Hexanuclear and undecanuclear iron(III) carboxylates as catalyst precursors for cyclohexane oxidation

Two multinuclear complexes [Fe-6(mu(3)-O)(2)(mu(4)-O-2)L-10(OAc)(2)(H2O)(2)]center dot 2.625Et(2)O center dot 2.375H(2)O (1) and [(Fe11Cl)-Cl-III-(mu(4)-O)(3)(mu(3)-O)(5)L-16(dmf)(2.5)(H2O)(0.5)]center dot Et2O center dot 1.25dmf center dot 3.8H(2)O (2), where HL = 3,4,5-trimethoxybenzoic acid and dmf = dimethylformamide, have been prepared from trinuclear iron(III) carboxylates via their structural rearrangement in dimethylformamide or diethyl ether-dimethylformamide 9:1, respectively, and slow vapor diffusion of diethyl ether into the reaction mixture. Both compounds have been characterized by X-ray diffraction, optical, Mossbauer spectroscopy, and magnetic measurements. Complex 1 possesses a hexanuclear ferric peroxido-dioxido {Fe-6(O-2)(O)(2)}(12+) core unit, which adopts a recliner conformation, while complex 2 contains an unprecedented {Fe11O8Cl}(16+) core, in which 9 ferric ions are six-coordinate and the remaining two are five-coordinate. Another structural feature of note of the undecanuclear core is the presence of a deformed cubane entity {Fe-4(mu(3)-O)(mu(4)-O)(3)}(4+). Both complexes act as catalyst precursors for the oxidation of cyclohexane to cyclohexanol and cyclohexanone with aqueous H2O2, in the presence of pyrazinecarboxylic acid. Remarkable TONs and TOFs (the latter mainly for 1) with concomitant quite good yields have been achieved under mild conditions. Moreover, 1 exhibits remarkably high activity in an exceptionally short reaction time (45 min), being unprecedented for any metal catalyzed alkane oxidation by H2O2. The catalytic reactions proceed via Fenton type chemistry

Socialist Paradise or Tower of Total Surveillance? Metamorphoses of the Crystal Palace in Chernyshevsky and Dostoevsky

In this thesis, I attempt to re-evaluate the symbolic meaning of the Crystal Palace in Russian literature (particularly in Chernyshevsky and Dostoevsky) in order to highlight its complexity and thus supplement and advance the existing scholarship. Drawing upon works by Chernyshevsky and Dostoevsky, I showcase different manifestations of this multi-faceted symbol, which became an embodiment of both Russian dreams and nightmares about the West. I also attempt to trace the ways in which the image of the Crystal Palace has been transformed by these two Russian writers.Master of Art

El examen de Bachillerato como reflejo de ideologías lingüísticas : Los discursos de los estudiantes de Bachillerato sobre los estudios de español como lengua extranjera

En Finlandia se nota un descenso en la cantidad de jóvenes que estudian lenguas optativas en la educación obligatoria. La mayoría estudia solo las dos lenguas nacionales y una lengua extranjera, generalmente el inglés, lo cual ha generado una preocupación sobre la diversidad de la reserva de lenguas, o sea, el conjunto de las lenguas que se habla en el país. Sin embargo, la cantidad de estudiantes de español ha aumentado casi toda la década 2010. Por consiguiente, el objetivo de este trabajo es investigar las razones detrás de la decisión de estudiar el español o no. Examinaré los discursos de los estudiantes del bachillerato en un corpus compuesto por más de 27 000 ensayos del examen de finés de la primavera de 2022, en la cual el tema fueron las lenguas. En el análisis combinaré los métodos de la lingüística de corpus y el análisis del discurso. El análisis revela que gran parte de los discursos se centran en los estudios de español dentro del contexto escolar, específicamente en la decisión de empezar o terminar dichos estudios. Las razones principales para empezar a estudiar español enfatizan la utilidad de la lengua y la motivación intrínseca de los estudiantes. Por otro lado, los factores políticos, como la admisión basada en certificados o problemas en la organización de la enseñanza en los centros escolares, son entre las razones más frecuentes para abandonar los estudios de español. Los resultados demuestran la influencia significativa de la política lingüística de la educación en las decisiones de los jóvenes respecto al aprendizaje de lenguas. Por lo tanto, si se busca garantizar una reserva de lenguas diversa en el país, las decisiones políticas deben alinearse con este objetivo. Asimismo, enfatizar la utilidad y relevancia de las competencias lingüísticas tanto en el discurso general como en las políticas, podría aumentar la voluntad y motivación de los jóvenes para estudiar lenguas optativas

Integrating Assembly Ergonomics in Product Development Process

Tämän diplomityön tavoitteena oli tutkia asennusergonomian nykytilaa Sandvik Mining Oy:n Turun tehtaalla sekä muodostaa ohjeistus asennusergonomian huomioimiseksi tuotekehityksessä. Työssä tarkasteltiin kahden Turun tehtaan valmistuksessa olevan lastauskoneen asennusergonomiaa. Tarkoituksena oli tutustua ensin ergonomiaan ja tuotekehitykseen liittyvään perusteoriaan kirjallisuuden avulla sekä aiheita yhdistäviin tutkimustuloksiin artikkelien kautta. Ergonomian merkitys ja tiedostaminen yleisesti on lisääntynyt kohdeyrityksessä, joten lähtökohtana oli halu kiinnittää enemmän huomiota myös asennettavuuteen liittyvään ergonomiaan. Tuotekehityksessä ei myöskään ole aiemmin ollut minkäänlaista kirjallista ohjeistusta asennusergonomian huomioimiseksi. Varsinainen tutkimus aloitettiin muodostamalla kyselylomake asennusergonomiaan liittyvien ongelmien löytämiseksi tuotannosta. Tuloksia kerättiin kyselylomakkeen avulla yhdestä tuotantosolusta ja yhdeltä tuotantolinjalta. Lomakkeilla saatuja tietoja täydennettiin haastattelujen avulla. Kaikki löydetyt ongelmakohdat kuvattiin kirjallisesti työssä ja niistä otettiin mahdollisimman havainnollistavat valokuvat. Neljä ongelmakohtaa käsiteltiin tarkemmin ratkaisujen löytämiseksi. Kaikki ongelmakohdat jaettiin kuuteen eri luokkaan, jotka muodostettiin ongelmien yhteisten piirteiden perusteella. Tämän jälkeen nykytuotekehityksessä työskenteleviä tuoteinsinöörejä haastateltiin. Tarkoituksena oli selvittää tuoteinsinöörien mielipiteitä ja näkemyksiä sekä ohjeen muodosta että ohjeessa huomioitavista asioista. Ohjeistus kehitettiin lopulta etsimällä yhteisiä syitä luokitelluille ongelmille ja ottamalla huomioon tuoteinsinöörien kommentit ja mielipiteet. Tulosten perusteella tarkastelluissa lastauskoneissa on runsaasti asennusergonomiaan liittyviä ongelmia. Ongelmista ei kuitenkaan tule tietoa tuotekehitykselle asti ennen kuin asennus on käytännössä mahdotonta. Ongelmien keräämiseksi on kehitettävä toimiva järjestelmä ja tiedonkulkua on tehostettava sekä tuotannon ja tuotekehityksen että myös tuotekehityksen ja tuotannonsuunnittelun välillä. Tämän tutkimuksen tuloksena saatu ohjeistus on otettava käyttöön tuotekehityksessä ja ohjeistuksen toimivuutta ja hyödyllisyyttä on tarkasteltava. Jos ohjeistus on epäkäytännöllinen tai se on muuten hankalasti hyödynnettävissä, sitä on kehitettävä toimivammaksi. Tässä työssä saatuja tuloksia on syytä hyödyntää myös muuten tuotekehityksessä, ja löydetyt ongelmakohdat on pyrittävä korjaamaan

Organisaation muutosvalmius liiketoimintamallin muutoksessa kohti palveluliiketoimintaa

This thesis examines organization’s readiness for change when moving towards service business. Especially for traditionally product-centric manufacturing companies, services can be seen as a potential way to gain competitive advantage. The focus of this thesis is on Finnish-based product-oriented companies operating in metals, engineering and construction industries. The main research question is as follows: How can the readiness for change be taken into account at the early phase of the transformation process towards service business? The objective is to identify factors and elements of organizational readiness for change that are relevant in the business transformation and thus give suggestions to managers at companies willing to make transformation from products towards services. Multiple case study method was used and the empirical data were collected through semi-structured thematical interviews. Altogether 31 interviews were conducted in 6 different business units. The theoretical part of the study reports the relevant literature from the fields of strategic change and its management, organizational readiness for change and transformation towards services. Based on the literature review, a conceptual framework for organizational readiness for change was built to assist the analysis of the empirical data. The empirical part of the thesis is concerned with the results of the interviews, namely the elements of the organizational readiness for change and how those appear in the early stage of the business transformation. The main finding is that the content of the change, i.e. the clarity of objectives, scope of change and the change message, is somewhat unclear and needs to be taken into account at the early stage of the business transformation. Clarifying the objectives regarding services and thus initiating so-called service-talk within the organization is suggested. Also, allocating needed resources, top management support, and using an IT system supporting the services are requirements in the transformation. The receptivity of customers and the industry’s readiness for change for new kinds of business models must be assessed before taking further steps. In turn, the psychological readiness of individuals seems to be at a good level, promoting the organizational readiness for change. Bringing changes step-by-step to the organization and building an organization culture receptive for changes is a mean to improve organizational readiness for change in the transformation from products towards services. Possible future research topics could include industry’s readiness for change, validating the framework used, and reviewing the whole readiness for change literature. /Kir1

Organisaation muutosvalmius liiketoimintamallin muutoksessa kohti palveluliiketoimintaa

This thesis examines organization’s readiness for change when moving towards service business. Especially for traditionally product-centric manufacturing companies, services can be seen as a potential way to gain competitive advantage. The focus of this thesis is on Finnish-based product-oriented companies operating in metals, engineering and construction industries. The main research question is as follows: How can the readiness for change be taken into account at the early phase of the transformation process towards service business? The objective is to identify factors and elements of organizational readiness for change that are relevant in the business transformation and thus give suggestions to managers at companies willing to make transformation from products towards services. Multiple case study method was used and the empirical data were collected through semi-structured thematical interviews. Altogether 31 interviews were conducted in 6 different business units. The theoretical part of the study reports the relevant literature from the fields of strategic change and its management, organizational readiness for change and transformation towards services. Based on the literature review, a conceptual framework for organizational readiness for change was built to assist the analysis of the empirical data. The empirical part of the thesis is concerned with the results of the interviews, namely the elements of the organizational readiness for change and how those appear in the early stage of the business transformation. The main finding is that the content of the change, i.e. the clarity of objectives, scope of change and the change message, is somewhat unclear and needs to be taken into account at the early stage of the business transformation. Clarifying the objectives regarding services and thus initiating so-called service-talk within the organization is suggested. Also, allocating needed resources, top management support, and using an IT system supporting the services are requirements in the transformation. The receptivity of customers and the industry’s readiness for change for new kinds of business models must be assessed before taking further steps. In turn, the psychological readiness of individuals seems to be at a good level, promoting the organizational readiness for change. Bringing changes step-by-step to the organization and building an organization culture receptive for changes is a mean to improve organizational readiness for change in the transformation from products towards services. Possible future research topics could include industry’s readiness for change, validating the framework used, and reviewing the whole readiness for change literature. /Kir1

N,N′-(1,4-Phenyl­ene)bis­(4-chloro­butanamide)

The title mol­ecule, C14H18Cl2N2O2, lies on a crystallographic inversion center and the each 4-chloro­butanamide group adopts an anti-staggered conformation. In the crystal, adjacent mol­ecules are linked through N—H⋯O contacts, forming infinite ribbons extending parallel to the a axis

Antibiotics, obesity and the link to microbes - what are we doing to our children?

BACKGROUND: Childhood obesity and overweight are among the greatest health challenges in the pediatric population. Obese individuals exhibit marked differences in the composition of the intestinal microbial community as compared to lean subjects. These changes in the gut microbiota precede the clinical manifestation of overweight. Convincing experimental data suggest a causal role for intestinal microbes in the development of obesity and associated metabolic disorders. DISCUSSION: Exposure to antibiotics exerts a devastating impact on the intestinal microbial community. Epidemiological studies have provided evidence indicating that early or repeated childhood exposure to antibiotics is associated with increased risk of overweight later in childhood but the causal role of this exposure in obesity development is not clear. However, data from studies conducted using experimental animal models indicate that antibiotic-induced changes in the gut microbiota influence host metabolism and lead to fat accumulation. The intestinal microbiota perturbation caused by antibiotic exposure in the perinatal period appears to program the host to an obesity-prone metabolic phenotype, which persists after the antibiotics have been discontinued and the gut microbiota has recovered. These observations may have serious implications in the clinical setting, since a substantial number of human infants are subjected to antibiotic treatment through the mother during delivery or directly in the immediate neonatal period. The clinical significance of these exposures remains unknown. SUMMARY: Prudent use of antibiotics is paramount not only to reduce the propagation of antibiotic-resistant organisms but also to minimize the potentially detrimental long-term metabolic consequences of early antibiotic exposure. Improved means of reliably detecting neonates with bacterial infection would reduce the need for empirical antibiotic exposure initiated based on nonspecific symptoms and signs or risk factors. Finally, means to support healthy microbial contact in neonates and infants requiring antibiotic treatment are needed

Intracluster interactions in butterfly {Fe3 LnO2} molecules with the non-Kramers ions Tb(III) and Ho(III)

The intracluster exchange interactions within the "butterfly" Fe3Ln(µ3-O)2(CCl3COO)8(H2O)(THF)3] molecules, where Ln(III) represents a lanthanide cation, have been determined by a combination of x-ray magnetic circular dichroism (XMCD) and vibrating sample magnetometry (VSM) along with an interaction model. We have studied the compounds with Ln=Tb and Ho, both non-Kramers lanthanides and with high uniaxial anisotropy, and Ln=Lu(III) and Y(III) as pseudolanthanides, which supply nonmagnetic Ln reference cases. At low temperature, the three Fe atoms can be considered as a self-unit with total spin SFe3=5/2. Using the element selectivity of the XMCD magnetometry, measured at the Ln L2,3 edges, together with the VSM measurements, the local magnetization of the Ln ion and the Fe3 subcluster, as a function of the field and low temperature (T˜2.5K), has been determined separately. These results are described quantitatively in the framework of a theoretical model based on an effective spin Hamiltonian, which considers the competing effects of intracluster interactions and the external applied magnetic field. The Ln-Fe3 exchange interaction within the {Fe3LnO2} cluster has been determined to be antiferromagnetic, in both Tb and Ho compounds, with JFeTb/kB=-0.13(1)K and JFeHo/kB=-0.18(1)K, respectively. In both cases, a field-induced reorientation of the Fe3 and Ln spins from antiparallel to parallel orientation takes place at a threshold field µ0H=1.1 and 2 T, for the {Fe3TbO2} and {Fe3HoO2} compounds, respectively. By comparison with other compounds of the series with uniaxial anisotropy, it is concluded that the polarizability of the Fe3 subcluster magnetic moment decreases in the trend {Fe3YO2}¿{Fe3TbO2}¿{Fe3HoO2}¿{Fe3DyO2}, because of the increasing opposition of the exchange antiferromagnetic field caused by the Ln ion. In the Ln=Tb, Ho, and Dy, the magnetization of the whole molecule is dominated by the anisotropy of the Ln ion. The intracluster Fe3-Ln exchange interactions are very weak compared to the Ln ligand field and Fe-Fe exchange interactions