Combination of Suzuki cross-coupling reaction and biocatalysis in one-pot cascade processes

Paris J. Combination of Suzuki cross-coupling reaction and biocatalysis in one-pot cascade processes. Bielefeld: Universität Bielefeld; 2019.Among several achievements realised throughout this research, the highlight is the use of Deep eutectic solvents for one-pot chemoenzymatic cascades. Amine transaminases and alcohol dehydrogenases displayed praiseworthy performances in these neoteric solvents for the synthesis of bulky chiral compounds. Besides the broadening of the substrate scope, a variety of of different enzymes has been tested for both cascade reactions. These results emphasize the value of nature’s biodiversity as an ever-increasing source of new genomes and metagenomes to identify unprecedented catalytic activities which can lead to novel robust biocatalysts. Furthermore medium engineering was demonstrated to be a valuable solution for the optimisation of chemical transformations and biocatalytic reactions with the possibility to overcome a set of hurdles and and reach improvement of the overall process

Electropolishing of laser powder bed-fused IN625 components in an ionic electrolyte

This work presents the first practical application of ionic electrolytes for electropolishing of nickel-based superalloys. It contains the results of an experiment-driven optimization of the applied potential and electrolyte temperature during electropolishing of laser powder bed-fused IN625 components containing surfaces oriented to the building platform under angles varying from 0 to 135°. For comparative purposes, the roughness profilometry and confocal microscopy techniques were used to characterize the surface finish topographies and the material removal rates of IN625 components subjected to electropolishing in ionic and acidic (reference) electrolytes. After 4 h of electropolishing in both electrolytes, a roughness of Ra ≤ 6.3 μm (ISO N9 grade number of roughness) was obtained for all the build orientations. To elaborate, both electrolytes manifested identical roughness evolutions with time on the 45° (75% Ra reduction) and 90°-oriented (65% Ra reduction) surfaces. Although the roughness reduction on the 135°-oriented surface in the ionic electrolyte was 17% less than in the acidic electrolyte, the former provided a more uniform roughness profile on the 0°-oriented surface (30% Ra reduction) and 44% higher current efficiency than the acidic electrolyte. This work proves that ionic electrolytes constitute a greener alternative to industrial acidic mixtures for electropolishing of three-dimensional (3D)-printed parts from nickel-based superalloys

Influence of additives on the electrodeposition of zinc from a deep eutectic solvent

The effects of nicotinic acid (NA), boric acid (BA) and benzoquinone (BQ) on the electrodeposition of Zn have been studied in a choline chloride (ChCl) ethylene glycol (EG) based deep eutectic solvent (DES), (1ChCl:2 EG), and for the first time a bright zinc coating has been achieved when NA was used. In metal electroplating processes, small-molecule additives are often included in the plating bath to improve properties of coating such as brightness, roughness, thickness, hardness and resistance to corrosion. The effects of additives on the electrodeposition of Zn from aqueous solution have been extensively investigated. However, very few studies have considered the effects of additives on the electrodeposition of Zn from ionic liquids or deep eutectic solvents. The electrochemical properties of the plating liquid have been studied here using cyclic voltammetry, chronocoulometry, chronoamperometry and microgravimetry (EQCM). Redox peak currents decrease when additives were included in the Zn solution and total charge was also reduced in experiments where additives were present. The Zn deposition in the absence of additive is in good agreement with an instantaneous growth mechanism at short experimental time scales (being indeterminate over longer periods), however, this changes to one of a progressive growth mechanism when additives were included in the coating bath. The current efficiency of zinc deposition in the DES without additives was 95%, which was reduced when additives were included. The resultant surface morphologies, thickness, topography, roughness and crystal structure of the Zn coating were revealed by scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray diffraction (XRD), demonstrating that those additives serve as effective brighteners that can produce highly uniform and smooth zinc deposits

Electrodeposition of Cu, Sn and Cu-Sn alloy from choline chloride ionic liquid

PhD ThesisCopper, tin and their alloy deposits are popular for its various applications in industrial aspects like enhance corrosion resistance and provide decorative finish. This work concentrated on the fabrication of these coatings, accomplished by electrodeposition technique which allows the control of thickness and microstructure of the films. Previously these metals and alloy were electrodeposited from different aqueous electrolytes. However these baths suffer from various environmental issues and deposits suffers from H evolution and metal oxide formation. As a result solution 2 ionic liquid (IL) was proposed as an alternative. ILs are categorized as salts liquid at room temperature and consist only of cations and anions. Presently Choline chloride based IL was used due to its advantages of low cost, low melting point, low toxicity, low viscosity and high conductivity than other ILs. Physical properties of the ILs like density, viscosity and conductivity were measured with variation of temperature and concentration of added metallic salts. To determine the electrochemical properties of individual metals and alloy, voltammetry scans were carried out using various scan rates and agitation rates. For all these measurements the concentration of Cu and Sn were varied in a range of 0.01 to 0.2 M and 0.01 to 0.1 M respectively at temperature range of 25 to 55 °C using a platinum rotating disk electrode (RDE). Deposition experiments were then carried out under potentiostatic and galvanostatic conditions using a stainless steel RDE. Material properties of the deposits like crystalline structure, grain size, strain, deposit morphology and chemical composition were analyzed using x-ray diffraction (XRD), optical microscope and scanning electron microscopy (SEM). The measurement showed that density and viscosity decreases and conductivity increases with rise in operation temperature for the electrolyte with and without metal ions. The reduction of both the metal was found to be mass transfer control and limiting current for metal deposition was found. The diffusion co-efficient -7 2 -7 2 obtained for Cu and Sn in the IL system was 1.22x10 cm /s and 1.96x10 cm /s -3 respectively. For individual metal Cu and Sn, best deposits were obtained at 4.7x10 2 -3 2 A/cm and 1.6x10 A/cm respectively using RDE speed of 700 rpm at 25 °C. The Cu deposit showed face centered cubic structure of 66±10 nm grain size and that of Sn was 62±10 nm with tetragonal crystalline structure. The smooth and bright Cu-Sn alloy deposit was obtained by applying potential in the range of 0.35 to 0.36 V vs. Ag wire or -3 2 0.8 to 0.9x10 A/cm of RDE speed is 220 rpm at 25 °C. The obtained deposits showed orthorhombic CuSn structure with a grain size of 21±10 nm. On annealing the 3 crystalline structure changed to hexagonal CuSn structure and the crystalline size 103 was obtained as 77±50 nm.NUPIS, ORSA

Reactivity of polar organometallic compounds in unconventional reaction media : challenges and opportunities

Developing new green solvents in designing chemical products and processes or successfully employing the already existing ones is one of the key subjects in green chemistry and is especially important in organometallic chemistry, which is an interdisciplinary field. Can we advantageously also use unconventional reaction media in place of current harsh organic solvents for polar organometallic compounds? This microreview critically analyses the state of the art with regard to this topic and showcases recent developments and breakthroughs that are becoming new research directions in this field. Because metals cover a vast swath of the Periodic Table the content is organised into three sections discussing the reactivity of organometallic compounds of s-, p- and d-block elements in unconventional solvents

Eletrosíntese de nanopartículas metálicas 1-D de DES usando modelos anódicos porosos

Doutoramento em Ciência e Engenharia de MateriaisO método de síntese de nanoparticulas 1-D assistido por um modelo tornou-se um tópico em voga na química após o desenvolvimento de filmes anódicos com poros bem ordenados. Contudo, a maioria dos trabalhos nesta área tem sido feita utilizando filmes porosos destacados devido à presença de uma barreira no fundo dos poros. No entanto, esta estratégia segue demasiados passos, o que aumenta o seu custo, torna mais difícil a execução e impõe várias limitações. Consequentemente, existe a necessidade de uma técnica que permita o enchimento (electrofilling) dos tubos sem remover a camada barreira – esta tese representa o nosso contributo para esse trabalho. Utilizámos uma técnica mais simples que permite a electrodeposição e “electrofilling” de nanoestruturas directamente nos modelos sobre o substrato metálico, utilizando solventes eutécticos profundos à base de cloreto de colina como electrólito. Relativamente à água, os solventes eutécticos profundos demonstram superior estabilidade térmica e uma janela electroquímica mais alargada, o que aumenta o número de materais secundários depositados. Como materiais a investigar foram escolhidos titânia e alumina dada a sua capacidade para formar estruturas porosas altamente ordenadas, propriedades eletroquímicas distintas e uso generalizado em síntese assistida por padrão. O estudo aqui apresentado encontra-se dividido em duas etapas. Primeiramente, a influência da camada barreira foi investigada em sistemas modelo através da utilização de filmes barreira densos na superfície dos elétrodos. Para os filmes de alumina e titânia, identificaram-se vários parâmetros que afectam a electrodeposição, dos quais se destacam a influência da voltagem de anodização, a espessura da camada de barreira, a dupla camada eléctrica e o perfil de corrente. Durante esta etapa detectaram-se efeitos nefastos, como a formação de uma densa camada orgânica na superfície do eléctrodo, que foram ultrapassados aumentando a temperatura ou alternando o potencial aplicado. A segunda etapa consistiu em passar de elétrodos planos (primeira etapa) para modelos porosos (segunda etapa). Foi realizado, com sucesso, o preenchimento dos poros de alumina e dos poros de titânia. Parâmetros como o perfil de corrente, temperatura de solução, entre outras, foram ajustadas para melhorar o fator de preenchimento e a homogeneidade do preenchimento. Foi desenvolvido um processo de preenchimento de moldes de alumina anódica em duas etapas, nucleação AC (1º passo) e preenchimento galvanostático (2º passo). Foram utilizadas três condições diferentes de modelos de titânia anódica porosa no “electrofilling”. O primeiro é sem modificação e demonstrou que a electroredução do zinco ocorre de forma aleatória ao longo de todo o comprimento do poro, o que leva ao fecho do poro e a um enchimento não homogéneo. A segunda modificação, cristalização total por têmpera, permite a preparação de estruturas coaxiais devido à deposição uniforme de zinco nas paredes dos poros. A última modificação foi a cristalização selectiva do fundo do poro. Foi descoberto que uma anodização adicional em eletrólitos não agressivos leva à cristalização da parte barreira dos tubos (fundo) e, consequentemente, a maior condutividade na parte inferior do que nas paredes. Este efeito permite um enchimento ascendente dos modelos porosos de titânia. As estratégias aqui apresentadas alargam a gama de possibilidades para a aplicação de modelos porosos anódicos na electrodeposição de diferentes nanoestruturas.The template assisted method of 1-D nanoparticles synthesis has become a hot topic in Chemistry after the development of high-ordered porous anodic films. Most studies in this field have focused on the use of detached porous films due to the presence of the barrier layer on the pore bottom. However, this strategy follows a great number of steps, which raises its cost while decreasing convenience of operation and imposing several limitations. Consequently, there is a need for a technique which allows electrofilling of tubes without removing the barrier layer – this thesis represents our contribution to that enterprise. We have devised a simpler technique which allows electrodeposition of nanostructures directly in the templates on metallic substrate, using choline chloride based deep eutectic solvents (DES) as electrolyte. Compared to water, DES have improved thermal stability and a wider electrochemical window, dramatically increasing the number of possible secondary materials deposited. Titania and alumina were chosen as materials under study due to their known capacity to form highly-ordered porous structures, different electrochemical profiles and widespread use in template assisted synthesis. The present work is divided in two parts. First, the influence of the barrier layer has been investigated by using dense barrier films on the electrode surface as a model system. For both alumina and titania films, several parameters affecting the electrodeposition of zinc have been identified, notably the influence of the anodization voltage, barrier layer thickness, electrical double layer and current profile. During this stage, some negative effects have been detected, such as a dense organic layer formation on electrode surface, a hurdle which has been overcome by either increasing the temperature or applying the alternating potential. The second stage consisted in transferring the method from the flat electrodes (the first stage) to the porous templates. The successful filling of both porous alumina and porous titania, has been achieved. Parameters such as current profile, solution temperature, among others, have been tuned to improve the fill factor and homogeneity of the filling. A two-step porous anodic alumina template filling with AC nucleation (1st step) and galvanostatic filling (2nd step) has been developed. Three different types of porous anodic titania templates have been used for electrofilling. The first one was used as-prepared, showing that zinc electroreduction occurs in random places along all pore length, resulting in pore sealing and non-homogeneous filling. The second modification, full crystallization by annealing, allows the preparation of coaxial structures due to uniform zinc deposition on the pore walls. The last modification is selective bottom crystallization. It has been found that additional anodization in unaggressive electrolytes leads to crystallization of the barrier (bottom) part of the tubes and, thus, to higher conductivity of the bottom part than that of the walls. This effect allows a bottom-up filling of the titania porous template. The strategies presented here widen the range of possibilities for the application of porous anodic templates in the electrodeposition of different nanostructures

Novel polymeric and oligomeric materials for organic electronic devices

Die enormen Fortschritte im Bereich der organischen Elektronik in den letzten Jahrzehnten haben zur Entwicklung effizienter optoelektronischer Bauelemente geführt wie z. B. organische Leuchtdioden (OLEDs), organische Feldeffekttransistoren (OFETs) und organische Photovoltaikzellen (OPV). Darüber hinaus ermöglichen halbleitende Polymere die Herstellung kostengünstiger, großflächiger elektronischer Bauelemente mit Hilfe von Niedertemperatur Lösungsverfahren auf flexiblen Substraten. Der erste Teil dieser Arbeit befasste sich mit der Entwicklung von Host-Materialien für die emittierende Schicht (EML) von OLEDs. Effiziente Host-Materialien sollten bestimmte Eigenschaften aufweisen, z. B. eine hohe Triplett-Energie, einen hohen und ausgeglichenen Ladungsträgertransport, geeignete Grenzorbitalniveaus, die mit denen der Nachbarschichten übereinstimmen, und morphologische Stabilität. Zu diesem Zweck wurden Polymere auf Carbazolbasis mit einer elektronenziehenden Gruppe (EWG) an verschiedenen Stellen der Kette entworfen und durch Suzuki Kupplung synthetisiert. Die Polymere wurden chemisch und optisch charakterisiert, bevor sie nach Dotierung mit Tris(2-phenylpyridin)iridium(III) (Ir(ppy)3) in eine funktionierende grüne OLED eingebaut wurden. Zusätzlich wurden die Ladungstransporteigenschaften durch die Herstellung von Einzelträgergeräte untersucht. Der zweite Teil widmete sich der Herstellung von Halbleitermaterialien für OFET Anwendungen. Nach einem neuartigen Moleküldesign wurde eine Reihe von Verbindungen auf der Basis von Diketopyrrolopyrrol (DPP) und Thiophen durch Stille-Kupplung und phosphinfreie direkte Heteroarylierung synthetisiert. Dieses molekulare Design erwies sich als flexibel für die Synthese neuartiger Derivate durch Modifikation der Endgruppen. Die Korrelation zwischen Struktur und Morphologie wurde ebenfalls untersucht. Die Mobilität der Ladungsträger, welche von der chemischen Struktur und Morphologie des Halbleiters beeinflusst wird, ist einer der wichtigsten Parameter eines OFET. Daher wurden die erhaltenen Materialien mit niedriger Bandlücke in Transistoren verschiedener Architekturen integriert, die durch Lösungsverfahren wie Spin-Coating und Scherbeschichtung hergestellt wurden. Die Mobilität sowie andere OFET-Parameter wurden im p- und n-Typ-Betrieb gemessen.:1 Theoretical background 1.1 Introduction 1.2 Organic semiconductors 1.3 Organic Light Emitting Diodes 1.3.1 Physics of OLEDs 1.3.2 Solution processable OLEDs 1.3.3 Polymer Light-Emitting Diodes 1.4 Organic Field-Effect Transistors 1.4.1 Device operation 1.4.2 Ambipolar transistors 1.5 Synthesis of π-conjugated polymers 1.6 Characterisation methods 1.6.1 Chemical structure characterisation 1.6.2 Optical characterisation 1.6.3 Morphology and microstructure 2 Motivation and aim 3 Results and discussion 3.1 Polymers for ambipolar semiconductors 3.1.1 Molecular design 3.1.2 (N-carbazole)triphenylphosphine oxide polymers 3.1.3 Bis(carbazol-3-yl)triphenylphosphine oxide polymers 3.1.4 ((Carbazol-3-yl)phenoxy)hexyl diphenylphosphinate polymers 3.1.5 ((Phenothiazin-10-yl)phenyl)diphenylphosphine oxide polymers 3.1.6 Device integration 3.1.7 Summary 3.2 DPP based molecules for OFETs 3.2.1 Molecular design 3.2.2 DBT-I series 3.2.3 DBT-II 3.2.4 Device integration 3.2.5 Summary 4 Conclusions and outlook 5 Experimental part 6 Supporting Information 7 BibliographyStaggering progress in the field of organic electronics over the past decades has led to the development of efficient optoelectronic devices, such as organic light-emitting diodes (OLEDs), organic field-effect transistors (OFETs)and organic photovoltaic cells (OPV). Moreover, semiconducting polymers enable the fabrication of low-cost, large-area electronic devices using low-temperature solution-processing methodologies on flexible substrates. The first part of this thesis focused on the development of host materials for the emitting layer (EML) of an OLED. Efficient hosts should possess a number of properties, such as high triplet energy, good and balanced charge-carrier transport, suitable frontier orbital levels that match those of the neighbouring layers, and morphological stability. To this end, carbazole-based polymers featuring an electron-withdrawing group (EWG) at different positions of the chain were designed and synthesised by Suzuki coupling. Chemical and optical characterisations of the polymers were performed prior to their incorporation into a functioning green OLED upon doping with tris(2-phenylpyridine)iridium(III) (Ir(ppy)3). Additionally, the charge-transport properties were studied through the fabrication of single-carrier devices. The second part was dedicated to the production of semiconductor materials for OFET applications. Following a novel molecular design, a series of compounds based on diketopyrrolopyrrole (DPP) and thiophene were synthesised by Stille coupling and phosphine-free direct heteroarylation. This molecular design was proven to be flexible for the synthesis of novel derivatives by modification of the end-groups. The correlation between structure and morphology was also studied. Mobility, influenced by the chemical structure and morphology of the semiconductor, is one of the most important parameters of an OFET. Thus, the obtained low bandgap materials were integrated into devices of different architectures, fabricated by solution processing methodologies, such as spin coating and shear coating, and the mobility, as well as other OFET parameters, were measured in p- and n-type operation.:1 Theoretical background 1.1 Introduction 1.2 Organic semiconductors 1.3 Organic Light Emitting Diodes 1.3.1 Physics of OLEDs 1.3.2 Solution processable OLEDs 1.3.3 Polymer Light-Emitting Diodes 1.4 Organic Field-Effect Transistors 1.4.1 Device operation 1.4.2 Ambipolar transistors 1.5 Synthesis of π-conjugated polymers 1.6 Characterisation methods 1.6.1 Chemical structure characterisation 1.6.2 Optical characterisation 1.6.3 Morphology and microstructure 2 Motivation and aim 3 Results and discussion 3.1 Polymers for ambipolar semiconductors 3.1.1 Molecular design 3.1.2 (N-carbazole)triphenylphosphine oxide polymers 3.1.3 Bis(carbazol-3-yl)triphenylphosphine oxide polymers 3.1.4 ((Carbazol-3-yl)phenoxy)hexyl diphenylphosphinate polymers 3.1.5 ((Phenothiazin-10-yl)phenyl)diphenylphosphine oxide polymers 3.1.6 Device integration 3.1.7 Summary 3.2 DPP based molecules for OFETs 3.2.1 Molecular design 3.2.2 DBT-I series 3.2.3 DBT-II 3.2.4 Device integration 3.2.5 Summary 4 Conclusions and outlook 5 Experimental part 6 Supporting Information 7 Bibliograph

Electrodepósito de nanopartículas bimetálicas (Paladio–Níquel y Paladio–Cobalto), utilizando disolventes eutécticos profundos, como centros catalíticos en la electro–oxidación de ácido fórmico

203 páginas. Doctorado en Ciencias e Ingeniería de Materiales.El presente estudio está enfocado en la síntesis y caracterización de nanopartículas (NPs) bimetálicas (Pd–Ni y Pd–Co) como aleación usando disolventes eutécticos profundos (DEP) formados a base de cloruro de colina con urea (reline) o etilenglicol (ethaline), y su evaluación en la reacción de oxidación electroquímica de ácido fórmico (ROAF). Estos DEP son mezclas eutécticas de un ácido y una base de Lewis que contienen especies catiónicas y aniónicas, también denominados disolventes verdes. Tanto el reline como el ethaline han sido utilizados en electroquímica, como medio para la electrodeposición de NPs, a causa de sus excelentes propiedades, tales como: bajo costo, biodegradabilidad, conductividad eléctrica alta, casi nula presencia de protones y agua. Hay que mencionar, además su excelente capacidad para solvatar iones metálicos, permitiendo con ello la síntesis de aleaciones binarias y ternarias, con control en morfologías y tamaños. Las sales precursoras de Pd, Ni y Co se disolvieron en cada DEP para estudiar mediante técnicas electroquímicas, como: Voltamperometría Cíclica (VC) y Cronoamperometría (CA) la cinética de nucleación y crecimiento de las NPs sobre el electrodo de carbono vítreo. El electrodo modificado con las NPs bimetálicas (NPs-BM) fue empleado para ROAF, la cual es una reacción clave en las celdas de combustible de ácido fórmico directo. Los electrodepósitos fueron caracterizados por Microscopia Electrónica de Barrido (SEM), Espectroscopía de Energía Dispersiva de Rayos X (EDX) y Espectroscopía de Fotoelectrones de Rayos X (XPS) para determinar diámetros, composición, morfología y estados de oxidación de elementos que integran a las NPs-BM.The present study focuses on the synthesis and characterization of bimetallic nanoparticles (NPs) (Pd-Ni and Pd-Co) as an alloy using deep eutectic solvents (DES’s) formed from choline chloride and urea (reline) or ethylene glycol (ethaline) and choline chloride), and their evaluation in the electrochemical formic acid (FAOR) oxidation reaction. These DES are eutectic mixtures of a Lewis acid and a Lewis base containing cationic and anionic species, also called green solvents. Both reline and ethaline have been increasingly used in electrochemistry, as a medium for the electrodeposition of NPs, due to their excellent properties, such as: low cost, biodegradability, high electrical conductivity, almost no presence of protons and water. It is also worth underlining their excellent ability to solvate metal ions, thus allowing the synthesis of binary and ternary alloys, with control over morphologies and sizes. The precursor salts of Pd, Ni and Co were dissolved in each DES to study through electrochemical techniques, such as: Cyclic Voltammetry (VC) and Chronoamperometry (CA) the nucleation and growth kinetics of the NPs on the glassy carbon electrode. The modified electrode with the bimetallic NPs (NPs-BM) was used forFAO R, which is a key reaction in direct formic acid fuel cells. Electrodeposits were characterized by Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Spectroscopy (EDX) and X-ray Photoelectron Spectroscopy (XPS) to determine diameters, composition, morphology, and oxidation states of elements that make up the deposits bimetallic NPs.Investigación realizada con el apoyo del Programa Nacional de Posgrados de Calidad del Consejo Nacional de Ciencia y Tecnología (CONACYT)

Kinetic studies on the solvolyses of alkyl halides in the presence of added nucleophiles

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On Modeling, Analysis and Nonlinear Control of Hydraulic Systems

Mit der vorliegenden Arbeit werden Untersuchungen zur Modellbildung, Stabilität und nichtlinearen Regelung hydraulischer Systeme vorgelegt. Ein neues Minimalmodell einer verstellbaren Flügelzellenpumpe wird auf Basis kinematischer und physikalischer Zusammenhänge in der Pumpe abgeleitet und auf Stabilität in einem druckgeregelten Kreislauf untersucht. Darauf aufbauend erfolgt die Diskussion nichtlinearer Regelungskonzepte für die Regelung des Volumenstroms der Pumpe. Dabei werden auch Fragen des Beobachterentwurfs sowie der Mehrgrößenregelung adressiert