Article
Chemistry, Physical
Chengxi Li, Kang Huang, Chen Xiao, Yonghong Shi, Pengfei Duan
Summary: In this study, a vortex-assisted chiral supramolecular polymerization process is proposed to generate chiral polymers from achiral monomers. The mechanism of symmetry-breaking is systematically investigated, showing that highly ordered assemblies can be formed as the initial chiral nuclei through increasing supersaturation. The study concludes that chiral assemblies in the nucleation stage possess low energy barrier and can be fractured and replicated by the vortex, leading to the evolvement into final chiral polymers.
Article
Chemistry, Physical
Yusen Su, Andy Berbille, Zhong Lin Wang, Wei Tang
Summary: Chemical functional groups on solid surfaces play a vital role in contact electrification at water-solid interfaces. In this study, ion coupled plasma etching was used to modify a high-density polyethylene (HDPE) film and generate fluoride (HDPE-F) and hydroxyl (HDPE-OH) functional groups, which endowed HDPE with charge withdrawing ability. HDPE-F withdrew 2.5-2.7 times more charges than HDPE-OH, and the accumulated surface charges altered the motion of droplets. This study provides an alternative approach to study contact electrification and evaluate the contribution of electrons to solid-liquid CE, and also demonstrates the superior activity of HDPE-F in contact-electro-catalysis compared to commercial fluorinated films.
Article
Chemistry, Applied
Sneha A. Akhade, Mal-Soon Lee, Laura C. Meyer, Simuck F. Yuk, Manh-Thuong Nguyen, Udishnu Sanyal, Jonathan D. Egbert, Oliver Y. Gutierrez, Vassiliki-Alexandra Glezakou, Roger Rousseau
Summary: In this study, the adsorption and reduction processes of organic molecules on a charged Pd surface were investigated using density-functional-theory based molecular dynamics simulations. The results show that the functional groups and electrode charge have a strong impact on the adsorption and reduction of organic molecules, and the solvent effect also significantly influences the interaction between the organic molecules and the electrode.
Article
Multidisciplinary Sciences
Sebastian Echeverria-Alar, Marcel G. Clerc, Ignacio Bordeu
Summary: Spatial branching processes are observed in chiral nematic liquid crystals, where a cholesteric phase self-organizes into extended branching patterns. We study the spatial and temporal organization of thermally driven branching patterns in chiral nematic liquid crystal cells experimentally, and describe the observations using a mean-field model.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2023)
Article
Chemistry, Multidisciplinary
Shucong Li, Gabriele Librandi, Yuxing Yao, Austin J. Richard, Alyssha Schneider-Yamamura, Joanna Aizenberg, Katia Bertoldi
Summary: By fabricating cellular microstructures out of liquid crystalline elastomers with user-defined liquid crystal mesogen orientation, it is possible to achieve director-determined symmetry breakings and mechanical reconfigurations, resulting in microcellular materials with switchable and direction-dependent frictional properties, as well as the ability to locally modulate transmitted light and guide object movement accurately.
ADVANCED MATERIALS
(2021)
Article
Mechanics
Ivan V. Vorontsov, Sergey A. Chivilikhin, Igor Y. Popov
Summary: A molecular dynamics-based model is proposed for describing the shape of nanobubbles on the liquid-solid interface, with results in good agreement with experimental AFM measurements. The study investigates nanobubbles in water and in oil, considering their evolution, movement, and interactions. Furthermore, it explores the impact of various external factors and internal characteristics on the evolution and behavior of nanobubbles.
Article
Thermodynamics
Yoshitaka Ueki, Satoshi Matsuo, Masahiko Shibahara
Summary: This study investigated the influence of nanotextured surface geometry on the interfacial thermal resistance (ITR) between hydrophilic solid walls and water/ice using molecular dynamics simulations. The results showed that narrower nanostructure gaps led to decreased ITR. Particularly, when H2O molecules were in the crystal form, the local ITR significantly increased.
INTERNATIONAL COMMUNICATIONS IN HEAT AND MASS TRANSFER
(2022)
Article
Multidisciplinary Sciences
Semih Sevim, Alessandro Sorrenti, Joao Pedro Vale, Zoubir El-Hachemi, Salvador Pane, Andreas D. Flouris, Tiago Sotto Mayor, Josep Puigmarti-Luis
Summary: This article presents an example of chirality transfer from the chiral shape of a 3D helical channel to chiral supramolecular aggregates, where the handedness of the helical channel determines the direction of enantioselection. By combining numerical simulations and experimental data, the authors demonstrate the possibility of controlling enantioselectively molecular processes at the nanometer scale by modulating the geometry and operating conditions of fluidic reactors.
NATURE COMMUNICATIONS
(2022)
Article
Materials Science, Multidisciplinary
Yange Zhang, Jingdan Zhang, Xiangyan Li, Yichun Xu, Xuebang Wu, Junfeng Yang, Xianping Wang
Summary: The interaction between liquid Pb and irradiation defects at the structural materials/liquid metal interface plays a crucial role in understanding the irradiation-enhanced corrosion of structural materials in nuclear systems. Molecular dynamics simulations were employed to investigate the primary damage on iron surfaces and the characteristics of the irradiated Fe/Pb solid-liquid interfaces. It was found that vacancy clusters are dominant on the surfaces, with vacancy loops appearing more frequently under Fe(110) surface compared to Fe(100) surface under Fe particle irradiation. Liquid Pb can facilitate the migration of irradiation damages, particularly vacancies, to the surface, which in turn promotes the corrosion of Pb on the Fe surface by forming bonds with Pb atoms. The transport properties of Pb atoms near the interface exhibit anisotropy due to the different structural symmetry of the Fe/Pb interfaces.
JOURNAL OF NUCLEAR MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Xiaoxiao Cheng, Tengfei Miao, Yafei Ma, Xiaoyan Zhu, Wei Zhang, Xiulin Zhu
Summary: By controlling the tail length and degree of polymerization of Azo blocks, the multiple chiroptical inversion of Azo-polymer supramolecular assemblies can be modulated.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Ansgar Pausch, Melanie Gebele, Wim Klopper
Summary: This study explores the description of molecular symmetry in static external magnetic fields using group theory, presenting a general scheme for identifying the molecular point group under such conditions and providing character tables for point groups that are non-existent in the absence of a field. It is mathematically proven that all possible point groups are Abelian.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Multidisciplinary
Johannes M. Scheiger, Mariia A. Kuzina, Michael Eigenbrod, Yanchen Wu, Fei Wang, Stefan Heissler, Steffen Hardt, Britta Nestler, Pavel A. Levkin
Summary: A novel liquid confinement device called liquid well is introduced, which can stably contain immiscible fluids using hydrophobic-hydrophilic core-shell patterns on a surface. Liquid wells exhibit unique properties such as self-repair, dynamic behavior, and functionality arising from their liquid aggregate state.
ADVANCED MATERIALS
(2021)
Article
Chemistry, Physical
Lei He, Ping-Ping Shi, Meng-Meng Zhao, Cai-Ming Liu, Wen Zhang, Qiong Ye
Summary: Solid solution has been traditionally used in inorganic oxides to modify properties, whereas in molecular solid solutions, unique properties may arise due to different molecular conformations and spatial orientations. This study achieved a three-dimensional molecular perovskite ferroelastic solid solution for the first time, demonstrating the generation of a novel chiral phase with second harmonic generation response at specific mixing ratios, offering a new approach for tuning crystal structures.
CHEMISTRY OF MATERIALS
(2021)
Article
Chemistry, Physical
M. Mohib Ur Rehman, Gyoko Nagayama
Summary: In this study, it was found that the presence of micro/nanostructured surfaces significantly affects the evaporation rate of droplets, with the wettability and volume of the droplets further influencing this effect. Theoretical and experimental results showed agreement when the scale of the solid-liquid-vapor interface (slv) was negligible. For microstructured surfaces, the scale of the slv interface could reach 253-940 μm, and the evaporation rate at the slv interface accounted for 16-48% of the total evaporation rate. The scale and rate of the slv interface increased with a decrease in the initial contact angle or an increase in the droplet volume. These findings are important for practical engineering and medical applications involving droplet evaporation on micro/nanostructured surfaces.
COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS
(2023)
Article
Chemistry, Physical
Gerhard H. Fecher, Jurgen Kubler, Claudia Felser
Summary: Chirality is a property that depends on specific symmetries. This study quantifies chirality using Hausdorff distances and continuous chirality measures and discusses its impact on bulk solids and surfaces. The study proposes using optical circular dichroism in the angular distribution of photoelectrons to distinguish the handedness of chiral solids and their surfaces. The importance of chirality is also discussed in the context of crystal structures, band structure, and the Berry curvature.
Article
Chemistry, Physical
Renan Villarreal, Pin-Cheng Lin, Zviadi Zarkua, Harsh Bana, Hung-Chieh Tsai, Manuel Auge, Felix Junge, Hans Hofsaess, Ezequiel Tosi, Steven De Feyter, Stefan De Gendt, Steven Brems, E. Harriet ahlgren, Lino M. C. Pereira
Summary: Ultralow energy (ULE) ion implantation is increasingly used to modify 2D materials, in particular, graphene. However, the disorder induced by ion irradiation in this low-energy limit remains poorly understood.
Article
Chemistry, Physical
Tamara Rinkovec, Demian Kalebic, Mark Van der Auweraer, Wim Dehaen, Jeremy N. Harvey, Steven De Feyter
Summary: In this study, the effect of concentration on the self-assembled molecular network formation process was investigated using scanning tunneling microscopy. Isophthalic acids were chosen as a model system, and the adsorption behavior was evaluated at the nanoscale. The results showed the existence of a critical concentration for self-assembly, with the molecular structure having a significant impact on this threshold value. Furthermore, highly cooperative behavior was observed at the liquid/solid interface, providing a rare example of quantitative measurement of cooperative phenomena.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Multidisciplinary
Yuan Fang, Oleksandr Ivasenko, Ana Sanz-Matias, Kunal S. Mali, Kazukuni Tahara, Yoshito Tobe, Steven De Feyter
Summary: Self-assembled molecular networks (SAMNs) are spontaneously formed through the assembly of molecules on surfaces. Scanning tunneling microscopy (STM) can track their growth dynamics on conductive atomically flat surfaces and at the liquid-solid interface. Desorption and adsorption dynamics are challenging to investigate through the liquid-solid interface. Porous molecular networks have attracted particular interest as they can act as platforms for sensing and host-guest chemistry. However, their stability in a liquid environment is still poorly understood. In this study, the authors investigated the desorption/adsorption dynamics of supramolecular porous monolayers at the interface between highly oriented pyrolytic graphite and 1-phenyloctane, and revealed the time scales, temperature dependence, and the role of STM tip in inducing dynamics.
Article
Chemistry, Physical
Gangamallaiah Velpula, Jian Xiang Lian, David Cornil, David Beljonne, Roberto Lazzaroni, Kunal S. Mali, Steven De Feyter
Summary: This study investigates the impact of the anions in imidazolium-based ionic liquids (ILs) on the interface between ILs and graphene, as well as on the electronic structure of graphene. Raman spectroscopy reveals that ILs with smaller anions lead to n-type doping, while ILs with larger anions have a negligible effect on doping. Molecular modeling simulations suggest that changes in the electrostatic potential at the IL-graphene interface are responsible for the n-type doping.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Multidisciplinary
Sota Aoi, Shingo Hirose, Kanagawa Wakana Soeda, Hiromasa Kaneko, Kunal S. Mali, Steven De Feyter, Kazukuni Tahara
Summary: We demonstrate the controlled grafting of graphite surfaces using electrochemically generated aryl radicals templated by self-assembled molecular networks (SAMNs) of bisalkylurea derivatives. The degree of dynamics at the alkyl termini and strong intermolecular interactions play a crucial role in the covalent attachment.
Article
Thermodynamics
Elmira Ghanbari, Stephen J. Picken, Jan H. van Esch
Summary: We have developed an analytical method that can accurately determine the thermal properties of materials, with the ability to be performed automatically without the intervention of an operator. This method has been successfully applied to a wide range of samples, including those with obvious asymmetry in the melting peak.
JOURNAL OF THERMAL ANALYSIS AND CALORIMETRY
(2023)
Article
Chemistry, Multidisciplinary
Elmira Ghanbari, Zian Chen, Pooja Padmanabhan, Stephen J. Picken, Jan H. van Esch
Summary: We conducted a systematic study on the gelation behavior of nBA gelators in xylene, and found that the melting temperatures of nBA gels are lower than that of pure nBA gelators. This can be explained by the increase in entropy upon melting of the gel due to mixing with the solvent. The XRD patterns of nBA gels and their gelators indicated similar structures, with slight differences in the packing of odd nBA gels compared to the solid state. The rheological properties of nBA gels showed a possible odd-even effect.
Article
Chemistry, Multidisciplinary
Elmira Ghanbari, Stephen J. Picken, Jan H. van Esch
Summary: This study aims to develop design rules for binary mixtures of gelators and explore the impact of their assembly patterns on the rheological properties of gels. Examining nBA gelators with different spacer lengths, it is found that binary mixtures with a small difference in spacer length form compounds and co-assemble into fibers and sheets, while mixtures with a larger spacer length difference lead to phase separation. Self-sorting of odd and even gelators results in a decrease in gel strength, except for a specific gel with larger woven spheres.
Article
Chemistry, Multidisciplinary
Anne-Charlotte Nellissen, Eduard Fron, Jonathan B. F. Vandenwijngaerden, Steven De Feyter, Stijn F. L. Mertens, Mark van der Auweraer
Summary: This study investigates the physisorption of dyes on hexagonal boron nitride (hBN) and analyzes their decay characteristics. The results show that different dyes exhibit different decay behaviors in the adsorption environment, and increasing adsorption leads to increased energy transfer.
Article
Chemistry, Physical
Nick Goossens, Konstantina Lambrinou, Bensu Tunca, Vrushali Kotasthane, Miriam C. Rodriguez Gonzalez, Anastasiia Basylevska, Per O. A. Persson, Steven De Feyter, Miladin Radovic, Francisco Molina-Lopez, Jozef Vleugels
Summary: This work proposes a next-generation MILD (NGMILD) synthesis protocol for phase-pure, colloidally stable MXenes that can withstand long periods of dry storage. NGMILD incorporates the synergistic effects of a secondary salt, a richer lithium (Li) environment, and iterative alcohol-based washing to achieve high-purity MXenes, while improving etching efficiency, intercalation, and shelf life. The NGMILD-produced MXenes clays showed minimal degradation after being dry-stored for six months and retained excellent redispersibility.
Article
Chemistry, Multidisciplinary
Sasikumar Rahul, Miriam C. Rodriguez C. Gonzalez, Shingo Hirose, Hiromasa Kaneko, Kazukuni Tahara, Kunal S. Mali, Steven De Feyter
Summary: Chemical patterning surfaces have significant value in various fields such as electronics, catalysis, sensing, and photonics. We propose a new strategy for chemical patterning of graphite using a combination of covalent and non-covalent methods. By modifying the design of the template alkane and using alkane with alkoxy terminal groups, better pattern transfer fidelity can be achieved. We also introduce the use of chronoamperometry (CA) instead of cyclic voltammetry (CV) for functionalization, enabling the formation of patterns at different length scales.
Article
Chemistry, Multidisciplinary
Thi Mien Trung Huynh, Kazukuni Tahara, Steven De Feyter, Thanh Hai Phan
Summary: Multilayered growth is commonly seen when aryl diazonium derivatives are electrografted onto graphitic substrates. The mechanism of this growth has been studied through various methods, including measuring layer thickness, charge transfer, and simulations. However, spectroscopy and microscopy approaches have been underrepresented. This study presents a comparative characterization of multilayer growth using cyclic voltammetry, atomic force microscopy, and scanning tunneling microscopy, showing the influence of functional groups on the growth mechanism.
Article
Chemistry, Physical
Tamara Rinkovec, Demian Kalebic, Mark Van der Auweraer, Wim Dehaen, Jeremy N. Harvey, Steven De Feyter
Summary: This study investigates the effect of concentration on the self-assembly process of molecular networks using scanning tunneling microscopy. The research aims to improve the understanding of 2D supramolecular chemistry by obtaining quantitative data. The results show highly cooperative behavior and the significant impact of molecular structure on the critical concentration.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Multidisciplinary
Yuta Sato, Steven De Feyter, Kazukuni Tahara
Summary: This study reports the formation of porous structures on alkane buffer layers on graphite through molecular self-assembly. Dehydrobenzo[12]-annulene (DBA) derivative was found to form hexagonal structures on n-pentacontane and n-hexacontane buffer layers through van der Waals interactions. The nucleation and structural growth of the DBA network on a buffer layer were discussed, and a hierarchical multicomponent structure was formed through heteromolecular coadsorption. This study provides insights into the construction of intricate 3D nanoarchitectures using self-assembly at interfaces.
Article
Chemistry, Multidisciplinary
Matsuhiro Maeda, Kazuya Sato, Steven De Feyter, Kazukuni Tahara
Summary: We report the construction of homochiral, hierarchical self-assembled molecular networks at the liquid/graphite interface using a single chiral molecular building block through dynamic self-sorting.
