Catalysis by gold for biomass transformations

The development of new technologies to supplement fossil resources has led to a growing interest in the utilization of alternative routes. Biomass is a rich renewable feedstock for producing fine chemicals, polymers, and a variety of commodities replacing petroleumderived chemicals. Transformation of biomass into diverse valuable chemicals is the key concept of a biorefinery. Catalytic conversion of biomass, which reduces the use of toxic chemicals is one of the important approaches to improve the profitability of biorefineries. Utilization of gold catalysts allows conducting reactions under environmentally-friendly conditions, with a high catalytic activity and selectivity. Gold-catalyzed valorization of several biomass-derived compounds as an alternative approach to the existing technologies was studied in this work. Isomerization of linoleic acid via double bond migration towards biologically active conjugated linoleic acid isomers (CLA) was investigated. The activity and selectivity of various gold catalysts towards cis-9,trans-11-CLA and trans-10,cis-12-CLA were investigated in a semi-batch reactor, showing that the yield of the desired products varied, depending on the catalyst support. The structure sensitivity in the selective oxidation of arabinose was demonstrated using a series of gold catalysts with different Au cluster sizes in a shaker reactor operating in a semibatch mode. The gas-phase selective oxidation of ethanol was studied and the influence of the catalyst support on the catalytic performance was investigated. The selective oxidation of the lignan hydroxymatairesinol (HMR), extracted from the Norway spruce (Picea abies) knots, to the lignan oxomatairesinol (oxoMAT) was extensively investigated. The influence of the reaction conditions and catalyst properties on the yield of oxoMAT was evaluated. In particular, the structure sensitivity of the reaction was demonstrated. The catalyst deactivation and regeneration procedures were studied. The reaction kinetics and mechanism were advanced.

Gold recovery from cyanideand chloride solution using activated carbon

Uusia keinoja kullan erottamiseksi malmista on etsitty viimeaikoina taloudellisista ja ympäristöllisistä syistä kautta maailman. Syanidointimenetelmä on hallinnut kullan talteenottoayli sata vuotta. Menetelmässä kulta liuotetaan laimeaan syanidiliuokseen, jostase otetaan talteen aktiivihiilen avulla. Syanidin käyttöä pyritään kuitenkin vähentämään sen myrkyllisyyden takia. Lisäksi nykyään louhitaan enenemässä määrin malmia, josta on hankala rikastaa kulta kustannustehokkaasti syanidia käyttäen. Kullan talteenottoa syanidi- ja kloridiliuoksesta on selvitetty kirjallisuuden avulla. Kullan kemiaan liuotuksen aikana on perehdytty ennen kullan talteenottoa aktiivihiilellä. Aktiivihiilen elinkaari kullan adsorbenttinaon käsitelty valmistuksesta hylkäämiseen mukaan lukien hiilen myrkyttyminen prosessissa ja regenerointi. Aktiivi-hiilen käyttäytyminen syanidi- ja kloridiliuoksessa on selvitetty erikseen. Kullan talteenottoa kuparipitoisista malmeista on käsitelty. Kullan talteenottoa kloridiliuoksesta aktiivihiiltä käyttäen on tutkittu kokeellisesti. Pääasialliset tutkimuskohteet ovat adsorption kinetiikka, kuparin vaikutus adsorptioon, aktiivihiilen vaikutus adsorptioonja adsorboituneiden metallien strippaus hiilestä selektiivisesti. Hapettavan stippauksen vaikutus kullan desorptioon hiilestä on tutkittu yksityiskohtaisesti. Kullan erotusmenetelmät kuparimalmista aktiivihiiltä käyttäen on selvitetty diplomityön tulosten pohjalta. Diplomityön keskeisten tulosten perusteella kulta ei välttämättä saostu aktiivihiilen pinnalle kloridiliuoksesta. Havainto varmistettiin ladattujen hiilipartikkelien pyyhkäisyelektronimikroskooppikuvista ja partikkeleille tehdyistä mikroanalyyseistä. Kullan pelkistyminen metalliseksi kullaksi aktiivihiilessä voitaneen välttää käyttämällä erittäin hapettavia olosuhteita. Aktiivihiili ilmeisesti hapettuu näissä olosuhteissa, mikä mahdollistaa kultakloridin adsorboitumisen hiileen.

Gold investments and short- and long-run price determinants of the price of gold

Tämän tutkielman tavoitteena on tutkia tekijöitä jotkavaikuttavat lyhyellä ja pitkällä aikavälillä kullan hintaan. Toiseksi tutkielmassa selvitetään mitä eri sijoitusmahdollisuuksia löytyy kultaan sijoitettaessa. Aineistona käytetään kuukausitasoista dataa Yhdysvaltain ja maailman hintaindekseistä, Yhdysvaltain ja maailman inflaatiosta ja inflaation volatiliteetista, kullan beetasta, kullan lainahinnasta, luottoriskistä ja Yhdysvaltojen ja maailman valuuttakurssi indeksistä joulukuulta 1972 elokuulle 2006. Yhteisintegraatio regressiotekniikoita käytettiin muodostamaan malli jonka avullatutkittiin päätekijöitä jotka vaikuttavat kullan hintaan. Kirjallisuutta tutkimalla selvitettiin miten kultaan voidaan sijoittaa. Empiirisettulokset ovat yhteneväisiä edellisten tutkimusten kanssa. Tukea löytyi sille, että kulta on pitkän ajan suoja inflaatiota vastaan ja kulta ja Yhdysvaltojen inflaatio liikkuvat pitkällä aikavälillä yhdessä. Kullan hintaan vaikuttavat kuitenkin lyhyen ajan tekijät pitkän ajan tekijöitä enemmän. Kulta on myös sijoittajalle helppo sijoituskohde, koska se on hyvin saatavilla markkinoilla ja eri instrumentteja on lukuisia.

Modeling of Gold Cyanidation

The chemistry of gold dissolution in alkaline cyanide solution has continually received attention and new rate equations expressing the gold leaching are still developed. The effect of leaching parameters on gold gold cyanidation is studied in this work in order to optimize the leaching process. A gold leaching model, based on the well-known shrinking-core model, is presented in this work. It is proposed that the reaction takes place at the reacting particle surface which is continuously reduced as the reaction proceeds. The model parameters are estimated by comparing experimental data and simulations. The experimental data used in this work was obtained from Ling et al. (1996) and de Andrade Lima and Hodouin (2005). Two different rate equations, where the unreacted amount of gold is considered in one equation, are investigated. In this work, it is presented that the reaction at the surface is the rate controlling step since there is no internal diffusion limitation. The model considering the effect of non-reacting gold shows that the reaction orders are consistent with the experimental observations reported by Ling et al. (1996) and de Andrade Lima and Hodouin (2005). However, it should be noted that the model obtained in this work is based on assumptions of no side reactions, no solid-liquid mass transfer resistances and no effect from temperature.

The Structural Basis for inorganic Pyrophosphatase Catalysis and Regulation

Inorganic pyrophosphatases (PPases) are essential enzymes for every living cell. PPases provide the necessary thermodynamic pull for many biosynthetic reactions by hydrolyzing pyrophosphate. There are two types of PPases: integral membrane-bound and soluble enzymes. The latter type is divided into two non-homologous protein families, I and II. Family I PPases are present in all kingdoms of life, whereas family II PPases are only found in prokaryotes, including archae. Family I PPases, particularly that from Saccharomyces cerevisiae, are among the most extensively characterized phosphoryl transfer enzymes. In the present study, we have solved the structures of wild-type and seven active site variants of S. cerevisiae PPase bound to its natural metal cofactor, magnesium ion. These structures have facilitated derivation of the complete enzyme reaction scheme for PPase, fulfilling structures of all the reaction intermediates. The main focus in this study was on a novel subfamily of family II PPases (CBSPPase) containing a large insert formed by two CBS domains and a DRTGG domain within the catalytic domain. The CBS domain (named after cystathionine beta-synthase in which it was initially identified) usually occurs as tandem pairs with two or four copies in many proteins in all kingdoms of life. The structure formed by a pair of CBS domains is also known as a Bateman domain. CBS domains function as regulatory units, with adenylate ligands as the main effectors. The DRTGG domain (designated based on its most conserved residues) occurs less frequently and only in prokaryotes. Often, the domain co-exists with CBS domains, but its function remains unknown. The key objective of the current study was to explore the structural rearrangements in the CBS domains induced by regulatory adenylate ligands and their functional consequences. Two CBS-PPases were investigated, one from Clostridium perfringens (cpCBS-PPase) containing both CBS and DRTGG domains in its regulatory region and the other from Moorella thermoacetica (mt CBS-PPase) lacking the DRTGG domain. We additionally constructed a separate regulatory region of cpCBS-PPase (cpCBS). Both full-length enzymes and cpCBS formed homodimers. Two structures of the regulatory region of cpCBS-PPase complexed with the inhibitor, AMP, and activator, diadenosine tetraphosphate, were solved. The structures were significantly different, providing information on the structural pathway from bound adenylates to the interface between the regulatory and catalytic parts. To our knowledge, these are the first reported structures of a regulated CBS enzyme, which reveal large conformational changes upon regulator binding. The activator-bound structure was more open, consistent with the different thermostabilities of the activator- and inhibitor-bound forms of cpCBS-PPase. The results of the functional studies on wild-type and variant CBS-PPases provide support for inferences made on the basis of structural analyses. Moreover, these findings indicate that CBS-PPase activity is highly sensitive to adenine nucleotide distribution between AMP, ADP and ATP, and hence to the energy level of the cell. CBS-PPase activity is markedly inhibited at low energy levels, allowing PPi energy to be used for cell survival instead of being converted into heat.

Development of simple and efficient synthetic strategies for production of fine chemicals of pharmaceutical relevance : metal-mediated allylation combined with applied catalysis

Den snart 200 år gamla vetenskapsgrenen organisk synteskemi har starkt bidragit till moderna samhällens välfärd. Ett av flaggskeppen för den organiska synteskemin är utvecklingen och produktionen av nya läkemedel och speciellt de aktiva substanserna däri. Därmed är det viktigt att utveckla nya syntesmetoder, som kan tillämpas vid framställningen av farmaceutiskt relevanta målstrukturer. I detta sammanhang är den ultimata målsättningen dock inte endast en lyckad syntes av målmolekylen, utan det är allt viktigare att utveckla syntesrutter som uppfyller kriterierna för den hållbara utvecklingen. Ett av de centralaste verktygen som en organisk kemist har till förfogande i detta sammanhang är katalys, eller mera specifikt möjligheten att tillämpa olika katalytiska reaktioner vid framställning av komplexa målstrukturer. De motsvarande industriella processerna karakteriseras av hög effektivitet och minimerad avfallsproduktion, vilket naturligtvis gynnar den kemiska industrin samtidigt som de negativa miljöeffekterna minskas avsevärt. I denna doktorsavhandling har nya syntesrutter för produktion av finkemikalier med farmaceutisk relevans utvecklats genom att kombinera förhållandevis enkla transformationer till nya reaktionssekvenser. Alla reaktionssekvenser som diskuteras i denna avhandling påbörjades med en metallförmedlad allylering av utvalda aldehyder eller aldiminer. De erhållna produkterna innehållende en kol-koldubbelbindning med en närliggande hydroxyl- eller aminogrupp modifierades sedan vidare genom att tillämpa välkända katalytiska reaktioner. Alla syntetiserade molekyler som presenteras i denna avhandling karakteriseras som finkemikalier med hög potential vid farmaceutiska tillämpningar. Utöver detta tillämpades en mängd olika katalytiska reaktioner framgångsrikt vid syntes av dessa molekyler, vilket i sin tur förstärker betydelsen för de katalytiska verktygen i organiska kemins verktygslåda.

62 gold 60 silver 63 bronze

kuv., 10 x 13 cm

62 gold 60 silber 63 bronze

kuv., 10 x 13 cm

Pretreatment processes in gold recovery by thiosulphate leaching

This thesis describes several different pretreatment processes for gold concentrates and ores. The thesis is divided to theoretical part and experimental part. The theoretical part presents the operating principle of the main pretreatment methods and their suitability for thiosulphate leaching. In the theoretical part also the whole recovery process for gold from ore to elemental gold is presented. In the experimental part the study is focused on pretreatment of sulphidic refractory concentrates with mechanical activation and chemical oxidation under alkaline environment; and their effect on leachability in the thiosulphate leaching. In the experimental part a combined 2-step process, where chemical oxidation under ammoniacal environment is cascaded with thiosulphate leaching in the same conditions, is also tested. The main sulphuric mineral components in the studied refractory concentrate are pyrite (49.4 %) and arsenopyrite (27.7 %). The gold content in the concentrate is 11.3 ppm and silver content is 90 ppm. Without pretreatment the gold conversion in thiosulphate leaching was 30 %, which was analyzed at the time point of 9 hours. At that time the silver conversion was 17 %. By using mechanical activation the gold conversion reached was 59 % and silver conversion 26 %. With chemical oxidation under alkaline environment, where the used chemical was sodium hydroxide, the reached conversion of gold was 72 % and 31 % for silver. In the combined oxidation and leaching experiment the conversion of gold remained at 49 % and 18 % for silver.

A new climatic periodisation of the Gold and Guinea Coasts in West Africa, 1750-1798 : a reconstruction of the climate during the slave trade era, including an analysis of the climatically facilitated Trans-Atlantic slave trade

Avsikten med studien är att producera den första rekonstruktionen av det västafrikanska klimatet mellan 1750 och 1798. Kunskapen om det västafrikanska klimatet före 1800-talet är till dags dato bristfällig, vilket gör det svårare att förstå framtida klimatvariationer. Det är bristen på instrumentell meteorologisk data (temperatur, regnmängd, och lufttryck), vilket i princip bara täcker det senaste århundradet, som är orsaken till att tidigare klimat är bristfälligt kartlagda. Klimatet och miljön är även sådana att proxydata från ’naturens arkiv’ (såsom t.ex. trädringar) har begränsad användning. Således är historiska dokument, främst från gästande kulturer/nationer/intressenter, innehållande deskriptiv information om vädret och klimatet, klimatforskarens viktigaste källa. Genom att använda tidigare, för det här syftet, oanvända källor påvisade den här undersökningen att klimatet i västra Afrika och Guldkusten (Ghana) har ändrats sedan 1700-talet. Monsunregnen var svagare och kortvarigare, speciellt den sekundära regnperioden under hösten var betydligt svagare än idag. Det förekom kraftiga årliga variationer i monsunregnen, men sett ur längre tidsperspektiv utmärktes torrare och blötare perioder. Studien kunde också visa en viss korrelation mellan det globala väderfenomenet El Niño och regnperiodens intensitet längs med kusten. Flera torrperioder sammanföll med tidigare registrerade El Niño sekvenser. Speciellt slutet av 1760-talet påverkades kraftigt av El Niño och även det globala klimatet verkar ha genomgått graftiga förändringar just dessa år. På basis av den nya klimatrekonstruktionen genomfördes också en jämförelse av klimatets inverkan på den transatlantiska slavhandeln från 1750 till 1798, en fråga som historikerna gjort anspelningar på i över 30 år. Utförseln av slavar från västra Afrika var som kraftigast under 1700-talets andra hälft. Analysen visade att slavhandeln delvis tilltog i samband med klimatanomalierna.

Modeling of high pressure pretreatment process for gold leaching

Investigation of high pressure pretreatment process for gold leaching is the objective of the present master's thesis. The gold ores and concentrates which cannot be easily treated by leaching process are called "refractory". These types of ores or concentrates often have high content of sulfur and arsenic that renders the precious metal inaccessible to the leaching agents. Since the refractory ores in gold manufacturing industry take a considerable share, the pressure oxidation method (autoclave method) is considered as one of the possible ways to overcome the related problems. Mathematical modeling is the main approach in this thesis which was used for investigation of high pressure oxidation process. For this task, available information from literature concerning this phenomenon, including chemistry, mass transfer and kinetics, reaction conditions, applied apparatus and application, was collected and studied. The modeling part includes investigation of pyrite oxidation kinetics in order to create a descriptive mathematical model. The following major steps are completed: creation of process model by using the available knowledge; estimation of unknown parameters and determination of goodness of the fit; study of the reliability of the model and its parameters.

Terpenoid transformations over gold catalysts

Nowadays biomass transformation has a great potential for the synthesis of value-added compounds with a wide range of applications. Terpenoids, extracted from biomass, are inexpensive and renewable raw materials which often have a biological activity and are widely used as important organic platform molecules in the development of new medicines as well as in the synthesis of fine chemicals and intermediates. At the same time, special attention is devoted to the application of gold catalysts to fine chemical synthesis due to their outstanding activity and/or selectivity for transformations of complex organic compounds. Conversion of renewable terpenoids in the presence of gold nanoparticles is one of the new and promising directions in the transformation of biomass to valuable chemicals. In the doctoral thesis, different kinds of natural terpenoids, such as α-pinene, myrtenol and carvone were selected as starting materials. Gold catalysts were utilized for the promising routes of these compounds transformation. Investigation of selective α-pinene isomerization to camphene, which is an important step in an industrial process towards the synthesis of camphor as well as other valuable substrates for the pharmaceutical industry, was performed. A high activity of heterogeneous gold catalysts in the Wagner-Meerwein rearrangement was demonstrated for the first time. Gold on alumina carrier was found to reach the α-pinene isomerization conversion up to 99.9% and the selectivity of 60-80%, thus making this catalyst very promising from an industrial viewpoint. A detailed investigation of kinetic regularities including catalyst deactivation during the reaction was performed. The one-pot terpene alcohol amination, which is a promising approach to the synthesis of valuable complex amines having specific physiological properties, was investigated. The general regularities of the one-pot natural myrtenol amination in the presence of gold catalysts as well as a correlation between catalytic activity, catalyst redox treatment and the support nature were obtained. Catalytic activity and product distribution were shown to be strongly dependent on the support properties, namely acidity and basicity. The gold-zirconia (Au/ZrO2) catalyst pretreated under oxidizing atmosphere was observed to be rather active, resulting in the total conversion of myrtenol and the selectivity to the corresponding amine of about 53%. The reaction kinetics was modelled based on the mechanistic considerations with the catalyst deactivation step incorporated in the mechanism. Carvone hydrogenation over a gold catalyst was studied with the general idea of investigating both the activity of gold catalysts in competitive hydrogenation of different functional groups and developing an approach to the synthesis of valuable carvone derivatives. Gold was found to promote stereo- and chemoselective carvone hydrogenation to dihydrocarvone with a predominant formation of the trans-isomer, which generally is a novel synthetic method for an industrially valuable dihydrocarvone. The solvent effect on the catalytic activity as well as on the ratio between trans- and cis-dihydrocarvone was evaluated.

Interdependence of International Stock Markets, European Government Bond Market and Gold Market

This thesis examines the interdependence of international stock markets (the USA, Europe, Japan, emerging markets, and frontier markets), European government bond market, and gold market during the 21st century. Special focus is on the dynamics of the correlations between the markets, as well as on, spillovers in mean returns and volatility. The mean return spillovers are examined on the basis of the bivariate VAR(1) model, whereas the bivariate BEKK-GARCH(1, 1) model is employed for the analysis of the volatility spillovers. In order to analyze the spillover effects in different market conditions, the full sample period from 2000 to 2013 is divided into the pre-crisis period (2000–2006) and the crisis period (2007–2013). The results indicate an increasing interdependence especially within international stock markets during the periods of financial turbulence, and are thus consistent with the existing literature. Hence, bond and gold markets provide the best diversification benefits for equity investors, particularly during the periods of market turmoil.

Lipase and omega-transaminase catalysis in preparation of alcohol and amine enantiomers

Enantiopure intermediates are of high value in drug synthesis. Biocatalysis alone or combined with chemical synthesis provides powerful tools to access enantiopure compounds. In biocatalysis, chemo-, regio- and enantioselectivity of enzymes are combined with their inherent environmentally benign nature. Enzymes can be applied in versatile chemical reactions with non-natural substrates under synthesis conditions. Immobilization of an enzyme is a crucial part of an efficient biocatalytic synthesis method. Successful immobilization enhances the catalytic performance of an enzyme and enables its reuse in successive reactions. This thesis demonstrates the feasibility of biocatalysis in the preparation of enantiopure secondary alcohols and primary amines. Viability and synthetic usability of the studied biocatalytic methods have been addressed throughout this thesis. Candida antarctica lipase B (CAL-B) catalyzed enantioselective O-acylation of racemic secondary alcohols was successfully incorporated with in situ racemization in the dynamic kinetic resolution, affording the (R)-esters in high yields and enantiopurities. Side reactions causing decrease in yield and enantiopurity were suppressed. CAL-B was also utilized in the solvent-free kinetic resolution of racemic primary amines. This method produced the enantiomers as (R)-amides and (S)-amines under ambient conditions. An in-house sol-gel entrapment increased the reusability of CAL-B. Arthrobacter sp. omega-transaminase was entrapped in sol-gel matrices to obtain a reusable catalyst for the preparation enantiopure primary amines in an aqueous medium. The obtained heterogeneous omega-transaminase catalyst enabled the enantiomeric enrichment of the racemic amines to their (S)-enantiomers. The synthetic usability of the sol-gel catalyst was demonstrated in five successive preparative kinetic resolutions.