Journal
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Volume 20, Issue 5, Pages 3373-3380Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c7cp06348b
Keywords
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Funding
- JSPS KAKENHI [JP25104011]
- Japan Synchrotron Radiation Research Institute (JASRI) [2011B1548]
- EPSRC [EP/K039245/1]
- University of Birmingham
- EU (Marie Curie SusNano)
- EPSRC [EP/K039245/1] Funding Source: UKRI
- Engineering and Physical Sciences Research Council [EP/K039245/1] Funding Source: researchfish
- Grants-in-Aid for Scientific Research [25104011, 15H03801] Funding Source: KAKEN
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Contrast-variation small-angle neutron scattering (CV-SANS), small-angle X-ray scattering (SAXS), nuclear magnetic resonance (NMR) measurements of diffusion and isothermal titration calorimetry (ITC) are used to gain insight into the aggregation of an alkyl-C-60 derivative, molecule 1, in n-hexane, n-decane and toluene as a function of concentration and temperature. Results point to an associative mechanism of aggregation similar to other commonly associating molecules, including non-ionic surfactants or asphaltenes in non-aqueous solvents. Little aggregation is detected in toluene, but small micelle-like structures form in n-alkane solvents, which have a C-60-rich core and alkyl-rich shell. The greatest aggregation extent is found in n-hexane, and at 0.1 M the micelles of 1 comprise around 6 molecules at 25 degrees C. These micelles become smaller when the concentration is lowered, or if the solvent is changed to n-decane. The solution structure is also affected by temperature, with a slightly larger aggregation extent at 10 degrees C than at 25 degrees C. At higher concentrations, for example in solutions of 1 above 0.3 M in n-decane, a bicontinuous network becomes apparent. Overall, these findings aid our understanding of the factors driving the assembly of alkyl-pi-conjugated hydrophobic amphiphiles such as 1 in solution and thereby represent a step towards the ultimate goal of exploiting this phenomenon to form materials with well-defined order.
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