organic synthesis; naphthalenediimides; supramolecular functional systems; surface-initiated polymerization; anion-pi interactions; halogen bonds; cellular uptake; artificial photosynthesis; oligothiophenes; fluorescent membrane probes
Jentzsch Andreas Vargas, Matile Stefan (2015), Anion Transport with Halogen Bonds, in HALOGEN BONDING I: IMPACT ON MATERIALS CHEMISTRY AND LIFE SCIENCES
Zhao Yingjie, Cotelle Yoann, Avestro Alyssa-Jennifer, Sakai Naomi, Matile Stefan (2015), Asymmetric Anion-pi Catalysis: Enamine Addition to Nitroolefins on pi-Acidic Surfaces, in JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
, 138(36), 11582-11585.
Zhao Yingjie, Huang Guangxi, Besnard Celine, Mareda Jiri, Sakai Naomi, Matile Stefan (2015), Big, Strong, Neutral, Twisted, and Chiral pi Acids, in CHEMISTRY-A EUROPEAN JOURNAL
, 21(16), 6202-6207.
Chuard Nicolas, Gasparini Giulio, Roux Aurelien, Sakai Naomi, Matile Stefan (2015), Cell-penetrating poly(disulfide)s: the dependence of activity, depolymerization kinetics and intracellular localization on their length, in ORGANIC & BIOMOLECULAR CHEMISTRY
, 13(1), 64-67.
Gasparini Giulio, Bang Eun-Kyoung, Montenegro Javier, Matile Stefan (2015), Cellular uptake: lessons from supramolecular organic chemistry, in CHEMICAL COMMUNICATIONS
, 51(52), 10389-10402.
Zhang Kang-Da, Sakai Naomi, Matile Stefan (2015), Colorful surface architectures with three different types of dynamic covalent bonds: integration of anthocyanins, tritylium ions and flavins, in ORGANIC & BIOMOLECULAR CHEMISTRY
, 13(32), 8687-8694.
Yushchenko Oleksandr, Villamaina Diego, Sakai Naomi, Matile Stefan, Vauthey Eric (2015), Comparison of Charge-Transfer Dynamics of Naphthalenediimide Triads in Solution and pi-Stack Architectures on Solid Surfaces, in JOURNAL OF PHYSICAL CHEMISTRY C
, 119(27), 14999-15008.
Zhang Kang-Da, Matile Stefan (2015), Complex Functional Systems with Three Different Types of Dynamic Covalent Bonds, in ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
, 54(31), 8980-8983.
Miros Francois N., Huang Guangxi, Zhao Yingjie, Sakai Naomi, Matile Stefan (2015), Coumarin synthesis on pi-acidic surfaces, in SUPRAMOLECULAR CHEMISTRY
, 27(5-6), 303-309.
Verolet Quentin, Soleimanpour Saeideh, Fujisawa Kaori, Dal Molin Marta, Sakai Naomi, Matile Stefan (2015), Design and Synthesis of Mixed Oligomers with Thiophenes, Dithienothiophene S,S-Dioxides, Thieno[3,4]pyrazines and 2,1,3-Benzothiadiazoles: Flipper Screening for Mechanosensitive Systems, in CHEMISTRYOPEN
, 4(3), 264-267.
Lopez-Andarias Javier, Bolag Altan, Nancoz Christoph, Vauthey Eric, Atienza Carmen, Sakai Naomi, Martin Nazario, Matile Stefan (2015), Electron-deficient fullerenes in triple-channel photosystems, in CHEMICAL COMMUNICATIONS
, 51(35), 7543-7545.
Dal Molin Marta, Verolet Quentin, Colom Adai, Letrun Romain, Derivery Emmanuel, Gonzalez-Gaitan Marcos, Vauthey Eric, Roux Aurelien, Sakai Naomi, Matile Stefan (2015), Fluorescent Flippers for Mechanosensitive Membrane Probes, in JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
, 137(2), 568-571.
Fujisawa Kaori, Humbert-Droz Marie, Letrun Romain, Vauthey Eric, Wesolowski Tomasz A., Sakai Naomi, Matile Stefan (2015), Ion Pair-pi Interactions, in JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
, 137(34), 11047-11056.
Dal Molin Marta, Verolet Quentin, Soleimanpour Saeideh, Matile Stefan (2015), Mechanosensitive Membrane Probes, in CHEMISTRY-A EUROPEAN JOURNAL
, 21(16), 6012-6021.
Gasparini Giulio, Sargsyan Gevorg, Bang Eun-Kyoung, Sakai Naomi, Matile Stefan (2015), Ring Tension Applied to Thiol-Mediated Cellular Uptake, in ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
, 54(25), 7328-7331.
Zhao Yingjie, Benz Sebastian, Sakai Naomi, Matile Stefan (2015), Selective Acceleration of Disfavored Enolate Addition Reactions by Anion-π Interactions, in Chem. Sci.
, 6(11), 6219-6223.
Yushchenko Oleksandr, Licari Giuseppe, Mosquera-Vazquez Sandra, Sakai Naomi, Matile Stefan, Vauthey Eric (2015), Ultrafast Intersystem-Crossing Dynamics and Breakdown of the Kasha-Vavilov's Rule of Naphthalenediimides, in JOURNAL OF PHYSICAL CHEMISTRY LETTERS
, 6(11), 2096-2100.
Bolag Altan, Lopez-Andarias Javier, Lascano Santiago, Soleimanpour Saeideh, Atienza Carmen, Sakai Naomi, Martin Nazario, Matile Stefan (2014), A Collection of Fullerenes for Synthetic Access Toward Oriented Charge-Transfer Cascades in Triple-Channel Photosystems, in ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
, (19), 4890-4895.
Fujisawa Kaori, Beuchat Cesar, Humbert-Droz Marie, Wilson Adam, Wesolowski Tomasz A., Mareda Jiri, Sakai Naomi, Matile Stefan (2014), Anion-pi and Cation-pi Interactions on the Same Surface, in ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
, (42), 11266-11269.
Zhao Yingjie, Beuchat Cesar, Domoto Yuya, Gajewy Jadwiga, Wilson Adam, Mareda Jiri, Sakai Naomi, Matile Stefan (2014), Anion-pi Catalysis, in JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
, 136(5), 2101-2111.
Hayashi Hironobu, Sobczuk Adam, Bolag Altan, Sakai Naomi, Matile Stefan (2014), Antiparallel Three-Component Gradients in Double-Channel Surface Architectures, in Chem. Sci.
, 5(12), 4610-4614.
Bang Eun-Kyoung, Ward Sandra, Gasparini Giulio, Sakai Naomi, Matile Stefan (2014), Cell-penetrating poly(disulfide)s: focus on substrate-initiated co-polymerization, in POLYMER CHEMISTRY
, 5(7), 2433-2441.
Gasparini Giulio, Bang Eun-Kyoung, Molinard Guillaume, Tulumello David V., Ward Sandra, Kelley Shana O., Roux Aurelien, Sakai Naomi, Matile Stefan (2014), Cellular Uptake of Substrate-Initiated Cell-Penetrating Poly(disulfide)s, in JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
, 136(16), 6069-6074.
Zhao Yingjie, Sakai Naomi, Matile Stefan (2014), Enolate chemistry with anion-pi interactions, in NATURE COMMUNICATIONS
, 5(1), 3911-1-3911-5.
Wilson Adam, Gasparini Giulio, Matile Stefan (2014), Functional systems with orthogonal dynamic covalent bonds, in CHEMICAL SOCIETY REVIEWS
, 43(6), 1948-1962.
Sakai Naomi, Charbonnaz Pierre, Ward Sandra, Matile Stefan (2014), Ion-Gated Synthetic Photosystems, in JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
, 136(15), 5575-5578.
Alonso Doval David, Dal Molin Marta, Ward Sandra, Fin Andrea, Sakai Naomi, Matile stefan (2014), Planarizable Push-Pull Probes: In Search of the Perfect Twist, in Chem. Sci.
, 5(7), 2819-2825.
Charbonnaz Pierre, Zhao Yingjie, Turdean Raluca, Lascano Santiago, Sakai Naomi, Matile Stefan (2014), Surface Architectures Built around Perylenediimide Stacks, in CHEMISTRY-A EUROPEAN JOURNAL
, 20(51), 17143-17151.
Vargas Jentzsch Andreas, Hennig Andreas, Mareda Jiri, Matile Stefan (2013), Synthetic Ion Transporters that Work with Anion-π Interactions, Halogen Bonds and Anion-Macrodipole Interactions, in Acc. Chem. Res.
, 46(12), 2791-2800.
Matile Stefan, Fyles Tom (2013), Transport across membranes, in Accounts of Chemical Research
, 46(12), 2741-2742.
The general objective of this proposal is to develop conceptually innovative approaches to functional biosupramolecular systems for use in materials sciences, chemical sciences and life sciences. The specific aims are(a) to develop new synthetic methods to create supramolecular functional architectures, as sophisticated as possible, directly on solid surfaces (e.g., double- and triple-channel architectures with antiparallel, counterion-assisted gradients composed of up to four components, as in nature),(b) to discover new interactions for the creation of function (e.g., anion-p interactions and halogen bonds for transport and catalysis), and(c) to establish substrate-initiated synthesis of cell-penetrating poly(disulfide)s for the cellular uptake of unmodified probes and drugs in covalent form, and planarizable push-pull oligothiophenes as fluorescent membrane probes.In specific aim a, synthetic organic chemistry is applied to a central challenge in the materials sciences. In nature, function is accomplished by supramolecular architectures of highest sophistication. No one knows what we would obtain if we could create complexity with similar precision because the synthetic methods to do so do not exist. To help changing this situation, efforts to learn how to grow multicomponent photosystems directly on solid surfaces will be continued. As an example, photosystems with 2-3 channels comprising antiparallel, counterion-assisted 2-4-component gradients will be built with oligothiophenes and fullerenes, the two key components of today’s organic solar cells. The concepts and synthetic methods developed during this grant period are expected to help building the organic materials of the future.In specific aim b, lessons from ion transport are used to expand the interactions available to create function, a truly fundamental effort, far beyond biomimicry, comparable to increasing the number of letters available to write, or notes to make music. Emphasis during this grant period is on the use anion-p interactions for catalysis, for the very first time. The plan is to move from classical test reactions (Kemp elimination) to more adventurous substitution on carbonyls and enolate chemistry (would be relevant to polyketide biosynthesis as carbocation stabilization by the complementary cation-p interactions is in terpenoid cyclizations). New interactions for catalysis would have a huge impact in the chemical sciences.In specific aim c, synthetic organic chemistry is applied to tackle two current challenges in the life sciences. Lessons from 1) surface-initiated disulfide exchange polymerization (specific aim a) and 2) transport with halogen bonds (specific aim b) will be applied to achieve the covalent uptake of unmodified probes and drugs into cells. Substrate-initiated cell-penetrating poly(disulfide)s have all it takes to become the delivery system of the future. Impact in biology and medicine could be significant, but step-by-step development of the transporters will need time and fruitful collaborations (in the context of the NCCR Chemical Biology). Planarizable push-pull probes apply a demanding concept from nature (chemistry of vision, lobster pigmentation) to the development of innovative fluorescent membrane probes. With prove-of-principle in hand, the deplanarization of push-pull oligothiophenes will be studied systematically. Although of more fundamental importance at this point, the approach promises contributions to tackle significant current challenges such as the imaging of membrane tension or, perhaps, neural activity.All projects use target-oriented multistep organic synthesis with intertopical crossfertilization. This demanding approach provides the perfect educational environment to form ambitious, broad-minded scientists. As far as significance and probability of success are concerned, it can be said that recent research from this group has appeared regularly in top journals (3 Science, 32 JACS, etc) and in the media (Le Temps, Tribune de Genève, Blick, Science, CEN, Chemistry World, Nature Chemistry, Chimia, etc). Continuation on this level is expected.