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Anomaly detection in process mining aims to recognize outlying or unexpected behavior in event logs for purposes such as the removal of noise and identification of conformance violations. Existing techniques for this task are primarily frequency-based, arguing that behavior is anomalous because it is uncommon. However, such techniques ignore the semantics of recorded events and, therefore, do not take the meaning of potential anomalies into consideration. In this work, we overcome this caveat and focus on the detection of anomalies from a semantic perspective, arguing that anomalies can be recognized when process behavior does not make sense. To achieve this, we propose an approach that exploits the natural language associated with events. Our key idea is to detect anomalous process behavior by identifying semantically inconsistent execution patterns. To detect such patterns, we first automatically extract business objects and actions from the textual labels of events. We then compare these against a process-independent knowledge base. By populating this knowledge base with patterns from various kinds of resources, our approach can be used in a range of contexts and domains. We demonstrate the capability of our approach to successfully detect semantic execution anomalies through an evaluation based on a set of real-world and synthetic event logs and show the complementary nature of semantics-based anomaly detection to existing frequency-based techniques.
Immigrant integration has become a primary political concern for leaders in Germany and the United States. The information systems (IS) community has begun to research how information and communications technologies can assist immigrants and refugees, such as by examining how countries can facilitate social-inclusion processes. Migrants face the challenge of joining closed communities that cannot integrate or fear doing so. We conducted a panel discussion at the 2019 Americas Conference on Information Systems (AMCIS) in Cancun, Mexico, to introduce multiple viewpoints on immigration. In particular, the panel discussed how technology can both support and prevent immigrants from succeeding in their quest. We conducted the panel to stimulate a thoughtful and dynamic discussion on best practices and recommendations to enhance the discipline's impact on alleviating the challenges that occur for immigrants in their host countries. In this panel report, we introduce the topic of using ICT to help immigrants integrate and identify differences between North/Central America and Europe. We also discuss how immigrants (particularly refugees) use ICT to connect with others, feel that they belong, and maintain their identity. We also uncover the dark and bright sides of how governments use ICT to deter illegal immigration. Finally, we present recommendations for researchers and practitioners on how to best use ICT to assist with immigration.
The coronavirus disease of 2019 (COVID-19) pandemic has forced most academics to work from home. This sudden venue change can affect academics' productivity and exacerbate the challenges that confront universities as they face an uncertain future. In this paper, we identify factors that influence academics' productivity while working from home during the mandate to self-isolate. From analyzing results from a global survey we conducted, we found that both personal and technology-related factors affect an individual's attitude toward working from home and productivity. Our results should prove valuable to university administrators to better address the work-life challenges that academics face.
Since the beginning of the recent global refugee crisis, researchers have been tackling many of its associated aspects, investigating how we can help to alleviate this crisis, in particular, using ICTs capabilities. In our research, we investigated the use of ICT solutions by refugees to foster the social inclusion process in the host community. To tackle this topic, we conducted thirteen interviews with Syrian refugees in Germany. Our findings reveal different ICT usages by refugees and how these contribute to feeling empowered. Moreover, we show the sources of empowerment for refugees that are gained by ICT use. Finally, we identified the two types of social inclusion benefits that were derived from empowerment sources. Our results provide practical implications to different stakeholders and decision-makers on how ICT usage can empower refugees, which can foster the social inclusion of refugees, and what should be considered to support them in their integration effort.
Personal data increasingly serve as inputs to public goods. Like other types of contributions to public goods, personal data are likely to be underprovided. We investigate whether classical remedies to underprovision are also applicable to personal data and whether the privacy-sensitive nature of personal data must be additionally accounted for. In a randomized field experiment on a public online education platform, we prompt users to complete their profiles with personal information. Compared to a control message, we find that making public benefits salient increases the number of personal data contributions significantly. This effect is even stronger when additionally emphasizing privacy protection, especially for sensitive information. Our results further suggest that emphasis on both public benefits and privacy protection attracts personal data from a more diverse set of contributors.
During the observation of goal-directed actions, infants usually predict the goal at an earlier age when the agent is familiar (e.g., human hand) compared to unfamiliar (e.g., mechanical claw). These findings implicate a crucial role of the developing agentive self for infants' processing of others' action goals. Recent theoretical accounts suggest that predictive gaze behavior relies on an interplay between infants' agentive experience (top-down processes) and perceptual information about the agent and the action-event (bottom-up information; e.g., agency cues). The present study examined 7-, 11-, and 18-month-old infants' predictive gaze behavior for a grasping action performed by an unfamiliar tool, depending on infants' age-related action knowledge about tool-use and the display of the agency cue of producing a salient action effect. The results are in line with the notion of a systematic interplay between experience-based top-down processes and cue-based bottom-up information: Regardless of the salient action effect, predictive gaze shifts did not occur in the 7-month-olds (least experienced age group), but did occur in the 18-month-olds (most experienced age group). In the 11-month-olds, however, predictive gaze shifts occurred only when a salient action effect was presented. This sheds new light on how the developing agentive self, in interplay with available agency cues, supports infants' action-goal prediction also for observed tool-use actions.
This article discusses how Alex Garland’s The Beach (1996) engages with conceptions of utopian islands, nation, and colonialism in modernity and how it, from this basis, develops a different spatiality that reflects on a more deterritorialized form of imperial domination within late twentieth-century globalization, as exercised by the United States. The novel is shown to subvert, but not to abolish, two spatial formations that originated in early modernity: nation and utopia. Building on Jean Baudrillard’s elaborations regarding simulation and simulacra, the article argues that The Beach creates a hyperreal narrative that does away with the idea of isolated, bounded spaces and that in form and content corresponds with the worldwide dominance of the United States at the end of the twentieth century.
While W.E.B. Du Bois’s first novel, The Quest of the Silver Fleece (1911), is set squarely in the USA, his second work of fiction, Dark Princess: A Romance (1928), abandons this national framework, depicting the treatment of African Americans in the USA as embedded into an international system of economic exploitation based on racial categories. Ultimately, the political visions offered in the novels differ starkly, but both employ a Western literary canon – so-called ‘classics’ from Greek, German, English, French, and US American literature. With this, Du Bois attempts to create a new space for African Americans in the world (literature) of the 20th century. Weary of the traditions of this ‘world literature’, the novels complicate and begin to decenter the canon that they draw on. This reading traces what I interpret as subtle signs of frustration over the limits set by the literature that underlies Dark Princess, while its predecessor had been more optimistic in its appropriation of Eurocentric fiction for its propagandist aims.
Purpose
The objective of the investigation was to determine the concomitant effects of upper arm blood flow restriction (BFR) and inversion on elbow flexors neuromuscular responses.
Methods
Randomly allocated, 13 volunteers performed four conditions in a within-subject design: rest (control, 1-min upright position without BFR), control (1-min upright with BFR), 1-min inverted (without BFR), and 1-min inverted with BFR. Evoked and voluntary contractile properties, before, during and after a 30-s maximum voluntary contraction (MVC) exercise intervention were examined as well as pain scale.
Results
Inversion induced significant pre-exercise intervention decreases in elbow flexors MVC (21.1%, Z2p = 0.48, p = 0.02) and resting evoked twitch forces (29.4%, Z2p = 0.34, p = 0.03). The 30-s MVC induced significantly greater pre- to post-test decreases in potentiated twitch force (Z2p = 0.61, p = 0.0009) during inversion (75%) than upright (65.3%) conditions. Overall, BFR decreased MVC force 4.8% (Z2p = 0.37, p = 0.05). For upright position, BFR induced 21.0% reductions in M-wave amplitude (Z2p = 0.44, p = 0.04). There were no significant differences for electromyographic activity or voluntary activation as measured with the interpolated twitch technique. For all conditions, there was a significant increase in pain scale between the 40-60 s intervals and post-30-s MVC (upright< inversion, and without BFR< BFR).
Conclusion
The concomitant application of inversion with elbow flexors BFR only amplified neuromuscular performance impairments to a small degree. Individuals who execute forceful contractions when inverted or with BFR should be cognizant that force output may be impaired.
We present a microcontact printing (mu CP) routine suitable to introduce defined (sub-) microscale patterns on surface substrates exhibiting a high capillary activity and receptive to a silane-based chemistry. This is achieved by transferring functional trivalent alkoxysilanes, such as (3-aminopropyl)-triethoxysilane (APTES) as a low-molecular weight ink via reversible covalent attachment to polymer brushes grafted from elastomeric polydimethylsiloxane (PDMS) stamps. The brushes consist of poly{N-[tris(hydroxymethyl)-methyl]acrylamide} (PTrisAAm) synthesized by reversible addition-fragmentation chain-transfer (RAFT)-polymerization and used for immobilization of the alkoxysilane-based ink by substituting the alkoxy moieties with polymer-bound hydroxyl groups. Upon physical contact of the silane-carrying polymers with surfaces, the conjugated silane transfers to the substrate, thus completely suppressing ink-flow and, in turn, maximizing printing accuracy even for otherwise not addressable substrate topographies. We provide a concisely conducted investigation on polymer brush formation using atomic force microscopy (AFM) and ellipsometry as well as ink immobilization utilizing two-dimensional proton nuclear Overhauser enhancement spectroscopy (H-1-H-1-NOESY-NMR). We analyze the mu CP process by printing onto Si-wafers and show how even distinctively rough surfaces can be addressed, which otherwise represent particularly challenging substrates.
Paths Are Made by Walking
(2021)
The present work gives a detailed analysis of the metamorphic and structural evolution of the back-arc portion of the Famatinian Orogen exposed in the southern Sierra de Aconquija (Cuesta de La Chilca segment) in the Sierras Pampeanas Orientales (Eastern Pampean Sierras). The Pampeanas Orientales include from north to south the Aconquija, Ambato and Ancasti mountains. They are mainly composed of middle to high grade metasedimentary units and magmatic rocks.
At the south end of the Sierra de Aconquija, along an east to west segment extending over nearly 10 km (Cuesta de La Chilca), large volumes of metasedimentary rocks crop out. The eastern metasediments were defined as members of the El Portezuelo Metamorphic-Igneous Complex (EPMIC) or Eastern block and the western ones relate to the Quebrada del Molle Metamorphic Complex (QMMC) or Western block. The two blocks are divided by the La Chilca Shear Zone, which is reactivated as the Rio Chanarito fault.
The EPMIC, forming the hanging wall, is composed of schists, gneisses and rare amphibolites, calc- silicate schists, marbles and migmatites. The rocks underwent multiple episodes of deformation and a late high strain-rate episode with gradually increasing mylonitization to the west. Metamorphism progrades from a M-1 phase to the peak M-3, characterized by the reactions: Qtz + Pl + Bt +/- Ms -> Grt + Bt(2) + Pl(2) +/- Sil +/- Kfs, Qtz + Bt + Sil -> Crd + Kfs and Qtz + Grt + Sil -> Crd. The M-3 assemblage is coeval with the dominant foliation related to a third deformational phase (D-3).
The QMMC, forming the foot wall, is made up of fine-grained banded quartz - biotite schists with quartz veins and quartz-feldspar-rich pegmatites. To the east, schists are also overprinted by mylonitization. The M-3 peak assemblage is quartz + biotite + plagioclase +/- garnet +/- sillimanite +/- muscovite +/- ilmenite +/- magnetite +/- apatite.
The studied segment suffered multiphase deformation and metamorphism. Some of these phases can be correlated between both blocks. D-1 is locally preserved in scarce outcrops in the EPMIC but is the dominant in the QMMC, where S-1 is nearly parallel to S-0. In the EPMIC, D-2 is represented by the S-2 foliation, related to the F-2 folding that overprints S-1, with dominant strike NNW - SSE and high angles dip to the E. D-3 in the EPMIC have F-3 folds with axis oblique to S-2; the S-3 foliation has striking NW - SE dipping steeply to the E or W and develops interference patterns. In the QMMC, S-2 (D-2) is a discontinuous cleavage oblique to S-1 and transposed by S-3 (D-3), subparallel to S-1. Such structures in the QMMC developed at subsolidus conditions and could be correlated to those of the EPMIC, which formed under higher P-T conditions. The penetrative deformation D-2 in the EPMIC occurred during a prograde path with syntectonic growth of garnet reaching P-T conditions of 640 degrees C and 0.54 GPa in the EPMIC. This stage was followed by a penetrative deformation D-3 with syn-kinematic growth of garnet, cordierite and plagioclase. Peak P-T conditions calculated for M-3 are 710 degrees C and 0.60 GPa, preserved in the western part of the EPMIC, west of the unnamed fault.
The schists from the QMMC suffered the early low grade M-1 metamorphism with minimum PT conditions of ca 400 degrees C and 0.35 GPa, comparable to the fine schists (M-1) outcropping to the east. The D-2 deformation is associated with the prograde M-2 metamorphism. The penetrative D-3 stage is related to a medium grade metamorphism M-3, with peak conditions at ca 590 degrees C and 0.55 GPa.
The superimposed stages of deformation and metamorphism reaching high P-T conditions followed by isothermal decompression, defining a clockwise orogenic P-T path. During the Lower Paleozoic, folds were superimposed and recrystallization as well as partial melting at peak conditions occurred. Similar characteristics were described from the basement from other Famatinian-dominated locations of the Sierra de Aconquija and other ranges of the Sierras Pampeanas Orientales.
Development of functional and stable solid polymer electrolytes (SPEs) for battery applications is an important step towards both safer batteries and for the realization of lithium-based or anode-less batteries. The interface between the lithium and the solid polymer electrolyte is one of the bottlenecks, where severe degradation is expected. Here, the stability of three different SPEs - poly(ethylene oxide) (PEO), poly(epsilon-caprolactone) (PCL) and poly(trimethylene carbonate) (PTMC) - together with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt, is investigated after they have been exposed to lithium metal under UHV conditions. Degradation compounds, e.g. Li-O-R, LiF and LixSyOz, are identified for all SPEs using soft X-ray photoelectron spectroscopy. A competing degradation between polymer and salt is identified in the outermost surface region (<7 nm), and is dependent on the polymer host. PTMC:LiTFSI shows the most severe decomposition of both polymer and salt followed by PCL:LiTFSI and PEO:LiTFSI. In addition, the movement of lithium species through the decomposed interface shows large variation depending on the polymer electrolyte system.
This study investigates the use of pulse stretching (skew-sized) inverters for monitoring the variation of count rate and linear energy transfer (LET) of energetic particles. The basic particle detector is a cascade of two pulse stretching inverters, and the required sensing area is obtained by connecting up to 12 two-inverter cells in parallel and employing the required number of parallel arrays. The incident particles are detected as single-event transients (SETs), whereby the SET count rate denotes the particle count rate, while the SET pulsewidth distribution depicts the LET variations. The advantage of the proposed solution is the possibility to sense the LET variations using fully digital processing logic. SPICE simulations conducted on IHP's 130-nm CMOS technology have shown that the SET pulsewidth varies by approximately 550 ps over the LET range from 1 to 100 MeV center dot cm(2) center dot mg(-1). The proposed detector is intended for triggering the fault-tolerant mechanisms within a self-adaptive multiprocessing system employed in space. It can be implemented as a standalone detector or integrated in the same chip with the target system.
This paper presents two new pollen records and quantitative climate reconstructions from northern Chukotka documenting environmental changes over the last 27.9 ka. Open tundra- and steppe-like habitats dominated between 27.9 and 18.7 cal. ka BP. Betula and Alnus shrubs might have grown in sheltered microhabitats but disappeared after 18.7 cal. ka BP. Although the climate was rather harsh, local herb-dominated communities supported herbivores as is evident by the presence of coprophilous spores in the sediments. The increase in Salix and Cyperaceae similar to 16.1 cal. ka BP suggests climate amelioration. Shrub Betula appeared similar to 15.9 cal. ka BP, and became dominant after similar to 15.52 cal. ka BP, whilst typical steppe communities drastically reduced. Very high presence of Botryococcus in the Lateglacial sediments reflects widespread shallow habitats, probably due to lake level increase. Shrub Alnus became common after similar to 13 cal. ka BP reflecting further climate amelioration. Simultaneously, herb communities gradually decreased in the vegetation reaching a minimum similar to 11.8 cal. ka BP. A gradual decrease of algae remains suggests a reduction of shallow-water habitats. Shrubby and graminoid tundra was dominant similar to 11.8-11.1 cal. ka BP, later Salix stands significantly decreased. The forest-tundra ecotone established in the Early Holocene, shortly after 11.1 cal. ka BP. Low contents of green algae in the Early Holocene sediments likely reflect deeper aquatic conditions. The most favourable climate conditions were between similar to 10.6 and 7 cal. ka BP. Vegetation became similar to the modern after similar to 7 cal. ka BP but Pinus pumila came to the Ilirney area at about 1.2 cal. ka BP. It is important to emphasize that the study area provided refugia for Betula and Alnus during MIS 2. It is also notable that our records do not reflect evidence of Younger Dryas cooling, which is inconsistent with some regional environmental records but in good accordance with some others.
In this paper, we employ a comparative life course approach for Canada and Germany to unravel the relationships among general and vocational educational attainment and different life course activities, with a focus on labour market and income inequality by gender. Life course theory and related concepts of 'time,' 'normative patterns,' 'order and disorder,' and 'discontinuities' are used to inform the analyses. Data from the Paths on Life's Way (Paths) project in British Columbia, Canada and the German Pathways from Late Childhood to Adulthood (LifE) which span 28 and 33 years, respectively, are employed to examine life trajectories from leaving school to around age 45. Sequence analysis and cluster analyses portray both within and between country differences - and in particular gender differences - in educational attainment, employment, and other activities across the life course which has an impact on ultimate labour market participation and income levels. 'Normative' life courses that follow a traditional order correspond with higher levels of full-time work and higher incomes; in Germany more so than Canada, these clusters are male dominated. Clusters characterised by 'disordered' and 'discontinuous' life courses in both countries are female dominated and associated with lower income levels.
The leniency rule revisited
(2021)
The experimental literature on antitrust enforcement provides robust evidence that communication plays an important role for the formation and stability of cartels. We extend these studies through a design that distinguishes between innocuous communication and communication about a cartel, sanctioning only the latter. To this aim, we introduce a participant in the role of the competition authority, who is properly incentivized to judge the communication content and price setting behavior of the firms. Using this novel design, we revisit the question whether a leniency rule successfully destabilizes cartels. In contrast to existing experimental studies, we find that a leniency rule does not affect cartelization. We discuss potential explanations for this contrasting result.
Coherent network partitions
(2021)
We continue to study coherent partitions of graphs whereby the vertex set is partitioned into subsets that induce biclique spanned subgraphs. The problem of identifying the minimum number of edges to obtain biclique spanned connected components (CNP), called the coherence number, is NP-hard even on bipartite graphs. Here, we propose a graph transformation geared towards obtaining an O (log n)-approximation algorithm for the CNP on a bipartite graph with n vertices. The transformation is inspired by a new characterization of biclique spanned subgraphs. In addition, we study coherent partitions on prime graphs, and show that finding coherent partitions reduces to the problem of finding coherent partitions in a prime graph. Therefore, these results provide future directions for approximation algorithms for the coherence number of a given graph.
Elaeidobius kamerunicus Faust. (Coleoptera: Curculionidae) is an essential insect pollinator in oil palm plantations. Recently, researches have been undertaken to improve pollination efficiency using this species. A fundamental understanding of the genes related to this pollinator behavior is necessary to achieve this goal. Here, we present the draft genome sequence, annotation, and simple sequence repeat (SSR) marker data for this pollinator. In total, 34.97 Gb of sequence data from one male individual (monoisolate) were obtained using Illumina short-read platform NextSeq 500. The draft genome assembly was found to be 269.79 Mb and about 59.9% of completeness based on Benchmarking Universal Single-Copy Orthologs (BUSCO) assessment. Functional gene annotation predicted about 26.566 genes. Also, a total of 281.668 putative SSR markers were identified. This draft genome sequence is a valuable resource for understanding the population genetics, phylogenetics, dispersal patterns, and behavior of this species.
Fast Holocene slip and localized strain along the Liquiñe-Ofqui strike-slip fault system, Chile
(2021)
In active tectonic settings dominated by strike-slip kinematics, slip partitioning across subparallel faults is a common feature; therefore, assessing the degree of partitioning and strain localization is paramount for seismic hazard assessments. Here, we estimate a slip rate of 18.8 +/- 2.0 mm/year over the past 9.0 +/- 0.1 ka for a single strand of the Liquirie-Ofqui Fault System, which straddles the Main Cordillera in Southern Chile. This Holocene rate accounts for similar to 82% of the trench-parallel component of oblique plate convergence and is similar to million-year estimates integrated over the entire fault system. Our results imply that strain localizes on a single fault at millennial time scale but over longer time scales strain localization is not sustained. The fast millennial slip rate in the absence of historical Mw> 6.5 earthquakes along the Liquine-Ofqui Fault System implies either a component of aseismic slip or Mw similar to 7 earthquakes involving multi-trace ruptures and > 150-year repeat times. Our results have implications for the understanding of strike-slip fault system dynamics within volcanic arcs and seismic hazard assessments.
The goal of limiting global warming to well below 2°C as set out in the Paris Agreement calls for a strategic assessment of societal pathways and policy strategies. Besides policy makers, new powerful actors from the private sector, including finance, have stepped up to engage in forward-looking assessments of a Paris-compliant and climate-resilient future. Climate change scenarios have addressed this demand by providing scientific insights on the possible pathways ahead to limit warming in line with the Paris climate goal. Despite the increased interest, the potential of climate change scenarios has not been fully unleashed, mostly due to a lack of an intermediary service that provides guidance and access to climate change scenarios. This perspective presents the concept of a climate change scenario service, its components, and a prototypical implementation to overcome this shortcoming aiming to make scenarios accessible to a broader audience of societal actors and decision makers.
The Bayesian solution to a statistical inverse problem can be summarised by a mode of the posterior distribution, i.e. a maximum a posteriori (MAP) estimator. The MAP estimator essentially coincides with the (regularised) variational solution to the inverse problem, seen as minimisation of the Onsager-Machlup (OM) functional of the posterior measure. An open problem in the stability analysis of inverse problems is to establish a relationship between the convergence properties of solutions obtained by the variational approach and by the Bayesian approach. To address this problem, we propose a general convergence theory for modes that is based on the Gamma-convergence of OM functionals, and apply this theory to Bayesian inverse problems with Gaussian and edge-preserving Besov priors. Part II of this paper considers more general prior distributions.
We derive Onsager-Machlup functionals for countable product measures on weighted l(p) subspaces of the sequence space R-N. Each measure in the product is a shifted and scaled copy of a reference probability measure on R that admits a sufficiently regular Lebesgue density. We study the equicoercivity and Gamma-convergence of sequences of Onsager-Machlup functionals associated to convergent sequences of measures within this class. We use these results to establish analogous results for probability measures on separable Banach or Hilbert spaces, including Gaussian, Cauchy, and Besov measures with summability parameter 1 <= p <= 2. Together with part I of this paper, this provides a basis for analysis of the convergence of maximum a posteriori estimators in Bayesian inverse problems and most likely paths in transition path theory.
For around a decade, deep learning - the sub-field of machine learning that refers to artificial neural networks comprised of many computational layers - modifies the landscape of statistical model development in many research areas, such as image classification, machine translation, and speech recognition. Geoscientific disciplines in general and the field of hydrology in particular, also do not stand aside from this movement. Recently, the proliferation of modern deep learning-based techniques and methods has been actively gaining popularity for solving a wide range of hydrological problems: modeling and forecasting of river runoff, hydrological model parameters regionalization, assessment of available water resources. identification of the main drivers of the recent change in water balance components. This growing popularity of deep neural networks is primarily due to their high universality and efficiency. The presented qualities, together with the rapidly growing amount of accumulated environmental information, as well as increasing availability of computing facilities and resources, allow us to speak about deep neural networks as a new generation of mathematical models designed to, if not to replace existing solutions, but significantly enrich the field of geophysical processes modeling. This paper provides a brief overview of the current state of the field of development and application of deep neural networks in hydrology. Also in the following study, the qualitative long-term forecast regarding the development of deep learning technology for managing the corresponding hydrological modeling challenges is provided based on the use of "Gartner Hype Curve", which in the general details describes a life cycle of modern technologies.
We systematically explore the effect of calibration data length on the performance of a conceptual hydrological model, GR4H, in comparison to two Artificial Neural Network (ANN) architectures: Long Short-Term Memory Networks (LSTM) and Gated Recurrent Units (GRU), which have just recently been introduced to the field of hydrology. We implemented a case study for six river basins across the contiguous United States, with 25 years of meteorological and discharge data. Nine years were reserved for independent validation; two years were used as a warm-up period, one year for each of the calibration and validation periods, respectively; from the remaining 14 years, we sampled increasing amounts of data for model calibration, and found pronounced differences in model performance. While GR4H required less data to converge, LSTM and GRU caught up at a remarkable rate, considering their number of parameters. Also, LSTM and GRU exhibited the higher calibration instability in comparison to GR4H. These findings confirm the potential of modern deep-learning architectures in rainfall runoff modelling, but also highlight the noticeable differences between them in regard to the effect of calibration data length.
Donors of development assistance for health typically provide funding for a range of disease focus areas, such as maternal health and child health, malaria, HIV/AIDS, and other infectious diseases. But funding for each disease category does not match closely its contribution to the disability and loss of life it causes and the cost-effectiveness of interventions. We argue that peer influences in the social construction of global health priorities contribute to explaining this misalignment. Aid policy-makers are embedded in a social environment encompassing other donors, health experts, advocacy groups, and international officials. This social environment influences the conceptual and normative frameworks of decision-makers, which in turn affect their funding priorities. Aid policy-makers are especially likely to emulate decisions on funding priorities taken by peers with whom they are most closely involved in the context of expert and advocacy networks. We draw on novel data on donor connectivity through health IGOs and health INGOs and assess the argument by applying spatial regression models to health aid disbursed globally between 1990 and 2017. The analysis provides strong empirical support for our argument that the involvement in overlapping expert and advocacy networks shapes funding priorities regarding disease categories and recipient countries in health aid.
The paper introduces the principle Maximise Presupposition and its cognates. The main focus of the literature and this article is on the inferences that arise as a result of reasoning with Maximise Presupposition ('anti-presuppositions'). I will review the arguments put forward for distinguishing them from other inference types, most notably presuppositions and conversational implicatures. I will zoom in on three main issues regarding Maximise Presupposition and these inferences critically discussed in the literature: epistemic strength(ening), projection, and the role of alternatives. I will discuss more recent views which argue for either a uniform treatment of anti-presuppositions and implicatures and/or a revision of the original principle in light of new data and developments in pragmatics.
Internships during tertiary education have become substantially more common over the past decades in many industrialised countries. This study examines the impact of a voluntary intra-curricular internship experience during university studies on the probability of being invited to a job interview. To estimate a causal relationship, we conducted a randomised field experiment in which we sent 1248 fictitious, but realistic, resumes to real job openings. We find that applicants with internship experience have, on average, a 12.6% higher probability of being invited to a job interview.
Manganese (Mn) and zinc (Zn) are not only essential trace elements, but also potential exogenous risk factors for various diseases. Since the disturbed homeostasis of single metals can result in detrimental health effects, concerns have emerged regarding the consequences of excessive exposures to multiple metals, either via nutritional supplementation or parenteral nutrition. This study focuses on Mn-Zn-interactions in the nematode Caenorhabditis elegans (C. elegans) model, taking into account aspects related to aging and age-dependent neurodegeneration.
Label-free optical sensors are attractive candidates, for example, for detecting toxic substances and monitoring biomolecular interactions. Their performance can be pushed by the design of the sensor through clever material choices and integration of components. In this work, two porous materials, namely, porous silicon and plasmonic nanohole arrays, are combined in order to obtain increased sensitivity and dual-mode sensing capabilities. For this purpose, porous silicon monolayers are prepared by electrochemical etching and plasmonic nanohole arrays are obtained using a bottom-up strategy. Hybrid sensors of these two materials are realized by transferring the plasmonic nanohole array on top of the porous silicon. Reflectance spectra of the hybrid sensors are characterized by a fringe pattern resulting from the Fabry–Pérot interference at the porous silicon borders, which is overlaid with a broad dip based on surface plasmon resonance in the plasmonic nanohole array. In addition, the hybrid sensor shows a significant higher reflectance in comparison to the porous silicon monolayer. The sensitivities of the hybrid sensor to refractive index changes are separately determined for both components. A significant increase in sensitivity from 213 ± 12 to 386 ± 5 nm/RIU is determined for the transfer of the plasmonic nanohole array sensors from solid glass substrates to porous silicon monolayers. In contrast, the spectral position of the interference pattern of porous silicon monolayers in different media is not affected by the presence of the plasmonic nanohole array. However, the changes in fringe pattern reflectance of the hybrid sensor are increased 3.7-fold after being covered with plasmonic nanohole arrays and could be used for high-sensitivity sensing. Finally, the capability of the hybrid sensor for simultaneous and independent dual-mode sensing is demonstrated.
Less is more!
(2021)
Enhancing consumer satisfaction and well-being is an important objective of companies, retailers and public policy makers. In the current debate on climate change, a consistent theme is that consumers in developed countries must learn to consume less. The present study (based on representative data sets from the US, N = 1,017, and Germany, N = 1030) addresses these issues by using a scenario-based experiment to analyze how satisfied voluntary simplifiers (people who voluntarily abstain from consumption) are with their purchase decisions in the case of a muesli brand. The research question is whether people who follow a sustainable, simple lifestyle are more satisfied with their daily consumption choices than people who have a more consumerist lifestyle. If so, it would be easier for many people to change their lifestyles and consume less. In addition, this scenario experiment manipulates consumer empowerment and decision complexity since both factors are supposed to influence purchase satisfaction. The results are consistent across both countries and indicate that voluntary simplifiers experience a higher level of purchasing satisfaction than non-simplifiers, whereby empowerment and decision complexity play different roles.
Metal sulfide nanoparticle synthesis with ionic liquids state of the art and future perspectives
(2021)
Metal sulfides are among the most promising materials for a wide variety of technologically relevant applications ranging from energy to environment and beyond. Incidentally, ionic liquids (ILs) have been among the top research subjects for the same applications and also for inorganic materials synthesis. As a result, the exploitation of the peculiar properties of ILs for metal sulfide synthesis could provide attractive new avenues for the generation of new, highly specific metal sulfides for numerous applications. This article therefore describes current developments in metal sulfide nano-particle synthesis as exemplified by a number of highlight examples. Moreover, the article demonstrates how ILs have been used in metal sulfide synthesis and discusses the benefits of using ILs over more traditional approaches. Finally, the article demonstrates some technological challenges and how ILs could be used to further advance the production and specific property engineering of metal sulfide nanomaterials, again based on a number of selected examples.
Enzymes can support the synthesis or degradation of biomacromolecules in natural processes. Here, we demonstrate that enzymes can induce a macroscopic-directed movement of microstructured hydrogels following a mechanism that we call a "Jack-in-the-box" effect. The material's design is based on the formation of internal stresses induced by a deformation load on an architectured microscale, which are kinetically frozen by the generation of polyester locking domains, similar to a Jack-in-thebox toy (i.e., a compressed spring stabilized by a closed box lid). To induce the controlled macroscopic movement, the locking domains are equipped with enzyme-specific cleavable bonds (i.e., a box with a lock and key system). As a result of enzymatic reaction, a transformed shape is achieved by the release of internal stresses. There is an increase in entropy in combination with a swelling-supported stretching of polymer chains within the microarchitectured hydrogel (i.e., the encased clown pops-up with a pre-stressed movement when the box is unlocked). This utilization of an enzyme as a physiological stimulus may offer new approaches to create interactive and enzyme-specific materials for different applications such as an optical indicator of the enzyme's presence or actuators and sensors in biotechnology and in fermentation processes.
In this short survey article, we showcase a number of non-trivial geometric problems that have recently been resolved by marrying methods from functional calculus and real-variable harmonic analysis. We give a brief description of these methods as well as their interplay. This is a succinct survey that hopes to inspire geometers and analysts alike to study these methods so that they can be further developed to be potentially applied to a broader range of questions.
The Eastern Mediterranean is the most seismically active region in Europe due to the complex interactions of the Arabian, African, and Eurasian tectonic plates. Deformation is achieved by faulting in the brittle crust, distributed flow in the viscoelastic lower-crust and mantle, and Hellenic subduction, but the long-term partitioning of these mechanisms is still unknown. We exploit an extensive suite of geodetic observations to build a kinematic model connecting strike-slip deformation, extension, subduction, and shear localization across Anatolia and the Aegean Sea by mapping the distribution of slip and strain accumulation on major active geological structures. We find that tectonic escape is facilitated by a plate-boundary-like, translithospheric shear zone extending from the Gulf of Evia to the Turkish-Iranian Plateau that underlies the surface trace of the North Anatolian Fault. Additional deformation in Anatolia is taken up by a series of smaller-scale conjugate shear zones that reach the upper mantle, the largest of which is located beneath the East Anatolian Fault. Rapid north-south extension in the western part of the system, driven primarily by Hellenic Trench retreat, is accommodated by rotation and broadening of the North Anatolian mantle shear zone from the Sea of Marmara across the north Aegean Sea, and by a system of distributed transform faults and rifts including the rapidly extending Gulf of Corinth in central Greece and the active grabens of western Turkey. Africa-Eurasia convergence along the Hellenic Arc occurs at a median rate of 49.8mm yr(-1) in a largely trench-normal direction except near eastern Crete where variably oriented slip on the megathrust coincides with mixed-mode and strike-slip deformation in the overlying accretionary wedge near the Ptolemy-Pliny-Strabo trenches. Our kinematic model illustrates the competing roles the North Anatolian mantle shear zone, Hellenic Trench, overlying mantle wedge, and active crustal faults play in accommodating tectonic indentation, slab rollback and associated Aegean extension. Viscoelastic flow in the lower crust and upper mantle dominate the surface velocity field across much of Anatolia and a clear transition to megathrust-related slab pull occurs in western Turkey, the Aegean Sea and Greece. Crustal scale faults and the Hellenic wedge contribute only a minor amount to the large-scale, regional pattern of Eastern Mediterranean interseismic surface deformation.
Frailty assessment is recommended before elective transcatheter aortic valve implantation (TAVI) to determine post-interventional prognosis. Several studies have investigated frailty in TAVI-patients using numerous assessments; however, it remains unclear which is the most appropriate tool for clinical practice. Therefore, we evaluate which frailty assessment is mainly used and meaningful for ≤30-day and ≥1-year prognosis in TAVI patients. Randomized controlled or observational studies (prospective/retrospective) investigating all-cause mortality in older (≥70 years) TAVI patients were identified (PubMed; May 2020). In total, 79 studies investigating frailty with 49 different assessments were included. As single markers of frailty, mostly gait speed (23 studies) and serum albumin (16 studies) were used. Higher risk of 1-year mortality was predicted by slower gait speed (highest Hazard Ratios (HR): 14.71; 95% confidence interval (CI) 6.50–33.30) and lower serum albumin level (highest HR: 3.12; 95% CI 1.80–5.42). Composite indices (five items; seven studies) were associated with 30-day (highest Odds Ratio (OR): 15.30; 95% CI 2.71–86.10) and 1-year mortality (highest OR: 2.75; 95% CI 1.55–4.87). In conclusion, single markers of frailty, in particular gait speed, were widely used to predict 1-year mortality. Composite indices were appropriate, as well as a comprehensive assessment of frailty. View Full-Text
Pivots revisited
(2021)
The term "pivot" usually refers to two overlapping syntactic units such that the completion of the first unit simultaneously launches the second. In addition, pivots are generally said to be characterized by the smooth prosodic integration of their syntactic parts. This prosodic integration is typically achieved by prosodic-phonetic matching of the pivot components. As research on such turns in a range of languages has illustrated, speakers routinely deploy pivots so as to be able to continue past a point of possible turn completion, in the service of implementing some additional or revised action. This article seeks to build on, and complement, earlier research by exploring two issues in more detail as follows: (1) what exactly do pivotal turn extensions accomplish on the action dimension, and (2) what role does prosodic-phonetic packaging play in this? We will show that pivot constructions not only exhibit various degrees of prosodic-phonetic (non-)integration, i.e., differently strong cesuras, but that they can be ordered on a continuum, and that this cline maps onto the relationship of the actions accomplished by the components of the pivot construction. While tighter prosodic-phonetic integration, i.e., weak(er) cesuring, co-occurs with post-pivot actions whose relationship to that of the pre-pivot tends to be rather retrospective in character, looser prosodic-phonetic integration, i.e., strong(er) cesuring, is associated with a more prospective orientation of the post-pivot's action. These observations also raise more general questions with regard to the analysis of action.
“Chunking” spoken language
(2021)
In this introductory paper to the special issue on “Weak cesuras in talk-in-interaction”, we aim to guide the reader into current work on the “chunking” of naturally occurring talk. It is conducted in the methodological frameworks of Conversation Analysis and Interactional Linguistics – two approaches that consider the interactional aspect of humans talking with each other to be a crucial starting point for its analysis. In doing so, we will (1) lay out the background of this special issue (what is problematic about “chunking” talk-in-interaction, the characteristics of the methodological approach chosen by the contributors, the cesura model), (2) highlight what can be gained from such a revised understanding of “chunking” in talk-in-interaction by referring to previous work with this model as well as the findings of the contributions to this special issue, and (3) indicate further directions such work could take starting from papers in this special issue. We hope to induce a fruitful exchange on the phenomena discussed, across methodological divides.
The imagination of clearly separated core-shell structures is already outdated by the fact, that the nanoparticle core-shell structures remain in terms of efficiency behind their respective bulk material due to intermixing between core and shell dopant ions. In order to optimize the photoluminescence of core-shell UCNP the intermixing should be as small as possible and therefore, key parameters of this process need to be identified. In the present work the Ln(III) ion migration in the host lattices NaYF4 and NaGdF4 was monitored. These investigations have been performed by laser spectroscopy with help of lanthanide resonance energy transfer (LRET) between Eu(III) as donor and Pr(III) or Nd(III) as acceptor. The LRET is evaluated based on the Forster theory. The findings corroborate the literature and point out the migration of ions in the host lattices. Based on the introduced LRET model, the acceptor concentration in the surrounding of one donor depends clearly on the design of the applied core-shell-shell nanoparticles. In general, thinner intermediate insulating shells lead to higher acceptor concentration, stronger quenching of the Eu(III) donor and subsequently stronger sensitization of the Pr(III) or the Nd(III) acceptors. The choice of the host lattice as well as of the synthesis temperature are parameters to be considered for the intermixing process.
Moving spiral wave chimeras
(2021)
We consider a two-dimensional array of heterogeneous nonlocally coupled phase oscillators on a flat torus and study the bound states of two counter-rotating spiral chimeras, shortly two-core spiral chimeras, observed in this system. In contrast to other known spiral chimeras with motionless incoherent cores, the two-core spiral chimeras typically show a drift motion. Due to this drift, their incoherent cores become spatially modulated and develop specific fingerprint patterns of varying synchrony levels. In the continuum limit of infinitely many oscillators, the two-core spiral chimeras can be studied using the Ott-Antonsen equation. Numerical analysis of this equation allows us to reveal the stability region of different spiral chimeras, which we group into three main classes-symmetric, asymmetric, and meandering spiral chimeras.
Stereoselective [4+2] Cycloaddition of Singlet Oxygen to Naphthalenes Controlled by Carbohydrates
(2021)
Stereoselective reactions of singlet oxygen are of current interest. Since enantioselective photooxygenations have not been realized efficiently, auxiliary control is an attractive alternative. However, the obtained peroxides are often too labile for isolation or further transformations into enantiomerically pure products. Herein, we describe the oxidation of naphthalenes by singlet oxygen, where the face selectivity is controlled by carbohydrates for the first time. The synthesis of the precursors is easily achieved starting from naphthoquinone and a protected glucose derivative in only two steps. Photooxygenations proceed smoothly at low temperature, and we detected the corresponding endoperoxides as sole products by NMR. They are labile and can thermally react back to the parent naphthalenes and singlet oxygen. However, we could isolate and characterize two enantiomerically pure peroxides, which are sufficiently stable at room temperature. An interesting influence of substituents on the stereoselectivities of the photooxygenations has been found, ranging from 51:49 to up to 91:9 dr (diastereomeric ratio). We explain this by a hindered rotation of the carbohydrate substituents, substantiated by a combination of NOESY measurements and theoretical calculations. Finally, we could transfer the chiral information from a pure endoperoxide to an epoxide, which was isolated after cleavage of the sugar chiral auxiliary in enantiomerically pure form.
Large-scale literature mining to assess the relation between anti-cancer drugs and cancer types
(2021)
Background:
There is a huge body of scientific literature describing the relation between tumor types and anti-cancer drugs. The vast amount of scientific literature makes it impossible for researchers and physicians to extract all relevant information manually.
Methods:
In order to cope with the large amount of literature we applied an automated text mining approach to assess the relations between 30 most frequent cancer types and 270 anti-cancer drugs. We applied two different approaches, a classical text mining based on named entity recognition and an AI-based approach employing word embeddings. The consistency of literature mining results was validated with 3 independent methods: first, using data from FDA approvals, second, using experimentally measured IC-50 cell line data and third, using clinical patient survival data.
Results:
We demonstrated that the automated text mining was able to successfully assess the relation between cancer types and anti-cancer drugs. All validation methods showed a good correspondence between the results from literature mining and independent confirmatory approaches. The relation between most frequent cancer types and drugs employed for their treatment were visualized in a large heatmap. All results are accessible in an interactive web-based knowledge base using the following link: .
Conclusions:
Our approach is able to assess the relations between compounds and cancer types in an automated manner. Both, cancer types and compounds could be grouped into different clusters. Researchers can use the interactive knowledge base to inspect the presented results and follow their own research questions, for example the identification of novel indication areas for known drugs.
The rapid emergence of online targeted political advertising has raised concerns over data privacy and what the government's response should be. This paper tested and confirmed the hypothesis that public attitudes toward stricter regulation of online targeted political advertising are partially motivated by partisan self-interest. We conducted an experiment using an online survey of 1549 Americans who identify as either Democrats or Republicans. Our findings show that Democrats and Republicans believe that online targeted political advertising benefits the opposing party. This belief is based on their conviction that their political opponents are more likely to be mobilized by online targeted political advertising than are supporters of their own party. We exogenously manipulated partisan self-interest considerations of a random subset of participants by truthfully informing them that, in the past, online targeted political advertising has benefited Republicans. Our findings show that Republicans informed about this had less favorable attitudes toward regulation than did their uninformed co-partisans. This suggests that Republicans' attitudes regarding stricter regulation are based not solely on concerns about privacy violations, but also, in part, are caused by beliefs about partisan advantage. The results imply that people are willing to accept violations of their privacy if their preferred party benefits from the use of online targeted political advertising.
Nonribosomal peptides (NRP) are crucial molecular mediators in microbial ecology and provide indispensable drugs. Nevertheless, the evolution of the flexible biosynthetic machineries that correlates with the stunning structural diversity of NRPs is poorly understood. Here, we show that recombination is a key driver in the evolution of bacterial NRP synthetase (NRPS) genes across distant bacterial phyla, which has guided structural diversification in a plethora of NRP families by extensive mixing andmatching of biosynthesis genes. The systematic dissection of a large number of individual recombination events did not only unveil a striking plurality in the nature and origin of the exchange units but allowed the deduction of overarching principles that enable the efficient exchange of adenylation (A) domain substrates while keeping the functionality of the dynamic multienzyme complexes. In the majority of cases, recombination events have targeted variable portions of the A(core) domains, yet domain interfaces and the flexible A(sub) domain remained untapped. Our results strongly contradict the widespread assumption that adenylation and condensation (C) domains coevolve and significantly challenge the attributed role of C domains as stringent selectivity filter during NRP synthesis. Moreover, they teach valuable lessons on the choice of natural exchange units in the evolution of NRPS diversity, which may guide future engineering approaches.
The mean free path of ionizing photons, lambda(mfp), is a key factor in the photoionization of the intergalactic medium (IGM). At z greater than or similar to 5, however, lambda(mfp) may be short enough that measurements towards QSOs are biased by the QSO proximity effect. We present new direct measurements of lambda(mfp) that address this bias and extend up to z similar to 6 for the first time. Our measurements at z similar to 5 are based on data from the Giant Gemini GMOS survey and new Keck LRIS observations of low-luminosity QSOs. At z similar to 6 we use QSO spectra from Keck ESI and VLT X-Shooter. We measure lambda(mfp) = 9.09(-1.28)(+1.62) proper Mpc and 0.75(-0.45)(+0.65) proper Mpc (68 percent confidence) at z = 5.1 and 6.0, respectively. The results at z = 5.1 are consistent with existing measurements, suggesting that bias from the proximity effect is minor at this redshift. At z = 6.0, however, we find that neglecting the proximity effect biases the result high by a factor of two or more. Our measurement at z = 6.0 falls well below extrapolations from lower redshifts, indicating rapid evolution in lambda(mfp) over 5 < z < 6. This evolution disfavours models in which reionization ended early enough that the IGM had time to fully relax hydrodynamically by z = 6, but is qualitatively consistent with models wherein reionization completed at z = 6 or even significantly later. Our mean free path results are most consistent with late reionization models wherein the IGM is still 20 percent neutral at z = 6, although our measurement at z = 6.0 is even lower than these models prefer.
Infection is a common and often deadly complication after burn injury. A major underlying factor is burn-induced immune dysfunction, particularly with respect to neutrophils as the primary responders to infection. Temporally after murine scald injury, we demonstrate impaired bone marrow neutrophil chemotaxis toward CXCL1 ex vivo. Additionally, we observed a reduced recruitment of neutrophils to the peritoneal after elicitation 7 days after injury. We demonstrate that neutrophil ceramide levels increase after burn injury, and this is associated with decreased expression of CXCR2 and blunted chemotaxis. A major signaling event upon CXCR2 activation is Akt phosphorylation and this was reduced when ceramide was elevated. In contrast, PTEN levels were elevated and PTEN-inhibition elevated phospho-Akt levels and mitigated the burn-induced neutrophil chemotaxis defect. Altogether, this study identifies a newly described pathway of ceramide-mediated suppression of neutrophil chemotaxis after burn injury and introduces potential targets to mitigate this defect and reduce infection-related morbidity and mortality after burn.
A characterization of the essential spectrum of Schrodinger operators on infinite graphs is derived involving the concept of R-limits. This concept, which was introduced previously for operators on N and Z(d) as "right-limits," captures the behaviour of the operator at infinity. For graphs with sub-exponential growth rate, we show that each point in sigma(ss)(H) corresponds to a bounded generalized eigenfunction of a corresponding R-limit of H. If, additionally, the graph is of uniform sub-exponential growth, also the converse inclusion holds.
With recent experimental advances in laser-driven electron dynamics in polyatomic molecules, the need arises for their reliable theoretical modelling. Among efficient, yet fairly accurate methods for many-electron dynamics are Time-Dependent Configuration Interaction Singles (TD-CIS) (a Wave Function Theory (WFT) method), and Real-Time Time-Dependent Density Functional Theory (RT-TD-DFT), respectively. Here we compare TD-CIS combined with extended Atomic Orbital (AO) bases, TD-CIS/AO, with RT-TD-DFT in a grid representation of the Kohn-Sham orbitals, RT-TD-DFT/Grid. Possible ionization losses are treated by complex absorbing potentials in energy space (for TD-CIS/AO) or real space (for RT-TD-DFT), respectively. The comparison is made for two test cases: (i) state-to-state transitions using resonant lasers (pi-pulses), i.e., bound electron motion, and (ii) large-amplitude electron motion leading to High Harmonic Generation (HHG). Test systems are a H-2 molecule and cis- and trans-1,2-dichlorethene, C2H2Cl2, (DCE). From time-dependent electronic energies, dipole moments and from HHG spectra, the following observations are made: first, for bound state-to-state transitions enforced by pi-pulses, TD-CIS nicely accounts for the expected population inversion in contrast to RT-TD-DFT, in agreement with earlier findings. Secondly, when using laser pulses under non-resonant conditions, dipole moments and lower harmonics in HHG spectra are obtained by TD-CIS/AO which are in good agreement with those obtained with RT-TD-DFT/Grid. Deviations become larger for higher harmonics and at low laser intensities, i.e., for low-intensity HHG signals. We also carefully test effects of basis sets for TD-CIS/AO and grid size for RT-TD-DFT/Grid, different exchange-correlation functionals in RT-TD-DFT, and absorbing boundaries. Finally, for the present examples, TD-CIS/AO is observed to be at least an order of magnitude more computationally efficient than RT-TD-DFT/Grid.
The chemical nature, the number length of integrated building blocks, as well as their sequence structure impact the phase morphology of multiblock copolymers (MBC) consisting of two non-miscible block types. We hypothesized that a strictly alternating sequence should favour phase segregation and in this way the elastic properties. A library of well-defined MBCs composed of two different hydrophobic, semi-crystalline blocks providing domains with well-separated melting temperatures (T(m)s) were synthesized from the same type of precursor building blocks as strictly alternating (MBCsalt) or random (MBCsran) MBCs and compared. Three different series of MBCsalt or MBCsran were synthesized by high-throughput synthesis by coupling oligo(e-caprolactone) (OCL) of different molecular weights (2, 4, and 8 kDa) with oligotetrahydrofuran (OTHF, 2.9 kDa) via Steglich esterification in which the molar ratio of the reaction partners was slightly adjusted. Maximum of weight average molecular weight (M-w) were 65,000 g center dot mol(-1), 165,000 g center dot mol(-1), and 168,000 g center dot mol(-1) for MBCsalt and 80,500 g center dot mol(-1), 100,000 g center dot mol(-1), and 147,600 g center dot mol(-1) for MBCsran. When Mw increased, a decrease of both Tms associated to the melting of the OCL and OTHF domains was observed for all MBCs. T-m (OTHF) of MBCsran was always higher than Tm (OTHF) of MBCsalt, which was attributed to a better phase segregation. In addition, the elongation at break of MBCsalt was almost half as high when compared to MBCsran. In this way this study elucidates role of the block length and sequence structure in MBCs and enables a quantitative discussion of the structure-function relationship when two semi-crystalline block segments are utilized for the design of block copolymers.
The chemical nature, the number length of integrated building blocks, as well as their sequence structure impact the phase morphology of multiblock copolymers (MBC) consisting of two non-miscible block types. It is hypothesized that a strictly alternating sequence should impact phase segregation. A library of well-defined MBC obtained by coupling oligo(epsilon-caprolactone) (OCL) of different molecular weights (2, 4, and 8 kDa) with oligotetrahydrofuran (OTHF, 2.9 kDa) via Steglich esterification results in strictly alternating (MBCalt) or random (MBCran) MBC. The three different series has a weight average molecular weight (M-w) of 65 000, 165 000, and 168 000 g mol(-1) for MBCalt and 80 500, 100 000, and 147 600 g mol(-1) for MBCran. When the chain length of OCL building blocks is increased, the tendency for phase segregation is facilitated, which is attributed to the decrease in chain mobility within the MBC. Furthermore, it is found that the phase segregation disturbs the crystallization by causing heterogeneities in the semi-crystalline alignment, which is attributed to an increase of the disorder of the OCL semi-crystalline alignment.