Cosima Stubenrauch

Universität Stuttgart, Stuttgart, Baden-Württemberg, Germany

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Publications (89)307.07 Total impact

  • [Show abstract] [Hide abstract]
    ABSTRACT: The critical micelle concentration (cmc), the surface excess (Γ), as well as the micelle aggregation number (m) of the surfactant dodecyldimethylamine oxide (C12DMAO) have been reported to strongly depend on the pH-value of the aqueous surfactant solution. At high ionic strength, the cmc displays a minimum, while both Γ and m have a maximum at a pH-value close to the pKa of the surfactant. These experimental observations have been explained as being due to specific hydrogen bonds between the head groups, which are formed once the surfactant is partly or fully protonated. This investigation addresses the question of whether the pH also affects the foaming properties of C12DMAO solutions. To answer this question we measured the foamability and the foam stability of C12DMAO solutions at a fixed C12DMAO concentration of 5 cmc for five different pH-values, namely pH = 2, 3, 5, 8, and 10. We found that the foamability is hardly affected by the pH-value, while the foam stability strongly depends on the pH. As is the case for the above mentioned properties, the foam stability also displays an extremum in the studied pH-range, namely a maximum at pH = 5. We discuss our results in terms of the hydrogen bond hypothesis and show that this hypothesis indeed is in line with the observed trend for the foam stability. Moreover, we discuss that hydrogen bond formation may rationalize how the molecular structure of a surfactant affects foam stability.
    Soft Matter 11/2014; · 4.15 Impact Factor
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    ABSTRACT: An orthogonal self-assembled system consists of different structures which coexist independently. Furthermore, the characteristic properties of the respective “base systems”, i.e. of the systems which contain only one of the structures, are retained in the orthogonal self-assembled system. We have identified gelled bicontinuous microemulsions as orthogonal self-assembled systems and reported in a preceding paper (Soft Matter, 2013, 9, 3661) that their phase behaviour and rheological properties are in perfect agreement with those of the two base systems, namely a non-gelled bicontinuous microemulsion and a binary gel. In the paper at hand we present the results of structural investigations. With FT-PGSE 1H-NMR measurements we verified the bicontinuity of our gelled model system H2O–n-decane/12-hydroxyoctadecanoic acid (12-HOA)–tetraethylene glycol monodecyl ether (C10E4) at appropriate temperatures. Apart from that, we proved the coexistence of the bicontinuous microemulsion domains with the gelator network in a small angle neutron scattering (SANS) study. A qualitative comparison between the SANS data of the gelled bicontinuous microemulsion and those of its base systems reveals that the characteristic scattering features of both base systems are present. Moreover, we were able to quantitatively describe and interpret the SANS data, yielding at the same time the structural parameters of the bicontinuous microemulsion and the gelator network.
    Soft Matter 10/2014; · 4.15 Impact Factor
  • Laurie Saulnier, Julia Boos, Cosima Stubenrauch, Emmanuelle Rio
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    ABSTRACT: The purpose of this article is to compare experiments carried out with single vertical foam films and with foams. We focus on the generation of films and foams and measure (i) the quantity of water entrained and (ii) the stability of the systems. The surfactants we used are C12E6, β-C12G2 and their 1 : 1 mixture because those systems are very well characterised in the literature and are known to stabilise foams with very different properties. We show that the quantity of water uptake in foams and single vertical films scales in the same way with the velocity of generation. However, the different surfactant solutions have different foamabilities, whereas the films they stabilise have exactly the same thickness. Moreover, the foamability of a C12E6 solution is much lower than that of a β-C12G2 solution or of a solution of the 1 : 1 mixture. This is due to the rapid rupture of the C12E6 foam films during foam generation. Surprisingly, the isolated films have exactly the same lifetime for all the surfactant solutions. We conclude that, though drawing a correlation between films and foams is tempting, the results obtained do not allow correlating of film and foam stability during the generation process. The only difference we observed between the single films stabilised by the different solutions is the stability of their respective black films. We thus suggest that the stability of black films during foam generation plays an important role which should be explored further in future work.
    Soft Matter 05/2014; · 4.15 Impact Factor
  • Michaela Laupheimer, Cosima Stubenrauch
    Tenside Surfactants Detergents 01/2014; 51(1):17-25. · 0.98 Impact Factor
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  • Julia Boos, Natalie Preisig, Cosima Stubenrauch
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    ABSTRACT: It is time to review latest activities on the dilational surface rheology of the two nonionic surfactants n-dodecyl-β-d-maltoside (β-C12G2) and hexaoxyethylene dodecyl ether (C12E6) and their 1:1 mixture as a lot of different data generated with different techniques have been published in the last years. As the data are scattered throughout different papers and were generated with different techniques, we carried out an extensive study with one technique, which we will use as reference for the discussion of different data sets. We found that the results are in most of the cases in line with already published data as regards the general trends. However, a quantitative comparison reveals differences, which may result in different interpretations of the data. In the review at hand, we summarize, compare and discuss our latest and previously published data.
    Advances in Colloid and Interface Science 05/2013; · 8.64 Impact Factor
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    ABSTRACT: Microemulsions in a gelled form are desirable for applications like topical and transdermal drug delivery as they enable local application and enhanced residence times of the drug. One method for gelling microemulsions consists of adding an appropriate low molecular weight gelator. Although our group has reported this method before, a systematic study on the nature and properties of such gelled microemulsions has been missing to date. In this paper we present phase studies and rheology results which demonstrate that microemulsions gelled by a low molecular weight gelator are orthogonal self-assembled systems. We studied the gelled microemulsion H2O–n-decane/12-hydroxyoctadecanoic acid (12-HOA)–tetraethylene glycol monodecyl ether (C10E4) with 1.5 wt%, 2.5 wt% and 5.0 wt% of the low molecular weight organogelator 12-HOA. We found that the phase boundaries of the gelled microemulsion are about 6 K below those of the non-gelled “base” microemulsion H2O–n-decane–C10E4, irrespective of the gelator concentration. Moreover, we detected by differential scanning calorimetry and rheological measurements a sol–gel boundary about 20 K below that of the respective binary gel n-decane/12-HOA. Both temperature shifts are not surprising considering that (a) 12-HOA is surface active, thus influencing the microemulsion's phase behaviour and (b) that the microemulsion can be treated as a solvent in a 12-HOA gel which influences the gel properties. The general phase behaviour of both base systems, however, is indeed maintained in the gelled microemulsion. For the rheological properties we found, accordingly, perfect agreement with the respective binary gel. Thus, our data clearly substantiate that gelled microemulsions are orthogonal self-assembled systems.
    Soft Matter 03/2013; 9(13):3661-3670. · 4.15 Impact Factor
  • Enda Carey, Cosima Stubenrauch
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    ABSTRACT: The study at hand investigates the influence of the composition of a surfactant mixture on the free drainage of the respective foams. The Foam Conductivity Apparatus (FCA) was used to study free drainage of foams of homogeneous initial liquid fraction εinit. The foams were stabilized with mixtures of the non-ionic surfactant dodecyldimethyl phosphineoxide (C12DMPO) and the cationic surfactant dodecyl trimethylammonium bromide (C12TAB) at mixing ratios of C12DMPO:C12TAB = 1:0, 50:1, 1:1, 1:50 and 0:1. In all cases the liquid fraction ε follows a power law with respect to time t, i.e.ε ∼ tη with −1.0 < η < −0.8. The η-values are all very similar which indicates a Poiseuille-like flow (−1 < η < −2/3) for all samples irrespective of changes in composition and bubble size. For all studied mixtures drainage led to fairly dry foams (ε ∼ 10−3), which then either coalesce (C12DMPO and 50:1 mixture) or drain further (1:1 mixture). An evaluation of the critical liquid fraction εcrit (liquid fraction at which foam coalescence sets in abruptly) revealed that εcrit is independent of the foam height and the bubble size which is in line with literature. However, it depends on the composition of the surfactant mixture and decreases with increasing content of C12TAB.
    Colloids and Surfaces A Physicochemical and Engineering Aspects 02/2013; 419:7–14. · 2.11 Impact Factor
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    ABSTRACT: The synthesis of porous “sponge-like” TiO2 via a polymer gel coating technique is presented. The experimental procedure involves the preparation of a gelled polymerizable microemulsion. The polymerization of the latter leads to porous poly-N-isopropylacrylamide which forms a hydrogel in the presence of water. Via solvent exchange, a suitable TiO2 precursor is infiltrated into this structure after which its in situ hydrolysisis triggered to form porous amorphous TiO2. The subsequent calcination step allows the removal of the polymer template and the transformation of amorphous TiO2 in to porous, crystalline anatase with domain sizes ranging from 200 to 250nm. As a means of verification and proof of concept, this material is tested as light-scattering layer in dye-sensitized solar cells (DSSC), and it is found that the resulting solar cell performance is comparable to commercially available TiO2. However, an increased tendency to form rutile during DSSC fabrication was noticed when compared to commercial TiO2. As there is a large potential for optimizing the synthesis, the proposed procedure is a promising route towards porous TiO2 that performs significantly better as scattering layer in light-harvesting and optical devices.
    Colloid and Polymer Science 09/2012; 291:805. · 2.16 Impact Factor
  • Julia Boos, Wiebke Drenckhan, Cosima Stubenrauch
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    ABSTRACT: Although it is known that foaming a surfactant solution results in a depletion of the surfactant in the bulk phase, this effect is often overlooked and has never been quantified. Therefore, the influence of surfactant depletion on foam properties using solutions of the two nonionic surfactants, n-dodecyl-β-D-maltoside (β-C(12)G(2)) and hexaethyleneglycol monododecyl ether (C(12)E(6)), were investigated. These investigations were conducted in two steps. First, different foam volumes were generated with the same surfactant solution at a concentration of c = 2 cmc. It was found that the higher the foam volume, the larger the surfactant depletion. Second, two different bulk concentrations (c = 2 and 1.33 cmc) were used for the generation of 50 and 110 mL of foam, respectively. For a foam volume of 50 mL, no differences were observed, whereas generating 110 mL led to different results. The surfactant loss in the bulk solution was measured via surface tension measurements and then compared to the results of purely geometric considerations that take into account the amount of interface created in the foam. Both results were in very good agreement, which means that surfactant depletion can be calculated in the way suggested here. Under conditions where depletion plays a role, our approach can also be used to estimate the bubble size of a foam of known volume by measuring the surfactant concentration in the bulk solution after foaming.
    Langmuir 06/2012; 28(25):9303-10. · 4.38 Impact Factor
  • Cosima Stubenrauch, Felix Kleinschmidt, Claudia Schmidt
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    ABSTRACT: We showed in a previous study that a water-nonionic surfactant system, where the surfactant is a 9:1 mixture of tetraethylene glycol monodecyl ether (C(10)E(4)) and pentaethylene glycol monodecyl ether (C(10)E(5)), forms a disconnected lamellar (L(α)) phase. Thus, the isotropic phase spans the whole concentration range from the water-rich L(1) region to the surfactant-rich L(2) region of the phase diagram. The L(1) and L(2) regions are connected via an isotropic channel that separates the two regions of the L(α) phase. In this letter, we monitored the structural evolution of the isotropic phase along a path through this isotropic channel via (1)H NMR self-diffusion measurements. We used this technique because it enables us to distinguish between discrete and bicontinuous structures by comparing the relative self-diffusion coefficients (obstruction factors) D/D(0) of the solvents (i.e. of water and surfactant in the present case). We found that the obstruction factor of water decreases whereas the obstruction factor of the surfactant increases with increasing surfactant concentration and increasing temperature. This trend is interpreted as the transition from a water-continuous L(1) region, which contains discrete micelles, to a bicontinuous structure, which may extend to very high surfactant concentrations. Although there is good evidence of bicontinuity over a broad concentration range, there is no evidence of inverse micelles or any other microstructure at the highest concentration studied in the surfactant-rich L(2) phase.
    Langmuir 06/2012; 28(25):9206-10. · 4.38 Impact Factor
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    ABSTRACT: The adsorption isotherms of n-decyl-β-D-glucoside (β-C(10)G(1)) as well as various n-alkyl-β-D-maltosides (β-C(n)G(2)) with n=8, 10, 12 and 14 were determined from surface tension measurements. Based on the analysis of the adsorption isotherms, the total free energy change of adsorption was determined and a novel method was proposed to determine the maximum adsorbed amount of surfactant. It can be concluded that the driving force for adsorption first increases with increasing adsorbed amount of the sugar surfactants and then levels off in a plateau. This peculiar behaviour is interpreted as formation of a thin liquid-like alkane film of overlapping alkyl chains at the air/water interface once a certain adsorbed amount is exceeded. The driving force of adsorption depends on the alkyl chain length only and is not affected by the type of the head group. The hydrophobic contribution to the standard free energy change of adsorption was compared with the values of sodium alkylsulfate and alkyltrimethylammonium bromide surfactants. This comparison reveals that the hydrophobic driving force of adsorption is the largest for the sodium alkylsulfates, whereas it is the same for the sugar surfactants and the alkyltrimethylammonium bromides.
    Journal of Colloid and Interface Science 04/2012; 379(1):78-83. · 3.55 Impact Factor
  • Gabriela Catanoiu, Dirk Blunk, Cosima Stubenrauch
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    ABSTRACT: Carbohydrate- and oligoethylene oxide-based surfactants behave quite differently despite the fact that they are both classes of nonionic surfactants. Intensive studies of a mixture at fixed molar ratio (1:1) of two very common sugar- and oligoethylene oxide-based surfactants, namely n-dodecyl-β-D-maltoside (β-C(12)G(2)) and n-dodecyl hexaethylene oxide (C(12)E(6)), revealed that most properties of the mixture are similar to those of the oligoethylene oxide-based surfactant. In the present work, this mixture is compared to respective "hybrid surfactants". Such hybrid surfactants are surfactants whose head group contains chemically linked carbohydrate and oligoethylene oxide units. In order to study the behaviour of this sort of compounds, we synthesised a new class of surfactants whose head group consists of one carbohydrate-like unit (myo-inositol) and three ethylene oxide units. New regiochemically defined ethoxylated inositol derivatives (referred to as C(12)I(1)E(3) and C(12)E(3)I(1) in the following) were synthesised and studied for their thermotropic and lyotropic liquid crystalline properties as well as for their surface activities. The results are compared with those of the reference systems β-C(12)G(2) and C(12)E(6), and their 1:1 mixture, respectively, and are discussed in terms of structure-property relations.
    Journal of Colloid and Interface Science 04/2012; 371(1):82-8. · 3.55 Impact Factor
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    ABSTRACT: An ideal template for the production of macroporous polystyrene can be prepared from foamed oil-in-water emulsions containing styrene, water, glycerol, and sodium dodecylsulfate. After addition of a photoinitiator the mixture is polymerized with UV light and the foam structure of the precursor is transferred to the polymer. The resulting materials display densely packed cells with windows between adjacent pores (see SEM image; scale bar: 250 μm).
    Angewandte Chemie International Edition 02/2012; 51(9):2213-7. · 11.34 Impact Factor
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    Angewandte Chemie 02/2012; 124(9).
  • Nils Bongartz, Sandeep R. Patil, Cosima Stubenrauch, Dirk Blunk
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    ABSTRACT: Carbohydrates are versatile materials of natural origin and thus they are interesting hydrophilic head groups for surfactants. Especially myo-inositol derivatives have advantages over pyranosidic or furanosidic sugar derivatives, namely a higher thermal and chemical stability. The main disadvantage turned out to be the poor water solubility of myo-inositol surfactants, which, however, can be overcome by introducing an oligoethylene oxide group between the inositol head group and the apolar chain. Our goal was to combine the favourable properties of surfactants based on myo-inositol with those of fluorinated surfactants, which are becoming increasingly important as CO2 solvation mediators or stabilizers for reverse water-in-fluorocarbon microemulsions. Thus we synthesized a new surfactant which combines the three units of interest, namely an inositol head group, an oligoethylene oxide linker to provide sufficient solubility and a fluorinated chain. We studied the thermotropic and lyotropic liquid crystalline behaviour as well as the surface tension and compared these results with those of a fully protonated surfactant which has a similar structure.
    Colloids and Surfaces A Physicochemical and Engineering Aspects 01/2012; 414:320-326. · 2.11 Impact Factor
  • Julia Boos, Wiebke Drenckhan, Cosima Stubenrauch
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    ABSTRACT: Even though foams have been the subject of intensive investigations over the last decades, many important questions related to their properties remain open. This concerns in particular foams which are stabilized by mixtures of surfactants. The present study deals with the fundamental question: which are the important parameters one needs to consider if one wants to characterize foams properly? We give an answer to this question by providing a measuring protocol which we apply to well-known surfactant systems. The surfactants of choice are the two non-ionic surfactants n-dodecyl-β-d-maltoside (β-C12G2) and hexaethyleneglycol monododecyl ether (C12E6) as well as their 1:1 mixture. Following the suggested protocol, we generated data which allow discussion of the influence of the surfactant structure and of the composition on the time evolution of the foam volume, the liquid fraction, the bubble size and the bubble size distribution. This paper shows that different foam properties can be assigned to different surfactant structures, which is the crucial point if one wants to tailor-make surfactants for specific applications.
    Journal of Surfactants and Detergents 01/2012; 16(1). · 1.52 Impact Factor
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    ABSTRACT: The phase behaviour of different ternary mixtures containing water, a hydrophobic ionic liquid (IL) and Triton X-100 have been examined as a function of surfactant concentration and temperature, maintaining equal volumes of water and IL. In all previously published studies on water–IL microemulsions the hydrophobic IL contained hexafluorophosphate (PF6−) as anion. As this anion is not stable towards hydrolysis, our aim was to replace it by the hydrolysis-stable anion bis-triflimide (NTf2−). The challenge was to find a suitable cation, which, in combination with the chosen anion, forms microemulsions with an efficiency equal or greater than reported values. The cation leading to the most efficient microemulsion was [ali336]+, which is based on the phase transfer catalyst aliquat 336. Thus the IL [ali336]NTf2 turned out to be a suitable choice for a hydrophobic room temperature IL which forms microemulsions of efficiencies comparable to those of water–[bmim]PF6 systems, whilst being stable towards hydrolysis.
    Soft Matter 07/2011; 7(15):6805-6810. · 4.15 Impact Factor
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    ABSTRACT: PtPb intermetallic nanoparticles (3-6 nm) with precise control (±0.8 nm) were prepared under mild conditions by using water-in-oil (w/o) microemulsions as reaction media. The amount of the aqueous phase has no significant effect on the composition of the NPs, while it indeed affects the size of the resulting NPs in a systematic way. A precise size control can be obtained by controlling the size of the w/o-microemulsions containing the metal salts and the reducing agent, respectively.
    Physical Chemistry Chemical Physics 05/2011; 13(20):9134-6. · 4.20 Impact Factor
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    ABSTRACT: In water/oil systems, surfactants partition between the water phase and the oil phase according to their solubility in both phases. The ratio between the concentration of the surfactant in the oil phase and in the water phase at equilibrium is known as the partition or distribution coefficient (K(p)). The partition coefficient (K(p)) is an important fundamental parameter essential to understanding and controlling phenomena in water-oil-surfactant systems under both equilibrium and non-equilibrium conditions. In the present work we report on the partitioning of three different classes of nonionic surfactants in the pre-cmc regime, namely polyoxyethylene alkyl ethers (C(i)E(j)), alkyl dimethyl phosphine oxides (C(n)DMPO) and alkyl glycosides (β-C(n)G(m)) between water and different n-alkanes. We focus on the influence of the surfactant's molecular structure (alkyl chain length, head group size and type), and oil chain length on K(p) to derive systematic structure-property relationships. Moreover, we discuss the influence of the surfactant purity on partition coefficients of technical grade alkyl glycosides and polyoxyethylene alkyl ethers, respectively.
    Journal of Colloid and Interface Science 03/2011; 355(1):150-6. · 3.55 Impact Factor

Publication Stats

446 Citations
307.07 Total Impact Points


  • 2010–2014
    • Universität Stuttgart
      • Institute of Physical Chemistry
      Stuttgart, Baden-Württemberg, Germany
    • Flinders University
      • School of Chemical and Physical Sciences
      Adelaide, South Australia, Australia
    • Technische Universität Berlin
      • Department of Chemistry
      Berlin, Land Berlin, Germany
  • 2005–2012
    • University College Dublin
      • • School of Chemical and Bioprocess Engineering
      • • Centre for Synthesis and Chemical Biology
      Dublin, Leinster, Ireland
    • Forschungszentrum Jülich
      • Jülich Centre for Neutron Science (JCNS)
      Düren, North Rhine-Westphalia, Germany
  • 2007–2010
    • KTH Royal Institute of Technology
      • Department of Chemistry
      Stockholm, Stockholm, Sweden
  • 2008
    • University of Tabriz
      • Faculty of Chemistry
      Tabrīz, East Azarbaijan, Iran
  • 2001–2007
    • University of Cologne
      • Institute of Physical Chemistry
      Köln, North Rhine-Westphalia, Germany
  • 2006
    • Yokohama National University
      • Graduate School of Environment and Information Sciences
      Yokohama-shi, Kanagawa-ken, Japan