Electronic Structure, Band Formation and Singlet Fission Dynamics at Metal/Organic Interfaces

Charge carrier injection at the metal/organic interface is crucial for the performance of organic semiconductor based (opto)electronic devices. To achieve an efficient charge carrier injection a detailed knowledge of the electronic properties at the metal/organic interface is needed. In this thesis ultraviolet photoemission spectroscopy and (time-resolved, angle-resolved) two-photon photoemission spectroscopy were utilized to reveal occupied as well as unoccupied electronic states including excitonic states and transport levels. On the one hand the electronic structure and excited state dynamics of a pentacene derivative, in particular regarding the singlet fission dynamics with respect to the film thickness on an Au(111) surface, were examined. On the other hand the electronic structure at the interface between several promising Nheteropolycyclic semiconductors, including a porphyrin, a N-heteroacene and different N-heteroperopyrenes, and Au(111) was revealed. The investigations of the N-heteroperopyrenes stand out as the observation of band formation via hybridization between delocalized metal bands and localized molecular orbitals at the metal/organic interface should foster efficient charge injection

Electronic structure of an iron porphyrin derivative on Au(1 1 1)

Surface-bound porphyrins are promising candidates for molecular switches, electronics and spintronics. Here, we studied the structural and the electronic properties of Fe-tetra-pyridil-porphyrin adsorbed on Au(1 1 1) in the monolayer regime. We combined scanning tunneling microscopy/spectroscopy, ultraviolet photoemission, and two-photon photoemission to determine the energy levels of the frontier molecular orbitals. We also resolved an excitonic state with a binding energy of 420 meV, which allowed us to compare the electronic transport gap with the optical gap

Pediatric T- and NK-cell lymphomas: new biologic insights and treatment strategies

T- and natural killer (NK)-cell lymphomas are challenging childhood neoplasms. These cancers have varying presentations, vast molecular heterogeneity, and several are quite unusual in the West, creating diagnostic challenges. Over 20 distinct T- and NK-cell neoplasms are recognized by the 2008 World Health Organization classification, demonstrating the diversity and potential complexity of these cases. In pediatric populations, selection of optimal therapy poses an additional quandary, as most of these malignancies have not been studied in large randomized clinical trials. Despite their rarity, exciting molecular discoveries are yielding insights into these clinicopathologic entities, improving the accuracy of our diagnoses of these cancers, and expanding our ability to effectively treat them, including the use of new targeted therapies. Here, we summarize this fascinating group of lymphomas, with particular attention to the three most common subtypes: T-lymphoblastic lymphoma, anaplastic large cell lymphoma, and peripheral T-cell lymphoma-not otherwise specified. We highlight recent findings regarding their molecular etiologies, new biologic markers, and cutting-edge therapeutic strategies applied to this intriguing class of neoplasms

ARTEFACTS: How do we want to deal with the future of our one and only planet?

The European Commission’s Science and Knowledge Service, the Joint Research Centre (JRC), decided to try working hand-in-hand with leading European science centres and museums. Behind this decision was the idea that the JRC could better support EU Institutions in engaging with the European public. The fact that European Union policies are firmly based on scientific evidence is a strong message which the JRC is uniquely able to illustrate. Such a collaboration would not only provide a platform to explain the benefits of EU policies to our daily lives but also provide an opportunity for European citizens to engage by taking a more active part in the EU policy making process for the future. A PILOT PROGRAMME To test the idea, the JRC launched an experimental programme to work with science museums: a perfect partner for three compelling reasons. Firstly, they attract a large and growing number of visitors. Leading science museums in Europe have typically 500 000 visitors per year. Furthermore, they are based in large European cities and attract local visitors as well as tourists from across Europe and beyond. The second reason for working with museums is that they have mastered the art of how to communicate key elements of sophisticated arguments across to the public and making complex topics of public interest readily accessible. That is a high-value added skill and a crucial part of the valorisation of public-funded research, never to be underestimated. Finally museums are, at present, undergoing something of a renaissance. Museums today are vibrant environments offering new techniques and technologies to both inform and entertain, and attract visitors of all demographics.JRC.H.2-Knowledge Management Methodologies, Communities and Disseminatio

Cardiovascular disease, chronic kidney disease, and diabetes mortality burden of cardiometabolic risk factors from 1980 to 2010: A comparative risk assessment

Background: High blood pressure, blood glucose, serum cholesterol, and BMI are risk factors for cardiovascular diseases and some of these factors also increase the risk of chronic kidney disease and diabetes. We estimated mortality from cardiovascular diseases, chronic kidney disease, and diabetes that was attributable to these four cardiometabolic risk factors for all countries and regions from 1980 to 2010. Methods: We used data for exposure to risk factors by country, age group, and sex from pooled analyses of population-based health surveys. We obtained relative risks for the effects of risk factors on cause-specific mortality from meta-analyses of large prospective studies. We calculated the population attributable fractions for each risk factor alone, and for the combination of all risk factors, accounting for multicausality and for mediation of the effects of BMI by the other three risks. We calculated attributable deaths by multiplying the cause-specific population attributable fractions by the number of disease-specific deaths. We obtained cause-specific mortality from the Global Burden of Diseases, Injuries, and Risk Factors 2010 Study. We propagated the uncertainties of all the inputs to the final estimates. Findings: In 2010, high blood pressure was the leading risk factor for deaths due to cardiovascular diseases, chronic kidney disease, and diabetes in every region, causing more than 40% of worldwide deaths from these diseases; high BMI and glucose were each responsible for about 15% of deaths, and high cholesterol for more than 10%. After accounting for multicausality, 63% (10·8 million deaths, 95% CI 10·1-11·5) of deaths from these diseases in 2010 were attributable to the combined effect of these four metabolic risk factors, compared with 67% (7·1 million deaths, 6·6-7·6) in 1980. The mortality burden of high BMI and glucose nearly doubled from 1980 to 2010. At the country level, age-standardised death rates from these diseases attributable to the combined effects of these four risk factors surpassed 925 deaths per 100 000 for men in Belarus, Kazakhstan, and Mongolia, but were less than 130 deaths per 100 000 for women and less than 200 for men in some high-income countries including Australia, Canada, France, Japan, the Netherlands, Singapore, South Korea, and Spain. Interpretation: The salient features of the cardiometabolic disease and risk factor epidemic at the beginning of the 21st century are high blood pressure and an increasing effect of obesity and diabetes. The mortality burden of cardiometabolic risk factors has shifted from high-income to low-income and middle-income countries. Lowering cardiometabolic risks through dietary, behavioural, and pharmacological interventions should be a part of the global response to non-communicable diseases. Funding: UK Medical Research Council, US National Institutes of Health. © 2014 Elsevier Ltd

Systematic review and cumulative analysis of oncologic and functional outcomes after robot-assisted radical cystectomy

CONTEXT: Although open radical cystectomy (ORC) is still the standard approach, laparoscopic radical cystectomy (LRC) and robot-assisted radical cystectomy (RARC) are increasingly performed. OBJECTIVE: To report on a systematic literature review and cumulative analysis of pathologic, oncologic, and functional outcomes of RARC in comparison with ORC and LRC. EVIDENCE ACQUISITION: Medline, Scopus, and Web of Science databases were searched using a free-text protocol including the terms robot-assisted radical cystectomy or da Vinci radical cystectomy or robot* radical cystectomy. RARC case series and studies comparing RARC with either ORC or LRC were collected. A cumulative analysis was conducted. EVIDENCE SYNTHESIS: The searches retrieved 105 papers, 87 of which reported on pathologic, oncologic, or functional outcomes. Most series were retrospective and had small case numbers, short follow-up, and potential patient selection bias. The lymph node yield during lymph node dissection was 19 (range: 3-55), with half of the series following an extended template (yield range: 11-55). The lymph node-positive rate was 22%. The performance of lymphadenectomy was correlated with surgeon and institutional volume. Cumulative analyses showed no significant difference in lymph node yield between RARC and ORC. Positive surgical margin (PSM) rates were 5.6% (1-1.5% in pT2 disease and 0-25% in pT3 and higher disease). PSM rates did not appear to decrease with sequential case numbers. Cumulative analyses showed no significant difference in rates of surgical margins between RARC and ORC or RARC and LRC. Neoadjuvant chemotherapy use ranged from 0% to 31%, with adjuvant chemotherapy used in 4-29% of patients. Only six series reported a mean follow-up of >36 mo. Three-year disease-free survival (DFS), cancer-specific survival (CSS), and overall survival (OS) rates were 67-76%, 68-83%, and 61-80%, respectively. The 5-yr DFS, CSS, and OS rates were 53-74%, 66-80%, and 39-66%, respectively. Similar to ORC, disease of higher pathologic stage or evidence of lymph node involvement was associated with worse survival. Very limited data were available with respect to functional outcomes. The 12-mo continence rates with continent diversion were 83-100% in men for daytime continence and 66-76% for nighttime continence. In one series, potency was recovered in 63% of patients who were evaluable at 12 mo. CONCLUSIONS: Oncologic and functional data from RARC remain immature, and longer-term prospective studies are needed. Cumulative analyses demonstrated that lymph node yields and PSM rates were similar between RARC and ORC. Conclusive long-term survival outcomes for RARC were limited, although oncologic outcomes up to 5 yr were similar to those reported for ORC. PATIENT SUMMARY: Although open radical cystectomy (RC) is still regarded as the standard treatment for muscle-invasive bladder cancer, laparoscopic and robot-assisted RCs are becoming more popular. Templates of lymph node dissection, lymph node yields, and positive surgical margin rates are acceptable with robot-assisted RC. Although definitive comparisons with open RC with respect to oncologic or functional outcomes are lacking, early results appear comparable

Epstein-Barr virus–associated lymphoproliferative disorders

Epstein-Barr virus (EBV) is a member of the human herpesvirus family that was initially isolated from a cultured Burkitt lymphoma cell line by Epstein et al in 1964. Subsequent studies have proven that it is the causative agent in most cases of infectious mononucleosis. Primary infection is usually asymptomatic in childhood; but in adulthood, it is associated with a self-limiting infectious mononucleosis syndrome in approximately one third of the cases. EBV has been linked to many human neoplasms including hematopoietic, epithelial, and mesenchymal tumors. In this review, we will only discuss the EBV-associated lymphoproliferative disorders, dividing them into B-cell, T/NK-cell, and HIV-related lymphoproliferative disorders

Prevalence of, and work-related risk factors for, hand eczema in a Norwegian general population (The HUNT Study)

Background Chemical exposures at work and at home may cause hand eczema. However, this has been scarcely described for Norway. Objectives To investigate the prevalence of, and occupational risk factors for, hand eczema in Norway. Methods Among 50 805 respondents (aged ≥20 years) to the third Nord‐Trøndelag Health Study (HUNT3), 5757 persons reported ever having hand eczema, and 4206 answered a hand eczema questionnaire. Results The lifetime prevalences of hand eczema were 8.4% in men and 13.8% in women (p < 0.001), with onset at age ≤10 years in 24% (men) and 20% (women), and onset at age ≥30 years in 37% (men) and 25% (women) (p < 0.001). Work‐related hand eczema affected 4.8% of the population, and was most frequently associated with health/social work (29%) and occupational cleaning (20%) in women, and with farming (26%) and industrial occupations (27%) in men. Cleaning detergents (75%) and other chemicals (36%) were the most common exacerbating factors. Conclusions The prevalence of hand eczema was 11.3%, and that of work‐related hand eczema was 4.8%. Hand eczema was more common in women than in men, but with a later onset in men. Cleaning detergents were the most common aggravating factors. A large proportion of the Nord‐Trøndelag population is employed in farming, providing the possibility to identify farming as an important risk factor for hand eczema.acceptedVersionThis is the peer reviewed version of an article, which has been published in final form at [https://doi.org/10.1111/cod.12800]. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving

2,6-bis(5,6-diisopropyl-1,2,4-triazine-3-yl)pyridine: A highly selective N-donor ligand studied by TRLFS, liquid-liquid extraction and molecular dynamics

The complexation of Cm(III) and Eu(III) with 2,6-bis(5,6-di-i-propyl-1,2,4-triazin-3-yl)-pyridine (iPr-BTP) is studied in methanol : water (1 : 1, vol) by time-resolved laser-induced fluorescence spectroscopy (TRLFS). With increasing ligand concentration [Cm(iPr-BTP)3]3+ and [Eu(iPr-BTP)3]3+ are formed, respectively. Stability constants of log β3′([Cm(iPr-BTP)3]3+) = 16.3 ± 0.3 and log β3′([Eu(iPr-BTP)3]3+) = 14.9 ± 0.3 are determined. Thermodynamic data of the complexation reactions is obtained in a temperature range of 20–60 °C. The complexation of iPr-BTP with both metal ions is exothermic (Cm(III): ΔrH3′ = −(64.1 ± 3.0) kJ mol−1; Eu(III): ΔrH3′ = −(42.6 ± 2.0) kJ mol−1). The reaction entropy for the formation of [Eu(iPr-BTP)3]3+ is higher compared to the Cm(III) complex (Cm(III): ΔrS3′ = (96.5 ± 6.5) J mol−1 K−1; Eu(III): ΔrS3′ = (136.0 ± 15.2) J mol−1 K−1). Different complexation entropies for the formation of [Cm(iPr-BTP)3] and [Cm(nPr-BTP)3] are explained by molecular dynamics simulations. Results from liquid–liquid extraction tests confirm the ligand's peculiar extraction kinetics observed in previous studies and link them to the thermodynamic data