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Synthetic Biosupramolecular Systems at Work

English title Synthetic Biosupramolecular Systems at Work
Applicant Matile Stefan
Number 150000
Funding scheme Project funding
Research institution Département de Chimie Organique Université de Genève
Institution of higher education University of Geneva - GE
Main discipline Organic Chemistry
Start/End 01.10.2013 - 30.09.2015
Approved amount 631'444.00
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Keywords (10)

organic synthesis; naphthalenediimides; supramolecular functional systems; surface-initiated polymerization; anion-pi interactions; halogen bonds; cellular uptake; artificial photosynthesis; oligothiophenes; fluorescent membrane probes

Lay Summary (French)

Lead
L’objectif est de développer des approches innovatrices à la création des systèmes moléculaires avec des activités intéressantes. Les sujets spécifiques concernent des défis actuels dans les sciences des matériaux, du vivant et chimiques, notamment des photosystèmes avec des « autoroutes » pour les électrons (énergie), des transporteurs qui entrent dans une cellule d’une manière jamais vue (santé publique), ou des catalyseurs qui travaillent avec des interactions sans précédence (environnement).
Lay summary

La chimie, et la chimie organique en particulier, permet de créer de la matière nouvelle. L’importance sociétale de cette expertise unique, permettant de préparer presque n’importe quelle petite molécule, est avérée (>25% des exportations en Suisse, etc.). Or, la création de grandes structures fonctionnelles reste très difficile. Il est essentiel de maîtriser cette compétence car la biologie nous montre que les activités vraiment importantes sont accomplies uniquement par des architectures moléculaires très sophistiquées. Les quatre sous-projets de ce projet abordent ce défi par différents angles. Avec les interactions « exotiques », soit anion-π ou liaisons halogènes, nous chercherons de nouveaux outils pour la construction d’édifices moléculaires fonctionnels, surtout des catalyseurs. Cet objectif est comparable à l’introduction d’une nouvelle couleur sur la palette d’un peintre. Avec les photosystèmes artificiels, le but est de créer des « autoroutes » moléculaires pour des électrons avec le but de minimiser la perte d’énergie solaire. Avec des stratégies similaires, nous chercherons de nouvelles manières d’entrer dans une cellule et des sondes membranaires fluorescentes qui changent de couleur comme le homard dans la casserole.

La réussite de ces projets aidera à relever des défis centraux dans les sciences des matériaux (dispositifs optoélectroniques, dont les cellules solaires organiques), du vivant (entrée cellulaire, sondes membranaires) ou chimiques (organo-catalyseurs). Bien que fondamentaux par nature, ces projets ont donc une pertinence sociétale sur le long terme par rapport à l’énergie, la santé publique (transport ciblé des médicaments dans les cellules) et l’environnement (meilleurs catalyseurs).

Direct link to Lay Summary Last update: 27.09.2013

Responsible applicant and co-applicants

Employees

Publications

Publication
Anion Transport with Halogen Bonds
Jentzsch Andreas Vargas, Matile Stefan (2015), Anion Transport with Halogen Bonds, in HALOGEN BONDING I: IMPACT ON MATERIALS CHEMISTRY AND LIFE SCIENCES, 205-239.
Asymmetric Anion-pi Catalysis: Enamine Addition to Nitroolefins on pi-Acidic Surfaces
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.
Big, Strong, Neutral, Twisted, and Chiral pi Acids
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.
Cell-penetrating poly(disulfide)s: the dependence of activity, depolymerization kinetics and intracellular localization on their length
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.
Cellular uptake: lessons from supramolecular organic chemistry
Gasparini Giulio, Bang Eun-Kyoung, Montenegro Javier, Matile Stefan (2015), Cellular uptake: lessons from supramolecular organic chemistry, in CHEMICAL COMMUNICATIONS, 51(52), 10389-10402.
Colorful surface architectures with three different types of dynamic covalent bonds: integration of anthocyanins, tritylium ions and flavins
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.
Comparison of Charge-Transfer Dynamics of Naphthalenediimide Triads in Solution and pi-Stack Architectures on Solid Surfaces
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.
Complex Functional Systems with Three Different Types of Dynamic Covalent Bonds
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.
Coumarin synthesis on pi-acidic surfaces
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.
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
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.
Electron-deficient fullerenes in triple-channel photosystems
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.
Fluorescent Flippers for Mechanosensitive Membrane Probes
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.
Ion Pair-pi Interactions
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.
Mechanosensitive Membrane Probes
Dal Molin Marta, Verolet Quentin, Soleimanpour Saeideh, Matile Stefan (2015), Mechanosensitive Membrane Probes, in CHEMISTRY-A EUROPEAN JOURNAL, 21(16), 6012-6021.
Ring Tension Applied to Thiol-Mediated Cellular Uptake
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.
Selective Acceleration of Disfavored Enolate Addition Reactions by Anion-π Interactions
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.
Ultrafast Intersystem-Crossing Dynamics and Breakdown of the Kasha-Vavilov's Rule of Naphthalenediimides
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.
A Collection of Fullerenes for Synthetic Access Toward Oriented Charge-Transfer Cascades in Triple-Channel Photosystems
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.
Anion-pi and Cation-pi Interactions on the Same Surface
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.
Anion-pi Catalysis
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.
Antiparallel Three-Component Gradients in Double-Channel Surface Architectures
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.
Cell-penetrating poly(disulfide)s: focus on substrate-initiated co-polymerization
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.
Cellular Uptake of Substrate-Initiated Cell-Penetrating Poly(disulfide)s
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.
Enolate chemistry with anion-pi interactions
Zhao Yingjie, Sakai Naomi, Matile Stefan (2014), Enolate chemistry with anion-pi interactions, in NATURE COMMUNICATIONS, 5(1), 3911-1-3911-5.
Functional systems with orthogonal dynamic covalent bonds
Wilson Adam, Gasparini Giulio, Matile Stefan (2014), Functional systems with orthogonal dynamic covalent bonds, in CHEMICAL SOCIETY REVIEWS, 43(6), 1948-1962.
Ion-Gated Synthetic Photosystems
Sakai Naomi, Charbonnaz Pierre, Ward Sandra, Matile Stefan (2014), Ion-Gated Synthetic Photosystems, in JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 136(15), 5575-5578.
Planarizable Push-Pull Probes: In Search of the Perfect Twist
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.
Surface Architectures Built around Perylenediimide Stacks
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.
Synthetic Ion Transporters that Work with Anion-π Interactions, Halogen Bonds and Anion-Macrodipole Interactions
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.
Transport across membranes
Matile Stefan, Fyles Tom (2013), Transport across membranes, in Accounts of Chemical Research, 46(12), 2741-2742.

Collaboration

Group / person Country
Types of collaboration
Aurelien Roux / U Geneva Switzerland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure
- Exchange of personnel
Tomas Wesolowski / U Geneva Switzerland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure
Nazario Martin / Complutense Spain (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Exchange of personnel
Kurt Gothelf / Aarhus Denmark (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Research Infrastructure
Fraser Stoddart / Northwestern United States of America (North America)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Exchange of personnel
Andreas Zumbuehl / Fribourg Switzerland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Research Infrastructure
- Exchange of personnel
Oliver Hantschel / EPFL Switzerland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Research Infrastructure
- Exchange of personnel
Cornelia Palivan / Basel Switzerland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Research Infrastructure
- Exchange of personnel
Marcos Gonzalez-Gaitan / U Geneva Switzerland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure
- Exchange of personnel
Tom Ward / Basel Switzerland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Research Infrastructure
- Exchange of personnel
Kaori Sugihara / U Geneva Switzerland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Research Infrastructure
- Exchange of personnel
Karl Gademann / U Zurich Switzerland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Research Infrastructure
Shana Kelley / U Toronto Canada (North America)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Exchange of personnel
Suliana Manely / EPFL Switzerland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Research Infrastructure
- Exchange of personnel
Tom Fyles / Victoria Canada (North America)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
Howard Reizman / U Geneva Switzerland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure
- Exchange of personnel
Jiri Mareda / U Geneva Switzerland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure
- Exchange of personnel
Eric Vauthey / U Geneva Switzerland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure
Alexander Adibekian / U Geneva Switzerland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Research Infrastructure
- Exchange of personnel
Hagan Bayley / Oxford Great Britain and Northern Ireland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Research Infrastructure

Scientific events

Active participation

Title Type of contribution Title of article or contribution Date Place Persons involved
International CRC Symposium Talk given at a conference Synthetic Supramolecular Systems at Work 29.09.2015 Essen, Germany Matile Stefan;
Swiss Chemical Society (SCS) Fall Meeting Poster Synthetic Biosupramolecular Systems at Work 04.09.2015 Lausanne, Switzerland Alatengbaolige Altan;
Departmental Lecture, Tsinghua University Individual talk Synthetic Supramolecular Systems at Work 13.08.2015 Beijing, China Matile Stefan;
Departmental Lecture, Nanyang Technological University Individual talk Synthetic Biosupramolecular Systems at Work 05.08.2015 Singapore, Singapore Matile Stefan;
Departmental Lecture, Institute of Bioengineering and Nanotechnology, A*Star Individual talk Synthetic Biosupramolecular Systems at Work 04.08.2015 Singapore, Singapore Matile Stefan;
16th International Symposium on Novel Aromatic Compounds (ISNA-16) Poster Synthetic Biosupramolecular Systems at Work 06.07.2015 Madrid, Spain Alatengbaolige Altan;
16th International Symposium on Novel Aromatic Compounds (ISNA-16) Talk given at a conference Synthetic Biosupramolecular Systems at Work 06.07.2015 Madrid, Spain Matile Stefan;
10th International Symposium on Macrocyclic and Supramolecular Chemistry (ISMSC-10) Poster Synthetic Biosupramolecular Systems at Work 28.06.2015 Strasbourg, France Fujisawa Kaori; Benz Sebastian;
Summer School, Cluster of Excellence RESOLV Talk given at a conference Synthetic Biosupramolecular Systems at Work 28.05.2015 Bochum, Germany Matile Stefan;
Swiss Chemical Society (SCS) Spring Meeting Talk given at a conference Synthetic Biosupramolecular Systems at Work 24.04.2015 Basel, Switzerland Matile Stefan;
Departmental Lecture, University of Lyon Individual talk Synthetic Biosupramolecular Systems at Work 09.04.2015 Lyon, France Matile Stefan;
Departmental Lecture, iNANO Individual talk Synthetic Biosupramolecular Systems at Work 26.03.2015 Aarhus, Denmark Matile Stefan;
Departmental Lecture, Politechnico di Milano Individual talk Synthetic Biosupramolecular Systems at Work 19.03.2015 Milano, Italy Matile Stefan;
Suprachem 15 Talk given at a conference Synthetic Biosupramolecular Systems at Work 23.02.2015 Berlin, Germany Matile Stefan;
10th International Symposium of Bioorganic Chemistry (ISBOC 10) Talk given at a conference Synthetic Biosupramolecular Systems at Work 12.01.2015 Pune, India Matile Stefan;
Departmental Lecture, IIT Guwahati Individual talk Synthetic Biosupramolecular Systems at Work 06.01.2015 Guwahati, India Matile Stefan;
Labex CSC Minisymposium Complex Chemical Systems for (Bio)material Science Talk given at a conference Synthetic Biosupramolecular Systems at Work 18.12.2014 Strasbourg, France Matile Stefan;
RSC Macrocyclic and Supramolecular Chemistry Symposium (MASC-2014) Individual talk Synthetic Biosupramolecular Systems at Work 15.12.2014 Norwich, Great Britain and Northern Ireland Matile Stefan;
Swiss Chemical Society (SCS) Fall Meeting Poster Synthetic Biosupramolecular Systems at Work 11.09.2014 Zurich, Switzerland Lascano Santiago; Fujisawa Kaori;
XXVth IUPAC Symposium on Photochemistry Talk given at a conference Synthetic Biosupramolecular Systems at Work 14.07.2014 Bordeaux, France Lascano Santiago;
1st International Symposium on Halogen Bonding (ISXB-1) Talk given at a conference Synthetic Biosupramolecular Systems at Work 18.06.2014 Porto Cesareo, Italy Matile Stefan;
9th International Symposium on Macrocyclic and Supramolecular Chemistry (ISMSC-9) Talk given at a conference Synthetic Biosupramolecular Systems at Work 07.06.2014 Shanghai, China Matile Stefan;
Chemistry, a Crossway Toward Interdisciplinarity: A Symposium for the Dissemination of Chemical Development Talk given at a conference Synthetic Biosupramolecular Systems at Work 02.06.2014 Namur, Belgium Matile Stefan;
48th European Symposium in Bio-Organic Chemistry (ESBOC 48) Poster Synthetic Biosupramolecular Systems at Work 16.05.2014 Gregynog, Great Britain and Northern Ireland Fujisawa Kaori;
48th European Symposium in Bio-Organic Chemistry (ESBOC 48) Talk given at a conference Synthetic Biosupramolecular Systems at Work 16.05.2014 Gregynog, Great Britain and Northern Ireland Matile Stefan;
Chemical Society of Berne Individual talk Synthetic Biosupramolecular Systems at Work 02.04.2014 Berne, Switzerland Matile Stefan;
Departmental Lecture, University of Fribourg Individual talk Synthetic Biosupramolecular Systems at Work 12.11.2013 Fribourg, Switzerland Matile Stefan;


Awards

Title Year
K S Krishnan Memorial Lecture, Indian Association for the Cultivation of Science, Kolkata 2015
Molecular Science Frontier Lecture, Institute of Chemistry Chinese Academy of Sciences (ICCAS), Beijing 2015
Heilbronner-Hückel Lectureship 2014

Associated projects

Number Title Start Funding scheme
144953 Open access MALDI for the chemistry, biochemistry and pharmaceutical sciences sections of the University of Geneva 01.09.2013 R'EQUIP
125781 NCCR Chemical Biology: Visualisation and Control of Biological Processes Using Chemistry (phase I) 01.12.2010 National Centres of Competence in Research (NCCRs)
162363 Synthetic Biosupramolecular Systems at Work 01.10.2015 Project funding
128746 A CryoProbe for the Chemistry Section of the University of Geneva 01.12.2009 R'EQUIP
141825 NCCR MSE: Molecular Systems Engineering (phase I) 01.07.2014 National Centres of Competence in Research (NCCRs)
113020 Acquisition af a Circular Dichroism Spectrometer 01.11.2006 R'EQUIP
137487 Synthetic Biosupramolecular Systems at Work 01.10.2011 Project funding

Abstract

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.
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