Volume 33 Issue 5
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Ying-ying Peng, Yi-fan Liao, Wei Gan, Qing-xiao Tong, Qun-hui Yuan. Hydroxyl Group Modifies Aggregation Behavior of a Non-ionic Hydro-fluorocarbon Hybrid Surfactant by Disrupting Interfacial Water†[J]. Chinese Journal of Chemical Physics , 2020, 33(5): 623-627. doi: 10.1063/1674-0068/cjcp2006092
Citation: Ying-ying Peng, Yi-fan Liao, Wei Gan, Qing-xiao Tong, Qun-hui Yuan. Hydroxyl Group Modifies Aggregation Behavior of a Non-ionic Hydro-fluorocarbon Hybrid Surfactant by Disrupting Interfacial Water[J]. Chinese Journal of Chemical Physics , 2020, 33(5): 623-627. doi: 10.1063/1674-0068/cjcp2006092

Hydroxyl Group Modifies Aggregation Behavior of a Non-ionic Hydro-fluorocarbon Hybrid Surfactant by Disrupting Interfacial Water

doi: 10.1063/1674-0068/cjcp2006092
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  • Corresponding author: Wei Gan, Email: ganwei@hit.edu.cn; Qing-xiao Tong, Email: qingxiaotong@stu.edu.cn; Qun-hui Yuan, Email: yuanqunhui@hit.edu.cn
  • Part of the special issue on "the Chinese Chemical Society's 16th National Chemical Dynamics Symposium".Two non-ionic hydro-fluorocarbon hybrid surfactants with and without hydroxyl groups.
  • Received Date: 2020-06-11
  • Accepted Date: 2020-06-29
  • Publish Date: 2020-10-27
  • Two non-ionic hydro-fluorocarbon hybrid surfactants with and without hydroxyl groups were synthesized and compared. They exhibited good thermal stability and superior surface activity. It was observed that the hydroxyl group had a profound effect on modifying the surface tension of their solutions and the morphology of the formed micelles. This effect may be attributed to the rearranging of the alkane group from above the air/aqueous surface to below it and the disrupting of the interfacial water structure induced by the hydroxyl groups. This work provides a strategy to weaken the immiscibility between hydrocarbon and fluorocarbon chains by modifying their orientational structure at the interface, thus it is helpful for the design of surfactants with varied interfacial properties.
  • Part of the special issue on "the Chinese Chemical Society's 16th National Chemical Dynamics Symposium".Two non-ionic hydro-fluorocarbon hybrid surfactants with and without hydroxyl groups.
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Hydroxyl Group Modifies Aggregation Behavior of a Non-ionic Hydro-fluorocarbon Hybrid Surfactant by Disrupting Interfacial Water

doi: 10.1063/1674-0068/cjcp2006092

Abstract: Two non-ionic hydro-fluorocarbon hybrid surfactants with and without hydroxyl groups were synthesized and compared. They exhibited good thermal stability and superior surface activity. It was observed that the hydroxyl group had a profound effect on modifying the surface tension of their solutions and the morphology of the formed micelles. This effect may be attributed to the rearranging of the alkane group from above the air/aqueous surface to below it and the disrupting of the interfacial water structure induced by the hydroxyl groups. This work provides a strategy to weaken the immiscibility between hydrocarbon and fluorocarbon chains by modifying their orientational structure at the interface, thus it is helpful for the design of surfactants with varied interfacial properties.

Part of the special issue on "the Chinese Chemical Society's 16th National Chemical Dynamics Symposium".Two non-ionic hydro-fluorocarbon hybrid surfactants with and without hydroxyl groups.
Ying-ying Peng, Yi-fan Liao, Wei Gan, Qing-xiao Tong, Qun-hui Yuan. Hydroxyl Group Modifies Aggregation Behavior of a Non-ionic Hydro-fluorocarbon Hybrid Surfactant by Disrupting Interfacial Water†[J]. Chinese Journal of Chemical Physics , 2020, 33(5): 623-627. doi: 10.1063/1674-0068/cjcp2006092
Citation: Ying-ying Peng, Yi-fan Liao, Wei Gan, Qing-xiao Tong, Qun-hui Yuan. Hydroxyl Group Modifies Aggregation Behavior of a Non-ionic Hydro-fluorocarbon Hybrid Surfactant by Disrupting Interfacial Water[J]. Chinese Journal of Chemical Physics , 2020, 33(5): 623-627. doi: 10.1063/1674-0068/cjcp2006092
  • The synthesis and application of fluorocarbon surfactants have attracted extensive attentions because of the superior surface activity, better thermal and chemical properties of the fluorocarbon surfactants compared with their hydrocarbon-based analogues [1-5]. Fluorocarbon surfactants have been widely used as active-materials in practical respects where hydrocarbon surfactants are not qualified, e.g. foaming agents in fire technology [6, 7], wetting agents in painting and emulsifying agents in supercritical carbon dioxide [8-11]. The ability to form micelles of various shape/size also broadens their application in the fields of nanoscience, drug delivery and life science over the last decades [12, 13]. Mixing fluorocarbon and hydrocarbon surfactants at a proper ratio may enrich the micellization of fluorocarbon surfactant [4, 14-17], the hydro-fluorocarbon hybrid surfactant combining fluorocarbon and hydrocarbon chains in a molecule has also been designed and synthesized in recent years to modify its surface or self-assembled properties [18-23]. So far most of the latter studies focused on adjusting the length of the fluorocarbon or hydrocarbon chains to modify its micellar shape or size [24-28]. For example, recently we synthesized fluorocarbon surfactants with different alkane chains and compared their surface activities. It was observed that the immiscibility between hydrocarbon and fluorocarbon chains had significant effect on their surface behavior [29].

    In this work we synthesized hydro-fluorocarbon hybrid surfactants with and without hydroxyl groups (C9F19AH and C9F19AE shown in Scheme 1) from a one-step reaction to investigate the effect of hydroxyl groups on modifying the micellar morphology and interfacial property of the surfactants. It was found that C9F19AE, whose surface activity has been studies in our recent work [29], only formed spherical micelle; while the newly designed C9F19AH formed spherical, rod like and branched micelles at varied concentrations. The difference in the surface tension of the surfactant solutions were also studied and the effect of the hydroxyl groups on adjusting the interfacial structure of the surfactants was analyzed. This work demonstrates a valuable strategy to weaken the immiscibility between the hydrocarbon and fluorocarbon chains [18, 30, 31], and adjust the interfacial behavior of the hydro-fluorocarbon hybrid surfactants.

    Figure Scheme 1.  Molecular structures of the non-ionic hydro- fluorocarbon hybrid surfactants: (a) C$ _9 $F$ _{19} $AE and (b) C$ _9 $F$ _{19} $AH.

  • All the reagents and solvents were purchased from Sigma-Aldrich and used directly without further purification. The synthesis routes of C9F19AE and C9F19AH are depicted in Scheme 2 and in the supplementary materials in detail.

    Figure Scheme 2.  Synthesis routes of (a) C$ _9 $F$ _{19} $AE and (b) C$ _9 $F$ _{19} $AH.

  • Thermal properties of C9F19AE and C9F19AH were investigated with TGA (thermogravimetric analysis, SYSTEM DSC Q100) under nitrogen atmosphere with a heating rate of 10 ℃/min.

  • Surface tension measurements were carried out using an Automatic Surface & interface Tension Meter (KRUSS GmbH K11) with the Du Nouy ring method. Before the measurements, surfactant solutions with different concentrations were prepared and stored in a thermostat overnight. The temperature was controlled at (25$ \pm $0.5) ℃ in the experiments.

  • Dynamic light scattering (DLS) analysis were carried out using a Brookhaven 90 Plus particle size analyzer with a detection angle of 90 ℃ and the temperature controlled at 25$ \pm $0.5 ℃. Surfactants solutions with different concentration were stored in a thermostat for at least 3 days to reach an equilibrium before the measurements.

    The micellar shape of these two hybrid surfactants were analyzed by TEM using Hitachi FEI spirit T12 at 120 kV and SEM (only for C9F19AH) using Hitachi SU8220, respectively. The samples used in DLS measurements were dropped on a copper grid for TEM and a silicon chip for SEM, respectively. They were dried overnight before the TEM and SEM measurements.

  • The thermal properties of C9F19AE and C9F19AH were investigated through TGA. The results are shown in FIG. 1. The decomposition temperatures ($ T_{\rm{d}} $, corresponding to 5% weight loss) were measured up to 173 ℃ and 202 ℃ for C9F19AE and C9F19AH, respectively, which suggested that these two kinds of hybrid surfactants exhibited good thermal stability.

    Figure 1.  Weight loss vs. temperature from the TGA measurements for C9F19AE (a) and C9F19AH (b).

    FIG. 2 shows the relationship between the surface tension and the natural logarithm of the concentration for C9F19AE and C9F19AH in water. Clearly, they exhibit superior surface activity with low critical micelle concentration (CMC, as pointed by the arrows, 0.12 mmol/L for C9F19AE and 0.14 mmol/L for C9F19AH). For C9F19AH, the decrease of the surface tension has two different slopes at the low and high concentration ranges, respectively. The mechanism behind it will be discussed latter.

    Figure 2.  The surface tensions of the surfactants solutions vs. the natural logarithm of the concentrations for C9F19AE and C9F19AH.

    The relatively smaller CMC values for C9F19AE compared with C9F19AH indicate a higher hydrophobicity because of the absence of the hydroxyl group although this difference is not very significant. To further study the difference between the two surfactants, the morphology of the micelles in the solutions was characterized by transmission electron microscopy (TEM) and scanning electron microscope (SEM).

    The TEM images in FIG. 3(a-d) show that the micelles formed in the C9F19AE solutions at different concentrations all exhibit spherical shape with a diameter of approximately 200 nm, which may be confirmed by a number mean diameter of $ \sim $220 nm from the dynamic light scattering (DLS) measurements. It is observed that the C9F19AE concentration does not have a significant influence on the size and morphology of the micelles. On the other hand, the DLS results show the average diameter of the C9F19AH micelles increases from $ \sim $200 nm to $ \sim $400 nm with the increasing concentration. The TEM images of C9F19AH solutions (FIG. S3 in supplementary materials) are not very clear, possibly because of the relatively high viscosities of the C9F19AH solutions. Though, some complex structures at relatively high concentrations are able to be discerned. To make it clearer, SEM images from the C9F19AH solutions were measured and used for comparison, as shown in FIG. 3(e-h). It is confirmed that there is rod like and branched structures in the C9F19AH solutions, especially at relatively high concentrations.

    Figure 3.  TEM micrographs of spherical micelles formed by C9F19AE in different concentration: (a) 10 times of CMC, (b) 20 times of CMC, (c) 30 times of CMC, (d) 40 times of CMC; and SEM micrographs of micelles formed by C9F19AH in different concentration: (e) 10 times of CMC, (f) 20 times of CMC, (g) 30 times of CMC, (h) 40 times of CMC.

    The mechanism behind the formation of different kinds of micelles must be related to the absence/existence of the hydroxyl group in the surfactants. The two hydroxyl groups increase the hydrophilicity of the alkane chain in C9F19AH. This effect may drive the alkane chain of C9F19AH molecules in the micelles into the aqueous phase, instead of overlapping with the fluorocarbon chains which form the core of the micelles. This adjustment of the alkane chain direction and the hydrogen bonding between the hydroxyl groups and the water molecules may induce a thicker solvation layer around the micelles. With the approaching of micelles to each other, the solvation layers of the micelles may merge and benefit the formation of hydrogen bonding between the hydroxyl groups in one micelle and the hydroxyl groups in another micelle. As shown in FIG. 4, the formation of the intra-molecule hydrogen bonding between the micelles then promotes the fusion of micelles and the generation of more rod like or branched structures, as shown in FIG. 3(e-h). On the other hand, the absence of hydroxyl group results in a thinner solvation layer around the C9F19AE micelles, which remain spherical even at the concentration up to 40 times of CMC.

    Figure 4.  Diagrams showing the fusion of micelles in the solution of C9F19AH.

    The formation of thicker solvation layer and the disrupting of water molecules by the alkane chain of C9F19AH may also be supported by the surface tension curves shown in FIG. 2. Based on the Gibbs adsorption equation [32-36]

    where $ n $ = 1 for non-ionic surfactants such as C9F19AE and C9F19AH, $ \frac{{{\rm{d}}\gamma }}{{{\rm{d}}\ln C}} $ being the slope of the curves shown in FIG. 2, the surface excess $ {\Gamma _{\max }} $ for C9F19AE and C9F19AH on the air/aqueous surface may be deduced. For C9F19AE, a surface excess of 0.59$ \times $10$ ^{-5 }$ mol/m$ ^2 $ is deduced, which corresponds to an averaged surface area per C9F19AE molecule as 0.27 nm$ ^2 $. It needs to be noted that there is a mistake in estimating the surface excess of this molecule in previous report [29], the term $ \lg C $ should be $ \ln C $ for the Gibbs adsorption equation. Thus, a factor of 2.3 needs to be involved to make the reported values to be correct. For example, the value of 0.10 nm$ ^2 $ should be 0.23 nm$ ^2 $ for the averaged surface area per C9F19AE molecule. It also needs to be noted that there is a small difference between the value of 0.27 obtained in this work and 0.23 in the previous report, which is most possibly from the difference in the apparatus used for the surface tension measurements and the experimental fluctuation. Because there are two different slopes at the relatively low (marked as A) and high (B) concentration ranges for the C9F19AH case, two surface excess values of 0.48$ \times $10$ ^{-5} $ (A) and 0.89$ \times $10$ ^{-5} $ (B) mol/m$ ^2 $ are deduced. They correspond to the averaged surface area per molecule as 0.34 nm$ ^2 $ and 0.18 nm$ ^2 $ for the low and high concentration ranges, respectively. The illustration shown in FIG. 5 provides an explanation for this observation. Both the fluorocarbon and the alkane chains may be oriented above the water surface at relatively low concentrations. With the increase of the surfactant concentration, the higher surface C9F19AH density causes an intruding of the alkane chains in the aqueous phase with the help of the hydrophilicity of hydroxyl groups (as shown in the FIG. 5(b)) [37, 38]. It is known that the van de Waals interaction between the long chains may benefit the formation of compact interface layers [39-42]. With the absence of the alkane chains between the fluorocarbon chains, the averaged surface area per C9F19AH molecule drops notably from 0.34 nm$ ^2 $ to 0.18 nm$ ^2 $.

    Figure 5.  Diagrams for the orientational structure of the adsorbed surfactants on the air/aqueous interface. (a) C9F19AE, (b) C9F19AH.

    It is noticeable in FIG. 2 that the decrease of the surface tension with the increase of C9F19AH concentration is accelerated after the turning point as marked by the star. This observation indicates that the change in the orientational structure of C9F19AH molecules forms an increased solvation layer and disrupts the interfacial water within a larger depth. Although the origin of the surface tension and its relationship with interfacial water structure is not completely understood yet, especially in the presence of multiple surfactants at surfaces [30, 43, 44], the observations in this work clearly imply that the contribution to the interfacial tension is most possibly from the structure of multiple water layers at the interface. That is to say, the deeper the hydrophobic species extend into the aqueous interface, the severer the water structures being disrupted and the larger effect on the surface tension are observed. With the change of the interfacial C9F19AH structure at relatively high concentrations, the interfacial structure, surface tension and micelle morphology of the C9F19AH solutions is modified significantly. On the other hand, C9F19AE molecules may keep the similar interfacial structure at both low and high concentrations, as shown in FIG. 5(a).

  • In summary, two non-ionic hydro-fluorocarbon hybrid surfactants with and without hydroxyl groups were designed and synthesized via a facile synthesis. The hydroxyl groups may drag the alkane chain of the surfactants into the aqueous phase at a relatively high surface density to weaken the immiscibility between the fluorocarbon and the hydrocarbon chains. Similarly, the rearranging of the alkane chain and the hydroxyl groups from the hydrophobic core of the micelles into the aqueous phase increased the solvation depth of the micelles. This effect combined with the hydrogen bonding formation benefits the formation of rod like and branched micelle structures. The relationship between the disruption of the interfacial water structure and the surface tension is also discussed. This work not only provides a facial method for the modification of interfacial structure and property of hydro-fluorocarbon hybrid surfactants, but also sheds light on understanding the origin of surface tension, which is an important question to be answered in the surface science.

    Supplementary materials: Detailed synthesis procedures and the NMR characterizations of the surfactants, TEM images of the micelles formed by C9F19AH are available.

  • This work was supported by the National Natural Science Foundation of China (No.21673285 and No.21973022), the Guangdong Basic and Applied Basic Research Foundation (No.2019A1515012117), and the Guangdong Province Universities and Colleges Pearl River Scholar Funded Scheme 2019 (No.GDUPS2019).

  • C9F19AE. Under the protection of nitrogen atmosphere, 5 g (9.73 mmol) nonadecafluorodecanoic acid and 25 mL toluene were added into a 100 mL three-neck flask with 30 minutes of stirring, then 1.5 g (11.52 mmol) N1, N1-diethylpropane-1, 3-diamine was added. The mixture was refluxed for 12 h. with the temperature controlled at 90 ℃. The raw product was treated with vacuum distillation and recrystallized with dichloromethane for 3 times. Yield: 90 %. 1HNMR (Tecnai G2 F20 S-Twin, 400 MHz, DMSO) δ (ppm)7.60 (s, 1H), 2.81 (t, J = 7.1 Hz, 2H), 2.42 (dd, J = 14.1, 7.0 Hz, 6H), 1.72 - 1.57 (m, 2H), 0.90 (t, J = 7.1 Hz, 6H). 19FNMR (471 MHz, DMSO) δ (ppm) -82.23 (t, J = 9.4 Hz), -116.10 (s), -122.16 (s), -122.72 (d, J = 91.5 Hz), -123.68 (s), -127.26 (s). MS(ESI+) for C17H17F19N2O, [M + H+] calculated 627.10, found 627.20.

    Figure S1.  1HNMR spectra (a), 19FNMR spectra (b) and MS spectra (c) for C9F19AE.

    C9F19AH. Under the protection of nitrogen atmosphere, 5 g (9.73 mmol) nonadecafluorodecanoic acid and 25 mL toluene were added into a 100 mL three-neck flask with 30 minutes of stirring, then 1.89 g (11.65 mmol) 2, 2'-((3-aminopropyl)azanediyl)bis(ethan-1-ol) was added and refluxed for 12 h with the temperature controlled at 90 ℃. The raw product was treated with vacuum distillation and recrystallized with dichloromethane for 3 times. Yield: 93 %.1H NMR (Tecnai G2 F20 S-Twin, 400 MHz, DMSO-d6) δ 6.58 (s, 1H), 3.48 (t, J = 5.8 Hz, 4H), 2.89 (t, J = 6.4 Hz, 2H), 2.59 (t, J = 6.1 Hz, 2H), 2.50 (t, J = 5.8 Hz, 4H), 1.65 (p, J = 6.2 Hz, 2H). 19F NMR (376 MHz, DMSO-d6) δ -80.96 (t, J = 9.8 Hz), -115.42 (t, J = 12.3 Hz), -121.71 (t, J = 15.7 Hz), -122.09 (d, J = 36.5 Hz), -122.97 (dt, J = 22.4, 10.9 Hz), -126.35 (dt, J = 17.9, 8.2 Hz).MS(ESI+) for C17H17F19N2O3, [M + H+] calculated 512.98 (C9F19CONH) and 163.14(H2N(CH2)3N[CH2CH2OH]2), found 512.95 and 163.14.

    Figure S2.  1HNMR spectra (a), 19FNMR spectra (b) and MS spectra (c and d) for C9F19AH.

  • Figure S3.  TEM images of the micelles formed by C9F19AH at different concentrations (a) 10 times of CMC, (b) 20 times of CMC, (c) 30 times of CMC, and (d) 40 times of CMC.

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