Aggregation of Amphiphilic Carbocyanines: Fluorination Favors Cylindrical Micelles over Bilayered Tubes
Abstract
chains attached to the nitrogen atoms in the 1,1'-position, CF8O3, is reported. Depending on the dye concentration and the addition of MeOH, CF8O3 forms J- and H-aggregates in aqueous solutions. The aggregation behavior was investigated using steady-state absorption, linear dichroism, and fluorescence spectroscopy, as well as by cryogenic transmission electron microscopy (cryo-TEM). The J-band of the MeOH-free solution is monomer-like, rather broad, and less red-shifted with respect to the monomer absorption, indicating weak excitonic coupling and disorder effects. Cryo-TEM reveals a diversity of supramolecular structures, wherein linear and branched cylindrical micelles dominate. It is concluded that the high stiffness of fluoroalkyl chains does not allow the chains to splay and completely fill up the hydrophobic gap between opposing chromophores. This destabilizes the bilayers and favors the micellar structure motifs instead. The aggregates appearing at 30% MeOH show a split absorption spectrum consisting of a broad blue-shifted H-band and an accompanying sharp red-shifted J-band with perpendicular polarizations. These HJ-type aggregates are also composed of micellar fibers, but these bundle into rope-like strands. For 10% MeOH, a narrow bilayered tube is the dominating morphology. The observed MeOH dependence of aggregation reveals a clear cosolvent effect.
Integrity signals
Registry
Cites
Statistics
Claims the paper makes
Claims other papers make about this one
Each is checked against this paper’s own text: does it say what the citing paper says it does?
The self-assembly of dyes can be controlled at the level of molecular design through substituent coupling so that the bulkiness of the donor substituent leads to strong H-type or strong J-type exciton coupling.
“The self-assembly of dyes can be controlled at the level of molecular design through substituent coupling so that the bulkiness of the donor substituent leads to strong H-type or strong J-type exciton coupling.98−100”
From The Pursuit of Shortwave Infrared-Emitting Nanoparticles with Bright Fluorescence through Molecular Design and Excited-State Engineering of Molecular Aggregates (2022) · cites this paper as [100]
Cites
Intermolecular and Surface Forces
Israelachvili, J. N. (2011) · Elsevier eBooks · doi:10.1016/c2009-0-21560-1 · Cited by 8,185 · see citing works
J‐Aggregates: From Serendipitous Discovery to Supramolecular Engineering of Functional Dye Materials
Würthner, F., Kaiser, T. E., & Saha‐Möller, C. R. (2011) · Angewandte Chemie International Edition · doi:10.1002/anie.201002307 · Cited by 2,597 · see citing works
Hestand, N. J., & Spano, F. C. (2018) · Chemical Reviews · doi:10.1021/acs.chemrev.7b00581 · Cited by 1,934 · see citing works
The Spectral Signatures of Frenkel Polarons in H- and J-Aggregates
Spano, F. C. (2009) · Accounts of Chemical Research · doi:10.1021/ar900233v · Cited by 1,729 · see citing works
Davydov, A. S. (1971) · Springer eBooks · doi:10.1007/978-1-4899-5169-4 · Cited by 1,205 · see citing works
Light Absorption and Energy Transfer in the Antenna Complexes of Photosynthetic Organisms
Mirkovic, T., Ostroumov, E. E., Anna, J. M., van Grondelle, R., Jee, G., & Scholes, G. D. (2016) · Chemical Reviews · doi:10.1021/acs.chemrev.6b00002 · Cited by 1,190 · see citing works
Fluorescent J-aggregates of cyanine dyes: basic research and applications review
Bricks, J. L., Slominskiĭ, Y. L., Panas, I. D., & Demchenko, A. P. (2017) · Methods and Applications in Fluorescence · doi:10.1088/2050-6120/aa8d0d · Cited by 435 · see citing works
J-aggregates of meso-[2.2]paracyclophanyl-BODIPY dye for NIR-II imaging
Li, K., Duan, X., Jiang, Z., Ding, D., Chen, Y., Zhang, G.-Q., & Liu, Z. (2021) · Nature Communications · doi:10.1038/s41467-021-22686-z · Cited by 301 · see citing works
Lipids: Molecular organization, physical functions and technical applications
Wertz, P. W. (1994) · Chemistry and Physics of Lipids · doi:10.1016/0009-3084(94)90116-3 · Cited by 212 · see citing works
Supramolecular Structures of J-Aggregates of Carbocyanine Dyes in Solution
von Berlepsch, H., Böttcher, C., Ouart, A., Burger, C., Dähne, S., & Kirstein, S. (2000) · The Journal of Physical Chemistry B · doi:10.1021/jp000220z · Cited by 207 · see citing works
Self-citationEisele, D. M., Cone, C. W., Bloemsma, E. A., Vlaming, S. M., van der Kwaak, C., Silbey, R., Bawendi, M. G., Knoester, J., Rabe, J. P., & Bout, D. A. V. (2012) · Nature Chemistry · doi:10.1038/nchem.1380 · Cited by 205 · see citing works
Inverse lyotropic phases of lipids and membrane curvature
Shearman, G. C., Ces, O., Templer, R. H., et al. (2006) · Journal of Physics Condensed Matter · doi:10.1088/0953-8984/18/28/s01 · Cited by 186 · see citing works
Vibronic origin of long-lived coherence in an artificial molecular light harvester
Lim, J., Paleček, D., Caycedo-Soler, F., Lincoln, C. N., Prior, J., von Berlepsch, H., Huelga, S. F., Plenio, M. B., Zigmantas, D., & Hauer, J. (2015) · Nature Communications · doi:10.1038/ncomms8755 · Cited by 162 · see citing works
Linear dichroism and circular dichroism in photosynthesis research
Garab, G., & van Amerongen, H. (2009) · Photosynthesis Research · doi:10.1007/s11120-009-9424-4 · Cited by 157 · see citing works
Self-assembly of organic dyes in supramolecular aggregates
Heyne, B. (2016) · Photochemical & Photobiological Sciences · doi:10.1039/c6pp00221h · Cited by 150 · see citing works
Improved Photostability and Fluorescence Properties through Polyfluorination of a Cyanine Dye
Renikuntla, B. R., Rose, H. C., Eldo, J., et al. (2004) · Organic Letters · doi:10.1021/ol036081w · Cited by 148 · see citing works
Gillissen, M. A. J., Koenigs, M. M. E., Spiering, J., et al. (2013) · Journal of the American Chemical Society · doi:10.1021/ja4104183 · Cited by 143 · see citing works
Su, M., Han, Q., Yan, X., Liu, Y., Luo, P., Zhai, W., Zhang, Q., Li, L., & Li, C. (2021) · ACS Nano · doi:10.1021/acsnano.0c09993 · Cited by 120 · see citing works
Robust excitons inhabit soft supramolecular nanotubes
Eisele, D. M., Arias, D. H., Fu, X., Bloemsma, E. A., Steiner, C. P., Jensen, R. A., Rebentrost, P., Eisele, H., Tokmakoff, A., Lloyd, S., et al. (2014) · Proceedings of the National Academy of Sciences · doi:10.1073/pnas.1408342111 · Cited by 119 · see citing works
Effect of Fluorination of 2,1,3-Benzothiadiazole
Nielsen, C. B. O., White, A. J. P., & McCulloch, I. A. (2015) · The Journal of Organic Chemistry · doi:10.1021/acs.joc.5b00430 · Cited by 111 · see citing works
Fluorescent Cyanine Dye J-Aggregates in the Fluorous Phase
Cao, W., & Sletten, E. M. (2018) · Journal of the American Chemical Society · doi:10.1021/jacs.7b11925 · Cited by 102 · see citing works
Surfactant-Induced Changes of Morphology of J-Aggregates: Superhelix-to-Tubule Transformation
von Berlepsch, H., Böttcher, C., Ouart, A., Regenbrecht, M., Akari, S., Keiderling, U., Schnablegger, H., Dähne, S., & Kirstein, S. (2000) · Langmuir · doi:10.1021/la000014i · Cited by 94 · see citing works
Self-citationvon Berlepsch, H., Kirstein, S., Hania, P. R., Pugzlys, A., & Böttcher, C. (2007) · The Journal of Physical Chemistry B · doi:10.1021/jp065826n · Cited by 94 · see citing works
Self-citationLocal Structures of Methanol–Water Binary Solutions Studied by Soft X-ray Absorption Spectroscopy
Nagasaka, M., Mochizuki, K., Leloup, V., et al. (2014) · The Journal of Physical Chemistry B · doi:10.1021/jp4091602 · Cited by 91 · see citing works
Mustroph, H., Reiner, K., Mistol, J., Ernst, S., Keil, D., & Hennig, L. (2009) · ChemPhysChem · doi:10.1002/cphc.200800755 · Cited by 87 · see citing works
Controllable Self‐Assembly of Peptide‐Cyanine Conjugates In Vivo as Fine‐Tunable Theranostics
Zheng, R., Yang, J., Mamuti, M., Hou, D., An, H., Zhao, Y., & Wang, H. (2021) · Angewandte Chemie International Edition · doi:10.1002/anie.202015126 · Cited by 84 · see citing works
Fluorofluorophores: Fluorescent Fluorous Chemical Tools Spanning the Visible Spectrum
Sletten, E. M., & Swager, T. M. (2014) · Journal of the American Chemical Society · doi:10.1021/ja507848f · Cited by 82 · see citing works
Validation of new microvolume Couette flow linear dichroism cells
Marrington, R., Dafforn, T. R., Halsall, D. J., et al. (2005) · The Analyst · doi:10.1039/b506149k · Cited by 81 · see citing works
Fluorous Soluble Cyanine Dyes for Visualizing Perfluorocarbons in Living Systems
Lim, I., Vian, A., van de Wouw, H. L., et al. (2020) · Journal of the American Chemical Society · doi:10.1021/jacs.0c07761 · Cited by 66 · see citing works
Nandakumar, A., Ito, Y., & Ueda, M. (2020) · Journal of the American Chemical Society · doi:10.1021/jacs.0c03425 · Cited by 66 · see citing works
Pawlik, A., Ouart, A., Kirstein, S., Abraham, H., & Daehne, S. (2003) · European Journal of Organic Chemistry · doi:10.1002/ejoc.200300095 · Cited by 64 · see citing works
Effect of Alcohols on J-Aggregation of a Carbocyanine Dye
von Berlepsch, H., Kirstein, S., & Böttcher, C. (2002) · Langmuir · doi:10.1021/la0203640 · Cited by 63 · see citing works
Self-citationLin, Y., Penna, M. J., Thomas, M. R., et al. (2019) · ACS Nano · doi:10.1021/acsnano.8b08117 · Cited by 63 · see citing works
Shin, S., Gihm, S. H., Park, C. R., Kim, S., & Park, S. Y. (2013) · Chemistry of Materials · doi:10.1021/cm400988a · Cited by 62 · see citing works
Junctions and end-caps in self-assembled non-ionic cylindrical micelles
Dan, N. R., & Safran, S. A. (2006) · Advances in Colloid and Interface Science · doi:10.1016/j.cis.2006.05.027 · Cited by 61 · see citing works
Control of the J-Aggregation Phenomenon by variation of the N-alkyl-substituents
Rossi, U. D., Moll, J., Spieles, M., Bach, G., D�hne, S., Kriwanek, J., & Lisk, M. (1995) · Journal für praktische Chemie · doi:10.1002/prac.19953370144 · Cited by 55 · see citing works
Structure and interactive properties of highly fluorinated phospholipid bilayers
McIntosh, T. J., Simon, S. A., Vierling, P., et al. (1996) · Biophysical Journal · doi:10.1016/s0006-3495(96)79385-2 · Cited by 53 · see citing works
Scheblykin, I. G., Drobizhev, M. A., Varnavsky, O. P., et al. (1996) · Chemical Physics Letters · doi:10.1016/0009-2614(96)00946-3 · Cited by 52 · see citing works
Impact of backbone fluorination on nanoscale morphology and excitonic coupling in polythiophenes
Hu, Z., Haws, R. T., Fei, Z., et al. (2017) · Proceedings of the National Academy of Sciences · doi:10.1073/pnas.1620722114 · Cited by 51 · see citing works
Struganova, I. A., Lim, H., & Morgan, S. A. (2002) · The Journal of Physical Chemistry B · doi:10.1021/jp013511w · Cited by 50 · see citing works
Megow, J., Röhr, M. I. S., Busch, M. S. A., et al. (2015) · Physical Chemistry Chemical Physics · doi:10.1039/c4cp05945j · Cited by 50 · see citing works
Supramolecular Structure of TTBC J-Aggregates in Solution and on Surface
von Berlepsch, H., & Böttcher, C. (2013) · Langmuir · doi:10.1021/la400417d · Cited by 49 · see citing works
Self-citationSteering Self-Assembly of Amphiphilic Molecular Nanostructures via Halogen Exchange
Kriete, B., Bondarenko, A. S., Jumde, V. R., et al. (2017) · The Journal of Physical Chemistry Letters · doi:10.1021/acs.jpclett.7b00967 · Cited by 49 · see citing works
Lafleur, R. P. M., Lou, X., Pavan, G. M., et al. (2018) · Chemical Science · doi:10.1039/c8sc02257g · Cited by 48 · see citing works
Fluorinated Boron‐Dipyrromethene (BODIPY) Dyes: Bright and Versatile Probes for Surface Analysis
Hecht, M., Fischer, T., Dietrich, P., et al. (2013) · ChemistryOpen · doi:10.1002/open.201200039 · Cited by 47 · see citing works
Controlled Formation of the Two-Dimensional TTBC J-Aggregates in an Aqueous Solution
Birkan, B., Gülen, D., & Özçelik, S. (2006) · The Journal of Physical Chemistry B · doi:10.1021/jp0573846 · Cited by 46 · see citing works
Piwoński, H., Nozue, S., Fujita, H., Michinobu, T., & Habuchi, S. (2021) · Nano Letters · doi:10.1021/acs.nanolett.0c04928 · Cited by 45 · see citing works
Wood, S., Kim, J., Kim, J.-H., et al. (2015) · Chemistry of Materials · doi:10.1021/acs.chemmater.5b01503 · Cited by 44 · see citing works
Friedl, C., Renger, T., von Berlepsch, H., Ludwig, K., Busch, M. S. A., & Megow, J. (2016) · The Journal of Physical Chemistry C · doi:10.1021/acs.jpcc.6b05856 · Cited by 43 · see citing works
von Berlepsch, H., Kirstein, S., & Böttcher, C. (2004) · The Journal of Physical Chemistry B · doi:10.1021/jp046546f · Cited by 41 · see citing works
Self-citationExciton band structures in 2D aggregates of cyanine dyes
Kirstein, S., & Möhwald, H. (1995) · Advanced Materials · doi:10.1002/adma.19950070509 · Cited by 40 · see citing works
von Berlepsch, H., Thota, B. N. S., Wyszogrodzka, M., Carlo, S. D., Haag, R., & Böttcher, C. (2018) · Soft Matter · doi:10.1039/c8sm00243f · Cited by 36 · see citing works
Self-citationDeshmukh, A. P., Bailey, A., Forte, L., Shen, X., Geue, N., Sletten, E. M., & Caram, J. R. (2020) · The Journal of Physical Chemistry Letters · doi:10.1021/acs.jpclett.0c02204 · Cited by 32 · see citing works
von Berlepsch, H., Regenbrecht, M., Dähne, S., et al. (2002) · Langmuir · doi:10.1021/la011602e · Cited by 30 · see citing works
Mixtures of achiral amphiphilic cyanine dyes form helical tubular J-aggregates
von Berlepsch, H., Ludwig, K., Kirstein, S., & Böttcher, C. (2011) · Chemical Physics · doi:10.1016/j.chemphys.2011.04.027 · Cited by 27 · see citing works
Self-citationMolecular arrangement of the Davydov-split dye aggregates
Basko, D. M., Lobanov, A. N., Pimenov, A. V., & Vitukhnovsky, A. G. (2003) · Chemical Physics Letters · doi:10.1016/s0009-2614(02)02004-3 · Cited by 27 · see citing works
New Polyfluorinated Cyanine Dyes for Selective NIR Staining of Mitochondria
Braun, A. B., Wehl, I., Kölmel, D. K., et al. (2019) · Chemistry - A European Journal · doi:10.1002/chem.201900412 · Cited by 23 · see citing works
Pugzlys, A., Hania, P. R., Augulis, R., et al. (2006) · International Journal of Photoenergy · doi:10.1155/ijp/2006/29623 · Cited by 22 · see citing works
Structural characterization of supramolecular hollow nanotubes with atomistic simulations and SAXS
Patmanidis, I., de Vries, A. H., Wassenaar, T. A., Wang, W., Portale, G., & Marrink, . J. (2020) · Physical Chemistry Chemical Physics · doi:10.1039/d0cp03282d · Cited by 22 · see citing works
Ravily, V., Santaella, C., Vierling, P., et al. (1997) · Biochimica et Biophysica Acta (BBA) - Biomembranes · doi:10.1016/s0005-2736(96)00203-9 · Cited by 21 · see citing works
Buhler, E., Oelschlaeger, C., Waton, G., et al. (2006) · Langmuir · doi:10.1021/la0525832 · Cited by 21 · see citing works
Order Parameter Profile of Perfluorinated Chains in a Micelle
Furó, I., & Sitnikov, R. (1999) · Langmuir · doi:10.1021/la980576q · Cited by 21 · see citing works
von Berlepsch, H., & Böttcher, C. (2012) · WORLD SCIENTIFIC eBooks · doi:10.1142/9789814365796_0004 · Cited by 15 · see citing works
Self-citationIncreased laser action in commercial dyes from fluorination regardless of their skeleton
Durán‐Sampedro, G., Agarrabeitia, A. R., Lopez, T. A., Bañuelos, J., López‐Arbeloa, Í., Chiara, J. L., García‐Moreno, I., & Ortiz, M. J. (2014) · Laser Physics Letters · doi:10.1088/1612-2011/11/11/115818 · Cited by 13 · see citing works
Schade, B., Singh, A. K., Wycisk, V., Cuellar‐Camacho, J. L., von Berlepsch, H., Haag, R., & Böttcher, C. (2020) · Chemistry - A European Journal · doi:10.1002/chem.201905745 · Cited by 13 · see citing works
Self-citationFliri, L., Partl, G., Winkler, D., et al. (2020) · Dyes and Pigments · doi:10.1016/j.dyepig.2020.108798 · Cited by 9 · see citing works
Münchner Chemische Gesellschaft. Sitzung am 23. Januar 1936 in der Technischen Hochschule
Scheibe, G., & Hönigschmid, O. (1936) · Angewandte Chemie · doi:10.1002/ange.19360490804 · Cited by 4 · see citing works
Sutton, J. J., Li, Y., Ryu, H. S., et al. (2020) · The Journal of Physical Chemistry A · doi:10.1021/acs.jpca.0c05210 · Cited by 4 · see citing works
Training of Industrial Physicists
(1936) · Nature · doi:10.1038/1371009a0 · Cited by 1 · see citing works
Flagged first, then by citations
Cited by
Sorted by citations
Piwoński, H., Nozue, S., & Habuchi, S. (2022) · ACS Nanoscience Au · doi:10.1021/acsnanoscienceau.1c00038 · Cited by 39 · see citing works
- Authors
- Singh, A. K., Schade, B., Wycisk, V., Böttcher, C., Haag, R., & von Berlepsch, H.
- Affiliations
- Freie Universität Berlin (DE)
- Core Facility BioSupraMol, Institut für Chemie und Biochemie, Freie Universität Berlin, Fabeckstraße 36a, 14195 Berlin, Germany
- Corresponding author
- Haag, Rainer
- Venue
- The Journal of Physical Chemistry B
- Publisher
- American Chemical Society (ACS)
- Published
- 2021-09-10
- Volume
- 125
- Issue
- 37
- Pages
- 10538-10550
- ISSN
- 1520-5207 (ISSN-L)
- 1520-6106
- OpenAlex
- W3198327140
- Cited by
- 7
- References
- 69
- Citations by year
- 2026: 2 · 2025: 1 · 2024: 3 · 2022: 1
- FWCI
- 0.40
- Type
- journal article
- Language
- en
- Open access
- closed
- Licence
- Locations
- The Journal of Physical Chemistry B (publishedVersion)
- PubMed (publishedVersion)
- Funders
- Deutsche Forschungsgemeinschaft (BioSupraMol, BO 1000/11-1, HA 2549/18-1, SFB 1349 (TP C6 (387284271)))
- Topics
- Physical Sciences › Chemistry › Organic Chemistry › Surfactants and Colloidal Systems
- Physical Sciences › Chemistry › Physical and Theoretical Chemistry › Photochemistry and Electron Transfer Studies
- Physical Sciences › Materials Science › Biomaterials › Supramolecular Self-Assembly in Materials
- Keywords
- carbocyanine dyes, amphiphilic dyes, fluorinated alkyl chains, cylindrical micelles, J-aggregates, H-aggregates, cosolvent effects, methanol, supramolecular aggregation, excitonic coupling, dye self-assembly
- MeSH terms
- Carbocyanines, Micelles, Spectrometry, Fluorescence, Microscopy, Electron, Transmission, Halogenation
About these checks
Registry, retraction, Cites and statistics results are computed, not judged, with one exception: a printed reference that no index lists is read once by a model before it counts as a citation error. Claims are extracted by a model and kept only when their quote appears verbatim in the text; each cited source is then checked, with a model’s help, for whether it says what the claim relies on. Those verdicts can be wrong — read the claim’s quote and the cited source before relying on one.
Statistics and arithmetic are recomputed, not judged.
Confidence bands are shown only for fields calibrated on our annotated test set. None is calibrated yet, so no band is shown.
What counts as a claim ›How we measure confidence ›How we check this ›
Are you an author, or do you see a problem with this page? Request a review
