Tesis sobre el tema "Amine solvents"

An introduction and overview of the work is given in Chapter 1. In Chapter 2, a description of the equipment and the kinetics modelling used in this thesis is explained in detail. Chapter 3 includes an overview of traditional solvents and shows the kinetics and mass transfer results of the absorption of CO2 in amine solvents. Chapter 4 starts with a literature review on organic solvents and hybrid solutions (organic-amine aqueous solutions) and includes the mass transfer and kinetic results of the absorption of CO2 in selected hybrid solvents containing amines. Chapters 3 and 4 sum up the 11 solutions tested for the absorption of CO2 and include their physical characterization (density, viscosity and N2O solubility), at unloaded and loaded conditions and from 298 to 353K. Chapter 5 is focused on the thermodynamic modelling of new amine solvents in ASPEN PLUS and Chapter 6 includes the modelling at pilot plant scale of absorber and desorber. Every chapter includes conclusions and final remarks are given at the end of this thesis. Chapter 7 presents the conclusions of the whole thesis and recommendations for future work.

Thesis (Ph.D)--Chemical Engineering, Georgia Institute of Technology, 2010.
Committee Chair: Charles Eckert; Committee Co-Chair: Charles Liotta; Committee Member: Amyn Teja; Committee Member: Christopher Jones; Committee Member: William Koros. Part of the SMARTech Electronic Thesis and Dissertation Collection.

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This study describes the development of an analytical methodology for the separation of quaternary amines using nonaqueous electrophoresis microchips coupled with capacitively coupled contactless conductivity detection (C4D). Initially, preliminary experiments were performed to evaluate two electrokinetic modes for sample introduction on chip, known as gated and floating approaches. Gated injection showed repeatability slightly better than floating mode. In addition, it also provided better analytical responses on the C4D system. During the development of analytical methodology for NAME-C4D, the electrolyte composition was optimized to ensure satisfactory separations on electrophoresis microchips. The electrolyte composed of sodium deoxycholate (NaDCHA) at concentration of 10 mmol/L dissolved in a mixture of MeOH/ACN at the ratio 90:10 (v/v) exhibited separations with high efficiency and resolution above 1. Then, it was realized the optimization of potential injection, separation and detection parameters (frequency and amplitude). Running electrolyte was prepared in both DMSO and DMF, however, the use of a mixture containing MeOH/ACN provided best analytical performance. The best results were obtained with electrolyte containing 10% ACN and 90% MeOH. In addition, different electrolyte compositions were also evaluated, but the electrolyte containing NaDCHA offered results slightly better when compared to others. The optimization of running buffer allowed the separation of nine quaternary amines in electrophoresis channels with effective length of 7.0 cm with analysis time lower than 120 s. The peak resolution was higher than 1 and the calculated separation efficiencies ranged from 77.000 to 185.000 pratos/m. This excellent performance was achieved using NAME conditions under high electric fields. The developed methodology was used for the analysis of quaternary amines in samples containing high salinity levels through the standard addition method. Linear correlation coefficients were obtained up to 0,990 for eight quaternary amines. Lastly, the use of NAME-C4D allowed to observe a strong dependence of the detector response according to the carbon number of quaternary amine molecules.
O presente trabalho descreve o desenvolvimento de uma metodologia analítica para separação de aminas quaternárias utilizando eletroforese não aquosa em microchips (NAME, do inglês non-aqueous microchip electrophoresis) com detecção condutométrica sem contato acoplada capacitivamente (C4D, do inglês capacitively coupled contactless conductivity detection). Inicialmente foi realizado um estudo para avaliação de dois modos de introdução da amostra nos microchips, denominados de gated e floating. O modo gated apresentou repetitividade ligeiramente melhor que o modo floating, além de proporcionar melhores respostas do detector C4D. No desenvolvimento da metodologia utilizando NAME-C4D, foi realizado um estudo para encontrar a composição ideal do eletrólito para as separações eletroforéticas. O eletrólito constituído de deoxicolato de sódio (NaDCHA), na concentração de 10 mmol/L, dissolvido em uma mistura de MeOH/ACN na proporção 90:10 (v/v), apresentou separações com alta eficiência e resolução superior a 1. A partir de então, foi realizada a otimização dos potenciais de injeção, separação e dos parâmetros de detecção (frequência e amplitude). Durante o desenvolvimento da metodologia, foram avaliados eletrólitos preparados em outros dois solventes, DMSO e DMF. Porém, a mistura de MeOH/ACN como solvente forneceu os melhores resultados, desta maneira também foi avaliada a adição de diferentes proporções de MeOH/ACN. Os melhores resultados foram obtidos com o eletrólito contendo 10% de ACN e 90% de MeOH. Na sequência, foram avaliadas diferentes composições do eletrólito, com a adição de outros compostos em substituição ao NaDCHA. Todos os eletrólitos avaliados apresentaram ótimas separações, porém o eletrólito com NaDCHA apresentou resultados ligeiramente superiores. Com a otimização da metodologia desenvolvida, obteve-se separações eletroforéticas de nove aminas quaternárias em microssistema contendo comprimento efetivo de 7,0 cm, com um tempo de análise inferior a 120 s. As separações apresentaram resolução superior a 1 e valores de eficiência entre 77,000 e 185,000 pratos/m, uma vez que com a utilização de solventes orgânicos, foi possível a aplicação de campos elétricos elevados. A metodologia desenvolvida foi avaliada através da determinação das aminas quaternárias, pelo método de adição de padrão, em uma matriz com elevada salinidade. Foram obtidos coeficientes de correlação lineares acima de 0,990 para oito aminas quaternárias. Durante o desenvolvimento do trabalho, foi observada uma clara dependência das respostas analítica em função da quantidade de carbono da molécula.

Thesis (Ph.D.)--Tufts University, 2004.
Adviser: Krishna Kumar. Submitted to the Dept. of Chemistry. Includes bibliographical references (leaves 190-197). Access restricted to members of the Tufts University community. Also available via the World Wide Web;

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A combinação de diferentes tipos de materiais para obtenção de novas propriedades tem despertado grande interesse em vários campos da ciência de materiais. Em processos de separação, é de considerável interesse o uso de materiais com propriedades básicas extremamente diferentes. Entre os suportes mais usados está a sílica gel, um material com tamanho de partículas e porosidade bem definidas, elevada área superficial, e estabilidades mecânica, química e térmica elevadas. Neste contexto, a sílica gel modificada com grupos organofuncionais pode ser utilizada para a adsorção de íons metálicos em soluções aquosas e não aquosas, pré-concentração e separação de íons metálicos. Neste trabalho, a sílica gel 60 (Merck), com tamanho de partículas entre 0,2 e 0,05 mm e área superficial específica de 486 m2.g-1, foi quimicamente modificada em duas etapas. Primeiro, a sílica gel foi quimicamente modificada com 3-cloropropiltrimetoxisilano, resultando o 3-cloropropil sílica gel (CPSG). Na segunda etapa, o produto resultante, CPSG, reagiu com 2-mercaptopirimidina e 4-amino-2-mercaptopirimidina, resultando os materiais sólidos 2-mercaptopirimidina-propil sílica gel (MPSG) e 4-amino-2-mercaptopirimidinapropil sílica gel (AMSG). As quantidades de grupos funcionais conectados na superfície da sílica gel, N0, foram 7,007 x 10-4 mols e 7,416 x 10-4 mols de moléculas por grama de sílica, para MPSG e AMSG, respectivamente. Conhecendo a área superficial específica e assumindo que as moléculas cobrem uniformemente a superfície, a densidade média, d, das moléculas ancoradas e a distância intermolecular média, l, podem ser calculadas aplicando as equações d = N0 N/SBET e l = (l/d) 1/2 , onde N é o número de Avogadro. Os valores calculados são d = 1,42 moléculas.nm2 e l = 0,979 nm, e d = 1,166 moléculas.nm2 e l = 0,926 nm, para MPSG e... .
The combination of different type of materials for achieving novel properties has always been of high interest in many fields of the materials sciences. The use of materials with extremely different basic properties, like organic and inorganic compounds, is of considerable interest in separation processes. Among the supports the most used is silica gel, a material of well-established particle sizes and well-define porosity, high surface area, and high mechanical, chemical, and thermal stability. In this context, silica gel modified with organofunctional groups has been used for adsorption of metal ions from aqueous and non-aqueous solutions, pre-concentration and separation of metallic ions. In this work, silica gel 60 (Merck) having secondary particles sized between 0,2 and 0,05 mm and specific surface area of 486 m2.g-1 was modified using a two step approach. First, the silica gel was chemically modified with 3- chloropropyltrimetoxysilane, resulting the 3-chloropropyl-silica gel (CPSG). Second, the resultant product, CPSG, reacted with 2-mercaptopyrimidine and 4-amino-2- mercaptopyrimidine, resulting the solid materials 2-mercaptopyrimidine-propyl-silica gel (MPSG) and 4-amino-2-mercaptopyrimidine-propyl-silica gel (AMSG). The quantities of functional groups attached on the silica gel surface, No, were 7,007 x 10-4 mols e 7,416 x 10-4 mols .g-1 of molecules per gram of silica, for MPSG and AMSG, respectively. It being known the specific surface area and assuming that the molecules uniformly cover the surface, the average density, d, of the attached molecules and the average intermolecular distance, l, can be calculated by applying the equations: d = N0 N /SBET and l = (l/d)1/2, where N is Avogadro's number. The calculated values were d = 1,042 molecules.nm-2 and l = 0,979 nm and d = 1,166 molecules.nm-2 and... (Complete abstract click electronic address below).

Orientador: Newton Luiz Dias Filho
Banca: Andre Henrique Rosa
Banca: Wagner Luís Polito
Resumo: A combinação de diferentes tipos de materiais para obtenção de novas propriedades tem despertado grande interesse em vários campos da ciência de materiais. Em processos de separação, é de considerável interesse o uso de materiais com propriedades básicas extremamente diferentes. Entre os suportes mais usados está a sílica gel, um material com tamanho de partículas e porosidade bem definidas, elevada área superficial, e estabilidades mecânica, química e térmica elevadas. Neste contexto, a sílica gel modificada com grupos organofuncionais pode ser utilizada para a adsorção de íons metálicos em soluções aquosas e não aquosas, pré-concentração e separação de íons metálicos. Neste trabalho, a sílica gel 60 (Merck), com tamanho de partículas entre 0,2 e 0,05 mm e área superficial específica de 486 m2.g-1, foi quimicamente modificada em duas etapas. Primeiro, a sílica gel foi quimicamente modificada com 3-cloropropiltrimetoxisilano, resultando o 3-cloropropil sílica gel (CPSG). Na segunda etapa, o produto resultante, CPSG, reagiu com 2-mercaptopirimidina e 4-amino-2-mercaptopirimidina, resultando os materiais sólidos 2-mercaptopirimidina-propil sílica gel (MPSG) e 4-amino-2-mercaptopirimidinapropil sílica gel (AMSG). As quantidades de grupos funcionais conectados na superfície da sílica gel, N0, foram 7,007 x 10-4 mols e 7,416 x 10-4 mols de moléculas por grama de sílica, para MPSG e AMSG, respectivamente. Conhecendo a área superficial específica e assumindo que as moléculas cobrem uniformemente a superfície, a densidade média, d, das moléculas ancoradas e a distância intermolecular média, l, podem ser calculadas aplicando as equações d = N0 N/SBET e l = (l/d) 1/2 , onde N é o número de Avogadro. Os valores calculados são d = 1,42 moléculas.nm2 e l = 0,979 nm, e d = 1,166 moléculas.nm2 e l = 0,926 nm, para MPSG e... (Resumo completo, clicar acesso eletrônico abaixo).
Abstract: The combination of different type of materials for achieving novel properties has always been of high interest in many fields of the materials sciences. The use of materials with extremely different basic properties, like organic and inorganic compounds, is of considerable interest in separation processes. Among the supports the most used is silica gel, a material of well-established particle sizes and well-define porosity, high surface area, and high mechanical, chemical, and thermal stability. In this context, silica gel modified with organofunctional groups has been used for adsorption of metal ions from aqueous and non-aqueous solutions, pre-concentration and separation of metallic ions. In this work, silica gel 60 (Merck) having secondary particles sized between 0,2 and 0,05 mm and specific surface area of 486 m2.g-1 was modified using a two step approach. First, the silica gel was chemically modified with 3- chloropropyltrimetoxysilane, resulting the 3-chloropropyl-silica gel (CPSG). Second, the resultant product, CPSG, reacted with 2-mercaptopyrimidine and 4-amino-2- mercaptopyrimidine, resulting the solid materials 2-mercaptopyrimidine-propyl-silica gel (MPSG) and 4-amino-2-mercaptopyrimidine-propyl-silica gel (AMSG). The quantities of functional groups attached on the silica gel surface, No, were 7,007 x 10-4 mols e 7,416 x 10-4 mols .g-1 of molecules per gram of silica, for MPSG and AMSG, respectively. It being known the specific surface area and assuming that the molecules uniformly cover the surface, the average density, d, of the attached molecules and the average intermolecular distance, l, can be calculated by applying the equations: d = N0 N /SBET and l = (l/d)1/2, where N is Avogadro's number. The calculated values were d = 1,042 molecules.nm-2 and l = 0,979 nm and d = 1,166 molecules.nm-2 and... (Complete abstract click electronic address below).
Mestre

The research addressed in this thesis is focused on the solubility and pseudo-polymorphic transition of L-serine in mixed water-methanol systems. Cooling re-crystallizations were carried out that varied both temperature and methanol concentration. Solubilities were measured with high-performance liquid chromatography. It is found that the solubility increased with increase in temperature and decreased drastically with methanol concentration. The effect of temperature at which there is a transition of L-serine crystals from the rod-shaped (anhydrous) form to hexagonal (monohydrate) form was confirmed and that transition temperatures decreased with methanol concentrations in a non-linear manner. The solubility data were correlated and plotted using the vant Hoff equation and the enthalpy and entropy of dissolution were determined. These values increased with increase in methanol concentration. The solid crystals were analyzed by optical microscopy and powder X-ray diffraction. The rod-shaped crystals were identified to be anhydrous L-serine, while the hexagonal crystals were L-serine monohydrate. Dehydration of the monohydrated crystals in their solid-state was examined and the onset of such phenomenon was known to start once the crystals were removed from the solutions.

This project was undertaken to gain a better understanding of the hydration behaviors of gas phase ions from solutions containing amino acids and peptides. In order to characterize their hydration behavior, the molecules of interest in solutions were first converted into gas phase ions by electrospray ionization (ESI). The completely desolvated ions were then deliberately dispersed into an inert bath gas, usually nitrogen, containing accurately known concentrations of solvent vapor. The resulting mixtures of ions and bath gas were subsequently passed into a vacuum chamber by way of an adiabatic supersonic free jet expansion. The cooling during that expansion caused solvation of the ions, the extent of which was determined by a quadrupole mass analyzer. Mass analysis of the solute ions in the absence of vapor showed peaks with the mass to charge ratios corresponding to the desolvated ions. On the other hand, mass spectrometric analyses of ions in the presence of solvent vapor showed sequences of peaks corresponding to the solvated ions with varying numbers of water molecules. The extent of the ion solvation was controlled by varying the concentration of solvent vapor in the bath gas. Two different scales were proposed for the evaluation of the relative affinities of amino acids for water molecules. One was based primarily on the assumption that the affinities of amino acids for water molecules are directly proportional to their gas phase solvation rate constants (k). An alternative approach produced an affinity scale based on the extent of ion hydration occurred during the free jet expansion. It was found that the addition of a polar solvent vapor to the bath gas at low concentrations substantially enhanced the production of the bare solute ions from the evaporating charged droplets. This remarkable result not only provided a means to increase the ion production and thus detection sensitivity of mass spectrometric analyses, but also yielded important information regarding the ion formation mechanism of ESI. Additional studies revealed that the extent of the increase in ion yield was directly related to the charge state and molecular weight of the solute ions. In sum, this evidence strongly indicated that gas phase ions produced from charged droplets, as in electrospray ionization, must proceed by the sequence of events assumed in the Ion Evaporation Model proposed by Iribarne and Thomson rather than in the Charged Residue Model originally proposed by Malcolm Dole and coworkers. The hydration behaviors of electrospray ions from peptides with similar primary amino acid sequences and capable of forming ions with more than one charge state were also investigated. In a study with dipeptides, the extent of hydration was found to vary widely and to depend not only on the chemical composition of the ions but also on their configurations and charge states. The results obtained with lysine oligomers clearly indicated that the number of charges on an ion played an important role in the solvation process. An exception to this generalization was found in an experiment with multiply protonated pentalysine ions. For example, the quadruply protonated monomers of that species were found to undergo charge reduction via proton exchange with the surrounding water molecules in such a way as to maximize the distance between charges on the molecule, thereby reducing the internal repulsive forces.The hydration study of angiotensin II and III showed that while the former has an additional hydrophilic amino acid on the N-terminus, the latter peptide was more hydrophilic. This result suggests that the hydrophilicities of peptides are not a simple sum of the hydrophilicities of the individual amino acid components. As further evidence of interaction complexity, the Magic Number Clusters containing 21 water molecules were obtained with the doubly protonated angiotensin III, but not with the doubly protonated angiotensin II. Taken together, these observations seem to indicate that the multiply charged ions of angiotensin II and III had different structural conformations.

MCM-41 anchored n-propylamine (MCM-41-nPrNH2) was found to be a highly efficient and recoverable nanocatalyst for the synthesis of new class of phenylpyrido[4,3-d]pyrimidin-2-amine derivatives under solvent free conditions in high to quantitative yields. All the structures of title compounds 3a-j were elucidated by comprehensive 1H NMR, 13C NMR, IR and Mass spectra When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/35002

The necessity of reprocessing spent nuclear fuel has arisen from increasing awareness and concern for the environment, in addition to the potential of minimising proliferation. A number of different reprocessing techniques are currently being developed around the world to allow useful spent nuclear fuel (SNF) to be recycled and reused and the remaining waste to be treated. One such technique, currently being developed in the USA is the TALSPEAK process, an advanced reprocessing method for the separation of trivalent lanthanide (Ln3+) and minor actinide (MA3+) components. This process, developed in the 1960s at Oak Ridge National Laboratory, uses DTPA to act as a holdback reagent for MA3+, in a lactate buffered aqueous phase at pH 3.6, allowing Ln3+ to be selectively extracted by organophosphate HDEHP into an organic phase of DIPB or dodecane. TALSPEAK is one of the most promising techniques being researched due to its numerous advantages, particularly its relative resistance to radiolysis and its ability to be carried out without the need for high reagent concentrations. Additionally it gives high separation factors, in the region of ~50-100, comparable to other advanced reprocessing methods under development. The chemistry of the process is very complex and not particularly well understood so it would be advantageous to simplify the process by removing the need for a separate holdback reagent and buffer. In collaboration with colleagues at the Idaho National Lab, the use of amino acids as a potential combined buffer and soft donor was investigated. Although it was found that amino acids do not act as holdback reagents in their own right, optimisation of an L-alanine buffered TALSPEAK system with DTPA was found to allow the process to be carried out effectively at a lower pH of 2, which is more preferable for industrial application. As an extension of this, separation studies were carried out using the tripeptide L-glutathione (GSH) to determine its potential for use as a combined buffer and soft-donor. As with the studies with amino acids, it was found that GSH also does not act as a holdback reagent in its own right, however it does interact with Ln-DTPA complexes at pH 4. When optimised at this pH, separation factors of up to 1200 were achieved for Eu3+/Am3+, whilst still maintaining low MA3+ partitioning. However, further studies by ICP-MS and luminescence spectroscopy showed that a GSH buffered system was not effective for extraction of heavier lanthanides, although the results show the potential for further investigation into other short and longer chain peptide buffered systems and possibly lanthanide-lanthanide separations. Further studies were carried on amino acid appended DTPA ligands which were synthesised in a one step reaction in order to create a combined buffer and soft donor. The ligands were found to self-buffer at around pH 2 and allow successful separation of Eu3+/Am3+ (SF ~ 100). The results from initial investigations by luminescence spectroscopy and solvent extraction are promising and are presented here. Further work is needed on these systems in order to optimise their extraction capability and minimise Am3+ partitioning. In the future this work could promote studies for better understanding of TALSPEAK chemistry that could be used in industrial partitioning processes.

This project divides into two halves: the synthesis, purification and characterisation of numerous ionic liquids including amino acid based chiral ionic liquids and polarity studies, which have been undertaken to further the understanding and quantification ofthe solvent-solute interactions by use of Kalmet-Taft measurements. In the early 1980s, the introduction of cleaner technologies to eliminate or significantly reduce hazardous waste generation became a major concern. In particular, a high priority to find alternatives to volatile organic compounds (VOC's), which were found to be very damaging solvents, was realised. Ionic liquids (IL's) remained a curiosity until recently, when the chemists discovered that it was possible to replace the VOC's with IL's and in some cases, the reactions were much improved. Since then, the field of IL's has exploded, which led to a vast increase in the number of publications and in the number of groups throughout the world who have started to work in the field. This project has reviewed some of the synthesis, purification and characterisation of chiral amino acid ILs and improved upon these procedures. The second halfofthe project involved investigating the overall solvating ability some of these purified IL's to obtain a better understanding ofhow these solvents may affect a reaction. This ability is not dependant on one particular physical measurement of the solvent, but is rather a sum ofall the specific and non-specific interactions that might occur between a solvent and solute. A large number of interactions are involved; these could include columbic, directional, inductive, dispersion, hydrogen-bonding, and electron pair donor/acceptor forces. The polarity ofthe IL's and mixtures of ILs with water or dichloromethane were investigated using UV dyes.

In dieser Dissertation wird ein Prozess für die absorptive CO2-Abtrennung aus Gasströmen vorgestellt, der durch die Nutzung des neu entwickelten Waschmittels GenosorbN in einem Postcombustion-Prozess einen geringeren Energiebedarf als bisher bekannte Verfahren aufweist. Für die Nachrüstung bereits vorhandener Kraftwerke ist der Postcombustion-Prozess vorteilhaft, da er im Vergleich zum IGCC- oder dem Oxyfuel-Verfahren die geringsten Änderungen im Kraftwerksprozess selbst erfordert. Die bisher für die CO2-Abtrennung diskutierten Absorptionsmittel, wie z. B. MEA (Mono-Ethanol-Amin), haben allerdings vor allem in der Regeneration einen sehr hohen Energiebedarf, der vom Kraftwerk zusätzlich zur Verfügung gestellt werden muss. In Zusammenarbeit zwischen dem Institut für Verfahrenstechnik und Umwelttechnik der TU Dresden und der Clariant GmbH wurde das Absorptionsmittel GenosorbN (chemische Bezeichnung: Poly(methyldiglykol)amin) entwickelt. GenosorbN weist als Hybrid-Waschmittel gegenüber CO2 sowohl physikalische als auch chemische Bindungseigenschaften auf. Ausgehend von der Löslichkeitscharakteristik dieses Absorptionsmittels für CO2 und wichtigen Stoffwerten (z. B. Wärmekapazität und Lösungswärme von CO2) wurden mit Hilfe eines umfangreichen Versuchsprogramms an einer Technikumsanlage Betriebsparameter für einen energetisch günstigen technischen Einsatz ermittelt. Dabei hat sich herausgestellt, dass der Absorptionsprozess mit unverdünntem GenosorbN gegenüber einer MEA-Wäsche bei einem CO2-Abscheidegrad von ca. 90 % einen um ca. 20 - 27 % geringeren Energiebedarf in der Waschmittelregeneration aufweisen kann. Außerdem ist für die Desorption ein energetisch minderwertiger Heizdampf mit geringerem Temperatur- bzw. Druckniveau als bei dem MEA-Prozess ausreichend, da die Regenerationstemperatur um 40 - 50 K niedriger ist. Eine zusätzliche Druckabsenkung auf 400 mbar Absolutdruck im Desorber begünstigt die Regeneration deutlich
This dissertation presents a process for the absorptive CO2-separation from gas streams, which shows a lower energy requirement than established methods by using the newly developed absorption liquid GenosorbN in a postcombustion-process. To retrofit an already existing power plant, the postcombustion-process is advantageous, because it needs the least changes in the power plant-process itself compared to the IGCC- or the Oxyfuel-process. The absorbents discussed for the CO2-separation up to now, for example MEA (mono-ethanol-amine), cause a high energy requirement mainly in the solvent regeneration, which has to be provided additionally from the power plant. The solvent GenosorbN (chemical notation: poly(methyldiglycol)amine) was developed in cooperation between the Institute of Process Engineering and Environmental Engineering of the Technical University of Dresden and the Clariant GmbH. GenosorbN is a hybrid-absorbent and therefore it shows both physical and chemical bonding forces. Based on the solvents characteristic of solubility for CO2 and important data on chemical media (for example heat capacity and enthalpy of solution) operating parameters for an energetic advantageous technical application were identified by a lot of test series at a pilot plant. The measurements show that the absorption process with the undiluted GenosorbN has a circa 20 - 27 % lower energy demand for the solvent regeneration compared to the MEA-process to reach a degree of separation of 90 %. Furthermore a low-value heating steam with lower temperature and therefore lower pressure level suffices because of the significant lower (40 - 50 K) regeneration temperature. An additional pressure reduction to 400 mbar absolute pressure in the regeneration column favours the solvent regeneration considerably

The work presented in this thesis deals with the analysis of protein crystal structures with an emphasis on the stereochemical aspects of the folded conformation of proteins. The various analyses described have been performed on a data-set of 250 high resolution and non-homologous protein structures derived from the Protein Data Bank. The overall objective of the work has been to analyse conformational features of the non-secondary structural regions in proteins and identify structural motifs present therein. The results can be useful in the three-dimensional modelling of proteins, altering the stability of proteins, design of peptide mimics and in understanding the structural rules that guide protein folding. The contents of this thesis can be broadly classified into three parts, (a) Conformational preferences of amino acid residues to occur in the partially allowed regions of the Ramachandran map, (b) conformational features of structural motifs formed by side-chain/main-chain hydrogen bonds by polar residues and (c) analysis and characteristic features of isolated β-strands. Chapter 1 of the thesis gives an introduction, briefly discussing the conformation of polypeptide chains, structural features of globular proteins and applications of protein structural analysis etc. Chapter 2 describes the occurrence of left-handed α-helical conformation in protein structures. A data-set of 250 high resolution (< 2.0A) non-homologous protein crystal structures derived from the Protein Data Bank (PDB) has been analysed for occurrences of left-handed α-helical (αL) conformations. A total of 2,573 αL residues were identified from the data-set. About 59% of the observed examples of at conformations were found to be glycyl residues and about 41% non-glycyl. Continuous long stretches of αL residues are seldom found in protein structures. They are most commonly found as singlets represented by 78% of the observed αL examples. The doublets, triplets and quadruplets account for a very minor fraction of the observed examples. There is only a single example of a stretch of four contiguous αL residues, from the protein thermolysin, which forms a single turn of a left-handed α-helix. A majority of the αL residues are nevertheless part of well-defined substructures in proteins. They play singular roles as part of β-turns and helix termination sites in maintaining the characteristic main-chain hydrogen bonds needed for the stability of these structures. They are also found to be effective in the termination of β-strands. The stereo-chemistry and sequence environment around such structures are discussed. The analysis of the side-chain torsion angles of αL residues indicate that the g+ rotamer is highly unfavourable due to stereo-chemical violations posed by the atoms of the side-chain with those of the backbone. The αL residues are highly conserved by residue type as well as conformation among related proteins indicating their vital importance in protein structures Chapter 3 provides an explanation for the unusual preference of glycyl residues to occur in the bridge regions of the Ramachandran map. The Ramachandran steric map and energy diagrams for the glycyl residue are fully symmetric. Though a plot of the (Φ,Ψ) angles of glycyl residues derived from a data-set of 250 non-homologous and high-resolution protein structures is also largely symmetric, there is a clear aberration in the symmetry. While there is a cluster of points corresponding to the right-handed a-helical region, the "equivalent" cluster is shifted to centre around the (Φ,Ψ)values of (90°, 0°) instead of being centred at the left-handed a-helical region of (60°, 40°). An analysis of glycyl conformations in small peptide structures and in "coil" proteins, which are largely devoid of helical and sheet regions, shows that glycyl residues prefer to adopt conformations around (±90°, 0°) instead of right and left handed a-helical regions. Using theoretical calculations, such conformations are shown to have highest solvent accessibility in a system of two-linked peptide units with glycyl residue at the central Cα atom. This is found to be consistent with the observations from 250 non-homologous protein structures where glycyl residues with conformations close to (±90°, 0°) are seen to have high solvent accessibility. Analysis of a sub-set of non-homologous structures with very high resolution (1.5A or better) shows that water molecules are indeed present at distances suitable for hydrogen bond interaction with glycyl residues possessing conformations close to (±90°, 0°). It is concluded that water molecules play a key role in determining and stabilising these conformations of glycyl residues and explains the aberration in the symmetry of glycyl conformations in proteins. Chapter 4 discusses an analysis of backbone mimicry performed by polar side-chains in protein structures. Backbonemimicry bythe formation of closed loop C7, C10, C13 (mimics of γ-, β- and α-turns) conformations through side-chain main-chain hydrogen bonds by polar groups is found to be a frequent observation in protein structures. A data-set of 250 non-homologous and high-resolution protein structures was used to analyse these conformations for their characteristic features. Seven out of the nine polar residues (Ser, Thr, Asn, Asp, Gin, Glu and His) have hydrogen bonding groups in their side-chains which can participate in such mimicry and as many as 15% of all these polar residues engage in such conformations. The distributions of dihedral angles of these mimics indicate that only certain combinations of the involved dihedral angles aids the formation of these mimics. The observed examples have been categorised into various classes based on these combinations resulting in well-defined motifs. Asn and Asp residues show a very high capability to perform such backbone secondary structural mimicry. The most highly mimicked backbone structure is of the Cio conformation by the Asx residues. The mimics formed by His, Ser, Thr and Glx residues are also discussed. The role of such conformations in initiating the formation of regular secondary structures during the course of protein folding seems significant. Chapter 5 presents a description of deterministic features of side-chain main-chain hydrogen bonds as observed in protein structures. A total of 19,835 polar residues from the data set of 250 non-homologous and highly resolved protein crystal structures were used to identify side-chain main-chain (SC-MC) hydrogen bonds. The ratio of the total number of polar residues to the number of SC-MC hydrogen bonds is close to 2:1, indicating the ubiquitous nature of such hydrogen bonds. Close to 56% of the SC-MC hydrogen bonds are local involving side-chain acceptor/donor (‘i’) and a main-chain donor/acceptor within the window i-5 to i+5. These short-range hydrogen bonds form well defined conformational motifs characterised by specific combinations of backbone and side-chain torsion angles. Some of the salient features of such hydrogen bonds are as follows, (a) The Ser/Thr residues show the greatest preference in forming intra-helical hydrogen bonds between the atoms Oyi and Oi-4 Such hydrogen bonds form motifs of the form αRαRαRαR(g") and are most commonly observed at the middle of α-helices. (b) These residues also show great preference to form hydrogen bonds between OYi and Oi-3, which are closely related to the previous type and though intra-helical, these hydrogen bonds are more often found at the C-termini of helices than at the middle. The motif represented by αRαRαRaR(g+) is most preferred in these cases, (c) The Ser, Thr and Glu (between the side-chain and main-chain of the same residue), (d) The side-chain acceptor atoms of Asn/Asp and Ser/Thr residues show high preference to form hydrogen bonds with acceptors two residues ahead in the chain, which are characterised by the motifs β(tt’)αR and β(t)αR, respectively. These hydrogen bonded segments referred to as Asx turns, are known to provide stability to type I and type I’ β-turns. (e) Ser/Thr residues often form a combination of SC-MC hydrogen bonds, with the side-chain donor hydrogen bonded to the carbonyl oxygen of its own peptide backbone and the side-chain acceptor hydrogen bonded to an amide hydrogen three residues ahead in the sequence. Such motifs are quite often seen at the beginning of a-helices, which are characterised by the β (g+)αRαR motif. A remarkable majority of all these hydrogen bonds are buried from the protein surface, away from the surrounding solvent. This strongly indicates the possibility of side-chains playing the role of the backbone, in the protein interiors, to satisfy the potential hydrogen bonding sites and maintaining the network of hydrogen bonds which is crucial to the structure of the protein. Chapter 6 provides a detailed characterisation of isolated β-strands. Reason for the formation of β-strands in proteins is often associated with the formation of β -sheets. However β-strands, not part of β-sheets, commonly occur in proteins. This raises questions about the structural role and stability of such isolated β-strands. Using a data set consisting of 250 proteins, 518 isolated β-strands have been identified from 187 proteins. The two important features that distinguish isolated β-strands from p-strands occurring in β-sheets are (i) the high preponderance of prolyl residues to occur in isolated β-strands and (ii) their high solvent exposure. It is shown that the high propensity for proline residues to occur in isolated β-strands is not due to the occurrence of polyproline type segments in the data-set. The propensities of other amino acids to occur in isolated β-strands follows the same trend as those for β-sheet forming β-strands. Isolated β-strands are characterised often by their main-chain amide and carbonyl groups involved in hydrogen bonding with polar side-chains or water. They are often flanked by irregular loop structures indicating that they are part of long of loops. Analysis of the conservation of such strands among families of homologous protein structures indicates that a sizeable fraction of them are highly conserved. It is suggested that though the formation of isolated β-strands are driven by the intrinsic preferences of amino acid residues, they have many characteristics like loop segments but with repetitive (Φ,Ψ) values falling within the β-region of the Ramachandran map. In addition of the material described in the six chapters above, the thesis also contains the details of work carried out on an aspect slightly different from the main theme of the thesis. This pertains to the comparative analysis of the members of a family of cytokine receptors to derive information to model new members of the family. The three dimensional modelling of the leptin receptor has been used as a case study and the details are included as an appendix. Appendix describes the 3-dimensional model of the satiety factor receptor (the leptin receptor) modelled using principles of homology modelling. Recessive mutations in the mouse obese (ob) and diabetes (db) genes result in obesity and diabetes in a syndrome resembling human obesity. Data from parabiosis (cross circulation) experiments suggested that the ob gene coded, and was responsible for the generation of a circulating factor called leptin which regulated energy balance and the db gene encoded the receptor for this factor. While the structure of the leptin has been determined that of its cognate receptor is as yet unknown. The leptin receptor shows low but clear sequence similarity to the members of the interleukin type 6 family of receptors. The structures of the members of this family are characterised by two p-sandwich like domains connected by a short 4-residue helical linker. The 3-dimensional models for the N- and C-terminal domains of the leptin receptor was generated using the corresponding structures of the signal transducing component of gpl30, the erythropoetin receptor and the prolactin receptor. Further using the evidence that the leptin binds to its receptor with a stoichiometry of 1:1, the relative orientation of the two domains was modelled based on the structure of the human growth hormone receptor, which also binds its ligand with similar stoichiometry. The complex of leptin with its receptor was also modelled based on the structure of human growth hormone/receptor complex. The final energy minimised model of the complex elucidates the mode of interaction between the leptin and its receptor.

Proteins have an indispensable role in the cell. They carry out a wide variety of structural, catalytic and signaling functions in all known biological systems. To perform their biological functions, proteins establish interactions with other bioorganic molecules including other proteins. Therefore, protein-protein interactions is one of the central topics in molecular biology. My thesis is devoted to three different topics in the field of protein-protein interactions. The first one focuses on solvent contribution to protein interfaces as it is an important component of protein complexes. The second topic discloses the structural and functional potential of fluorine's unique properties, which are attractive for protein design and engineering not feasible within the scope of canonical amino acids. The last part of this thesis is a study of the impact of charged amino acid residues within the hydrophobic interface of a coiled-coil system, which is one of the well-established model systems for protein-protein interactions studies. I. The majority of proteins interact in vivo in solution, thus studies of solvent impact on protein-protein interactions could be crucial for understanding many processes in the cell. However, though solvent is known to be very important for protein-protein interactions in terms of structure, dynamics and energetics, its effects are often disregarded in computational studies because a detailed solvent description requires complex and computationally demanding approaches. As a consequence, many protein residues, which establish water-mediated interactions, are neither considered in an interface definition. In the previous work carried out in our group the protein interfaces database (SCOWLP) has been developed. This database takes into account interfacial solvent and based on this classifies all interfacial protein residues of the PDB into three classes based on their interacting properties: dry (direct interaction), dual (direct and water-mediated interactions), and wet spots (residues interacting only through one water molecule). To define an interaction SCOWLP considers a donor–acceptor distance for hydrogen bonds of 3.2 Å, for salt bridges of 4 Å, and for van der Waals contacts the sum of the van der Waals radii of the interacting atoms. In previous studies of the group, statistical analysis of a non-redundant protein structure dataset showed that 40.1% of the interfacial residues participate in water-mediated interactions, and that 14.5% of the total residues in interfaces are wet spots. Moreover, wet spots have been shown to display similar characteristics to residues contacting water molecules in cores or cavities of proteins. The goals of this part of the thesis were: 1. to characterize the impact of solvent in protein-protein interactions 2. to elucidate possible effects of solvent inclusion into the correlated mutations approach for protein contacts prediction To study solvent impact on protein interfaces a molecular dynamics (MD) approach has been used. This part of the work is elaborated in section 2.1 of this thesis. We have characterized properties of water-mediated protein interactions at residue and solvent level. For this purpose, an MD analysis of 17 representative complexes from SH3 and immunoglobulin protein families has been performed. We have shown that the interfacial residues interacting through a single water molecule (wet spots) are energetically and dynamically very similar to other interfacial residues. At the same time, water molecules mediating protein interactions have been found to be significantly less mobile than surface solvent in terms of residence time. Calculated free energies indicate that these water molecules should significantly affect formation and stability of a protein-protein complex. The results obtained in this part of the work also suggest that water molecules in protein interfaces contribute to the conservation of protein interactions by allowing more sequence variability in the interacting partners, which has important implications for the use of the correlated mutations concept in protein interactions studies. This concept is based on the assumption that interacting protein residues co-evolve, so that a mutation in one of the interacting counterparts is compensated by a mutation in the other. The study presented in section 2.2 has been carried out to prove that an explicit introduction of solvent into the correlated mutations concept indeed yields qualitative improvement of existing approaches. For this, we have used the data on interfacial solvent obtained from the SCOWLP database (the whole PDB) to construct a “wet” similarity matrix. This matrix has been used for prediction of protein contacts together with a well-established “dry” matrix. We have analyzed two datasets containing 50 domains and 10 domain pairs, and have compared the results obtained by using several combinations of both “dry” and “wet” matrices. We have found that for predictions for both intra- and interdomain contacts the introduction of a combination of a “dry” and a “wet” similarity matrix improves the predictions in comparison to the “dry” one alone. Our analysis opens up the idea that the consideration of water may have an impact on the improvement of the contact predictions obtained by correlated mutations approaches. There are two principally novel aspects in this study in the context of the used correlated mutations methodology : i) the first introduction of solvent explicitly into the correlated mutations approach; ii) the use of the definition of protein-protein interfaces, which is essentially different from many other works in the field because of taking into account physico-chemical properties of amino acids and not being exclusively based on distance cut-offs. II. The second part of the thesis is focused on properties of fluorinated amino acids in protein environments. In general, non-canonical amino acids with newly designed side-chain functionalities are powerful tools that can be used to improve structural, catalytic, kinetic and thermodynamic properties of peptides and proteins, which otherwise are not feasible within the use of canonical amino acids. In this context fluorinated amino acids have increasingly gained in importance in protein chemistry because of fluorine's unique properties: high electronegativity and a small atomic size. Despite the wide use of fluorine in drug design, properties of fluorine in protein environments have not been yet extensively studied. The aims of this part of the dissertation were: 1. to analyze the basic properties of fluorinated amino acids such as electrostatic and geometric characteristics, hydrogen bonding abilities, hydration properties and conformational preferences (section 3.1) 2. to describe the behavior of fluorinated amino acids in systems emulating protein environments (section 3.2, section 3.3) First, to characterize fluorinated amino acids side chains we have used fluorinated ethane derivatives as their simplified models and applied a quantum mechanics approach. Properties such as charge distribution, dipole moments, volumes and size of the fluoromethylated groups within the model have been characterized. Hydrogen bonding properties of these groups have been compared with the groups typically presented in natural protein environments. We have shown that hydrogen and fluorine atoms within these fluoromethylated groups are weak hydrogen bond donors and acceptors. Nevertheless they should not be disregarded for applications in protein engineering. Then, we have implemented four fluorinated L-amino acids for the AMBER force field and characterized their conformational and hydration properties at the MD level. We have found that hydrophobicity of fluorinated side chains grows with the number of fluorine atoms and could be explained in terms of high electronegativity of fluorine atoms and spacial demand of fluorinated side-chains. These data on hydration agrees with the results obtained in the experimental work performed by our collaborators. We have rationally engineered systems that allow us to study fluorine properties and extract results that could be extrapolated to proteins. For this, we have emulated protein environments by introducing fluorinated amino acids into a parallel coiled-coil and enzyme-ligand chymotrypsin systems. The results on fluorination effect on coiled-coil dimerization and substrate affinities in the chymotrypsin active site obtained by MD, molecular docking and free energy calculations are in strong agreement with experimental data obtained by our collaborators. In particular, we have shown that fluorine content and position of fluorination can considerably change the polarity and steric properties of an amino acid side chain and, thus, can influence the properties that a fluorinated amino acid reveals within a native protein environment. III. Coiled-coils typically consist of two to five right-handed α-helices that wrap around each other to form a left-handed superhelix. The interface of two α-helices is usually represented by hydrophobic residues. However, the analysis of protein databases revealed that in natural occurring proteins up to 20% of these positions are populated by polar and charged residues. The impact of these residues on stability of coiled-coil system is not clear. MD simulations together with free energy calculations have been utilized to estimate favourable interaction partners for uncommon amino acids within the hydrophobic core of coiled-coils (Chapter 4). Based on these data, the best hits among binding partners for one strand of a coiled-coil bearing a charged amino acid in a central hydrophobic core position have been selected. Computational data have been in agreement with the results obtained by our collaborators, who applied phage display technology and CD spectroscopy. This combination of theoretical and experimental approaches allowed to get a deeper insight into the stability of the coiled-coil system. To conclude, this thesis widens existing concepts of protein structural biology in three areas of its current importance. We expand on the role of solvent in protein interfaces, which contributes to the knowledge of physico-chemical properties underlying protein-protein interactions. We develop a deeper insight into the understanding of the fluorine's impact upon its introduction into protein environments, which may assist in exploiting the full potential of fluorine's unique properties for applications in the field of protein engineering and drug design. Finally we investigate the mechanisms underlying coiled-coil system folding. The results presented in the thesis are of definite importance for possible applications (e.g. introduction of solvent explicitly into the scoring function) into protein folding, docking and rational design methods. The dissertation consists of four chapters: ● Chapter 1 contains an introduction to the topic of protein-protein interactions including basic concepts and an overview of the present state of research in the field. ● Chapter 2 focuses on the studies of the role of solvent in protein interfaces. ● Chapter 3 is devoted to the work on fluorinated amino acids in protein environments. ● Chapter 4 describes the study of coiled-coils folding properties. The experimental parts presented in Chapters 3 and 4 of this thesis have been performed by our collaborators at FU Berlin. Sections 2.1, 2.2, 3.1, 3.2 and Chapter 4 have been submitted/published in peer-reviewed international journals. Their organization follows a standard research article structure: Abstract, Introduction, Methodology, Results and discussion, and Conclusions. Section 3.3, though not published yet, is also organized in the same way. The literature references are summed up together at the end of the thesis to avoid redundancy within different chapters.

Conselho Nacional de Desenvolvimento Científico e Tecnológico
In this work we use the Density Functional Theory (DFT) to analyze the influence of a water environment in the interaction between amino acids and a semiconductor carbon nanotube (CNT). To the study of the interaction in vacuum we use both an ab initio and a parameterized tight-binding method. To the study of the same interactions in water we performed finite temperature (300 K) molecular dynamics calculations, using the parameterized tight-binding method. The selected amino acids have different hydrophobicity and polarity indexes. Our study shows that for the neutral amino acids, a direct relationship between the variation in the bonding distances and the hydrophobicity indexes when changing from vacuum to water environments, with the hydrophobic (hydrophilic) amino acids getting nearer (farther) of the carbon nanotube. The change in the binding energies, when going from the vacuum to the water environments, shows an inverse relationship with the polarity, with the amino acids that have more polar (nonpolar) side chains showing lower (greater) variations in the binding energies. We also analyze the variations in the binding energies in vacuum and water for the neutral and zwitterionic forms of glicine. We show that the zwitterionic form is more stable in the polar environment of water, whereas the neutral form is more stable in vacuum.
Neste trabalho utilizamos a teoria do funcional da densidade (DFT) para analisar a influência de um meio solvente, a água, na interação de aminoácidos com um nanotubo de carbono (CNT) semicondutor. Para o estudo das interações no vácuo utilizamos tanto um método ab-initio quanto um método tight binding parametrizado. Os estudos destas mesmas interações (CNT-aminoácidos) no meio aquoso foram realizados empregando o método de dinâmica molecular a uma temperatura de 300 K usando o método tight binding parametrizado. Os aminoácidos selecionados para o estudo tinham diferentes valores de índice de hidrofobicidade e de polaridade. Nossos resultados mostram que para a forma neutra destes aminoácidos, há uma relação direta entre a variação da distância da ligação, do vácuo em relação a água, e o índice de hidrofobicidade com os aminoácidos mais hidrofóbicos (hidrofílicos) se aproximando (afastando) do nanotubo de carbono. A variação da energia de ligação, quando se passa do vácuo para o ambiente aquoso, apresenta uma relação inversa com a polaridade, com os aminoácidos que possuem a cadeia lateral mais polares (menos polares) apresentado os menores (maiores) variações na energia de ligação. Analisamos ainda as variações na energia de ligação no vácuo e na água para o aminoácido glicina em relação as suas possíveis formas elétricas: neutra e como íon dipolar (zwiteri onica). Mostramos que a forma zwiteriônica é mais estável no ambiente polar da água, enquanto a forma neutra apresenta maior estabilidade no vácuo.

This dissertation describes the design and synthesis of a series of half-sandwich amino acid complexes of the form), (aa = α-amino carboxylate), and their utility as asymmetric transfer hydrogenation catalysts of ketones. Variation of the metal center, the n-ring, and the aa was used to tune these systems for specific sets of ketones. Upon reaction with homochiral]s, the ligand environment in all of these complexes is pseudotetrahedral, leading to stereogenic metal ions (SM, RM). The addition of another stereogenic center from the amino acid ligand (the carbon, RC or SC;glycine) gives rise to two pairs of diastereomeric complexes.
Ph. D.

Ce travail porte sur l'étude de la capacité d'absorption du CO2 par différents types d'amines dissoutes en milieux aqueux et non aqueux. Ce dernier est constitué d'un mélange de chlorure de choline et d'éthylène glycol dans une proportion molaire respectivement de 1 pour 2. Ce solvant, communément appelé "Ethaline", appartient à la catégorie dite des « Solvants à Eutectique Profond » ainsi désignés car leur composition eutectique permet d'obtenir des mélanges généralement liquides à température ambiante. Pour ce faire un appareil d'équilibre liquide-vapeur avec analyse en ligne de la phase vapeur par GC a été réalisé et son fonctionnement validé. Les isothermes d'absorption du CO2 ainsi que la volatilité (composition de la phase vapeur) des mélanges étudiés, avec et sans CO2, ont été déterminées à différentes températures et pour différentes compositions en amines. Le domaine de pression exploré est particulièrement large : du Pascal à 800 kPa. L'étude a montré que la substitution de l'eau par "l'Ethaline" conduit à une capacité d'absorption du CO2 presque identique à celle de la MEA et DEA en solution aqueuse. Par contre dans le cas de la MDEA on observe une capacité d'absorption plus faible en milieu « Ethaline » qu'en milieu aqueux. Les isothermes d'absorption du CO2 des trois classes d'amines en milieu aqueux et non aqueux ont été corrélés par les modèles semi empiriques de (Gabrielsen et al., 2005) initialement établis par ces auteurs pour les solutions aqueuses (un modèle pour les amines primaires et secondaires conduisant à la formation de carbamates en présence de CO2, un modèle pour les amines tertiaires donnant des sels d'ammonium avec le CO2). Nous avons montré que ces deux modèles représentent avec succès les isothermes d'absorption en milieu non aqueux. Les constantes d'équilibre et les enthalpies de réaction qui s'en déduisent montrent que ces dernières sont plus faibles (en valeur absolue) pour la MEA et TMDEA en solution éthaline qu'en solution aqueuse. Dans le cas de la MDEA la nature du solvant n'a qu'une influence minime sur l'enthalpie de réaction. Les valeurs expérimentales des volatilités des amines dans les différents mélanges Amine- CO2 en milieu aqueux ont été corrélées par différents modèles semi-empiriques. Trois modèles thermodynamiques de coefficients d'activité ; le modèle de Wilson, NRTL et UNIQUAC ont été utilisés afin de restituer les données expérimentales de l'équilibre liquide-vapeur des systèmes aqueux d'amines (sans CO2). Une représentation satisfaisante des résultats expérimentaux par les trois modèles a été obtenue
This work focuses on the study of the absorption capacity of CO2 by different types of dissolved amines in aqueous and non-aqueous media. The latter consists of a mixture of choline chloride and ethylene glycol in a molar proportion of 1 to 2 respectively. This solvent, commonly called "Ethaline", belongs to the category called "Deep Eutectic Solvents" so designated because their eutectic composition makes it possible to obtain mixtures that are generally liquid at room temperature. With this aim, a liquid-vapor equilibrium apparatus with on-line analysis of the vapor phase by GC was performed and its operation validated. The CO2 absorption isotherms and the volatility (composition of the vapor phase) of the studied mixtures, with and without CO2, were determined at different temperatures and for different amine compositions. The explored pressure range is particularly large: from 1 Pa to 800 kPa. The study showed that the substitution of water by "Ethaline" leads to a CO2 absorption capacity almost identical to that of MEA and DEA in aqueous solution. On the other hand, in the case of MDEA, a lower absorption capacity is observed in Ethaline than in aqueous medium. In the hypothesis of a use of the DES+amine solvent for CO2 capture in post-combustion process, a decrease of the vapor pressure of the solvent (comparing to that of water+amine) has an advantage because of the low solvent loss due to vaporization in the absorber. The second advantage is most likely a lower effect of equipment corrosion, the third positive point is a lower enthalpy of absorption of MEA and MDEA in (1 ChCl : 2 EG) comparing to aqueous medium, resulting in a possible saving of energy in the regenerator of almost 40%. The disadvantage of the use of amines in "Ethaline" solution is the high viscosity of this solvent which decreases the kinetics of material transfer and reaction with CO2. The CO2 absorption isotherms and the experimental values of the amine volatilities in the different Amine-H2O-CO2 mixtures were well correlated by different semi-empirical models. Three thermodynamic models based on the activity coefficients; the Wilson model, NRTL and UNIQUAC were used to restitute experimental data for the liquid-vapor equilibrium of aqueous amine systems (without CO2). A satisfactory representation of the experimental results by the three models was obtained

Nucleophilic substitution reactions of alkylamines, cyclic alkylamines, and hydroxyalkylamines with 5-substituted-1,4-naphthoquinones have been studied. It has been found that the nature of the solvent employed in the reaction influences the position of mono-substitution at either the 2- or 3-position. Although both regioisomers were produced in all the reactions, protic polar solvents favoured the formation of the 3-regioisomer, whereas non-protic solvents favoured the formation of the 2-regioisomer. It has also been found that formation of 2,3-diaminoalkyl derivatives is normally unlikely. A series of hydroxyalkylamino-1,4-naphthoquinones were also synthesised. The collision-induced dissociation mass spectra of protonated hydroxyalkylamino-1,4- naphthoquinones showed fragmentation patterns which were dependent on the nature and length of the side chain and the presence and nature of the adjacent group on the 3-position on the 1,4-naphthoquinone ring. A total of 27 novel compounds were synthesised during the course of this research, the structures of which were confirmed via 1D and 2D NMR spectroscopy, mass spectrometry (ESI), IR spectroscopy and high resolution mass spectrometry (HRESIMS and HREIMS).

Thesis (Ph.D.); Submitted to Iowa State Univ., Ames, IA (US); 19 Dec 2004.
Published through the Information Bridge: DOE Scientific and Technical Information. "IS-T 2134" Meera Jay Desai. US Department of Energy 12/19/2004. Report is also available in paper and microfiche from NTIS.

Les amines aromatiques sont largement considérées comme des intermédiaires réactionnels prometteurs pour la production de colorants, d'antioxydants, de produits pharmaceutiques et de produits chimiques agricoles. La méthode la plus utilisée pour la préparation des amines aromatiques est l’hydrogénation catalytique en général. Les procédés d'hydrogénation catalytique des composés nitroaromatiques utilisent des métaux de transition, tels que (Pt, Ni, Pd,..), de solvants organiques et source d’hydrogène comme H2. Cependant, l'utilisation de catalyseurs métalliques présente certains inconvénients tels que le coût élevé, le recyclage du système, ainsi que certaines préoccupations environnementales. Les solvants organiques ont également été utilisés au cours de ces processus, ce qui a nécessité une consommation d'énergie élevée pour la récupération des amines aromatiques. Enfin, l’utilisation de H2 peut entraîner également des risques liés à la sécurité. Dans le présent travail, des procédés « verts » et sûrs pour la réduction des composés nitroaromatiques en amines aromatiques en présence de matériaux carbonés ou de biomasse lignocellulosique dans des conditions subcritiques ont été développés. Dans un premier temps notre intérêt dans ce travail s'est porté sur l'utilisation directe du carbone qui présente comme avantages, son faible coût et sa disponibilité, cela a donné lieux à un nouveau procédé plus « vert » et plus sécuritaire. Le mécanisme réactionnel de ce dernier a été étudié en utilisant le logiciel CIRCE qui est un logiciel de thermodynamique basé sur la méthode de Monte Carlo. Ce procédé a été ensuite appliqué à différents composés nitrés aromatiques substitués par une fonction organique en particulier pour la préparation du 3-aminobenzoique à partir du 3-nitrobenzaldehyde. Par la suite les matériaux carbonés ont été remplacés par de la biomasse lignocellulosique qui est la sciure de bois imprégné par une base dans l’eau à l’état subcritique. En effet l'eau connue comme solvant vert pourraient impliquer de nouveaux procédés « verts » en conditions critiques et engendrer H2 permet d’apporter le dihydrogène nécessaire pour la faisabilité de la réaction
Aromatic amines are widely regarded as promising reaction intermediates for the production of dyes, antioxidants, pharmaceuticals and agricultural chemicals. The most widely used method for the preparation of aromatic amines is catalytic hydrogenation in general. The catalytic hydrogenation processes of nitroaromatic compounds use transition metals, such as (Pt, Ni, Pd, ..), organic solvents and hydrogen source like H2. However, the use of metal catalysts has certain disadvantages such as the high cost, recycling of the system, as well as certain environmental concerns. Organic solvents were also used during these processes, which required high energy consumption for the recovery of aromatic amines. Finally, the use of H2 can also lead to safety risks. In the present work, “green” and safe processes for the reduction of nitroaromatic compounds into aromatic amines in the presence of carbonaceous materials or lignocellulosic biomass under subcritical conditions have been developed. Initially, our interest in this work focused on the direct use of carbon which has the advantages, its low cost and its availability, this gave rise to a new process that is "greener" and safer. The reaction mechanism of the latter was studied using CIRCE software which is thermodynamic software based on the Monte Carlo method. This process was then applied to various aromatic nitro compounds substituted by an organic function in particular for the preparation of 3-aminobenzoic starting from 3-nitrobenzaldehyde. Subsequently carbonaceous materials were replaced by lignocellulosic biomass which is sawdust impregnated with a base in water in the subcritical state. Indeed, water known as a green solvent could involve new "green" processes in critical conditions and generate H2 makes it possible to supply the dihydrogen necessary for the feasibility of the reaction

Green chemistry principles have been applied to the enhancement of two industrial chemistry problems. An industrially used reaction to form alcohols from aldehydes and ketones, the Meerwein-Ponndorf-Verley reduction, was improved by introducing a new catalyst Al(OtBu)₃. Due to the lower state of aggregation of this catalyst versus the conventional Al(OiPr)₃ catalyst, reduction rates were found to be faster in both pure iPrOH and mixed solvent systems for three model compounds: benzaldehyde, acetophenone, and a complex, chiral ketone, (S)-CMK. This allowed for the successful implementation of two important milestones; lowering the amount of catalyst needed necessary to complete the reactions (an economic benefit and lower waste) and the conversion from traditional batch reactions to continuous flow (a processing benefit) whereby reactions can be scaled-out rather than scaled-up. Another industrially important field of research that was focused on was CO₂ capture. High energy demands from current CO₂ capture methods such as aqueous amine solvents, specifically from coal-fired power plant flue gas, led to the development of non-aqueous reversible ionic liquids based on silylated amines. Structural modifications of the substitution around the silicon atom, the length of the alkyl chain bonding the silicon and amine, branching along the alkyl backbone, and investigating secondary and primary amines within this class of silylated amines were completed. These amines were reacted with CO₂ and the CO₂ capacity, the ionic liquid viscosity, reversal temperature and reaction enthalpy were all considered as a function of structure. In all cases the capacity was found to be not only greater than that of monethanolamine, an industrial standard, but higher than theoretical predictions through the formation of carbamic acid. Viscosity, reversal temperature, and reaction enthalpy were all found to be tunable through structure. These modifications gave significant insight into the necessary direction for optimization of these solvents as energy-efficient replacements of current CO₂ capture technology.

Mechanistic studies on three different ruthenium-based catalysts have been performed. The catalysts have in common that they have been employed in hydrogen transfer reactions involving alcohols and ketones, amines and imines or both. Bäckvall’s catalyst, η5-(Ph5C5)Ru(CO)2Cl, finds its application as racemization catalyst in dynamic kinetic resolution, where racemic alcohols are converted to enantiopure acetates in high yields. The mechanism of the racemization has been investigated and both alkoxide and alkoxyacyl intermediates have been characterized by NMR spectroscopy and in situ FT-IR measurements. The presence of acyl intermediates supports a mechanism via CO assistance. Substantial support for coordination of the substrate during the racemization cycle is provided, including exchange studies with both external and internal potential ketone traps. We also detected an unexpected alkoxycarbonyl complex from 5-hydroxy-1-hexene, which has the double bond coordinated to ruthenium. Shvo’s catalyst, [Ru2(CO)4(μ-H)(C4Ph4COHOCC4Ph4)] is a powerful catalyst for transfer hydrogenation as well as for dynamic kinetic resolution. The mechanism of this catalyst is still under debate, even though a great number of studies have been published during the past decade. In the present work, the mechanism of the reaction with imines has been investigated. Exchange studies with both an external and an internal amine as potential traps have been performed and the results can be explained by a stepwise inner-sphere mechanism. However, if there is e.g. a solvent cage effect, the results can also be explained by an outer-sphere mechanism. We have found that there is no cage effect in the reduction of a ketone containing a potential internal amine trap. If the mechanism is outer-sphere, an explanation as to why the solvent cage effect is much stronger in the case of imines than ketones is needed. Noyori’s catalyst, [p-(Me2CH)C6H4Me]RuH(NH2CHPhCHPhNSO2C6H4-p-CH3), has successfully been used to produce chiral alcohols and amines via transfer hydrogenation. The present study shows that the mechanism for the reduction of imines is different from that of ketones and aldehydes. Acidic activation of the imine was found necessary and an ionic mechanism was proposed.

Les céramides sont des lipides de la classe des sphingolipides issus de la N-acylation d'une base sphingoide par un acide gras. Ces lipides et leurs analogues suscitent un grand intérêt comme composants actifs dans les industries pharmaceutique et cosmétique. Parmi les biocatalyseurs capables de réaliser la synthèse de ce type de lipide, la lipase B de Candida antarctica semble être l'enzyme la plus adaptée à la production de " pseudo-céramides " à partir d'amino-polyols. Dans ce contexte, nous avons abordé l'étude de l'acylation de composés de type " amino-alcool "catalysée par la lipase B de Candida antarctica, en gardant à l'esprit une approche fondamentale afin d'élargir les connaissances actuelles sur ce sujet. La première partie de notre travail a ainsi traité de l'étude cinétique de l'acylation de composés monofonctionnels afin de déterminer les mécanismes réactionnels et l'énantio sélectivité de la lipase B de Candida antarctica pour les réactions de N-acylation et de O-acylation. Les parties suivantes de notre travail ont porté sur une étude structure-réactivité du substrat accepteur d'acyle et sur l'étude de l'influence du solvant utilisé (solvant organique ou liquide ionique) afin de déterminer les facteurs clés influençant la chimio sélectivité et la régio sélectivité de la lipase B de Candida antarctica lors de l'acylation de composés multifonctionnels de type " amino-alcool ". Finalement, à partir des connaissances acquises dans les différentes parties, nous avons développé et optimisé un procédé de synthèse enzymatique de " pseudo-céramides " (O,N-diacyl aminopropanediols) mis en oeuvre en réacteur continu à " lit fixe ".

Molecular Biology has allowed the characterization and manipulation of the molecules of life in the wet lab. Also the structures of those macromolecules are being continuously elucidated. During the last decades of the past century, there was an increasing interest to study how the different genes are organized into different organisms (‘genomes’) and how those genes are expressed into proteins to achieve their functions. Currently the sequences for many genes over several genomes have been determined. In parallel, the efforts to have the structure of the proteins coded by those genes go on. However it is experimentally much harder to obtain the structure of a protein, rather than just its sequence. For this reason, the number of protein structures available in databases is an order of magnitude or so lower than protein sequences. Furthermore, in order to understand how living organisms work at molecular level we need the information about the interaction of those proteins. Elucidating the structure of protein macromolecular assemblies is still more difficult. To that end, the use of computers to predict the structure of these complexes has gained interest over the last decades.

The main subject of this thesis is the evaluation of current available computational methods to predict protein – protein interactions and build an atomic model of the complex. The core of the thesis is the evaluation protocol I have developed at Service de Conformation des Macromolécules Biologiques et de Bioinformatique, Université Libre de Bruxelles, and its computer implementation. This method has been massively used to evaluate the results on blind protein – protein interaction prediction in the context of the world-wide experiment CAPRI, which have been thoroughly reviewed in several publications [1-3]. In this experiment the structure of a protein complex (‘the target’) had to be modeled starting from the coordinates of the isolated molecules, prior to the release of the structure of the complex (this is commonly referred as ‘docking’).

The assessment protocol let us compute some parameters to rank docking models according to their quality, into 3 main categories: ‘Highly Accurate’, ‘Medium Accurate’, ‘Acceptable’ and ‘Incorrect’. The efficiency of our evaluation and ranking is clearly shown, even for borderline cases between categories. The correlation of the ranking parameters is analyzed further. In the same section where the evaluation protocol is presented, the ranking participants give to their predictions is also studied, since often, good solutions are not easily recognized among the pool of computer generated decoys.

An overview of the CAPRI results made per target structure and per participant regarding the computational method they used and the difficulty of the complex. Also in CAPRI there is a new ongoing experiment about scoring previously and anonymously generated models by other participants (the ‘Scoring’ experiment). Its promising results are also analyzed, in respect of the original CAPRI experiment. The Scoring experiment was a step towards the use of combine methods to predict the structure of protein – protein complexes. We discuss here its possible application to predict the structure of protein complexes, from a clustering study on the different results.

In the last chapter of the thesis, I present the preliminary results of an ongoing study on the conformational changes in protein structures upon complexation, as those rearrangements pose serious limitations to current computational methods predicting the structure protein complexes. Protein structures are classified according to the magnitude of its conformational re-arrangement and the involvement of interfaces and particular secondary structure elements is discussed. At the end of the chapter, some guidelines and future work is proposed to complete the survey.
Doctorat en Sciences
info:eu-repo/semantics/nonPublished

Les propriétés électrochimiques des complexes co-base de Schiff (phenylene-bis(salicylideneiminoto)-co, ou Co(II)saloph, et n-methylenepropylene-bis-(salicylideneiminoto)-co, ou co-selnmedpt) et de tetraphenylporphine-co, ou CoTPP, sont utilisées pour étudier la réduction électroassistée d'halogénures organiques, Rx, avec un catalyseur fixe sur support conducteur, en milieu organique. On étudie: 1) la réduction du chlorure de benzyle électrocatalysée par des électrodes de graphite modifiées par du co-saloph et 2) l'oxydation par l'oxygène moléculaire du di-tert-butylphenol, électrocatalysée par des films de polypyrrole contenant la porphyrine mntcpp.

The purpose of this research activity has been the development of new and efficient systems for the capture of CO2 from a gas stream in a sustainable way from an energetic, economic and environmental point of view. The chemical absorption by aqueous alkanolamines is considered the most efficient and mature technique for the CO2 capture and separation. Alkanolamines are widely used due to the fast reaction with CO2 and to their solubility in water. In particular aqueous 2-amine ethanol (MEA) has a long story as efficient systems for CO2 separation in ammonia and hydrogen plants, natural gas extraction and gas refinery. Recently, these aqueous sorbents have been also studied for application on CO2 removing from industrial exhaust streams. However, the high operating costs associated to the thermal regeneration of the sorbents because of the particularly high evaporation enthalpy and heat capacity of water, are the major obstacles to extensive application to large scale commercial plants. In addition, the higher is the desorption temperature, the greater are the amine decomposition and evaporation, as well as equipment corrosion, thus increasing the maintenance costs of the CCS process. With the aim of taking advantages of the high efficiency of conventional aqueous alkanolamines yet reducing their disadvantages, we have been pursuing a lab-scale research on alternative absorbent formulations aimed at reducing the energy of the absorbent regeneration and the amine degradation, yet maximising the CO2 capture. With the objective of reducing the energy required by the desorption process, in this thesis has been devised the strategy to avoid water. The replacement of water by organic solvents, or the absence of any solvents, may redirect the reaction of amines with CO2 towards less stable species which, consequently, require lower stripping temperatures at room pressure. The study has been focused on amines which combine high reaction rate with CO2 in a non-aqueous environment, with lower reaction enthalpy (in absolute value) and therefore these absorbents require lower regeneration temperatures compared to those of the aqueous solutions (75-95 °C at room pressure instead of 120-140 °C under pressure). Furthermore, the lower operating temperatures reduce the decomposition rate and the loss of the amines. As additional, not negligible benefit, the absence of water strongly reduces the equipment corrosion and avoids foaming problems. A first stage of this study has been devoted to solutions of alkanolamines in organic solvents. Replacing water with organic solvents may provide significant advantages in regard to the reduced absorbent decomposition and to the energy saving in the regeneration step due to the lower heat capacity (about half), the lower heat of vaporization of organic solvents and the higher boiling temperature compared to water. Furthermore, the use of organic solvents does not require major changes to the equipment which works with aqueous solutions. The sorbents formulated comprised some single or blended alkanolamines and alcohol mixtures containing ethylene glycol. 13C NMR analysis indicates that CO2 is reversibly captured in solution as either monoalkyl carbonate (R-OCO2−) and amine carbamate. Due to the lower stability of monoalkyl carbonates with respect to HCO3− and to the carbamates which are formed in the aqueous solutions, stripping temperatures of 75–90°C at room pressure are sufficient to attain absorption efficiencies greater than 90%. Between different formulation designed, one of the best performing was tested on the pilot plant of the ENEL coal-fired power plant located in Brindisi. Even if the replacement of water by organic solvents may reduce the costs of the stripping process, a lot of energy is wasted by the organic solvent heating from the absorption to the desorption temperatures. Moreover, the solvent, either water or alcohols account for about 70% of the absorbent and therefore requires very large equipments. The avoidance of any solvent, should be a decisive improvement towards the ideal absorbent. Therefore, the study has been focused on amines capable of absorbing CO2 without any dilution provided they are liquid before and after the carbon dioxide uptake. A technique of reversible CO2 capture that does not require absorbent dilution would have beneficial effects over those based on diluted absorbents, in that it avoids the sensible heat and vaporization heat of the solvent that contribute to the overall reboiler duty, as long as the operational conditions and the efficiency of the two techniques were comparable. Further potential benefits would be the reduced mass of the absorbent (water accounts for 70 wt % of the mass of aqueous MEA) and, consequently, an appreciable reduction of the plant size. In this study has been formulated two different classes of solvent-free single-component absorbents based on inexpensive and commercially available amine, in particular some secondary amines and some secondary alkanolamines. CO2 is captured with high efficiency (over 90%) as amine carbamate and amine-carbamic acid. In another part of the study has been devised and developed the use of biphasic sorbents. In such technique, the absorbent solution, after the reaction with CO2, separates into two phases (liquid/liquid or liquid/solid) that comprise the solvent and, separately, the carbonatated species. In this way it is possible to desorb the sole carbonatated phase, preventing the energy wasted by solvent heating. After its thermal regeneration, the absorbent is mixed again with the solvent to get back the starting absorbent solution. This biphasic technique combines the advantages of both organic solvents and solvent–free sorbents previously studied. A first series of experiments, which involves sodium and potassium carbonates and some amines (piperazine and AMP), has been completed with good results. Another series of tests very promising, using alkanolamines in low viscous solvents, is still under development. In these three years, in our laboratory, has been also developed a new concept of CO2 capture technology which combines the CO2 abatement with the production of commercially valuable products. Turning carbon dioxide into useful chemicals in relatively mild conditions circumvent most of the drawbacks of the energy consuming steps of CO2 desorption, absorbent regeneration as well as of CO2 transporting and ultimate disposal. It has been verified the efficient absorption of CO2 by water-ethanol ammonia and by some non-aqueous amines. These experiments were addressed to recover the captured CO2 as solid ammonium carbamate or carbamates of the protonated amines. By heating the solid ammonium carbonate and bicarbonate mixtures or the amine carbamates in a closed reactor, we obtained their conversion into urea and, respectively, 1,3-disubstituted ureas with reasonable yields (30-50%). Urea is the world's most used fertilizer and it is produced in large quantities, while 1,3-disubstituted ureas are valuable products with a wide range of application as intermediates in agrochemical, pharmaceutical, dye chemicals and raw materials of polyurethanes. In addition, it has been studied the chemistry of the CO2 uptake by resorcinol (1,3-dihydroxy benzene) in alkaline aqueous and water/glycerol solutions under different experimental conditions, with the purpose of unveiling the reaction mechanism and maximizing the resorcinol conversion into β-resorcylic acid (2,4-dihydroxybenzoic acid).

With the ever increasing environmental concerns in terms of the need for a vast improvement in clean energy and clean air technologies, this thesis focuses on analyzing the underlying principles that determine the activity of catalysts/sorbents for fuel cell applications and CO₂ capture using first principles based simulations with a view point to help fabricate efficient catalysts. We attempt to clarify the fuzzy concepts of existing surface-nearsurface interactions in Pd based electrocatalysts with particular attention to Pd₃Co alloy catalysts by presenting a thorough inter and intra-layer orbital analysis and bring forth the crucial role played by the surface-subsurface binding driven by the out of plane d-state interactions in determining the surface reactivity. We first decouple the effects induced by the different Pd-Pd and Pd-Co lattice parameters (lattice strain effect) from the hetero atom induced surface-subsurface interaction (we call it "interlayer ligand effect") and clearly demonstrate how enhanced surface-subsurface d [subscript xz+yz] interaction leads to an increased oxygen hydrogenation to H₂O in Pd₃Co based electrocatalysts. We then extend the concept of hetero atom induced surface-subsurface binding to a series of 3d transition metals and provide guidelines for the right choice of metals that may be potential ORR candidates. Finally, we describe the facet dependence and the effect of surface Au alloying on the surface reactivity of Pd₃Co electrocatalysts. In the second section of the thesis, we emphasize on the underlying principles of CO₂ capture by MEA and study the synergetic interplay of various factors that may lead to better CO₂ capture , also enabling efficient solvent regeneration. Though extensive studies are carried out on the most traditionally used alkanol amine MEA for CO₂ capture, there are several less studied aspects like the molecular orbital redistribution on CO₂ binding that decides the fate of the intermediate species and the role of water arrangement in assisting/hindering the progress of the reaction. We study the fundamental CO₂-amine interactions and highlight the crucial importance of alkanol-amine configuration, water arrangement and protonation/de-protonation tendencies at various basic sites in the development of the reaction. We then analyze the synergetic interplay between the inductive effect, the steric hindrance and the resonance in enhancing efficient CO₂ binding and allowing an alternative O-driven mechanism resulting into easy solvent regeneration. We believe that our efforts may help fabricate better catalysts and sorbents and help improve the existing clean energy and clean air technologies.
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This dissertation seeks to reduce the energy consumption of steam stripping to regenerate aqueous amine used for CO₂ capture from coal-fired power plants. Rigorous rate-based models in Aspen Plus® were developed, and rate-based simulations were used for packed vapor/liquid separation units. Five main configurations with varying levels of complexity were evaluated with the two solvents. 8 m piperazine (PZ) always performed better than 9 m monoethanolamine (MEA). More complex flowsheets stripped CO₂ with higher efficiency due to the more reversible separation. Multi-stage flash configurations were competitive at their optimal lean loadings, but they had poor efficiency at low lean loading. The most efficient configuration was an interheated column, with more effective and distributed heat exchange. It had a secondary benefit of a cooler overhead temperature, so less water vapor exited with the CO₂. Using a rich loading of 0.40 mol CO₂/mol alkalinity in 8 m PZ, the optimal lean loading was 0.28 and the energy requirement was 30.9 kJ/mol CO₂. Case studies were also performed on cold rich bypass and the use of geothermal heat. When cold rich bypass is used with the 2-stage flash and 8 m PZ, it reduces equivalent work by 11% to 30.7 kJ/mol CO₂. PZ benefited the most from cold rich bypass because it had a higher water concentration in the overhead vapor than with MEA. In an advanced 2-stage flash with 8 m PZ, geothermal heat available from 150 down to 100 °C requires 35.5 kJ work/mol CO₂. The heat duty and equivalent work was higher than other optimized configurations, but it would be a valid option if separating the heat source from the steam cycle of a coal-fired power plant was highly valued. Pilot plant campaigns were simulated with the available thermodynamic models. Two campaigns with 8 m PZ were simulated within small deviation from the measured values. The average absolute errors in these campaigns were 2.5 and 2.7%. A campaign with 9 m MEA in a simple stripper demonstrated that the MEA model did not predict the solvent properties well enough to appropriately represent the pilot plant operation.
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碩士
國立交通大學
生物資訊研究所
93
The prediction of the three-dimensional structure from its sequence is probably one of the most important goals of modern biology. The accurate prediction of protein relative solvent accessibility is useful for the prediction of tertiary structure of a protein. Amino acid solvent accessibility is the degree to which a residue in a protein is accessible to a solvent molecule. Because the binding sites of a protein are usually located on its surface, accurately predicting the surface residues can be regarded as an important step toward determining its function. On the other hand, it has been observed that the distribution of surface residues of a protein is correlated with its subcellular environments; consequently, information of surface residues may improve the prediction of protein subcellular localization. Presently, out best method is based on the support vector machines using as the input feature vectors, the sliding window that includes the local environment descriptors such as PSSM, secondary structure profile and hydropathy indexes. In my work, relative solvent accessibility based on a 2-state model, for 25%, 16%, 5%, and 0% accessibility are predicted at 77.2%, 77.1%, 80.4%, and 88.4% accuracy, respectively. Furthermore, solvent accessibility prediction methods have in recent years reached accuracy in the range of 75.0-78.3% at 25% threshold. And the results based in a 10-state model can reach 15.2% mean absolute error and 0.51 correlations.

Thesis (Ph.D) -- New Jersey Institute of Technology, Dept. of Chemical Engineering, Chemistry and Environmental Science, 2002.
Includes bibliographical references. Also available via the World Wide Web.

1-Decene is a valuable product in linear alpha olefins plants that is contaminated with 2-EHA (2-ethyl hexyl amine). Using organic solvent nanofiltration membranes for this separation is quite challengeable. A membrane has to be a chemically stable in this environment with reasonable and stable separation factor. This paper shows that Teflon AF 2400 and cellulose acetate produced interesting results in 1-decene/2-EHA separation. The separation factor of Teflon AF 2400 is 3 with a stable permeance of 1.1x10-2 L/(m2·h·bar). Likewise, cellulose acetate gave 2-EHA/1-decene separation factor of 2 with a lower permeance of 3.67x10-3 L/(m2·h·bar). A series of hydrophilic membranes were tested but they did not give any separation due to high degree of swelling of 2-EHA with these polymers. The large swelling causes the membrane to lose its diffusivity selectivity because of an increase in the polymer's chain mobility.

碩士
國立中興大學
化學系所
104
To understand the physical behavior of solvent system in microscopic structure, such as amino acids in aqueous solution, the Voronoi tessellation method was employed to analyze space distribution of solvent surrounding the solute. The Voronoi polyhedra can be constructed through Delaunay simplexes. In our analysis, each non-hydrogen atom is treated as an independent element and a space-dependent factor is introduced for every element. In an equilibrium homogenous system, each Voronoi polyhedron is not identical but should have same average factor which is treated as the standard by definition. Compared with the standard factor of the homogenous system, i.e., pure water system, the factor on the solute surface should give out the information of interaction between the solvent and the solute. Therefore, this space-dependent factor must include the locally abnormal distribution with statistical significance. We then constructed the statistical entropy based on this factor to interpret thermodynamic behavior of amino acids, peptides and even proteins. Through analyzing the solvation differences between 20 standard amino acids, we quantify contribution of the different side-chain toward solvation of the solute surfaces in terms of statistical entropy.

碩士
國立宜蘭大學
化學工程與材料工程學系碩士班
104
Environmental protection is an important issue to the future. It is an important challange to decrease the level of volatile organic concentration (VOC) recently. Therefore, solvent based PU resins will be gradually replaced by aqueous based polyurethane dispersions (PUDs). Acetone process is the most important manufacture process, which had 5 to 50 wt. % acetone added. Then, it also requires vacuum distillation to remove solvents from PUDs, but still has some residual and odd exist. PUDs usually can be made to have 30 – 40 wt. % solid content. If we can increase the solid content to 50 – 60 wt. ％, it has the advantages of low capital investment, low product cost and high yield rate. The incorporation of anionic groups into polyurethanes and neutralizing the anionomer carboxylic group is the most widely used to make PUDs. Amine neutralizing agent contented PUDs evaporate delocalized amine after drying which cause the air pollution and health hazard. The development of non-delocalized amine PUDs is another essential topic for environmental friendly PUDs. The purpose of this research is to creat a solvent free, high solid content (50 wt. %), non-delocalized amine PUDs fit the following criteria: (1) solvent free process, (2) solids content ≧ 50 wt. %, (3) viscosity < 3,000 cps, (4) particle size < 200 nm, (5) tensile strength > 30 MPa, (6) storage stability > 6 months, (7) non-delocalized amine. There are three parts of this research focused on. Part I: investigate three parameters of high solid content PUDs: (1) chain extension ratio from 0 % to 100 %, (2) hydrophilic group content (HGC) : 2.5, 2.7, 3.0 and 5.0 wt. %, respectively. (3) incorporating of polyester polyol (PBA 2000) blend with polycarbonate diol (PCD 4671) with the equivalent ratio of 10:0, 5:5, 4:6, 3:7 and 0:10, respectively to reduce the viscosity of PUDs. Part II, high solid content (50 wt. %) PUDs based on polyester polyol (PBA 2000 and PHA 2000) can more easily occur phase inversion and prepolymer equivalent were controlled at 3,900 g/ eq. mol or 4,517 g/ eq. mol, and the storage stability of the PUDs and the properties of the PUDs are investigated. Part III, high solid content (50 wt. %) PUDs with non-delocalized amine of sodium hydroxide (NaOH) and soldium hydrogen carbonate (Na2CO3) as the non amine neutralizing agent. The non amine neutralizing agent was incorporated by NaOH and Na2CO3 with the molar ratio of 10:0, 9:1, 8:2, 7:3, 6:4 and 5:5, respectively. The properties of these PUDs were characterized by particle size, viscosity tests and tensile property. From the experiments results, we adopted HDI:IPDI, PBA2000, DMBA, neutralizing agent that incorporating of NaOH and Na2CO3 with the molar ratio 8:2, chain extender EDA with a chain extension ratio of 100 % and HGC = 5 wt. %. We successfully synthesis a solid content 50 wt. % PUD product by solvent free process, with a particle size of 182 nm, viscosity of 508 cps, tensile strength of 31.5 MPa, and storage stability above 6 months were obtained. The product has fulfilled the seven criteria above. We have successfully developed a solvent free, non-delocalized amine, high solid content, low production costs and environment friendly PUD with competitive price.