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Thesis--Uppsala. / In Periodical Room.

Thesis advisor: Amir H. Hoveyda / We have synthesized Ru-carbene isocyanide complexes that promote both ring-opening metathesis polymerization of norbornene as well as cycloisomerization of diethyl diallylmalonate. We have also synthesized a N-heterocyclic carbene complex bearing a biphenylthiol moiety, and we installed this ligand on a Ru-carbene to produce a racemic chiral bidentate Ru-thiolate complex. Although the Ru-thiolate was found to initiate more slowly than the corresponding biphenoxide catalyst, both perform ring-opening/cross-metathesis (ROCM) with similar efficiency. Several other bidentate Ru-complexes were synthesized where the anionic ligand was varied (tosylate, pivalate, and phenylthiolate), as well as a new Re-alkylidene bis-pyrrolide. We have expanded the scope of Ru-catalyzed enantioselective ROCM of cyclopropenes utilizing a variety of ester, ketone, ether, and aliphatic olefin cross-partners. The utility of this method was demonstrated in the enantioselective total synthesis of the marine natural product (+)-sporochnol, which was synthesized in 8% overall yield across eleven linear steps. Additionally, we have developed an enantio- and Z-selective ROCM of enol ethers and oxabicycles; we propose the origin of Z-selectivity to arise from a lower barrier to ruthancyclobutane cleavage/formation for the cis-substituted ruthenacyclobutane vs the trans-substituted ruthenacyclobutane (which is favored for ROCM of oxabicycles and styrene). We also have found that stereogenic-at-Ru complexes are capable of undergoing non-metathesis isomerization through polytopal rearrangements. This observation may explain why cyclopropene ROCM suffers from low enantioselectivity for many substrates. We have developed a diasteroselective ROCM reaction, which utilizes commercially available ruthenium dichloride catalysts in the presence of chiral allylic alcohols and cyclopropenes. Our investigation revealed that the presence of a hydroxyl group dramatically accelerates the rate of ROCM vs the corresponding methyl ether and delivered products in high yield and diastereoselectivity. Furthermore, we found that the methyl ether delivered the opposite diastereomer vs the allylic alcohol; this led us to propose that intramolecular H-bonding between the hydroxyl proton and a chloride ligand controls the diastereoselectivity and enhances the rate of the ROCM. Protic additives have also been found to promote polytopal rearrangements in stereogenic-at-Ru complexes; H-bonding may facilitate olefin metathesis in a similar fashion to polytopal rearrangement by reducing the trans effect during the transition state to ruthenacyclobutane formation. A number of synthetically useful allylic alcohols and strained olefin substrates efficiently provide products in high diastereoselectivity and with good E:Z selectivity (89:11-97:3 dr, 4:1-11:1 E:Z). We have developed a Mo-catalyzed Z-selective cross-metathesis (CM) reaction. A wide range of olefin cross partners were found to be effective for both enol ether and allylic amide substrates (51-97% yield, 81 to 98% Z). We applied our Z-selective CM method to the synthesis of KRN7000, a potent immunostimulant (the Z-allylic amide was obtained in 85% yield and 96% Z). We also utilized Z-selective CM in the formal synthesis of an enol ether plasmalogen C18 (plasm)-16:0 (PC), a lipid membrane component found in mammalian brain tissue (the enol ether was obtained in >98:2 Z selectivity). Z-selective cross-metathesis is therefore a new tool for synthetic chemists to access important building blocks for the synthesis of biologically active molecules. We have developed a Z-selective cross-metathesis of vinyl and allyl boronates. Reactions of both substrate classes proceed to between 50-95% conv and deliver Z-vinylboronate and Z-crotylboronate products in 85-93% Z selectivity. Allylboronate CM provides Z-crotylboronates which can be used for diastereoselective crotylation. The utility of Z-selective vinylboronate CM was demonstrated in the synthesis of a dienyl boronate (obtained in 83% yield and >98% Z) that will be utilized in the total synthesis of the potent anti-cancer agent disorazole C1. / Thesis (PhD) — Boston College, 2012. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

This thesis is dedicated to export funding to CIS countries. Among CIS countries, the author chose the three most important - Russia, Ukraine and Kazakhstan. The work creates detailing recommendations relating to trading in these areas. The main aim was to analyze the most commonly used methods of financing exports to CIS countries and to highlight their difficulties. The central hypothesis is the following statement: Russia, Kazakhstan and Ukraine are very interesting countries for Czech goods.

Postcranial non-metric skeletal traits are documented in two Cis-Baikal populations: the Kitoi, dating to the Early Neolithic (8000-7000/6800 BP), and the Isakovo/Serovo/Glazkovo (ISG) cultural complex, dating to the Late Neolithic (Isakavo/Serovo: 6000/5800-5200 BP) and Early Bronze Age (Glazkovo: 5200/5000-4000 BP). A major cultural discontinuity is thought to have occurred in the Middle Neolithic (7000/6800-6000/5800 BP). Current and previous research suggests that the Early Neolithic Kitoi were bioculturally distinct from the Late Neolithic-Bronze Age ISG cultural complex. Population, side, sex, and age differences in the expression of non-metric traits were explored as indicators of differing activity patterns and divisions of labour between and within the Kitoi and ISG samples, as well as two Kitoi cemeteries: Shamanka II and Lokomotiv. Results of analyses indicate that the Kitoi, particularly males, were taking part in locomotion over steep terrain while carrying heavy loads, probably related to hunting trips. The ISG do not show evidence of these types of activities, suggesting a population difference in the frequency and degree of physically strenuous activity. Kitoi and Shamanka II males and young adult individuals show evidence of having performed the majority of the strenuous lifting and carrying, as well as evidence of increased mobility relative to females. These results indicative of strong divisions of labour in the Kitoi population. Patterns in trait frequencies were also examined for indications of how multiple underlying factors may be interacting. Trait distribution throughout the body provides evidence of the dominance of biomechanical stress as a causative factor in the expression of postcranial non-metric traits. Other factors that become visible when the influence of biomechanical stress is lower include genotype, trauma, and cartilage degeneration. The results of this project are consistent with current theories on the adaptive regimes of the Kitoi and ISG populations and strongly support previous work by BAP researchers in the areas of skeletal robusticity, osteoarthritis, and musculoskeletal stress markers. The research also helps to broaden the knowledge base about the etiologies of the non-metric traits involved.

Postcranial non-metric skeletal traits are documented in two Cis-Baikal populations: the Kitoi, dating to the Early Neolithic (8000-7000/6800 BP), and the Isakovo/Serovo/Glazkovo (ISG) cultural complex, dating to the Late Neolithic (Isakavo/Serovo: 6000/5800-5200 BP) and Early Bronze Age (Glazkovo: 5200/5000-4000 BP). A major cultural discontinuity is thought to have occurred in the Middle Neolithic (7000/6800-6000/5800 BP). Current and previous research suggests that the Early Neolithic Kitoi were bioculturally distinct from the Late Neolithic-Bronze Age ISG cultural complex. Population, side, sex, and age differences in the expression of non-metric traits were explored as indicators of differing activity patterns and divisions of labour between and within the Kitoi and ISG samples, as well as two Kitoi cemeteries: Shamanka II and Lokomotiv. Results of analyses indicate that the Kitoi, particularly males, were taking part in locomotion over steep terrain while carrying heavy loads, probably related to hunting trips. The ISG do not show evidence of these types of activities, suggesting a population difference in the frequency and degree of physically strenuous activity. Kitoi and Shamanka II males and young adult individuals show evidence of having performed the majority of the strenuous lifting and carrying, as well as evidence of increased mobility relative to females. These results indicative of strong divisions of labour in the Kitoi population. Patterns in trait frequencies were also examined for indications of how multiple underlying factors may be interacting. Trait distribution throughout the body provides evidence of the dominance of biomechanical stress as a causative factor in the expression of postcranial non-metric traits. Other factors that become visible when the influence of biomechanical stress is lower include genotype, trauma, and cartilage degeneration. The results of this project are consistent with current theories on the adaptive regimes of the Kitoi and ISG populations and strongly support previous work by BAP researchers in the areas of skeletal robusticity, osteoarthritis, and musculoskeletal stress markers. The research also helps to broaden the knowledge base about the etiologies of the non-metric traits involved.

After human beings entered in a later period of industrial society, the competitiveness of cities and regions was gradually affected by their own impressions. The reason was that due to the important elements, tourist, cultural industry and knowledge industry business, of city-developing at present stage, new city-demanders were more sensitive to the city¡¦s image than space-consumers in the past. Also, after 1980, because of this kind of economical change, western developed industrial cities led the marketing principles of region and city to administration and paid much attention to the strategy of city¡¦s image. Penghu Makung , a historical coast city, is the center of humanity, history, economy, politics and culture in Penghu Islands. In the future, facing with the world competitiveness between cities and the goal of sustainable development, how does Makung city to be modeled into a unique style city by conducting the strategy of developing the city brand? This research was based on two stages of Delphi Method to combine the cognition of of Makung city of industry, official and university specialists and based on CIS, Corporate Identity System, as examination construction to sketch the contours of the vision of the strategy of modeling Makung¡¦s city brand. According to statistics, in the future, Makung city should be characterized by its historical and suitable living place in order to develop its brand orientation and should be shaped into a low-carbon coast traveling city and a resort center of Sea Islands which are the core of city¡¦s development. As for its visual image, the symbol and the sign of the city should be redesign; the slogan and mascot could immediately become the marketing strategy in the future. Besides, basalts on Tongpanyu is the highest landscape brand and Mazu Temple is the most typical building. As for the brand of local activity, Qigui Ceremony which should be enhanced by branding and combing with the city is the most impressive. In sum, with the integration of history and humanity and the combination of story and landscape environmental construction, the city brand of Makung city would be developed.

In this experiment, selenides are used as the precursor and CIGS thin films are synthesized through selenization. At the first stage, the precursor with the layers of In-Se/Ga-Se/Cu-Se failed to produce CIGS thin films when the temperature is going up 10¢J per minute to the target temperature during selenization and the change of the composition of the precursor, the temperature duration and the temperature of selenization is tried. Later, the reaction is successfully done when the layers are changed into In-Ga-Se/Cu-Se with the temperature going up 10¢J per minute to 550¢J, lasting for 5 minutes. With various Ga containments, I analyize the optical and electronic properties. In order to see the composition of CIGS thin films in different propotion of Cu/In+Ga and Ga/In+Ga, I use EPMA and the properties of XRD peak shift with the containment of Ga to estimate the proportion of the containment of Ga. I found the conclusions by EPMA and XRD are very similar. At 150¢J, the precursors Cu-Se, In-Se and Ga-Se are fabricated and XPS, Raman, XRD or else are used to speculate the bonding of them. In addition, using XRD and Raman to analyze In-Ga-Se/Cu-Se selenides, I found, between 150¢J and 300¢J, Cu2-xSe bonding is the main; at 350¢J, InSe bonding intensifies obviously; at 400¢J, CIGS is formed.

In this research, CuInSe2 thin film is grown at 350¢J low temperature by photo-assisted co-evaporation system to fabricate PI (polyimide) substrate flexible thin film solar cells. The low temperature growing CuInSe2 is analyzed by raman spectroscopy. Besides, sputtering Mo thin film on PI and CIS/Mo/PI contact properties are also researched for device fabrication. By studying the Ar pressure and Mo internal stress relationship during the deposition, the Mo layer has been fabricated with both low resistivity and good adhesion. The sheet resistance of Mo layer is 1.95 £[/¡¼ and shows ohmic contact with CuInSe2 at temperature below 350¢J. Raman spectroscopy shows that photo-assisted CuInSe2 has stronger and thinner A1 peak than which without light. Two-stage growing can help eliminating Cu2Se and background signals further. CA structure vibration modes are involved in the asymmetric A1 peak broadening. The SLG/Mo/CIS/CdS/ZnO:Al/Al structured device has open voltage, Voc = 0.320 V, short cut current, Isc = 3.61 mA, and solar cell fill factor, FF = 49.8 %. On the other hand, PI/Mo/CIS/CdS/ZnO:Al/Al structured device has open voltage, Voc = 0.318 V, short cut current, Isc = 2.71 mA, and solar cell fill factor, FF = 39.0 %¡C

This thesis analyses Russia's military, economic and diplomatic policies towards the newly independent states, particularly towards the members of the CIS, during Boris Yeltsin's first term as President of an independent Russia (December 1991 to July 1996). The objective is to determine whether after the collapse of the Soviet Union the new Russian state tried to restore a sphere of influence or informal empire over the former Soviet republics - as the French did in sub-Saharan Africa after decolonisation - or whether instead Russia's policies reflected a genuine desire to establish normal state-to-state relations with the new states. Chapter one analyses the underlying principles of Russia's foreign policy towards the former Soviet states and examines the debate on Russian foreign policy priorities which took place during the first years of Russia's independence. This section also overviews Russia's policies towards the Russian minorities that inhabit the Baltic states, in order to determine whether Russia attempted to use this diplomatic tool to further its own interests in the area. Chapter two analyses the peculiar structure of the Commonwealth of Independent States and the extent to which Russia used this political framework to achieve hegemony over the former Soviet republics. Chapter three looks at Russia's participation in the wars in Transdniestria, Abkhazia, Nagorno-Karabagh, and Tajikistan, and Chapter four analyses Russia's energy trade with Ukraine, Belarus, and the Caspian states. The thesis reaches the conclusion that during 1992- mid 1996 Russia's policies only partially reflected an attempt to reassert the country's influence over the republics of the former Soviet Union and create an informal empire in the post-Soviet space. Russia's behaviour was particularly assertive in the military field as well as in its attempts to build a Russian dominated CIS military infrastructure. However, Russia's policies were less aggressive in the economic sphere, except probably as far as energy policy is concerned, and regarding the fate of Russians living beyond the new borders. More often than not, though, Russia's policies followed an ambivalent and incoherent pattern, a result of the weak and fragmented character of the Russian state.