Wikipedia

Draft:Donor-acceptor Stenhouse Adducts


Donor-acceptor Stenhouse adducts (DASAs) were first reported as a class of photoswitching molecules by Helmy et al. in 2014.[1] Unlike many other photoswitches which respond to light in the infrared or ultraviolet parts of the spectrum, they respond to visible light.[2] This means they are well suited for uses where visible light is preferable over other wavelengths, for example in biomedical settings where UV light can have cytotoxic effects.

Chemical structure showing equilibrium between the “open” and the polar, hydrophilic, and colourless “closed” form of first-generation DASAs.
Photoswitching in first generation DASAs. The “open” form (left) is favored under dark equilibrium, whereas colorless “closed” form is favored upon irradiation with visible light.

DASA Photoswitching

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Upon irradiation, a 4π-electrocyclisation reaction causes them to switch from their "open", linear triene-enol form to their "closed" cyclopentenone form. Thermal relaxation can cause reversion of this transition, returning the DASA to its original "open" conformation. These processes are in constant equilibrium, hence, the dark-equilibrium position of a DASA lies towards the “open” form, whereas the photostationary state lies towards the “closed” form.

DASAs are negative photochromes, meaning they become colorless upon photoswitching.[1] Photoswitching also drives an increase in polarity[3] and releases energy as heat.[4]

Applications and Uses

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While their translation into products is still in its early stages, DASAs hold promise across many diverse applications. Promising research includes their use in chemical sensing,[5][6][7][8] incorporation into hydrogels for drug delivery,[9] cryptography,[10][11][12] rewritable data storage,[13] actuation of soft materials,[14][15] and design of nanoreactors and cell mimics.[16]

References

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  1. 1 2 Helmy, Sameh (2014-11-12). "Design and Synthesis of Donor–Acceptor Stenhouse Adducts: A Visible Light Photoswitch Derived from Furfural". The Journal of Organic Chemistry. 79 (23): 11316–11329. Bibcode:2014JOrgC..7911316H. doi:10.1021/jo502206g. PMID 25390619.
  2. ↑ Clerc, Michèle; Sandlass, Sara; Rifaie-Graham, Omar; Peterson, Julie A.; Bruns, Nico; Alaniz, Javier Read de; Boesel, Luciano F. (2023-11-27). "Visible light-responsive materials: the (photo)chemistry and applications of donor–acceptor Stenhouse adducts in polymer science". Chemical Society Reviews. 52 (23): 8245–8294. doi:10.1039/D3CS00508A. ISSN 1460-4744. PMC 10680135. PMID 37905554.
  3. ↑ Sinawang, Garry; Wu, Bing; Wang, Jilei; Li, Shang; He, Yaning (2016-08-22). "Polystyrene Based Visible Light Responsive Polymer with Donor-Acceptor Stenhouse Adduct Pendants". Macromolecular Chemistry and Physics. 217 (21): 2409–2414. doi:10.1002/macp.201600351.
  4. ↑ Seshadri, Serena; Gockowski, Luke F.; Lee, Jaejun; Sroda, Miranda; Helgeson, Matthew E.; Read de Alaniz, Javier; Valentine, Megan T. (2020-05-25). "Self-regulating photochemical Rayleigh-Bénard convection using a highly-absorbing organic photoswitch". Nature Communications. 11 (1): 2599. Bibcode:2020NatCo..11.2599S. doi:10.1038/s41467-020-16277-7. ISSN 2041-1723. PMC 7248117. PMID 32451397.
  5. ↑ Balamurugan, A.; Lee, Hyung-il (2016-03-23). "A Visible Light Responsive On–Off Polymeric Photoswitch for the Colorimetric Detection of Nerve Agent Mimics in Solution and in the Vapor Phase". Macromolecules. 49 (7): 2568–2574. Bibcode:2016MaMol..49.2568B. doi:10.1021/acs.macromol.6b00309. ISSN 0024-9297.
  6. ↑ Cai, You-De; Chen, Tian-Yang; Chen, Xiu Qin; Bao, Xin (2019-09-10). "Multiresponsive Donor–Acceptor Stenhouse Adduct: Opportunities Arise from a Diamine Donor". Organic Letters. 21 (18): 7445–7449. doi:10.1021/acs.orglett.9b02753. ISSN 1523-7060. PMID 31502465.
  7. ↑ Ling, Yao; Dong, Yu; Huang, Wei; Liu, Jie; Feng, Shiyu; Huang, Weiguo (2022-08-20). "Orthogonally Responsive Donor–Acceptor Stenhouse Adduct/Poly(2-ethylsulfonyl-2-oxazoline) Colorimetric Sensors with Nonvolatile Memories". Applied Polymer Materials. 4 (9): 6505–6513. Bibcode:2022AAPM....4.6505L. doi:10.1021/acsapm.2c00915.
  8. ↑ Zhong, Dan; Cao, Ziquan; Wu, Bo; Zhang, Qing; Wang, Guojie (2017-07-14). "Polymer dots of DASA-functionalized polyethyleneimine: Synthesis, visible light/pH responsiveness, and their applications as chemosensors". Sensors and Actuators B: Chemical. 254: 385–392. doi:10.1016/j.snb.2017.07.107. ISSN 0925-4005.
  9. ↑ Dell, Tristan N.; Cammack-Najera, Ana; Tresa, Rea; Matubbar, Farzina; Kaya, Beyzanur; Lathan, Uthaya; Chami, Mohamed; DiNardi, Ray G.; Rifaie-Graham, Omar; Wojciechowski, Jonathan P.; Stevens, Molly M. (2026-01-31). "Hydrogels Incorporating Donor–Acceptor Stenhouse Adducts as a Platform for Photoinduced, On-Off Switchable Release of Small Molecule Cargos". Macromolecular Rapid Communications. 47 (8) e00868. doi:10.1002/marc.202500868. ISSN 1022-1336. PMC 13087835. PMID 41619178.
  10. ↑ Dong, Yu; Ling, Yao; Wang, Donghui; Liu, Yang; Chen, Xiaowei; Zheng, Shiya; Wu, Xiaosong; Shen, Jinghui; Feng, Shiyu; Zhang, Jianyuan; Huang, Weiguo (2022-11-04). "Harnessing molecular isomerization in polymer gels for sequential logic encryption and anticounterfeiting". Science Advances. 8 (44) eadd1980. Bibcode:2022SciA....8D1980D. doi:10.1126/sciadv.add1980. ISSN 2375-2548. PMC 9629717. PMID 36322650.
  11. ↑ Mao, Lijun; Wang, Zhen; Duan, Yongli; Xiong, Chaoyue; He, Chao; Deng, Xu; Zheng, Yonghao; Wang, Dongsheng (2021-05-26). "Designing of Rewritable Paper by Hydrochromic Donor–Acceptor Stenhouse Adducts". ACS Nano. 15 (6): 10384–10392. Bibcode:2021ACSNa..1510384M. doi:10.1021/acsnano.1c02629. ISSN 1936-0851. PMID 34036790.
  12. ↑ Xiong, Xiaoyu; Sun, Fanxi; Gao, Ang; Wang, Zhen; Duan, Yongli; Yao, Zhangjun; He, Chao; Han, Rui; Deng, Xu; Zheng, Yonghao; Wang, Dongsheng (2022-12-15). "Ester matters? Promoting photoisomerization of donor–acceptor Stenhouse adducts in the solid state and "burn after reading" encryption". Chemical Engineering Journal. 450 138090. Bibcode:2022ChEnJ.45038090X. doi:10.1016/j.cej.2022.138090. ISSN 1385-8947.
  13. ↑ Ulrich, Sebastian; Hemmer, James R.; Page, Zachariah A.; Dolinski, Neil D.; Rifaie-Graham, Omar; Bruns, Nico; Hawker, Craig J.; Boesel, Luciano F.; Read de Alaniz, Javier (2017-06-23). "Visible Light-Responsive DASA-Polymer Conjugates". ACS Macro Letters. 6 (7): 738–742. doi:10.1021/acsmacrolett.7b00350. ISSN 2161-1653. PMID 35650854.
  14. ↑ Sroda, Miranda M.; Lee, Jaejun; Kwon, Younghoon; Stricker, Friedrich; Park, Minwook; Valentine, Megan T.; Read de Alaniz, Javier (2022-01-05). "Role of Material Composition in Photothermal Actuation of DASA-Based Polymers". ACS Applied Polymer Materials. 4 (1): 141–149. Bibcode:2022AAPM....4..141S. doi:10.1021/acsapm.1c01108. ISSN 2637-6105.
  15. ↑ Lee, Jaejun; Sroda, Miranda M.; Kwon, Younghoon; El-Arid, Sara; Seshadri, Serena; Gockowski, Luke F.; Hawkes, Elliot W.; Valentine, Megan T.; Read de Alaniz, Javier (2020-11-19). "Tunable Photothermal Actuation Enabled by Photoswitching of Donor–Acceptor Stenhouse Adducts". ACS Applied Materials & Interfaces. 12 (48): 54075–54082. Bibcode:2020AAMI...1254075L. doi:10.1021/acsami.0c15116. ISSN 1944-8244. PMID 33210539.
  16. ↑ Rifaie-Graham, Omar; Yeow, Jonathan; Najer, Adrian; Wang, Richard; Sun, Rujie; Zhou, Kun; Dell, Tristan N.; Adrianus, Christopher; Thanapongpibul, Chalaisorn; Chami, Mohamed; Mann, Stephen; de Alaniz, Javier Read; Stevens, Molly M. (2022-11-07). "Photoswitchable gating of non-equilibrium enzymatic feedback in chemically communicating polymersome nanoreactors". Nature Chemistry. 15 (1): 110–118. doi:10.1038/s41557-022-01062-4. ISSN 1755-4330. PMC 9836937. PMID 36344820.
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