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Conducting Redox Polymers for Electrode Materials : Synthetic Strategies and Electrochemical PropertiesHuang, Xiao January 2017 (has links)
Organic electrode materials represent an intriguing alternative to their inorganic counterparts due to their sustainable and environmental-friendly properties. Their plastic character allows for the realization of light-weight, versatile and disposable devices for energy storage. Conducting redox polymers (CRPs) are one type of the organic electrode materials involved, which consist of a π-conjugated polymer backbone and covalently attached redox units, the so-called pendant. The polymer backbone can provide conductivity while it is oxidized or reduced (i. e., p- or n-doped) and the concurrent redox chemistry of the pendant provides charge capacity. The combination of these two components enables CRPs to provide both high charge capacity and high power capability. This dyad polymeric framework provides a solution to the two main problems associated with organic electrode materials based on small molecules: the dissolution of the active material in the electrolyte, and the sluggish charge transport within the material. This thesis introduces a general synthetic strategy to obtain the monomeric CRPs building blocks, followed by electrochemical polymerization to afford the active CRPs material. The choice of pendant and of polymer backbone depends on the potential match between these two components, i.e. the redox reaction of the pendant and the doping of backbone occurring within the same potential region. In the thesis, terephthalate and polythiophene were selected as the pendant and polymer backbone respectively, to get access to low potential CRPs. It was found that the presence of a non-conjugated linker between polymer backbone and pendant is essential for the polymerizability of the monomers as well as for the preservation of individual redox activities. The resulting CRPs exhibited fast charge transport within the polymer film and low activation barriers for charge propagation. These low potential CRPs were designed as the anode materials for energy storage applications. The combination of redox active pendant as charge carrier and a conductive polymer backbone reveals new insights into the requirements of organic matter based electrical energy storage materials.
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Self-Diffusion and Microstructure of Some Ionic Liquids in Bulk and in ConfinementFilippov, Andrei January 2016 (has links)
An ionic liquid (IL) is a salt, which usually is in the liquid state at normal temperature and pressure. The properties of ILs can be adjusted for various processes and applications by choosing different combinations of ions. Similar to other salts, ILs contain only ions with positive (cations) and negative (anions) charges in equal proportions. However, to prevent solidification, ions in ionic liquids usually contain bulky organic chemical groups, which, apart from electrostatic interactions, promote other types of interactions between ions, such as: (i) van-der-Waals interactions; (ii) hydrogen bonding; (iii) - stacking, etc., depending on the particular chemical structure of the ions. All these interactions, in combination, may lead to formation of specific microstructures in ILs, which may vary with temperature caused by changing thermal rotational and translational energies of the ions. Ions in these microstructures may have preferential orientations relative to each other, maintain anisotropic properties similar to those in liquid crystals or, in some specific cases, may even separate into microscopically organised liquid phases. Therefore, the dynamics of ILs may also be dependent on their microstructure. In many practical applications ionic liquids are placed on surfaces or in confinements. Solid surfaces introduce extra forces, which may be specific to the charge of the ions or/and to functional groups in the ILs. The geometry and interactions of ions in confinements or/and pores of materials may also disrupt specific bulk microstructures of ILs. Both confinement effects and interactions of ions with surfaces are manifested in the translational dynamics of the ions. One of the most direct and informative methods to study translational dynamics of ILs is pulse-field-gradient nuclear magnetic resonance (PFG-NMR).In this thesis the results of PFG-NMR studies on a few classes of ILs are reported: (i) the historically “standard” (since Walden’s discovery in 1914) ionic liquid, the ethylammonium nitrate (EAN) and (ii) halogen-free orthoborate-based phosphonium, imidazolium and pyrrolidinium ILs with varied structure and lengths of alkyl chains in cations, and varied structures of orthoborate anions. These ILs were studied in bulk at different temperatures, and also in confinements, such as between parallel glass and Teflon plates and in mesoporous Vycor glass. It was found that diffusion coefficients of cations and anions in EAN, phosphonium and pyrrolidinium orthoborate ILs in bulk are different, but according to the standard Stocks-Einstein model, they correspond to diffusion of ions in homogeneous liquids. A change in the chemical structure of one of the ions results in a change in both the diffusion coefficient of the oppositely charged ion and the activation energy of diffusion for both ions in an IL. Similar effects were observed from the chemical shifts and diffusion coefficients measured by NMR for imidazolium orthoborate ILs dissolved in polyethylene glycol solutions, in which imidazolium cations strongly interact with PEG molecules, further affecting the diffusion of orthoborate anions via electrostatic interactions. A liquid-liquid phase separation was suggested for a few phosphonium and pyrrolidinium bis(mandelato)borate ILs, in which a divergence of diffusion coefficients and activation energies of diffusion for cations and anions was detected at temperatures below ca 50 °C. In addition, a free-volume theory was invoked to explain the dependences of density of ILs on the alkyl chain length in cations.It was also found that for a phosphonium bis(salicylato)borate IL confined in 4 nm mesoporous Vycor glass the diffusion coefficients of ions increase by a factor of 35! This phenomenon was explained by the dynamic heterogeneity of this IL in micropores and empty voids of the Vycor glass. For EAN IL in confinements between glass and Teflon plates, the diffusion of ethylammonium cations and nitrate anions is significantly anisotropic, i.e. slower in the direction of the normal to the plates and faster along the plates compared to diffusion of the ions in bulk. A plausible explanation of this PFG NMR data is that EAN forms layers near polar and non-polar solid surfaces. A similar phenomenon, to a lesser extent, was also observed for phosphonium cations of bis(mandelato)borate, bis(salicylato)borate and bis(oxalato)borate confined between glass plates. The results of these studies may have implications in modeling tribological performance, i.e., friction and wear reduction for contact pairs of different materials lubricated by various classes of ionic liquids. / För godkännande; 2016; 20160420 (andfil)
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Stereoselective Nucleophilic Additions to Aldehydes and Synthesis of α-Amino-β- Hydroxy-EstersDanielsson, Jakob January 2012 (has links)
This thesis deals with the development of new reaction methodology as well as stereochemical investigations. The first part concerns the investigation of 1,2- and merged 1,2- and 1,3- asymmetric induction in Mukaiyama aldol additions to α-heteroatom and α,β- heteroatom substituted aldehydes respectively. In particular, the unexpected 1,2-syn selectivity obtained in the addition of sterically hindered nucleophiles to α-chloroaldehydes is examined, and an explanation for the observed stereochemical trends is proposed. The second part describes the development of a novel entry to α-amino-β- hydroxy esters by a 1,3-dipolar cycloaddition reaction of aldehydes and azomethine ylides, generated by thermolysis of aziridines. The third part deals with our efforts to develop a novel entry to vicinal all- carbon quaternary centers, based on an intramolecular domino Heck- carbonylation reaction using tetrasubstituted olefins. / QC 20120611
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Grön kemi och hållbar utveckling : Laborationsdesign för gymnasium och högskolaHammarberg, Daniel January 2013 (has links)
This thesis is about sustainability within chemistry, the so-called, green chemistry. With this work I seek to combine green chemistry with sustainable development and find methods for teaching green chemistry in a laboratory environement. I have designed and tested two labs with ingredients of green chemistry and sustainable development in my study. I wanted to determine if my design model leads to conception for the students. The students have through forms and interviews declared their perspective on the education and their conception. In a laboratory environment the pros of a laboratory way of work should be recognized. Pre- and post-work puts the lab in a context. The students understand the concepts better if they are allowed to test their knowledge in a discussion. The teachers role in the discussion should be to lift the level of the discussion by controlling the conversation and in a constructiveway contribute to making the discussion move forward whenever necessary. / Denna uppsats behandar hållbarhet inom kemi, den så kallade gröna kemin. Med arbetet söker jag förena grön kemi med hållbar utveckling och hitta metoder för att undervisa grön kemi i en laborativ miljö. I undersökningen har jag designat och testat två laborationer med inslag av grön kemi och hållbar utveckling. Jag ville undersöka om undervisningsmodellen leder till en begreppsutveckling hos studenter och elever. Studenterna/eleverna har genom enkäter och intervjuer uttalat sig om dels sina egna kunskaper och dels om undervisningens inslag och dess bidrag till deras begreppsutveckling. I ett laborativt sammanhang bör fördelarna med ett laborativt arbetssätt utnyttjas. Förarbete och efterarbete ger laborationen ett sammanhang. Studenten/eleven förstår begreppen bättre om de får testa sina kunskaper i en diskussion. Lärarens roll i diskussionen bör vara att lyfta diskussionsnivån genom att styra samtalet och på ett konstruktivt sätt bidra till att föra diskussionen framåt när det är nödvändigt.
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Photoredox catalysis enabled C–O bond activation: Access to unnatural amino acids / Fotoredoxkatalyserad aktivering av C–O bindningar: Syntes av icke-naturliga aminosyrorLantz, Josefin January 2021 (has links)
Fotoredoxkatalys tillhandahåller möjligheter att utveckla nya hållbara kemiska reaktionsvägar. När fotokatalysatorn bestrålas med synligt ljus möjliggörs elektronöverföring till eller från substratet som i sin tur medför alstring av reaktiva fria radikaler. Kolradikaler, genererade med fotoredox-katalys från alkyloxalataktiverade alkoholer, har framgångsrikt kopplats till sulfinyliminer och möjliggör därigenom syntes av onaturliga α-aminosyror. Reaktionen utförs vid rumstemperatur och kräver endast extern energi i form av synligt ljus för att aktivera den iridium-baserade fotokatalysatorn. Den höga tillgängligheten av alkoholer utgör ett rimligt skäl för att använda dem som startmaterial. I detta projekt har tertiära alkoholer resulterat i framgångsrika reaktioner. / Photoredox catalysis provides opportunities to develop new sustainable chemical reaction pathways through single-electron transfer events and generation of reactive free-radical species. In this thesis carbon radicals, generated with photoredox catalysis from alkyl oxalate-activated alcohols, have successfully been coupled to sulfinyl imines and thereby enabling synthesis of unnatural α-amino acids. The reaction is performed at room temperature and only requires external energy in the form of visible light to activate the iridium-based photocatalyst. The abundance and availability of alcohols presents good reasons to use them as radical precursors. Under the developed reaction conditions, tertiary alcohols proved to be successful radical precursors, giving the desired product in good yield.
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Stereoselective synthesis of unnatural α-amino acids through photoredox catalyzed C–H activation / Stereoselektiv syntes av icke-naturliga α-aminosyror genom fotoredoxkatalyserad C–H-aktiveringWåhlin, Ludwig January 2021 (has links)
Fotoredoxkatalys har nyligen genomgått en renässans inom organisk kemi då metoden har möjliggjort framtagandet utav nya reaktionsvägar med milda reaktionsbetingelser genom att använda sig av synligt ljus. I det här arbetet undersöktes metodens bredd genom att kombinera metoden med väteatomöverföringskatalys för att funktionalisera C–H bindningar i α-position till heteroatomer och på så sätt skapa icke-naturliga α-aminosyror. Resultaten från detta arbete gav upp till 60% utbyte genom att kombinera dessa två katalysmetoder för substrat med Boc som skyddsgrupp, medan tertiära aminer inte krävde en väteatomöverföringskatalysator för kunna funktionaliseras. Den syntetiska metoden utan väteatomöverföringskatalys verkar dock inte vara applicerbara för sekundära aminer, men ser ut att fungera för C–H aktivering i α-position till svavelatomer vilket tyder på denna simplare metod utan väteatomsöverföring bör vara applicerbar för flera typer av substrat än för bara aminer / Photoredox catalysis has recently undergone a renaissance in the field of organic chemistry due the enabling of new reaction pathways under mild reaction conditions using visible light. In this work, the scope of this technology was explored by combining it with hydrogen atom transfer (HAT) to perform C–H functionalization in α-position to heteroatoms for synthesis of unnatural α-amino acids. The results showed that this is a viable method, gaining up to 60% yield using a dual catalytic system for Boc protected amines, while the functionalization of tertiary amines does not require HAT in order to work. Secondary amines proved to be non-applicable using the developed synthetic route without HAT catalyst while C–H activation in α-position to sulfur atoms gave similar response as tertiary amines – indicating that C–H activation without HAT should be applicable to a wider substrate scope than only using amines.
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Performance effects of operational efficiency and bargainingpower through different types of growth : A study between organic and inorganic growthNäslund, Daniel, Hugoh, Theodor January 2023 (has links)
Previous literature often argues that acquisitions are used as a tool for growth, and the value creation derives from the combination of businesses through synergy effects and the economies of scale. In the same academical and theoretical context, there is often a discussion on growth with a more organically approach, where the value comes throughresource utilization and internal efficiency. There is a broad range of research in the area,focusing on the impact of different types of growth strategies. More emphasis has been on inorganic growth. Hence, is there a superior combination of both, and how will each strategy impact the value creation for different types of stakeholders through internal and external efficiency. Previous results are not always harmonious regarding the relationship between the two growth strategies and the efficiency of a company. This study has focused on examining the relationship with a broad range of industries using accounting measures to answer the research question: What are the effects of organic and inorganic growth on operating efficiency and bargaining power? For the thesis, panel data analysis has been used which includes 8675 specific firm-year observed values from companies that is publicly listed in Sweden. The collected archival data has been tested through OLS regressions with fixed effects. Throughout the thesis and conducted research, a positivist paradigm has been used under a deductive approach. Emphasis is placed on previous literature and studies for more accurate statistical results. Further contributions to theoretical literature and the scientific research community have been added. This thesis has been analyzing empirical results using Resource-based view along with the Stakeholder- and Shareholder theory. With the conclusion that there is a significant relationship between organic growth and operating efficiency. On the other hand, it cannot be concluded that there is a relationship between inorganic growth and bargaining power. In addition, the relationship between growth strategy and efficiency measures will depend on which industry the company operates in.
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Operation of the heat and power complex Alatyr to power Russian oil and gas facilitiesBoltyanskiy, Boris January 2018 (has links)
B. Boltyansky Operation of the heat and power complex Alatyr to power Russian oil and gas facilities, Master's Dissertation, 2017 - 102 pages, 26 tables, 30 figures Supervisor Prof. V. G. Kucherov, Doctor of Sciences, Department of Energy Technology. The work includes the following. A calculation of the main thermodynamic cycle of the heat and power complex Alatyr heat and power complex. A consideration of various schemes of using the Rankine organic cycle WERE integrated in the Alatyr heat and power complex with the aim of increasing energy efficiency. Conclusions about the feasibility of using the heat and power complex Alatyr. Conclusions about the feasibility of integration of the organic Rankine cycle. Economic comparison of the heat and power complex Alatyr with similar facilities on the distributed power generation market. Economic analysis of the comparison of energy blocks of HPC Alatyr with similar designs from other countries. / B. Boltyansky Drift av värme- och kraftkomplexet Alatyr till makten Ryska olje- och gasanläggningar, Masters uppläggning, 2017 - 102 sidor, 26 tabeller, 30 figurer Handledare Prof. VG Kucherov, doktorsexamen, kandidatexamen för teknisk vetenskap, institutionen för termodynamik och termisk motorer. Arbetet innehåller följande. En beräkning av värmekraftkomplexets värmeoch kraftkomplex Alatyrs värmekomplex. En övervägning av olika system för användning av Rankine organiska cykeln var integrerad i Alatyr värme- och kraftkomplexet i syfte att öka energieffektiviteten. Slutsatser om möjligheten att använda värme- och kraftkomplexet Alatyr. Slutsatser om möjligheten att integrera den organiska Rankine-cykeln. Ekonomisk jämförelse av värme- och kraftkomplexet Alatyr med liknande anläggningar på den distribuerade kraftproduktionsmarknaden. Ekonomisk analys av jämförelsen av energiblock av HPC Alatyr med liknande konstruktioner från andra länder.
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Catalytic synthesis of benign bisphenols / Katalytisk syntes av ofarliga bisfenolerChu, Victoria, Lundqvist, Emma, Hagelin, Hampus January 2022 (has links)
This study analyzes the reactivity and selectivity of Friedel-Crafts alkylations using benzylic alcohols and phenols in the presence of a Lewis acid, to synthesize methoxylated bisphenols as a benign alternative to BPA. The degree of methoxylation on the electrophile appears to affect the yield of the reaction while the degree of methoxylation on the nucleophile appears to affect the selectivity. A more methoxylated electrophile results in a lower yield whereas a more methoxylated nucleophile results in a change in ratio between the bisphenol isomers and/or causes other isomers to form. Neither the yield nor the selectivity appears to be affected significantly by the temperature.
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Study of yield variation in a pharmaceutical manufacturing process and optimization of purification subsection : By a design of experiments study of the production parameters and a laboratory study of the purification step / Studie av utbytesvariation i farmaceutisk tillverkningsprocess och optimering av processens reningssteg : Genom en försöksplaneringsstudie av produktionsparametrar och en laborativstudie av renings stegetLord, Sandra January 2022 (has links)
The product R1-MR2E is an ester formed from an esterification of a carboxylic acid and an alcohol at Cambrex Karlskoga AB. The production of the intermediate R1-MR2E is a large-scale production and there are two main objectives and two sub-objectives that this project aims to study of the manufacturing.The manufacturing of R1-MR2E experience big variations in the product yield which is affecting theproductions stability and economic aspects of it. Thus, one of the main objectives in this project was to use experimental design to find significant factors that causes yield variations. The results from this study showed five significant factors that affect the yield positively or negatively by resulting in higher or lower product weight. The factors found are the amount of charged toluene solution containing the by-product R1-DR2E from the recycling system, the amount of charged carboxylic acid, the reaction time, the amount of added Na2SO3 in the neutralisation step and the regulated pH value after the crystallisation step. The other main objective is to optimize the purification sub-section using activated carbon (AC). There are two sub-objectives for this part of the study where the first sub-objective is to evaluate how much activated carbon that is needed to remove the impurities and colouration in the product. The second sub-objective is to investigate if an activated carbon filter could be used as a substitute for the commonly used loose powder activated carbon. To answer this objective a laboratory method was used, where the large-scale purification- and crystallisation step as well as after treatment were scaled down to lab scaleand then experiments were conducted to determine the effects of different amounts of activated carbon, using no carbon, and utilizing another type of activated carbon known as activated carbon filters. The results were then analysed for colour and purity by a visual observation method and High-Performance Liquid Chromatography (HPLC) method. The conclusion from this study is that only 25% of the amount of activated carbon used today is needed to remove the colouration in the product. The activated carbon did not completely remove the impurities in the product. The other conclusion was that the idea that the activated carbon removed the small impurities was wrong, and the levels of the impurities are already small enough in the large-scale production that the purification step is not needed to reach approved levels of these impurities. The activated carbon filter also works to remove the colouration with only one filtration but does not work well on removing the impurities in the product. / Produkten R1-MR2E är en ester som formas med en förestring av en karboxylsyra och en alkohol på Cambrex Karlskoga AB. Produktionen av intermediet R1-MR2E är en storskalig produktion och det finns två huvudmål och två delmål som studeras i studien. Produktionen av R1-MR2E upplever stora variationer i produktsutbytet vilket påverkar produktionensstabilitet och ekonomiska aspekter. Ett av målen med detta projekt är därmed att använda experimentell design för att hitta signifikanta faktorer som orsakar utbytesvariationer. Resultatet från den här studien visar på fem faktorer som påverkar utbytet positivt eller negativt genom att bidra till högre eller lägre utpackad vikt. Faktorerna som hittades är mängden av den satsade R1-DR2E från återvinningssystemet, mängden av den satsade karboxylsyran, reaktionstiden, mängden av den adderade Na2SO3 under neutralisation steget och de reglerade pH efter kristallisations steget. Det andra målet är att optimera ett av produktionens delsteg, rening med aktivt kol (AC). Det finns två delmål för den delen av studien, de två delmålen är att ta reda på hur mycket aktivt kol som behövs för att ta bort föroreningar och förbättra färgen i produkten samt undersöka om aktivt kolfilter kan användas som ett substitut för det vanligen använda lösa aktiva kolpulver. För att genomföra det här målet så användes en laborativ metod, där det storskaliga renings- och kristallisationssteget samt efterbehandling skalades ner till laborativ skala. Sedan genomomfördes experiment för att bestämma effekten av olika mängder aktivt kol, inget aktivt kol, och använda en annan typ av aktivt kol i formen av ett aktivtkolfilter. Resultaten från det laborativa arbetet analyserades sedan med en visuell metod samt högpresterande vätskekromatografisk (HPLC) metod. Slutsatsen från studien är att bara en 25% av den mängd aktivt kol som används i dagens läge behövs för att ta bort färgen i produkten. Det aktiva kolet tog dock inte bort föroreningarna i produkten speciellt bra. Det betyder att idén om att det aktiva kolet tar bort föroreningar är fel och att nivåerna av föroreningarna redan är tillräckligt låga i den storskaligaproduktionen för att bli godkända i koncentration utan reningssteget. AC filter fungerar också för att ta bort färgen med endast en filtrering men fungerar inte att använda för att ta bort föroreningarna i produkten.
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