Showing papers by "University of Jyväskylä published in 2023"

Halogen-bonded halogen(I) ion complexes

Abstract: Halogen bonding occurs between a positive region of a polarized halogen (X), most commonly with an iodine or bromine atom. The polarization, caused by an electron withdrawing group (R), induces electron deficiency onto the halogen atom, creating an electropositive region known as a σ-hole. This σ-hole then interacts with electron-rich nucleophiles (such as Lewis bases, B) forming a linear R–X···B halogen bond. When an electron is completely removed from a halogen, a halogen (I) ion (X + ) is formed. A halogen(I) ion itself is highly reactive, but can be ‘trapped’ in between two Lewis bases creating a [L–X–L] + 3-center, 4-electron halogen bond between the halogen(I) ion and two donor atoms of the Lewis bases (typically nitrogen). Halogen(I) complexes form a special family manifesting a strong halogen bond, which demonstrate good stability in both the solution and solid-states. An overview of the current state of halogen bonding of halogen(I) ion complexes is included, as well as the many advancements made to those fields in recent years.

Theory for polaritonic quantum tunneling

Abstract: I investigate the tunneling decay rate of a polaritonic system formed by a strong coupling between a vacuum cavity mode and $N$ metastable systems. Using a simple model potential, I find the instanton solutions controlling the low-temperature tunneling rate. The resulting rate modification due to the cavity is proportional to the mean of the second power of the light-matter coupling. No collective effect that would enhance the rates by a factor of $\sqrt{N}$ is present, which is in line with the results in the thermal activation regime.

Ecological and evolutionary consequences of selective interspecific information use

Abstract: Recent work has shown that animals frequently use social information from individuals of their own species as well as from other species; however, the ecological and evolutionary consequences of this social information use remain poorly understood. Additionally, information users may be selective in their social information use, deciding from whom and how to use information, but this has been overlooked in an interspecific context. In particular, the intentional decision to reject a behaviour observed via social information has received less attention, although recent work has indicated its presence in various taxa. Based on existing literature, we explore in which circumstances selective interspecific information use may lead to different ecological and coevolutionary outcomes between two species, such as explaining observed co-occurrences of putative competitors. The initial ecological differences and the balance between the costs of competition and the benefits of social information use potentially determine whether selection may lead to trait divergence, convergence or coevolutionary arms race between two species. We propose that selective social information use, including adoption and rejection of behaviours, may have far-reaching fitness consequences, potentially leading to community-level eco-evolutionary outcomes. We argue that these consequences of selective interspecific information use may be much more widespread than has thus far been considered.

High-resolution spatial patterns and drivers of terrestrial ecosystem carbon dioxide, methane, and nitrous oxide fluxes in the tundra

Abstract: Abstract. Arctic terrestrial greenhouse gas (GHG) fluxes of carbon dioxide (CO2), methane (CH4) and nitrous oxide (N2O) play an important role in the global GHG budget. However, these GHG fluxes are rarely studied simultaneously, and our understanding of the conditions controlling them across spatial gradients is limited. Here, we explore the magnitudes and drivers of GHG fluxes across fine-scale terrestrial gradients during the peak growing season (July) in sub-Arctic Finland. We measured chamber-derived GHG fluxes and soil temperature, soil moisture, soil organic carbon and nitrogen stocks, soil pH, soil carbon-to-nitrogen (C/N) ratio, soil dissolved organic carbon content, vascular plant biomass, and vegetation type from 101 plots scattered across a heterogeneous tundra landscape (5 km2). We used these field data together with high-resolution remote sensing data to develop machine learning models to predict (i.e., upscale) daytime GHG fluxes across the landscape at 2-m resolution. Our results show that this region was on average a daytime net GHG sink during the growing season. Although our results suggest that this sink was driven by CO2 uptake, it also revealed small but widespread CH4 uptake in upland vegetation types, shifting this region to an average net CH4 sink at the landscape scale during growing season, despite the presence of high-emitting wetlands. Average N2O fluxes were negligible. CO2 fluxes were controlled primarily by annual average soil temperature and biomass (both increase net sink) and vegetation type, CH4 fluxes by soil moisture (increases net emissions) and vegetation type, and N2O fluxes by soil C/N (lower C/N increases net source). These results demonstrate the potential of high spatial resolution modelling of GHG fluxes in the Arctic. They also reveal the dominant role of CO2 fluxes across the tundra landscape, but suggest that CH4 uptake might play a significant role in the regional GHG budget.

Undoing Power Hierarchies

Abstract: Abstract What alternatives have been created within feminist pedagogy to question power hierarchies and to make teaching more inclusive? What approaches were adopted in the Gender and Philosophy summer schools in order to achieve these goals? After discussing these questions, I demonstrate how the concepts of “alienation”and “situation” can be used to analyse power dynamics and the framework they provide to the rest of the book.

The effect of atmospherically relevant aminium salts on water uptake

Abstract: Abstract. Atmospheric new particle formation is initiated by clustering of gaseous precursors, such as small acids and bases. The hygroscopic properties of those precursors therefore affect the hygroscopic properties of aerosol particles. In this work, the water uptake of different salts consisting of atmospheric small acids and amines was studied computationally using the conductor-like screening model for real solvents (COSMO-RS). This method allows for the prediction of water activities in atmospherically relevant salts that have not been included in other thermodynamics models. Water activities are reported here for binary aqueous salt solutions, as well as ternary solutions containing proxies for organic aerosol constituents. The order of the studied cation species regarding water activities is similar in sulfate, iodate and methylsulfonate, as well as in bisulfate and nitrate. Predicted water uptake strengths (in mole fraction) follow the orders: tertiary > secondary > primary amines, and guanidinos > amino acids. The addition of water soluble organic to the studied salts generally leads to weaker water uptake compared to pure salts. On the other hand, water-insoluble organic likely phase separates with aqueous salt solutions, leading to minimal effects on water uptake.

Thirty Years of Progress in Single/Multi-disciplinary Design Optimization with Evolutionary Algorithms and Game Strategies in Aeronautics and Civil Engineering

Abstract: This article reviews the major improvements in efficiency and quality of evolutionary multi-objective and multi-disciplinary design optimization techniques achieved during 1994–2021. At first, we introduce briefly Evolutionary Algorithms (EAs) of increasing complexity as accelerated optimizers. After that, we introduce the hybridization of EAs with game strategies to gain higher efficiency. We review a series of papers where this technique is considered an accelerator of multi-objective optimizers and benchmarked on simple mathematical functions and simple aeronautical model optimization problems using friendly design frameworks. Results from numerical examples from real-life design applications related to aeronautics and civil engineering, with the chronologically improved EAs models and hybridized game EAs, are listed and briefly summarized and discussed. This article aims to provide young scientists and engineers a review of the development of numerical optimization methods and results in the field of EA-based design optimization, which can be further improved by, e.g., tools of artificial intelligence and machine learning.

Curiously Empty Intersection of Proof Engineering and Computational Sciences

Abstract: The tools and techniques of proof engineering have not yet been applied to the computational sciences. We try to explain why and investigate their potential to advance the field. More concretely, we formalize elementary group theory in an interactive theorem prover and discuss how the same technique could be applied to formalize general computational methods, such as discrete exterior calculus. We note that such formalizations could reveal interesting insights into the mathematical structure of the methods and help us implement them with stronger guarantees of correctness. We also postulate that working in this way could dramatically change the way we study and communicate computational sciences.

Age But <scp>n</scp>ot Menopausal Status <scp>i</scp>s Linked to Lower Resting Energy Expenditure

Abstract: It remains uncertain whether aging before late adulthood and menopause are associated with fat-free mass and fat mass-adjusted resting energy expenditure (REEadj).We investigated whether REEadj differs between middle-aged and younger women and between middle-aged women with different menopausal statuses. We repeated the age group comparison between middle-aged mothers and their daughters to partially control for genotype. We also explored whether serum estradiol and follicle-stimulating hormone concentrations explain REEadj in midlife.We divided 120 women, including 16 mother-daughter pairs, into age groups; group I (n=26) consisted of participants aged 17-21, group II (n=35) of those aged 22-38 and group III (n=59) of those aged 41-58 years. The women in group III were further categorized as pre- or perimenopausal (n=19), postmenopausal (n=30) or postmenopausal hormone therapy users (n=10). REE was assessed using indirect calorimetry, body composition using dual-energy X-ray absorptiometry and hormones using immunoassays.The REEadj of group I was 126 kcal/d (95% CI: 93-160) higher than that of group III, and the REEadj of group II was 88 kcal/d (95% CI: 49-127) higher. Furthermore, daughters had a 100 kcal/d (95% CI: 63-138 kcal/d) higher REEadj than their middle-aged mothers (all P<0.001). In group III, REEadj was not lower in postmenopausal women and did not vary by sex hormone concentrations.We demonstrated that REEadj declines with age in women before late adulthood, also when controlling partially for genetic background, and that menopause may not contribute to this decline.

Effects of Parasocial Experiences With Spokespersons on Consumer Behavior

Abstract: Abstract This chapter discusses the utility of examining parasocial experiences (PSEs) in marketing, communication, and advertising research, specifically in the context of brand and product endorsements. The role of PSEs in various theories of persuasion in consumer research is applied to two domains: traditional celebrity endorsements on legacy media and social media and endorsements made by social media influencers, such as YouTubers and Instagram celebrities. Further, the chapter explicates the differences between these two types of media figures in the context of brand and product endorsements and discusses the unique importance of PSEs in driving their effects. Finally, a review of research and theoretical models highlights the importance of PSEs in the underlying effects of endorsers.

Noncovalent Modulation of Chemoselectivity in the Gas Phase Leads to a Switchover in Reaction Type from Heterolytic to Homolytic to Electrocyclic Cleavage

Abstract: Diversity in chemical reactivity unfolds even in the gas phase when noncovalent tools such as macrocyclic encapsulation are being used. Two distinct reaction pathways of a multifunctional bicyclic azoalkane (bottom) can be chemoselectively activated inside the cavity of a macrocycle (in gold), leading either to ejection of molecular dinitrogen (top) or ethylene (right), depending on its protonation state. In sharp contrast, the free substrate prefers to eject ammonia upon thermal activation (left), as reported by Werner M. Nau, Elina Kalenius, Tung-Chun Lee et al. in their Research Article (e202303491).

The Ambivalence of Human Sociality: Rousseau and Recognition

Abstract: Although Jean-Jacques Rousseau does not use the term “recognition” in the sense that it has been known since Fichte and Hegel, he has had an influence on various theorists of recognition. Undoubtedly, the key reason for this is his insightful writings that deal with various aspects of human sociality. In this essay, I shall reconstruct key elements of Rousseau’s work to highlight how he understands human sociality. The second task of the essay is to highlight the meaning of Rousseau’s insights to contemporary recognition theory. Rousseau is well known for his scepticism of modern social life. This shows especially in his analysis of amour-propre, a self-love that appears as a desire for social recognition and distinction from others. Unlike recognition theorists, Rousseau focuses on the inequalizing force of pride and search for esteem. In other words, Rousseau emphasizes the potential social harms that might rise from various struggles for recognition. In his view, individuals face a challenge to balance amour-propre in a healthy, and not inflamed manner. If the balancing is unsuccessful, the unchecked desire for social value leads into increasing (and institutionalized) inequality. However, Rousseau is also aware of the more positive and constructive elements of human sociality and puts value on the social bonds that are built upon respect and goodwill. Furthermore, although Rousseau is highly sceptical of the possibilities of respect and freedom in modern society, in Emile he outlines how freedom could be achieved through upbringing that invites (or even forces) one to be free—not unlike Fichte’s idea of summoning one to realize one’s own agency. Ultimately, Rousseau presents an ambivalent picture of the nature of social relationships. This is a position that has been developed in detail recognition theories only recently (e.g. Ikäheimo et al., Recognition and Ambivalence, Columbia University Press, New York, 2021). Although Rousseau does not have all the conceptual tools of the recent recognition theories at his disposal, he arguably has a developed picture of the positive and the negative effects that stem from the very same desire for recognition.

Empowering Absence? Assessing the Impact of Transnational Male Out-Migration on Left behind Wives

Abstract: Experiences of left-behind family members of transnational migrant workers have been in the shadow of academic discourse on migration. To contribute to the slowly growing body of literature, this study explores the impact of male out-migration on left-behind wives. The study proposes and applies a novel framework to estimate Women Empowerment Index (WEI) for comparing the empowerment level across households with and without men in transnational labor. Cross-sectional surveys and unstructured interviews were used to collect data from 373 respondents from three selected areas in Nepal. Results indicate that left-behind wives experience a higher degree of decision-making authority, physical mobility, and involvement in socio-political spheres compared to women with husbands at home. However, left behind wives were found to experience increased unpaid workload and decreased access to information, together with emotional and psychological costs in the absence of their husbands.

The Moral Situation: Self and Other

Abstract: Abstract Questions of power and ethics were implicitly present in the previous chapters. In this chapter, I deal with them in more detail, examining the power struggles in the classroom in terms of the relationship between the student and the lecturer as well as that between students. I also discuss ways out of the struggle, including a reflective attitude, classroom practices and considerations of spatial arrangements. Further, recognition, generosity and care are suggested as possible ways to overcome the difficult ethical situations in learning and teaching philosophy. In this context, I discuss the Oslo Summer School, where care ethics was used as the theoretical point of departure.

From Legal Fiction to Collective Agency: Contemporary Arguments for Collective Personhood

Abstract: In our everyday language, groups are described as if they had intentions, beliefs, attitudes, rights, and responsibilities. This practice of group personification is especially prevalent in the legal context where corporations are taken to be fully capable legal entities. It is not difficult to find similar references to group personhood in the so-called canon of Western philosophy either (e.g. Hobbes, Rousseau, and Hegel). However, when we get to the latter half of the twentieth century, more individualistic notions of personhood have come to the fore. This paper focuses on three contemporary theories—by Peter French, by Carol Rovane, and by Christian List and Philip Pettit—that go against this common trend and argue for a robust group personhood. They all argue for the group personhood through collective rationality, shared purposes, group decision-making, and social performances. To what end though? On the one hand, their arguments want to place responsibility and blameworthiness at the group level as well. On the other hand, their aim is to map out the metaphysical conditions of personhood. Analysis of group personhood is an attempt to clear up the concept of personhood, which can have interesting consequences for our thinking about the (legal) status of social robots and animals as well.

Noncovalent Modulation of Chemoselectivity in the Gas Phase Leads to a Switchover in Reaction Type from Heterolytic to Homolytic to Electrocyclic Cleavage

Abstract: Diversity in chemical reactivity unfolds even in the gas phase when noncovalent tools such as macrocyclic encapsulation are being used. Two distinct reaction pathways of a multifunctional bicyclic azoalkane (bottom) can be chemoselectively activated inside the cavity of a macrocycle (in gold), leading either to ejection of molecular dinitrogen (top) or ethylene (right), depending on its protonation state. In sharp contrast, the free substrate prefers to eject ammonia upon thermal activation (left), as reported by Werner M. Nau, Elina Kalenius, Tung-Chun Lee et al. in their Research Article (e202303491).

Ontology of Power Relations in Peter Olivi

Abstract: This chapter concentrates on Peter Olivi’s (ca. 1248–98) theory of the ontological foundations of political power—and, by extension, property and other social institutions. After briefly presenting his view of political power as a relation between a ruler and his subjects (which he presents in his famous Quid ponat ius), the chapter focuses more generally on Olivi’s theory of relations. Drawing from previous works by Alain Boureau, Sylvain Piron, Christian Rode, Robert Pasnau and others, it explores the ontology of relations and endeavors to shed new light on this notoriously difficult aspect of Olivi’s philosophy. A special focus is placed on the non-Aristotelian notion of rationes reales, which Olivi uses to make room between realism and nominalism, as he argues that power relations are real (i.e. they are not mind-dependent) although they are not based on any real properties in the relata. After showing that political power and other institutional facts must be understood in light of this peculiar ontological notion, the final section of the essay argues that the freedom of the human will entails an ability to change social reality. It is also suggested that despite this rather modern aspect of Olivi’s his social ontology, he remains firmly within medieval worldview by grounding the normative aspect of social institutions in the will of God.

Nature exposure is not associated with parent-reported or objectively measured sleep quality in 6-year-old children – a study in Finland

Abstract: Exposure to green environments has been associated with better sleep quality in adults. This study examined whether nature exposure is associated with parent-reported or actigraphy measured sleep quality in children. Against the hypotheses, no differences in sleep quality between the case and control groups or a moderating effect of socioeconomic status or sex were found. Green environment exposure may not serve as an environmental intervention to increase sleep quality in children.