moiety near the hydrophilic group, which remains highly solvated below and above the CMC, namely, the slight change in microenvironment, if any, cannot be detected by fluorimetry.

Conclusions The synthesized bis-galactobenzimidazolones are soluble in water and form micellar aggregates at very low concentration. Their surface properties are similar to some ethoxylated nonionic surfactants. The synthesized compounds are also capable of forming lyotropic liquid crystals within a certain range of alkyl chain lengths. Moreover, they show UV–Vis absorption and fluorescence emission properties; the latter can be used for ion sensing as the fluorescence is quenched by cations that form complexes with the benzimidazolone moiety. Hence, the reported new amphiphiles are promising as self-assembling chemosensors. The quenching efficiency is higher in the monomer state as compared to the micellar state. It was also found that the emission intensity increased with decreasing alkyl chain length. Acknowledgments This work was supported by CNRST-CSIC project (2007MA0055). The ‘‘Ministe`re Marocain de l’Enseignement Supe´rieur’’ is gratefully acknowledged. C.R-A is also grateful to the Ministerio de Ciencia e Innovacioń, Spain (Project CTQ2008-01979/ BQU) for research funding. J.M.R and N. H. thank Direccion Xeral de Promocioń Cientı´fica e Tecnolo´gica del sistema Universitario de Galicia for their financial support.

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References 1. Rodrı´guez-Abreu C, Aramaki K, Tanaka Y, Lopez-Quintela MA, Ishitobi M, Kunieda H (2005) Wormlike micelles and microemulsions in aqueous mixtures of sucrose esters and nonionic cosurfactants. J Colloid Interf Sci 291:560–569 2. Rauter AP, Lucas S, Almeida T, Sacoto D, Ribeiro V, Justino J, Neves A, Silva FV, Oliveira MC, Ferreira MJ, Santos M-S, Barbosa E (2005) Synthesis, surface active and antimicrobial properties of new alkyl 2, 6-dideoxy-l-arabino-hexopyranosides. Carbohydr Res 340:191–201 3. Van Hamme JD, Singh A, Ward OP (2006) Physiological aspects: part 1 in a series of papers devoted to surfactants in microbiology and biotechnology. Biotechnol Adv 24:604–620 4. Singh A, Van Hamme JD, Ward OP (2007) Surfactants in microbiology and biotechnology: Part 2. Application aspects. Biotechnol Adv 25:99–121 5. Ro´z_ ycka-Roszak B, Jurczak B, Wilk KA (2007) Effects of nonionic sugar surfactants on the phase transition of DPPC membranes. Thermochim Acta 453:27–30 6. Ren X, Mao X, Cao L, Xue K, Si L, Qiu J, Schimmer AD, Li G (2009) Nonionic surfactants are strong inhibitors of cytochrome P450 3A biotransformation activity in vitro and in vivo. Eur J Pharm Sci 36:401–411 7. Jiao J (2008) Polyoxyethylated nonionic surfactants and their applications in topical ocular drug delivery. Adv Drug Deliver Rev 60:1663–1673 8. Tracy DJ, Ruoxin L, Yang JY (1999) Nonionic Gemini surfactants having multiple hydrophobic and hydrophilic sugar groups. US Patent 5863886 9. Bais D, Trevisan A, Lapasin R, Partal P, Gallegos C (2005) Rheological characterization of polysaccharide-surfactant matrices for cosmetic O/W emulsions. J Colloid Interf Sci 290:546–556 10. Ahsan F, Arnold JJ, Meezan E, Pillion DJ (2003) Sucrose cocoate, a component of cosmetic preparations, enhances nasal and ocular peptide absorption. Int J Pharm 251:195–203 11. Uchegbu IF, Vyas SP (1998) Non-ionic surfactant based vesicles (niosomes) in drug delivery. Int J Pharm 172:33–70 12. Wu D-Q, Lu B, Chang C, Chen C-S, Wang T, Zhang Y-Y, Cheng S-X, Jiang X-J, Zhang X-Z, Zhuo R-X (2009) Galactosylated fluorescent labeled micelles as a liver targeting drug carrier. Biomaterials 30:1363–1371 13. Nakamura N, Yamaguchi Y, Hakansson B, Olsson U, Tagawa T, Kunieda H (1999) Formation of microemulsion and liquid crystal in biocompatible sucrose alkanoate systems. J Disper Sci Technol 20:535–557 14. Stradner A, Mayer B, Sottmann T, Hermetter A, Glatter O (1999) Sugar surfactant-based solutions as host systems for enzyme activity measurements. J Phys Chem B 103:6680–6689 15. Castro MJL, Kovensky J, Fernańdez-Cirelli A (2002) New family of nonionic gemini surfactants. Determination and analysis of interfacial properties. Langmuir 18:2477–2482 16. Terefenko EA, Kern J, Fensome A, Wrobel J, Zhu Y, Cohen J, Winneker R, Zhang Z, Zhang P (2005) SAR studies of 6-aryl-1, 3-dihydrobenzimidazol-2-ones as progesterone receptor antagonists. Bioorg Med Chem Lett 15:3600–3603 17. Monforte AM, Rao A, Logoteta P, Ferro S, De Luca L, Barreca ML, Iraci N, Maga G, De Clercq E, Pannecouque C, Chimirri A (2008) Novel N1-substituted 1,3-dihydro-2H-benzimidazol2-ones as potent non-nucleoside reverse transcriptase inhibitors. Bioorg Med Chem 16:7429–7435 19. Li S-K, Ji Z-Q, Zhang J-W, Guo Z-Y, Wu W-J (2010) Synthesis of 1-Acyl-3-isopropenylbenzimidazolone derivatives and their

123

494

20.

21.

22.

23. 24.

25.

26.

27.

28.

29.

30.

31.

32.

33.

34. 35.

36.

J Surfact Deterg (2011) 14:487–495 activity against Botrytis cinerea. J Agric Food Chem 58:2668–2672 Meth-Cohn O, Smith DI (1982) N-bridged heterocycles. Part 5.a,x-bis-(2-oxobenzimidazolinyl)-alkanes and -ethers as selective ligands for group-1 and -2 metals, J Chem Soc Perkin I 261–270 Lazar Z, Benali B, Elblidi K, Zenkouar M, Lakhrissi B, Massoui M, Kabouchi B, Cazeau-Dubroca C (2003) Photophysical study of benzimidazolone and its derivative molecules in solution. J Mol Liq 106(1):89–95 Benali B, Lazar Z, Elblidi K, Lakhrissi B, Massoui M, Elassyry A, Cazeau-Dubroca C (2006) Solvatochromic effect on photophysical properties of benzimidazolone. J Mol Liq 128:42–45 Mancin F, Rampazzo E, Tecilla P, Tonellato U (2006) Selfassembled fluorescent chemosensors. Chem Eur J 12:1844–1854 El Majzoub A, Cadiou C, Dećhamps-Olivier I, Chuburu F, Aplincourt M, Tinant B (2009) Mono- and bis-N-functionalised cyclen with benzimidazolylmethyl pendant arms: sensitive and selective fluorescent probes for zinc and copper ions. Inorg Chim Acta 362:1169–1178 Pina F, Bernardo MA, Garcıá-Espanã E (2000) Fluorescent chemosensors containing polyamine receptors. Eur J Inorg Chem 2143–2157 Lakhrissi B, Ejjiyar S, Massoui M, Comelles F, Garcia MT, Ribosa I, Azemar N, Solans C (2002) Surface and self-aggregation properties of bis-benzimidazolone derivatives of D-glucose. Jorn Com Esp Deterg 32:365–373 Lakhrissi L, Lakhrissi B, Lakhrissi M, Massoui M, Essassi EM, Solans C, Azemar N, Morales D, Comelles F (2007) Synthesis and evaluation of surfactants properties of new amphiphile and bolaamphiphile derivatives of bis-glucobenzimidazolones. Jorn Com Esp Deterg 37:347–353 Lakhrissi B, Benksim A, Massoui M, Essassi EM, Lequart V, Joly N, Beaupe`re D, Wadouachi A, Martin P (2008) Towards the synthesis of new benzimidazolone derivatives with surfactant properties. Brahim Lakhrissi. Carbohydr Res 343:421–433 Lakhrissi B, Lakhrissi L, Massoui M, Essassi EM, Comelles F, Esquena J, Solans C, Rodriguez-Abreu C (2010) Surface and selfaggregation properties of bis-benzimidazolones derivatives of D-glucose. J Surfact Deterg 13:329–338 Goueth PY, Ronco G, Villa P (1994) Synthesis of novel bis(glycosyl) ethers as bolaamphiphile surfactants. J Carbohydr Chem 13:679–696 Lakhrissi B, Essassi EM, Massoui M, Goethals G, Lequart V, Monflier E, Cecchelli R, Martin P (2004) Synthesis and amphiphilic behavior of N, N-bis-glucosyl-1,5-benzodiazepin-2, 4-dione. J Carbohydr Chem 23:389–401 Ko¨ll P, Saak W, Pohl S, Steiner B, Miroslav Koos M (1994) Preparation and crystal and molecular structure of 6-O-[(2S)-2, galacto-pyra3-epoxypropyl]-1,2:3,4-di-O-isopropylidene-a-D nose. Pyranoid ring conformation in 1,2:3,4-di-O-isopropylidene galactopyranose and related systems. Carbohyd Res 265:237–248 Baggett N, Buck KW, Foster AB, Jefferis R, Rees BH, Webber JM (1965) Aspects of stereochemistry. Part XIX. Isopropylidene derivatives of some polyhydric alcohols. Observations on the hydrolytic behaviour and migration of cyclic ketals. J Chem Soc 3382–3387 Rosen MJ (1989) Surfactant and interfacial phenomena, 2nd edn. Wiley, New York Lu JR, Thomas RK, Penfold J (2000) Surfactant layers at the air/ water interface: structure and composition. Adv Colloid Interf Sci 143–304 Fabbrizzi L, Licchelli M, Pallavicini P, Perotti A, Taglietti A, Sacchi D (1996) Fluorescent sensors for transition metals based on electron-transfer and energy-transfer mechanisms. Chem Eur J 2:75–82

123

37. Zhou LL, Sun H, Zhang XH, Wu SK (2005) An effective fluorescent chemosensor for the detection of copper(II). Spectrochim Acta A 61:61–65 38. Stern O, Volrner M (1919) The fading time of fluorescence. Z Phys 20:183–188 39. Lakowicz JR, Weber G (1973) Quenching of fluorescence by oxygen. Probe for structural fluctuations in macromolecules. Biochemistry 12:4161–4170 40. Tan C, Pinto MR, Schanze KS (2002) Photophysics, aggregation and amplified quenching of a water-soluble poly(phenylene ethynylene). Chem Commun 446–447 41. Pu S, Li M, Fan C, Liu G, Shen L (2009) Synthesis and the optoelectronic properties of diarylethene derivatives having benzothiophene and n-alkyl thiophene units. J Mol Struct 919:100–111 42. Iwunze MO, Lambert M, Silversmith EF (1997) Characterization of fluorescent surfactant aggregates by fluorimetric and viscosimetric techniques. Monatsh Chem 128:585–592

Author Biographies L. Lakhrissi studied chemistry at the Mohamed V University of Rabat (Morocco) and then at the Ibn Tofaı¨l University of Keńitra (Morocco). She is now a Ph.D. candidate in organic synthesis and surfactant properties, at the Mohamed V University of Rabat (Morocco). N. Hassan studied chemistry at the University of Chile (SantiagoChile) and she is currently a Ph.D. candidate in Science and Technology of Materials at the University of Santiago de Compostela (Spain). B. Lakhrissi studied chemistry at the Henri Poincare´ University of Nancy (France) and obtained his Ph.D. in organic and analytic chemistry from the same University in 1988. Since 1989 he has been an assistant professor at the Ibn Tofaı¨l University in Keńitra (Morocco). He obtained his state doctorate thesis in organic chemistry from Ibn Tofaı¨l University of Keńitra (Morocco) in 2003 and since then he has been a professor at that university. Since 2005 he has also been Director of the Agro resources and Process Engineering Laboratory. His areas of scientific activity are organic synthesis, surfactant properties and complexant systems. M. Massoui studied chemistry at the Picardie University of Amiens (France) and received his doctorate in Organic Chemistry from the same University in 1985. Since then he has been Professor at Ibn Tofaı¨l University in Keńitra (Morocco). He was also Director of the Agro resources and Process Engineering Laboratory. His area of scientific activity is the organic synthesis and the chemistry of glucids. E. M. Essassi studied chemistry at the Mohamed V University of Rabat (Morocco) and received his doctorate in Organic Chemistry from the University of Montpellier (France) in 1977. He then joined the University Mohammed V in Rabat and was promoted to Professor in 1981. Professor Essassi is currently Director of the Heterocyclic Organic Chemistry Laboratory. In 2006 he was named a member of Hassan II Academy of Science and Technology. His area of scientific activity is organic synthesis. J. M. Ruso is an associate professor at the University of Santiago de Compostela. He received his Ph.D. (1998) from the University of Santiago de Compostela. He was a visiting researcher at the

J Surfact Deterg (2011) 14:487–495 University of Manchester, Columbia University and Universidad Nacional del Sur. His research focuses on design and characterization of mesoporous materials, nanotechnology, self assembled supramolecular structures and physicochemical characterization of proteins and protein aggregates. C. Solans is a researcher at the Institute for Advanced Chemistry of Catalonia of the Spanish Council for Scientific Research (CSIC) in Barcelona, Spain. She received a B.Sc. degree in Chemistry (1970) from the University of Barcelona (Spain) an M.Sc. degree in Chemistry (1980) from the University of Missouri-Rolla (U.S.A.) and a Ph.D. in Chemistry (1983) from the University of Sevilla (Spain). Her current research interests include surfactant phase behavior and their application to emulsification processes by lowenergy methods, detergency, solubilization and synthesis of materials.

495 C. Rodriguez-Abreu received his B.Sc. and M.Sc. in Chemical Engineering from the University of Los Andes (Venezuela) and obtained his Ph.D. in engineering from the Yokohama National University (Japan) in 2001. After working as an associate professor at the University of Los Andes (Venezuela) and as a research fellow at Yokohama National University (Japan), University of Santiago de Compostela (Spain), and the Institute for Advanced Chemistry of Catalonia (IQAC)-Spanish Council of Scientific Research (CSIC), he joined the International Iberian Nanotechnology Laboratory in 2010. His area of scientific activity is the physical-chemistry of amphiphilic systems, and their application in the synthesis of nanomaterials.

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