TY - JOUR
T1 - The aggregation of an alkyl-C60 derivative as a function of concentration, temperature and solvent type
AU - Hollamby, Martin J.
AU - Smith, Catherine F.
AU - Britton, Melanie M.
AU - Danks, Ashleigh E.
AU - Schnepp, Zoe
AU - Grillo, Isabelle
AU - Pauw, Brian R.
AU - Kishimura, Akihiro
AU - Nakanishi, Takashi
N1 - Funding Information:
This work was partially supported by Grants-in-Aid for Scientific Research (JSPS KAKENHI Grant Number JP25104011). The SPring-8 synchrotron radiation experiment was performed on BL40B2 with the approval the Japan Synchrotron Radiation Research Institute (JASRI; proposal no. 2011B1548). The authors thank the beamline contact (N. Ohta, SPring8) for his help with performing SAXS measurements. We thank the ILL for the beam time on the D11 instrument. The neutron data set is available at DOI: 10.5291/ILL-DATA.9-10-1422. MMB and CFS thank the EPSRC (grant EP/K039245/1) and University of Birmingham for financial support. AD thanks the University of Birmingham and the EU (Marie Curie "SusNano") for his PhD studentship. Finally, STFC is acknowledged for the allocation of beam time, consumables and travel.
Funding Information:
This work was partially supported by Grants-in-Aid for Scientific Research (JSPS KAKENHI Grant Number JP25104011). The SPring-8 synchrotron radiation experiment was performed on BL40B2 with the approval the Japan Synchrotron Radiation Research Institute (JASRI; proposal no. 2011B1548). The authors thank the beamline contact (N. Ohta, SPring8) for his help with performing SAXS measurements. We thank the ILL for the beam time on the D11 instrument. The neutron data set is available at DOI: 10.5291/ILL-DATA.9-10-1422.12 MMB and CFS thank the EPSRC (grant EP/K039245/1) and University of Birmingham for financial support. AD thanks the University of Birmingham and the EU (Marie Curie ‘‘SusNano’’) for his PhD studentship. Finally, STFC is acknowledged for the allocation of beam time, consumables and travel.
Publisher Copyright:
© 2018 the Owner Societies.
PY - 2018/2/7
Y1 - 2018/2/7
N2 - 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-C60 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 C60-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 °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 °C than at 25 °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-π-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.
AB - 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-C60 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 C60-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 °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 °C than at 25 °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-π-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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U2 - 10.1039/c7cp06348b
DO - 10.1039/c7cp06348b
M3 - Article
C2 - 29260811
AN - SCOPUS:85041667462
VL - 20
SP - 3373
EP - 3380
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
SN - 1463-9076
IS - 5
ER -