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Design, Synthesis and Characterization of Polyethylene-Based Macromolecular Architectures by Combining Polyhomologation with Powerful Linking ChemistryAlkayal, Nazeeha 05 September 2016 (has links)
Polyhomologation is a powerful method to prepare polyethylene-based materials with controlled molecular weight, topology and composition. This dissertation focuses on the discovery of new synthetic routes to prepare polyethylene-based macromolecular architectures by combining polyhomologation with highly orthogonal and efficient linking reactions such as Diels Alder, copper-catalyzed azide-alkyne cycloaddition (CuAAC), and Glaser. Taking advantage of functionalized polyhomologation initiators, as well as of the efficient coupling chemistry, we were able to synthesize various types of polymethylene (polyethylene)-based materials with complex architectures including linear co/terpolymers, graft terpolymers, and tadpole copolymers.
In the first project, a facile synthetic route towards well-defined polymethylene-based co/terpolymers, by combining the anthracene/maleimide Diels–Alder reaction with polyhomologation, is presented. For the synthesis of diblock copolymers the following approach was applied: (a) synthesis of α-anthracene-ω-hydroxy-polymethylene by polyhomologation using tri (9 anthracene-methyl propyl ether) borane as the initiator, (b) synthesis of furan-protected-maleimide-terminated poly(ε-caprolactone) or polyethylene glycol and (c) Diels–Alder reaction between anthracene and maleimide-terminated polymers. In the case of triblock terpolymers, the α-anthracene-ω-hydroxy polymethylene was used as a macroinitiator for the ring-opening polymerization of D, L-lactide to afford an anthracene-terminated PM-b-PLA copolymer, followed by the Diels–Alder reaction with furan-protected maleimide-terminated poly (ε-caprolactone) or polyethylene glycol to give the triblock terpolymers. The synthetic methodology is general and potentially applicable to a range of polymers.
The coupling reaction applied in the second project of this dissertation was copper-catalyzed “click” cycloaddition of azides and alkynes (CuAAC). Novel well-defined polyethylene-based graft terpolymers were synthesized via the “grafting onto” strategy by combining nitroxide-mediated radical polymerization (NMP), polyhomologation and copper(I)-catalyzed azide–alkyne cycloaddition (CuAAC). Three steps were involved in this approach: (a) synthesis of alkyne-terminated polyethylene-b-poly(ε-caprolactone) (PE-b-PCL-alkyne) block copolymers (branches) by esterification of PE-b-PCL-OH with 4-pentynoic acid; the PE-b-PCL-OH was obtained by polyhomologation of dimethylsulfoxonium methylide to afford PE-OH, followed by ring opening polymerization of ε-caprolactone using PE-OH as a macroinitiator (b) synthesis of random copolymers of styrene (St) and 4-chloromethylstyrene (4-CMS) with various CMS contents, by nitroxide-mediated radical copolymerization (NMP), and conversion of chloride to azide groups by reaction with sodium azide (NaN3) (backbone) and (c) “click” linking reaction to afford the PE-based graft terpolymers. This method opens up new routes for the creation of polyethylene-based graft terpolymers by a combination of polyhomologation, NMP and CuAAC.
The third project deals with the synthesis of polyethylene-based tadpole copolymer (c-PE)-b-PSt. Cyclic polymers represent a class of understudied polymer architecture mainly due to the synthetic challenges. Within this dissertation, a new method was reported for the synthesis of cyclic polymers in exceptionally high purity and yield. The main approaches to synthesize macrocycles are based on the end-to-end ring-closure (coupling) of homo difunctional linear precursors under high dilution. Our process relies on the preparation of well-defined linear α, ω-dihydroxy polyethylene and a bromide group at the middle of the chain through polyhomologation of ylide using functionalized initiator, followed by ATRP of styrene monomer. The two hydroxyl groups were transformed into alkyne groups, via esterification reaction, followed by Glaser reaction between terminal alkynes to afford the tadpole-shaped copolymers with PE ring and PSt tail.
In Our PhD research, we also studied the self-assembly properties of the amphiphilic copolymers PM-b-PEG in aqueous solution by DLS, Cryo-TEM, and AFM. Furthermore, the critical micelle concentration (CMC) was estimated from the intensity of the pyrene emissions by the fluorescence technique.
All the findings presented in this dissertation are emphasizing the utility of polyhomologation for the synthesis of well-defined polyethylene-based complex macromolecular architectures, almost impossible through other kind of polymerization including the catalytic polymerization of ethylene.
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From Unnatural Amino Acid Incorporation to Artificial MetalloenzymesMakki, Arwa 04 December 2016 (has links)
Studies and development of artificial metalloenzymes have developed into vibrant areas of research. It is expected that artificial metalloenzymes will be able to combine the best of enzymatic and homogenous catalysis, that is, a broad catalytic scope, high selectivity and activity under mild, aqueous conditions.
Artificial metalloenzyme consist of a host protein and a newly introduced artificial metal center. The host protein merely functions as ligand controlling selectivity and augmenting reactivity, while the metal center determines the reactivity. Potential applications range from catalytic production of fine chemicals and feedstock to electron transfer utilization (e.g. fuel cells, water splitting) and medical research (e.g. metabolic screening). Particularly modern asymmetric synthesis is expected to benefit from a successful combination of the power of biocatalysis (substrate conversion via multi-step or cascade reactions, potentially immortal catalyst, unparalleled selectivity and optimization by evolutionary methods) with the versatility and mechanism based optimization methods of homogeneous catalysis. However, so far systems are either limited in structural diversity (biotin-avidin technology) or fail to deliver the selectivities expected (covalent approaches).
This thesis explores a novel strategy based on the site-selective incorporation of unnatural, metal binding amino acids into a host protein. The unnatural amino acids can either serve directly as metal binding centers can be used as anchoring points for artificial metallo-cofactors.
The identification expression, purification and modification of a suitable protein scaffolds is fundamental to successfully develop this field. Chapter 2 and 3 detail a rational approach leading to a highly engineered host protein. Starting with fluorescent proteins, which combine high thermal and pH stability, high expression yields, and fluorescence for ease of quantification and monitoring an efficient and fast purification protocol was developed first. The purification protocol uses a combination of heat precipitation and three-phase-partitioning (TPP). It provides high yield and purity without requiring any tag.
Building on the favourable properties of fluorescent proteins, the non-metal binding, highly stable host-scaffold mTFP* was generated through rational design. The incorporation of artificial metal binding sites, the allowed the selective formation of artificial metalloenzymes, which show catalytic activity and moderat to good chiral induction in the Diels-Alder Cyclization and Friedl-Crafts Acylation
Chapter 4 of the thesis describes the use of UAA incorporation to generate artificial metal binding sites. Computational studies and homology modelling successfully highlighted several positions in mTFP*, which are particularly suitable for UAA incorporation without any disruption of the protein structure. Application of a functional orthogonal aaRS/tRNA pair developed by P.G. Schultz and co-workers allowed the site-specific incorporation of UAAs in the host protein framework. Changes in fluorescence intensity revealed preferences of varieous UAAs for specific incorporations sites. The three UAAs, pIF, pAzF, and pEynF were incorporated into mTFP* in good yields, while pBF does only deliver low protein yields. A successfully established on-protein MIYAURA borylation reaction allows convert well-incorporated pIF into pBF circumventing the problem of low expression yields.
Chapter 5 details the use of the azide-functionality of pAzF for the bioconjugation of artificial metal-binding cofactors through CuAAC. The triazole ring formed during this reaction serves as an additional moderate σ -donor/π –acceptor ligand of the metal binding site. We demonstrated the potential of site-specific modifications within the protein host with a versatile subset of artificial cofactors. Following transition metal binding, the newly created metal sites show catalytic activities that nature does not provide. The proof of concept study highlights the potential of the present mTFP* based catalysts in asymmetric Tsuji Trost allylation reactions and Diels-Alder cycloadditions. Dual anchoring of the cofactor lead to increased enantioselectivities, which is a direct result of a better-defined orientation of the catalytic center on the protein surface.
Following the utilization of the CuAAC click reaction for the generation of artificial metalloenzymes, the last chapter of this thesis reports the development of a heterogeneous catalyst system for this reaction, which overcomes limitations of homogenous protocols. The recyclable core-shell structured Cu2O/Cu-nanowire catalyst is highly active, does not lead to protein precipitation, can be filtered off after the reaction and provides copper free bioconjugation products.
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OLAP-Auswertung von WebzugriffenStöhr, Thomas, Rahm, Erhard, Quitzsch, Stephan 18 October 2018 (has links)
Die Analyse des Zugriffsverhaltens auf Web-Seiten ist von großer Wichtigkeit, um die Attraktivität und Nützlichkeit von Internet-Angeboten zu bewerten und Rückschlüsse auf eine Verbesserung der Web-Präsentation zu erhalten. Im kommerziellen Umfeld (E-Commerce-Angebote wie Online-Buchhandel,
-Reisebuchung, etc.) soll die sogenannte “Click Stream”-Analyse wertvolle Informationen über das Zugriffsverhalten von Kunden bzw. potentiellen Kunden liefern, mit dem Ziel den Wünschen der Kunden stärker entgegenzukommen, eine verbesserte Kundenbindung zu erreichen und letztlich den Umsatz zu steigern [8],[3]. Weiterhin ermöglicht die Analyse der Web-Zugriffe Erkenntnisse hinsichtlich von Performance-Anforderungen und daraus abgeleitet hinsichtlich der bereitzustellenden Hardware-Konfiguration, um ein gutes Durchsatz- und Antwortzeitverhalten zu erreichen.
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Is it game over for physical retailers? : A study on Swedish video game industryFarhana, Mosarrat, Swietlicki, Daniel January 2020 (has links)
Purpose - The purpose of this study is to extend the understanding of the business model of video game retailers using online and physical stores focusing on the impact of digital platforms on the retailing industry within the context of video game industry considering different actor’s perspectives like retailers and consumers. Design/methodology/approach - This is a multiple-case study based on deductive reasoning. In this qualitative study, two cases of click-and-mortar retailers operating in the Swedish video game industry have been considered along with feedback from customers. Online personal interviews and semi-structured interviews have been conducted with retailers and customers respectively. Both primary and secondary data have been used to conduct the study. Findings - Findings show that video game retailers need to encourage engagement through incentives and other activities in order to create value and change up their formats and sales strategies through pricing to reach new customers and focus on design of their online store fronts to convey trustworthiness. Research limitations - A major limitation has been the COVID-19 pandemic spreading during the writing of this paper, which resulted in companies backing out to refocus their efforts. Another limitation has been the legal aspect as companies owned by bigger publishers denied to take part in the study to avoid revealing sensitive information. Practical implications - It offers some insightful practical suggestions to retailers who are struggling hard to adopt digital transformations in the industry. Originality - Authors’ proposed research model, based on Sorescu et al. (2011)’s retail business model and the empirical findings, contribute in the less explored domain of research on business models from retailer’s perspectives. Moreover, it adds values in industry specific study like the video game industry in Sweden considering all actors, which is argued as scarce.
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A comparative study of the materials of Villa Zero project using LCAAlkhuder, Juma, Alnabhani, Mazen January 2021 (has links)
In this thesis a future-world case was undertaken of the life cycle assessment (from cradleto grave) of a single-family house. The house is expected to be constructed by the end of2021 in Borlänge, a city located in Dalarna County. The aim of this study is to investigatewhether the building materials in external walls and roof surpass in terms ofenvironmental impacts compared with other building materials suggested by the authorsof this thesis.Six scenarios were evaluated in terms of the environmental impacts for two buildingelements, external wall, and roof. A base case scenario is taken into consideration foreach building element, considering the fact, that the thermal performance characteristicsof the building materials are comprehensively provided. Consequently, four scenarios aredetermined by the authors.One Click LCA program was used to calculate the environmental impacts of thebuilding materials through the lifecycle of the house during a time horizon of 50 years.Hemp fiber insulation material is planned to be used in the external walls; thus, it isconsidered the baseline case for this thesis. The first study is corresponded to the externalwalls, and it was found that glass wool insulation is more environmentally friendly thanhemp fiber and rock wool insulation.Wood material is planned to be used in the roof; thus, it is considered the baseline casefor this thesis. The second study is corresponded to the roof, and it was found that woodmaterial is more environmentally friendly than concrete and steel.Therefore, the suggested material by the authors surpasses the baseline case materialenvironmentally in respect of external walls, but this was not the case regarding the roof.
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TQM inom livsmedelsindustrin : Chefernas egna uppfattningar kring förändringar och reformerEstberg, Joel, Poznic, Daniel January 2021 (has links)
In today's society, it is of great interest to constantly streamline and improve yourorganization for the better. How to do this, however, is not obvious and there are usually anumber of solutions, ideas and recipes that claim to solve various problems. When we in Sweden in the 90's started to focus more and more on quality - with the quality movement that started in the western world called TQM (total quality management) - both regarding the produce of our goods and services as well as how we organize ourselves, we think it isinteresting to study how managers themselves experience these organizational changes. The study is based on Rövik's theories of administrative reforms. The analysis of the empirics was conducted through the two perspectives that are presented by Rövik; the symbolic perspective and the tool perspective. TQM is represented in this study by Self-Control, Quality Certification and Click and Collect. The purpose of this study is to examine how store managers in the food industry themselves view TQM reforms that they have been involved in and if any of these recipes are loosely linked. The study uses a qualitative research strategy by interviewing a total of three respondents from both Coop and Ica. The respondents' reasoning could most easily be understood from a symbolic perspective, and the results also showed a difference in freedom of action and loosely linked recipes. Coop tends to loosely link these recipes to a greater extent compared to Ica. Nevertheless, both Self-Control as well as the Quality Certification can be best understood with a symbolic perspective as they, quite forcefully, offer meaning and legitimacy to organisations, rather than a voluntary solution to a, already defined, quality related issue within the organisations.
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Click & collect: En studie kring COVID-19 och dess påverkan i fysiska butiker : En kvalitativ studie angående hur COVID-19 har påverkat fysiska butiker och dess click & collectDahl, Sebastian, Hamajalal, Daniar January 2021 (has links)
Due to COVID-19 the authors of the following study aim to examine how COVID-19 has affected society by studying its impact on grocery stores. The following study is based on a case study design where a total of four respondents have participated. All respondents are store managers and they have all been interviewed regarding questions that emphasise COVID-19 and its effect on their business, as well as how click & collect has played a role during COVID-19. The following study has used a qualitative research strategy with intentions to generate qualitative interviews that will underpin the result of the study. In order to answer the thesis, an issue was formulated that reads as follows: How and why has restrictions in physical stores during COVID-19 affected store managers in grocery stores and their sales through click & collect? In order to answer the issue that the study has presented, the study has been delimited to stores that are based in Stockholm. Furthermore it shall be said that the respondents who have participated in the study did so with the intention to remain anonymous. The conclusion of the study showed that click & collect has had an impact on grocery stores during COVID-19 due to the fact that store purchases have increased through the shopping channel. Furthermore the study presented that a new state of normality due to COVID-19 has occurred which benefits sales through click & collect. Finally the study has also shown that a synergy between the grocery stores physical and digital sales channels have occurred which benefits click & collect.
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Diagnostic accuracy of CE ChirpVan Dyk, Zandri January 2019 (has links)
The auditory brainstem response is an evoked potential that can be clinically used to estimate hearing sensitivity and to identify auditory nervous system pathology. Recently, there has been an increase in the implementation of the CE-Chirp stimulus in AABR equipment for neonatal hearing screening. The purpose of this study is to evaluate the diagnostic accuracy of the LS CE-Chirp-evoked ABR compared to the traditionally used click-evoked ABR for the identification of different degrees and configurations of sensorineural (SNHL) hearing loss.
An exploratory within-subject comparative research design was used. 49 ears with mild to moderate sensorineural hearing loss were assessed. Participants were assessed in a single session. Audiometric pure tone thresholds were obtained at 125-8000 Hz and ABR thresholds were measured using the click and LS CE-Chirp stimuli respectively. Click- and LS CE-Chirp-evoked thresholds were compared with each other and with behavioural pure tone average (PTA), high frequency average (HFA) and low frequency average (LFA). Diagnostic accuracy of the two ABR stimuli was also compared by using ROC curves.
Differences between click- and LS CE Chirp-evoked ABR, and behavioural thresholds were not statistically significant (p>0.05). The strongest significant correlation for ABR using clicks to behavioural thresholds was found at 2000 and 4000 Hz, whereas, the strongest correlation for LS CE-Chirp ABRs to behavioural thresholds was found at 1000, 2000 and 4000 Hz (r>0.7, p<0.001). A very strong, positive correlation was found between both click (r=0.805) and LS CE-Chirp (r=0.825) and the behavioural PTA (p<0.001). The mean differences for LS CE-Chirp were smaller than those of the click for PTA and low frequency range. ROC curves indicated better AUC values for the LS CE-Chirp at LFA and HFA compared to the click, also showing a narrower confidence interval and less variance than the click.
The predictive accuracy of the LS CE-Chirp-evoked ABR was slightly better than that of the click with reference to PTA, HFA and LFA thresholds; furthermore, it is less variable and more accurate than the click-evoked ABR with reference to HFA. Thus, the LS CE-Chirp is an accurate stimulus for estimation of hearing sensitivity using ABR when compared to the gold standard click stimulus for the purpose of identification of different configurations of SNHL. / Dissertation (MA Audiology) University of Pretoria, 2019. / Speech-Language Pathology and Audiology / MA (Audiology) / Unrestricted
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Avtal i riggade system / Contracts in fixed systemsGramenius, Tore January 2020 (has links)
Avtalslagen trädde i kraft för över hundra år sedan, och har sedan dess varit hörnstenen i den svenska avtalsrätten. Trots att avtalslagen endast var tänkt att behandla avtal som sluts genom korrespendens används den av dagens jurister för att beskriva avtalsslut för nästan alla typer av avtal, med blandade resultat. En typ av avtal för vilken avtalslagen passar särskilt dåligt är avtal slutna i riggade system, d.v.s. avtal där bara den ena parten aktivt handlar med ett på förhand uppriggat system. Ett nytt sätt att tänka kring avtal måste därför ställas upp för avtalstypen. Uppsatsens syfte är att klargöra vilken avtalsmekanism som används för avtal i riggade system samt hur avtalsinnehållet fastsälls i dessa. Syftet uppnås genom att analysera fyra typfall (Shrink och Click wrap-villkor, onlineauktioner, butikshandel och parkering) och sedan med grund i dessa ställa upp allmänna riktlinjer för hur avtal i riggade system bör behandlas.
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Site-specific chemical modification of mitochondrial respiratory complex I / ミトコンドリア呼吸鎖複合体Iの位置特異的化学修飾に関する研究Masuya, Takahiro 23 March 2017 (has links)
京都大学 / 0048 / 新制・課程博士 / 博士(農学) / 甲第20418号 / 農博第2203号 / 新制||農||1047(附属図書館) / 学位論文||H29||N5039(農学部図書室) / 京都大学大学院農学研究科応用生命科学専攻 / (主査)教授 三芳 秀人, 教授 宮川 恒, 教授 森 直樹 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DGAM
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