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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.

On 12 December 2019, our colleague and friend Professor Dr. Gerhard H. Findenegg (cf. Figure 1) passed away after just having completed the eighty-first year of his life. He leaves behind his wife Irmgard Findenegg-Gröll with whom he was married for fifty-four years, their three daughters Klara, Helene, and Eva with their spouses, and seven grandchildren. The Findenegg family lost a loving and caring husband, father, father-in-law, and grandfather who cannot be replaced. At the moment of writing this foreword our thoughts are once again with Gerhard's family.

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., A 2D hyperbranched polyglycerol and its sulfated counterpart are synthesized using a graphene‐assisted strategy. The synthesized 2D polymers are used to inhibit the infection by severe acute respiratory syndrome corona virus 2 and show an inhibitory concentration as low as 3 nm.

Amphiphilic cyanine dyes in aqueous solution self-assemble into J-aggregates with diverse structures. In particular, the dye 3,3′-bis(3-sulfopropyl)-5,5′,6,6′-tetrachloro-1,1′-dioctylbenzimida-carbo-cyanine (C8S3) forms micrometer long double walled tubular J-aggregates with a uniform outer diameter of 13 ± 0.5 nm. Interestingly, these J-aggregates exhibit strong exciton delocalization and migration, similar to natural light harvesting systems. However, their structural integrity and hence their optical properties are very sensitive to their chemical environment as well as to mechanical deformation, rendering detailed studies on individual tubular J-aggregates difficult. We addressed this issue and examined a previously published route for their chemical and mechanical stabilization by in situ synthesis of a silica coating that leaves their absorbance and emission unaltered in solution. Here, we demonstrate that the silica shell with a thickness of a few nanometers is able to stabilize the tubular J-aggregates of C8S3 against changes of pH of solutions down to values where pure aggregates are oxidized, against drying under ambient conditions, and even against the vacuum conditions within an electron microscope. Dried silica–covered aggregates are brittle, as demonstrated by manipulation with a scanning force microscope on a surface. Transmission electron microscope images confirm that the thickness of the coatings is homogeneous and uniform with a thickness of less than 5 nm; scanning TEM energy dispersive X-ray spectroscopy confirms the chemical composition of the shell as SiO2; and electron energy loss spectra could be recorded across a single freely suspended aggregate. Such a silica shell may not only serve for stabilization but also could be the base for further functionalization of the aggregates by either chemical attachment of other units on top of the shell or by inclusion during the synthesis.

A controlled, reproducible, gram‐scale method is reported for the covalent functionalization of graphene sheets by a one‐pot nitrene [2+1] cycloaddition reaction under mild conditions. The reaction between commercially available 2,4,6‐trichloro‐1,3,5‐triazine and sodium azide with thermally reduced graphene oxide (TRGO) results in defined dichlorotriazine‐functionalized sheets. The different reactivities of the chlorine substituents on the functionalized graphene allow stepwise post‐modification by manipulating the temperature. This new method provides unique access to defined bifunctional 2D nanomaterials, as exemplified by chiral surfaces and multifunctional hybrid architectures.

Application of transition metal dichalcogenides (TMDC) in photonic, optoelectronic or valleytronic devices requires the growth of continuous monolayers, heterostructures and alloys of different materials in a single process. We present a facile pulsed thermal deposition method which provides precise control over layer thickness and stoichiometry of two-dimensional systems. The versatility of the method is demonstrated on ternary monolayers of Mo$_{1-x}$W$_{x}$S$_{2}$ and on heterostructures combining metallic TaS$_{2}$ and semiconducting MoS$_{2}$ layers. The fabricated ternary monolayers cover the entire composition range of $x$ = 0...1 without phase separation. Band gap engineering and control over the spin-orbit coupling strength is demonstrated by absorption and photoluminescence spectroscopy. Vertical heterostructures are grown without intermixing. The formation of clean and atomically abrupt interfaces is evidenced by high-resolution transmission electron microscopy. Since both the metal components as well as the chalcogenides are thermally evaporated complex alloys and heterostructures can thus be prepared.

Polyethylene glycol (PEG) is a structurally simple and nontoxic water-soluble polymer that is widely used in medical and pharmaceutical applications as molecular linker and spacer. In such applications, PEG's elastic response against conformational deformations is key to its function. According to text-book knowledge, a polymer reacts to the stretching of its end-to-end separation by a decrease in entropy that is due to the reduction of available conformations, which is why polymers are commonly called entropic springs. By a combination of single-molecule force spectroscopy experiments with molecular dynamics simulations in explicit water, we show that entropic hydration effects almost exactly compensate the chain conformational entropy loss at high stretching. Our simulations reveal that this entropic compensation is due to the stretching-induced release of water molecules that in the relaxed state form double hydrogen bonds with PEG. As a consequence, the stretching response of PEG is predominantly of energetic, not of entropic, origin at high forces and caused by hydration effects, while PEG backbone deformations only play a minor role. These findings demonstrate the importance of hydration for the mechanics of macromolecules and constitute a case example that sheds light on the antagonistic interplay of conformational and hydration degrees of freedom.

Control of intermolecular interactions is crucial to the exploitation of molecular semiconductors for both organic electronics and the viable manipulation and incorporation of single molecules into nano-engineered devices. Here we explore the properties of a class of materials that are engineered at a supramolecular level by threading a conjugated macromolecule, such as poly(para-phenylene), poly(4,4'-diphenylene vinylene) or polyfluorene through alpha- or beta-cyclodextrin rings, so as to reduce intermolecular interactions and solid-state packing effects that red-shift and partially quench the luminescence. Our approach preserves the fundamental semiconducting properties of the conjugated wires, and is effective at both increasing the photoluminescence efficiency and blue-shifting the emission of the conjugated cores, in the solid state, while still allowing charge-transport. We used the polymers to prepare single-layer light-emitting diodes with Ca and Al cathodes, and observed blue and green emission. The reduced tendency for polymer chains to aggregate allows solution-processing of individual polyrotaxane wires onto substrates, as revealed by scanning force microscopy.

Next-generation molecular devices and machines demand the integration of molecular switches into hierarchical assemblies to amplify the response of the system from the molecular level to the meso- or macro-scale. Here, we demonstrate that multi-azobenzene oligomers can assemble to form robust supramolecular nanofibers in which they can be switched repeatedly between the E- and Z-configuration. While in isolated oligomers the azobenzene units undergo reversible photoisomerization independently, in the nanofibers they are coupled via intermolecular interactions and switch cooperatively as evidenced by unusual thermal and kinetic behavior. We find that the photoisomerization rate from the Z-isomer to the E-isomer depends on the fraction of Z-azobenzene in the nanofibers and is increased by more than a factor of 4 in Z-rich fibers when compared to E-rich fibers. This demonstrates the great potential of coupling individual photochromic units for increasing their quantum efficiency in the solid state with potential relevance for actuation and sensing.

Supramolecular assemblies that interact with light have recently garnered much interest as well-defined nanoscale materials for electronic excitation energy collection and transport. However, to control such complex systems it is essential to understand how their various parts interact and whether these interactions result in coherently shared excited states (excitons) or in diffusive energy transport between them. Here, we address this by studying a model system consisting of two concentric cylindrical dye aggregates in a light-harvesting nanotube. Through selective chemistry we are able to unambiguously determine the supramolecular origin of the observed excitonic transitions. These results required the development of a new theoretical model of the supramolecular structure of the assembly. Our results demonstrate that the two cylinders of the nanotube have distinct spectral responses and are best described as two separate, weakly coupled excitonic systems. Understanding such interactions is critical to the control of energy transfer on a molecular scale, a goal in various applications ranging from artificial photosynthesis to molecular electronics.

PCR was successfully implemented into polymer chemistry to produce linear multiblock structures up to pentablock architectures. Salient features of the generated DNA polymer hybrids were the ultrahigh molecular weights and their structural accuracy. Besides pushing the limits in block copolymer synthesis. a highly sophisticated characterization of the DNA/synthetic polymer hybrids was carried out by scanning force microscopy (SFM). Direct visualization revealed single polymer chains with the expected contour lengths for the DNA blocks and a characteristic kink at the central organic polymer unit bridging them. Furthermore, DNA triblock copolymers were manipulated by SFM, which so far has only been demonstrated for neat DNA and dendronized polymers. Upon blowing circular topologies, the DNA and the organic polymer chain have been extended and the contours of the three blocks could thereby be imaged separately.

We demonstrate that an inverse Monte Carlo approach allows to reconstruct effective interaction potentials from real-space images. The method is exemplified on monomolecular ethanol-water films imaged with scanning force microscopy (SFM), which provides the spatial distribution of the molecules. Direct Monte Carlo simulations with the reconstructed potential allow for obtaining characteristics of the system which are unavailable in the experiment, such as the heat capacity of the monomolecularly thin film, and for a prediction of the critical temperature of the demixing transition., Accepted for publication as a Regular Article in Physical Review E; 12 pages, 12 figures

Multivalent biomolecular interactions allow for a balanced interplay of mechanical stability and malleability, and nature makes widely use of it. For instance, systems of similar thermal stability may have very different rupture forces. Thus it is of paramount interest to study and understand the mechanical properties of multivalent systems through well-characterized model systems. We analyzed the rupture behavior of three different bivalent pyridine coordination complexes with Cu2+ in aqueous environment by single-molecule force spectroscopy. Those complexes share the same supramolecular interaction leading to similar thermal off-rates in the range of 0.09 and 0.36 s−1, compared to 1.7 s−1 for the monovalent complex. On the other hand, the backbones exhibit different flexibility, and we determined a broad range of rupture lengths between 0.3 and 1.1 nm, with higher most-probable rupture forces for the stiffer backbones. Interestingly, the medium-flexible connection has the highest rupture forces, whereas the ligands with highest and lowest rigidity seem to be prone to consecutive bond rupture. The presented approach allows separating bond and backbone effects in multivalent model systems.

On the recently recorded-high resolution STM images of large polycyclic aromatic hydrocarbons (PAHs), submolecularly resolved patterns are observed, that differentiate between parts of the molecules in which, according to the Clar aromatic sextet theory, the ‘full’ and the ‘empty’ rings are located. This phenomenon has been explained by the shape of the frontier orbitals of the PAHs, usually by the HOMO or LUMO. We now put forward a simple theoretical model of the distribution of π-electrons in PAHs, that results in patterns remarkably similar to those observed in the STM images. A possible explanation for this coincidence is offered.

We correlate the morphology and energy level alignment of bilayer structures comprising the donor poly(3-hexylthiophene) (P3HT) and the acceptor polyfluorene copolymer poly(9,90dialklylfluorene-alt-4,7-bis(2,5-thiendiyl)-2,1,3-benzothiadiazole) (PFTBTT) with the performance of these bilayers in organic photovoltaic cells (OPVCs). The conducting polymer poly(ethylenedioxythiophene): poly (styrenesulfonate) (PEDT:PSS) was used as the bottom electrode and Ca as the top electrode. Ultraviolet photoelectron spectroscopy (UPS) revealed that notable interface dipoles occur at all interfaces across the OPVC structure, highlighting that vacuum level alignment cannot reliably be used to estimate the electronic properties for device design. Particularly the effective electrode work function values (after contact formation with the conjugated polymers) differ significantly from those of the pristine electrode materials. Chemical reactions between PEDT: PSS and P3HT on the one hand and Ca and PFTBTT on the other hand are identified as cause for the measured interface dipoles. The vacuum level shift between P3HT and PFTBTT is related to mutual energy level pinning at gap states. Annealing induced morphological changes at the P3HT/PFTBTT interface increased the efficiency of OPVCs, while the electronic structure was not affected by thermal treatment.

Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich. This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively. The combination of two techniques of controlled free radical polymerization, namely the reversible addition fragmentation chain transfer (RAFT) and the atom transfer radical polymerization (ATRP) techniques, together with the use of a macromonomer allowed the synthesis of symmetrical triblock copolymers, designed as amphiphilic dual brushes. One type of brush was made of poly(n-butyl acrylate) as soft hydrophobic block, i.e. characterized by a low glass transition temperature, while the other one was made of hydrophilic poly(ethylene glycol) (PEG). The new triblock polymers represent “giant surfactants” according to their molecular architecture. The hydrophobic and hydrophilic blocks microphase separate in the bulk. In aqueous solution, they aggregate into globular micellar aggregates, their size being determined by the length of the stretched polymer molecules. As determined by the combination of various scattering techniques for the dual brush copolymer, a rather compact structure is formed, which is dominated by the large hydrophobic poly(n-butyl acrylate) block. The aggregation number for the dual brush is about 10 times larger than for the “semi-brush” precursor copolymer, due to the packing requirements for the much bulkier hydrophobic core. On mica surfaces the triblock copolymers adsorb with worm-like backbones and stretched out side chains.

Molecular brush diblock copolymers were synthesized by the orthogonal overlay of the RAFT (reversible addition-fragmentation chain transfer), the ATRP (atom transfer radical polymerization), and the NMP (nitroxide-mediated polymerization) techniques. This unique combination enabled the synthesis of the complex amphiphilic polymers without the need of postpolymerization modifications, using a diblock copolymer intermediate made from two selectively addressable inimers and applying a sequence of four controlled free radical polymerization steps in total. The resulting polymers are composed of a thermosensitive poly(N-isopropylacrylamide) brush as hydrophilic block and a polystyrene brush as hydrophobic block, thus translating the structure of the established amphiphilic diblock copolymers known as macro surfactants to the higher size level of ""giant surfactants"". The dual molecular brushes and the aggregates formed on ultra flat solid substrates were visualized by scanning force microscopy (SFM).

Amphiphilic dual brush diblock as well as symmetrical triblock polymers were synthesized by the overlay of the reversible addition-fragmentation chain transfer (RAFT) and the nitroxide mediated polymerization (NMP) techniques. While poly(ethylene glycol) brushes served as hydrophilic block, the hydrophobic block was made of polystyrene brushes. The resulting "giant surfactants" correspond structurally to the established amphiphilic diblock and triblock copolymer known as macrosurfactants. The aggregation behavior of the novel "giant surfactants" in aqueous solution was studied by dynamic light scattering, small-angle neutron scattering (SANS), and small-angle X-ray scattering (SAXS) over a large range in reciprocal space. Further, the self-assembled aggregates were investigated by scanning force microscopy (SFM) after deposition on differently functionalized ultraflat solid substrates. Despite the high fraction of hydrophobic segments, the polymers form stable mesoscopic, spherical aggregates with hydrodynamic diameters in the range of 150-350 nm. Though prepared from well-defined individual polymers, the aggregates show several similarities to hard core latexes. They are stable enough to be deposited without much changes onto surfaces, where they cluster and show spontaneous sorting according to their size within the clusters, with the larger aggregates being in the center.

Thelightweight,simple processability,andmechanical flexibilityofconjugatedorganicsemiconductorshasrecentlyledtoremark-able research efforts towards realizing new (opto) electronicdevices, their manifold known as organic electronics. Amongstthese devices, organic field-effect transistors (OFETs) arerecognized as key tools/building blocks for the implementationof electronic logic circuits

We report on the realization of fully flexible and transparent n-type and ambipolar all-organic OFETs. A double layer, pentacene-C60 heterojunction, was used as the semiconductor layer. The contacts were made with poly(ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT:PSS) and patterned by means of Soft Lithography MicroContact Printing (mu CP). Interestingly, as demonstrated by atomic force microscopy and X-ray diffraction investigations, growing C60 on a pre-deposited pentacene buffer layer leads to a clear improvement in the morphology and crystallinity of the deposited film allowing to obtain n-type conduction despite the very high electron injection barrier at the interface between PEDOT:PSS and C60. As a result, it was possible to realize n-type and ambipolar all-organic OFETs by optimizing the thicknesses of the pentacene buffer layer. All devices, measured in air, worked in accumulation mode with mobilities up to 1 x 10(-2) cm(2)/V S and 3.5 x 10(-4) cm(2)/V s for p-type and n-type regimes, respectively. This is particularly interesting because it demonstrates, also for n-type and ambipolar transistors, the possibility of avoiding problems normally associated to metal contacts: the lack of mechanical robustness, flexibility, and the unfeasibility of realizing contacts with low cost techniques like printing or soft lithography. These results confirm the importance of the substrate properties for the ordered growth of organic semiconductors, which determines the transport properties of organic materials. (c) 2007 Elsevier B.V. All rights reserved.

Thin films of pentacene (P) have been vacuum codeposited on SiO2 with low concentrations of 6,13-pentacenequinone (PQ) in order to investigate the impact on the pentacene thin film structure. Within a range of 2%–20% PQ concentration no intercalation of the compounds can be observed by means of x-ray diffraction and infrared absorption spectroscopy. The crystalline quality of the P films stays unchanged by the presence of PQ, whereas P bulk phase contributions are being suppressed at PQ concentrations ⩾5%, which could be confirmed by means of atomic force microscopy. From the results the authors suggest phase-separated PQ growth as well as PQ nucleation at P grain boundaries.

Pentacene (P) and 6,13-pentacenequinone (PQ) have been vacuum codeposited onto $\mathrm{Si}{\mathrm{O}}_{2}$ in order to control phase separation in thin films for the application as bulk heterojunctions in organic photovoltaic devices. Structural investigations by means of scanning electron microscopy (SEM) and atomic force microscopy revealed pronounced phase separation of the two materials at length scales that turned out to be tunable by the variation of the deposition rate. X-ray diffraction provided evidence for polymorphism in pure films of P and PQ on $\mathrm{Si}{\mathrm{O}}_{2}$. While pure films exhibited both the bulk and thin-film phase, the bulk phase is mainly suppressed within the co-deposited films $(\mathrm{P}+\mathrm{PQ})$. This was corroborated by Fourier-transform infrared spectroscopy results. SEM investigations of pure and codeposited films indicated that PQ bulk crystallites of up to $200\phantom{\rule{0.3em}{0ex}}\mathrm{nm}$ height form continuous paths to the substrate and grow within a matrix formed of P and PQ thin-film phases. The obtained heterojunction morphologies thus appear interesting for the application in organic-based photovoltaic cells.

We use ultraviolet photoelectron spectroscopy to investigate the effect of oxygen and air exposure on the electronic structure of pentacene thin films. It is found that O2 and water do not react noticeably with pentacene, whereas singlet oxygen/ozone readily oxidize the organic compound. Also, we obtain no evidence for considerable p-type doping of pentacene by O2 at low pressure. However, oxygen exposure lowers the hole injection barrier at the interface between Au and pentacene by 0.25 eV, presumably due to a modification of the Au surface.

The energy-level alignment at interfaces between three electroactive conjugated organic materials and Au was systematically varied by adjusting the precoverage of the metal substrate with the electron acceptor tetrafluoro-tetracyanoquinodimethane (F4-TCNQ). Photoelectron spectroscopy revealed that electron transfer from Au to adsorbed F4-TCNQ was responsible for lowering the hole-injection barrier by as much as 1.2 eV. This novel interface modification scheme is independent of the charge transfer complex formation ability of the organic materials with the electron acceptor.

Lining up: Polyisocyanide derivatives bearing L-alanyl-D-alanine methyl ester side groups (PIAA) have been adsorbed on the surface of muscovite mica. Scanning force microscopy images reveal single polymer chains with contour lengths ranging from several hundred nanometers up to several micrometers. Their orientation on the micrometer scale is attributed to hydrodynamic flow during the sample preparation (see figure). These long and stiff polymers, which exhibit a persistence length of 76 nm if equilibrated on a surface, can possess an even higher anisometry when brought into non-equilibrium states.

Highly ordered monolayers of a long‐chain molecule, dotriacontane (C32H66), have been obtained by self‐assembly at the interface between an organic solution and the basal planes of two semiconductors, MoSe2 and MoS2. Scanning tunneling microscopy in situ at the solid–fluid interfaces revealed that the adsorbate lattices are close packed and oriented relative to the substrate lattices, but that they are not simply commensurate. The results indicate that for flexible chain molecules, which interact only weakly with the surface of a solid substrate, a high degree of order in the adsorbed monolayers is induced by the atomical flatness of the substrate, while the coincidence of lattice parameters and the specific surface chemistry play only a minor role. Details of the packing, including the symmetry of the adsorbate unit cell, depend on the particular substrate. The results imply that atomical flatness is a key factor for the fabrication of highly ordered organic/inorganic heterostructures.

The vertical dimensions of the well-characterized test samples tobacco mosaic virus, T4 bacteriophage polyhead, purple membrane, and hexagonally packed intermediate (HPI) layer were investigated by tapping mode scanning force microscopy (SFM) in solution. Purple membrane and HPI layer were imaged in both contact mode and tapping mode SFM for direct comparison. All vertical dimensions match the known heights. The practical implications of the absence of frictional forces in tapping mode are discussed.