Study of NAP adsorption and assembly on the surface of HOPG

NAP is an octapeptide that has demonstrated a neuroprotective/therapeutic efficacy at very low concentrations in preclinical studies and in a number of clinical trials. Yet little is known about its structural organization at low concentrations. Here, we have employed atomic force microscopy to investigate NAP peptide assembly on graphite in aqueous media at nanomolar concentration. High spatial resolution scans of NAP assemblies reveal their fine structure with clearly resolved single NAP units. This observation leads us to conclude that NAP molecules do not form complex self-assembled structures at nanomolar concentration when adsorbed on graphite surface

Adsorption of Hexacontane on Hexagonal Boron Nitride

© 2018 American Chemical Society. We have investigated the adsorption of hexacontane (C60H122) on hexagonal boron nitride (hBN) using atomic force microscopy (AFM). The molecules can be deposited either by sublimation or from solution and form lamellar rows with dimensions of the order of 0.1-1 μm in three different rotational domains. High-resolution AFM images reveal that, similar to alkanes on graphite, the molecules are adsorbed parallel to the lattice vectors of hBN and we show using molecular mechanics that this corresponds to the lowest energy configuration. Lamellar rows with the same periodicity are observed even when several layers of hexacontane are deposited, although there is some orientational disorder in these multilayers. We also observe heat-induced modification of hexacontane, including recrystallization. We compare our results with recent X-ray studies of alkane adsorption on hBN and discuss the possible role of alkanes on steering molecular self-assembly on hBN

High-speed impact of the metal projectile on the barrier containing porous corundum-based ceramics with chemically active filler

The paper presents a calculation-experimental study on high-speed interaction of the metal projectile with a combined barrier made of porous corundum-based ceramics filled with chemically active composition (sulfur, nitrate of potash) in the wide range of speeds. A mathematical behavior model of porous corundum-based ceramics with chemically active filler is developed within the scope of mechanics of continuous media taking into account the energy embedding from a possible chemical reaction between a projectile metal and filler at high-speed impact. Essential embedding of inlet heat is not observed in the considered range of impact speeds (2.5 … 8 km/s)

Triplet Excitation and Electroluminescence from a Supramolecular Monolayer Embedded in a Boron Nitride Tunnel Barrier

© 2019 American Chemical Society. We show that ordered monolayers of organic molecules stabilized by hydrogen bonding on the surface of exfoliated few-layer hexagonal boron nitride (hBN) flakes may be incorporated into van der Waals heterostructures with integral few-layer graphene contacts forming a molecular/two-dimensional hybrid tunneling diode. Electrons can tunnel through the hBN/molecular barrier under an applied voltage VSD, and we observe molecular electroluminescence from an excited singlet state with an emitted photon energy hν > eVSD, indicating upconversion by energies up to ∼1 eV. We show that tunneling electrons excite embedded molecules into singlet states in a two-step process via an intermediate triplet state through inelastic scattering and also observe direct emission from the triplet state. These heterostructures provide a solid-state device in which spin-triplet states, which cannot be generated by optical transitions, can be controllably excited and provide a new route to investigate the physics, chemistry, and quantum spin-based applications of triplet generation, emission, and molecular photon upconversion

van der Waals-induced chromatic shifts in hydrogen-bonded two-dimensional porphyrin arrays on boron nitride

The fluorescence of a two-dimensional supramolecular network of 5,10,15,20-tetrakis(4-carboxylphenyl)porphyrin (TCPP) adsorbed on hexagonal boron nitride (hBN) is red shifted due to, primarily, adsorbate–substrate van der Waals interactions. TCPP is deposited from solution on hBN and forms faceted islands with typical dimensions of 100 nm and either square or hexagonal symmetry. The molecular arrangement is stabilized by in-plane hydrogen bonding as determined by a combination of molecular resolution atomic force microscopy performed under ambient conditions and density functional theory; a similar structure is observed on MoS2 and graphite. The fluorescence spectra of submonolayers of TCPP on hBN are red-shifted by ∼30 nm due to the distortion of the molecule arising from van der Waals interactions, in agreement with time-dependent density functional theory calculations. Fluorescence intensity variations are observed due to coherent partial reflections at the hBN interface, implying that such hybrid structures have potential in photonic applications

Bimolecular porous supramolecular networks deposited from solution on layered materials: graphite, boron nitride and molybdenum disulphide

A two-dimensional porous network formed from perylene tetracarboxylic diimide (PTCDI) and melamine may be deposited from solution on the surfaces of highly oriented pyrolytic graphite (HOPG), hexagonal boron nitride (hBN) and molybdenum disulphide (MoS2). Images acquired using high resolution atomic force microscopy (AFM) operating under ambient conditions have revealed that the network forms extended orderedmonolayers (41 lm2) on HOPG and hBN whereas on MoS2 much smaller islands are observed

Fluorescence and Electroluminescence of J-Aggregated Polythiophene Monolayers on Hexagonal Boron Nitride

The photophysics of a semiconducting polymer is manipulated through molecular self-assembly on an insulating surface. Adsorption of polythiophene (PT) monolayers on hexagonal boron nitride (hBN) leads to a structurally induced planarization and a rebalancing of inter- and intrachain excitonic coupling. This conformational control results in a dominant 0–0 photoluminescence peak and a reduced Huang–Rhys factor, characteristic of J-type aggregates, and optical properties which are significantly different to both PT thin films and single polymer strands. Adsorption on hBN also provides a route to explore electroluminescence from PT monolayers though incorporation into hybrid van der Waals heterostructures whereby the polymer monolayer is embedded within a hBN tunnel diode. In these structures we observe up-converted singlet electroluminescence from the PT monolayer, with an excitation mechanism based upon inelastic electron scattering. We argue that surface adsorption provides a methodology for the study of fundamental optoelectronic properties of technologically relevant polymers

Ultra-high resolution imaging of thin films and single strands of polythiophene using atomic force microscopy

Real-space images of polymers with sub-molecular resolution could provide valuable insights into the relationship between morphology and functionality of polymer optoelectronic devices, but their acquisition is problematic due to perceived limitations in atomic force microscopy (AFM). We show that individual thiophene units and the lattice of semicrystalline spin-coated films of polythiophenes (PTs) may be resolved using AFM under ambient conditions through the low-amplitude (≤ 1 nm) excitation of higher eigenmodes of a cantilever. PT strands are adsorbed on hexagonal boron nitride near-parallel to the surface in islands with lateral dimensions ~10 nm. On the surface of a spin-coated PT thin film, in which the thiophene groups are perpendicular to the interface, we resolve terminal CH3-groups in a square arrangement with a lattice constant 0.55 nm from which we can identify abrupt boundaries and also regions with more slowly varying disorder, which allow comparison with proposed models of PT domains

Lattice-matched epitaxial graphene grown on boron nitride

Lattice-matched graphene on hexagonal boron nitride is expected to lead to the formation of a band-gap but requires the formation of highly strained material and has not hitherto been realised. We demonstrate that aligned, lattice-matched graphene can be grown by molecular beam epitaxy using substrate temperatures in the range 1600-1710 °C and co-exists with a topologically-modified moiré pattern, and with regions of strained graphene which have giant moiré periods up to ~80 nm. Raman spectra reveal narrow red-shifted peaks due to isotropic strain, while the giant moiré patterns result in complex splitting of Raman peaks due to strain variations across the moiré unit cell. The lattice-matched graphene has a lower conductance than both the Frenkel-Kontorova-type domain walls, and also the topological defects where they terminate. We relate these results to theoretical models of band-gap formation in graphene/boron nitride heterostructures

Volatile Heterobimetallic Complexes from PdIIand CuIIβ-Diketonates: Structure, Magnetic Anisotropy, and Thermal Properties Related to the Chemical Vapor Deposition of Cu-Pd Thin Films

A novel approach for preparing volatile heterometallic complexes for use as precursors for the chemical vapor deposition of various materials is reported. New Cu¢Pd complexes based on b-diketonate units were prepared, and their structures and compositions were determined. [PdL2*CuL2] (1) and [PdL2*Cu(tmhd)2] (2) (L=2-methoxy-2,6,6-trimethylheptane-3,5-dionate; tmhd=2,2,6,6- tetramethylheptane-3,5-dionate) are 1D coordination polymers with alternating metal complexes, which are connected through weak interactions between the Cu atoms and the OCH3 groups from the ligand of the Pd complexes. The volatility and thermal stability were studied using thermogravimetric and differential thermal analyses and mass spectrometry. Compound 1 vaporizes without decomposition into monometallic complexes. It exhibits magnetic anisotropy, which was revealed from the angular variations in the EPR spectrum of a single crystal. The vapor thermolysis process for 1 was investigated using mass spectrometry, allowing the process to be framed within the temperature range of 200–3508C. The experimental data, supported by QTAIM calculations of the allowed intermolecular interactions, suggest that 1 likely exists in the gas phase as bimetallic molecules. Compound 1 proved to be suitable as a single-source precursor for the efficient preparation of Cu¢Pd alloy films with tunable Cu/Pd ratio. A possible mechanism for the film growth is proposed based on the reported data