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Leveraging large-deviation statistics to decipher the stochastic properties of measured trajectories
(2021)
Thapa, Samudrajit ; Wyłomańska, Agnieszka ; Sikora, Grzegorz ; Wagner, Caroline E. ; Krapf, Diego ; Kantz, Holger ; Chechkin, Aleksei V. ; Metzler, Ralf
Extensive time-series encoding the position of particles such as viruses, vesicles, or individualproteins are routinely garnered insingle-particle tracking experiments or supercomputing studies.They contain vital clues on how viruses spread or drugs may be delivered in biological cells.Similar time-series are being recorded of stock values in financial markets and of climate data.Such time-series are most typically evaluated in terms of time-averaged mean-squareddisplacements (TAMSDs), which remain random variables for finite measurement times. Theirstatistical properties are different for differentphysical stochastic processes, thus allowing us toextract valuable information on the stochastic process itself. To exploit the full potential of thestatistical information encoded in measured time-series we here propose an easy-to-implementand computationally inexpensive new methodology, based on deviations of the TAMSD from itsensemble average counterpart. Specifically, we use the upper bound of these deviations forBrownian motion (BM) to check the applicability of this approach to simulated and real data sets.By comparing the probability of deviations fordifferent data sets, we demonstrate how thetheoretical bound for BM reveals additional information about observed stochastic processes. Weapply the large-deviation method to data sets of tracer beads tracked in aqueous solution, tracerbeads measured in mucin hydrogels, and of geographic surface temperature anomalies. Ouranalysis shows how the large-deviation properties can be efficiently used as a simple yet effectiveroutine test to reject the BM hypothesis and unveil relevant information on statistical propertiessuch as ergodicity breaking and short-time correlations.
Coordinated subjects often show variable number agreement with the finite verb, but linguistic approaches to this phenomenon have rarely been informed by systematically collected data. We report the results from three experiments investigating German speakers' agreement preferences with complex subjects joined by the correlative conjunctions sowohl horizontal ellipsis als auch ('both horizontal ellipsis and'), weder horizontal ellipsis noch ('neither horizontal ellipsis nor') or entweder horizontal ellipsis oder ('either horizontal ellipsis or'). We examine to what extent conjunction type and a conjunct's relative proximity to the verb affect the acceptability and processibility of singular vs. plural agreement. Experiment 1 was an untimed acceptability rating task, Experiment 2 a timed sentence completion task, and Experiment 3 was a self-paced reading task. Taken together, our results show that number agreement with correlative coordination in German is primarily determined by a default constraint triggering plural agreement, which interacts with linear order and semantic factors. Semantic differences between conjunctions only affected speakers' agreement preferences in the absence of processing pressure but not their initial agreement computation. The combined results from our offline and online experimental measures of German speakers' agreement preferences suggest that the constraints under investigation do not only differ in their relative weighting but also in their relative timing during agreement computation.
A convenient method for the synthesis of gamma-spirolactams in only three steps is described. Birch reduction of inexpensive and commercially available aromatic carboxylic acids in the presence of chloroacetonitrile affords nitriles in moderate to good yields. Suitable precursors are methyl-substituted benzoic acids, naphthoic, and anthroic acid. Subsequent catalytic hydrogenation proceeds smoothly with PtO2 or Raney Ni as catalysts and lactams are isolated in excellent yields and stereoselectivities. Thus, up to 3 new stereogenic centers can be constructed as sole diastereomers from achiral benzoic acids. Furthermore, it is possible to control the degree of saturation at different pressures, affording products with 0, 1, or 2 double bonds. Overall, more than 15 new gamma-spirolactams have been synthesized in analytically pure form.
Influence of functional groups on the ene reaction of singlet oxygen with 1,4-cyclohexadienes
(2021)
Fudickar, Werner ; Metz, Melanie ; Mai-Linde, Yasemin ; Krüger, Tobias ; Kelling, Alexandra ; Sperlich, Eric ; Linker, Torsten
The photooxygenation of 1,4-cyclohexadienes has been studied with a special focus on regio- and stereoselectivities. In all examples, only the methyl-substituted double bond undergoes an ene reaction with singlet oxygen, to afford hydroperoxides in moderate to good yields. We explain the high regioselectivities by a "large-group effect" of the adjacent quaternary stereocenter. Nitriles decrease the reactivity of singlet oxygen, presumably by quenching, but can stabilize proposed per-epoxide intermediates by polar interactions resulting in different stereoselectivities. Spiro lactams and lactones show an interesting effect on regio- and stereoselectivities of the ene reactions. Thus, singlet oxygen attacks the double bond preferentially anti to the carbonyl group, affording only one regioisomeric hydroperoxide. If the reaction occurs from the opposite face, the other regioisomer is exclusively formed by severe electrostatic repulsion in a perepoxide intermediate. We explain this unusual behavior by the fixed geometry of spiro compounds and call it a "spiro effect" in singlet oxygen ene reactions.
In the absence of a stranded auxiliary or modal, VP-topicalization in most Germanic languages gives rise to the presence of a dummy verb meaning 'do'. Cross-linguistically, this is a rather uncommon strategy as comparable VP-fronting constructions in other languages, e.g. Hebrew, Polish, and Portuguese, among many others, exhibit verb doubling. A comparison of several recent approaches to verb doubling in VP-fronting reveals that it is the consequence of VP-evacuating head movement of the verb to some higher functional head, which saves the (low copy of the) verb from undergoing copy deletion as part of the low VP copy in the VP-topicalization dependency. Given that almost all Germanic languages have such V-salvaging head movement, namely V-to-C movement, but do not show verb doubling, this paper suggests that V-raising is exceptionally impossible in VP-topicalization clauses and addresses the question of why it is blocked. After discussing and rejecting some conceivable explanations for the lack of verb doubling, I propose that the blocking effect arises from a bleeding interaction between V-to-C movement and VP-to-SpecCP movement. As both operations are triggered by the same head, i.e. C, the VP is always encountered first by a downward search algorithm. Movement of VP then freezes it and its lower copies for subextraction precluding subsequent V-raising. Crucially, this implies that there is no V-to-T raising in most Germanic languages. V2 languages with V-to-T raising, e.g. Yiddish, are correctly predicted to not exhibit the blocking effect.
Background
Despite the prevalence of obsessive-compulsive disorder (OCD), its precise identification remains challenging. With the Zohar-Fineberg Obsessive-Compulsive Screen (ZF-OCS; 5 or 6 items), a brief instrument is widely available mainly in English. As there is a lack of empirical studies on the ZF-OCS, the aim of the present study was to translate the items into German and investigate the instrument in a nonclinical sample.
Methods
In two consecutive online surveys, n = 304 and n = 51 students participated. Besides the ZF-OCS, they answered established measures on OCD, depression, health anxiety, general anxiety and health-related well-being.
Results
Whereas internal consistency was low (α = .53–.72; ω = .55–.69), retest reliability (rt1,t2 = .89) at two weeks was high. As expected, we found high correlations with other OCD instruments (r > .61; convergent validity), and significantly weaker correlations with measures of depression (r = .39), health anxiety (r = .29), and health-related well-being (r = −.28, divergent validity). Nonetheless, the correlations with general anxiety were somewhere in between (r = .52).
Conclusions
Due to heterogeneous OCD subtypes, the ZF-OCS asks diverse questions which probably resulted in the present internal consistency. Nevertheless, the results on retest reliability and validity were promising. As for other OCD instruments, divergent validity regarding general anxiety seems problematic to establish. Even so, the ZF-OCS seems valuable for screening purposes, as it is short and easy to administer, and may facilitate initiating subsequent clinical assessment. Further studies should determine the instrument’s diagnostic accuracy.
Recent research provides evidence that aggressive sexual fantasies predict aggressive sexual behavior in the general population. However, sexual fantasies including fantasies about the infliction of pain and humiliation, should be frequent and often consensually acted upon among individuals with sadomasochistic likings. The question arises whether sexual fantasies with aggressive content still predict presumably non-consensual aggressive sexual behavior in individuals with sadomasochistic likings, given that BDSM encounters are generally considered consensual. To investigate this question, we conducted a questionnaire survey of sexual fantasies, as sessing the frequency of seventy sexual fantasies involving non-aggressive, masochistic, and aggressive acts. Our sample (N = 182) contained 99 respondents who self-identified as sadist, masochist, or switcher; 44 reported no such identification. For respondents reporting BDSM identification, we replicated a factor structure for sexual fantasies similar to that previously found in the general population, including three factors reflecting fantasies about increasingly severe aggressive sexual acts. Fantasies about injuring a partner and/or using weapons and fantasies about sexual coercion predicted presumably non-consensual sexual behavior independently of other risk factors for aggressive sexual behavior and irrespective of BDSM identification. Hence, severely aggressive sexual fantasies may predispose to presumably non-consensual sexual behavior in both individuals with and without BDSM identification.
This paper intends to explore the interaction between aspect and lexical means, in this case temporal adverbials, in the bounding of representations of situations. First, the theoretical basis is outlined, followed by the results of a corpus analysis of coccurrences with adverbs that limit situations. The term situation encompasses all representable processes, states, events, or actions. Finally, some theoretical conclusions are drawn concerning the cognitive category of bounding, using the example of aspectuality. The imperfective verb forms maintain their aspectuality in delimiting connections with adverbs, resulting in a complex, multi-dimensional aspectuality. In nongrammaticalized forms, such as lexical markers, the speaker is free to make a temporal localization or an aspectual perspective. Lexical expressions can make temporal and aspect markings even more precisely and clearly than tenses. They can also limit or extend situations and thus express aspect. Aspectuality thus presents itself as a compositional category, in which external bounding and the internal representation of a course of action or development can interact.
Analogy-based collective decision-making and incremental change in international organizations
(2021)
We examine how analogy-based collective decision-making of member states contributes to the endogenous emergence of informal rules and the incremental change of international organizations (IOs). Decision-making by analogy is an important characteristic of day-to-day decision-making in IOs. Relating current decisions to previous ones through analogies drives incremental change and simultaneously reinforces organizational resilience. Whereas the foreign policy analysis literature shows that analogies can be used as cognitive shortcuts in fuzzy and complex foreign policy situations, we focus on their use to overcome social ambiguity (indeterminacy) of coordination situations in IOs. Drawing on psychological conceptions, we develop two micro-level mechanisms that elucidate the effects of analogy-based collective decision-making in member-driven IOs. Analogy-based collective decisions emphasizing similarity between a current situation and previous ones follow an established problem schema and produce expansive and increasingly well-established informal rules. Collective decisions that are analogy-based but emphasize a crucial difference follow different problem schemas and trigger the emergence of additional informal rules that apply to new classes of cases. The result is an increasingly fine-grained web of distinct organizational solutions for a growing number of problems. Accordingly, an IO can increasingly facilitate collective decision-making and gains resilience. Empirically, we probe these propositions with a documentary analysis of decision-making in the Yugoslavia sanctions committee, established by the United Nations Security Council to deal with a stream of requests for exempting certain goods or services from the comprehensive economic embargo imposed on Yugoslavia in response to the War in the Balkans.