Covalently bonded networks through surface-confined polymerization

The prospect of synthesizing ordered, covalently bonded structures directly on a surface has recently attracted considerable attention due to its fundamental interest and for potential applications in electronics and photonics. This prospective article focuses on efforts to synthesize and characterize epitaxial one- and two-dimensional (1D and 2D, respectively) polymeric networks on single crystal surfaces. Recent studies, mostly performed using scanning tunneling microscopy (STM), demonstrate the ability to induce polymerization based on Ullmann coupling, thermal dehalogenation and dehydration reactions. The 2D polymer networks synthesized to date have exhibited structural limitations and have been shown to form only small domains on the surface. We discuss different approaches to control 1D and 2D polymerization, with particular emphasis on the surface phenomena that are critical to the formation of larger ordered domains.

Self-assembly of a halogenated molecule on oxide-passivated Cu(110)

The supramolecular self-assembly of brominated molecules was investigated and compared on Cu(110) and Cu(110)[BOND]O(2×1) surfaces under ultrahigh vacuum. By using scanning tunnelling microscopy, we show that brominated molecules form a disordered structure on Cu(110), whereas a well-ordered supramolecular network is observed on the Cu(110)[BOND]O(2×1) surface. The different adsorption behaviors of these two surfaces are described in terms of weakened molecule–substrate interactions on Cu(110)[BOND]O(2×1) as opposed to bare Cu(110). The effect of oxygen-passivation is to suppress debromination and it can be a convenient approach for investigating other self-assembly processes on copper-based substrates.

In situ investigation of explosive crystallization in a-Ge: Experimental determination of the interface response function using dynamic transmission electron microscopy

The crystallization of amorphous semiconductors is a strongly exothermic process. Once initiated the release of latent heat can be sufficient to drive a self-sustaining crystallization front through the material in a manner that has been described as explosive. Here, we perform a quantitative in situ study of explosive crystallization in amorphous germanium using dynamic transmission electron microscopy. Direct observations of the speed of the explosive crystallization front as it evolves along a laser-imprinted temperature gradient are used to experimentally determine the complete interface response function (i.e., the temperature-dependent front propagation speed) for this process, which reaches a peak of 16 m/s. Fitting to the Frenkel-Wilson kinetic law demonstrates that the diffusivity of the material locally/immediately in advance of the explosive crystallization front is inconsistent with those of a liquid phase. This result suggests a modification to the liquid-mediated mechanism commonly used to describe this process that replaces the phase change at the leading amorphous-liquid interface with a change in bonding character (from covalent to metallic) occurring in the hot amorphous material.

Substrate, molecular structure, and solvent effects in 2D self-assembly via hydrogen and halogen bonding

Recently, halogen···halogen interactions have been demonstrated to stabilize two-dimensional supramolecular assemblies at the liquid–solid interface. Here we study the effect of changing the halogen, and report on the 2D supramolecular structures obtained by the adsorption of 2,4,6-tris(4-bromophenyl)-1,3,5-triazine (TBPT) and 2,4,6-tris(4-iodophenyl)-1,3,5-triazine (TIPT) on both highly oriented pyrolytic graphite and the (111) facet of a gold single crystal. These molecular systems were investigated by combining room-temperature scanning tunneling microscopy in ambient conditions with density functional theory, and are compared to results reported in the literature for the similar molecules 1,3,5-tri(4-bromophenyl)benzene (TBPB) and 1,3,5-tri(4-iodophenyl)benzene (TIPB). We find that the substrate exerts a much stronger effect than the nature of the halogen atoms in the molecular building blocks. Our results indicate that the triazine core, which renders TBPT and TIPT stiff and planar, leads to stronger adsorption energies and hence structures that are different from those found for TBPB and TIPB. On the reconstructed Au(111) surface we find that the TBPT network is sensitive to the fcc- and hcp-stacked regions, indicating a significant substrate effect. This makes TBPT the first molecule reported to form a continuous monolayer at room temperature in which molecular packing is altered on the differently reconstructed regions of the Au(111) surface. Solvent-dependent polymorphs with solvent coadsorption were observed for TBPT on HOPG. This is the first example of a multicomponent self-assembled molecular networks involving the rare cyclic, hydrogen-bonded hexamer of carboxylic groups, R66(24) synthon.

The influence of the gas environment on morphology and chemical composition of surfaces micro-machined with a femtosecond laser

We investigated the influence of different gas environments on the fabrication of surfaces, homogeneously covered with equally sized and spaced micro-structures. Two types of structures have been successfully micro-machined with a femtosecond laser on titanium surfaces in various atmospheres. The surface chemistry of samples machined in oxygen and helium shows TiO2, while machining in nitrogen leads to an additional share of TiN. The actual surface structure was found to vary significantly as a function of the gas environment. We found that the ablated particles and their surface triggered two consecutive events: The optical properties of the gas environment became non-isotropic which then led to the pulse intensity being redistributed throughout the cross section of the laser beam. Additionally, the effective intensity was further reduced for TiN surfaces due to TiN's high reflectivity. Thus, the settings for the applied raster-scanning machining method had to be adjusted for each gas environment to produce comparable structures. In contrast to previous studies, where only noble gases were found suitable to produce homogeneous patches, we obtained them in an oxygen environment.

With great structure comes great functionality: Understanding and emulating spider silk

The overarching aim of biomimetic approaches to materials synthesis is to mimic simultaneously the structure and function of a natural material, in such a way that these functional properties can be systematically tailored and optimized. In the case of synthetic spider silk fibers, to date functionalities have largely focused on mechanical properties. A rapidly expanding body of literature documents this work, building on the emerging knowledge of structure–function relationships in native spider silks, and the spinning processes used to create them. Here, we describe some of the benchmark achievements reported until now, with a focus on the last five years. Progress in protein synthesis, notably the expression on full-size spidroins, has driven substantial improvements in synthetic spider silk performance. Spinning technology, however, lags behind and is a major limiting factor in biomimetic production. We also discuss applications for synthetic silk that primarily capitalize on its nonmechanical attributes, and that exploit the remarkable range of structures that can be formed from a synthetic silk feedstock.

Supporting the development and deployment of sustainable energy technologies through targeted scientific training

Sustainable energy technologies rely heavily on advanced materials and modern engineering controls. These promising new technologies cannot be reliably deployed without ensuring that there is a sufficient “capacity,” i.e., trained technical personnel with the expertise to implement, monitor, and maintain the energy infrastructure. This same capacity is critical to the local development of new technologies, especially those that respond directly to regional priorities, strengths, and needs. One way to build capacity is through targeted programs that integrate the training and development of locals at an advanced technical level. In practical terms, these programs usually produce a small number of highly educated individuals with skills in science and engineering. The goal of Part VI of this book is to highlight contributing factors in successfully operating capacity building programs.

Talousmetafysiikan kritiikkiä

Jakke Holvas: A Critique of the Metaphysics of Economy The research problem of this dissertation is the commonly held opinion according to which everything has become a question of economy in the present day. Economy legitimates and justifies. In this study, the pattern of thinking and conceptualizing in which economy figures as the ultimate reason is called the metaphysics of economy. The defining characteristic of the metaphysics of economy is its failure to recognize non-economic rules, ethics, or ways of existence. The sources included in the study cover certain classics of philosophy (Plato, Aristotle, Friedrich Nietzsche) and sociology (Karl Marx, Max Weber, Marcel Mauss), as well as the more recent French social theory (Jean Baudrillard, Michel Foucault). The research methods used are textual analysis and evaluation of concepts by means of historical comparison. The background to the study is given by the views of historians and sociologists according to whom traditional forms have ceased to exist and the market economy become established as the western system of values. The study identifies points of transition from the traditional forms to economic values. In addition, the dissertation focuses on the modern non-economic forms. The study examines the economic and ethical meanings of gift in antiquity in Homer, Plato, and Aristotle. Following Marcel Mauss, the study analyzes the forms and principles of gift exchange. The study also applies Nietzsche’s philosophy to evaluate under what conditions giving a gift becomes an act of exercising power that puts its receiver into debt. The conclusion of the study is that the classics of philosophy and sociology can rightly be interpreted in terms of the metaphysics of economy, but they also offer grounds for criticizing this metaphysics, even alternatives. One such alternative is non-economic archaic ethic. The study delineates a duality between economy and non-economy as well as creating concepts which could be used in the future to critically analyze economy from a position external to the economic system of concepts.

Heräämisten poetiikkaa : Lajeja ja intertekstejä Arvid Järnefeltin romaaneissa Isänmaa, Maaemon lapsia ja Veneh'ojalaiset

Poetics of Awakenings. Genres and Intertexts in Arvid Järnefelt s Novels Isänmaa, Maaemon lapsia and Veneh ojalaiset This doctoral dissertation focuses on Arvid Järnefelt s (1961 1932) novels Isänmaa (1893), Maaemon lapsia (1905) and Veneh ojalaiset (1909). The study applies the genre theory and concepts Alastair Fowler has introduced in his Kinds of Literature (1982). Fowler s theory of the novel is developed further and applied to Finnish realist novels. The generic analysis is supplemented by intertextual analysis, which is mainly based on the idea of specific intertextual relations as presented by Kiril Taranovsky. Generic and intertextual analyses form the basis for hermeneutic interpretation, in which attention is paid to the fact that the novels are written by the designated writer in specific historical and cultural circumstances. Instead of the author s intention , the study focuses on the realised intention , in other words the novels as they are published. Järnefelt s first novel Isänmaa is understood to be a classical Bidungsroman that depicts the socialisation of a young male protagonist. From an intertextual point of view, the novel appears to be a novel of conversion, too, due to the biblical allusions concealed in the depiction of the events. Furthermore, Isänmaa is seen to stand in an intertextual relation to Hegel s, Snellman s and Topelius s writings. Maaemon lapsia is argued to be a thesis novel, which persuades the reader to adopt a certain ideological and political stance, namely Henry George s view on the private ownership of land. The novel is modulated by the generic repertoires of fairy tale and tragedy. The mythical frame of the novel supports the thesis novel, as it gives universal validity to the particular events depicted in the novel. Maaemon lapsia also comments on the contemporary political debate on the relations between Finland and Russia by presenting the relationship as analogous to the relationship between tenant farmer and landowner. Veneh ojalaiset exhibits a wide range of genres. Comic, tragic and mythical mode is combined with, for example, family novel, romance, conversion novel and revolutionary novel. From a rhetorical viewpoint, the novel is an apology, which accuses society of generating criminality by means of unjust laws and procedures. The novel discusses the question of resistance to evil by using the themes of Faust and Job, as well as by confronting the philosophies of Epictetus and Nietzsche. The novel is a thesis novel, which disputes the possibility of violent revolution as a way to a better society and recommends passive resistance for an individual living in an unjust society. The poetics of Järnefelt s novels is regarded as the poetics of conversion, as all the novels in focus depict the protagonist s awakening to see the society in a new light, be it a patriotic vision of the reality or a conception of the unfairness of society.

Kampen om Eros : Om kön och kärlek i Pahlensviten

The Struggle for Eros: On Love and Gender in the Pahlen Series The present dissertation examines how gender, sexuality and motherhood are constructed in the novel series Fröknarna von Pahlen (The Misses von Pahlen, I VII, 1930 1935) by the Swedish author Agnes von Krusenstjerna. The aim of the study is to analyze how the Pahlen series relates to the discourses on gender and sexuality circulating in the 1930s, and how the series opens a dialogue with the feminist thinking of the time especially with the book Lifslinjer I (Love and Marriage, 1903) by the Swedish author Ellen Key. Fröknarna von Pahlen holds a central position in the research on Agnes von Krusenstjerna partly due to the literary debate that the novel series triggered. The debate was connected to the development taking place in the Swedish society in the beginning of the 1930s, in the so-called second phase of the Modern Breakthrough. Sweden was at that time characterized by struggle over the definitions of gender, sexuality and parenthood, and this struggle is also visible in the Pahlen series. The literary debate took place in 1934 1935 and it began after an article by the modernist writer Karin Boye was published in Social-Demokraten on 28 January 1934. In her polemic article, Boye saw the Pahlen series as a sign that the family institution is on the verge of a breakdown and with it the whole moral system that has come to existence through it . Boye went on to state that Krusenstjerna only sees and describes and that she explores neither new literary forms nor new values. Boye wrote the article before the last two parts of the novel series were published, so obviously she could not discuss the utopian vision characterizing those parts. This study, however, strives to demonstrate that Krusenstjerna not only sees and describes, but that she like many of her contemporary female colleagues appears to take the request of Friedrich Nietzsche to revaluate all values seriously. Like the works of her contemporaries, Krusenstjerna s Pahlen series is marked by a double vision on the one hand a critique of the prevailing social order, and on the other hand a dream of a new world and a new human being. In this research the vision of the Pahlen series is characterized as queer in order to emphasize that the series not only criticizes the prevailing gender order and its morals, but is also open for new ways of doing gender, parenthood, and family.

Konstteoretikern och livet : Mikael Lybecks Breven till Cecilia i nietzscheansk belysning

I avhandlingen analyseras den finlandssvenska författaren Mikael Lybecks (1864-1925) verk Breven till Cecilia. Denna brevroman hör till Lybecks senare produktion och utkom 1920. Verket har kommit att betraktas som en klassiker inom den finlandssvenska litteraturen. Av författarensövriga produktion är det strängt taget endast Tomas Indal (1911) som haft en jämförbar genomslagskraft. Trots detta har romanen inte varit föremål för en enda mer omfattande studie. l sin Lybeckbiografi relaterar Erik Kihlman i första hand verket till det biografiska och till samhällssituationen vid tiden för romanens tillkomst. Vetenskapen, konsten och livet bildar tillsammans den triangel som utgör romanens stomme. Antiken är starkt närvarande i romanen och med begrepp som härrör från denna era kan man tala om det sokratiska, det apollinska och det dionysiska. Detta är begrepp som Friedrich Nietzsche utgår i från i sitt ungdomsverk Tragedins födelse (Die Geburt der Tragödie aus dem Geiste der Musik) från 1872. Nietzsches vetenskapskritik och hans syn på den högsta konsten som ett brödraförbund mellan Dionysos och Apollon står i förvånansvärt hög grad i samklang med den övergripande tematiken i Lybecks verk. När Nietzsche därtill framhäver musiken som grunden förall konst får många inslag i romanen sin förklaring. l Breven till Cecilia skildras en vändpunkt i huvudpersonen Sven Ingelets liv. Därför ligger tyngdpunkten i den tematiska analysen vid det som gör att verket kan betraktas som en utvecklingsroman. Även om romanen skildrar en tidsperiod på endast ett och ett halvt år så hinnerhuvudpersonen ändå undergå en betydande personlighetsförändring. Nietzsches Tragedinsfödelse med dess ovannämnda grundläggande begrepp lämpar sig ypperligt som referensram för en analys av denna förändring. Avhandlingen har också strukturerats utgående från de nietzscheanska begreppen sokratiskt, dionysiskt och apollinskt vilka alltså återspeglar huvudpersonens utvecklingsfaser. Från att ha varit en renodlad förnuftsmänniska väcks Sven Ingelet genom ett kortvarigt kärleksförhållande till det dionysiska med allt vad det innebär av känslorus och lidande. Att Ingelet nästan helt uppgått i sin roll som konstteoretiker har medfört att hans förhållningssätt till omvärlden utmärks av intresselös betraktelse. Till följd av sin viljesvaghet och bristande handlingskraft måstehan försöka behålla sin älskades gunst genom magiska pseudohandlingar. Detta leder in Ingelet i myternas värld. Hans verklighetsuppfattning får andra dimensioner än den vetenskapliga. Det dionysiska uppvaknandet medför tillsammans med det efterföljande brevskrivandet att Ingeletnår fram till en självkännedom och upphör att vara en främling i tillvaron. Ingelet utvecklar ocksåen ny konstsyn som förutsätter ett samband mellan konsten och livet. Detta apollinska utvecklingsstadium kännetecknas också av sanningsförmedlande drömmar, och av en tilltagande resignation som till slut utmynnar i ett självmord. Nyckelord: brevroman, Dionysos, Apollon, främlingskap, verklighetsflykt

Making the most of spatial information in health: A tutorial in Bayesian disease mapping for areal data

Disease maps are effective tools for explaining and predicting patterns of disease outcomes across geographical space, identifying areas of potentially elevated risk, and formulating and validating aetiological hypotheses for a disease. Bayesian models have become a standard approach to disease mapping in recent decades. This article aims to provide a basic understanding of the key concepts involved in Bayesian disease mapping methods for areal data. It is anticipated that this will help in interpretation of published maps, and provide a useful starting point for anyone interested in running disease mapping methods for areal data. The article provides detailed motivation and descriptions on disease mapping methods by explaining the concepts, defining the technical terms, and illustrating the utility of disease mapping for epidemiological research by demonstrating various ways of visualising model outputs using a case study. The target audience includes spatial scientists in health and other fields, policy or decision makers, health geographers, spatial analysts, public health professionals, and epidemiologists.

Unravelling the self-assembly of hydrogen bonded NDI semiconductors in 2D and 3D

Supramolecular ordering of organic semiconductors is the key factor defining their electrical characteristics. Yet, it is extremely difficult to control, particularly at the interface with metal and dielectric surfaces in semiconducting devices. We have explored the growth of n-type semiconducting films based on hydrogen-bonded monoalkylnaphthalenediimide (NDI-R) from solution and through vapor deposition on both conductive and insulating surfaces. We combined scanning tunneling and atomic force microscopies with X-ray diffraction analysis to characterize, at the submolecular level, the evolution of the NDI-R molecular packing in going from monolayers to thin films. On a conducting (graphite) surface, the first monolayer of NDI-R molecules adsorbs in a flat-lying (face-on) geometry, whereas in subsequent layers the molecules pack edge-on in islands (Stranski–Krastanov-like growth). On SiO2, the NDI-R molecules form into islands comprising edge-on packed molecules (Volmer–Weber mode). Under all the explored conditions, self-complementary H bonding of the imide groups dictates the molecular assembly. The measured electron mobility of the resulting films is similar to that of dialkylated NDI molecules without H bonding. The work emphasizes the importance of H bonding interactions for controlling the ordering of organic semiconductors, and demonstrates a connection between on-surface self-assembly and the structural parameters of thin films used in electronic devices.

A multi-centre open-label randomised non-inferiority trial comparing watchful waiting to antibiotic treatment for acute otitis media without perforation in low-risk urban Aboriginal and Torres Strait Islander children (the WATCH trial): study protocol for a randomised controlled trial

Background Treatment guidelines recommend watchful waiting for children older than 2 years with acute otitis media (AOM) without perforation, unless they are at high risk of complications. The high prevalence of chronic suppurative otitis media (CSOM) in remote Aboriginal and Torres Strait Islander communities leads these children to be classified as high risk. Urban Aboriginal and Torres Strait Islander children are at lower risk of complications, but evidence to support the subsequent recommendation for watchful waiting in this population is lacking. Methods/Design This non-inferiority multi-centre randomised controlled trial will determine whether watchful waiting is non-inferior to immediate antibiotics for urban Aboriginal and Torres Strait Islander children with AOM without perforation. Children aged 2 − 16 years with AOM who are considered at low risk for complications will be recruited from six participating urban primary health care services across Australia. We will obtain informed consent from each participant or their guardian. The primary outcome is clinical resolution on day 7 (no pain, no fever of at least 38 °C, no bulging eardrum and no complications of AOM such as perforation or mastoiditis) as assessed by general practitioners or nurse practitioners. Participants and outcome assessors will not be blinded to treatment. With a sample size of 198 children in each arm, we have 80 % power to detect a non-inferiority margin of up to 10 % at a significance level of 5 %, assuming clinical improvement of at least 80 % in both groups. Allowing for a 20 % dropout rate, we aim to recruit 495 children. We will analyse both by intention-to-treat and per protocol. We will assess the cost- effectiveness of watchful waiting compared to immediate antibiotic prescription. We will also report on the implementation of the trial from the perspectives of parents/carers, health professionals and researchers. Discussion The trial will provide evidence for the safety and effectiveness of watchful waiting for the management of AOM in Aboriginal and Torres Strait Islander children living in urban settings who are considered to be at low risk of complications.

Evil Gods and Reckless Saviours : Adaptation and Appropriation in Late Twentieth Century Jesus-Novels

Late twentieth century Jesus-novels search after a completely new picture of Jesus. Novels written for instance by Norman Mailer, José Saramago, Michèle Roberts, Marianne Fredriksson, and Ki Longfellow provide an inversive revision of the canonic Gospels. They read the New Testament in terms of the present age. In their adaptation the story turns often into a critique of the whole Christian history. The investigated contrast-novels end up with an appropriation that is based on prototypical rewriting. They aim at the rehabilitation of Judas, and some of them make Mary Magdalane the key figure of Christianity. Saramago describes God as a blood thirsty tyrant, and Mailer makes God combat with the Devil in a manichean sense as with an equal. Such ideas are familiar both from poststructuralist philosophy and post-metaphysical death-of-God theology. The main result of the intertextual analysis is that these scholars have adopted Nietzschean ideas in their writing. Quite unlike earlier Jesus-novels, these more recent novels present a revision that produces discontinuity with the original source text, the New Testament. The intertextual strategy is based on contradiction. The reader wittnesses contesting and challenging, the authors attack Biblical beliefs and attempt to dissolve Christian doctrines. An attack on Biblical slave morality and violent concept of God deprives Jesus of his Jewish Messianic identity, makes Old Testament law a contradiction of life, calls sacrificial soteriology a violent pattern supporting oppression, and presents God as a cruel monster who enslaves people under his commandments and wishes their death. The new Jesus-figure contests Mosaic Law, despises orthodox Judaism, abandons Jewish customs and even questions Old Testament monotheism. In result, the novels intentionally transfer Jesus out of Judaism. Furthermore, Jewish faith appears in a negative light. Such an intertextual move is not open anti-Semitism but it cannot avoid attacking Jewish worship. Why? One reason that explains these attitudes is that Western culture still carries anti-Judaic attitudes beneath the surface covered with sentiments of equality and tolerance. Despite the evident post-holocaust consciousness present in the novels, they actually adopt an arrogant and ironical refutation of Jewish beliefs and Old Testament faith. In these novels, Jesus is made a complete opposite and antithesis to Judaism. Key words: Jesus-novel, intertextuality, adaptation, slave morality, Nietzsche, theodicy, patriarchy.