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@ARTICLE{Blayo:861706,
      author       = {Blayo, Camille and Houston, Judith E. and King, Stephen M.
                      and Evans, Rachel C.},
      title        = {{U}nlocking {S}tructure–{S}elf-{A}ssembly {R}elationships
                      in {C}ationic {A}zobenzene {P}hotosurfactants},
      journal      = {Langmuir},
      volume       = {34},
      number       = {34},
      issn         = {1520-5827},
      address      = {Washington, DC},
      publisher    = {ACS Publ.},
      reportid     = {FZJ-2019-02136},
      pages        = {10123 - 10134},
      year         = {2018},
      abstract     = {Azobenzene photosurfactants are light-responsive
                      amphiphiles that have garnered significant attention for
                      diverse applications including delivery and sorting systems,
                      phase transfer catalysis, and foam drainage. The azobenzene
                      chromophore changes both its polarity and conformation
                      (trans–cis isomerization) in response to UV light, while
                      the amphiphilic structure drives self-assembly. Detailed
                      understanding of the inherent relationship between the
                      molecular structure, physicochemical behavior, and micellar
                      arrangement of azobenzene photosurfactants is critical to
                      their usefulness. Here, we investigate the key
                      structure–function–assembly relationships in the popular
                      cationic alkylazobenzene trimethylammonium bromide (AzoTAB)
                      family of photosurfactants. We show that subtle changes in
                      the surfactant structure (alkyl tail, spacer length) can
                      lead to large variations in the critical micelle
                      concentration, particularly in response to light, as
                      determined by surface tensiometry and dynamic light
                      scattering. Small-angle neutron scattering studies also
                      reveal the formation of more diverse micellar aggregate
                      structures (ellipsoids, cylinders, spheres) than predicted
                      based on simple packing parameters. The results suggest that
                      whereas the azobenzene core resides in the effective
                      hydrophobic segment in the trans-isomer, it forms part of
                      the effective hydrophilic segment in the cis-isomer because
                      of the dramatic conformational and polarity changes induced
                      by photoisomerization. The extent of this shift in the
                      hydrophobic–hydrophilic balance is determined by the
                      separation between the azobenzene core and the polar head
                      group in the molecular structure. Our findings show that
                      judicious design of the AzoTAB structure enables selective
                      tailoring of the surfactant properties in response to light,
                      such that they can be exploited and controlled in a reliable
                      fashion.},
      cin          = {JCNS-FRM-II / Neutronenstreuung ; JCNS-1},
      ddc          = {540},
      cid          = {I:(DE-Juel1)JCNS-FRM-II-20110218 /
                      I:(DE-Juel1)JCNS-1-20110106},
      pnm          = {6G4 - Jülich Centre for Neutron Research (JCNS) (POF3-623)
                      / 6G15 - FRM II / MLZ (POF3-6G15)},
      pid          = {G:(DE-HGF)POF3-6G4 / G:(DE-HGF)POF3-6G15},
      experiment   = {EXP:(DE-MLZ)External-20140101},
      typ          = {PUB:(DE-HGF)16},
      pubmed       = {pmid:30071720},
      UT           = {WOS:000443524300027},
      doi          = {10.1021/acs.langmuir.8b02109},
      url          = {https://juser.fz-juelich.de/record/861706},
}