Arrays of chiral nanotubes and a layered coordination polymer containing gallium-sulfide supertetrahedral clusters

We report here a unique chiral hybrid gallium sulfide, [NC2H8]2[Ga10S16(N2C12H12)(NC2H7)2] 1, consisting of helical chains of organically-functionalised supertetrahedral clusters which form quadruple-stranded helical nanotubes of ca. 3 nm diameter. This material therefore consists of discrete metal-organic nanotubes which, to the best of our knowledge, are extremely rare. Whilst solvothermal reactions involving 1,2-di(4-pyridyl)ethylene (DPE) resulted in the formation of such single-walled chiral nanotubes, the use of longer 4,4’-trimethylenedipyridine (TMP) ligands resulted in the synthesis of a two-dimensional hybrid gallium sulfide, [C5H6N]3[Ga10S16(OH)(N2C13H14)] 2 in which, for the first time, inorganic and organic linkages between supertetrahedral clusters coexist.

Clusters, connectivity and catch-up: Bollywood and Bangalore in the Global Economy

In this article, we make two important contributions to the literature on clusters. First, we provide a broader theory of cluster connectivity that has hitherto focused on organization-based pipelines and MNE subsidiaries, by including linkages in the form of personal relationships. Second, we use the lens of social network theory to derive a number of testable propositions. We propose that global linkages with decentralized network structures have the highest potential for local spillovers. In the emerging economy context, our theory implies that clusters linked to the global economy by decentralized pipelines have potential for in-depth catch-up, focused in industry and technology scope. In contrast, clusters linked through decentralized personal relationships have potential for in-breadth catch-up over a range of related industries and technologies. We illustrate our theoretical propositions by contrasting two emerging economy case studies: Bollywood, the Indian filmed entertainment cluster in Mumbai and the Indian software cluster in Bangalore.

Following the creation of active gold nanocatalysts from phosphine-stabilized molecular clusters

The phosphine-stabilised gold cluster [Au6(Ph2P-o-tolyl)6](NO3)2 is converted into an active nanocatalyst for the oxidation of benzyl alcohol through low-temperature peroxide-assisted removal of the phosphines, avoiding the high-temperature calcination process. The process was monitored using in-situ X-ray absorption spectroscopy, which revealed that after a certain period of the reaction with tertiary butyl hydrogen peroxide, the phosphine ligands are removed to form nanoparticles of gold which matches with the induction period seen in the catalytic reaction. Density functional theory calculations show that the energies required to remove the ligands from the [Au6Ln]2+ increase significantly with successive removal steps, suggesting that the process does not occur at once but sequentially. The calculations also reveal that ligand removal is accompanied by dramatic re-arrangements in the topology of the cluster core.

Pit clusters and the temporality of occupation: an earlier Neolithic site at Kilverstone, Thetford, Norfolk

This paper discusses 226 earlier Neolithic pits found at Kilverstone in Norfolk. In particular, it focuses on the dynamics involved in the site's creation, investigating what had happened to the material found in the pits prior to deposition, and exploring the material connections (refitting sherds and flints) across the site. As a result of these material insights, it proved possible to shed important light on the character of that place in particular, and on the temporality of Neolithic deposition and occupation in general.

Simple M-factor algorithm for improved estimation of the basic maximum usable frequency of radio waves reflected from the ionospheric F-region

The equations of Milsom are evaluated, giving the ground range and group delay of radio waves propagated via the horizontally stratified model ionosphere proposed by Bradley and Dudeney. Expressions for the ground range which allow for the effects of the underlying E- and F1-regions are used to evaluate the basic maximum usable frequency or M-factors for single F-layer hops. An algorithm for the rapid calculation of the M-factor at a given range is developed, and shown to be accurate to within 5%. The results reveal that the M(3000)F2-factor scaled from vertical-incidence ionograms using the standard URSI procedure can be up to 7.5% in error. A simple addition to the algorithm effects a correction to ionogram values to make these accurate to 0.5%.

Phosphorescence quantum yield enhanced by intermolecular hydrogen bonds in Cu4I4 clusters in the solid state

Organo-copper(I) halide complexes with a Cu4I4 cubane core and cyclic amines as ligands have been synthesized and their crystal structures have been defined. Their solid state photophysical properties have been measured and correlated with the crystal structure and packing. A unique and remarkably high luminescence quantum yield (76%) has been measured for one of the complexes having the cubane clusters arranged in a columnar structure and held together by N–HI hydrogen bonds. This high luminescence quantum yield is correlated with a slow radiationless deactivation rate of the excited state and suggests a rather strong enhancement of the cubane core rigidity bestowed by the hydrogen bond pattern. Some preliminary thin film deposition experiments show that these compounds could be considered to be good candidates for applications in electroluminescent devices because of their bright luminescence, low cost and relatively easy synthesis processes

Hybrid materials through linkage of chalcogenide tetrahedral clusters

Tetrahedral chalcogenide clusters, with their well-defined molecular structures and interesting properties, are attractive building blocks for hybrid materials, in which porosity may be integrated with electronic or optical properties. Linkage of tetrahedral clusters often occurs through bridging chalcogenolate ligands, and results in extended structures of inorganic connectivity. However, linkage of tetrahedral clusters via organic ligands is also possible and a number of coordination polymers have already been reported. Recent advances on the synthesis and crystal structures of extended hybrid structures based on tetrahedral clusters are described here.

When innovation becomes inefficient: reexamining Britain's radio industry

I examine the factors underpinning the British radio-equipment sector's particularly poor interwar productivity performance relative to the United States. Differences in socio-legal environments were crucial in allowing key players in the British industry to derive higher monopoly rents than their American counterparts. Higher British rents in turn, had the unintended outcome of stimulating innovation around restrictive patents, initiating a path-dependent process of technical change in favor of expensive multifunctional valves. These valves both raised direct production costs and prevented British firms from following the American path of broadening the radio market beyond the household's prime receiver.

Temporally stable feature clusters for maritime object tracking in visible and thermal imagery

This paper describes a new approach to detect and track maritime objects in real time. The approach particularly addresses the highly dynamic maritime environment, panning cameras, target scale changes, and operates on both visible and thermal imagery. Object detection is based on agglomerative clustering of temporally stable features. Object extents are first determined based on persistence of detected features and their relative separation and motion attributes. An explicit cluster merging and splitting process handles object creation and separation. Stable object clus- ters are tracked frame-to-frame. The effectiveness of the approach is demonstrated on four challenging real-world public datasets.

Voices of Occupiers/Liberators: The BBC's Radio Propaganda in Italy between 1942 and 1945

The ambiguity of the role played by British propaganda in Italy during the Second World War is clearly reflected in the phenomenon of Radio London. While Radio London raised the morale of the Italian civilians living under the Fascist regime and provided them with alternative information on the conflict, the microphones of the BBC were also used by the British government to address a country they were planning to occupy. In this article, I will analyse the occupation/liberation operations that were run at the BBC Italian Service from two separate angles. On the one hand, the analysis of the programmes broadcast between the months preceding the Allies’ landing in Sicily and the actual occupation shows how the Allies built their image as liberators and guarantors of better living conditions. On the other, the analysis of the relationships between the Foreign Office and the anti-Fascist exiles reveals that the Italian BBC broadcasters were not always allowed to freely express their political opinion or to dispose of their own lives.

Production of bioactive diterpenoids in the Euphorbiaceae depends on evolutionarily conserved gene clusters

The Euphorbiaceae produce a diverse range of diterpenoids, many of which have pharmacological activities. These diterpenoids include ingenol mebutate, which is licensed for the treatment of a precancerous skin condition (actinic keratosis), and phorbol derivatives such as resiniferatoxin and prostratin, which are undergoing investigation for the treatment of severe pain and HIV, respectively. Despite the interest in these diterpenoids, their biosynthesis is poorly understood at present, with the only characterized step being the conversion of geranylgeranyl pyrophosphate into casbene. Here, we report a physical cluster of diterpenoid biosynthetic genes from castor (Ricinus communis), including casbene synthases and cytochrome P450s from the CYP726A subfamily. CYP726A14, CYP726A17, and CYP726A18 were able to catalyze 5-oxidation of casbene, a conserved oxidation step in the biosynthesis of this family of medicinally important diterpenoids. CYP726A16 catalyzed 7,8-epoxidation of 5-keto-casbene and CYP726A15 catalyzed 5-oxidation of neocembrene. Evidence of similar gene clustering was also found in two other Euphorbiaceae, including Euphorbia peplus, the source organism of ingenol mebutate. These results demonstrate conservation of gene clusters at the higher taxonomic level of the plant family and that this phenomenon could prove useful in further elucidating diterpenoid biosynthetic pathways.