Synthesis of Chiral Triazine Frameworks for Enantiodiscrimination.

Manipulation of the structure of covalent organic frameworks at the molecular level is an efficient strategy to shift their biological, physicochemical, optical, and electrical properties in the desired windows. In this work, we report on a new method to construct chiral triazine frameworks using metal-driven polymerization for enantiodiscrimination. The nucleophilic substitution reaction between melamine and cyanuric chloride was performed in the presence of PdCl2, ZnCl2, and CuCl2 as chirality-directing agents. Palladium, with the ability of planar complex formation, was able to assemble monomers in two-dimensions and drive the reaction in two directions, leading to a two-dimensional triazine network with several micrometers lateral size. Nonplanar arrangements of monomers in the presence of ZnCl2 and CuCl2, however, resulted in calix and bouquet structures, respectively. While 2D and bouquet structures showed strong negative and positive bands in the CD spectra, respectively, their calix counterparts displayed long-range weak negative bands. In spite of the ability of both calix and bouquet networks to load l-histidine 35 and 50% more than d-histidine from pure enantiomers, respectively, only calix counterparts were able to take up this enantiomer (78%) from the racemic mixture. The two-dimensional polytriazine network did not show any specific interactions with pure enantiomers or their racemic mixtures.

Room Temperature On-Surface Synthesis of a Vinylene-Linked Single Layer Covalent Organic Framework.

Conjugated single-layered two-dimensional covalent organic frameworks are flat and extended polymer networks with a unique combination of material properties, giving rise to potential applications in sensing, optoelectronics, and photonics. Despite their great potential, thus far only a few reactions to access such extended conjugated 2D polymers have been reported. Here, the on-surface polymerization of the first vinylene-linked single layered two-dimensional covalent organic framework using reversible Knoevenagel polycondensation under solvothermal conditions is described. Self-assembly of the two monomer building blocks at the solid-liquid interface led to the formation of extended covalent networks at room temperature without the need of additional catalysts or reagents. The described approach grants access to extended conjugated 2D polymers under unprecedentedly mild conditions and paves the way to new hybrid material systems.

Collective States in Molecular Monolayers on 2D Materials.

Collective excited states form in organic two-dimensional layers through Coulomb coupling of the molecular transition dipole moments. They manifest as characteristic strong and narrow peaks in the excitation and emission spectra that are shifted to lower energies compared with the monomer transition. We study experimentally and theoretically how robust the collective states are against homogeneous and inhomogeneous broadening, as well as spatial disorder that occurs in real molecular monolayers. Using a microscopic model for a two-dimensional dipole lattice in real space, we calculate the properties of collective states and their extinction spectra. We find that the collective states persist even for 1-10% random variation in the molecular position and in the transition frequency, with a peak position and integrated intensity similar to those for the perfectly ordered system. We measured the optical response of a monolayer of the perylene derivative MePTCDI on two-dimensional materials. On the wide-band-gap insulator hexagonal boron nitride, it shows strong emission from the collective state with a line width that is dominated by the inhomogeneous broadening of the molecular state. When the semimetal graphene is used as a substrate, however, the luminescence is completely quenched. By combining optical absorption, luminescence, and multiwavelength Raman scattering, we verify that the MePTCDI molecules form very similar collective monolayer states on hexagonal boron nitride and graphene substrates, but on graphene the line width is dominated by nonradiative excitation transfer from the molecules to the substrate. Our study highlights the transition from the localized molecular state of the monomer to a delocalized collective state in the two-dimensional molecular lattice that is entirely based on Coulomb coupling between optically active excitations of the electrons and molecular vibrations. The excellent properties of organic monolayers make them promising candidates for components of soft-matter optoelectronic devices.

Bottom-up Solution Synthesis of Graphene Nanoribbons with Precisely Engineered Nanopores.

The incorporation of nanopores into graphene nanostructures has been demonstrated as an efficient tool in tuning their band gaps and electronic structures. However, precisely embedding the uniform nanopores into graphene nanoribbons (GNRs) at the atomic level remains underdeveloped especially for in-solution synthesis due to the lack of efficient synthetic strategies. Herein we report the first case of solution-synthesized porous GNR (pGNR) with a fully conjugated backbone via the efficient Scholl reaction of tailor-made polyphenylene precursor (P1) bearing pre-installed hexagonal nanopores. The resultant pGNR features periodic subnanometer pores with a uniform diameter of 0.6 nm and an adjacent-pores-distance of 1.7 nm. To solidify our design strategy, two porous model compounds (1 a, 1 b) containing the same pore size as the shortcuts of pGNR, are successfully synthesized. The chemical structure and photophysical properties of pGNR are investigated by various spectroscopic analyses. Notably, the embedded periodic nanopores largely reduce the π-conjugation degree and alleviate the inter-ribbon π-π interactions, compared to the nonporous GNRs with similar widths, affording pGNR with a notably enlarged band gap and enhanced liquid-phase processability.

At Least 10-fold Higher Lubricity of Molecularly Thin D2O vs H2O Films at Single-Layer Graphene-Mica Interfaces.

Interfacial water is a widespread lubricant down to the nanometer scale. We investigate the lubricities of molecularly thin H2O and D2O films confined between mica and graphene, via the relaxation of initially applied strain in graphene employing Raman spectroscopy. Surprisingly, the D2O films are at least 1 order of magnitude more lubricant than H2O films, despite the similar bulk viscosities of the two liquids. We propose a mechanism based on the known selective permeation of protons vs deuterons through graphene. Permeated protons and left behind hydroxides may form ion pairs clamping across the graphene sheet and thereby hindering the graphene from sliding on the water layer. This explains the lower lubricity but also the hindering diffusivity of the water layer, which yields a high effective viscosity in accordance with findings in dewetting experiments. Our work elucidates an unexpected effect and provides clues to the behavior of graphene on hydrous surfaces.

Resonant Electron Tunneling Induces Isomerization of π-Expanded Oligothiophene Macrocycles in a 2D Crystal.

Macrocyclic oligothiophenes and their π-expanded derivatives constitute versatile building blocks for the design of (supra)molecularly engineered active interfaces, owing to their structural, chemical, and optoelectronic properties. Here, it is demonstrated how resonant tunneling effect induces single molecular isomerization in a 2D crystal, self-assembled at solid-liquid interfaces under ambient conditions. Monolayers of a series of four π-expanded oligothiophene macrocycles are investigated by means of scanning tunneling microscopy and scanning tunneling spectroscopy (STS) at the interface between their octanoic acid solutions and the basal plane of highly oriented pyrolytic graphite. Current-voltage characteristics confirm the donor-type character of the macrocycles, with the highest occupied molecular orbital and the lowest unoccupied molecular orbital (LUMO) positions consistent with time-dependent density functional theory calculations. Cyclic STS measurements show the redox isomerization from Z,Z-8T6A to its isomer E,E-8T6A occurring in the 2D crystal, due to the formation of a negatively charged species when the tunneling current is in resonance with the LUMO of the macrocycle.

Graphene-Assisted Synthesis of 2D Polyglycerols as Innovative Platforms for Multivalent Virus Interactions.

2D nanomaterials have garnered widespread attention in biomedicine and bioengineering due to their unique physicochemical properties. However, poor functionality, low solubility, intrinsic toxicity, and nonspecific interactions at biointerfaces have hampered their application in vivo. Here, biocompatible polyglycerol units are crosslinked in two dimensions using a graphene-assisted strategy leading to highly functional and water-soluble polyglycerols nanosheets with 263 ± 53 nm and 2.7 ± 0.2 nm average lateral size and thickness, respectively. A single-layer hyperbranched polyglycerol containing azide functional groups is covalently conjugated to the surface of a functional graphene template through pH-sensitive linkers. Then, lateral crosslinking of polyglycerol units is carried out by loading tripropargylamine on the surface of graphene followed by lifting off this reagent for an on-face click reaction. Subsequently, the polyglycerol nanosheets are detached from the surface of graphene by slight acidification and centrifugation and is sulfated to mimic heparin sulfate proteoglycans. To highlight the impact of the two-dimensionality of the synthesized polyglycerol sulfate nanosheets at nanobiointerfaces, their efficiency with respect to herpes simplex virus type 1 and severe acute respiratory syndrome corona virus 2 inhibition is compared to their 3D nanogel analogs. Four times stronger in virus inhibition suggests that 2D polyglycerols are superior to their current 3D counterparts.

Reversible Switching of Charge Transfer at the Graphene-Mica Interface with Intercalating Molecules.

Understanding and controlling charge transfer through molecular nanostructures at interfaces is of paramount importance, particularly for electronic devices but also for contact electrification or in bioelectronics. We investigate the influence of intercalation and exchange of molecularly thin layers of small molecules (water, ethanol, 2-propanol, and acetone) on charge transfer at the well-defined interface between an insulator (muscovite mica) and a conductor (graphene). Raman spectroscopy is used to probe the charge carriers in graphene. While a molecular layer of water blocks charge transfer between mica and graphene, a layer of the organic molecules allows for it. The exchange of molecular water layers with ethanol layers switches the charge transfer very efficiently from off to on and back. We propose a charge transfer model between occupied mica trap states and electronic states of graphene, offset by the electrostatic potentials produced by the molecular dipole layers, as supported by molecular dynamics simulations. Our work demonstrates how intercalation of molecules of volatile liquids can reversibly affect charge transfer at interfaces. This implies its strong impact on the function of hybrid inorganic-organic electronic devices in different ambients and potential applications, including sensors and actuators.

Quantification of Multivalent Interactions between Sialic Acid and Influenza A Virus Spike Proteins by Single-Molecule Force Spectroscopy.

Multivalency is a key principle in reinforcing reversible molecular interactions through the formation of multiple bonds. The influenza A virus deploys this strategy to bind strongly to cell surface receptors. We performed single-molecule force spectroscopy (SMFS) to investigate the rupture force required to break individual and multiple bonds formed between synthetic sialic acid (SA) receptors and the two principal spike proteins of the influenza A virus (H3N2): hemagglutinin (H3) and neuraminidase (N2). Kinetic parameters such as the rupture length (χß) and dissociation rate (koff) are extracted using the model by Friddle, De Yoreo, and Noy. We found that a monovalent SA receptor binds to N2 with a significantly higher bond lifetime (270 ms) compared to that for H3 (36 ms). By extending the single-bond rupture analysis to a multibond system of n protein-receptor pairs, we provide an unprecedented quantification of the mechanistic features of multivalency between H3 and N2 with SA receptors and show that the stability of the multivalent connection increases with the number of bonds from tens to hundreds of milliseconds. Association rates (kon) are also provided, and an estimation of the dissociation constants (KD) between the SA receptors to both proteins indicate a 17-fold higher binding affinity for the SA-N2 bond with respect to that of SA-H3. An optimal designed multivalent SA receptor showed a higher binding stability to the H3 protein of the influenza A virus than to the monovalent SA receptor. Our study emphasizes the influence of the scaffold on the presentation of receptors during multivalent binding.

Metal-Assisted and Solvent-Mediated Synthesis of Two-Dimensional Triazine Structures on Gram Scale.

Covalent triazine frameworks are an emerging material class that have shown promising performance for a range of applications. In this work, we report on a metal-assisted and solvent-mediated reaction between calcium carbide and cyanuric chloride, as cheap and commercially available precursors, to synthesize two-dimensional triazine structures (2DTSs). The reaction between the solvent, dimethylformamide, and cyanuric chloride was promoted by calcium carbide and resulted in dimethylamino-s-triazine intermediates, which in turn undergo nucleophilic substitutions. This reaction was directed into two dimensions by calcium ions derived from calcium carbide and induced the formation of 2DTSs. The role of calcium ions to direct the two-dimensionality of the final structure was simulated using DFT and further proven by synthesizing molecular intermediates. The water content of the reaction medium was found to be a crucial factor that affected the structure of the products dramatically. While 2DTSs were obtained under anhydrous conditions, a mixture of graphitic material/2DTSs or only graphitic material (GM) was obtained in aqueous solutions. Due to the straightforward and gram-scale synthesis of 2DTSs, as well as their photothermal and photodynamic properties, they are promising materials for a wide range of future applications, including bacteria and virus incapacitation.

Edge Phonon Excitations in a Chiral Self-Assembled Supramolecular Nanoribbon.

By design, coupled mechanical oscillators offer a playground for the study of crystalline topology and related properties. Particularly, non-centrosymmetric, supramolecular nanocrystals feature a complex phonon spectrum where edge modes may evolve. Here we show, employing classical atomistic calculations, that the edges of a chiral supramolecular nanoribbon can host defined edge phonon states. We suggest that the topology of several edge modes in the phonon spectrum is nontrivial and thermally insulated from bulk states. By means of molecular dynamics, we excite a supramolecular bond to launch a directional excitation along the edge without considerable bulk or back-propagation. Our results suggest that supramolecular monolayers can be employed to engineer phonon states that are robust against backscattering, toward supramolecular thermal waveguides, diodes, and logics.

Construction and Evaluation of a Self-Calibrating Multiresponse and Multifunctional Graphene Biosensor.

Recently, many studies have been focused on the development of graphene-based biosensors. However, they rely on one type of signal and need to be calibrated by other techniques. In this study, a nonenzymatic graphene-based biosensor has been designed and constructed. Its ability to detect glucose and Escherichia coli by three different types of signals has been investigated. For its preparation, dopamine-functionalized polyethylene glycol and 2,5-thiophenediylbisboronic acid were conjugated onto the surface of graphene sheets by nitrene [2 + 1] cycloaddition and condensation reactions, respectively. Multivalent interactions between boronic acid segments and biosystems consequently increased the quantifiable fluorescence emission and UV absorption of dopamine segments. Additionally, changing the electrochemical behavior of the functionalized graphene sheets was possible and resulted in a measurable output signal. Conjugation of mannose onto the surface of the biosensor improved its magnitude of signals and specificity for sensing E. coli in a complex medium. The efficiency and accuracy of each signal was monitored by others, which resulted in a real-time self-calibrating biosensor. Taking advantage of the versatility of the three different indicators, including florescence, UV, and electrochemistry, the functionalized graphene sheets have been used as self-regulating biosensors to detect a variety of biosystems with a high accuracy and specificity in a short time.

Scalable Production of Nanographene and Doping via Nondestructive Covalent Functionalization.

A new method for top-down, one-pot, gram-scale production of high quality nanographene by incubating graphite in a dilute sodium hypochlorite solution at only 40 °C is reported here. The produced sheets have only 4 at% oxygen content, comparable with nanographene grown by chemical vapor deposition. The nanographene sheets are covalently functionalized using a nondestructive nitrene [2+1] cycloaddition reaction that preserves their π-conjugated system. Statistical analyses of Raman spectroscopy and X-ray photoelectron spectroscopy indicate a low number of sp3 carbon atoms on the order of 2% before and 4% after covalent functionalization. The nanographene sheets are significantly more conductive than conventionally prepared nanographene oxide, and conductivity further increases after covalent functionalization. The observed doping effects and theoretical studies suggest sp2 hybridization for the carbon atoms involved in the [2+1] cycloaddition reaction leading to preservation of the π-conjugated system and enhancing conductivity via n-type doping through the bridging N-atom. These methods are easily scalable, which opens the door to a mild and efficient process to produce high quality nanographenes and covalently functionalize them while retaining or improving their physicochemical properties.

Force Spectroscopy Shows Dynamic Binding of Influenza Hemagglutinin and Neuraminidase to Sialic Acid.

The influenza A virus infects target cells through multivalent interactions of its major spike proteins, hemagglutinin (HA) and neuraminidase (NA), with the cellular receptor sialic acid (SA). HA is known to mediate the attachment of the virion to the cell, whereas NA enables the release of newly formed virions by cleaving SA from the cell. Because both proteins target the same receptor but have antagonistic functions, virus infection depends on a properly tuned balance of the kinetics of HA and NA activities for viral entry to and release from the host cell. Here, dynamic single-molecule force spectroscopy, based on scanning force microscopy, was employed to determine these bond-specific kinetics, characterized by the off rate koff, rupture length xß and on rate kon, as well as the related free-energy barrier ΔG and the dissociation constant KD. Measurements were conducted using surface-immobilized HA and NA of the influenza A virus strain A/California/04/2009 and a novel, to our knowledge, synthetic SA-displaying receptor for functionalization of the force probe. Single-molecule force spectroscopy at force loading rates between 100 and 50,000 pN/s revealed most probable rupture forces of the protein-SA bond in the range of 10-100 pN. Using an extension of the widely applied Bell-Evans formalism by Friddle, De Yoreo, and co-workers, it is shown that HA features a smaller xß, a larger koff and a smaller ΔG than NA. Measurements of the binding probability at increasing contact time between the scanning force microscopy force probe and the surface allow an estimation of KD, which is found to be three times as large for HA than for NA. This suggests a stronger interaction for NA-SA than for HA-SA. The biological implications in regard to virus binding to the host cell and the release of new virions from the host cell are discussed.

Influence of interface hydration on sliding of graphene and molybdenum-disulfide single-layers.

Humidity influences friction in layered materials in peculiar ways. For example, while water improves the lubricating properties of graphite, it deteriorates those of molybdenum disulfide (MoS2). The reasons remain debated, not the least due to the difficulty in experimentally comparing dry and hydrated interface frictions. Here we show that the hydration of interfaces between a mica substrate and single-layers of graphene and MoS2 with a molecularly thin water layer affects strain transfer from the substrate to the 2D materials. For this, we strain the substrate and detect strain in graphene and MoS2 by changes in Raman and photoluminescence spectra, respectively. Strain relaxation in graphene changes from stick-slip in dry contact, to viscous when hydrated. In contrast, there is no viscous relaxation in MoS2 regardless of hydration. Our work provides a novel approach for better understanding the impact of hydration on friction in layered materials.

Sialyl-LacNAc-PNA⋠DNA Concatamers by Rolling-Circle Amplification as Multivalent Inhibitors of Influenza†A Virus Particles.

The surfaces of influenza A virus (IAV) particles are packed with hundreds of homo-trimeric hemagglutinins (HAs). Monovalent sugars have low affinity for HA, but distance-optimized bivalent sialyl-LacNAc (SLN) conjugates bind it with 103 -fold enhanced potency. Herein, we describe the oligomerization of distance-optimized bivalent binders by branched and linear hybridization on long repetitive DNA templates. The most effective complexes fully inhibited IAVs at a DNA template concentration of 10-9 m. Although a 10-2 m concentration of free trisaccharide ligand is required for full inhibition of the virus, DNA templating enables a 104 -fold reduction in the amount of sugar required. Notably, hybridization-induced rigidification of the DNA templates increased the serospecificity. Cryo-TEM analysis revealed that both spaghetti-type linear forms and cotton-ball-like clusters are able to bridge several adjacent HA molecules on the IAV surface. Programmed self-assembly of ligand-nucleic acid conjugates on long DNA templates might provide generic access to target-specific, high-affinity binders of proteins on globular objects such as cells and viruses.

Non-monotonous Wetting of Graphene-Mica and MoS2-Mica Interfaces with a Molecular Layer of Water.

Hydration of interfaces with a layer of water is a ubiquitous phenomenon, which has important implications for numerous natural and technologically important processes. Nevertheless, at the nanoscale, the understanding of the wetting process is still limited, since it is experimentally difficult to follow. Here, graphene and monolayers of MoS2 deposited on dry mica are used to investigate wetting of the two-dimensional (2D) material-mica interfaces with a molecularly thin layer of water employing scanning force microscopy in different modes. Wetting occurs non-monotonously in time and space for both types of interfaces. It starts at relative humidities (RH) of 10-17% for graphenes and 8-9% for MoS2 and concludes with a homogeneous layer at 25-30 and 15-20%, respectively. Investigation of the process at the graphene-mica interface indicates that up to about 25% RH, initially a highly compliant and unstable layer of water spreads, which subsequently stabilizes by developing labyrinthine nanostructures. Moreover, these nanostructures exhibit distinct mechanical deformability and dissipation, which is ascribed to different densities of the confined water layer. The laterally structured morphology is explained by the interplay of counteracting long-range dipole-dipole repulsion and short-range line tension, with the latter causing at least in part by the mechanical deformation of the 2D material. The proposed origins of the interactions are common for thin layers of polar molecules at interfaces, implying that the lateral structuring of thin wetting layers at submonolayer concentrations may also be a quite general phenomenon.

Reversible Photoisomerization of Monolayers of π-Expanded Oligothiophene Macrocycles at Solid-Liquid Interfaces.

Self-assembled monolayers of a π-expanded oligothiophene macrocycle undergo photoisomerization between their Z,Z and E,E diastereomers at the interface between octanoic acid solutions and highly oriented pyrolytic graphite (HOPG). The switching process proceeds in situ at the solid-liquid interface and was followed by scanning tunneling microscopy (STM). Upon illumination with light at 365 nm (546 nm), a monolayer of Z,Z-8mer (E,E-8mer) photoisomerizes to the E,E-8mer (Z,Z-8mer) form with changes in 2D hexagonal packing. These findings provide insight towards the design of photoresponsive surfaces with desirable optoelectronic and structural (host-guest) properties.