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, 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, Multidisciplinary
Niklas B. Arndt, Friederike Schlueter, Marcus Boeckmann, Thorsten Adolphs, Heinrich F. Arlinghaus, Nikos L. Doltsinis, Bart Jan Ravoo
Summary: In this study, a photoswitchable self-assembled monolayer based on arylazopyrazoles (AAPs) is presented. The surface coating exhibits excellent photoswitchability and responsive wettability upon alternating irradiation with UV and green light. The AAP-based silane coupling provides an easy functionalization of glass and silicon oxide surfaces. The properties of the self-assembled monolayers are characterized using various analytical techniques.
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
Chemistry, Physical
Rebekah L. Thimes, Alyssa V. B. Santos, Ran Chen, Gurkiran Kaur, Lasse Jensen, David M. Jenkins, Jon P. Camden
Summary: N-Heterocyclic carbenes (NHCs) are explored as a potential replacement for thiol ligands in self-assembled monolayers on noble-metal surfaces. The study uses surface-enhanced Raman spectroscopy (SERS) and first-principles theory to examine the effect of alkyl wingtip groups on the orientation of NHC monolayers on gold nanoparticles. The results show that both smaller and bulkier wingtip groups can lead to stable flat configurations.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Nanoscience & Nanotechnology
Yangbiao Liu, Egbert Zojer, Michael Zharnikov
Summary: Self-assembled monolayers (SAMs) of ferrocene-substituted thiofluorene on Au(111) exhibit two distinct conductance states (CSs) with high rectification ratio (RR). The CSs and RR depend on the bias voltage sweep direction, with the high CS preserved under negative bias and switched to low CS under positive bias. In symmetric sweeps, the CS depends on the polarity of the first sweep.
ACS APPLIED MATERIALS & INTERFACES
(2022)
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.
Review
Chemistry, Multidisciplinary
Hira Khalid, Lixian Tian, Xi Yu, Irshad Hussain, Wenping Hu
Summary: This review summarizes the preparation, characterization, structure modulation, and applications of mixed self-assembled monolayers (mixed SAMs) in molecular electronics. The ability to tune the intermolecular interactions and optimize charge transport in desired devices is a key advantage of SAM-based molecular devices compared to single molecular devices. The qualitative and quantitative examination of the nanoscale organization and intermolecular interactions of mixed SAMs obtained by various techniques is reviewed. The challenges of using mixed SAMs for the development of novel electronic functional devices in the future are also discussed.
Article
Chemistry, Multidisciplinary
Seung-Min Lee, Woo-Jin Lee, Jae-Young Bae, Ji-Woo Gu, Seunghwan Lee, Ki Baek Yeo, Jaewook Lee, Joon-Woo Kim, Ju-Yong Lee, Jeonghyun Kim, Hyejin Jang, Sang Ho Jun, Seung-Kyun Kang
Summary: This study introduces a straightforward and efficient fabrication method for creating high-performance biodegradable electronic devices. By controlling the adhesion between the biodegradable device and substrate, photolithography-based fabrication and transfer printing are achieved, offering potential for mass manufacturing of biodegradable electronics.
ADVANCED FUNCTIONAL MATERIALS
(2023)
Article
Polymer Science
Zhao-yang Zhang, Tao Li
Summary: Molecular-scale electronics is an emerging research field that aims to achieve electronic functions using single molecules and their monolayer assemblies. Advances in fabricating SAM devices and optimizing their performance can lead to practical applications in molecular electronics. Conjugated polymers show distinct advantages in SAM devices, outperforming small molecular materials in optoelectronic functions such as on-off ratios for switches.
ACTA POLYMERICA SINICA
(2021)
Article
Nanoscience & Nanotechnology
Yunsoo Choi, Chul Soon Park, Hung-Vu Tran, Chien-Hung Li, Cathleen M. Crudden, Randall Lee
Summary: This study reports the development and use of bench-stable NHC adsorbates for the direct formation of NHC films on gold surfaces under ambient conditions. The generated NHC SAMs were fully characterized and compared to analogous SAMs generated from a different adsorbate. Furthermore, the potential utility of these NHC films as surface-initiated polymerization platforms was demonstrated.
ACS APPLIED MATERIALS & INTERFACES
(2022)
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
Electrochemistry
Junwei Mao, Pengfei Xu, Zhenju Zhou, Yu Zhou, Yongming Tang
Summary: Three N-heterocyclic carbenes (NHCs) were synthesized and their self-assembled monolayers (SAMs) were built up on gold substrate. The NHC-based SAMs exhibited high stability in 0.1 M HCl solution, with negligible effect of the unsaturated level of heterocyclic moiety on stability. Theoretical calculations revealed the bonding mechanism of NHC molecules and the contribution of molecular orbitals to bonding.
JOURNAL OF THE ELECTROCHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Hui Tan, Shen-An Wang, Zixi Yan, Jianzhong Liu, Jialiang Wei, Song Song, Ning Jiao
Summary: This study demonstrates a novel N-heterocyclic carbene (NHC) catalyzed oxidative transformation of organic halides into esters utilizing O-2 as the oxygen source. Mechanistic studies show the oxidation of deoxy Breslow intermediate to Breslow intermediate for further transformation. This method expands the field of NHC catalysis and promotes oxygenation reactions with O-2.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Juan J. Navarro, Mowpriya Das, Sergio Tosoni, Felix Landwehr, Maximilian Koy, Markus Heyde, Gianfranco Pacchioni, Frank Glorius, Beatriz Roldan Cuenya
Summary: N-Heterocyclic carbenes (NHCs) show superior properties in self-assembled monolayers (SAMs) and understanding the influence of the substrate on the molecular arrangement is crucial. This study reveals that on Cu(100), NHCs form mostly disordered phases, while on Cu(111), well-defined structures ranging from magic-number islands to molecular ribbons are observed. Diffusion and commensurability play a key role in determining the observed arrangements, providing insights into molecule-substrate interaction and the potential for tuning nanopatterned structures based on NHC assemblies.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
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)
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
Biochemical Research Methods
Thorsten Adolphs, Marcel Heeger, Florian Bosse, Bart Jan Ravoo, Richard E. Peterson, Heinrich F. Arlinghaus, Bonnie J. Tyler
Summary: Time-of-flight secondary ion mass spectrometry (TOF-SIMS) is a promising technique for label-free analysis of biomolecules with nanoscale spatial resolution. However, high-resolution imaging of larger biomolecules such as phospholipids and peptides is often limited by low yields of molecular ions. Matrix-enhanced SIMS (ME-SIMS), which involves adding an organic matrix to the sample, offers a solution to enhance the ion yield for biomolecules. This study explores the use of the matrix a-cyano-4-hydroxycinnamic acid (HCCA) combined with cluster primary ion analysis to better understand the role of protonation and fragmentation on lipid molecule ion yield. The results show that the HCCA matrix enhances protonation and reduces fragmentation, and the migration of analytes to the surface of the matrix coating is crucial for signal enhancement in imaging applications. Overall, this work highlights the potential of using the HCCA matrix for improved high spatial resolution imaging with ME-SIMS.
JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY
(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)
Review
Chemistry, Multidisciplinary
Lukas Lueckemeier, Marco Pierau, Frank Glorius
Summary: This review aims to present the state-of-the-art in transition-metal catalysed asymmetric hydrogenation of (hetero)arenes, highlighting recent advances and important trends, and providing a broad overview for the reader.
CHEMICAL SOCIETY REVIEWS
(2023)
