Andrew R. Pike

DNA-based routes to semiconducting nanomaterials

The controlled preparation and assembly of opto-electronic nanoscale materials is being tackled by top-down and bottom-up approaches. The latter draws inspiration from biology, where complex hierarchical systems are assembled from simpler building blocks. One of these, DNA, is proving especially useful: its size, stability, topology; the assorted chemical functional groups; plus its capacity for self-assembly provide a powerful nanoscale toolbox for materials preparation. Here we review recent research that shows the roles DNA can play in the preparation and organisation of semiconductor nanomaterials. Studies show that both hard inorganic and soft polymer materials can be directed to grow at nanoscale lengths using DNA and its constituents. In some cases the resulting materials have been used as components in simple electrical devices and the methodology has been extended to analytical tools. Intriguingly, these DNA-semiconductor hybrid materials have been found to self-assemble themselves, forming highly regular rope-like assemblies and conducting network structures.

Immobilisation and synthesis of DNA on Si(111), nanocrystalline porous silicon and silicon nanoparticles.

Oligonucleotides have been synthesized on hydrogen-terminated Si(111) and porous silicon using surface hydrosilation of difunctional molecules (1,(omega)-dimethoxytritylundecenol) to produce a monolayer bearing suitable reactive groups to allow automated solid-phase DNA synthesis. The absence of an intervening oxide enables electrochemical characterisation of the surface-bound oligonucleotides. Complementary sequences to the DNA synthesized on Si(111) undergo hybridisation at the surface and a straightforward electrochemical quantitation of the amount of synthesized DNA and its hybridisation efficiency (47%) is possible using Ru(NH3)6(3+) as a redox label. In the case of DNA synthesized in porous silicon, electron transfer (ET) between DNA and the underlying bulk semiconductor can be studied by cyclic voltammetry, however the anisotropic diffusion inside the porous layer and the large resistance of the porous silicon results in voltammograms for which thin-layer behaviour is not observed and the peak currents increase with the square root of scan rate. We interpret these voltammograms in terms of charge transport limitations in the layer of metal centres bound to the DNA inside the pores. Further evidence for this interpretation has been obtained using scanning electrochemical microscopy (SECM) to study the charge transport between redox species in films of DNA synthesized on Si(111) surfaces that are in contact with an aqueous phase. As the bulk concentration of Ru(NH3)6(3+) is reduced below about 250 microM the SECM feedback indicates that the rate of charge transport between surface-bound Ru(NH3)6(3+) exceeds that due to diffusion in the liquid phase. Electrochemical quantitation of the DNA is not possible in this situation, however we have been able to obtain independent determinations using radioassay based on 32P or UV/VIS spectrophotometry of dimethoxytrityl cation cleaved from the porous layer. In the case of the former, use of labelled complementary sequences shows an inverse relationship between the current density used to prepare the porous silicon and the amount of hybridisation. This can be interpreted in terms of the specific surface area of the porous silicon layers since the hybridisation efficiencies (ca. 40%) obtained by comparing DMT+ cleaved from sequences synthesized on the surface and then from complementary sequences after hybridisation were relatively insensitive to the current density used to prepare the layers. Our recent work has also been concerned with individual Si nanocrystals generated by breaking up porous silicon during thermal hydrosilation reactions. FTIR spectroscopy shows these particles are also coated with an organic Si-C-bonded monolayer and they form stable, non-turbid and strongly luminescent (lambdamax = 600-650 nm) dispersions in apolar solvents (L. H. Lie, M. S. Duerdin, E. M. Tuite, A. Houlton and B. R. Horrocks, J. Electroanal. Chem., 2002, 538/539, 183). The effect of carrying out synthetic reactions on the porous silicon prior to breaking up the layer is to produce instead larger, micron-scale assemblies with a nanometre scale internal structure. Micron-sized particles of porous silicon produced by breaking up the layer can be probed by confocal Raman spectroscopy using the electric field of a focused laser to trap such particles. Although these particles are also luminescent, the use of relatively long wavelength laser excitation (lambda = 785 nm) allows acquisition of Raman spectra from individual particles in the optical trap. The bulk optical phonon mode at ca. 520 cm(-1) characteristic of crystalline silicon is red-shifted and broadened providing evidence for an internal nanometre scale substructure in these micron-sized particles and we also see evidence for this mode in the colloidal suspensions of the Si nanoparticles. We propose a model for the formation of these two types of particles and briefly discuss the prospects to extend our solid-phase synthesis on porous silicon to allow the facile synthesis of luminescent Si nanocrystals bearing DNA or other biomolecules.

DNA-templated nanowires: morphology and electrical conductivity

DNA-templating has been used to create nanowires from metals, compound semiconductors and conductive polymers. The mechanism of growth involves nucleation at binding sites on the DNA followed by growth of spherical particles and then, under favourable conditions, a slow transformation to a smooth nanowire. The final transformation is favoured by restricting the amount of templated material per unit length of template and occurs most readily for materials of low surface tension. Electrical measurements on DNA-templated nanowires can be facilitated using three techniques: (i) standard current-voltage measurements with contact electrodes embedded in a dielectric so that there is a minimal step height at the dielectric/electrode boundary across which nanowires may be aligned by molecular combing, (ii) the use of a dried droplet technique and conductive AFM to determine contact resistance by moving the tip along the length of an individual nanowire and (iii) non-contact assessment of conductivity by scanned conductance microscopy on Si/SiO2 substrates.

Subnational Governance and Economic and Social Development

In sum, this theme issue develops the literature on subnational government and governance and economic and social development. Some accepted wisdom has been challenged and qualified, and new insights have been provided. Collectively, the papers point towards a rich future research agenda. Such endeavour might include consideration of-inter alia-the following questions: to what extent can devolved territories and institutions convert the opportunities that devolution presents into more effective public policies? How can territorial justice and equity be combined with potential diversity in a devolving nation-state (Morgan, 2001)? What kinds of supporting interterritorial fiscal equalisation systems and regional policies at the supranational and national levels can support the subnational governance of economic and social development? What kinds of territorial politics can deliver progressive economic and social development under subnational governance? How can representative and participatory democracy be reconciled within subnational government and governance? As devolution continues to unfold internationally, the character, form, and substance of the evolution of subnational governance and its relations to economic and social development require close attention to interpret their enduring importance and significance.

The limits to localization in declining industrial regions? Trans‐National corporations and economic development in Sedgefield borough

Abstract ’Localization’ has been a recurrent theme in recent debates concerning the regeneration of declining industrial regions. ‘This paper explores the extent and nature of this ‘localization’ in relation to economic renewal and reports on a study of firms and business support organizations undertaken for Sedgefield Borough Council in north‐east England. The findings suggest that, first, production localization is of a limited extent and specific nature. In particular, the nature of localization remains highly dependent upon the decision‐making power concentrated in the hands of a few trans‐national firms. Their continual reorganizations have the capacity dramatically to reshape the fortunes of the local economy and to render local action relatively powerless. Second, the localized approaches to business support that are evident run the risk of reinforcing problems of duplication and fragmentation owing to their relatively narrow focus. In addition, prospects for local economic development remain criti...

Electrochemical scanning tunnelling spectroscopy of a ferrocene-modified n-Si(111)-surface: electrolyte gating and ambipolar FET behaviour

As revealed for the first time by in situ scanning tunnelling spectroscopy (STS), ferrocene-modified Si(111) substrates show ambipolar field effect transistor (FET) behaviour upon electrolyte gating.

Synthesis and binding of proflavine diazides as functional intercalators for directed assembly on DNA

Proflavine diazide (PD) with amido-azide substituents on the amine groups and its N-methylated analogue (MePD) bind strongly to DNA by nearest-neighbour intercalation with little sequence selectivity, presenting reactive azide groups in the major groove. PD is neutral in aqueous solution but experiences binding-coupled protonation on interaction with DNA with an apparent pKa shift of 2.5 units. MePD can be click modified in situ on DNA with alkyne-functionalised thienyl-pyrrole as a precursor for conducting polymer synthesis, and remains intercalated after reaction with the substituents aligned in the groove.

Backside-illuminated, high-QE, 3e- RoN, fast 700fps, 1760x1680 pixels CMOS imager for AO with highly parallel readout

The success of the next generation of instruments for 8 to 40-m class telescopes will depend upon improving the image quality (correcting the distortion caused by atmospheric turbulence) by exploiting sophisticated Adaptive Optics (AO) systems. One of the critical components of the AO systems for the E-ELT has been identified as the Laser/Natural Guide Star (LGS/NGS) WaveFront Sensing (WFS) detector. The combination of large format, 1760x1680 pixels to finely sample (84x84 sub-apertures) the wavefront and the spot elongation of laser guide stars, fast frame rate of 700 (up to 1000) frames per second, low read noise (< 3e-), and high QE (> 90%) makes the development of such a device extremely challenging. Design studies by industry concluded that a thinned and backside-illuminated CMOS Imager as the most promising technology. This paper describes the multi-phased development plan that will ensure devices are available on-time for E-ELT first-light AO systems; the different CMOS pixel architectures studied; measured results of technology demonstrators that have validated the CMOS Imager approach; the design explaining the approach of massive parallelism (70,000 ADCs) needed to achieve low noise at high pixel rates of ~3 Gpixel/s ; the 88 channel LVDS data interface; the restriction that stitching (required due to the 5x6cm size) posed on the design and the solutions found to overcome these limitations. Two generations of the CMOS Imager will be built: a pioneering quarter sized device of 880x840 pixels capable of meeting first light needs of the E-ELT called NGSD (Natural Guide Star Detector); followed by the full size device, the LGSD (Laser Guide Star Detector). Funding sources: OPTICON FP6 and FP7 from European Commission and ESO.

LGSD/NGSD: high speed visible CMOS imagers for E-ELT adaptive optics

The success of the next generation of instruments for ELT class telescopes will depend upon improving the image quality by exploiting sophisticated Adaptive Optics (AO) systems. One of the critical components of the AO systems for the European Extremely Large Telescope (E-ELT) has been identified as the Large Visible Laser/Natural Guide Star AO Wavefront Sensing (WFS) detector. The combination of large format, 1600x1600 pixels to finely sample the wavefront and the spot elongation of laser guide stars (LGS), fast frame rate of 700 frames per second (fps), low read noise (⪅ 3e-), and high QE (⪆ 90%) makes the development of this device extremely challenging. Results of design studies concluded that a highly integrated Backside Illuminated CMOS Imager built on High Resistivity silicon as the most suitable technology. Two generations of the CMOS Imager are planned: a) a smaller ‘pioneering’ device of ⪆ 800x800 pixels capable of meeting first light needs of the E-ELT. The NGSD, the topic of this paper, is the first iteration of this device; b) the larger full sized device called LGSD. The NGSD has come out of production, it has been thinned to 12μm, backside processed and packaged in a custom 370pin Ceramic PGA (Pin Grid Array). Results of comprehensive tests performed both at e2v and ESO are presented that validate the choice of CMOS Imager as the correct technology for the E-ELT Large Visible WFS Detector. These results along with plans for a second iteration to improve two issues of hot pixels and cross-talk are presented.

The Local Nexus Network: Exploring the Future of Localised Food Systems and Associated Energy and Water Supply

The Local Nexus Network is addressing the intersection of two important emerging research areas, re-distributed manufacturing and the food-energy-water nexus. It is an on-going initiative which aims to develop an evidence-based comprehensive research agenda and foster an inclusive community of researchers and stakeholders for sustainable local food-energy-water nexuses. This paper presents the conceptual framing for understanding the challenges of local nexus, reports empirical findings around a particular case study, and makes initial reflections on the research and practical challenges and opportunities.