The effect of an eight session skate treadmill and agility training program on the degree of separation in ice hockey players

The sport of ice hockey places multiple simultaneous demands on the physiological, mechanical, and cognitive abilities of individual players. The purpose of the study was to investigate the effect of an eight session degree of separation (DOS) training intervention on sport specific measures of skating, stick handling and puck control movements in competitive ice hockey players. All participants completed a battery of pre and pos t skill and DOS specific tests designed to evaluate DOS abilities: Ttest of agility, a modified Cunningham Faulkner test of anaerobic capacity performed on a skate treadmill and a DOS skate treadmill test. Statistically significant differences were found between groups on the post test scores, meaning that the training intervention had a specific effect on the post test scores of the experimental group (p~O.05). Results of this investigation suggested that a DOS specific training program has the potential to enhance the integration and automation of or sequencing and coordination of uncoordinated ice hockey movements.

Electronic, magnetic and thermal properties of Pb₂₋x AxCrO₅ (A = K or La)

Lead chromium oxide is a photoconductive dielectric material tha t has great potential of being used as a room temperature photodetector. In this research, we made ceramic pellets of this compound as well as potassium doped compound Pb2-xKxCr05, where x=O, 0.05, 0.125. We also investigate the properties of the lanthanum doped sample whose chemical formula is Pb1.85Lao.15Cr05' The electronic, magnetic and thermal properties of these materials have been studied. Magnetization measurements of the Pb2Cr05 sample indicate a transition at about 310 K, while for the lanthanum doped sample the transition temperature is at about 295 K indicating a paramagnetic behavior. However, the potassium doped samples are showing the transition from paramagnetic state to diamagnetic state at different temperatures for different amounts of potassium atoms present in the sample. We have studied resistivity as a function of temperature in different gas environments from 300 K to 900 K. The resistivity measurement of the parent sample indicates a conducting to insulating transition at about 300 K and upon increasing the temperature further, above 450 K the sample becomes an ionic conductor. As temperature increases a decrease in resistance is observed in the lanthanum/potassium doped samples. Using Differential Scanning Calorimetry experiment an endothermic peak is observed for the Pb2Cr05 and lanthanum/potassium doped samples at about 285 K.

Crystallinity, Magnetic and Electrical Properties of Bi doped LaVO3

We report the results of crystal structure, magnetization and resistivity measurements of Bi doped LaVO3. X-ray diffraction (XRD) shows that if doping Bi in the La site is less than ten percent, the crystal structure of La1-xBixVO3 remains unchanged and its symmetry is orthorhombic. However, for higher Bi doping (>10%) composite compounds are found where the XRD patterns are characterized by two phases: LaVO3+V2O3. Energy-dispersive analysis of the x-ray spectroscopy (EDAX) results are used to find a proper atomic percentage of all samples. The temperature dependence of the mass magnetization of pure and single phase doped samples have transition temperatures from paramagnetic to antiferromagnetic region at TN=140 K. This measurement for bi-phasic samples indicates two transition temperatures, at TN=140 K (LaVO3) and TN=170 K (V2O3). The temperature dependence of resistivity reveals semiconducting behavior for all samples. Activation energy values for pure and doped samples are extracted by fitting resistivity versus temperature data in the framework of thermal activation process.

Molecular Magnetism: The Design, Synthesis, and Characterization of New Building Blocks for Molecule-based Magnetic Materials

Two classes of building blocks have been prepared and characterized and their coordination chemistry explored working towards the preparation of new molecule-based magnetic materials. In the first project, the amine functionality of 3,3'-diamino-2,2'- bipyridine was exploited for the preparation of a new family of ligands (H2L 1)-(H2L 4). The molecular structures of three ligands have been fully characterized by X-ray crystallography. [molecular structure diagram will not copy here, but is available in full pdf.] The coordination chemistry of these ligands with divalent first row transition metal ions was investigated. For ligand (H2L1), the molecular structures of four coordination complexes with stoichiometries [Zn2(Ll)(OAc)(MeO)]2 (I), [Cu2(L1)(OAc)2 (II), [Li(L1)]3 (III), and [Ni(L1)]3 (IV) were determined by X-ray crystallography. For ligand (H2L2), a Cu(II) complex of stoichiometry [Cu3(L2)(OAc)3MeO] (V) was determined by X-ray crystallography. The magnetic properties of complexes (II), (III), and (V) have been fully elucidated. In project two, synthetic strategies for the preparation of porphyrin molecules bearing triol substituents is presented. Following this approach, three new porphyrin derivatives have been prepared and characterized [Zn(HPTPP-CH2C(CH20H)3)] (VI), [P(TPP)(OCH2C(CH2)H)3)2]+CL- (VII), and [P(OEP)(C6H5)(OCH2C(CH2OH)3)]+Cl- (VIII). Attempts to exchange the labile methoxide bridges of a tetraironIIl single molecule magnet of stoichiometry [Fe4(OMe)6(dpm)6] (Hdpm = dipivaloylmethane) with the triol appended porphyrins will be discussed. [molecular structure diagram will not copy here, but is available in full pdf.]

Optical Properties of Sb2Te3, and Dilute Magnetic Semiconductors Sb1.97 VO.03 Te3 and Sb1.94 CrO.06 Te3

This thesis reports on the optical properties of the dilute magnetic semiconductors, Sb1.97 V 0.03 Te3 and Sb1.94Cr0.06Te3, along with the parent compound Sb2Te3' These materials develop a ferromagnetic state at low temperature with Curie temperatures of 22 K and 16 K respectively. All three samples were oriented such that the electric field vector of the light was perpendicular to the c-axis. The reflectance profile of these samples in the mid-infrared (500 to 3000 cm-1) shows a pronounced plasma edge which retracts with decreasing temperature. The far-infrared region of these samples exhibits a phonon at ~ 60 cm-1 which softens as temperature decreases. Kramers-Kronig analysis and a Drude-Lorentz model were employed to determine the optical constants of the bulk samples. The real part of the optical conductivity is shown to consist of intraband contributions at frequencies below the energy gap (~0.26 eV) and interband contributions at frequencies above the energy gap. The temperature dependence of the scattering rate show that a mix of phonon and impurity scattering are present, while the signature of traditional spin disorder (magnetic) scattering was difficult to confirm.

Ligand design for molecule-based magnetic and/or conducting materials

Work in the area of molecule-based magnetic and/or conducting materials is presented in two projects. The first project describes the use of 4,4’-bipyridine as a scaffold for the preparation of a new family of tetracarboxamide ligands. Four new ligands I-III have been prepared and characterized and the coordination chemistry of these ligands is presented. This project was then extended to exploit 4,4’-bipyridine as a covalent linker between two N3O2 macrocyles. In this respect, three dimeric macrocycles have been prepared IV-VI. Substitution of the labile axial ligands of the Co(II) complex IV by [Fe(CN)6]4- afforded the self-assembly of the 1-D polymeric chain {[Co(N3O2)H2O]2Fe(CN)6}n•3H2O that has been structurally and magnetically characterized. Magnetic studies on the Fe(II) complexes V and VI indicate that they undergo incomplete spin crossover transitions in the solid state. Strategies for the preparation of chiral spin crossover N3O2 macrocycles are discussed and the synthesis of the novel chiral Fe(II) macrocyclic complex VII is reported. Magnetic susceptibility and Mössbauer studies reveal that this complex undergoes a gradual spin crossover in the solid state with no thermal hysteresis. Variable temperature X-ray diffraction studies on single crystals of VII reveal interesting structural changes in the coordination geometry of the macrocycle accompanying its SCO transition. The second project reports the synthesis and characterization of a new family of tetrathiafulvalene derivatives VIII – XII, where a heterocyclic chelating ligand is appended to a TTF donor via an imine linker. The coordination chemistries of these ligands with M(hfac)2.H2O (M( = Co, Ni, Mn, Cu) have been explored and the structural and magnetic properties of these complexes are described.

Triarylamminium radical-cation complexes: design and magnetic properties and Base-catalyzed hydrosilylation: mechanism and substrate scope

1. Triarylamminium radical-cation complexes. The detailed study of manganese, copper and nickel metal-radical complexes with triarylamminium ligands was conducted. Stable, neutral and pseudo-octahedral coordination monometallic complexes with simple monodentate 2,2`-bipyridine ligand containing a redox-active N,N`-(4,4`-dimethoxydiphenyl-amino) substituent were synthesized and fully characterized. The one-electron oxidation process and formation of persistent radical-cation complexes was observed by cyclic voltammetry and spectroelectrochemical measurements. Evans method measurements were performed with radical-cation complexes generated by chemical one-electron oxidation with NOPF6 in acetonitrile. The experimental results indicate ferromagnetic coupling between metal and triarylamminium cation in manganese (II) complex and antiferromagnetic coupling in nickel (II) complex. This data is supported by DFT calculations which also lend weight to the  spin polarization mechanism as an operative model for magnetic exchange coupling. Neutral bimetallic complexes with a new ditopic ligand were synthesized and fully characterized, including magnetic and electrochemical studies. Chemical oxidation of these precursor complexes did not generate radical-cations, but dicationic complexes, which was confirmed by UV-vis and EPR-experiments, as well as varied temperature magnetic measurements. DFT calculations for radical-cation complexes are included. A synthetic pathway for polytopic ligand with multiple redox-active triarylamine sites was developed. The structure of the ligand is presumably suitable for -spin polarization exchange model and allows for production of polymetallic complexes having high spin ground states. 2. Base-catalyzed hydrosilylation. A simple reductive base-catalyzed hydrosilation of aldehydes and ketones was adapted to the use of the cheap, safe, and non-toxic polymethylhydrosiloxane (PMHS) instead of the common PhSiH3 and (EtO)3SiH, which present significant cost and safety concerns, respectively. The conversion of silane into pentacoordinate silicate species upon addition of a base was studied in details for the cases of phenyl silane and PMHS and is believed to be essential for the hydrosilylation process. We discovered that nucleophiles (a base or fluoride-anion) induced the rearrangement of PMHS and TMDS into light silanes: MeSiH3 and Me2SiH2, respectively. The reductive properties of PMHS under basic conditions can be attributed to the formation of methyl silane and its conversion into a silicate species. A procedure for the generation of methyl silane and its use in further efficient reductions of aldehydes and ketones has been developed. The protocol was extended to the selective reduction of esters and tertiary amides into alcohols and aldimines into amines with good isolated yields and reduction of heterocyclic compounds was attempted.

Novel Magnetic Materials Based on Macrocyclic Ligands: Towards High Relaxivity Contrast Agents and Mononuclear Single-Molecule Magnets

The preparation and characterization of coordination complexes of Schiff-base and crown ether macrocycles is presented, for application as contrast agents for magnetic resonance imaging, Project 1; and single-molecule magnets (SMMs), Projects 2 and 3. In Project 1, a family of eight Mn(II) and Gd(III) complexes of N3X2 (X = NH, O) and N3O3 Schiff-base macrocycles were synthesized, characterized, and evaluated as potential contrast agents for MRI. In vitro and in vivo (rodent) studies indicate that the studied complexes display efficient contrast behaviour, negligible toxicity, and rapid excretion. In Project 2, DyIII complexes of Schiff-base macrocycles were prepared with a view to developing a new family of mononuclear Ln-SMMs with pseudo-D5h geometries. Each complex displayed slow relaxation of magnetization, with magnetically-derived energy barriers in the range Ueff = 4 – 24 K. In Project 3, coordination complexes of selected later lanthanides with various crown ether ligands were synthesized. Two families of complexes were structurally and magnetically analyzed: ‘axial’ or sandwich-type complexes based on 12-crown-4 and 15-crown-5; and ‘equatorial’ complexes based on 18-crown-6. Magnetic data are supported by ab initio calculations and luminescence measurements. Significantly, the first mononuclear Ln-SMM prepared from a crown ether ligand is described.