Artigo Revisado por pares

Responsive Cyclohexane‐Based Low‐Molecular‐Weight Hydrogelators with Modular Architecture

2004; Wiley; Volume: 116; Issue: 13 Linguagem: Inglês

10.1002/ange.200352396

ISSN

1521-3757

Autores

Kjeld J. C. van Bommel, Cornelia van der Pol, Inouk Muizebelt, Arianna Friggeri, André Heeres, Auke Meetsma, Ben L. Feringa, Jan H. van Esch,

Tópico(s)

Hydrogels: synthesis, properties, applications

Resumo

Angewandte ChemieVolume 116, Issue 13 p. 1695-1699 Zuschrift Responsive Cyclohexane-Based Low-Molecular-Weight Hydrogelators with Modular Architecture Kjeld J. C. van Bommel Dr., Kjeld J. C. van Bommel Dr. [email protected] BiOMaDe Technology Foundation, Nijenborgh 4, 9747 AG Groningen, The Netherlands, Fax: (+31) 503-634-429Search for more papers by this authorCornelia van der Pol, Cornelia van der Pol BiOMaDe Technology Foundation, Nijenborgh 4, 9747 AG Groningen, The Netherlands, Fax: (+31) 503-634-429Search for more papers by this authorInouk Muizebelt, Inouk Muizebelt BiOMaDe Technology Foundation, Nijenborgh 4, 9747 AG Groningen, The Netherlands, Fax: (+31) 503-634-429Search for more papers by this authorArianna Friggeri Dr., Arianna Friggeri Dr. BiOMaDe Technology Foundation, Nijenborgh 4, 9747 AG Groningen, The Netherlands, Fax: (+31) 503-634-429Search for more papers by this authorAndré Heeres Dr., André Heeres Dr. BiOMaDe Technology Foundation, Nijenborgh 4, 9747 AG Groningen, The Netherlands, Fax: (+31) 503-634-429Search for more papers by this authorAuke Meetsma, Auke Meetsma Crystal Structure Center, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The NetherlandsSearch for more papers by this authorBen L. Feringa Prof., Ben L. Feringa Prof. Department of Organic and Molecular Inorganic Chemistry, Stratingh Institute, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands, Fax: (+31) 503-634-296Search for more papers by this authorJan van Esch Dr., Jan van Esch Dr. [email protected] Department of Organic and Molecular Inorganic Chemistry, Stratingh Institute, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands, Fax: (+31) 503-634-296Search for more papers by this author Kjeld J. C. van Bommel Dr., Kjeld J. C. van Bommel Dr. [email protected] BiOMaDe Technology Foundation, Nijenborgh 4, 9747 AG Groningen, The Netherlands, Fax: (+31) 503-634-429Search for more papers by this authorCornelia van der Pol, Cornelia van der Pol BiOMaDe Technology Foundation, Nijenborgh 4, 9747 AG Groningen, The Netherlands, Fax: (+31) 503-634-429Search for more papers by this authorInouk Muizebelt, Inouk Muizebelt BiOMaDe Technology Foundation, Nijenborgh 4, 9747 AG Groningen, The Netherlands, Fax: (+31) 503-634-429Search for more papers by this authorArianna Friggeri Dr., Arianna Friggeri Dr. BiOMaDe Technology Foundation, Nijenborgh 4, 9747 AG Groningen, The Netherlands, Fax: (+31) 503-634-429Search for more papers by this authorAndré Heeres Dr., André Heeres Dr. BiOMaDe Technology Foundation, Nijenborgh 4, 9747 AG Groningen, The Netherlands, Fax: (+31) 503-634-429Search for more papers by this authorAuke Meetsma, Auke Meetsma Crystal Structure Center, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The NetherlandsSearch for more papers by this authorBen L. Feringa Prof., Ben L. Feringa Prof. Department of Organic and Molecular Inorganic Chemistry, Stratingh Institute, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands, Fax: (+31) 503-634-296Search for more papers by this authorJan van Esch Dr., Jan van Esch Dr. [email protected] Department of Organic and Molecular Inorganic Chemistry, Stratingh Institute, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands, Fax: (+31) 503-634-296Search for more papers by this author First published: 17 March 2004 https://doi.org/10.1002/ange.200352396Citations: 61Read the full textAboutPDF ToolsRequest permissionAdd to favorites ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat Graphical Abstract pH-empfindliche Gele: Durch Kupplung von Aminosäure-Substituenten an ein Cyclohexangerüst erhält man niedermolekulare Verbindungen, die in sehr niedrigen Konzentrationen Wasser gelieren. Ihr modularer Aufbau (siehe Bild; AA=Aminosäure(n), X=hydrophiler Substituent, hydrophobe Regionen violett, hydrophile Regionen rosa) ermöglicht die Abstimmung des thermisch und pH-induzierten Gel-Sol-Übergangs. Supporting Information Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2001/2004/z52396_s.pdf or from the author. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article. References 1For recent reviews see: Google Scholar 1aS. Deo, E. Moschou, S. Peteu, P. Eisenhardt, L. Bachas, M. Madou, S. Daunert, Anal. Chem. 2003, 75, 207A–213A; 10.1021/ac0313217 PubMedWeb of Science®Google Scholar 1bK. T. Nguyen, J. L. West, Biomaterials 2002, 23, 4307–4314; 10.1016/S0142-9612(02)00175-8 CASPubMedWeb of Science®Google Scholar 1cP. Gupta, K. Vermani, S. Garg, Drug Discov. Today 2002, 7, 569–579; 10.1016/S1359-6446(02)02255-9 CASPubMedWeb of Science®Google Scholar 1dN. A. Peppas, P. Bures, W. Leobandung, H. Ichikawa, Eur. J. Pharm. Biopharm. 2000, 50, 27–46. 10.1016/S0939-6411(00)00090-4 CASPubMedWeb of Science®Google Scholar 2 2aP. Terech, R. G. Weiss, Chem. Rev. 1997, 97, 3133–3159; 10.1021/cr9700282 CASPubMedWeb of Science®Google Scholar 2bD. J. Abdallah, R. G. Weiss, Adv. Mater. 2000, 12, 1237–1247; 10.1002/1521-4095(200009)12:17 3.0.CO;2-B CASWeb of Science®Google Scholar 2cJ. H. van Esch, B. L. Feringa, Angew. Chem. 2000, 112, 2351–2354; 10.1002/1521-3757(20000703)112:13 3.0.CO;2-2 Google ScholarAngew. Chem. Int. Ed. 2000, 39, 2263–2266; 10.1002/1521-3773(20000703)39:13 3.0.CO;2-V CASPubMedWeb of Science®Google Scholar 2dO. Gronwald, S. Shinkai, Chem. Eur. J. 2001, 7, 4328–4334; 10.1002/1521-3765(20011015)7:20 3.0.CO;2-S CASPubMedWeb of Science®Google Scholar 2eG. Mieden-Gundert, L. Klein, M. Fischer, F. Vögtle, K. Heuzé, J. L. Pozzo, M. Vallier, F. Fages, Angew. Chem. 2001, 113, 3266–3267; 10.1002/1521-3757(20010903)113:17 3.0.CO;2-W Google ScholarAngew. Chem. Int. Ed. 2001, 40, 3164–3166. 10.1002/1521-3773(20010903)40:17 3.0.CO;2-B CASWeb of Science®Google Scholar 3Previously published hydrogelators: Google Scholar 3aG. R. Newkome, G. R. Baker, S. Arai, M. J. Saunders, P. S. Russo, K. J. Theriot, C. N. Moorefield, L. E. Rogers, J. E. Miller, T. R. Lieux, M. E. Murray, B. Phillips, L. Pascal, J. Am. Chem. Soc. 1990, 112, 8458–8465; 10.1021/ja00179a034 CASWeb of Science®Google Scholar 3bJ.-H. Fuhrhop, W. Helfrich, Chem. Rev. 1993, 93, 1565–1582; 10.1021/cr00020a008 CASWeb of Science®Google Scholar 3cM. Jokić, J. Makarević, M. Žinić, J. Chem. Soc. Chem. Commun. 1995, 1723–1724; 10.1039/C39950001723 Web of Science®Google Scholar 3dT. Shimizu, M. Masuda, J. Am. Chem. Soc. 1997, 119, 2812–2818; 10.1021/ja961226y CASWeb of Science®Google Scholar 3eR. Oda, I. Huc, S. J. Candau, Angew. Chem. 1998, 110, 2835–2838; 10.1002/(SICI)1521-3757(19981002)110:19 3.0.CO;2-R Google ScholarAngew. Chem. Int. Ed. 1998, 37, 2689–2691; 10.1002/(SICI)1521-3773(19981016)37:19 3.0.CO;2-Z CASPubMedWeb of Science®Google Scholar 3fF. M. Menger, K. L. Caran, J. Am. Chem. Soc. 2000, 122, 11 679–11 691; 10.1021/ja0016811 CASWeb of Science®Google Scholar 3gL. A. Estroff, A. D. Hamilton, Angew. Chem. 2000, 112, 3589–3592; 10.1002/1521-3757(20001002)112:19 3.0.CO;2-P Google ScholarAngew. Chem. Int. Ed. 2000, 39, 3447–3450; 10.1002/1521-3773(20001002)39:19 3.0.CO;2-X CASPubMedWeb of Science®Google Scholar 3hK. Hanabusa, T. Hirata, D. Inoue, I. Kimura, H. Shirai, Colloids Surf. A 2000, 169, 307–315; 10.1016/S0927-7757(00)00445-3 CASWeb of Science®Google Scholar 3iU. Maitra, S. Mukhopadhyay, A. Sarkar, P. Rao, S. S. Indi, Angew. Chem. 2001, 113, 2341–2343; 10.1002/1521-3757(20010618)113:12 3.0.CO;2-N Google ScholarAngew. Chem. Int. Ed. 2001, 40, 2281–2283; 10.1002/1521-3773(20010618)40:12 3.0.CO;2-L CASPubMedWeb of Science®Google Scholar 3jC. Marmillon, F. Gauffre, T. Gulik-Krzywicki, C. Loup, A. M. Caminade, J. P. Majoral, J. P. Vors, E. Rump, Angew. Chem. 2001, 113, 2696–2699; 10.1002/1521-3757(20010716)113:14 3.0.CO;2-3 Google ScholarAngew. Chem. Int. Ed. 2001, 40, 2626–2629; 10.1002/1521-3773(20010716)40:14 3.0.CO;2-F CASPubMedWeb of Science®Google Scholar 3khydrogel with the lowest LMWG concentration reported to date: 0.65 mM H. Kobayashi, A. Friggeri, K. Koumoto, M. Amaike, S. Shinkai, D. N. Reinhoudt, Org. Lett. 2002, 4, 1423–1426; 10.1021/ol025519+ CASPubMedWeb of Science®Google Scholar 3lF. M. Menger, A. V. Peresypkin, J. Am. Chem. Soc. 2003, 125, 5340–5345. 10.1021/ja021298r CASPubMedWeb of Science®Google Scholar 4Only two pH-reversible LMWG systems have been described, however, in both cases only acidic gelators were reported: Google Scholar 4aJ. D. Hartgerink, E. Beniash, S. I. Stupp, Science 2001, 294, 1684–1688; 10.1126/science.1063187 CASPubMedWeb of Science®Google Scholar 4bS. R. Haines, R. G. Harrison, Chem. Commun. 2002, 2846–2847. 10.1039/b203462j CASPubMedWeb of Science®Google Scholar 5J. C. Tiller, Angew. Chem. 2003, 115, 3180–3183; 10.1002/ange.200301647 Google ScholarAngew. Chem. Int. Ed. 2003, 42, 3072–3075. 10.1002/anie.200301647 CASPubMedWeb of Science®Google Scholar 6Patent applications K. J. C. van Bommel, J. H. van Esch, M. de Loos, A. Heeres, B. L. Feringa, Applied Nanosystems BV, Groningen (the Netherlands), 2002, WO 03/097587 and Google ScholarR. H. E. Friesen, C. J. Leenhouts, G. T. Robillard, H. J. Hektor, A. H. Heeres, J. H. van Esch, Applied Nanosystems BV, Groningen (the Netherlands), 2002, WO 03/084508. Google Scholar 7 7aK. Hanabusa, A. Kawakami, M. Kimura, H. Shirai, Chem. Lett. 1997, 191–192; 10.1246/cl.1997.191 CASWeb of Science®Google Scholar 7bE. K. Fan, J. Yang, S. J. Geib, T. C. Stoner, M. D. Hopkins, A. D. Hamilton, J. Chem. Soc. Chem. Commun. 1995, 1251–1252; 10.1039/c39950001251 CASWeb of Science®Google Scholar 7cJ. J. van Gorp, J. A. J. M. Vekemans, E. W. Meijer, J. Am. Chem. Soc. 2002, 124, 14 759–14 769. 10.1021/ja020984n CASWeb of Science®Google Scholar 8D. J. Hill, M. J. Mio, R. B. Prince, T. S. Hughes, J. S. Moore, Chem. Rev. 2001, 101, 3893–4011, and references therein. 10.1021/cr990120t CASPubMedWeb of Science®Google Scholar 9For details on the synthesis of 1–8, see Supporting Information. Google Scholar 10Analogous to: A. Friggeri, O. Gronwald, K. J. C. van Bommel, S. Shinkai, D. N. Reinhoudt, Chem. Commun. 2001, 2434–2435. 10.1039/b108148a CASPubMedWeb of Science®Google Scholar 11L. J. Bellamy, The Infra-Red Spectra of Complex Molecules, Richard Clay and company Ltd., Bungay, Suffolk, UK, 1962. Google Scholar 12To obtain a more correct value for the critical gelation concentration (CGC), this value was determined in 1 n HCl, rather than pure water, thus minimizing the amount of deprotonated gelator which does not contribute to gelation. Google Scholar 13Firm gels could be made not only in water, but also in physiological saline solutions, demonstrating the salt tolerance of our hydrogelators. Google Scholar 14An X-ray crystal structure of a trifunctionalized cyclohexane showing a similar stacking has been reported: ref [7b]. Google Scholar 15Supplementary crystallographic data for this paper are available from the IUCr electronic archives. CCDC-214940 (9) contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or [email protected]). Google Scholar 16Gels were obtained at concentrations lower than shown in Figure 4, however, they were not strong enough to support the weight of the metal balls used for the determination of the Tgs values. Therefore, no Tgs values could be obtained for these gel samples. Google Scholar 17Ka values of similar, nongelating compounds: Google Scholar 17aP. Vallat, P. Gaillard, P.-A. Carrupt, R-.S. Tsai, B. Testa, Helv. Chim. Acta 1995, 78, 471–485; 10.1002/hlca.19950780218 CASWeb of Science®Google Scholar 17bG. N. Mukherjee, S. Sarkar, Indian J. Chem, Sect. A 1988, 27, 514–518. Web of Science®Google Scholar 18As the distances between the carboxylic acid (1, 2) or imidazole (5, 6) moieties within a single molecule are relatively large and no conjugation is present, the dissociation behavior of the acids or bases is assumed to be independent of one another; hence single pKa values were taken for all three acid or base moieties. Google Scholar 19Cognate behavior has been observed for micelle and monolayer systems: Google Scholar 19aO. Träger, S. Sowade, C. Böttcher, J.-H. Fuhrhop, J. Am. Chem. Soc. 1997, 119, 9120–9124; 10.1021/ja971803y Web of Science®Google Scholar 19bK. Aoki, T. Kakiuchi, J. Electroanal. Chem. 1999, 478, 101–107; 10.1016/S0022-0728(99)00419-2 CASWeb of Science®Google Scholar 19cH. Wang, X. Zhao, K. B. Eisenthal, J. Phys. Chem. B 2000, 104, 8855–8861; 10.1021/jp0018091 CASWeb of Science®Google Scholar 19dH. Munakata, S. Kuwabata, Chem. Commun. 2001, 1338–1339, and references therein. 10.1039/b102601c CASWeb of Science®Google Scholar 20A pKa value of 6.0 was used for the imidazole moieties.[18] For both gelators the concentrations of neutral gelator g corresponding to each point in the graph matched the CGC of the gelators (11.75 mM for 5 and 4.72 mM for 6, Table 1) quite well, as values ranged from 11.2 to 12.5 mM and from 4.3 to 5.1 mM for 5 and 6, respectively. Google Scholar 21The results of these studies will be published elsewhere. Google Scholar 22For possible application of such systems see: A. Heeres, C. van der Pol, M. Stuart, A. Friggeri, B. L. Feringa, J. van Esch, J. Am. Chem. Soc. 2003, 125, 14 252–14 253. 10.1021/ja036954h CASWeb of Science®Google Scholar Citing Literature Volume116, Issue13March 19, 2004Pages 1695-1699 This is the German version of Angewandte Chemie. Note for articles published since 1962: Do not cite this version alone. Take me to the International Edition version with citable page numbers, DOI, and citation export. We apologize for the inconvenience. ReferencesRelatedInformation

Referência(s)
Altmetric
PlumX