Article
Chemistry, Analytical
Nathaniel L. Dominique, Shelby L. Strausser, Jacob E. Olson, William C. Boggess, David M. Jenkins, Jon P. Camden
Summary: This study investigates the stability and potential biological applications of N-heterocyclic carbene (NHC) self-assembled monolayers (SAMs) on gold surfaces, while utilizing laser desorption ionization mass spectrometry (LDI-MS) to explore the surface chemistry of NHC. By studying NHC-functionalized gold nanoparticles using LDI-MS, insights into the packing of NHC monolayers on gold surfaces and the stability of NHC ligands post-ligation were gained. The ability of LDI-MS to probe postsynthetic modifications of anchored NHCs, such as the reduction of nitro-NHC-AuNPs to amine-NHC-AuNPs, highlights its importance for current and future applications of NHC surfaces.
ANALYTICAL CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Iris Berg, Einav Amit, Lillian Hale, F. Dean Toste, Elad Gross
Summary: In this study, a N-heterocyclic carbene (NHC) nanolayer was successfully anchored on the surface of a copper electrode using an electrochemical method, resulting in improved oxidation resistance of copper.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Chaofang Deng, Jiu Chen, Qing Tang
Summary: In this study, theoretical investigations were conducted to examine the binding of NHCMe ligands on different solid surfaces, revealing stronger adsorption on Pt (111) and Ti (0001) surfaces compared to the experimentally studied NHC-Au(111) interface. Furthermore, the distance of adatoms from the surface plays a crucial role in determining the molecular orientations of NHCMe, leading to different binding modes. These results suggest great promise for the design of stable NHC-based SAMs with attractive interface features beyond traditional coinage metals.
JOURNAL OF PHYSICAL CHEMISTRY C
(2021)
Article
Chemistry, Multidisciplinary
Iris Berg, Luca Schio, Justus Reitz, Elena Molteni, Linoy Lahav, Carolina Gutierrez Bolanos, Andrea Goldoni, Cesare Grazioli, Guido Fratesi, Max M. Hansmann, Luca Floreano, Elad Gross
Summary: In this study, the self-assembly of N-heterocyclic olefins (NHOs) on gold surface was investigated using experimental and computational methods. It was found that NHOs can self-assemble into dimers, trimers, and tetramers, forming stable monolayers. The study also revealed that NHOs can adsorb on gold surface in a flat-lying geometry through coordination with gold adatoms, and the surface interaction can be further increased by functionalizing the backbone with methyl groups, leading to enhanced thermal stability and impact on work-function values.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Eloise Angove, Federico Grillo, Herbert A. Fruchtl, Alex J. Veinot, Ishwar Singh, J. Hugh Horton, Cathleen M. Crudden, Christopher J. Baddeley
Summary: The benzannulated N-heterocyclic carbene forms a highly ordered structure on the Cu(111) surface, with vertical benzannulated NHC moieties coordinating to Cu adatoms and three surface-bound benzyl substituents controlling the formation of a highly ordered lattice.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Review
Chemistry, Physical
Maximilian Koy, Peter Bellotti, Mowpriya Das, Frank Glorius
Summary: This review discusses the use of N-heterocyclic carbenes as molecular modifiers for metal surfaces, aiming to improve the reactivity of metal-based heterogeneous catalysts. Combining sophisticated ligand systems from homogeneous catalysis with metal surfaces can enhance parameters such as stability and selectivity of catalysts.
Article
Nanoscience & Nanotechnology
Florian Bosse, Christian Gutheil, D. Thao Nguyen, Matthias Freitag, Mowpriya Das, Bonnie J. J. Tyler, Thorsten Adolphs, Andreas H. H. Schaefer, Heinrich F. F. Arlinghaus, Frank Glorius, Bart Jan Ravoo
Summary: Planar gold surfaces modified with N-heterocyclic carbene (NHC) were found to be more susceptible to wet chemical etching compared to undecorated areas. The selective decoration of NHCs on gold was achieved by microcontact printing, and the etching behavior could be tuned by changing the concentration of the NHC precursor. Surface patterning was confirmed by time-of-flight secondary-ion mass spectrometry and Kelvin probe force microscopy. The ability to selectively remove gold through surface ligand functionalization enables novel applications of NHCs in materials chemistry and nanofabrication.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Multidisciplinary
Laura Hippolyte, Omar Sadek, Salem Ba Sowid, Alexandre Porcheron, Nathalie Bridonneau, Sebastien Blanchard, Marine Desage-El Murr, David Gatineau, Yves Gimbert, Dimitri Mercier, Philippe Marcus, Clement Chauvier, Corinne Chaneac, Francois Ribot, Louis Fensterbank
Summary: In this paper, a straightforward synthesis method for NHC-coated gold nanoparticles (NHC-AuNPs) is reported. The commercially available gold(I) precursor is treated with an easy-to-synthesize NHC-BH3 reagent, serving as both the reducing agent and the source of surface ligands. The strategy allows efficient control over the nucleation and growth of gold particles, resulting in a wide range of particle size variation from 4.9±0.9 to 10.0±2.7 nm. The NHC-AuNPs obtained exhibit narrow size distributions, stability over months, and do not require extensive purification or size-selectivity techniques.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Einav Amit, Iris Berg, Wenhao Zhang, Rajarshi Mondal, Hadar Shema, Vitaly Gutkin, Tatyana Kravchuk, F. Dean Toste, Zackaria Nairoukh, Elad Gross
Summary: In this study, precise spatial control over the self-assembly process of organic self-assembled monolayers (SAMs) in microelectronic devices is achieved by selectively depositing N-heterocyclic carbenes (NHCs) on specific electrodes within a two-microelectrode array using pulsed electrodeposition. Spectroscopic analysis confirms the selective coating of each electrode with a designated NHC. Kelvin probe force microscopy measurements quantitatively demonstrate the impact of NHC monolayers on the electrodes' work function, showing that the work function values of each electrode can be independently tuned by the adsorption of a specific NHC. The presented deposition method allows for the selective coating of designated microelectrodes in an electrode array with chosen NHC monolayers for tuning their chemical and electronic functionality.
Article
Multidisciplinary Sciences
Alex Inayeh, Ryan R. K. Groome, Ishwar Singh, Alex J. Veinot, Felipe Crasto de Lima, Roberto H. Miwa, Cathleen M. Crudden, Alastair B. McLean
Summary: N-heterocyclic carbenes (NHCs) have emerged as a promising alternative to sulfur-based ligands for self-assembly on gold surfaces, but there are still many unanswered questions about their behavior on surfaces. This study examines fundamental questions such as NHC orientation, mobility, and self-assembly by analyzing NHC overlayers on Au(111).
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Lenka Pallova, Laura Abella, Marion Jean, Nicolas Vanthuyne, Cecile Barthes, Laure Vendier, Jochen Autschbach, Jeanne Crassous, Stephanie Bastin, Vincent Cesar
Summary: The first efficient chiral helicene-NHC gold(I) complexes for enantioselective catalysis have been synthesized. Their structural and stereochemical characterization confirms their potential in asymmetric catalysis, demonstrated by the benchmark cycloisomerization reaction with high enantiomeric excess.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Gurkiran Kaur, Rebekah L. Thimes, Jon P. Camden, David M. Jenkins
Summary: The discovery of N-heterocyclic carbenes (NHCs) has revolutionized organometallic chemistry by providing strong metal-ligand bonds. This review article highlights the applications of NHCs on gold surfaces and nanoparticles, focusing on their enhanced stability and synthetic tunability. Unique scientific questions and new applications in biomedicine, catalysis, and microelectronics are also discussed.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Martin Franz, Sandhya Chandola, Maximilian Koy, Robert Zielinski, Hazem Aldahhak, Mowpriya Das, Matthias Freitag, Uwe Gerstmann, Denise Liebig, Adrian Karl Hoffmann, Maximilian Rosin, Wolf Gero Schmidt, Conor Hogan, Frank Glorius, Norbert Esser, Mario Daehne
Summary: The study on the adsorption of N-heterocyclic carbenes (NHCs) on silicon reveals the formation of highly ordered monolayers with good thermal stability and strong work function reductions. The structure and ordering of the monolayers are controlled by the substrate geometry and reactivity, particularly by the NHC side groups. These findings pave the way for tailor-made organic functionalization of silicon surfaces and offer potential for new electronic and optoelectronic applications.
Article
Chemistry, Multidisciplinary
Lindy M. Sherman, Shelby L. Strausser, Rowan K. Borsari, David M. Jenkins, Jon P. Camden
Summary: N-heterocyclic carbenes (NHCs) have emerged as versatile ligands for noble metal surface modifications due to their ability to form compact, self-assembled monolayers. Different types of NHC moieties, such as saturated NHCs, can be more effective in homogeneous catalysis and offer advantages such as increased stability and access to chiral groups on NHC surfaces. This study explores the preparation and stability of NHC-coated gold surfaces using imidazolium and imidazolinium NHC ligands, with imidazolinium showing enhanced stability compared to traditional imidazolium under harsh acidic conditions.
Article
Chemistry, Multidisciplinary
Jindong Ren, Maximilian Koy, Helena Osthues, Bertram Schulze Lammers, Christian Gutheil, Marvin Nyenhuis, Qi Zheng, Yao Xiao, Li Huang, Arne Nalop, Qing Dai, Hong-Jun Gao, Harry Moenig, Nikos L. Doltsinis, Harald Fuchs, Frank Glorius
Summary: In this study, NHC polymers consisting of ballbot-type repeating units bound to single Au adatoms were synthesized on gold surfaces. The conformational, electronic, and charge transport properties of these polymers were assessed, and their high surface mobility and potential applications in nanoelectronics, surface functionalization, and catalysis were demonstrated.
Editorial Material
Chemistry, Multidisciplinary
Guangying Tan, Frank Glorius
Summary: Stereochemical editing, a recently prominent method, enables direct manipulation of organic molecules with stereocenters to adjust their relative stereochemistry. Various light-driven reactions, such as deracemization and epimerization, have been successfully developed. Wendlandt and colleagues have recently reported a versatile photochemical epimerization of unactivated tertiary stereogenic centers, providing rapid access to challenging stereoisomers.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Biochemistry & Molecular Biology
Yanjun Zheng, Tristan Wegner, Daniele Di Iorio, Marco Pierau, Frank Glorius, Seraphine V. Wegner
Summary: The nongenetic modification of cell membranes with proteins is a straightforward method in cellular engineering. A cholesterol analogue called CHIM-NTA has been developed for specific membrane immobilization of polyhistidine-tagged proteins, particularly in the liquid-ordered (Lo) domains. It can integrate into phase-separated giant unilamellar vesicles (GUVs) and live cell membranes, enabling the nongenetic modification of cell surfaces with proteins.
ACS CHEMICAL BIOLOGY
(2023)
Article
Chemistry, Multidisciplinary
Yujie Liang, Fritz Paulus, Constantin G. Daniliuc, Frank Glorius
Summary: We report a BF3-catalyzed [2 + 2] cycloaddition reaction between aldehydes and bicyclo[1.1.0]butanes (BCBs) to access polysubstituted 2-oxabicyclo[2.1.1]hexanes. A new BCB containing an acyl pyrazole group was discovered, which not only facilitates the reactions but also allows for diverse downstream transformations. Additionally, aryl and vinyl epoxides can be used as substrates that undergo cycloaddition with BCBs after in situ rearrangement to aldehydes. These results will promote the exploration of complex sp(3)-rich bicyclic frameworks and BCB-based cycloaddition chemistry.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Biochemistry & Molecular Biology
Maurice Dellin, Ina Rohrbeck, Purva Asrani, Julian A. Schreiber, Nadine Ritter, Frank Glorius, Bernhard Wuensch, Thomas Budde, Louisa Temme, Timo Struenker, Birgit Stallmeyer, Frank Tuettelmann, Sven G. Meuth, Marc Spehr, Johann Matschke, Andrea Steinbicker, Christos Gatsogiannis, Raphael Stoll, Nathalie Strutz-Seebohm, Guiscard Seebohm
Summary: The study identified two binding sites, PS1 and S0, for PI(3,5)P-2 on the KCNQ1/KCNE1 channel, and found that binding of PI(3,5)P-2 to both sites is necessary for stabilizing the channel's open state.
BIOLOGICAL CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Akash Kaithal, Himadri Sekhar Sasmal, Subhabrata Dutta, Felix Schafer, Lisa Schlichter, Frank Glorius
Summary: This study reports a catalytic approach to synthesizing cis-selective saturated carbo-and heterocyclic germanium compounds with a 3D framework through the hydrogenation of readily accessible aromatic germanes with a 2D framework. Nishimura's catalyst exhibited the best hydrogenation reactivity, achieving an isolated yield of up to 96%. The synthesized products showed versatile applications in coupling reactions and demonstrated orthogonal reactivity with boranes or silanes, acquiring a three-dimensional structure with high stability.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Roman Kleinmans, Subhabrata Dutta, Kristers Ozols, Huiling Shao, Felix Schafer, Rebecca E. Thielemann, Hok Tsun Chan, Constantin G. Daniliuc, Kendall N. Houk, Frank Glorius
Summary: The ortho-selective intermolecular photocycloaddition of bicyclic aza-arenes is reported, utilizing a strain-release approach. This reaction enables the construction of C-(sp(3))-rich bicyclo-[2.1.1]-hexanes directly connected to N-heteroarenes. Photophysical experiments and DFT calculations reveal the mechanism of this selective intermolecular photocycloaddition.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Review
Biochemistry & Molecular Biology
Yoon-Gyo Lee, Eun-Jin Cho, Shila Maskey, Dinh-Truong Nguyen, Hyeun-Jong Bae
Summary: Coffee waste can be transformed into valuable products through clean technologies and long-term waste management strategies. Various compounds, such as lipids, lignin, cellulose, antioxidants, caffeine, and biofuel, can be extracted or produced from coffee by-products. The full utilization of these by-products can reduce the economic and environmental burdens of coffee processing by establishing suitable infrastructure and networks between scientists, business organizations, and policymakers in a sustainable manner.
Article
Nanoscience & Nanotechnology
B. van de Ven, U. Alegre-Ibarra, P. J. Lemieszczuk, P. A. Bobbert, H. -c. Ruiz Euler, W. G. van der Wiel
Summary: Inspired by the brain's efficient information processing, any material system can be used for computation, but maximizing its computational potential is not always obvious. In this study, a dopant network processing unit (DNPU) is operated as a tuneable extreme learning machine (ELM) to optimize its performance on a non-linear classification task. The results show that a hybrid operation mode, called tuneable ELM mode, reduces the parameters needed for a vowel recognition benchmark task. This highlights the power of analog in-matter computing and the importance of designing specialized material systems for computation.
FRONTIERS IN NANOTECHNOLOGY
(2023)
Article
Nanoscience & Nanotechnology
Florian Bosse, Christian Gutheil, D. Thao Nguyen, Matthias Freitag, Mowpriya Das, Bonnie J. J. Tyler, Thorsten Adolphs, Andreas H. H. Schaefer, Heinrich F. F. Arlinghaus, Frank Glorius, Bart Jan Ravoo
Summary: Planar gold surfaces modified with N-heterocyclic carbene (NHC) were found to be more susceptible to wet chemical etching compared to undecorated areas. The selective decoration of NHCs on gold was achieved by microcontact printing, and the etching behavior could be tuned by changing the concentration of the NHC precursor. Surface patterning was confirmed by time-of-flight secondary-ion mass spectrometry and Kelvin probe force microscopy. The ability to selectively remove gold through surface ligand functionalization enables novel applications of NHCs in materials chemistry and nanofabrication.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Multidisciplinary
Mowpriya Das, Markus Kohlstaedt, Maria Enders, Stephan Burger, Himadri Sekhar Sasmal, Birger Zimmermann, Andreas Schaefer, Bonnie J. Tyler, Heinrich F. Arlinghaus, Ingo Krossing, Uli Wuerfel, Frank Glorius
Summary: This study demonstrates the modification of ITO surface using N-heterocyclic carbenes (NHCs) precursor, IPr-CO2, via spin coating method. The modified ITO electrodes exhibit significantly reduced work function and provide high electron selectivity contacts in organic photovoltaic devices.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Fritz Paulus, Colin Stein, Corinna Heusel, Tobias J. Stoffels, Constantin G. Daniliuc, Frank Glorius
Summary: In this study, a novel three-component 1,2,5-trifunctionalization reaction driven by visible light energy transfer-catalysis was reported. Selective installation of three different functional groups was achieved in one step by utilizing imine-based bifunctional reagents and two distinct alkenes. Mechanistic studies and downstream modifications demonstrated the synthetic utility of the obtained products.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Review
Chemistry, Multidisciplinary
Peter Bellotti, Frank Glorius
Summary: The concept of strain in organic compounds is essential for understanding the synthesis and properties of organic compounds. Recent advancements in strain-release reactions and photocatalysis have opened up new possibilities for creating unique chemical architectures and expanding the field of strain research.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Huamin Wang, Johannes E. Erchinger, Madina Lenz, Subhabrata Dutta, Constantin G. Daniliuc, Frank Glorius
Summary: This study presents a photoredox strategy that enables the high regio- and syn-selective difunctionalization of bicyclo[1.1.0]-butanes (BCBs). By cleaving C-S sigma bonds, sulfur-alkynylation, -alkenylation, and -allylation of BCBs can be achieved under mild conditions, demonstrating the generality of this approach.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Multidisciplinary Sciences
Herbert Jaeger, Beatriz Noheda, Wilfred G. G. van der Wiel
Summary: Approaching limitations of digital computing technologies have led to the exploration of neuromorphic and other unconventional computing methods. A formal theory beyond the classical symbolic-algorithmic Turing machine theory is needed to systematically engineer unconventional computing systems. This article proposes a general strategy for developing such a theory, particularly focusing on a bottom-up approach called fluent computing, which models physical computing systems based on what can be measured. The authors emphasize the challenges in learning from human brains to create powerful computers due to the absence of a guiding computing theory.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Linda Quach, Egy Adhitama, Valentin Goeldner, Ankita Das, Feleke Demelash, Martin Winter, Uwe Karst, Tobias Placke, Frank Glorius
Summary: Film-forming electrolyte additives are crucial for the performance and safety of high-energy-density lithium-ion batteries. This study synthesized derivatives and conducted analyses to investigate the impact of molecular substrate parameters on battery performance. The research aims to enhance the fundamental understanding of influential substrate parameters and guide the design of electrolyte additives for high-energy-density lithium-ion batteries.
ACS APPLIED ENERGY MATERIALS
(2023)
