Carbon dioxide as a reagent and solvent

The work described in this Thesis has been carried out within the Erasmus Mundus framework for Sustainable Industrial Chemistry (SINCHEM). The work concentrates on the possible utilisation of carbon dioxide as a solvent and as a starting material. Chapter 1 introduces carbon dioxide and its utilisation. In addition, the 12 Principles of CO2 Chemistry are presented, as well as continuous flow chemistry and self-optimising reactors. The relevant aspects of these reactors are discussed further in Chapter 2. The results of the research are presented in Chapters 3-6. A self-optimising reactor with FT-IR analysis was employed for the methylation of alcohols as explained in Chapter 3. Chapters 4-6 concentrate on N-alkylation reactions. In Chapter 4, the reactivity between aniline, tetrahydrofuran and dimethyl carbonate in supercritical carbon dioxide is discussed. This research led to the discovery of novel transformations. In Chapters 5 and 6, methanol was employed to methylate amines. A ruthenium triphosphate catalyst, which can produce methanol from carbon dioxide and hydrogen, was used to catalyse the reactions between methanol and aliphatic amines, as described in Chapter 5. Also the cyclisation and subsequent methylation of amino alcohols was studied. This reactivity is also the topic of Chapter 6, where γ-alumina was used as catalyst and supercritical carbon dioxide as solvent. Finally, Chapter 7 summarises the work described in this Thesis and evaluates the progress made towards achieving the aims that are introduced at the end of Chapter 1. One of these aims is to evaluate the work carried out in this Thesis according to the 12 principles of CO2 Chemistry. This evaluation is shown in Chapter 7

The twelve principles of CO2 Chemistry

This paper introduces a set of 12 Principles, based on the acronym CO2 CHEMISTRY, which are intended to form a set of criteria for assessing the viability of different processes or reactions for using CO2 as a feedstock for making organic chemicals. The principles aim to highlight the synergy of Carbon Dioxide Utilisation (CDU) with the components of green and sustainable chemistry as well as briefly pointing out the connection to the energy sector

Remote-controlled experiments with cloud chemistry

Developing cleaner chemical processes often involves sophisticated flow-chemistry equipment that is not available in many economically developing countries. For reactions where it is the data that are important rather than the physical product, the networking of chemists across the internet to allow remote experimentation offers a viable solution to this problem

Hiilidioksidin aktivointi metallikomplekseilla : mekanistinen näkökulma orgaanisten karbonaattien valmistukseen

Tässä tutkielmassa on käsitelty hiilidioksidin muuntamista orgaanisiksi karbonaateiksi. Orgaanisia karbonaatteja ovat sykliset karbonaatit ja polykarbonaatit, joita saadaan hiilidioksidin reagoidessa epoksidin kanssa, sekä lineaariset karbonaatit, jotka syntyvät reaktioissa esimerkiksi metanolin kanssa. Kirjallisuuteen perustuvassa osassa on esitelty eri metallikompleksien katalysoimien karbonaatti-synteesien mekanismeja. Oleellista katalyyttisysteemin aktiivisuuden kannalta on, että se koostuu Lewisin happo-emäsparista. Kompleksin keskusmetalli toimii happona aktivoiden epoksidin tai metanolin. Lewisin emäksenä toimii useimmiten kokatalyyttinen yhdiste, joka joko avaa epoksidirenkaan tai aktivoi hiilidioksidin ennen sen insertoitumista metalli-happi-sidokseen. Kokeellisessa osassa valmistettiin syklistä propyleenikarbonaattia titaanikompleksien avulla. Karbonaattisynteesin reaktio-olosuhteet optimoitiin ja lisäksi tutkittiin reaktion kinetiikkaa, jotta kyettiin selvittämään synteesin mekanismi

Carbon Dioxide as a Reagent and Solvent

The work described in this Thesis has been carried out within the Erasmus Mundus framework for Sustainable Industrial Chemistry (SINCHEM). The work concentrates on the possible utilisation of carbon dioxide as a solvent and as a starting material. Chapter 1 introduces carbon dioxide and its utilisation. In addition, the 12 Principles of CO2 Chemistry are presented, as well as continuous flow chemistry and self-optimising reactors. The relevant aspects of these reactors are discussed further in Chapter 2. The results of the research are presented in Chapters 3-6. A self-optimising reactor with FT-IR analysis was employed for the methylation of alcohols as explained in Chapter 3. Chapters 4-6 concentrate on N-alkylation reactions. In Chapter 4, the reactivity between aniline, tetrahydrofuran and dimethyl carbonate in supercritical carbon dioxide is discussed. This research led to the discovery of novel transformations.In Chapters 5 and 6, methanol was employed to methylate amines. A ruthenium triphosphate catalyst, which can produce methanol from carbon dioxide and hydrogen, was used to catalyse the reactions between methanol and aliphatic amines, as described in Chapter 5. Also the cyclisation and subsequent methylation of amino alcohols was studied. This reactivity is also the topic of Chapter 6, where γ-alumina was used as catalyst and supercritical carbon dioxide as solvent. Finally, Chapter 7 summarises the work described in this Thesis and evaluates the progress made towards achieving the aims that are introduced at the end of Chapter 1. One of these aims is to evaluate the work carried out in this Thesis according to the 12 principles of CO2 Chemistry. This evaluation is shown in Chapter 7

Carbon dioxide as a reagent and solvent

The work described in this Thesis has been carried out within the Erasmus Mundus framework for Sustainable Industrial Chemistry (SINCHEM). The work concentrates on the possible utilisation of carbon dioxide as a solvent and as a starting material. Chapter 1 introduces carbon dioxide and its utilisation. In addition, the 12 Principles of CO2 Chemistry are presented, as well as continuous flow chemistry and self-optimising reactors. The relevant aspects of these reactors are discussed further in Chapter 2. The results of the research are presented in Chapters 3-6. A self-optimising reactor with FT-IR analysis was employed for the methylation of alcohols as explained in Chapter 3. Chapters 4-6 concentrate on N-alkylation reactions. In Chapter 4, the reactivity between aniline, tetrahydrofuran and dimethyl carbonate in supercritical carbon dioxide is discussed. This research led to the discovery of novel transformations. In Chapters 5 and 6, methanol was employed to methylate amines. A ruthenium triphosphate catalyst, which can produce methanol from carbon dioxide and hydrogen, was used to catalyse the reactions between methanol and aliphatic amines, as described in Chapter 5. Also the cyclisation and subsequent methylation of amino alcohols was studied. This reactivity is also the topic of Chapter 6, where γ-alumina was used as catalyst and supercritical carbon dioxide as solvent. Finally, Chapter 7 summarises the work described in this Thesis and evaluates the progress made towards achieving the aims that are introduced at the end of Chapter 1. One of these aims is to evaluate the work carried out in this Thesis according to the 12 principles of CO2 Chemistry. This evaluation is shown in Chapter 7

Faktorer som stöder kultursensitivt föräldrasamarbete inom småbarnspedagogiken: en litteraturstudie

Lärdomsprovet är en litteraturstudie vars syfte är att undersöka vilka faktorer som stöder kultursensitivt föräldrasamarbete och hur barnet påverkas av det. Lärdomsprovet har två forskningsfrågor: ”Vad är centralt för ett fungerande samarbete mellan professionella och föräldrar med olika kultur?” och ”Vilka delaktighetsfrämjande effekter har mångkulturellt föräldrasamarbete på barnet?”. Den kulturella mångfalden ökar i vårt samhälle och därmed även inom småbarnspedagogiken, och där blir det viktigt att bemöta barn och föräldrar kultursensitivt. Enligt Grunderna för planen för småbarnspedagogik 2022 ska småbarnspedagogiken främja en öppen och respektfull atmosfär till mångfald och ett fungerande föräldrasamarbete. Föräldrasamarbetet är viktigt för föräldrar, barn och de professionella, och utmaningar kan förekomma då man samarbetar med familjer med olika kulturer. De 14 vetenskapliga artiklar som använts i litteraturstudien har sökts fram från följande databaser: Academic Search Complete (EBSCO) och ERIC. De slutsatser denna studie kommit fram till är att för att det kultursensitiva föräldrasamarbetet ska fungera behövs det kompetens och färdigheter av professionella och initiativtagande av föräldrarna. Föräldrasamarbetet och kvaliteten av det påverkar barnets utveckling och delaktighet. De resultat och den information som kommer fram i studien kan användas av personal inom småbarnspedagogiken, för att stöda dem i skapandet av ett gott föräldrasamarbete. Lärdomsprovet är ett beställningsarbete av Stiftelsen Semigradsky och temat är kultursensitivt föräldrasamarbete.This thesis is a literature review that aims to study the factors that support culturally sensitive parental cooperation and how the child is affected by it. The thesis answers two research questions: “What is key for successful cooperation between professionals and parents from different cultures?” and “How is the child’s social participation affected by multicultural parental cooperation?”. Multiculturalism keeps increasing in our society and therefore also in early childhood education, where it is important to treat children and parents with a culturally sensitive approach. According to Grunderna för planen för småbarnspedagogik 2022 early childhood education should promote an open and respectful environment for diversity and successful parental cooperation. Parental cooperation is important to parents, children, and professionals, and challenges may occur when cooperating with families from different cultures. The 14 research articles used in the literature study have been retrieved from the following databases: Academic Search Complete (EBSCO) and ERIC. The conclusions found in this thesis are that for culturally sensitive parental cooperation to be successful professionals need knowledge and abilities and that the parents take initiative. Parental cooperation and the quality of it affect the child’s development and social participation. The results and the information found in the thesis can be used by early childhood education professionals, to support them in developing successful parental cooperation. This thesis is commissioned by Stiftelsen Semigradsky and the theme is culturally sensitive parental cooperation.Tämä opinnäytetyö on kirjallisuustutkimus, jonka tavoitteena on tutkia mitkä tekijät tukevat kulttuurisensitiivistä vanhempainyhteistyötä ja mitä vaikutuksia sillä on lapseen. Opinnäytetyöllä on kaksi tutkimuskysymystä: “Mikä on keskeistä toimivassa yhteistyössä eri kulttuureista tulevien ammattilaisten ja vanhempien välillä?“ Ja “Mitä osallisuutta edistäviä vaikutuksia monikulttuurisella vanhempainyhteistyöllä on lapseen?". Kulttuurinen monimuotoisuus lisääntyy yhteiskunnassamme ja sitä mukaan myös varhaiskasvatuksessa, siksi on tärkeää osata kohdata lapset ja vanhemmat kulttuurisensitiivisesti. Varhaiskasvatussuunnitelman 2022 perusteiden mukaan varhaiskasvatuksen tulee edistää avointa ja monimuotoisuutta kunnioittavaa ilmapiiriä sekä toimivaa vanhempainyhteistyötä. Vanhempainyhteistyö on tärkeää vanhemmille, lapselle sekä ammattilaisille mutta erilaisia haasteita voi kuitenkin syntyä, kun työskentelee eri kulttuureista tulevien perheiden kanssa. Kirjallisuustutkimuksessa on käytetty 14 tieteellistä artikkelia, jotka on haettu seuraavista tietokannoista: Academic Search Complete (EBSCO) ja ERIC. Tämän tutkimuksen johtopäätökset ovat, jotta kulttuurisensitiivinen vanhempainyhteistyö toimisi edellyttää se ammattilaisilta osaamista ja taitoa sekä vanhemmilta oma-aloitteisuutta. Vanhempainyhteistyö ja sen laatu vaikuttaa lapsen kehitykseen ja osallisuuden tunteeseen. Tutkimuksessa saatuja tuloksia voidaan käyttää varhaiskasvatuksen henkilöstön tukena hyvän vanhempainyhteistyön luomisessa. Opinnäytetyö on Stiftelsen Semigradskyn tilaustyö ja teemana on kulttuurisensitiivinen vanhempainyhteistyö

Selective Synthesis of Trimethylamine by Catalytic N -Methylation of Ammonia and Ammonium Chloride by utilizing Carbon Dioxide and Molecular Hydrogen

The synthesis of trimethylamine (TMA) through a multicomponent combination of ammonia with carbon dioxide and molecular hydrogen by using a homogeneous ruthenium catalyst was explored. The use of [Ru(triphos)(tmm)] [triphos: 1,1,1-tris(diphenylphosphinomethyl)ethane, tmm: trimethylene methane] together with aluminum trifluoromethanesulfonate as a co-catalyst resulted in high ammonia conversion and excellent selectivity for TMA in organic solvents. Aqueous solutions of ammonium chloride were methylated almost quantitatively to the corresponding hydrochloride salt (i.e., TMA⋅HCl) in a biphasic solvent system by using the same Ru complex without the need for any co-catalyst