Student or educator? Sign up with your school email and get 6 months of Pro free.
CoChat
Sign Up
Cited by 224

The DOI matches its Crossref record; 2 of the 2 references it cites were found in a registry or an index.

Atomically precise organomimetic cluster nanomolecules assembled via perfluoroaryl-thiol SNAr chemistry

Open access
Qian, Elaine A., Wixtrom, Alex I., Axtell, Jonathan C., Saebi, Azin, Jung, Dahee, Rehak, Pavel, Han, Yanxiao, Moully, Elamar Hakim, Mosallaei, Daniel, Chow, Sylvia, Messina, Marco S., Wang, Jing Yang, Royappa, A. Timothy, Rheingold, Arnold L., Maynard, Heather D., Král, Petr, Spokoyny, Alexander M.·2017·Nature Chemistry
DOI 10.1038/nchem.2686
Open this paper in CoChat — free account

Abstract

The majority of biomolecules are intrinsically atomically precise, an important characteristic that enables rational engineering of their recognition and binding properties. However, imparting similar precision to hybrid nanoparticles has been challenging due to inherent limitations of the existing chemical methods and availability of properly designed functional building blocks. Here we report a new approach to form atomically precise and highly tunable hybrid nanomolecules with well-defined three-dimensionality. Perfunctionalization of atomically precise clusters with pentafluoroaryl-terminated linkers produces size-tunable rigid cluster nanomolecules. These species are amenable to facile modification with a variety of thiol-containing molecules and macromolecules. Assembly proceeds at room temperature within hours under mild conditions, and the resulting nanomolecules exhibit high stabilities due to their full covalency. We further demonstrate how these nanomolecules grafted with saccharides can exhibit dramatically improved binding affinity toward a protein. Ultimately, the developed strategy allows the rapid generation of precise molecular assemblies for investigating multivalent interactions.

Overview

The claims and statistics of this paper haven’t been checked yet.

Run the check — free, no account needed. It reads the open-access text and checks the sources it cites.

A few free checks a day · papers already verified open instantly · results are public

Integrity signals

Registry

Crossref · 10.1038/nchem.2686

Cites

2 of 2 references verified0 citation errors · 0 not checkable

Statistics

Verification

Claims the paper makes

The claims and statistics of this paper haven’t been checked yet.

Run the check — free, no account needed. It reads the open-access text and checks the sources it cites.

A few free checks a day · papers already verified open instantly · results are public

Self-check

Percentages, sums and reported differences re-computed from the paper’s own numbers.

The self-check needs the paper’s full text.

Citations

Cites

Show all 2 references

Research works printed but not linked: 53

  1. Mammen, M., Choi, S.-K. & Whitesides, G. M. Polyvalent interactions in biological systems: implications for design and use of multivalent ligands and inhibitors. Angew. Chem. Int. Ed. 37, 2754–2794 (1998). · DOI · Paper page
  2. Kiessling, L. L., Gestwicki, J. E. & Strong, L. E. Synthetic multivalent ligands as probes of signal transduction. Angew. Chem. Int. Ed. 45, 2348–2368 (2006). · DOI · Paper page
  3. Jones, L. H. Recent advances in the molecular design of synthetic vaccines. Nat. Chem. 7, 952–960 (2015). · DOI
  4. Rao, J. P. & Geckeler, K. E. Polymer nanoparticles: preparation techniques and size-control parameters. Prog. Polym. Sci. 36, 887–913 (2011). · DOI · Paper page
  5. Tomalia, D. A. et al. A new class of polymers: starburst-dendritic macromolecules. Polym. J. 17, 117–132 (1985). · DOI · Paper page
  6. Hawker, C. J. & Frechet, J. M. J. Preparation of polymers with controlled molecular architecture. A new convergent approach to dendritic macromolecules. J. Am. Chem. Soc. 112, 7638–7647 (1990). · DOI · Paper page
  7. Farokhzad, O. C. & Langer, R. Impact of nanotechnology on drug delivery. ACS Nano 3, 16–20 (2009). · DOI · Paper page
  8. Daniel, M.-C. & Astruc, D. Gold nanoparticles: assembly, supramolecular chemistry, quantum-size-related properties, and applications toward biology, catalysis, and nanotechnology. Chem. Rev. 104, 293–346 (2004). · DOI · Paper page
  9. Dreaden, E. C., Alkilany, A. M., Huang, X., Murphy, C. J. & El-Sayed, M. A. The golden age: gold nanoparticles for biomedicine. Chem. Soc. Rev. 41, 2740–2779 (2012). · DOI · Paper page
  10. Brust, M., Walker, M., Bethell, D., Schiffrin, D. J. & Whyman, R. Synthesis of thiol-derivatised gold nanoparticles in a two-phase liquid–liquid system. J. Chem. Soc., Chem. Commun. 801–802 (1994). · DOI · Paper page
  11. Giljohann, D. A. et al. Oligonucleotide loading determines cellular uptake of DNA-modified gold nanoparticles. Nano Lett. 7, 3818–3821 (2007). · DOI · Paper page
  12. Zhao, H. et al. Reversible trapping and reaction acceleration within dynamically self-assembling nanoflasks. Nat. Nanotech. 11, 82–88 (2016). · doi:10.1038/nnano.2015.256
  13. Jones, M. R., Seeman, N. C. & Mirkin, C. A. Programmable materials and the nature of the DNA bond. Science 347, 1260901 (2015). · DOI · Paper page
  14. Suzuki, K., Sato, S. & Fujita, M. Template synthesis of precisely monodisperse silica nanoparticles within self-assembled organometallic spheres. Nat. Chem. 2, 25–29 (2010). · DOI
  15. Heindl, C., Peresypkina, E. V., Virovets, A. V., Kremer, W. & Scheer, M. Giant rugby ball [{CpBnFe(η5-P5)}24Cu96Br96] derived from pentaphosphaferrocene and CuBr2 . J. Am. Chem. Soc. 137, 10938–10941 (2015). · DOI
  16. Ambrogio, M. W., Thomas, C. R., Zhao, Y.-L., Zink, J. I. & Stoddart, J. F. Mechanized silica nanoparticles: a new frontier in theranostic nanomedicine. Acc. Chem. Res. 44, 903–913 (2011). · DOI · Paper page
  17. Love, J. C., Estroff, L. A., Kriebel, J. K., Nuzzo, R. G. & Whitesides, G. M. Self-assembled monolayers of thiolates on metals as a form of nanotechnology. Chem. Rev. 105, 1103–1170 (2005). · DOI · Paper page
  18. Hostetler, M. J., Green, S. J., Stokes, J. J. & Murray, R. W. Monolayers in three dimensions: synthesis and electrochemistry of ω-functionalized alkanethiolate-stabilized gold cluster compounds. J. Am. Chem. Soc. 118, 4212–4213 (1996). · DOI · Paper page
  19. Hostetler, M. J., Templeton, A. C. & Murray, R. W. Dynamics of place-exchange reactions on monolayer-protected gold cluster molecules. Langmuir 15, 3782–3789 (1999). · DOI · Paper page
  20. MacLeod, M. J. & Johnson, J. A. PEGylated N-heterocyclic carbene anchors designed to stabilize gold nanoparticles in biologically relevant media. J. Am. Chem. Soc. 137, 7974–7977 (2015). · DOI · Paper page
  21. Häkkinen, H. The gold–sulfur interface at the nanoscale. Nat. Chem. 4, 443–455 (2012). · DOI · Paper page
  22. Yvon, C. et al. Polyoxometalate clusters integrated into peptide chains and as inorganic amino acids: solution- and solid-phase approaches. Angew. Chem. Int. Ed. 53, 3336–3341 (2014). · doi:10.1002/anie.201311135
  23. Lachkar, D., Vilona, D., Dumont, E., Lelli, M. & Lacôte, E. Grafting of secondary diolamides onto [P2W15V3O62]9− generates hybrid heteropoly acids. Angew. Chem. Int. Ed. 55, 5961–5965 (2016). · doi:10.1002/anie.201510954
  24. Gouzerh, P. & Proust, A. Main-group element, organic, and organometallic derivatives of polyoxometalates. Chem. Rev. 98, 77–112 (1998). · DOI
  25. Müller, A. & Gouzerh, P. From linking of metal–oxide building blocks in a dynamic library to giant clusters with unique properties and towards adaptive chemistry. Chem. Soc. Rev. 41, 7431–7463 (2012). · DOI · Paper page
  26. Li, G., Wang, L., Ni, H. & Pittman, C. U. Polyhedral oligomeric silsesquioxane (POSS) polymers and copolymers: a review. J. Inorg. Organomet. Polym. 11, 123–154 (2001). · DOI · Paper page
  27. Spokoyny, A. M. New ligand platforms featuring boron-rich clusters as organomimetic substituents. Pure Appl. Chem. 85, 903–919 (2013). · DOI · Paper page
  28. Lee, I. S., Long, J. R., Prusiner, S. B. & Safar, J. G. Selective precipitation of prions by polyoxometalate complexes. J. Am. Chem. Soc. 127, 13802–13803 (2005). · DOI
  29. Pitochelli, A. R. & Hawthorne, M. F. The isolation of the icosahedral B12H12−2 ion. J. Am. Chem. Soc. 82, 3228–3229 (1960). · doi:10.1021/ja01497a069
  30. Farha, O. K. et al.. Synthesis of stable dodecaalkoxy derivatives of hypercloso-B12H12 . J. Am. Chem. Soc. 127, 18243–18251 (2005). · DOI
  31. Jalisatgi, S. S. et al. A convenient route to diversely substituted icosahedral closomer nanoscaffolds. J. Am. Chem. Soc. 133, 12382–12385 (2011). · doi:10.1021/ja204488p
  32. Sarma, S. J., Khan, A. A., Goswami, L. N., Jalisatgi, S. S. & Hawthorne, M. F. A trimodal closomer drug-delivery system tailored with tracing and targeting capabilities. Chem. Eur. J. 22, 12715–12723 (2016). · DOI
  33. Wixtrom, A. I. et al. Rapid synthesis of redox-active dodecaborane B12(OR)12 clusters under ambient conditions. Inorg. Chem. Front. 3, 711–717 (2016). · doi:10.1039/c5qi00263j
  34. Messina, M. S. et al. Visible-light-induced olefin activation using 3D aromatic boron-rich cluster photooxidants. J. Am. Chem. Soc. 138, 6952–6955 (2016). · DOI
  35. Haynes, W. M. CRC Handbook of Chemistry and Physics (CRC/Taylor and Francis, 2016). · DOI · Paper page
  36. Lundquist, J. J. & Toone, E. J. The cluster glycoside effect. Chem. Rev. 102, 555–578 (2002). · DOI · Paper page
  37. Moore, J. S. & Xu, Z. Synthesis of rigid dendritic macromolecules: enlarging the repeat unit size as a function of generation, permitting growth to continue. Macromolecules 24, 5893–5894 (1991). · doi:10.1021/ma00021a030
  38. Birchall, J. M., Green, M., Haszeldine, R. N. & Pitts, A. D. The mechanism of the nucleophilic substitution reactions of polyfluoroarenes. Chem. Commun. Lond. 338–339 (1967). · doi:10.1039/c19670000338
  39. Becer, C. R., Hoogenboom, R. & Schubert, U. S. Click chemistry beyond metal-catalyzed cycloaddition. Angew. Chem. Int. Ed. 48, 4900–4908 (2009). · DOI · Paper page
  40. Becer, C. R. et al. Clicking pentafluorostyrene copolymers: synthesis, nanoprecipitation, and glycosylation. Macromolecules 42, 2387–2394 (2009). · DOI · Paper page
  41. Spokoyny, A. M. et al. A perfluoroaryl-cysteine SNAr chemistry approach to unprotected peptide stapling. J. Am. Chem. Soc. 135, 5946–5949 (2013). · DOI · Paper page
  42. Zhang, C. et al. π-Clamp-mediated cysteine conjugation. Nat. Chem. 8, 120–128 (2016). · DOI · Paper page
  43. Hoffman, A. S. The origins and evolution of ‘controlled’ drug delivery systems. J. Control. Release 132, 153–163 (2008). · DOI · Paper page
  44. Alconcel, S. N. S., Baas, A. S. & Maynard, H. D. FDA-approved poly(ethylene glycol)–protein conjugate drugs. Polym. Chem. 2, 1442–1448 (2011). · DOI · Paper page
  45. Veronese, F. M. & Pasut, G. PEGylation, successful approach to drug delivery. Drug Discov. Today 10, 1451–1458 (2005). · DOI · Paper page
  46. Dam, T. K., Roy, R., Das, S. K., Oscarson, S. & Brewer, C. F. Binding of multivalent carbohydrates to concanavalin A and Dioclea grandiflora lectin. Thermodynamic analysis of the ‘multivalency effect’. J. Biol. Chem. 275, 14223–14230 (2000). · DOI · Paper page
  47. Müller, C., Despras, G. & Lindhorst, T. K. Organizing multivalency in carbohydrate recognition. Chem. Soc. Rev. 45, 3275–3302 (2016). · DOI · Paper page
  48. Muñoz, A. et al. Synthesis of giant globular multivalent glycofullerenes as potent inhibitors in a model of Ebola virus infection. Nat. Chem. 8, 50–57 (2016). · doi:10.1038/nchem.2387
  49. Bhatia, S., Camacho, L. C. & Haag, R. Pathogen inhibition by multivalent ligand architectures. J. Am. Chem. Soc. 138, 8654–8666 (2016). · DOI · Paper page
  50. Bernardi, A. et al. Multivalent glycoconjugates as anti-pathogenic agents. Chem. Soc. Rev. 42, 4709–4727 (2013). · DOI · Paper page
  51. Munoz, E. M., Correa, J., Riguera, R. & Fernandez-Megia, E. Real-time evaluation of binding mechanisms in multivalent interactions: a surface plasmon resonance kinetic approach. J. Am. Chem. Soc. 135, 5966–5969 (2013). · DOI
  52. Fernandez-Megia, E., Correa, J., Rodríguez-Meizoso, I. & Riguera, R. A click approach to unprotected glycodendrimers. Macromolecules 39, 2113–2120 (2006). · DOI · Paper page
  53. Kamiya, N., Tominaga, M., Sato, S. & Fujita, M. Saccharide-coated M12L24 molecular spheres that form aggregates by multi-interaction with proteins. J. Am. Chem. Soc. 129, 3816–3817 (2007). · doi:10.1021/ja0693082

Cited by

See all 224

Metadata

Authors
Qian, E. A., Wixtrom, A. I., Axtell, J. C., Saebi, A., Jung, D., Rehak, P., Han, Y., Moully, E. H., Mosallaei, D., Chow, S., Messina, M. S., Wang, J. Y., Royappa, A. T., Rheingold, A. L., Maynard, H. D., Král, P., & Spokoyny, A. M.
Venue
Nature Chemistry
Publisher
Springer Science and Business Media LLC
Published
2016-12-19
Volume
9
Issue
4
Pages
333-340
ISSN
  • 1755-4330 (ISSN-L)
  • 1755-4349
DOI
10.1038/nchem.2686
OpenAlex
W2564079870
Cited by
224
References
2
FWCI
13.68
Type
journal article
Language
en
Open access
green
Licence
www.springer.com/tdm (tdm)

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

How to cite

Cite CoChat for the checks on this page, and the paper for its own findings.

This page
CoChat. (2026). Citation check: Atomically precise organomimetic cluster nanomolecules assembled via perfluoroaryl-thiol SNAr chemistry. https://app.cochat.ai/papers/10.1038/nchem.2686
The paper
Qian, E. A., Wixtrom, A. I., Axtell, J. C., Saebi, A., Jung, D., Rehak, P., Han, Y., Moully, E. H., Mosallaei, D., Chow, S., Messina, M. S., Wang, J. Y., Royappa, A. T., Rheingold, A. L., Maynard, H. D., Král, P., & Spokoyny, A. M. (2017). Atomically precise organomimetic cluster nanomolecules assembled via perfluoroaryl-thiol SNAr chemistry. Nature Chemistry. https://doi.org/10.1038/nchem.2686

Data sources

Bibliographic data: Semantic Scholar, OpenAlex, Crossref.

Contains information from the Semantic Scholar Academic Graph Datasets, made available under the ODC Attribution License (ODC-BY 1.0).

Semantic Scholar’s data is described in: Kinney, R., et al. (2023). The Semantic Scholar Open Data Platform. arXiv:2301.10140.