Kinetic analysis of nitroxide radical coupling reactions mediated by CuBr

In a previous paper, we described the room temperature rapid, selective, reversible, and near quantitative Cu-activated nitroxide radical coupling (NRC) technique to prepare 3-arm polystyrene stars. In this work, we evaluated the Cu-activation mechanism, either conventional atom transfer or single electron transfer (SET), through kinetic simulations. Simulation data showed that one can describe the system by either activation mechanism. We also found through simulations that bimolecular radical termination, regardless of activation mechanism, was extremely low and could be considered negligible in an NRC reaction. Experiments were carried out to form 2- and 3-arm PSTY stars using two ligands, PMDETA and Me6TREN, in a range of solvent conditions by varying the ratio of DMSO to toluene, and over a wide temperature range. The rate of 2- or 3-arm star formation was governed by the choice of solvent and ligand. The combination of Me6TREN and toluene/DMSO showed a relatively temperature independent rate, and remarkably reached near quantitative yields for 2-arm star formation after only 1 min at 25 °C.

Rapid, selective, and reversible Nitroxide Radical Coupling (NRC) reactions at amibient temperature

High activation of polystyrene with bromine end groups (PSTY-Br) to their incipient radicals occurred in the presence of Cu(I)Br, Me6TREN, and DMSO solvent. These radicals were then trapped by nitroxide species leading to coupling reactions between PSTY-Br and nitroxides that were ultrafast and selective in the presence of a diverse range of functional groups. The nitroxide radical coupling (NRC) reactions have the attributes of a “click” reaction with near quantitative yields of product formed, but through the reversibility of this reaction, it has the added advantage of permitting the exchange of chemical functionality on macromolecules. Conditions were chosen to facilitate the disproportionation of Cu(I)Br to the highly activating nascent Cu(0) and deactivating Cu(II)Br2 in the presence of DMSO solvent and Me6TREN ligand. NRC at room temperature gave near quantitative yields of macromolecular coupling of low molecular weight polystyrene with bromine chain-ends (PSTY-Br) and nitroxides in under 7 min even in the presence of functional groups (e.g., −≡, −OH, −COOH, −NH2, =O). Utilization of the reversibility of the NRC reaction at elevated temperatures allowed the exchange of chain-end groups with a variety of functional nitroxide derivatives. The robustness and orthogonality of this NRC reaction were further demonstrated using the Cu-catalyzed azide/alkyne “click” (CuAAC) reactions, in which yields greater than 95% were observed for coupling between PSTY-N3 and a PSTY chain first trapped with an alkyne functional TEMPO (PSTY-TEMPO-≡).

Studies of Phosphazenes. Part 13.' Thermal Rearrangement Reactions of Some Met hoxycyclo phosp hazenes

The methoxycyclophosphazenes [NP(OMe),], (n = 3-6) rearrange on heating to give oxocyclophosphazanes, [N(Me)PO(OMe)],. Isomeric products are formed when n = 4-6. The lH, ,lP, and 13C n.m.r. data for the starting materials and the products are presented. The ethoxy- and n-propoxy-derivatives N,P,( OR)* do not undergo the above rearrangement. The geminal derivatives N,P,R,(OMe), (R = Ph or NHBut) on heating yield both fully and partially rearranged products, namely dioxophosphaz-1 -enes and oxophosphazadienes, as shown by 270- MHz lH n.m.r. spectroscopy. The non-geminal derivative N,P,( NMe,),(OMe), gives only the fully rearranged product N,Me,P,(NMe,),O,(OMe), whose structure has been established from its lH and 31P n.m.r. spectra.

Photofragmentation Reactions Of Thiocarbonyl Compounds

Preferential yield of ring expansion and rearrangement products through α-cleavage of tetramethyl-3-thio-1,3-cyclobutanedione (1) and 3-mercapto-2,2,4-trimethyl-3-pentenoic acid β-(thio lactone) (2) involving diradical and carbene has been observed upon photolysis of 1 and 2.

Meillä ei ole ikuisia ystäviä eikä ikuisia vihollisia. Ikuisia ovat meidän omat etumme. : Suomen suhteet Kiinan kansantasavaltaan 1949 - 1989

"We have neither Eternal Friends nor Eternal Enemies. We have only Eternal Interests .Finland's Relations with China 1949-1989 The study focuses on the relations between Finland and the People s Republic of China from 1949-1989 and examines how a small country became embroiled in international politics, and how, at the same time, international politics affected Finnish-Chinese relations and Finland s China policy formulation. The study can be divided into three sections: relations during the early years, 1949-1960, before the Chinese and Soviet rift became public; the relations during the passive period during the 1960s and 1970s; and the impact of China s Open Door policy on Finland s China policy from 1978-1989. The diplomatically challenging events around Tiananmen Square and the reactions which followed in Finland bring the study to a close. Finland was among the first Western countries to recognise the People s Republic and to establish diplomatic relations with her, thereby giving Finland an excellent position from which to further develop good relations. Finland was also the first Western country to sign a trade agreement with China. These two factors meant that Finland was able to enjoy a special status with China during the 1950s. The special status was further strengthened by the systematic support of the government of Finland for China's UN membership. The solid reputation earned in the 1950s had to carry Finland all the way through to the 1980s. For the two decades in between, during the passive policy period of the 1960s and 1970s, relations between Finland and the Soviet Union also determined the state of foreign relations with China. Interestingly, however, it appeared that President Urho Kekkonen was encouraged by Ambassador Joel Toivola to envisage a more proactive policy towards China, but the Cultural Revolution cut short any such plan for nearly twenty years. Because of the Soviet Union, Finland held on to her passive China policy, even though no such message was ever received from the Soviet Union. In fact, closer relationships between Finland and China were encouraged through diplomatic channels. It was not until the presidency of Mauno Koivisto that the first high-level ministerial visit was made to China when, in 1984, Foreign Minister Paavo Väyrynen visited the People s Republic. Finnish-Chinese relations were lifted to a new level. Foreign Minister Väyrynen, however, was forced to remove the prejudices of the Chinese. In 1985, when the Speaker of the Finnish Parliament, Erkki Pystynen visited China he also discovered that Finland s passive China policy had caused misunderstandings amongst the Chinese politicians. The number of exchanges escalated in the wake of the ground-breaking visit by Foreign Minister Väyrynen: Prime Minister Kalevi Sorsa visited China in 1986 and President Koivisto did so in 1988. President Koivisto stuck to practical, China-friendly policies: his correspondence with Li Peng, the attitude taken by the Finnish government after the Tiananmen Square events and the subsequent choices made by his administration all pointed to a new era in relations with China.

Mycelial compatibility reactions of Australian Fusarium graminearum and F. pseudograminearum isolates compared with AFLP groupings

Using the mycelial reactions of 435 combinations of 14 Fusarium pseudograminearum and 15 F. graminearum isolates, it was demonstrated for the first time that mycelial reactions/barrage formation cannot be clearly used to distinguish F. graminearum and F. pseudograminearum. Mutually compatible isolates produced very different patterns of compatibility with other isolates. However, about 60% of pairings between F. graminearum and F. pseudograminearum isolates were compatible, indicating common ancestry. The Mantel tests used to determine any possible associations between mycelial compatibility reactions and AFLP genotypic diversity data revealed no association between the two systems in either species. In addition, no association was found between mycelial compatibility reactions and sexual reproduction in the two species. Implications of the higher frequency of mycelial compatibility reactions observed in F. pseudograminearum than in F. graminearum are discussed.

Evaluation of aerial photography for predicting trends in structural attributes of Australian woodland including comparison with ground-based monitoring data

The accurate assessment of trends in the woody structure of savannas has important implications for greenhouse accounting and land-use industries such as pastoralism. Two recent assessments of live woody biomass change from north-east Australian eucalypt woodland between the 1980s and 1990s present divergent results. The first estimate is derived from a network of permanent monitoring plots and the second from woody cover assessments from aerial photography. The differences between the studies are reviewed and include sample density, spatial scale and design. Further analyses targeting potential biases in the indirect aerial photography technique are conducted including a comparison of basal area estimates derived from 28 permanent monitoring sites with basal area estimates derived by the aerial photography technique. It is concluded that the effect of photo-scale; or the failure to include appropriate back-transformation of biomass estimates in the aerial photography study are not likely to have contributed significantly to the discrepancy. However, temporal changes in the structure of woodlands, for example, woodlands maturing from many smaller trees to fewer larger trees or seasonal changes, which affect the relationship between cover and basal area could impact on the detection of trends using the aerial photography technique. It is also possible that issues concerning photo-quality may bias assessments through time, and that the limited sample of the permanent monitoring network may inadequately represent change at regional scales

Effect of surface-applied treatments on the above-ground performance of simulated timber joinery

We examined the effect of surface-applied treatments on the above-ground decay resistance of the tenon of mortice-and-tenon timber joints designed to simulate joinery that is exposed to the weather. Joints made from untreated radiata pine, Douglas-fir, brush box, spotted gum and copper-chrome-arsenic (CCA) treated radiata pine were exposed to the weather for 9 y on above-ground racks at five sites throughout eastern Australia. Results indicate (1) a poorly maintained external paint film generally accelerated decay, (2) a brush coat of water-repellent preservative inside the joints often extended serviceability (in some cases by a factor of up to seven times that of untreated joints) and (3) the level of protection provided by a coat of primer applied inside the joint varied and in most cases was not as effective as the water-repellent preservative treatment.

The Origin of Regioselectivity in a-Cleavage Reactions of Cyclopropenethiones: Potential Role of Pseudo-Jahn-Teller Effect in Substituted Cyclopropenyl Systems

Arylalkylcyclopropenethiones undergo highly regioselective photochemical a-cleavage via thioketene carbene intermediates, giving rise to products derived from the less stabilized carbene. UHF MIND0/3 calculations provide an insight into this unexpected regioselectivity. The nx* triplet of cyclopropenethione is calculated to have a highly unsymmetrical geometry with an elongated C-C bond, a delocalized thiaaUyl fragment, and a pyramidal radicaloid carbon (which eventually becomes the carbene center). From this molecular electronic structure, aryl group stabilization is expected to be more effective at the thiaallyl group rather than at the pyramidal radical center. Thus, the stability of the substituted triplet thione rather than that of the thioketene carbene determines the preferred regiochemistry of cleavage. The unusual structure of the cyclopropenethione triplet is suggested to be related to one of the Jahn-Teller distorted forms of the cyclopropenyl radical. An alternative symmetrical structure is adopted by the corresponding triplet of cyclopropenone, partly accounting for its differing photobehavior. A similar structural dichotomy is demonstrated for the corresponding radical anions as well.

Preparation of Hexafluorodisilane and Reactions of Hexafluorodisilane and Hexachlorodisilane with Sulfur Trioxide

Hexafluorodisilane has been prepared by the fluorination of hexachlorodisilane or hexabromodisilane by potassium fluoride in boiling acetonitrile, in yields approximating 45 and 60% respectively. Hexafluorodisilane has been characterised by infrared spectral data, vapour density measurements and analytical data. Both hexafluorodisilane and hexachlorodisilane are found to react with sulfur trioxide when heated to 400°C for 12 h. The products of reaction are silicon tetrafluoride, silica and sulfur dioxide with hexafluorodisilane while hexachlorodisilane in addition gives rise to hexachlorodisiloxane.

Curing Reactions in Elastomers. 11. Carboxy- Terminated Polybutadiene

Attempts have been made to understand the curing reactions in carboxy-terminated polybutadiene (CTPB), which happens to be the most practical binder in advanced solid composite propellants. The curing of CTPB has been studied for different ratios of curing agents (MAPO and Epoxide) by gel content, molecular weight, crosslink density, and penetration temperature measurements, and the optimum composition of curators for effective curing of CTPB has been determined. Activation energy calculations on the curing of CTPB with 9.5% epoxide and 0.5% MAPO in the temperature range 75100°C gave 14.1 kcal/mol for which a diffusion-controlled or acid-catalyzed epoxide ring opening mechanism has been suggested for the curing process in CTPB.

Photochemical reactions of organic crystals

Abstract is not available.

The effect of ground leases on house prices in Helsinki

One imperfection in housing markets is imperfect knowledge about legal interests such as ground leases. Both actual reduced legal interest as well as uncertainty surrounding rights and future lease payments for houses constructed on leased land may affect prices relative to houses built on freehold land. We use regression analysis of sales prices of condominium transactions in Helsinki to examine the effect ground leases have on house prices. We find that prices on condominiums constructed on leased lots are discounted at least 5 %, on average. In addition, we see that the announcement of potentially large increases in base rents upon renewal contributes to the discount.

Designing serious gameplay from the ground up

This thesis investigated the use, design and evaluation of video games created for educational purposes. The outcomes from the research include analysis tools and design processes that can be used in the design and development of serious games, as well as games that can be used for training purposes. The contribution of this thesis is a greater understanding of how these types of video games lead to educational improvement, and how we can successfully frame game design and development processes to ensure such positive outcomes.