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.

Sustainable Gold Mining- Life Cycle Assessment of Cyanidation and Thiosulphate Leaching

With the increasing concern of the sustainable approach of gold mining, thiosulphate has been researched as an alternative lixiviant to cyanide since cyanide is toxic to the environment. In order to investigate the possibility of thiosulphate leaching application in the coming future, life cycle assessment, is conducted to compare the environmental footprint of cyanidation and thiosulphate leaching. The result showed the most significant environmental impact of cyanidation is toxicity to human, while the ammonia of thiosulphate leaching is also a major concern of acidification. In addition, an ecosystem evaluation is also performed to indicate the potential damages caused by an example of cyanide spill at Kittilä mine, resulting in significant environmental risk cost that has to be taken into account for decision making. From the opinion collected from an online LinkedIn discussion forum, the anxiety of sustainability alone would not be enough to contribute a significant change of conventional cyanidation, until the tighten policy of cyanide use. International Cyanide Code, therefore, is crucial for safe gold production. Nevertheless, it is still thoughtful to consider the values of healthy ecosystem and the gold for long-term benefit.

From gold money to fictitious money

ABSTRACT In the nineteenth century, money appear primarily as gold. In the twenty-first century, it appears as strictly fiduciary money. It is known that Marx said very clearly that the golden money was the effective basis of the monetary and credit system. Had the historical development finally shown that his theory of value and money would be false? Marxists have struggled continually with this problem. This paper tries to show that exist a simple and good answer to this crucial question. It comes just developing a little the dialectics of commodities and money found on Marx's Capital.

Improvement of Energy Efficiency in a Gold Mining Industry: Case Study of a Russian Gold Mining Company

The issue of energy efficiency is attracting more and more attention of academia, business and policy makers worldwide due to increasing environmental concerns, depletion of non-renewable energy resources and unstable energy prices. The significant importance of energy efficiency within gold mining industry is justified by considerable energy intensity of this industry as well as by the high share of energy costs in the total operational costs. In the context of increasing industrial energy consumption energy efficiency improvement may provide significant energy savings and reduction of CO2 emission that is highly important in order to contribute to the global goal of sustainability. The purpose of this research is to identify the ways of energy efficiency improvement relevant for a gold mining company. The study implements single holistic case study research strategy focused on a Russian gold mining company. The research involves comprehensive analysis of company’s energy performance including analysis of energy efficiency and energy management practices. This study provides following theoretical and managerial contributions. Firstly, it proposes a methodology for comparative analysis of energy performance of Russian and foreign gold mining companies. Secondly, this study provides comprehensive analysis of main energy efficiency challenges relevant for a Russian gold mining company. Finally, in order to overcome identified challenges this research conceives a guidance for a gold mining company for implementation of energy management system based on the ISO standard.

Variational Monte Carlo study of core-valence separation schemes for first-row atoms and positive ions /

All-electron partitioning of wave functions into products ^core^vai of core and valence parts in orbital space results in the loss of core-valence antisymmetry, uncorrelation of motion of core and valence electrons, and core-valence overlap. These effects are studied with the variational Monte Carlo method using appropriately designed wave functions for the first-row atoms and positive ions. It is shown that the loss of antisymmetry with respect to interchange of core and valence electrons is a dominant effect which increases rapidly through the row, while the effect of core-valence uncorrelation is generally smaller. Orthogonality of the core and valence parts partially substitutes the exclusion principle and is absolutely necessary for meaningful calculations with partitioned wave functions. Core-valence overlap may lead to nonsensical values of the total energy. It has been found that even relatively crude core-valence partitioned wave functions generally can estimate ionization potentials with better accuracy than that of the traditional, non-partitioned ones, provided that they achieve maximum separation (independence) of core and valence shells accompanied by high internal flexibility of ^core and Wvai- Our best core-valence partitioned wave function of that kind estimates the IP's with an accuracy comparable to the most accurate theoretical determinations in the literature.

Diffusion Monte Carlo study of electronic properties for H and Be atoms /

We examined three different algorithms used in diffusion Monte Carlo (DMC) to study their precisions and accuracies in predicting properties of isolated atoms, which are H atom ground state, Be atom ground state and H atom first excited state. All three algorithms — basic DMC, minimal stochastic reconfiguration DMC, and pure DMC, each with future-walking, are successfully impletmented in ground state energy and simple moments calculations with satisfactory results. Pure diffusion Monte Carlo with future-walking algorithm is proven to be the simplest approach with the least variance. Polarizabilities for Be atom ground state and H atom first excited state are not satisfactorily estimated in the infinitesimal differentiation approach. Likewise, an approach using the finite field approximation with an unperturbed wavefunction for the latter system also fails. However, accurate estimations for the a-polarizabilities are obtained by using wavefunctions that come from the time-independent perturbation theory. This suggests the flaw in our approach to polarizability estimation for these difficult cases rests with our having assumed the trial function is unaffected by infinitesimal perturbations in the Hamiltonian.

Dechanneling of 2 Mev Heâ ½ in gold

Thick gold single crystals of high quality were prepared for Rutherford Backscattering Dechanneling studies by electropolishing and annealing. The variation.; with temperature of the Random Fraction versus Depth spectrtnn for 2 MeV He+ on < 110> gold was extracted from measured Aligned and Random (Energy) Spectra. The measured dechanneling rate showed a sixfold increase in going from 4loK to 293°K and is in reasonable agreement with calculations made using the Steady Increase in Transverse Energy (SITE) approximation.

Studies of some cocondensations of nickel atoms with unsaturated organic ligands and with mixed ligand systems

The cocondensation of nickel with a number of unsaturated ligands was studied, as was the cocondensation with a number of mixed ligand systems. Enamines were found not to react with nickel while acrylonitrile was polymerized. In the mixed ligand syst.ems different products were obtained than when the ligands were cocondensed individually. Cocondensations of benzyl halide/allyl halide mixtures gave unstable products that were not observed when the halides were cocondensed individually. The effect of Kao-Wool insulation on nickel/benzyl halide cocondensations was found to be significant. Kao-Wool caused the bulk of the benzyl halide to be polymeri zed to a number of poly-benzylic species. An alkali metal reactor was designed for the evaporation of sodium and potassium atoms into cold solutions of metal halide and an or ganic substrate. This apparatus was used to synthesize Ni(P¢3 )3' but proved unsuccessful for synthesizing a nickel-enamine compound.

Synthesis of nanoporous materials for preconcentration and determination of trace elements by ICP-AES ; Investigation and elimination of the memory effects of mercury, gold, silver and boron in ICP-AES

Nanoporous materials with large surface area and well-ordered pore structure have been synthesized. Thiol groups were grafted on the materials' surface to make heavy metal ion pre-concentration media. The adsorption properties ofthe materials were explored. Mercury, gold and silver can be strongly adsorbed by these materials, even in the presence of alkaline earth metal ion. Though the materials can adsorb other heavy metal ions such as lead and copper, they show differential adsorption ability when several ions are present in solution. The adsorption sequence is: mercury> == silver> copper » lead and cadmium. In the second part of this work, the memory effects of mercury, gold, silver and boron were investigated. The addition of 2% L-cysteine and 1% thiourea eliminates the problems of the three metal ions completely. The wash-out time for mercury dropped from more than 20 minutes to 18 seconds, and the wash-out time for gold decreased from more than 30 minutes to 49 seconds. The memory effect of boron can be reduced by the use of mannitol.

Quantum Monte Carlo study of electrostatic polarizabilities of H and He atoms /

The infinitesimal differential quantum Monte Carlo (QMC) technique is used to estimate electrostatic polarizabilities of the H and He atoms up to the sixth order in the electric field perturbation. All 542 different QMC estimators of the nonzero atomic polarizabilities are derived and used in order to decrease the statistical error and to obtain the maximum efficiency of the simulations. We are confident that the estimates are "exact" (free of systematic error): the two atoms are nodeless systems, hence no fixed-node error is introduced. Furthermore, we develope and use techniques which eliminate systematic error inherent when extrapolating our results to zero time-step and large stack-size. The QMC results are consistent with published accurate values obtained using perturbation methods. The precision is found to be related to the number of perturbations, varying from 2 to 4 significant digits.

Gold Coast

Crate label for Gold Coast brand oranges picked and packaged by the Placentia Orange Company, which was owned and managed by Charles C. Chapman.

Gold Leaf

Gold leaf that belonged to great grandmother French. This is enclosed in an envelope which has Jas. Carruthers and Co. Grain Exporters, New York as a return address, n.d.

The Myth of Demonetarization of Gold

The aim of this paper is to discuss the crisis of the international financial system and the necessity of reforming it by new anchor or benchmark for the international currency, a money-commodity. The need for understanding the definition of a numéraire is a first necessity. Although most economists reject any connection between money and a particular commodity (gold) – because of the existence of legal tender money in every country – it will be shown that it is equivalent to reduce the real space to an abstract number (usually assumed 1) in order to postulate that money is neutral. This is sheer nonsense. It will also be shown that the concept of fiat money or state money does not preclude the existence of commodity money. This paper is divided in four sections. The first section analyses the definition and meaning of a numéraire for the international currency and the justification for a variable standard of value. In the second section, the market value of the US dollar is analysed by looking at new forms of value -the derivative products- the dollar as a safe haven, and the role of SDRs in reforming the international monetary system. In the third and fourth sections, empirical evidence concerning the most recent period of the financial crisis is presented and an econometric model is specified to fit those data. After estimating many different specifications of the model –linear stepwise regression, simultaneous regression with GMM estimator, error correction model- the main econometric result is that there is a one to one correspondence between the price of gold and the value of the US dollar. Indeed, the variance of the price of gold is mainly explained by the Euro exchange rate defined with respect to the US dollar, the inflation rate and negatively influenced by the Dow Jones index and the interest rate.