Scrutinizing Design Principles toward Efficient,Long‐Term Stable Green Light‐Emitting Electrochemical Cells

Enhancing the efficiency and lifetime of light emitting electrochemical cells (LEC) is the most important challenge on the way to energy efficient lighting devices of the future. To avail this, emissive Ir(III) complexes with fluoro‐substituted cyclometallated ligands and electron donating groups (methyl and tert ‐butyl)‐substituted diimine ancillary (N^{^}N) ligands and their associated LEC devices are studied. Four different complexes of general composition [Ir(4ppy)₂(N^{^}N)][PF₆] (4Fppy = 2‐(4‐fluorophenyl)pyridine) with the N^{^}N ligand being either 2,2′‐bipyridine ( 1 ), 4.4′‐dimethyl‐2,2′‐bipyridine ( 2 ), 5.5′‐dimethyl‐2,2′‐bipyridine ( 3 ), or 4.4′‐di‐tert ‐butyl‐2,2′‐bipyridine ( 4 ) are synthesized and characterized. All complexes emit in the green region of light with emission maxima of 529–547 nm and photoluminescence quantum yields in the range of 50.6%–59.9%. LECs for electroluminescence studies are fabricated based on these complexes. The LEC based on ( 1 ) driven under pulsed current mode demonstrated the best performance, reaching a maximum luminance of 1605 cd m^?2 resulting in 16 cd A^?1 and 8.6 lm W^?1 for current and power efficiency, respectively, and device lifetime of 668 h. Compared to this, LECs based on ( 3 ) and ( 4 ) perform lower, with luminance and lifetime of 1314 cd m^?2, 45.7 h and 1193 cd m^?2, 54.9 h, respectively. Interestingly, in contrast to common belief, the fluorine content of the Ir‐iTMCs does not adversely affect the LEC performance, but rather electron donating substituents on the N^{^}N ligands are found to dramatically reduce both performance and stability of the green LECs. In light of this, design concepts for green light emitting electrochemical devices have to be reconsidered.     

Measurements of endotoxin on ambient loaded PM filters after long-term storage

At present there exist unsolved questions, whether endotoxin measurements on PM filters show valid measurements after long-term storage of loaded PM filters. As part of the TRAPCA study we collected particles with a 50% aerodynamic cut-off diameter of 2.5 microm (PM(2.5)) at 40 outdoor sites and particles less than 10 microm in size (PM(10)) at a subset of these sites (N=12) in Munich. The PM filters were cut in halves and endotoxin was measured in the extract of one filter half 2-3 years after PM collection. Here we present the results of repeated endotoxin measurements, where the association between previously measured endotoxin concentrations, measurements from stored eluates, and measurements in extracts of the second filter halves were determined. No statistically significant changes were seen between our old measurements and those from the stored eluates. Additionally, no change was observed between previously measured endotoxin concentrations and those from the stored set of filter halves. We found an average increase of 5% between our old measurements and those from the stored eluates and of 19% between the old measurements and those from the stored set of filter halves. The correlations between the previously measured endotoxin concentrations and the repeated measurements from the stored eluates were high (r=0.789) for EU/m(3) PM(2.5). Since endotoxin was evaluated from the same set of filter halves, it is obvious that storage over three years did not substantially effect the correlation of the endotoxin content. Regarding the outliers from previous measurements unsymmetric endotoxin spots on one out of 48 filter halves could be determined. Apart from this we conclude that the endotoxin is homogenously distributed on the filter halves and that endotoxin levels, which were repeatedly measured from filters stored over three years, could be determined validly.     

Transformations of Planning Rationales: Changing Spaces for Governance in Recent Dutch National Planning

Dutch national planning has acquired an international reputation because it provides strong planning guidance while simultaneously being responsive to the particular spatial and political circumstances of different regions and areas. Spatial concepts, like the Randstad, are important vehicles for sustaining this approach. Such concepts incorporate select spatial planning rationales that justify operational decisions. Concepts can, however, also be ambiguous, and this can allow for different interpretations and deliberations about how guidance should take effect in different situations. In this paper we assess the degree of ambiguity contained in concepts outlined in Dutch national plans between 1988 and 2012. By focusing on the dimensions of spatial concepts, and the room for interpretation these create, we demonstrate how concepts were modified to accommodate a shifting appreciation of deliberation and, as a result, collaboration and governance. On a theoretical level, we propose a method that analyses in detail the ambiguity (“fuzzyness” or “softness”) of spatial concepts. We argue that such sophisticated understandings contribute to explaining the variety of governance responses that these geographies produce in practice. On an empirical level we seek to increase understanding of change in recent Dutch national planning.     

Modelling of heat stability and heat‐induced aggregation of casein micelles in concentrated skim milk using a Weibullian model

Heat stability is known to be limited in concentrated skim milk leading to severe coagulation and sediment formation during storage. It has often been found to be in conflict with the extension of the shelf life by thermal treatment. A Weibullian model was used to describe the course of coagulation of casein micelles in concentrated skim milk of different total solids and at different heating temperatures. A maximum heating temperature–time–total solids relationship was calculated based on a certain maximum allowance of sediment formation. Optimal heat treatment conditions for concentrated skim milk of different total solids content could be defined.     

Designing a robo-advisor for risk-averse,low-budget consumers

Banks have reacted much more enthusiastically to the FinTech revolution than many of their customers. Robo-advisory, automated web-based investment advisory, in particular promises many advantages for both banks and customers - but consumer adoption has been slow so far. Recent studies suggest that this might be due to a mix of low trust in banks, high expectations of transparency and general inability or unwillingness to engage with investment questions. Research in decision support and guidance shows customers’ willingness to interact with a decision support tool depends greatly on its usability. We identify requirements for robo-advisory, derive design principles and evaluate them in two iterations with a real robo-advisor in a controlled laboratory study. The evaluation results confirm the validity of our identified design principles.     

Discovery of complex mixtures of novel long-chain quorum sensing signals in free-living and host-associated marine alphaproteobacteria

More than 100 bacterial isolates from various marine habitats were screened for AHL production by using gfp reporter constructs based on the lasR system of Pseudomonas aeruginosa and the luxR system of Vibrio fischeri. Of the 67 Alphaproteobacteria tested, most of which belonged into the so-called Roseobacter clade, 39 induced fluorescence in either one or both sensor strains up to 103-fold compared to controls. Acylated homoserine lactones were identified by GC-MS analysis and shown to have chain lengths of C8, C10, C13-C16, and C18. One or two double bonds were often present, while a keto or hydroxyl group occurred only rarely in the side chain. Most strains produced several different AHLs. C18-en-HSL and C18-dien-HSL were produced by Dinoroseobacter shibae, an aerobic anoxygenic phototrophic bacterium isolated from dinoflagellates, and are among the longest AHLs found to date. Z7-C14-en-HSL, which has previously been detected in Rhodobacter sphaeroides, was produced by Roseovarius tolerans and Jannaschia helgolandensis. This signal molecule was synthesised and shown to induce a similar response to the culture supernatant in the respective sensor strain. The widespread occurrence of quorum-sensing compounds in marine Alphaproteobacteria, both free-living strains and those associated to eukaryotic algae, points to a great importance of this signalling mechanism for the adaptation of the organisms to their widely different ecological niches.     

Kairomonal Effects of Sawfly Sex Pheromones on Egg Parasitoids

The response of the two eulophid egg parasitoid species Chrysonotomyia ruforum and Dipriocampe diprioni to sex pheromones of their sawfly hosts Diprion pini and Neodiprion sertifer was studied in olfactometer bioassays. Females of C. ruforum were arrested when exposed to odor of the tested major sex pheromone components of Diprion pini [acetate and propionate of (2S,3R,7R)-3,7–dimethyl-2–tridecanol] or Neodiprion sertifer [(2S,3S,7S)-3,7–dimethyl-2–pentadecyl acetate]. This behavioral response of C. ruforum was observed whether (1) parasitoid females had oviposition experience with D. pini eggs or not, (2) parasitoid females emerged from D. pini eggs of a French population or from N. sertifer eggs of a Finnish population, and (3) the tested sex pheromone concentration was low (1 ng/l hexane) or high (100 ng/l hexane). However, C. ruforum did not behaviorally respond to a stereoisomer of the major sex pheromone component of N. sertifer, which is known to act as a sex pheromone antagonist [antagonist = (2S,3R,7R)-3,7–dimethyl-2–pentadecyl acetate]. Thus, C. ruforum responded stereospecifically to the S,S,S configured pheromone of N. sertifer, but not to the S,R,R configuration. Females of the parasitoid D. diprioni were also arrested by the tested major sex pheromone components of the host D. pini. The kairomonal effects of diprionid host sex pheromones on these egg parasitoids are compared to known responses of egg parasitoids to lepidopteran sex pheromones.     

Bimodal drop size distributions during the early stages of shear induced coalescence

Drop sizes and drop size distributions were determined by means of an optical shear cell in combination with an optical microscope for the systems polyisobutylene/poly(dimethylsiloxane) [I] and poly(dimethyl-co-methylphenylsiloxane)/poly(dimethylsiloxane) [II] at low concentrations of the suspended phases and at different constant shear rates ranging from 10 to 0.5 s⁻¹. After pre-shearing the two-phase mixtures [I: 50 s⁻¹; II: 100 s⁻¹] for the purpose of producing small drop radii, the shear rate was abruptly reduced to the preselected value and coalescence was studied as a function of time. In all cases one approaches dead end drop radii, i.e. breakup is absent. The drop size distributions are for sufficiently long shearing always unimodal, but within the early stages of coalescence they are in some cases bimodal; the shape of the different peaks is invariably Gaussian. The results are discussed by means of Elmendorp diagrams and interpreted in terms of collision frequencies and collision efficiencies.