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While the performance of laboratory-scale organic solar cells (OSCs) continues to grow, development of high efficiency large area OSCs remains a big challenge. Although a few attempts to produce large area organic solar cells (OSCs) have been reported, there are still challenges on the way to realizing efficient module devices, such as the low compatibility of the thickness-sensitive active layer with large area coating techniques, the frequent need for toxic solvents and tedious optimization processes used during device fabrication. In this work, highly efficient thickness-insensitive OSCs based on PTB7-Th:PC71BM that processed with single-component green solvent 2-methylanisole are presented, in which both junction thickness limitation and solvent toxicity issues are simultaneously addressed. Careful investigation reveals that this green solvent prevents the evolution of PC71BM into large area clusters resulting in reduced charge carrier recombination, and largely eliminates trapping centers, and thus improves the thickness tolerance of the films. These findings enable us to address the scalability and solvent toxicity issues and to fabricate a 16 cm(2) OSC with doctor-blade coating with a state-of-the-art power conversion efficiency of 7.5% using green solvent.
Nanoparticles can improve topical drug delivery: size, surface properties and flexibility of polymer nanoparticles are defining its interaction with the skin. Only few studies have explored skin penetration for one series of structurally related polymer particles with systematic alteration of material composition. Here, a series of rigid poly[acrylonitrile-co-(N-vinyl pyrrolidone)] model nanoparticles stably loaded with Nile Red or Rhodamin B, respectively, was comprehensively studied for biocompatibility and functionality. Surface properties were altered by varying the molar content of hydrophilic NVP from 0 to 24.1% and particle size ranged from 35 to 244 nm. Whereas irritancy and genotoxicity were not revealed, lipophilic and hydrophilic nanoparticles taken up by keratinocytes affected cell viability. Skin absorption of the particles into viable skin ex vivo was studied using Nile Red as fluorescent probe. Whilst an intact stratum corneum efficiently prevented penetration, almost complete removal of the horny layer allowed nanoparticles of smaller size and hydrophilic particles to penetrate into viable epidermis and dermis. Hence, systematic variations of nanoparticle properties allows gaining insights into critical criteria for biocompatibility and functionality of novel nanocarriers for topical drug delivery and risks associated with environmental exposure.
2-Deoxy-D-ribose-5-phosphate aldolase (DERA) is a biocatalyst that is capable of converting acetaldehyde and a second aldehyde as acceptor into enantiomerically pure mono- and diyhydroxyaldehydes, which are important structural motifs in a number of pharmaceutically active compounds. However, substrate as well as product inhibition requires a more-sophisticated process design for the synthesis of these motifs. One way to do so is to the couple aldehyde conversion with transport processes, which, in turn, would require an immobilization of the enzyme within a thin film that can be deposited on a membrane support. Consequently, we developed a fabrication process for such films that is based on the formation of DERA-poly(N-isopropylacrylamide) conjugates that are subsequently allowed to self-assemble at an air-water interface to yield the respective film. In this contribution, we discuss the conjugation conditions, investigate the interfacial properties of the conjugates, and, finally, demonstrate a successful film formation under the preservation of enzymatic activity.
4-Methyl-1-vinyl-1,2,4-triazolium triiodide ionic liquid and its polymer poly(4-methyl-1-vinyl-1,2,4-triazolium) triiodide were prepared for the first time from their iodide precursors via the reaction of iodide (I-) with elemental iodine (I-2). The change from iodide to triiodide (I-3(-)) was found to introduce particular variations in the physical properties of these two compounds, including lower melting point/glass transition temperature and altered solubility. The compounds were characterized by single-crystal X-ray diffraction, elemental analysis, and their electrochemical properties examined in solution and in the solid-state. Compared with their iodide analogues, the triiodide salts exhibited lower electrical impedance and higher current in the cyclic voltammetry. We found that poly(4-methyl-1,2,4-triazolium triiodide) was proven to be a promising solid polymer electrolyte candidate. (C) 2017 Elsevier Ltd. All rights reserved.
Many studies of synchronization properties of coupled oscillators, based on the classical Kuramoto approach, focus on ensembles coupled via a mean field. Here we introduce a setup of Kuramoto-type phase oscillators coupled via two mean fields. We derive stability properties of the incoherent state and find traveling wave solutions with different locking patterns; stability properties of these waves are found numerically. Mostly nontrivial states appear when the two fields compete, i.e. one tends to synchronize oscillators while the other one desynchronizes them. Here we identify normal branches which bifurcate from the incoherent state in a usual way, and anomalous branches, appearance of which cannot be described as a bifurcation. Furthermore, hybrid branches combining properties of both are described. In the situations where no stable traveling wave exists, modulated quasiperiodic in time dynamics is observed. Our results indicate that a competition between two coupling channels can lead to a complex system behavior, providing a potential generalized framework for understanding of complex phenomena in natural oscillatory systems.
We present the PINE (Plasma density in the Inner magnetosphere Neural network‐based Empirical) model ‐ a new empirical model for reconstructing the global dynamics of the cold plasma density distribution based only on solar wind data and geomagnetic indices. Utilizing the density database obtained using the NURD (Neural‐network‐based Upper hybrid Resonance Determination) algorithm for the period of 1 October 2012 to 1 July 2016, in conjunction with solar wind data and geomagnetic indices, we develop a neural network model that is capable of globally reconstructing the dynamics of the cold plasma density distribution for 2≤L≤6 and all local times. We validate and test the model by measuring its performance on independent data sets withheld from the training set and by comparing the model‐predicted global evolution with global images of He+ distribution in the Earth's plasmasphere from the IMAGE Extreme UltraViolet (EUV) instrument. We identify the parameters that best quantify the plasmasphere dynamics by training and comparing multiple neural networks with different combinations of input parameters (geomagnetic indices, solar wind data, and different durations of their time history). The optimal model is based on the 96 h time history of Kp, AE, SYM‐H, and F10.7 indices. The model successfully reproduces erosion of the plasmasphere on the nightside and plume formation and evolution. We demonstrate results of both local and global plasma density reconstruction. This study illustrates how global dynamics can be reconstructed from local in situ observations by using machine learning techniques.
This article offers a reconstruction of the vegetation and climate of the south-western Siberian Baraba forest-steppe area during the last ca. 8000 years. The analysis of palynological data from the sediment core of Lake Bolshie Toroki using quantitative methods has made it possible to reconstruct changes of the dominant types of vegetation and mean July air temperatures. Coniferous forests grew in the vicinity of the lake, and mean July air temperatures were similar to present-day ones between 7.9 and 7.0 kyr BP. The warmest and driest climate occurred at 7.0-5.0 kyr BP. At that time, the region had open steppe landscapes; birch groves began to spread. A cooling trend is seen after 5.5 kyr BP, when forest-steppe began to emerge. Steppe communities started to dominate again after 1.5 kyr BP. Mean July air temperatures lower than now are reconstructed for the period of 1.9-1 kyr BP, and then the temperatures became similar to present-day ones. Comparing the archaeological data on the types of economy of the population which inhabited the Baraba forest-steppe with the data on changes in the natural environment revealed a connection between the gradual transition from hunting and fishing to livestock breeding and the development of forest-steppe landscapes with a decrease in the area covered by forests. The development of the forest-steppe as an ecotonic landscape starting around 5 kyr BP might have contributed to the coexistence of several archaeological cultures with different types of economy on the same territory. (C) 2017 Elsevier Ltd. All rights reserved.
The isothermal vacuum-induced dehydration of thin films made of poly(methoxy diethylene glycol acrylate) (PMDEGA), which were swollen under ambient conditions, is studied. The dehydration behavior of the homopolymer film as well as of a nanostructured film of the amphiphilic triblock copolymer polystyrene-block-poly(methoxy diethylene glycol acrylate)-block-polystyrene, abbreviated as PS-b-PMDEGA-b-PS, are probed, and compared to the thermally induced dehydration behavior of such thin thermo-responsive films when they pass through their LCST-type coil-to globule collapse transition. The dehydration kinetics is followed by in-situ neutron reflectivity measurements. Contrast results from the use of deuterated water. Water content and film thickness are significantly reduced during the process, which can be explained by Schott second order kinetics theory for both films. The water content of the dehydrated equilibrium state from this model is very close to the residual water content obtained from the final static measurements, indicating that residual water still remains in the film even after prolonged exposure to the vacuum. In the PS-b-PMDEGA-b-PS film that shows micro-phase separation, the hydrophobic PS domains modify the dehydration process by hindering the water removal, and thus retarding dehydration by about 30%. Whereas residual water remains tightly bound in the PMDEGA domains, water is completely removed from the PS domains of the block copolymer film. (C) 2017 Elsevier Ltd. All rights reserved.
Urban climate is determined by a variety of factors, whose knowledge can help to attenuate heat stress in the context of ongoing urbanization and climate change. We study the influence of city size and urban form on the Urban Heat Island (UHI) phenomenon in Europe and find a complex interplay between UHI intensity and city size, fractality, and anisometry. Due to correlations among these urban factors, interactions in the multi-linear regression need to be taken into account. We find that among the largest 5,000 cities, the UHI intensity increases with the logarithm of the city size and with the fractal dimension, but decreases with the logarithm of the anisometry. Typically, the size has the strongest influence, followed by the compactness, and the smallest is the influence of the degree to which the cities stretch. Accordingly, from the point of view of UHI alleviation, small, disperse, and stretched cities are preferable. However, such recommendations need to be balanced against e.g. positive agglomeration effects of large cities. Therefore, trade-offs must be made regarding local and global aims.
BackgroundDisruptions of reading processes due to text substitutions can measure how readers use lexical information. MethodsWith eye-movement recording, children and adults viewed sentences with either identical, orthographically similar, homophonic or unrelated substitutions of the first characters in target words. To the extent that readers rely on orthographic or phonological cues, substitutions that contain such cues should cause less disruption reading than do unrelated substitutions. ResultsOn pretarget words, there was a reliable reduction in gaze duration due to homophonic substitution only for children. On target words, we observed reliable recovery effects due to orthographic similarity for adults. On post-target words, adults had better orthographic-based and phonological-based recovery abilities than children. ConclusionsThe combination of eye movement recording and the error detection paradigm offers a novel implicit paradigm for studying reading development: during sentence reading, beginning readers of Chinese may rely on phonological mediation, while skilled readers have more direct access to semantics from orthography.
The all-female Amazon molly (Poecilia formosa) is the result of a hybridization of the Atlantic molly (P. mexicana) and the sailfin molly (P. latipinna) approximately 120,000 years ago. As a gynogenetic species, P. formosa needs to copulate with heterospecific males including males from one of its bisexual ancestral species. However, the sperm only triggers embryogenesis of the diploid eggs. The genetic information of the sperm donor typically will not contribute to the next generation of P. formosa. Hence, P. formosa possesses generally one allele from each of its ancestral species at any genetic locus. This raises the question whether both ancestral alleles are equally expressed in P. formosa. Allele-specific expression (ASE) has been previously assessed in various organisms, e.g., human and fish, and ASE was found to be important in the context of phenotypic variability and disease. In this study, we utilized Real-Time PCR techniques to estimate ASE of the androgen receptor alpha (arα) gene in several distinct tissues of Amazon mollies. We found an allelic bias favoring the maternal ancestor (P. mexicana) allele in ovarian tissue. This allelic bias was not observed in the gill or the brain tissue. Sequencing of the promoter regions of both alleles revealed an association between an Indel in a known CpG island and differential expression. Future studies may reveal whether our observed cis-regulatory divergence is caused by an ovary-specific trans-regulatory element, preferentially activating the allele of the maternal ancestor.
The all-female Amazon molly (Poecilia formosa) is the result of a hybridization of the Atlantic molly (P. mexicana) and the sailfin molly (P. latipinna) approximately 120,000 years ago. As a gynogenetic species, P. formosa needs to copulate with heterospecific males including males from one of its bisexual ancestral species. However, the sperm only triggers embryo genesis of the diploid eggs. The genetic information of the sperm donor typically will not contribute to the next generation of P. formosa. Hence, P. formosa possesses generally one allele from each of its ancestral species at any genetic locus. This raises the question whether both ancestral alleles are equally expressed in P. formosa. Allele-specific expression (ASE) has been previously assessed in various organisms, e.g., human and fish, and ASE was found to be important in the context of phenotypic variability and disease. In this study, we utilized Real-Time PCR techniques to estimate ASE of the androgen receptor alpha (ara) gene in several distinct tissues of Amazon mollies. We found an allelic bias favoring the maternal ancestor (P. mexicana) allele in ovarian tissue. This allelic bias was not observed in the gill or the brain tissue. Sequencing of the promoter regions of both alleles revealed an association between an Indel in a known CpG island and differential expression. Future studies may reveal whether our observed cis-regulatory divergence is caused by an ovary-specific trans-regulatory element, preferentially activating the allele of the maternal ancestor.
The Kyoto Protocol’s Clean Development Mechanism (CDM) allows developed countries to meet part of their obligational emission reductions by carrying out emission reduction projects in developing countries. China imposed a price floor to the CDM carbon credits produced in China through its price review policy. Scholars have not agreed on the purpose of China’s price review policy. With a theoretical model and a coherent empirical study, the present study shows that the price floor imposed by China’s price review is more likely to protect those domestic project owners against price discrimination, rather than to distort the CDM market. Nevertheless, China’s price review has its own flaws. Although a regression study shows month of approval, types of projects and location of project can explain 55% of price floor designation, the operation of price review remains quite random and unpredictable in individual cases. This would bring extra bureaucratically uncertainty on its way to curb market uncertainty. Its function can be fulfilled by alternative policy tools with better economic efficiency and legal legitimacy, such as mandatory price disclosure and trading forum, which doesn’t have such drawback, but still be able to alleviate possible price discrimination in individual cases.
Mosses are a major component of the arctic vegetation, particularly in wetlands. We present C / N atomic ratio, delta C-13 and delta N-15 data of 400 brown-moss samples belonging to 10 species that were collected along hydrological gradients within polygonal mires located on the southern Taymyr Peninsula and the Lena River delta in northern Siberia. Additionally, n-alkane patterns of six of these species (16 samples) were investigated. The aim of the study is to see whether the inter-and intraspecific differences in C / N, isotopic compositions and n-alkanes are indicative of habitat, particularly with respect to water level. Overall, we find high variability in all investigated parameters for two different moisture-related groups of moss species. The C / N ratios range between 11 and 53 (median: 32) and show large variations at the intraspecific level. However, species preferring a dry habitat (xero-mesophilic mosses) show higher C / N ratios than those preferring a wet habitat (meso-hygrophilic mosses). The delta C-13 values range between 37.0 and 22.5% (median D 27.8 %). The delta N-15 values range between 6.6 and C 1.7%(median D 2.2 %). We find differences in delta C-13 and delta N-15 compositions between both habitat types. For some species of the meso-hygrophilic group, we suggest that a relationship between the individ-ual habitat water level and isotopic composition can be inferred as a function of microbial symbiosis. The n-alkane distribution also shows differences primarily between xeromesophilic and meso-hygrophilic mosses, i. e. having a dominance of n-alkanes with long (n-C29, n-C31 /and intermediate (n-C25 /chain lengths, respectively. Overall, our results reveal that C / N ratios, isotopic signals and n-alkanes of studied brown-moss taxa from polygonal wetlands are characteristic of their habitat.
Rotations of the principal stress axes are observed as a result of fluid injection into reservoirs. We use a generic, fully coupled 3-D thermo-hydro-mechanical model to investigate systematically the dependence of this stress rotation on different reservoir properties and injection scenarios. We find that permeability, injection rate, and initial differential stress are the key factors, while other reservoir properties only play a negligible role. In particular, we find that thermal effects do not significantly contribute to stress rotations. For reservoir types with usual differential stress and reservoir treatment the occurrence of significant stress rotations is limited to reservoirs with a permeability of less than approximately 10(-12)m(2). Higher permeability effectively prevents stress rotations to occur. Thus, according to these general findings, the observed principal stress axes rotation can be used as a proxy of the initial differential stress provided that rock permeability and fluid injection rate are known a priori.
Over the years, the Security Council has on several occasions dealt with humanitarian assistance issues. However, it is Security Council Resolution 2165(2014), related to the situation in Syria, that has brought the role of the Security Council to the forefront of the debate. It is against this background that the article discusses the legal issues arising from Security Council action facilitating humanitarian assistance to be delivered in situations of non-international armed conflict.
Following a brief survey of relevant practice of the Security Council related to humanitarian assistance, the article considers the relevance, if any, of Article 2(7) of the Charter of the United Nations (UN) to humanitarian assistance to be delivered in such situations. It then moves on to analyse whether a rejection by the territorial state of humanitarian aid to be delivered by third parties may amount to a situation under Article 39 of the UN Charter. It then considers in detail whether (at least implicitly) Resolution 2165 has been adopted under Chapter VII and, if this is not the case, whether it can be still considered to be legally binding.
The article finally considers what impact the adoption of Security Council Resolution 2165 might have on the interpretation of otherwise applicable rules of international humanitarian law and, in particular, the right of third parties to provide humanitarian assistance in a situation of a non-international armed conflict in spite of the absence of consent by the territorial state, and the obligations that members of the Security Council, permanent and non-permanent, have under Common Article 1 of the Geneva Conventions when faced with a draft resolution providing for the delivery of humanitarian assistance, notwithstanding the absence of consent by the territorial state.
Ecosystem boundaries, such as the Arctic-Boreal treeline, are strongly coupled with climate and were spatially highly dynamic during past glacial-interglacial cycles. Only a few studies cover vegetation changes since the last interglacial, as most of the former landscapes are inundated and difficult to access. Using pollen analysis and sedimentary ancient DNA (sedaDNA) metabarcoding, we reveal vegetation changes on Bol’shoy Lyakhovsky Island since the last interglacial from permafrost sediments. Last interglacial samples depict high levels of floral diversity with the presence of trees (Larix, Picea, Populus) and shrubs (Alnus, Betula, Ribes, Cornus, Saliceae) on the currently treeless island. After the Last Glacial Maximum, Larix re-colonised the island but disappeared along with most shrub taxa. This was probably caused by Holocene sea-level rise, which led to increased oceanic conditions on the island. Additionally, we applied two newly developed larch-specific chloroplast markers to evaluate their potential for tracking past population dynamics from environmental samples. The novel markers were successfully re-sequenced and exhibited two variants of each marker in last interglacial samples. SedaDNA can track vegetation changes as well as genetic changes across geographic space through time and can improve our understanding of past processes that shape modern patterns.
Organic matter deposited in ancient, ice-rich permafrost sediments is vulnerable to climate change and may contribute to the future release of greenhouse gases; it is thus important to get a better characterization of the plant organic matter within such sediments. From a Late Quaternary permafrost sediment core from the Buor Khaya Peninsula, we analysed plant-derived sedimentary ancient DNA (sedaDNA) to identify the taxonomic composition of plant organic matter, and undertook palynological analysis to assess the environmental conditions during deposition. Using sedaDNA, we identified 154 taxa and from pollen and non-pollen palynomorphs we identified 83 taxa. In the deposits dated between 54 and 51 kyr BP, sedaDNA records a diverse low-centred polygon plant community including recurring aquatic pond vegetation while from the pollen record we infer terrestrial open-land vegetation with relatively dry environmental conditions at a regional scale. A fluctuating dominance of either terrestrial or swamp and aquatic taxa in both proxies allowed the local hydrological development of the polygon to be traced. In deposits dated between 11.4 and 9.7 kyr BP (13.4-11.1 cal kyr BP), sedaDNA shows a taxonomic turnover to moist shrub tundra and a lower taxonomic richness compared to the older samples. Pollen also records a shrub tundra community, mostly seen as changes in relative proportions of the most dominant taxa, while a decrease in taxonomic richness was less pronounced compared to sedaDNA. Our results show the advantages of using sedaDNA in combination with palynological analyses when macrofossils are rarely preserved. The high resolution of the sedaDNA record provides a detailed picture of the taxonomic composition of plant-derived organic matter throughout the core, and palynological analyses prove valuable by allowing for inferences of regional environmental conditions.
Die langfristigen Auswirkungen von Frühgeburtlichkeit auf kognitive Entwicklung und Schulerfolg
(2017)
In einer prospektiven Längsschnittstudie wurde der Zusammenhang zwischen früher Responsivität der Mutter und kognitiver Entwicklung ihrer früh- bzw. reifgeborenen Kinder untersucht. Im Alter von drei Monaten wurde dafür die Mutter-Kind-Interaktion mittels Verhaltensbeobachtung erfasst. Bei n=351 der teilnehmenden Kinder (101 frühgeboren) wurde die allgemeine Intelligenz (IQ) im Alter von 11 Jahren und bei n=313 (85 frühgeboren) zusätzlich der höchste erreichte Schulabschluss bis 25 Jahren erhoben. Frühgeborene wiesen mit 11 Jahren einen signifikant niedrigeren IQ als Reifgeborene auf, nachdem für mögliche konfundierende Faktoren kontrolliert worden war. Nur bei Früh-, nicht aber bei Reifgeborenen zeigte sich ein signifikanter positiver Zusammenhang zwischen mütterlicher Responsivität und IQ. Für die Wahrscheinlichkeit einen höheren Schulabschluss (mind. Fachabitur) zu erreichen, fand sich weder ein signifikanter Effekt von Frühgeburtlichkeit noch von mütterlicher Responsivität.
In einer prospektiven Längsschnittstudie wurden Auswirkungen früher psychosozialer Risiken bis ins junge Erwachsenenalter untersucht und dabei die Rolle von affektiver und behavioraler Dysregulation im Kindesalter als vermittelndem Faktor überprüft. Drei Monate nach der Geburt wurde das Vorliegen von 11 psychosozialen Belastungsfaktoren erfasst. Im Alter von 8 – 15 Jahren wurde dreimal das Child Behavior Checklist-Dysregulationsprofil (CBCL-DP) erhoben. Mit 25 Jahren wurde ein Strukturiertes Klinisches Interview durchgeführt und 309 der Teilnehmer füllten den Young Adult Self-Report aus. Frühe psychosoziale Risiken gingen mit einem erhöhten Risiko für das Vorliegen eines Substanzmissbrauchs im jungen Erwachsenenalter sowie mit erhöhtem externalisierendem und internalisierendem Problemverhalten einher. Der Zusammenhang zwischen frühen psychosozialen Risiken und späterem externalisierendem bzw. internalisierendem Problemverhalten wurde durch das CBCL-DP vermittelt.