Use of side-chain for rational design of n-type diketopyrrolopyrrole-based conjugated polymers: what did we find out?

The primary role of substituted side chains in organic semiconductors is to increase their solubility in common organic solvents. In the recent past, many literature reports have suggested that the side chains play a critical role in molecular packing and strongly impact the charge transport properties of conjugated polymers. In this work, we have investigated the influence of side-chains on the charge transport behavior of a novel class of diketopyrrolopyrrole (DPP) based alternating copolymers. To investigate the role of side-chains, we prepared four diketopyrrolopyrrole-diketopyrrolopyrrole (DPP-DPP) conjugated polymers with varied side-chains and carried out a systematic study of thin film microstructure and charge transport properties in polymer thin-film transistors (PTFTs). Combining results obtained from grazing incidence X-ray diffraction (GIXD) and charge transport properties in PTFTs, we conclude side-chains have a strong influence on molecular packing, thin film microstructure, and the charge carrier mobility of DPP-DPP copolymers. However, the influence of side-chains on optical properties was moderate. The preferential ``edge-on'' packing and dominant n-channel behavior with exceptionally high field-effect electron mobility values of >1 cm(2) V-1 s(-1) were observed by incorporating hydrophilic (triethylene glycol) and hydrophobic side-chains of alternate DPP units. In contrast moderate electron and hole mobilities were observed by incorporation of branched hydrophobic side-chains. This work clearly demonstrates that the subtle balance between hydrophobicity and hydrophilicity induced by side-chains is a powerful strategy to alter the molecular packing and improve the ambipolar charge transport properties in DPP-DPP based conjugated polymers. Theoretical analysis supports the conclusion that the side-chains influence polymer properties through morphology changes, as there is no effect on the electronic properties in the gas phase. The exceptional electron mobility is at least partially a result of the strong intramolecular conjugation of the donor and acceptor as evidenced by the unusually wide conduction band of the polymer.

Effect of Chalcogens on Electronic and Photophysical Properties of Vinylene-Based Diketopyrrolopyrrole Copolymers

Three vinylene linked diketopyrrolopyrrole based donor acceptor (D-A) copolymers have been synthesized with phenyl, thienyl, and selenyl units as donors. Optical and electronic properties were investigated with UV-vis absorption spectroscopy, cyclic voltammetry, near edge X-ray absorption spectroscopy, organic field effect transistor (OFET) measurements, and density functional theory (DFT) calculations. Optical and electrochemical band gaps decrease in the order phenyl, thienyl, and selenyl. Only phenyl-based polymers are nonplanar, but the main contributor to the larger band gap is electronic, not structural effects. Thienyl and selenyl polymers exhibit ambipolar charge transport but with higher hole than electron mobility. Experimental and theoretical results predict the selenyl system to have the best transport properties, but OFET measurements prove the thienyl system to be superior with p-channel mobility as high as 0.1 cm(2) V-1 s(-1).

Morphology, biometry and distribution of Difflugia biwae Kawamura, 1918 (Protozoa : Rhizopoda)

The freshwater testate amoeba Difflugia biwae Kawamura, 1918, isolated from Mulan Lake, Hubei Province, China is investigated using light microscopy and scanning electron microscopy. The morphology, biometry and distribution of this little known species are supplied. After careful comparison with three other similar species, including D. delicatula Gauthier-Livre et Thomas, D. elegans Penard and D. oblonga caudata Stepanek, we believe that the characteristics of smooth fusiform shell, conspicuous great collar flare (always larger than body-width) around the aperture, constriction behind the aperture and a somewhat curved aboral horn set D. biwae apart from all other Difflugia species. This species shows a great diversity in total length, collar height and aboral horn length which have high variability (CV between 11.76 and 24.52). However, body width, collar diameter, neck width, body length and aperture diameter are fairly constant with low variability (CV between 5.34 and 8.79) which shows a remarkable uniformity of D. biwae. Also, the size frequency distributions of both body width and body length yield bell-shaped (normally distributed) curves and indicate that D. biwae is a size-monomorphic species, characterized by a main-size class and a small size range. D. biwae is probably endemic to East Asia (China and Japan) because it has such a large size (165-306 mu m) that it would have been easily found in Europe and North America, if it were there. Consequently, D. biwae must have a restricted geographical distribution, disproving the old hypothesis that microscopic organisms are cosmopolitan.

Euro-Commentary : Scenario Analysis and Regional Economic Development: The Case of Mid Wales

Fuller-Love, Nerys, et al., 'Euro-Commentary : Scenario Analysis and Regional Economic Development: The Case of Mid Wales', European Urban and Regional Studies (2006) 13(2) pp.143-149 RAE2008

Public service employment and the public-private wage differential in British regions

Thomas, Dennis, Henley, Andrew, 'Public service employment and the public-private wage differential in British regions', Regional Studies (2001) 35(3) pp.229-240 RAE2008

Inter-regional transfer trade flows in the English football league

Perdikis, Nicholas, Thomas, Dennis, Inter-regional transfer trade flows in the English football league', Tijdschrift voor Economie en Management (2002) 47 (4) 477-509 RAE2008

Entrepreneurship and rural economic development: a scenario analysis approach

Fuller-Love, N., Midmore, P., Thomas, D., Henley, A. (2006). Entrepreneurship and rural economic development: A scenario analysis approach. International Journal of Entrepreneurial Behaviour and Research, 12 (5), 289-305. RAE2008

Habit, aggregation and long memory: Evidence from television audience data

Byers, D., Peel, D., Thomas, D. (2007). Habit, aggregation and long memory: Evidence from television audience data. Applied Economics, 39 (3), 321-327. RAE2008

Home field effect and team performance: Evidence from English Premiership football

Thomas, Dennis, Carmichael, Fiona, 'Home field effect and team performance: Evidence from English Premiership football', Journal of Sports Economics (2005) 6(3) pp.264-281 RAE2008

Welsh Water: role model or special case?

Thomas, D. (2001). Welsh Water: role model or special case?. Utilities Policy, 10 (2), 99-114. RAE2008

Optimal Scheduling of Secondary Content for Aggregation in Video-on-Demand Systems

Dynamic service aggregation techniques can exploit skewed access popularity patterns to reduce the costs of building interactive VoD systems. These schemes seek to cluster and merge users into single streams by bridging the temporal skew between them, thus improving server and network utilization. Rate adaptation and secondary content insertion are two such schemes. In this paper, we present and evaluate an optimal scheduling algorithm for inserting secondary content in this scenario. The algorithm runs in polynomial time, and is optimal with respect to the total bandwidth usage over the merging interval. We present constraints on content insertion which make the overall QoS of the delivered stream acceptable, and show how our algorithm can satisfy these constraints. We report simulation results which quantify the excellent gains due to content insertion. We discuss dynamic scenarios with user arrivals and interactions, and show that content insertion reduces the channel bandwidth requirement to almost half. We also discuss differentiated service techniques, such as N-VoD and premium no-advertisement service, and show how our algorithm can support these as well.

A record of rapid Holocene climate change preserved in hyrax middens from southwestern Africa

The discovery of sensitive paleoenvironmental proxies contained within fossilized rock hyrax middens from the margin of the central Namib Desert, Africa, is providing unprecedented insight into the region's environmental history. High-resolution stable carbon and nitrogen isotope records spanning 0-11,700 cal (calibrated) yr B. P. indicate phases of relatively humid conditions from 8700-7500, 6900-6700, 5600-4900, and 4200-3500 cal yr B. P., with a period of marked aridity occurring from 3500 until ca. 300 cal yr B. P. Transitions between these phases appear to have occurred very rapidly, often within <200 years. Of particular importance are: (1) the observed relationship between regional aridification and the decline in Northern Hemisphere insolation across the Holocene, and (2) the significance of suborbital scale variations in climate that covary strongly with fluctuations in solar forcing. Together, these elements call for a fundamental reexamination of the role of orbital forcing on tropical African systems, and a reconsideration of what factors drive climate change in the region. The quality and resolution of these data far surpass any other evidence available from the region, and the continued development of this unique archive promises to revolutionize paleoenvironmental studies in southern Africa.