The role of structural and electronic factors in shaping the ambipolar properties of donor-acceptor polymers of thiophene and benzothiadiazole

The influence of different thiophene donor units on electrochemical and spectroscopic properties of benzothiadiazole based donor–acceptor π-conjugated organic materials is studied. Two different structure modification vectors of the donor units are being considered – one addressing the intermolecular interactions through off-conjugation side chain architecture, and the other focusing on intramolecular interactions tuned by in-conjugation substituents. Electrochemical and simultaneous in situ EPR-UV-Vis-NIR spectroelectrochemical studies of the oxidative (p-) and reductive (n-) doping processes, which are responsible for the optoelectronic properties of these materials, revealed their disparate course and dissimilar effects of redox reactions of the conjugated π-bond. While p-doping prevalent species were found to comprise intensively interacting spin bearing and spinless charge carriers, the n-doping state was found to involve only one type of negatively charged carrier, with spin carrying species being selectively generated at due cathodic potentials. No spin pairing of these negative polarons was observed with their increasing population behaving like a collection of localised charge carriers. Qualitative and quantitative comparisons between the p- and n-doping carrier populations provided independent support for the spin pairing phenomena of positive charge carriers. Steric effects of varying alkyl side chain substitution have demonstrated predominant impact on the electrochemical properties of investigated polymers, and, thereto related, stability of n-doped state, while mesomeric effects of different 3,4-ethylenechalcogenide thiophene functionalities have been found to shape the energy level related spectral properties of these polymers, with particular reference to p-doping induced charged states. These findings provide new insights into the factors requiring attention during structure tailoring of donor–acceptor assemblies for organic optoelectronic applications

Primary Treatment Results in Patients with Ovarian, Fallopian or Peritoneal Cancer—Results of a Clinical Cancer Registry Database Analysis in Germany

Simple Summary: Diagnosis and treatment of ovarian cancers has changed significantly over the last years. However, the role of primary surgery and chemotherapy remain important parts of the multimodal treatment. Furthermore, real life data are often lacking but are very important for improving quality indicators and for hypothesis generation for future trials. The present work represents the first major analysis of federal cancer registry data of OC patients in Germany. Overall, 2771 primary OC cases were included. The results clearly elucidate quality measurements and treatment results and show good treatment outcomes in patients with primary OC compared to other internationally reported outcomes. Abstract: Background: The current therapy of ovarian cancer is based on the so-called "Three-Pillar-Model", consisting of surgery, chemotherapy and maintenance therapy. This study represents the first major analysis of a federal cancer database of OC patients from the states Berlin/Brandenburg in Germany. The primary objective was to evaluate the prevailing established quality indicators surgical outcome, adjuvant chemotherapy and integrity of surgical staging in early stages. Methods: Data from the Clinical Cancer Registry for Brandenburg and Berlin of the years 2009-2019 were analyzed. Objectives were defined by a working group of selected physicians. Descriptive statistics were performed, as well as survival analysis. Results: A total of 2771 primary OC cases were included. Results regarding histological subtype met the suspected allocation with predominantly high-grade serous OC in advanced stage. The rate of complete surgical staging in FIGO stages I-IIA was 57%, and the rate of macroscopic complete resection in >FIGO III was 53%. Five-year survival rate varied from 79% (FIGO I) to 40% (FIGO III). Rate of adjuvant chemotherapy was above 50%. Conclusion: The results elucidate quality measurements and treatment results and show good treatment outcomes in patients with primary diagnosis. However, they also indicate deficits and can help to establish new quality indicators to further improve the treatment

Limits to reproduction and seed size-number trade-offs that shape forest dominance and future recovery

International audienceThe relationships that control seed production in trees are fundamental to understanding the evolution of forest species and their capacity to recover from increasing losses to drought, fire, and harvest. A synthesis of fecundity data from 714 species worldwide allowed us to examine hypotheses that are central to quantifying reproduction, a foundation for assessing fitness in forest trees. Four major findings emerged. First, seed production is not constrained by a strict trade-off between seed size and numbers. Instead, seed numbers vary over ten orders of magnitude, with species that invest in large seeds producing more seeds than expected from the 1:1 trade-off. Second, gymnosperms have lower seed production than angiosperms, potentially due to their extra investments in protective woody cones. Third, nutrient-demanding species, indicated by high foliar phosphorus concentrations, have low seed production. Finally, sensitivity of individual species to soil fertility varies widely, limiting the response of community seed production to fertility gradients. In combination, these findings can inform models of forest response that need to incorporate reproductive potential

Limits to reproduction and seed size-number tradeoffs that shape forest dominance and future recovery

The relationships that control seed production in trees are fundamental to understanding the evolution of forest species and their capacity to recover from increasing losses to drought, fire, and harvest. A synthesis of fecundity data from 714 species worldwide allowed us to examine hypotheses that are central to quantifying reproduction, a foundation for assessing fitness in forest trees. Four major findings emerged. First, seed production is not constrained by a strict trade-off between seed size and numbers. Instead, seed numbers vary over ten orders of magnitude, with species that invest in large seeds producing more seeds than expected from the 1:1 trade-off. Second, gymnosperms have lower seed production than angiosperms, potentially due to their extra investments in protective woody cones. Third, nutrient-demanding species, indicated by high foliar phosphorus concentrations, have low seed production. Finally, sensitivity of individual species to soil fertility varies widely, limiting the response of community seed production to fertility gradients. In combination, these findings can inform models of forest response that need to incorporate reproductive potential

Law and Popular Culture: Text, Notes, and Questions

This new Second Edition of Law and Popular Culture: Text, Notes, and Questions maintains the most appreciated features of the First Edition published in 2007. Each of the chapters begins with a list of readily available Hollywood films that are relevant to the particular chapter. After an introduction to the study of popular culture and an outline of the goals of the book, the chapters themselves fall into two categories. Half concern the pop culture portrayals of legal institutions and actors ― law schools, the legal profession, clients, witnesses, judges, and juries. The second half concern various areas of law ― Constitutional Law, Criminal Law, Torts, Business Law, Family Law, and International Law. Well over one hundred excerpts from articles by the leading law and popular culture scholars still are included. A majority of these excerpts appeared in the First Edition, but many appear for the first time in this Second Edition. Film remains the most prominent medium. The Second Edition also adds these exciting new features: An original chapter on Punishment explores the surprisingly large body of pop cultural works related to imprisonment and capital punishment. Law-related imagery and portrayals in such other media as television, inexpensive fiction, children\u27s literature, and the comics receive much greater attention in the text\u27s notes and comments sections than was the case in the First Edition. Emphasis on the reasons, forms, and ramifications of law related popular culture, moving away to some extent from attempts either to point out the legal errors in popular culture or to teach the law using popular culture.https://scholarship.stu.edu/faculty_books/1012/thumbnail.jp

The role of structural and electronic factors in shaping the ambipolar properties of donor-acceptor polymers of thiophene and benzothiadiazole

The influence of different thiophene donor units on electrochemical and spectroscopic properties of benzothiadiazole based donor–acceptor π-conjugated organic materials is studied. Two different structure modification vectors of the donor units are being considered – one addressing the intermolecular interactions through off-conjugation side chain architecture, and the other focusing on intramolecular interactions tuned by in-conjugation substituents. Electrochemical and simultaneous in situ EPR-UV-Vis-NIR spectroelectrochemical studies of the oxidative (p-) and reductive (n-) doping processes, which are responsible for the optoelectronic properties of these materials, revealed their disparate course and dissimilar effects of redox reactions of the conjugated π-bond. While p-doping prevalent species were found to comprise intensively interacting spin bearing and spinless charge carriers, the n-doping state was found to involve only one type of negatively charged carrier, with spin carrying species being selectively generated at due cathodic potentials. No spin pairing of these negative polarons was observed with their increasing population behaving like a collection of localised charge carriers. Qualitative and quantitative comparisons between the p- and n-doping carrier populations provided independent support for the spin pairing phenomena of positive charge carriers. Steric effects of varying alkyl side chain substitution have demonstrated predominant impact on the electrochemical properties of investigated polymers, and, thereto related, stability of n-doped state, while mesomeric effects of different 3,4-ethylenechalcogenide thiophene functionalities have been found to shape the energy level related spectral properties of these polymers, with particular reference to p-doping induced charged states. These findings provide new insights into the factors requiring attention during structure tailoring of donor–acceptor assemblies for organic optoelectronic applications

Synthesis by Stille Cross-Coupling Procedure and Electrochemical Characterization of Branched Polymers Based on Substituted 1,3,5-Triarylbenzenes

A series of various substituted 1,3,5-triarylbenzenes, 2,4,6-triaryl-1-phenoles, 1,3,5-triaryl-1-methoxybenzenes and 2,4,6-triaryl-1,3,5-trimethoxybenzenes were synthesized by a Stille cross-coupling procedure. Their structures were confirmed by 1H NMR, 13C NMR, and elemental analysis. Containing thienyl, furyl and EDOT groups polymers obtained in the process of electropolymerization could be carefully considered as a building material in a wide range of organic-electronic devices. We compare properties of monomers and related polymers depending on aryls moieties and their influence of hydroxyl and methoxyl groups attached to the central benzene core.</jats:p

Law and Popular Culture: Text, Notes, and Questions

https://digitalcommons.law.lsu.edu/books/1046/thumbnail.jp