Hollow structures with bilayer graphene walls

The formation of three-dimensional shell-like structures with bilayer graphene walls is described. The structures are produced by the passage of an electric current through graphite in an arc-discharge apparatus. High resolution transmission electron microscopy is used to characterize the carbon, and provides evidence that the structures are three-dimensional rather than flat. A striking feature of the material is that it contains bilayer nanotubes seamlessly joined to larger shell-like regions. The possible growth mechanism of the carbon is discussed, and potential applications considered.

Hollow capsules formed in a single stage via interfacial hydrogen-bonded complexation of methylcellulose with poly(acrylic acid) and tannic acid

Hollow capsules can be prepared in a single stage by the interfacial complexation of methylcellulose (MC) with poly(acrylic acid) (PAA) or tannic acid (TA) via hydrogen bonding in aqueous solutions. The formation of capsules is observed when viscous solution of methylcellulose is added drop-wise to diluted solutions of polyacids under acidic conditions. The optimal parameters such as polymer concentration and solution pH for the formation of these capsules were established in this work. It was found that tannic acid forms capsules in a broader range of concentrations and pHs compared to poly(acrylic acid). The TA/MC capsules exhibited better stability compared to PAA/MC in response to increase in pH: the dissolution of TA/MC capsules observed at pH > 9.5; whereas PAA/MC capsules dissolved at pH > 3.8. The interfacial complexation can be considered as a potential single stage alternative to the formation of capsules using multistage layer-by-layer deposition method.

Dipeptide nanotubes, with n-terminally located omega-amino acid residues, that are stable proteolytically, thermally, and over a wide range of pH

Two dipeptides containing an N-terminally positioned omega-amino acid residue (beta-alanine/delta-amino valeric acid) self-assembles to form nanotubes in the solid state as well as in aqueous solution. In spite of having hollow nanotubular structures in the solid state and in solution, their self-assembling nature in these two states are different and this leads to the formation of different internal diameters of these nanotubes in solution and in solid state structure. These nanotubes are stable proteolytically, thermally, and over a wide range of pH values (1-13). The role of water molecules in nanotube formation has been investigated in the solid state. These nanotubes can be considered as a new class of dipeptide nanotubes as they are consisting of N-terminally located protease resistant omega-amino acid residues and C-terminally positioned alpha-amino acid residues. These dipeptides can form an interesting class of short peptidic structure that can give rise to stable nanotubular structure upon self-assembly and these nanotubes can be explored in future for potential nanotechnological applications.

The adsorption geometry of sulphur on Ir{100}: a quantitative LEED study

A quantitative low energy electron diffraction (LEED) analysis has been performed for the p(2 x 2)-S and c(2 x 2)-S surface structures formed by exposing the (1 x 1) phase of Ir{100} to H2S at 750 K. S is found to adsorb on the fourfold hollow sites in both structures leading to Pendry R-factor values of 0.17 for the p(2 x 2)-S and 0.16 for the c(2 x 2)-S structures. The distances between S and the nearest and next-nearest Ir atoms were found to be similar in both structures: 2.36 +/- 0.01 angstrom and 3.33 +/- 0.01 angstrom, respectively. The buckling in the second substrate layer is consistent with other structural studies for S adsorption on fcc{100} transition metal surfaces: 0.09 angstrom for p(2 x 2)-S and 0.02 angstrom for c(2 x 2)-S structures. The (1 x 5) reconstruction, which is the most stable phase for clean Ir{100}, is completely lifted and a c(2 x 2)-S overlayer is formed after exposure to H,S at 300 K followed by annealing to 520 K. CO temperature-programmed desorption (TPD) experiments indicate that the major factor in the poisoning of Ir by S is site blocking. (c) 2005 Elsevier B.V. All rights reserved.

A new motif in the formation of peptide nanotubes: the crystallographic signature

Terminally protected acyclic tripeptides Boc-Tyr(1)-Val(2)-Tyr(3)-OMe 1 and Boc-Tyr(1)-lle(2)-Tyr(3)-OMe 2 self-assemble into nanotubes in crystals through various noncovalent interactions with an average internal diameter of 5 Angstrom (0.5 nm), and the tubular ensemble is developed through the hydrogen-bonded side chains of tyrosine residues. The inside of the hollow nanotubular structures is hydrophilic; however, no solvent molecules have been crystallographically detected.

Experimental structure determination of the chemisorbed overlayers of chlorine and iodine on Au{111}

We have performed an experimental structure determination of the ordered p(sqrt[3] x sqrt[3])R30 degrees structures of chlorine and iodine on Au{111} using low-energy electron diffraction (LEED). Despite great similarities in the structure of the underlying substrate, which shows only minor deviations from the bulk positions in both cases, chlorine and iodine are found to adsorb in different adsorption sites, fcc and hcp hollow sites, respectively. The experimental Au-Cl and Au-I bond lengths of 2.56 and 2.84 A are close to the sums of the covalent radii, supporting the view that the bond is essentially covalent in nature; however, they are significantly shorter than predicted theoretically.

The surface geometries of the medium and high coverage carbon monoxide structures c(2 × 4)–(2CO) and p(root7- x root7)R19°–(4CO) structure

The surface geometries of the p (root7- x root7)R19degrees-(4CO) and c(2 x 4)-(2CO) layers on Ni {111} and the clean Ni {111} surface were determined by low energy electron diffraction structure analysis. For the clean surface small but significant contractions of d(12) and d(23) (both 2.02 Angstrom) were found with respect to the bulk interlayer distance (2.03 Angstrom). In the c(2 x 4)-(2CO) structure these distances are expanded, with values of d(12) = 2.08 Angstrom and d(23) = 2.06 Angstrom and buckling of 0.08 and 0.02 Angstrom, respectively, in the first and second layer. CO resides near hcp and fcc hollow sites with relatively large lateral shifts away from the ideal positions leading to unequal C-Ni bond lengths between 1.76 and 1.99 Angstrom. For the p(root7- x root7-)R19'-(4CO) layer two best fit geometries were found, which agree in most of their atomic positions, except for one out of four CO molecules, which is either near atop or between bridge and atop. The remaining three molecules reside near hcp and fcc sites, again with large lateral deviations from their ideal positions. The average C Ni bond length for these molecules is, however, the same as for CO on hollow sites at low coverage. The average CNi bond length at hollow sites, the interlayer distances, and buckling in the first Ni layer are similar to the c(2 x 4)(2CO) geometry, only the buckling in the second layer (0.08 Angstrom) is significantly larger. Lateral and vertical shifts of the Ni atoms in the first layer lead to unsymmetric environments for the CO molecules, which can be regarded as an imprint of the chiral p(root7- x root7-)R19degrees lattice geometry onto the substrate.

Structural transformation of graphite by arc-discharge

The formation of novel structures by the passage of an electric current through graphite is described. These structures apparently consist of hollow three-dimensional graphitic shells bounded by curved and faceted planes, typically made up of two graphene layers. The curved structures were frequently decorated with nano-scale carbon particles, or short nanotubes. In some cases, nanotubes were found to be seamlessly connected to the thin shells, indicating that the formation of the shells and the nanotubes is intimately connected. Small nanotubes or nanoparticles were also sometimes found encapsulated inside the hollow structures, while fullerene-like particles were often seen attached to the outside surfaces. With their high surface areas and structural perfection, the new carbon structures may have applications as anodes of lithium ion batteries or as components of composite materials.

Electronic charge transfer between ceria surfaces and gold adatoms: a GGA+U investigation

We use density functional theory calculations with Hubbard corrections (DFT+U) to investigate electronic aspects of the interaction between ceria surfaces and gold atoms. Our results show that Au adatoms at the (111) surface of ceria can adopt Au0, Au+ or Au� electronic configurations depending on the adsorption site. The strongest adsorption sites are on top of the surface oxygen and in a bridge position between two surface oxygen atoms, and in both cases charge transfer from the gold atom to one of the Ce cations at the surface is involved. Adsorption at other sites, including the hollow sites of the surface, and an O–Ce bridging site, is weaker and does not involve charge transfer. Adsorption at an oxygen vacancy site is very strong and involves the formation of an Au� anion. We argue that the ability of gold atoms to stabilise oxygen vacancies at the ceria surface by moving into the vacancy site and attracting the excess electrons of the defect could be responsible for the enhanced reducibility of ceria surfaces in the presence of gold. Finally, we rationalise the differences in charge transfer behaviour from site to site in terms of the electrostatic potential at the surface and the coordination of the species.

Insights into the molecular architecture of a peptide nanotube using FTIR and solid-state NMR spectroscopic measurements on an aligned sample

The self-assembly of proteins and peptides into b-sheet-rich amyloid fibers is a process that has gained notoriety because of its association with human diseases and disorders. Spontaneous self-assembly of peptides into nonfibrillar supramolecular structures can also provide a versatile and convenient mechanism for the bottom-up design of biocompatible materials with functional properties favoring a wide range of practical applications.[1] One subset of these fascinating and potentially useful nanoscale constructions are the peptide nanotubes, elongated cylindrical structures with a hollow center bounded by a thin wall of peptide molecules.[2] A formidable challenge in optimizing and harnessing the properties of nanotube assemblies is to gain atomistic insight into their architecture, and to elucidate precisely how the tubular morphology is constructed from the peptide building blocks. Some of these fine details have been elucidated recently with the use of magic-angle-spinning (MAS) solidstate NMR (SSNMR) spectroscopy.[3] MAS SSNMR measurements of chemical shifts and through-space interatomic distances provide constraints on peptide conformation (e.g., b-strands and turns) and quaternary packing. We describe here a new application of a straightforward SSNMR technique which, when combined with FTIR spectroscopy, reports quantitatively on the orientation of the peptide molecules within the nanotube structure, thereby providing an additional structural constraint not accessible to MAS SSNMR.

Novel bilayer graphene structures produced by arc-discharge

A new form of carbon is described, which consists of hollow, three-dimensional shells bounded by bilayer graphene. The new carbon is produced very simply, by passing a current through graphite rods in a commercial arc-evaporation unit. Characterisation of the carbon using high resolution transmission electron microscopy is described, and the possible formation mechanism discussed.

The late Roman field army in Northern Britain? Mobility, material culture and multi-isotope analysis at Scorton (N. Yorks)

At Hollow Banks Quarry, Scorton, located just north of Catterick (N Yorks.), a highly unusual group of 15 late Roman burials was excavated between 1998 and 2000. The small cemetery consists of almost exclusively male burials, dated to the fourth century. An unusually large proportion of these individuals was buried with crossbow brooches and belt fittings, suggesting that they may have been serving in the late Roman army or administration and may have come to Scorton from the Continent. Multi-isotope analyses (carbon, nitrogen, oxygen and strontium) of nine sufficiently well-preserved individuals indicate that seven males, all equipped with crossbow brooches and/or belt fittings, were not local to the Catterick area and that at least six of them probably came from the European mainland. Dietary (carbon and nitrogen isotope) analysis only of a tenth individual also suggests a non-local origin. At Scorton it appears that the presence of crossbow brooches and belts in the grave was more important for suggesting non-British origins than whether or not they were worn. This paper argues that cultural and social factors played a crucial part in the creation of funerary identities and highlights the need for both multi-proxy analyses and the careful contextual study of artefacts.

Entrepreneurial failure and economic crisis: an historical perspective

This chapter analyses the major UK economic crises that have occurred since the speculative bubbles of the seventeenth century. It integrates insights from economic history and business history to analyse both the general economic conditions and the specific business and financial practices that led to these crises. The analysis suggests a significant reinterpretation of the evidence – one that questions economists’ conventional views.

Otherworlds: fantasy and history in medieval literature

This book offers a new perspective on the otherworlds of medieval literature. These fantastical realms are among the most memorable places in medieval writing, by turns beautiful and monstrous, alluring and terrifying. Passing over a river or sea, or entering into a hollow hill, heroes come upon strange and magical realms. These places are often very beautiful, filled with sweet music and adorned with precious stones and rich materials. There is often no darkness, time may pass at a different pace, and the people who dwell there are usually supernatural. Sometimes such a place is exactly what it appears to be-the land of heart's desire-but, the otherworld can also have a sinister side, trapping humans and keeping them there against their will. Otherworlds: Fantasy and History in Medieval Literature takes a fresh look at how medieval writers understood these places and why they found them so compelling. It focuses on texts from England, but places this material in the broader context of literary production in medieval Britain and Ireland. The narratives examined in this book tell a rather surprising story about medieval notions of these fantastical places. Otherworlds are actually a lot less 'other' than they might initially seem. Authors often use the idea of the otherworld to comment on very serious topics. It is not unusual for otherworld depictions to address political issues in the historical world. Most intriguing of all are those texts where locations in the real world are re-imagined as otherworlds. The regions on which this book focuses, Britain, Ireland and the surrounding islands, prove particularly susceptible to this characterization.

Using laboratory and field measurements to constrain a single habit shortwave optical parameterization for cirrus

A single habit parameterization for the shortwave optical properties of cirrus is presented. The parameterization utilizes a hollow particle geometry, with stepped internal cavities as identified in laboratory and field studies. This particular habit was chosen as both experimental and theoretical results show that the particle exhibits lower asymmetry parameters when compared to solid crystals of the same aspect ratio. The aspect ratio of the particle was varied as a function of maximum dimension, D, in order to adhere to the same physical relationships assumed in the microphysical scheme in a configuration of the Met Office atmosphere-only global model, concerning particle mass, size and effective density. Single scattering properties were then computed using T-Matrix, Ray Tracing with Diffraction on Facets (RTDF) and Ray Tracing (RT) for small, medium, and large size parameters respectively. The scattering properties were integrated over 28 particle size distributions as used in the microphysical scheme. The fits were then parameterized as simple functions of Ice Water Content (IWC) for 6 shortwave bands. The parameterization was implemented into the GA6 configuration of the Met Office Unified Model along with the current operational long-wave parameterization. The GA6 configuration is used to simulate the annual twenty-year short-wave (SW) fluxes at top-of-atmosphere (TOA) and also the temperature and humidity structure of the atmosphere. The parameterization presented here is compared against the current operational model and a more recent habit mixture model.