Surface Confined Hydrogenation of Graphene Nanoribbons.

On-surface synthesis with designer precursor molecules is considered an effective method for preparing graphene nanoribbons (GNRs) of well-defined widths and with tunable electronic properties. Recent reports have shown that the band gap of ribbons doped with heteroatoms (such as boron, nitrogen, and sulfur) remains unchanged in magnitude in most cases. Nevertheless, theory predicts that a tunable band gap may be engineered by hydrogenation, but experimental evidence for this is so far lacking. Herein, surface-confined hydrogenation studies of 7-armchair graphene nanoribbons (7-AGNRs) grown on Au(111) surfaces, in an ultrahigh vacuum environment, are reported. GNRs are first prepared, then hydrogenated by exposure to activated hydrogen atoms. High resolution electron energy loss spectroscopy (HREELS) and scanning tunneling microscopy (STM) images reveal a self-limited hydrogenation process. By means of a combination of bond-resolved scanning tunneling microscopy (BRSTM) imaging and tip-induced site-specific dehydrogenation, the hydrogenation mechanism is studied in detail, and density-functional theory (DFT) calculation methods are used to complement the experimental findings. In all cases, the results demonstrate the successful modification of the electronic properties of the GNR/Au(111) system by edge and basal-plane hydrogenation, and a mechanism for the hydrogenation process is proposed.

On-surface condensation of low-dimensional benzotriazole-copper assemblies.

The reactivity of benzotriazole with copper on a gold surface has been studied by a combination of surface sensitive methods with support from DFT (density functional theory) calculations. For some time benzotriazole has been known to enhance the corrosion resistance of copper at the monolayer level, although the exact mechanism is still a matter of discussion and disagreement in the literature. A single crystal Au(111) surface allows evaluation of the interaction of weakly physisorbed, intact benzotriazole molecules with copper atoms dosed to sub-monolayer amounts. These interactions have been characterised, in the temperature range ca. 300-650 K, by scanning tunnelling microscopy, high resolution electron energy loss spectroscopy and synchrotron-based X-ray photoemission spectroscopy and near-edge X-ray absorption fine structure studies. Supporting DFT calculations considered the stability of isolated, gas-phase, benzotriazole/Cu species and their corresponding spectroscopic signature at the N K absorption edge. In agreement with previous investigations, benzotriazole physisorbs on a clean Au(111) surface at room temperature forming a hydrogen-bonded network of flat-lying BTAH molecules, relatively weakly bonded to the underlying gold surface. However, in the presence of co-adsorbed copper atoms, proton removal from the molecules leads to species better described as BTA- interacting directly with Cu atoms. In these situations the molecules adopt a more upright orientation and Cu(BTA)2 and -[Cu(BTA)]n- species are formed, depending on temperature and coverage of the adsorbed species. These species are stable to relatively high temperatures, 550-600 K.

Biochemical and functional characterization of glycosaminoglycans released from degranulating rat peritoneal mast cells: Insights into the physiological role of endogenous heparin.

The properties of commercially prepared heparin as an anticoagulant and antithrombotic agent in medicine are better understood than is the physiological role of heparin in its native form, where it is uniquely found in the secretory granules of mast cells. In the present study we have isolated and characterised the glycosaminoglycans (GAGs) released from degranulating rat peritoneal mast cells. Analysis of the GAGs by NMR spectroscopy showed the presence of both heparin and the galactosaminoglycan dermatan sulphate; heparinase digestion profiles and measurements of anticoagulant activity were consistent with this finding. The rat peritoneal mast cell GAGs significantly inhibited accumulation of leukocytes in the rat peritoneal cavity in response to IL-1ß (p < 0.05, n = 6/group), and inhibited adhesion and diapedesis of leukocytes in the inflamed rat cremasteric microcirculation in response to LPS (p < 0.001, n = 4/group). FTIR spectra of human umbilical vein endothelial cells (HUVECs) were altered by treatment of the cells with heparin degrading enzymes, and restored by the addition of exogenous heparin. In conclusion, we have shown that rat peritoneal mast cells contain a mixture of GAGs that possess anticoagulant and anti-inflammatory properties.

Adsorption of a dihydro-TTF derivative on Au(111) via a thiolate complex bonding to gold adatoms.

A dihydro-TTF derivative with four acetyl-protected thiol ligands was synthesised and adsorbed on Au(111) under UHV conditions. Scanning Tunnelling Microscopy (STM) and Infrared (IR) spectroscopy show that self-organised structures are formed following annealing to 333 K, with each pair of bidentate thiolate ligands bonding to a single gold adatom in a S-Auad-S complex. Due to the lack of a direct orbital overlap between the dihydro-TTF moieties and the surface, relatively little charge transfer between TAT-TTF and the gold surface occurs.

Initial stages of benzotriazole adsorption on the Cu(111) surface.

Benzotriazole (BTAH) has been used as a copper corrosion inhibitor since the 1950s; however, the molecular level detail of how inhibition occurs remains a matter of debate. The onset of BTAH adsorption on a Cu(111) single crystal was investigated via scanning tunnelling microscopy (STM), vibrational spectroscopy (RAIRS) and supporting DFT modelling. BTAH adsorbs as anionic (BTA(-)), CuBTA is a minority species, while Cu(BTA)2, the majority of the adsorbed species, form chains, whose sections appear to diffuse in a concerted manner. The copper surface appears to reconstruct in a (2 × 1) fashion.

An ordered organic radical adsorbed on a Cu-doped Au(111) surface.

The tri-para-carboxylic polychlorotriphenylmethyl radical adsorption on a Cu/Au(111) surface has been investigated in ultra-high vacuum environment. The presence of copper favours the formation of metal-organic assemblies, which are analysed using scanning tunnelling microscopy (STM) and high resolution electron energy loss spectroscopy (HREELS). DFT methods indicate that the unpaired electron survives after adsorption, thus creating systems which could be regarded as potential candidates for spintronics applications.

Chiral Conformation at a Molecular Level of a Propeller-Like Open-Shell Molecule on Au(111).

A key stage in engineering molecular functional organizations is represented by controlling the supramolecular assembly of single molecular building blocks, tectons, into ordered networks. Here, we show how an open-shell, propeller-like molecule has been deposited under UHV conditions on Au(111) and its supramolecular organization characterized by scanning tunneling microscopy (STM). Racemic islands were observed at room temperature, and their chirality was imaged at the molecular level at low temperature. Modeling further suggests that the observed chirally alternating ordering dominated by intermolecular interactions is energetically favored. Electron paramagnetic resonance and ultraviolet photoemission spectroscopy evidences suggest that the supramolecular networks may preserve the open-shell character of the tecton. These results represent a fundamental step forward toward the engineering of purely organic spintronic devices.

1,2-diphosphaacenaphthene 1,2-dications: synthetic, stereochemical and computational study of the stabilising role of naphthalene-1,8-diyl backbone.

Syntheses and full characterisation data (including single crystal diffraction) of three 1,2-diphosphonium dicationic species with the naphthalene-1,8-diyl (Nap) backbone are reported. The oxidation of Nap[P(NMe(2))(2)](2) with P(2)I(4) to its 1,2-dication was achieved. meso- and rac-forms of "all carbon" 1,2-diphosphonium dications were obtained in good yields and purity by double alkylation of the parent diphosphine (1,2-diphenyl-1,2-diphosphaacenaphthene) with methyl triflate or trimethyloxonium tetrafluoroborate. Each methylating reagent produces one of the rac- or meso-forms of the dication diastereospecifically. Structural parameters of the new dications are discussed with respect to other phosphorus 1,2-dications. DFT (B3LYP) computations revealed the significant role of the naphthalene backbone in stabilisation of the dicationic motif and helped to assess the energy cost of the steric clash of a variety of groups attached to the peri-positions of naphthalene. The synthesis and single crystal X-ray data of the extremely crowded Nap[P(Se)(OiPr)(2)](2) are discussed, and are contrasted with the unsuccessful synthesis of Nap(PtBu(2))(2) from NapLi(2) and ClPtBu(2).

Molecular imaging of polyimide formation.

The reactions of 3,4,9,10-perylenetetracarboxylic dianhydride with 4,4'-diamino-p-terphenyl and with 2,4,6-tris(4-aminophenyl)-1,3,5-triazine on an Au(111) surface have been followed by low-temperature UHV-STM in the range of 300 to 700 K at coverages of up to one monolayer. Well-ordered, H-bonded structures are observed even after annealing at temperatures up to 470 K, while above 550 K reaction is initiated with evidence of amic acid intermediates. At higher temperatures, full imidisation leads to a covalently linked, surface polyimide networks. There is evidence of gold reconstruction playing a role in the early stages of imidisation and signs of limited order in the final polyimide. With the diamine as precursor, 1D-interconnectivity results, while with the triamine as partner, full 2D-connectivity is possible. In contrast to the situation in the bulk, the intermediate amic acid seems to be less stable and iso-imides are common in the final networks, as witnessed by the conformation of the product and the prevalence of triangular features in the case of the polyimide formed from the triamine precursor.

Tailoring low-dimensional organic semiconductor nanostructures.

The quest for miniaturization of organic nanostructures is fueled by their possible applications in future nanoscale electronic devices. Here we show how a range of nanostructures of reduced dimensionality of the organic semiconductor PTCDA can be realized on Au(111) by intermixing the latter with hydrogen bonding spacer molecules. The purpose of the spacers is to separate nanounits of pure PTCDA, using hydrogen bonds between the anhydride end of PTCDA and amine groups of the spacers. A highly regular array of potential quantum dots can be realized by this approach.

X-ray photoelectron and infrared spectroscopies of quartz samples of contrasting toxicity.

An exploratory XPS and FTIR investigation of the surfaces of bulk quartz powders widely used in toxicological studies (DQ12 and Min-U-Sil 5) was carried with the aim of correlating surface features with toxicity as reflected by indicators of biological response. Some patches of amorphous silica were identified as well as varying amounts of calcium but none of these features correlated with biological response. No evidence of widely-quoted surface silanol (SiOH) structures was found in this investigation and the possibility that FTIR artefacts have been previously misidentified as silanol structures is discussed.

Fabrication of surface-supported low-dimensional polyimide networks.

Interest in thermal and chemical stability of surface-supported organic networks has stimulated recent attempts to covalently interlink adsorbed molecular species into extended nanostructures. We show, using low-temperature scanning tunneling microscopy, that imidization of anhydrides and amines adsorbed on Au(111) can be thermally initiated under controlled ultrahigh vacuum conditions. Using two types of amine-functionalized polyphenyl molecules together with the organic semiconductor PTCDA, monolayer thick linear polymeric strands and a porous polymeric network with nanoscale dimensions are obtained.

Self-assembly of semifluorinated n-alkanethiols on {111}-oriented Au investigated with scanning tunneling microscopy experiment and theory.

The adsorption of semifluorinated alkanethiols on Au/mica was studied by scanning tunneling microscopy (STM). The adlayer structure produced is based on a p(2 x 2) structure though lines of molecules displayed extensive kinks and bends. In addition, a considerable variation in the contrast of molecular features is found. Molecular modeling calculations confirm that, for the fluorinated thiols, inequivalently adsorbed molecules within a p(2 x 2) registry are present, an aspect that endows the local structure of the adlayer with a higher flexibility in comparison to nonfluorinated thiols, where one adsorption site is strongly favored in a (radical 3 x radical 3) R30 degrees structure. Simulated STM imaging on the optimized systems successfully recovered the effects on the molecular feature contrast induced by the flexibility of the fluorinated thiol adlayer.

Anti-adhesive glycoproteins in echinoderm mucus secretions.

Marine invertebrates produce a large variety of mucus secretions which are rich in glycoproteins. As part of our studies of natural antifouling mechanisms, mucus secretions from the starfish Marthasterias glacialis and Porania pulvillus and the brittlestar Ophiocomina nigra have been used to characterise the structure and function of some of the glycoproteins present in these secretions. Mucus was collected from all three species and fractionated by size exclusion chromatography. A high molecular weight glycoprotein fraction was collected from each species. Monosaccharide analysis and FTIR demonstrated a composition consistent with a mucin-type glycoprotein. The mucin from M. glacialis and O. nigra inhibited in vitro bacterial adhesion in a dose-dependent manner. In contrast, the mucin from P. pulvillus promoted bacterial adhesion in a dose-dependent manner. All of the mucins inhibited the adhesion of human neutrophils to cultured human vascular endothelial cells (HUVECs) and had no anticoagulant activity. The mucins described here have adhesion-regulating functions that may have a role in the antifouling or feeding mechanisms of the organisms that produce them. These mucins may also be of therapeutic value through their ability to regulate human neutrophil adhesion or bacterial adhesion.