Enantioselective synthesis of aziridines using asymmetric transfer hydrogenation as a precursor for chiral derivatives used as bonding agent for rocket solid propellants

A rapid, expedient and enantioselective method for the synthesis of beta-hydroxy amines and monosubstituted aziridines in up to 99% e.e., via asymmetric transfer hydrogenation of a-amino ketones and cyclisation through treatment with tosyl chloride and base, is described. (1R,2R)-N-(para-toluenesulfonyl)-1,2-ethylenediamine with formic acid has been utilised as a ligand for the Ruthenium (II) catalysed enantioselective transfer hydrogenation of the ketones.The chiral 2-methyl aziridine, which is a potentially more efficient bonding agent for Rocket Solid Propellant has been successfully achieved.

Control and femtosecond time-resolved imaging of torsion in a chiral molecule

We study how the combination of long and short laser pulses can be used to induce torsion in an axially chiral biphenyl derivative (3,5-difluoro-3 ,5 -dibromo-4 -cyanobiphenyl). A long, with respect to the molecular rotational periods, elliptically polarized laser pulse produces 3D alignment of the molecules, and a linearly polarized short pulse initiates torsion about the stereogenic axis. The torsional motion is monitored in real-time by measuring the dihedral angle using femtosecond time-resolved Coulomb explosion imaging. Within the first 4 picoseconds (ps), torsion occurs with a period of 1.25 ps and an amplitude of 3◦ in excellent agreement with theoretical calculations. At larger times, the quantum states of the molecules describing the torsional motion dephase and an almost isotropic distribution of the dihedral angle is measured.We demonstrate an original application of covariance analysis of two-dimensional ion images to reveal strong correlations between specific ejected ionic fragments from Coulomb explosion. This technique strengthens our interpretation of the experimental data

Full instability behavior of N-dimensional dynamical systems with a one-directional nonlinear vector field

We show how certain N-dimensional dynamical systems are able to exploit the full instability capabilities of their fixed points to do Hopf bifurcations and how such a behavior produces complex time evolutions based on the nonlinear combination of the oscillation modes that emerged from these bifurcations. For really different oscillation frequencies, the evolutions describe robust wave form structures, usually periodic, in which selfsimilarity with respect to both the time scale and system dimension is clearly appreciated. For closer frequencies, the evolution signals usually appear irregular but are still based on the repetition of complex wave form structures. The study is developed by considering vector fields with a scalar-valued nonlinear function of a single variable that is a linear combination of the N dynamical variables. In this case, the linear stability analysis can be used to design N-dimensional systems in which the fixed points of a saddle-node pair experience up to N21 Hopf bifurcations with preselected oscillation frequencies. The secondary processes occurring in the phase region where the variety of limit cycles appear may be rather complex and difficult to characterize, but they produce the nonlinear mixing of oscillation modes with relatively generic features

Stereoselective syntheses of (+)- isoretronecanol and (+)-5-epi-tashiromine via addition of chiral titanium (iv) enolates to cyclic n-acyliminium ions

The stereoselective addition of the titanium (IV) enolates derived from (S)-4-isopropyl-N-4-chlorobutyryl-1,3-thiazolidine-2-thione (8) and from (S)-4-isopropyl-N-4-chloropentanoyl-1,3-thiazolidine-2-thione (9) to N-Boc-2-methoxypyrrolidine (5b) afforded the addition products (+)-10 and (+)-11 in 84% yield in both cases, as 8.6:1 and 10:1 diastereoisomeric mixtures, respectively. A three-step sequence allowed to convert these adducts to (+)-isoretronecanol (1) and (+)-5-epi-tashiromine (2) in 43% and 49% overall yield, respectively.

Chiral separations of mandelic acid by HPLC using molecularly imprinted polymers

Styrene is used in a variety of chemical industries. Environmental and occupational exposures to styrene occur predominantly through inhalation. The major metabolite of styrene is present in two enantiomeric forms, chiral R- and S- hydroxy-1-phenyl-acetic acid (R-and S-mandelic acid, MA). Thus, the concentration of MA, particularly of its enantiomers, has been used in urine tests to determine whether workers have been exposed to styrene. This study describes a method of analyzing mandelic acid using molecular imprinting techniques and HPLC detection to perform the separation of diastereoisomers of mandelic acid. The molecularly imprinted polymer (MIP) was prepared by non-covalent molecular imprinting using (+) MA, (-) MA or (+) phenylalanine, (-) phenylalanine as templates. Methacrylic acid (MAA) and ethylene glycol dimethacrylate (EGDMA) were copolymerized in the presence of the template molecules. The bulk polymerization was carried out at 4ºC under UV radiation. The resulting MIP was grounded into 25~44¼m particles, which were slurry packed into analytical columns. After the template molecules were removed, the MIP-packed columns were found to be effective for the chromatographic resolution of (±)-mandelic acid. This method is simpler and more convenient than other chromatographic methods.

On Undecidable Dynamical Properties of Reversible One-Dimensional Cellular Automata

Cellular automata are models for massively parallel computation. A cellular automaton consists of cells which are arranged in some kind of regular lattice and a local update rule which updates the state of each cell according to the states of the cell's neighbors on each step of the computation. This work focuses on reversible one-dimensional cellular automata in which the cells are arranged in a two-way in_nite line and the computation is reversible, that is, the previous states of the cells can be derived from the current ones. In this work it is shown that several properties of reversible one-dimensional cellular automata are algorithmically undecidable, that is, there exists no algorithm that would tell whether a given cellular automaton has the property or not. It is shown that the tiling problem of Wang tiles remains undecidable even in some very restricted special cases. It follows that it is undecidable whether some given states will always appear in computations by the given cellular automaton. It also follows that a weaker form of expansivity, which is a concept of dynamical systems, is an undecidable property for reversible one-dimensional cellular automata. It is shown that several properties of dynamical systems are undecidable for reversible one-dimensional cellular automata. It shown that sensitivity to initial conditions and topological mixing are undecidable properties. Furthermore, non-sensitive and mixing cellular automata are recursively inseparable. It follows that also chaotic behavior is an undecidable property for reversible one-dimensional cellular automata.

Symmetry

Soitinnus: piano.

Dynamical and structural properties of dendrimer macromolecules

This work is devoted to the study of the dynamical and structural properties of dendrimers. Different approaches were used: analytical theory, computer simulation results and experimental NMR studies. The theory of the relaxation spectrum of dendrimer macromolecules was developed. Relaxation processes which are manifest in the local orientational mobility of dendrimer macromolecules were established and studied in detail. Theoretical results and conclusions were used for experimental studies of carbosilane dendimers.

Soil CO2 emission as related to incorporation of sugarcane crop residues and aggregate breaking after rotary tiller

Soil tillage is a process that accelerates soil organic matter decomposition transferring carbon to atmosphere, mainly in the CO2 form. In this study, the effect of rotary tillage on soil CO2 emission was investigated, including the presence of crop residues on the surface.Emissions were evaluated during 15 days after tillage in 3 plots: 1) non-tilled and without crop residues on soil surface (NTwo), 2) rotary tiller without the presence of crop residues on soil surface (RTwo), and 3) rotary tiller with the presence of crop residues in soil surface (RTw). Emissions from the RTw plot were higher than the other plots, (0.777 g CO2 m-2 h-1), with the lowest emissions recorded in the NTwo plot (0.414 g CO2 m-2 h-1). Total emission indicates that the difference of C-CO2 emitted to atmosphere corresponds to 3% of the total additional carbon in the crop residues in the RTw plot compared to RTwo. The increase in the RTwo emission in comparison to NTwo was followed by changes in the aggregate size distribution, especially those with average diameter lower than 2 mm. The increase in emission from the RTw plot in relation to RTwo was related to a decrease in crop residue mass on the surface, and its higher fragmentation and incorporation in soil. When the linear correlation between soil CO2 emission, and soil temperature and soil moisture is considered, only the RTw treatment showed significant correlation (p<0.05) with soil moisture.

SEED DORMANCY BREAKING TREATMENTS FORAFRICAN PURSLANE (Zaleya pentandra)

ABSTRACT Understanding the mechanisms involved in releasing seed dormancy is crucial for effective plant management and renewal of species in the arid zone. Zaleya pentandra is an emerging invasive weed of the arid areas of Pakistan. We investigated the effects of different dormancy breaking treatments on the germination of Z. pentandra seeds. Seeds were treated with hot water (by placing them in boiling water for 5, 15, 30, 60, 90, 120, and 150 min), dry heat (by placing them in a preheated oven at 70 oC for 1, 2, and 4 hours; at 70 oC for 1, 2, 3, and 4 days, and at 200 oC for 5, 10, 15, 30, and 45 min) and stratification (by placing them at 2-5 ºC in a refrigerator for 5, 10, 30, and 60 min; for 3, 6, and 12 hours, and for 1, 2, 4, 8, 15, and 30 days). Seeds also were soaked in thiourea ([(NH2)2CS] (0, 2,500, 5,000, 7,500, and 10,000 mg L-1 for 24 h at 30 oC) and in KNO3 (0, 10,000, 20,000, 30,000, 40,000, 50,000, and 60,000 mg L-1 for 24 h at 30 oC). Additionally, seeds were scarified with HCl (for 3, 6, 9, 12, 15, 18, and 21 h), HNO3 (for 3, 6, 9, 12, 15, 18, and 21 h), and H2SO4 (for 20, 40, 60, 80, 100, and 120 min at 30 oC) and also mechanically scarified with sandpaper. Zaleya pentandra seeds showed typical signs of hard seed coat dormancy. Mechanical scarification and acid treatments promoted seed germination to a varying degree. Seed scarification with HNO3 for 12 to 18 h as well as with HCl for 12 h and 15 h was efficient in breaking dormancy of Z. pentandra seeds, providing germination up to 92.5%. Seed scarification with H2SO4 from 20 to 120 min showed little effect, whereas hot water, dry heat, stratification and various concentrations of thiourea and KNO3 were ineffective in breaking Z. pentandra seed dormancy.

Breaking down the boundaries to storing, sharing and publishing research data

Presentation at Open Repositories 2014, Helsinki, Finland, June 9-13, 2014

Dynamical and Chemical Structure of Galactic Halos

This doctoral dissertation presents studies of the formation and evolution of galaxies, through observations and simulations of galactic halos. The halo is the component of galaxies which hosts some of the oldest objects we know of in the cosmos; it is where clues to the history of galaxies are found, for example, by how the chemical structure is related to the dynamics of objects in the halo. The dynamical and chemical structure of halos, both in the Milky Way’s own halo, and in two elliptical galaxies, is the underlying theme in the research. I focus on the density falloff and chemistry of the two external halos, and on the dynamics, density falloff, and chemistry of the Milky Way halo. I first study galactic halos via computer simulations, to test the long- term stability of an anomalous feature recently found in kinematics of the Milky Way’s metal-poor stellar halo. I find that the feature is transient, making its origin unclear. I use a second set of simulations to test if an initially strong relation between the dynamics and chemistry of halo glob-ular clusters in a Milky Way-type galaxy is affected by a merging satellite galaxy, and find that the relation remains strong despite a merger in which the satellite is a third of the mass of the host galaxy. From simulations, I move to observing halos in nearby galaxies, a challenging procedure as most of the light from galaxies comes from the disk and bulge components as opposed to the halo. I use Hubble Space Tele scope observations of the halo of the galaxy M87 and, comparing to similar observations of NGC 5128, find that the chemical structure of the inner halo is similar for both of these giant elliptical galaxies. I use Very Large Telescope observations of the outer halo of NGC 5128 (Centaurus A) and, because of the difficultly in resolving dim extragalac- tic stellar halo populations, I introduce a new technique to subtract the contaminating background galaxies. A transition from a metal-rich stellar halo to a metal-poor has previously been discovered in two different types of galaxies, the disk galaxy M31 and the classic elliptical NGC 3379. Unexpectedly, I discover in this third type of galaxy, the merger remnant NGC 5128, that the density of metal-rich and metal-poor halo stars falls at the same rate within the galactocentric radii of 8 − 65 kpc, the limit of our observations. This thesis presents new results which open opportunities for future investigations.

Synthesis of chiral homoallylic alcohols and phthalans through the asymmetric allylation of carbonyl compounds /

The implementation of chiral centres within biologically active compounds has been a perplexing yet motivational force in chemistry. This work presents the attempted formation of a concurrent or sequential tandem catalyzed methodology of enantioselective nucleophilic addition and electrophilic cyclization. The 2'- arylalkynyl- aldehyde, ketone, and imine substrates used within were adeptly chosen with a dually activated structure; 1) for nucleophilic addition to the electrophilic substituents; and 2) for carbophilic activation of the alkyne substituent to undergo cyclization. To accomplish the nucleophilic addition, two distinct allylation methodologies were pursued: (/?)-BINOL catalyzed-allylboration and (5)- BINAP-AgF catalyzed-allylsilylation. BINAP catalyzed enantioselective allylation of 2'-arylalkynyl-aldehydes, to form chiral homoallylic alcohols, was successful. Homoallylic alcohols were isolated with high enantio-purity (>80%), which then underwent sequential cyclization to form chiral allylic phthalans, in moderate yields. An application of this methodology towards the construction of biologically active compounds was included with the partial synthesis of the natural product and H. pylori inhibitor, (+)-Spirolaxine methyl ether.

Synthesis of Chiral Benzimidazolylidenes from 1,10-Phenathrolines and 1,10-Phenathroline-2,9-dione /

A^-heterocyclic carbenes (NHCs) have become the focus of much interest as ancillary ligands for transition metal catalysts in recent years. Their structural variability and strong cy-donation properties have led to the preparation of demonstrably useful organometallic catalysts. Among the three general structural types of NHCs (imidazolylidenes, imidazolinylidenes, and benzimidazolylidenes), benzimidazolylidenes are the least investigated because of the limitation of current synthetic approaches. The preparation of chiral analogues is even more challenging. Previously, our group has demonstrated an alternative approach to synthesizing benzimidazolylidenes with a tetracyclic framework in three steps from 1,10-phenanthroline. This thesis is focused on approaches to chiral benzimidazolylidenes derived from substituted 1,10-phenanthrolines. A key step in the preparation of these ligands involves a reduction of the pyridyl rings in 1,10-phenanthrolines. Chirality can be introduced to phenanthrolines before, during, or after the reduction as illustrated by three approaches: 1) de novo construction of the phenanthroline from chiral ketones with endo and exo faces to provide a degree of diastereoselectivity during subsequent reduction; 2) introduction of substituents into the 2- and 2,9- position of phenanthroline by nucleophilic aromatic substitution, followed by a reduction-resolution sequence; and 3) use of the protected octahydrophenanthroline as a substrate for chiral induction a to nitrogen.