Model Systems for Characterizing the Intrinsic Properties of Polymer Semiconductors: Oligomers and Single Crystals

Polymer semiconductors hold great promise for the realization of inexpensive, flexible electronic devices. One of the greatest strengths of these materials, their low-cost processability from solution, results in a wide range of solid-state structures. The crystallinity and morphology of these materials strongly impacts their performance as charge carriers. Furthermore, the nature of polymerization inherently leads to the production of materials which are disperse in their molecular character, with regard to both coupling and molecular weight. Thus, it is difficult to deconvolute the intrinsic properties of polymer semiconductors from their synthetic and processing conditions. Polythiophenes are particularly susceptible to performance variations due to their dependence on crystallinity for effective charge transport. Moreover, it is difficult to characterize charge transport within their crystallites, which are often tens of nanometers in size. The approaches reported here are intended to provide well-defined model systems, oligomers and single crystals, for characterizing the crystallization and semiconductor physics of conjugated polymers. In Chapter 2, the characterization of monodisperse oligothiophenes is reported. In evaluating the evolution of crystalline, morphological, and optoelectronic properties with increasing chain length, the transition from monomer to polymer is described. The pentamer of poly[bis(3-dodecyl-2-thienyl)-2,2\u27-dithiophene -5,5\u27-diyl] (PQT-12) is identified as a potential model system for probing the intrinsic properties of the polymer. In Chapter 3, the interactions between a model oligomer, the trimer of poly[2,5-bis(3-dodecylthiophen-2-yl)thieno[3,2-b]thiophene] (PBTTT), and high molecular weight polymer are characterized. The effects of enhanced crystallinity and connectivity, from the oligomer and polymer, respectively, are reported. In particular, the morphology, crystallinity, and charge transport properties of films of blended oligomer-polymer systems were studied. Although oligomers are often considered impurities in the synthesis of semiconducting polymers for device applications, it was demonstrated that films consisting of up to 83% oligomer exhibited high charge transport mobilities equal to that of pure high molecular weight polymer. In Chapter 4, a novel technique for the fractionation and recrystallization of oligothiophenes in supercritical fluid is reported. Furthermore, the crystal habit, structure, and molecular coupling of the resulting crystals are described. This crystallization method leverages the solubilizing and transport properties of supercritical fluids to create a system that combines the advantages of crystallizations from vapor and solution and could be broadly applied to the crystallization of other polymeric systems

Frequent disturbances and chronic pressures constrain stony coral recovery on Florida’s Coral Reef

Acute disturbances and chronic pressures have an important and increasing influence on the structure of coral reef communities. For the viability of benthic taxa such as stony corals, a balance between loss following disturbance and recovery is vital. Coral populations on reefs with lower exposure to chronic pressures are often presumed to have increased resilience, enabling them to recover quickly following disturbance, but decades of anthropogenic stress and degradation may undermine the systematic recovery and reassembly of benthic communities. This study explored spatiotemporal changes in benthic community structure over a 15 yr period at three distinct coral reef regions with a gradient of chronic pressures in Florida, USA, (southeast Florida, the Florida Keys and the Dry Tortugas). We specifically assessed the spatial scale, potential drivers of change and resilience in stony coral, octocoral, sponge and macroalgae cover. Spatiotemporal changes were assessed at four different scales: among regions, habitats, sub-regions, and habitat types within regions. Cover of stony corals remained very low or declined in every region from 2004 to 2018, with corresponding increases in macroalgae cover. Stony coral recovery was limited regardless of regional differences in chronic pressure. Octocorals exhibited greater resilience due to increased recovery following disturbance and generally had higher cover than stony corals on Florida’s Coral Reef, while sponge cover was very stable over the study period. Acute disturbances, which affected sites on average once every 3 yr, negatively impacted stony coral and/or octocoral cover in every region and habitat, contributing to the regionwide proliferation of macroalgae. This study determined that high disturbance frequency and chronic anthropogenic pressures on Florida’s Coral Reef have led to sustained declines in stony corals and corresponding proliferation of macroalgae. Stony corals were expected to recover during inter-disturbance periods, but in Florida, even in locations with lower chronic pressure, recovery is severely limited

Directional Charge Separation in Isolated Organic Semiconductor Crystalline Nanowires

One of the fundamental design paradigms in organic photovoltaic device engineering is based on the idea that charge separation is an extrinsically driven process requiring an interface for exciton fission. This idea has driven an enormous materials science engineering effort focused on construction of domain sizes commensurate with a nominal exciton diffusion length of order 10 nm. Here, we show that polarized optical excitation of isolated pristine crystalline nanowires of a small molecule n-type organic semiconductor, 7,8,15,16-tetraazaterrylene, generates a significant population of charge-separated polaron pairs along the π-stacking direction. Charge separation was signalled by pronounced power-law photoluminescence decay polarized along the same axis. In the transverse direction, we observed exponential decay associated with excitons localized on individual monomers. We propose that this effect derives from an intrinsic directional charge-transfer interaction that can ultimately be programmed by molecular packing geometry

SiDCoN: A Tool to Aid Scoring of DNA Copy Number Changes in SNP Chip Data

The recent application of genome-wide, single nucleotide polymorphism (SNP) microarrays to investigate DNA copy number aberrations in cancer has provided unparalleled sensitivity for identifying genomic changes. In some instances the complexity of these changes makes them difficult to interpret, particularly when tumour samples are contaminated with normal (stromal) tissue. Current automated scoring algorithms require considerable manual data checking and correction, especially when assessing uncultured tumour specimens. To address these limitations we have developed a visual tool to aid in the analysis of DNA copy number data. Simulated DNA Copy Number (SiDCoN) is a spreadsheet-based application designed to simulate the appearance of B-allele and logR plots for all known types of tumour DNA copy number changes, in the presence or absence of stromal contamination. The system allows the user to determine the level of stromal contamination, as well as specify up to 3 different DNA copy number aberrations for up to 5000 data points (representing individual SNPs). This allows users great flexibility to assess simple or complex DNA copy number combinations. We demonstrate how this utility can be used to estimate the level of stromal contamination within tumour samples and its application in deciphering the complex heterogeneous copy number changes we have observed in a series of tumours. We believe this tool will prove useful to others working in the area, both as a training tool, and to aid in the interpretation of complex copy number changes

High mutation rates explain low population genetic divergence at copy-number-variable loci in Homo sapiens

Copy-number-variable (CNV) loci differ from single nucleotide polymorphic (SNP) sites in size, mutation rate, and mechanisms of maintenance in natural populations. It is therefore hypothesized that population genetic divergence at CNV loci will differ from that found at SNP sites. Here, we test this hypothesis by analysing 856 CNV loci from the genomes of 1184 healthy individuals from 11 HapMap populations with a wide range of ancestry. The results show that population genetic divergence at the CNV loci is generally more than three times lower than at genome-wide SNP sites. Populations generally exhibit very small genetic divergence (G(st) = 0.05 ± 0.049). The smallest divergence is among African populations (G(st) = 0.0081 ± 0.0025), with increased divergence among non-African populations (G(st) = 0.0217 ± 0.0109) and then among African and non-African populations (G(st) = 0.0324 ± 0.0064). Genetic diversity is high in African populations (~0.13), low in Asian populations (~0.11), and intermediate in the remaining 11 populations. Few significant linkage disequilibria (LDs) occur between the genome-wide CNV loci. Patterns of gametic and zygotic LDs indicate the absence of epistasis among CNV loci. Mutation rate is about twice as large as the migration rate in the non-African populations, suggesting that the high mutation rates play dominant roles in producing the low population genetic divergence at CNV loci

Large expert-curated database for benchmarking document similarity detection in biomedical literature search

Document recommendation systems for locating relevant literature have mostly relied on methods developed a decade ago. This is largely due to the lack of a large offline gold-standard benchmark of relevant documents that cover a variety of research fields such that newly developed literature search techniques can be compared, improved and translated into practice. To overcome this bottleneck, we have established the RElevant LIterature SearcH consortium consisting of more than 1500 scientists from 84 countries, who have collectively annotated the relevance of over 180 000 PubMed-listed articles with regard to their respective seed (input) article/s. The majority of annotations were contributed by highly experienced, original authors of the seed articles. The collected data cover 76% of all unique PubMed Medical Subject Headings descriptors. No systematic biases were observed across different experience levels, research fields or time spent on annotations. More importantly, annotations of the same document pairs contributed by different scientists were highly concordant. We further show that the three representative baseline methods used to generate recommended articles for evaluation (Okapi Best Matching 25, Term Frequency-Inverse Document Frequency and PubMed Related Articles) had similar overall performances. Additionally, we found that these methods each tend to produce distinct collections of recommended articles, suggesting that a hybrid method may be required to completely capture all relevant articles. The established database server located at https://relishdb.ict.griffith.edu.au is freely available for the downloading of annotation data and the blind testing of new methods. We expect that this benchmark will be useful for stimulating the development of new powerful techniques for title and title/abstract-based search engines for relevant articles in biomedical research.Peer reviewe

Scientific fundamentals of organization of geological prospecting on basis of sectoral system of technoscientific information under conditions of new economic mechanism

Available from VNTIC / VNTIC - Scientific & Technical Information Centre of RussiaSIGLERURussian Federatio

Bremsstrahlung radiation effects in rare earth permanent magnets

Advances in rare earth permanent magnet (REPM) technology have made possible new applications. Two such applications are the use of permanent magnetic lenses for accelerator and beam transport systems and the expanding use in undulators and wigglers of synchrotron radiation and free electron laser systems. Both applications involve potential exposure of REPM’s to high radiation fields. We have investigated the radiation hardness of several different varieties of REPM’s up to 2 gigarads of absorbed dose from a mixed electron-photon (bremsstrahlung) field. Sm2Col7, NdaFerdB and an experimental REPM, PrrnFe7gBu, from several different manufacturers have been investigated. Of the samples irradiated, Sm2Cor 7 proved to be the most resistant to bremsstrahlung radiation. However, details of manufacturing techniques produced significantly different results. We observed that REPM’s of nominally identical stoichiometric composition from different manufacturers did not show the same rate of remanence loss. We present details of our experiment and absorbed dose modeling and a summary of radiation effects measurements of which we are aware. Our study of these radiation damage experiments lead us to the empirical observation that the order of radiation hardness is SmzCo17, SmCo5 and NdzFeldB, ‘regardless of the source of radiation, i.e., gammas, electrons, protons or neutrons.Naval Postgraduate School Research CouncilU.S. Department of Energy by Lawrence Livermore National Laboratory under W-7405-ENG-48Department of Defense under SDIO/BMO/ATC MIPR No. W3-RPD-53-A12

Triisopropylsilylethynyl-functionalized dibenzo[def,mno]chrysene: a solution-processed small molecule for bulk heterojunction solar cells

This communication reports the synthesis of a new polycyclic aromatic hydrocarbon and its unique packing motif. This molecule is shown to be an efficient electron donor in organic bulk heterojunction solar cells, exhibiting a power conversion efficiency of [similar]2.0%

Controlled integration of oligo- and polythiophenes at the molecular scale

High molecular weight PBTTT-C₁₂ is blended with the pure trimer, BTTT-3, to enhance intergrain connectivity and charge transport. Analysis of the morphology and crystallinity of the blends shows that the polymer and oligomer are well-integrated, leading to high hole mobilities, greater than 0.1 cm² V⁻¹ s⁻¹, in films that contain as much as 83% oligomer