Selective Formation of Diblock Copolymers Using Radical Trap-Assisted Atom Transfer Radical Coupling

Polystyrene (PSt) radicals and poly(methyl acrylate) (PMA) radicals, derived from their monobrominated precursors prepared by atom transfer radical polymerization (ATRP), were formed in the presence of the radical trap 2-methyl-2-nitrosopropane (MNP), selectively forming PSt-PMA diblock copolymers with an alkoxyamine at the junction between the block segments. This radical trap-assisted, atom transfer radical coupling (RTA-ATRC) was performed in a single pot at low temperature (35 degrees C), while analogous traditional ATRC reactions at this temperature, which lacked the radical trap, resulted in no observed coupling and the PStBr and PMABr precursors were simply recovered. Selective formation of the diblock under RTA-ATRC conditions is consistent with the PStBr and PMABr having substantially different K-ATRP values, with PSt radicals initially being formed and trapped by the MNP and the PMA radicals being trapped by the in situ-formed nitroxide end-capped PSt. The midchain alkoxyamine functionality was confirmed by thermolysis of the diblock copolymer, resulting in recovery of the PSt segment and degradation of the PMA block at the relatively high temperatures (125 degrees C) required for thermal cleavage. A PSt-PMA diblock formed by chain extenstion ATRP using PStBr as the macroinitiator (thus lacking the alkoxyamine between the PSt-PMA segements) was inert to thermolysis. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3619-3626

An ice-core based history of Siberian forest fires since AD 1250

Forest fires play a key role in the global carbon cycle and thus, can affect regional and global climate. Although fires in extended areas of Russian boreal forests have a considerable influence on atmospheric greenhouse gas and soot concentrations, estimates of their impact on climate are hampered by a lack of data on the history of forest fires. Especially regions with strong continental climate are of high importance due to an intensified development of wildfires. In this study we reconstruct the fire history of Southern Siberia during the past 750 years using ice-core based nitrate, potassium, and charcoal concentration records from Belukha glacier in the continental Siberian Altai. A period of exceptionally high forest-fire activity was observed between AD 1600 and 1680, following an extremely dry period AD 1540-1600. Ice-core pollen data suggest distinct forest diebacks and the expansion of steppe in response to dry climatic conditions. Coherence with a paleoenvironmental record from the 200 km distant Siberian lake Teletskoye shows that the vegetational shift AD 1540-1680, the increase in fire activity AD 1600-1680, and the subsequent recovery of forests AD 1700 were of regional significance. Dead biomass accumulation in response to drought and high temperatures around AD 1600 probably triggered maximum forest-fire activity AD 1600-1680. The extreme dry period in the 16th century was also observed at other sites in Central Asia and is possibly associated with a persistent positive mode of the Pacific Decadal Oscillation (PDO). No significant increase in biomass burning occurred in the Altai region during the last 300 years, despite strongly increasing temperatures and human activities. Our results imply that precipitation changes controlled fire-regime and vegetation shifts in the Altai region during the past 750 years. We conclude that high sensitivity of ecosystems to occasional decadal-scale drought events may trigger unprecedented environmental reorganizations under global-warming conditions.

The Synthesis of Macrocyclic Polystyrene by Sequential Atom Transfer Radical Reactions

A method for the production of macrocyclic polystyrene via ring closing of a linear !,"-dibrominated polystyrene by an Atom Transfer Radical Coupling (ATRC) reaction is described. The dibrominated polystyrene chain was produced from two simultaneous atom transfer radical polymerizations (ATRPs) originating from a dibrominated benzal bromide initiator. To ensure the retention of the halogen end groups polymerization was allowed to proceed to less than 50% conversion. Using this precursor in an intramolecular ATRC (ring closing) reaction was found to yield in excess of 90% cyclic product based on refractive index-gel permeation chromatography (GPC) analysis. The cyclic architecture of the polymer was verified by GPC, Nuclear Magnetic Resonance (NMR), and mass spectrometry analysis. The utility of this method has been expanded by the addition of 2-methyl-2-nitrosopropane to the coupling reaction, which allows for the coupling to proceed at a faster rate and to yield macrocycles with incorporated alkoxyamine functionality. The alkoxyamine functionality allows for degradation of the cycles at high temperatures (>125° C) and we hypothesize that it may allow the macrocycles to act as a macroinitiator for a ring expansion polymerization in future studies.

Development and improvement of warm-mix asphalt technology

Traditionally, asphalt mixtures were produced at high temperatures (between 150°C to 180°C) and therefore often referred to as Hot Mix Asphalt (HMA). Recently, a new technology named Warm Mix Asphalt (WMA) was developed in Europe that allows HMA to be produced at a lower temperature. Over years of research efforts, a few WMA technologies were introduced including the foaming method using Aspha-min® and Advera® WMA; organic additives such as Sasobit® and Asphaltan B®; and chemical packages such as Evotherm® and Cecabase RT®. Benefits were found when lower temperatures were used to produce asphalt mixtures, especially when it comes to environmental and energy savings. Even though WMA has shown promising results in energy savings and emission reduction, however, only limited studies and laboratory tests have been conducted to date. The objectives of this project are to 1) develop a mix design framework for WMA by evaluating its mechanical properties; 2) evaluate performance of WMA containing high percentages of recycled asphalt material; and 3) evaluate the moisture sensitivity in WMA. The test results show that most of the WMA has higher fatigue life and TSR which indicated WMA has better fatigue cracking and moisture damage resistant; however, the rutting potential of most of the WMA tested were higher than the control HMA. A recommended WMA mix design framework was developed as well. The WMA design framework was presented in this study to provide contractors, and government agencies successfully design WMA. Mixtures containing high RAP and RAS were studied as well and the overall results show that WMA technology allows the mixture containing high RAP content and RAS to be produced at lower temperature (up to 35°C lower) without significantly affect the performance of asphalt mixture in terms of rutting, fatigue and moisture susceptibility. Lastly, the study also found that by introducing the hydrated lime in the WMA, all mixtures modified by the hydrated lime passed the minimum requirement of 0.80. This indicated that, the moisture susceptibility of the WMA can be improved by adding the hydrated lime.

Development of a direct evaporation bismuth Hall thruster

Hall thrusters have been under active development around the world since the 1960’s. Thrusters using traditional propellants such as xenon have been flown on a variety of satellite orbit raising and maintenance missions with an excellent record. To expand the mission envelope, it is necessary to lower the specific impulse of the thrusters but xenon and krypton are poor performers at specific impulses below 1,200 seconds. To enhance low specific impulse performance, this dissertation examines the development of a Hall-effect thruster which uses bismuth as a propellant. Bismuth, the heaviest non-radioactive element, holds many advantages over noble gas propellants from an energetics as well as a practical economic standpoint. Low ionization energy, large electron-impact crosssection and high atomic mass make bismuth ideal for low-specific impulse applications. The primary disadvantage lies in the high temperatures which are required to generate the bismuth vapors. Previous efforts carried out in the Soviet Union relied upon the complete bismuth vaporization and gas phase delivery to the anode. While this proved successful, the power required to vaporize and maintain gas phase throughout the mass flow system quickly removed many of the efficiency gains expected from using bismuth. To solve these problems, a unique method of delivering liquid bismuth to the anode has been developed. Bismuth is contained within a hollow anode reservoir that is capped by a porous metallic disc. By utilizing the inherent waste heat generated in a Hall thruster, liquid bismuth is evaporated and the vapors pass through the porous disc into the discharge chamber. Due to the high temperatures and material compatibility requirements, the anode was fabricated out of pure molybdenum. The porous vaporizer was not available commercially so a method of creating a refractory porous plate with 40-50% open porosity was developed. Molybdenum also does not respond well to most forms of welding so a diffusion bonding process was also developed to join the molybdenum porous disc to the molybdenum anode. Operation of the direct evaporation bismuth Hall thruster revealed interesting phenomenon. By utilizing constant current mode on a discharge power supply, the discharge voltage settles out to a stable operating point which is a function of discharge current, anode face area and average pore size on the vaporizer. Oscillations with a 40 second period were also observed. Preliminary performance data suggests that the direct evaporation bismuth Hall thruster performs similar to xenon and krypton Hall thrusters. Plume interrogation with a Retarding Potential Analyzer confirmed that bismuth ions were being efficiently accelerated while Faraday probe data gave a view of the ion density in the exhausted plume.

Nanomechanics of cellulose crystals and cellulose-based polymer composites

Cellulose-polymer composites have potential applications in aerospace and transportation areas where lightweight materials with high mechanical properties are needed. In addition, these economical and biodegradable composites have been shown to be useful as polymer electrolytes, packaging structures, optoelectronic devices, and medical implants such as wound dressing and bone scaffolds. In spite of the above mentioned advantages and potential applications, due to the difficulties associated with synthesis and processing techniques, application of cellulose crystals (micro and nano sized) for preparation of new composite systems is limited. Cellulose is hydrophilic and polar as opposed to most of common thermoplastics, which are non-polar. This results in complications in addition of cellulose crystals to polymer matrices, and as a result in achieving sufficient dispersion levels, which directly affects the mechanical properties of the composites. As in other composite materials, the properties of cellulose-polymer composites depend on the volume fraction and the properties of individual phases (the reinforcement and the polymer matrix), the dispersion quality of the reinforcement through the matrix and the interaction between CNCs themselves and CNC and the matrix (interphase). In order to develop economical cellulose-polymer composites with superior qualities, the properties of individual cellulose crystals, as well as the effect of dispersion of reinforcements and the interphase on the properties of the final composites should be understood. In this research, the mechanical properties of CNC polymer composites were characterized at the macro and nano scales. A direct correlation was made between: Dispersion quality and macro-mechanical properties Nanomechanical properties at the surface and tensile properties CNC diameter and interphase thickness Lastly, individual CNCs from different sources were characterized and for the first time size-scale effect on their nanomechanical properties were reported. Then the effect of CNC surface modification on the mechanical properties was studied and correlated to the crystalline structure of these materials.

Extrapolated difference technique for the determination of atomization energies of Sm, Eu, and Yb bromides

An approach for the determination of atomization energies based on the extrapolated difference technique in the framework of Knudsen effusion mass spectrometry is proposed. Its essence is the use of thermodynamic data for the determination of the appearance energy of fragment ions of a reference and a special mathematical treatment of the ionization efficiency functions. The advantages of this approach are demonstrated for the cases of incongruently vaporizing lanthanide bromides that suffer from decomposition or disproportionation at high temperatures. The atomization energies for SmBr2 (7.78±0.12 eV), EuBr2 (7.51±0.11 eV), YbBr2 (7.25±0.13 eV), SmBr3 (11.09±0.10 eV), and YbBr3 (10.23±0.09 eV) molecules have been determined for the first time.

Thermal right-handed neutrino production rate in the relativistic regime

The production rate of right-handed neutrinos from a Standard Model plasma at a temperature above a hundred GeV is evaluated up to NLO in Standard Model couplings. The results apply in the so-called relativistic regime, referring parametrically to a mass M ~ πT, generalizing thereby previous NLO results which only apply in the non-relativistic regime M ≫ πT. The non-relativistic expansion is observed to converge for M ≳ 15T, but the smallness of any loop corrections allows it to be used in practice already for M ≳ 4T. In the latter regime any non-covariant dependence of the differential rate on the spatial momentum is shown to be mild. The loop expansion breaks down in the ultrarelativistic regime M ≪ πT, but after a simple mass resummation it nevertheless extrapolates reasonably well towards a result obtained previously through complete LPM resummation, apparently confirming a strong enhancement of the rate at high temperatures (which facilitates chemical equilibration). When combined with other ingredients the results may help to improve upon the accuracy of leptogenesis computations operating above the electroweak scale.

Individual risk factors for Mycoplasma hyopneumoniae infections in suckling pigs at the age of weaning.

BACKGROUND In recent years, the occurrence and the relevance of Mycoplasma hyopneumoniae infections in suckling pigs has been examined in several studies. Whereas most of these studies were focused on sole prevalence estimation within different age groups, follow-up of infected piglets or assessment of pathological findings, none of the studies included a detailed analysis of individual and environmental risk factors. Therefore, the aim of the present study was to investigate the frequency of M. hyopneumoniae infections in suckling pigs of endemically infected herds and to identify individual risk factors potentially influencing the infection status of suckling pigs at the age of weaning. RESULTS The animal level prevalence of M. hyopneumoniae infections in suckling pigs examined in three conventional pig breeding herds was 3.6% (41/1127) at the time of weaning. A prevalence of 1.2% was found in the same pigs at the end of their nursery period. In a multivariable Poisson regression model it was found that incidence rate ratios (IRR) for suckling pigs are significantly lower than 1 when teeth grinding was conducted (IRR: 0.10). Moreover, high temperatures in the piglet nest during the first two weeks of life (occasionally >40°C) were associated with a decrease of the probability of an infection (IRR: 0.23-0.40). Contrary, the application of PCV2 vaccines to piglets was associated with an increased infection risk (IRR: 9.72). CONCLUSIONS Since single infected piglets are supposed to act as initiators for the transmission of this pathogen in nursery and fattening pigs, the elimination of the risk factors described in this study should help to reduce the incidence rate of M. hyopneumoniae infections and thereby might contribute to a reduced probability of high prevalences in older pigs.

L’archéologie entre glaciers et sommets. Dernières découvertes dans les Alpes Bernoises (Cantons de Berne et du Valais, Suisse)

Connus sous le nom populaire de palafittes, les habitats préhistoriques construits sur les rives des lacs subalpins du Néolithique à l’aube de l’âge du Fer (entre 5300 et 700 av. J.-C.) offrent des informations exceptionnelles sur l’évolution culturelle d’une importante région européenne, grâce à la préservation remarquable des matériaux organiques, en particulier du bois. À partir de la deuxième moitié du XXe siècle, le perfectionnement des techniques de fouille subaquatiques et de la dendrochronologie permettront la construction d’un schéma chronologique précis pour l’Europe nord-alpine. Les recherches contribueront à des observations d’ordre écologique à l’échelle locale et régionale et à l’identification des rythmes de développement des villages. Sous l’égide de l'UNESCO, les années 2010 verront la constitution d’un inventaire vaste et uniforme des sites préhistoriques des lacs circumalpins, classés Patrimoine culturel mondial en juin 2011. De nombreux objets préhistoriques, romains et médiévaux ont été découverts entre 2003 et 2010, au Schnidejoch, un col des Alpes bernoises occidentales à 2756 m d’altitude, à la frontière entre les cantons de Berne et du Valais. Les hautes températures de l'été 2003 ont provoqué la fonte d'un petit champ de glace et mis en lumière les vestiges. Les recherches ont été programmées à la suite d’une série d’informations fournies par des randonneurs. Les objets en matière organique (bois, écorce de bouleau, cuir, fibres végétales) revêtent une très grande importance car ils ont permis l’obtention de plus d’une cinquantaine de datations radiocarbone ; elles indiquent le passage du col entre la moitié du Ve millénaire av. J.-C. et l’année 1000 de notre ère. En outre, les séries de datations suggèrent l’alternance de périodes de praticabilité et d’inaccessibilité du col. Le Schnidejoch est actuellement le plus ancien témoignage de la traversée des Alpes, reliant l‘Oberland bernois par les vallées de la Simme et du Rhône.

Performance evaluation of a miniature laser ablation time-of-flight mass spectrometer designed for in situ investigations in planetary space research

Key performance features of a miniature laser ablation time-of-flight mass spectrometer designed for in situ investigations of the chemical composition of planetary surfaces are presented. This mass spectrometer is well suited for elemental and isotopic analysis of raw solid materials with high sensitivity and high spatial resolution. In this study, ultraviolet laser radiation with irradiances suitable for ablation (< 1 GW/cm2) is used to achieve stable ion formation and low sample consumption. In comparison to our previous laser ablation studies at infrared wavelengths, several improvements to the experimental setup have been made, which allow accurate control over the experimental conditions and good reproducibility of measurements. Current performance evaluations indicate significant improvements to several instrumental figures of merit. Calibration of the mass scale is performed within a mass accuracy (Δm/m) in the range of 100 ppm, and a typical mass resolution (m/Δm) ~600 is achieved at the lead mass peaks. At lower laser irradiances, the mass resolution is better, about (m/Δm) ~900 for lead, and limited by the laser pulse duration of 3 ns. The effective dynamic range of the instrument was enhanced from about 6 decades determined in previous study up to more than 8 decades at present. Current studies show high sensitivity in detection of both metallic and non-metallic elements. Their abundance down to tens of ppb can be measured together with their isotopic patterns. Due to strict control of the experimental parameters, e.g. laser characteristics, ion-optical parameters and sample position, by computer control, measurements can be performed with high reproducibility. Copyright © 2012 John Wiley & Sons, Ltd.

Eemian and Holocene sea-surface conditions in the southern Black Sea: organic-walled dinoflagellate cyst record from core 22-GC3

In order to compare the sea-surface conditions in the Black Sea during the Holocene and Eemian, sapropelic parts of marine core 22-GC3 (42°13.53′N/36°29.55′E, 838 m water depth) were studied for organic-walled dinoflagellate cyst content. The record shows a change from freshwater/brackish assemblages (Pyxidinopsis psilata, Spiniferites cruciformis, and Caspidinium rugosum) to more marine assemblages (Lingulodinium machaerophorum and Spiniferites ramosus complex) during each interglacial, due to the inflow of saline Mediterranean water. The lacustrine–marine transitions in 22-GC3 occurred at ~ 8.3 cal kyr BP during the early Holocene and ~ 128 kyr BP during the early Eemian, slightly later compared to the onset of interglacial conditions on the adjacent land. Dinoflagellate cyst assemblages reveal higher sea-surface salinity (~ 28–30) (e.g. Spiniferites pachydermus, Bitectatodinium tepikiense, and Spiniferites mirabilis) around ~ 126.5–121 kyr BP in comparison to the Holocene (~ 15–20) as well as relatively high sea-surface temperature (e.g. Tuberculodinium vancampoae, S. pachydermus, and S. mirabilis) especially at ~ 127.6–125.3 kyr BP. Establishment of high sea-surface salinity during the Eemian correlates very well with reconstructed relatively high global sea-level and is explained as a combined effect of increased Mediterranean supply and high temperatures at the beginning of the last interglacial. The observed changes in the dinocyst record highlight the importance of nutrients for the composition of the Eemian and Holocene dinocyst assemblages.

Identification of cadmium-induced mutations in a mammalian cell line

Epidemiological studies have shown cadmium to induce cancer in humans, while experimental studies have proven this metal to be a potent tumor inducer in animals. However, cadmium appears nonmutagenic in most prokaryotic and eukaryotic mutagenesis assays. In this study, we present the identification of mutations in normal rat kidney cells infected with the mutant MuSVts110 retrovirus (6m2 cells) as a result of treatment with cadmium chloride. The detection of these mutations was facilitated by the use of a novel mutagenesis assay established in this laboratory. The 6m2 reversion assay is a positive selection system based on the conditional expression of the MuSVts110 v-mos gene. In MuSVts110 the gag and mos genes are fused out of frame, thus the translation of the v-mos sequence requires a frameshift in the genomic RNA. In 6m2 cells this frameshift is accomplished by the temperature-dependent splicing of the primary MuSVts110 transcript. Splicing of MuSVts110, which is mediated by cis-acting sequences, occurs when 6m2 cells are grown at 33$\sp\circ$C and below, but not at 39$\sp\circ$C. Therefore, 6m2 cells appear transformed at low growth temperatures, but take on a morphologically normal appearance when grown at high temperatures. The treatment of 6m2 cells with cadmium chloride resulted in the outgrowth of a number of cells that reverted to the transformed state at high growth temperatures. Analysis of the viral proteins expressed in these cadmium-induced 6m2 revertants suggested that they contained mutations in their MuSVts110 DNA. Sequencing of the viral DNA from three revertants that constitutively expressed the P85$\sp{gag{-}mos}$ transforming protein revealed five different mutations. The Cd-B2 revertant contained three of those mutations: an A-to-G transition 48 bases downstream of the MuSVts110 3$\sp\prime$ splice site, plus a G-to-T and an A-to-T transversion 84 and 100 bases downstream of the 5$\sp\prime$ splice site, respectively. The Cd-15-5 revertant also contained a point mutation, a T-to-C transition 46 bases downstream of the 5$\sp\prime$ splice site, while Cd-10-5 contained a three base deletion of MuSVts110 11 bases upstream of the 3$\sp\prime$ splice site. A fourth revertant, Cd-10, expressed a P100$\sp{gag{-}mos}$ transforming protein, and was found to have a two base deletion. This deletion accomplished the frameshift necessary for v-mos expression, but did not alter MuSVts110 RNA splicing and the expression of p85$\sp{gag{-}mos}.$ Lastly, sequencing of the MuSVts110 DNA from three spontaneous revertants revealed the same G to T transversion in each one. This was the same mutation that was found in the Cd-B2 revertant. These findings provide the first example of mutations resulting from exposure to cadmium and suggest, by the difference in each mutation, the complexity of the mechanism utilized by cadmium to induce DNA damage. ^

The cyclotron laboratory and the RFQ accelerator in Bern

Two proton accelerators have been recently put in operation in Bern: an 18 MeV cyclotron and a 2 MeV RFQ linac. The commercial IBA 18/18 cyclotron, equipped with a specifically conceived 6 m long external beam line ending in a separate bunker, will provide beams for routine 18-F and other PET radioisotope production as well as for novel detector, radiation biophysics, radioprotection, radiochemistry and radiopharmacy developments. The accelerator is embedded into a complex building hosting two physics laboratories and four Good Manufacturing Practice (GMP) laboratories. This project is the result of a successful collaboration between the Inselspital, the University of Bern and private investors, aiming at the constitution of a combined medical and research centre able to provide the most cutting-edge technologies in medical imaging and cancer radiation therapy. The cyclotron is complemented by the RFQ with the primary goals of elemental analysis via Particle Induced Gamma Emission (PIGE), and the detection of potentially dangerous materials with high nitrogen content using the Gamma-Resonant Nuclear Absorption (GRNA) technique. In this context, beam instrumentation devices have been developed, in particular an innovative beam profile monitor based on doped silica fibres and a setup for emittance measurements using the pepper-pot technique. On this basis, the establishment of a proton therapy centre on the campus of the Inselspital is in the phase of advanced study.

Vulnerability to Heatwaves, Floods and Mass Movements in Mountainous Terrain: Test Cases in South Tyrol

South Tyrol is a region that has been often affected by various mountain hazards such as floods, flash floods, debris flows, rock falls, and snow avalanches. Furthermore, areas located in lower altitudes are often influenced by high temperatures and heat waves. Climate change is expected to influence the frequency, magnitude, and spatial extent of these natural phenomena. For this reason, local authorities and other stakeholders are in need of tools that can enable them to reduce the risk posed by these processes. In the present study, a variety of methods are applied at local level in different places in South Tyrol that aim at: (1) the assessment of future losses caused by the occurrence of debris flows by using a vulnerability curve, (2) the assessment of social vulnerability based on the risk awareness of the exposed people to floods, and (3) the assessment of spatial exposure and social vulnerability of the exposed population to heat waves. The results show that, in South Tyrol, the risk to a number of hazards can be reduced by: (1) improving documentation for past events in order to improve existing vulnerability curves and the assessment of future losses, (2) raising citizens' awareness and responsibility to improve coping capacity to floods, and (3) extending heat wave early warning systems to more low-lying areas of South Tyrol.