Applying direct heteroarylation synthesis to evaluate organic dyes as the core component in PDI-based molecular materials for fullerene-free organic solar cells

Direct heteroarylation has emerged as a versatile and powerful tool to access π-conjugated materials through atom-economical Pd-catalyzed carbon–carbon bond forming reactions. Employing this synthetic protocol has enabled the facile evaluation of a series of organic dyes in a PDI-dye-PDI framework. Material properties are largely dictated by the PDI components, but the incorporation of either thienoisoindigo, diketopyrrolopyrrole or isoindigo has been shown to influence the ionization potential and absorption profiles of the final materials. Solution-processable organic solar cell devices were fabricated to investigate the influence of the different dye cores on photovoltaic performance when paired with the donor polymer PTB7-Th. It was found that the diketopyrrolopyrrole-based material out-performed the other organic dyes, demonstrating energy losses of less than 0.6 eV, promising efficiencies when cast from non-halogenated solvents and the ability to dictate self-assembly induced by small volume fractions of the high-boiling solvent additive 1,8-diiodooctane to reach best device efficiencies of 4.1%

Effect of Concurrent Partnerships and Sex-Act Rate on Gonorrhea Prevalence

The disease gonorrhea (GC) is a major public health problem in the United States, and the dynamics of the spread of GC through popula tions are complicated and not well understood. Studies have drawn attention to the effect of concurrent sexual partnerships as an influen tial factor for determining disease prevalence. However, little has been done to date to quantify the combined effects of concurrency and within-partnership sex-act rates on the prevalence of GC. This simulation study examines this issue with a simplified model of GC transmission in closed human populations that include concurrent partnerships. Two models of within-partnership sex-act rate are compared; one is a fixed sex-act rate per partnership, and the other is perhaps more realistic in that the rate depends on the number of concurrent partners. After controlling for total number of sex acts, pseudo-equilibrium prevalence is higher with the fixed sex-act rate than under the concurrency-adjusted rate in all the modeled partnership formation conditions.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/68414/2/10.1177_003754979807100404.pd

Effect of side chains on the electronic and photovoltaic properties of diketopyrrolopyrrole-based molecular acceptors

Four molecular electron acceptors based on a common phthalimide end-capped diketopyrrolopyrrole pconjugated backbone, solubilized by different alkyl groups, have been synthesized. The influence of the nature and position of the solubilizing alkyl chains attached at the three constitutive blocks has been investigated. Results collected from UV-Vis absorption spectroscopy, cyclic voltammetry, solar cells fabrication and testing as well as atomic force microscopy show that the mode of substitution has negligible effect at the molecular level but strongly affects the material self-assembling properties, charge carrier transport and in turn, devices performances

Simply Complex: The Efficient Synthesis of an Intricate Molecular Acceptor for High-Performance Air-Processed and Air-Tested Fullerene-Free Organic Solar Cells

A perylene diimide (PDI) flanked diketopyrrolopyrrole (DPP) π-conjugated small molecule has been synthesized through an efficient and sustainable direct heteroarylation protocol. When paired with the donor polymer PTB7-Th, air-processed and tested bulk-heterojunction (BHJ) organic solar cells (OSCs) achieved a high power conversion efficiency (PCE) of 5.6%. The new acceptor showed favorable morphological changes upon solvent vapor annealing leading to a near 3-fold increase in PCE. This result is among the best reported utilizing DPP-based acceptors in air-processed and tested OSCs. All solar cells exhibited good air and light stability over a 35-day evaluation period

The Optimization of Direct Heteroarylation and Sonogashira Cross-Coupling Reactions as Efficient and Sustainable Synthetic Methods To Access π-Conjugated Materials with Near-Infrared Absorption

Two π-conjugated thienoisoindigo-based organic small molecules have been designed to be synthetically accessible through sustainable direct heteroarylation or Sonogashira C–C bond forming cross-coupling reactions utilizing a heterogeneous palladium catalyst. To access these materials, one molecule, TII-ThNaph2, contains a thiophene π-bridge to facilitate direct heteroarylation protocols, whereas the other, TII-AcNaph2, contains an acetylene π-bridge required for Sonogashira couplings. The synthetic route to both final materials was optimized to investigate the reactivity of thienoisoindigo, which to this point has not been significantly explored in comparison to other popular organic dyes such as diketopyrrolopyrrole and isoindigo. Considering the reported interest of thienoisoindigo-based materials in organic solar cells and field-effect transistors, both final materials have been characterized for their optical, electrochemical and thermal properties offering a comparison of the structure–property relationships that manifest as a result of the two different π-bridging units

Thienoisoindigo end-capped molecular donors for organic photovoltaics: Effect of the central π-conjugated connector

The synthesis, characterization and preliminary evaluation of two thienoisoindigo (TII) based molecules as donor materials in air processed bulk heterojunction solar cells are reported herein. The latter were built by grafting TII dyes on two different π-conjugated central cores, namely the cyclopentadithiophene and the fluorene units. Once blended with fullerene derivatives, power conversion efficiencies approaching 3% were measured, ranking amongst the highest reported value for thienoisoindigo-based molecular materials

Allen Telescope Array Multi-Frequency Observations of the Sun

We present the first observations of the Sun with the Allen Telescope Array (ATA). We used up to six frequencies, from 1.43 to 6 GHz, and baselines from 6 to 300 m. To our knowledge, these are the first simultaneous multifrequency full-Sun maps obtained at microwave frequencies without mosaicing. The observations took place when the Sun was relatively quiet, although at least one active region was present each time. We present multi-frequency flux budgets for each sources on the Sun. Outside of active regions, assuming optically thin bremsstrahlung (free--free) coronal emission on top of an optically thick ~10 000 K chromosphere, the multi-frequency information can be condensed into a single, frequency-independent, "coronal bremsstrahlung contribution function" [EM/sqrt(T)] map. This technique allows the separation of the physics of emission as well as a measurement of the density structure of the corona. Deviations from this simple relationship usually indicate the presence of an additional gyroresonance-emission component, as is typical in active regions.Comment: 16 pages, 11 figures. Accepted for publication in Solar Physic

On the use of Principal Component Analysis in analysing Cepheid light curves

We show how Principal Component Analysis can be used to analyse the structure of Cepheid light curves. This method is more efficient than Fourier analysis at bringing out changes in light curve shape as a function of period. Using this technique, we study the shape of fundamental and first overtone mode Cepheid light curves in the Galaxy, LMC and SMC over a wide period range. For fundamentals, we find evidence for structural changes at $\log P \approx 1.55, 2.1$. It is suggested that the feature at $\log P \approx 2.1$ is associated with a resonance in the Cepheid normal mode spectrum. For overtones, we recover the Z shape in the $R_{21}$ period plane and reproduce the metallicity dependence of this Z shape.Comment: Accepted for publication in MNRA

Shear-banding in a lyotropic lamellar phase, Part 1: Time-averaged velocity profiles

Using velocity profile measurements based on dynamic light scattering and coupled to structural and rheological measurements in a Couette cell, we present evidences for a shear-banding scenario in the shear flow of the onion texture of a lyotropic lamellar phase. Time-averaged measurements clearly show the presence of structural shear-banding in the vicinity of a shear-induced transition, associated to the nucleation and growth of a highly sheared band in the flow. Our experiments also reveal the presence of slip at the walls of the Couette cell. Using a simple mechanical approach, we demonstrate that our data confirms the classical assumption of the shear-banding picture, in which the interface between bands lies at a given stress $\sigma^\star$. We also outline the presence of large temporal fluctuations of the flow field, which are the subject of the second part of this paper [Salmon {\it et al.}, submitted to Phys. Rev. E]

Phenotypic Diversity for Seed Mineral Concentration in North American Dry Bean Germplasm of Middle American Ancestry

Dry bean (Phaseolus vulgaris L.) seeds are a major protein, carbohydrate, and mineral source in the human diet of peoples in multiple regions of the world. Seed mineral biofortification is an ongoing objective to improve this important food source. The objective of this research was to assess the seed mineral concentration of five macroelements and eight microelements in a large panel (n = 277) of modern race Durango and race Mesoamerica genotypes to determine if variability existed that could be exploited for targeted seed biofortification. Varieties that derive from these races are found in many diets throughout the world. The panel was grown in replicated trials under typical production conditions in the major bean growing regions of the United States, and a subset of the panel was also grown in replicated trials at three locations under control and terminal drought conditions. Except for K, seed mineral concentrations were higher for race Mesoamerica genotypes. Significantly higher seed concentrations for the majority of the minerals were observed for white-seeded genotypes and race Durango genotypes with the now preferred indeterminate, upright growth habit. Modern genotypes (since 1997) had equal or increased mineral concentrations compared with older genotypes. Drought affected mineral content differentially, having no effect on the microelement content but increased Co, Fe, and Ni concentrations. The correlation of Ca and Mn concentrations suggests that these elements may share seed deposition mechanisms. The high heritability for seed mineral concentration implies that breeding progress can be achieved by parental selection from this panel