Novel "green" catalysts for controlled ring-opening polymerization of lactide

Syntéza polylaktidu (PLA) polymerací za otevření kruhu cyklického monomeru (ROP) může být uskutečněna různými způsoby. Literatura uvádí více než 100 katalytických systémů, jejichž pomocí lze polylaktid a jiné biodegradabilní alifatické polyestery získat. Například organokovové katalyzátory na bázi Sn, Zn, Al atd. se po splnění své polymerační funkce stávají kontaminanty a pro humánní implantáty je použití takového materiálu diskutabilní. V současné době jsou v centru výzkumné pozornosti nové N-heterocyklické karbenové katalyzátory. Tyto „metal-free“ katalytické struktury jsou schopné reprodukovatelně řídit syntézu polymerů předem definované molekulové hmotnosti s definovanými koncovými skupinami a nízkou polydisperzitou, která je charakteristická pro živý průběh polymerace. Nabízí se možnost syntézy blokových kopolymerů a různorodých makromolekulárních architektur. Předložená diplomová práce se zabývá studiem polymerace cyklického monomeru D,L-laktidu katalyzované N-heterocyklickým karbenem. Polymerace byly vedeny v přítomnosti benzylalkoholu jako iniciátoru v roztoku THF. Byl sledován vliv složení reakčního systému monomer – iniciátor – katalyzátor. Dále byly připraveny polymery opticky čistého L-laktidu s makroiniciátory PEG s Mn = 1000 a 2000 g/mol. Střední číselná molekulová hmotnost (Mn) a polydisperzita (PDI) byly stanoveny pomocí GPC. Definovatelnost koncových skupin vybraných polymerů byla prokázána pomocí 1H NMR.The synthesis of polylactide (PLA) by ring-opening polymerization (ROP) of cyclic monomer can be realized by different routes. More than 100 catalysts for the synthesis of polylactide and other biodegradable aliphatic polyesters are published in the literature. For example organometallic catalysts based on Sn, Zn, Al etc. after finishing polymerization function became contaminants and using obtained polymer material in human body is controversial. At present, the research is focused on novel N-hererocyclic carbene catalysts. These metal-free catalysts are able to produce polymers with controlled molecular weight, narrow polydispersity, end-group fidelity with high reproducibility as well as to synthesize the block copolymers and complex macromolecular architectures, which is characteristic for living polymerization system. This diploma thesis is focused on study of polymerization of cyclic monomer D,L-lactide catalyzed by N-hererocyclic carbene. Polymerizations were carried out at the presence of benzylalcohol as initiator at THF. We were focused on the influence of composition of reaction system monomer – initiator – catalyst. Polymers of optically pure L-lactide with macroinitiators PEG with Mn of 1000 a 2000 g/mol were prepared as well. Number average molecular weight (Mn) and polydispersity index (PDI) was determined by GPC. 1H NMR was used to prove end-group fidelity.

Nucleosynthesis of Nickel-56 from Gamma-Ray Burst Accretion Disks

We examine the prospects for producing Nickel-56 from black hole accretion disks, by examining a range of steady state disk models. We focus on relatively slowly accreting disks in the range of 0.05 - 1 solar masses per second, as are thought to be appropriate for the central engines of long-duration gamma-ray bursts. We find that significant amounts of Nickel-56 are produced over a wide range of parameter space. We discuss the influence of entropy, outflow timescale and initial disk position on mass fraction of Nickel-56 which is produced. We keep careful track of the weak interactions to ensure reliable calculations of the electron fraction, and discuss the role of the neutrinos.Comment: 10 pages, 9 figure

Neutrino Interactions in the Outflow from Gamma-Ray Burst Accretion Disks

We examine the composition of matter as it flows away from gamma ray burst accretion disks, in order to determine what sort of nucleosynthesis may occur. Since there is a large flux of neutrinos leaving the surface of the disk, the electron fraction of the outflowing material will change due to charged current neutrino interactions. We calculate the electron fraction in the wind using detailed neutrino fluxes from every point on the disk and study a range of trajectories and outflow conditions for several different accretion disk models. We find that low electron fractions, conducive to making r-process elements, only appear in outflows from disks with high accretion rates that have a significant region both of trapped neutrinos and antineutrinos. Disks with lower accretion rates that have only a significant region of trapped neutrinos can have outflows with very high electron fractions, whereas the lowest accretion rate disks with little trapping have outflow electrons fractions of closer to one half.Comment: 11 pages, 10 figure

Open Sourcing Social Change: Inside the Constellation Model

The constellation model was developed by and for the Canadian Partnership for Children's Health and the Environment. The model offers an innovative approach to organizing collaborative efforts in the social mission sector and shares various elements of the open source model. It emphasizes self-organizing and concrete action within a network of partner organizations working on a common issue. Constellations are self-organizing action teams that operate within the broader strategic vision of a partnership. These constellations are outwardly focused, placing their attention on creating value for those in the external environment rather than on the partnership itself. While serious effort is invested into core partnership governance and management, most of the energy is devoted to the decision making, resources and collaborative effort required to create social value. The constellations drive and define the partnership. The constellation model emerged from a deep understanding of the power of networks and peer production. Leadership rotates fluidly amongst partners, with each partner having the freedom to head up a constellation and to participate in constellations that carry out activities that are of more peripheral interest. The Internet provided the platform, the partner network enabled the expertise to align itself, and the goal of reducing chemical exposure in children kept the energy flowing. Building on seven years of experience, this article provides an overview of the constellation model, discusses the results from the CPCHE, and identifies similarities and differences between the constellation and open source models

The impact of global nuclear mass model uncertainties on rr-process abundance predictions

Rapid neutron capture or `$r$-process' nucleosynthesis may be responsible for half the production of heavy elements above iron on the periodic table. Masses are one of the most important nuclear physics ingredients that go into calculations of $r$-process nucleosynthesis as they enter into the calculations of reaction rates, decay rates, branching ratios and Q-values. We explore the impact of uncertainties in three nuclear mass models on $r$-process abundances by performing global monte carlo simulations. We show that root-mean-square (rms) errors of current mass models are large so that current $r$-process predictions are insufficient in predicting features found in solar residuals and in $r$-process enhanced metal poor stars. We conclude that the reduction of global rms errors below $100$ keV will allow for more robust $r$-process predictions.Comment: 5 pages, 3 figures, invited talk at the 15th International Symposium on Capture Gamma-Ray Spectroscopy and Related Topics (CGS15), to appear in EPJ Web of Conference

Prospects for obtaining an r-process from Gamma Ray Burst Disk Winds

We discuss the possibility that r-process nucleosynthesis may occur in the winds from gamma ray burst accretion disks. This can happen if the temperature of the disk is sufficiently high that electron antineutrinos are trapped as well as neutrinos. This implies accretion disks with greater than a solar mass per second accretion rate, although lower accretion rates with higher black hole spin parameters may provide viable environments as well. Additionally, the outflow from the disk must either have relatively low entropy, e.g. around s = 10, or the initial acceleration of the wind must be slow enough that it is neutrino and antineutrino capture as opposed to electron and positron capture that sets the electron fraction.Comment: 8 pages, submitted to Nucl. Phys. A as part of the Nuclei in Cosmos 8 proceeding

On the Contribution of Gamma Ray Bursts to the Galactic Inventory of Some Intermediate Mass Nuclei

Light curves from a growing number of Gamma Ray Bursts (GRBs) indicate that GRBs copiously produce radioactive Ni moving outward at fractions of the speed of light. We calculate nuclear abundances of elements accompanying the outflowing Ni under the assumption that this Ni originates from a wind blown off of a viscous accretion disk. We also show that GRB's likely contribute appreciably to the galactic inventory of 42Ca, 45Sc, 46Ti, 49Ti, 63Cu, and may be a principal site for the production of 64Zn.Comment: 11 pages, 1 figur