Proton-Coupled Reduction of N2 Facilitated by Molecular Fe Complexes

The activation of Fe-coordinated N₂ via the formal addition of hydrogen atom equivalents is explored in this thesis. These reactions may occur in nitrogenase enzymes during the biological conversion of N₂ to NH₃. To understand these reactions, the N₂ reactivity of a series of molecular Fe(N₂) platforms is investigated. A trigonal pyramidal, carbon-ligated Fe^I complex was prepared that displays a similar geometry to that of the resting state 'belt' Fe atoms of nitrogenase. Upon reduction, this species was shown to coordinate N₂, concomitant with significant weakening of the C-Fe interaction. This hemilability of the axial ligand may play a critical role in mediating the interconversion of Fe(N_xH_y) species during N₂ conversion to NH₃. In fact, a trigonal pyramidal borane-ligated Fe complex was shown to catalyze this transformation, generating up to 8.49 equivalents of NH₃. To shed light on the mechanistic details of this reaction, protonation of a borane-ligated Fe(N₂) complex was investigated and found to give rise to a mixture of species that contains an iron hydrazido(2-) [Fe(NNH₂)] complex. The identification of this species is suggestive of an early N-N bond cleavage event en route to NH₃ production, but the highly-reactive nature of this complex frustrated direct attempts to probe this possibility. A structurally-analogous silyl-ligated Fe(N₂) complex was found to react productively with hydrogen atom equivalents, giving rise to an isolable Fe(NNH₂) species. Spectroscopic and crystallographic studies benefited from the enhanced stability of this complex relative to the borane analogue. One-electron reduction of this species initiates a spontaneous disproportionation reaction with an iron hydrazine [Fe(NH₂NH₂)] complex as the predominant reaction product. This transformation provides support for an Fe-mediated N₂ activation mechanism that proceeds via a late N-N bond cleavage. In hopes of gaining more fundamental insight into these reactions, a series of Fe(CN) complexes were prepared and reacted with hydrogen-atom equivalents. Significant quantities of CH₄ and NH₃ are generated in these reactions as a result of complete C-N bond activation. A series of Fe(CNH_x) were found to be exceptionally stable and may be intermediates in these reactions. The stability of these compounds permitted collection of thermodynamic parameters pertinent to the unique N-H bonds. This data is comparatively discussed with the theoretically-predicted data of the N₂-derived Fe(NNH_x) species. Exceptionally-weak N-H bond enthalpies are found for many of these compounds, and sheds light on their short-lived nature and tendency to evolve H₂. As a whole, these works both establish and provide a means to understand Fe-mediated N₂ activation via the addition of hydrogen atom equivalents.

Three-dimensional coupled wave study for finite-sized anisotropic volume holographic gratings under ultrashort pulsed beam readout

The three-dimensional coupled wave theory is extended to systematically investigate the diffraction properties of finite-sized anisotropic volume holographic gratings (VHGs) under ultrashort pulsed beam (UPB) readout. The effects of the grating geometrical size and the polarizations of the recording and readout beams on the diffraction properties are presented, in particular under the influence of grating material dispersion. The wavelength selectivity of the finite-sized VHG is analyzed. The wavelength selectivity determines the intensity distributions of the transmitted and diffracted pulsed beams along the output face of the VHG. The distortion and widening of the diffracted pulsed beams are different for different points on the output face, as is numerically shown for a VHG recorded in a LiNbO3 crystal. The beam quality is analyzed, and the variations of the total diffraction efficiency are shown in relation to the geometrical size of the grating and the temporal width of the readout UPB. In addition, the diffraction properties of the finite-sized and one-dimensional VHG for pulsed and continuous-wave readout are compared. The study shows the potential application of VHGs in controlling spatial and temporal features of UPBs simultaneously. (C) 2007 Optical Society of America

Miniature pulse compressor of deep-etched gratings

We propose a miniature pulse compressor that can be used to compensate the group velocity dispersion that is produced by a commercial femtosecond laser cavity. The compressor is composed of two identical highly efficient deep-etched transmissive gratings. Compared with prism pairs, highly efficient deep-etched transmissive grating pairs are lightweight and small. With an optimized groove depth and a duty cycle, 98% diffraction efficiency of the -1 transmissive order can be achieved at a wavelength of 800 nm under Littrow conditions. The deep-etched gratings are fabricated in fused silica by inductively coupled plasma etching. With a pair of the fabricated gratings, the input positively chirped 73.9 fs pulses are neatly compressed into the nearly Fourier transform-limited 43.2 fs pulses. The miniature deep-etched grating-based pulse compressor should be of interest for practical applications. (c) 2008 Optical Society of America

Quadratic nonlinear technologies for femtosecond lasers

Quadratic optical nonlinearity chi((2)) can be exploited in femtosecond lasers and regarded as a significant new degree of freedom for the design of short-pulse sources. We will review our recent progress on developing nonlinear quadratic technologies for femtosecond lasers. Our nonlinear laser technology offers new properties for femtosecond lasers, including optical parametric amplifier with novel working regime, efficient second harmonic generation, and time telescope.

Stable single frequency and single polarization DFB fiber lasers operated at 1053 nm

Stable single-frequency and single-polarization distributed-feedback (DFB) fiber laser was realized by giving a pressure on the phase shift region of the fiber grating. The output wavelength of the DFB fiber laser is 1053 nm. When the pump power of 980 nm laser diode is 100 and 254 mW, the output power can reach 8.3 and 37.1 mW and the polarization extinction ratio was 26 and 20 dB, respectively. After chopped by Acousto-optic modulator (0.3 Hz), the pulse peak value variance is 4.65%(peak to peak) and 1.098% (RMS) for 31 min. (C) 2006 Elsevier Ltd. All rights reserved.

Theoretical modelling of the effect of photon lifetime on the output dynamics of Er-doped distributed feedback fibre lasers

By employing a simple model of describing three-level lasers, we have theoretically investigated the effect of photon lifetime on the output dynamics of Er-doped distributed feedback fibre lasers. And based on the theoretical analysis we have proposed a promising method to suppress self-pulsing behaviour in the fibre lasers.

Analysis on the spin reorientation of GdFeCo/DyFeCo exchange-coupled double-layer films

In this paper, GdFeCo/DyFeCo exchange-coupled double-layer films used for center aperture type magnetically induced super resolution were investigated through experiments and theoretical calculation. The samples were prepared by magnetron sputtering method. The polar Kerr effect was measured to prove the spin reorientation of the readout layer. Theoretical study of magnetization profiles was performed on the basis of the mean-field theory and the continuum model. The theoretical results showed that the magnetization orientation of the readout layer changed gradually from in-plane to out-of-plane with the rise of the temperature. Theoretical analysis explained the experimental results successfully. (c) 2005 Elsevier B.V. All rights reserved.

Analysis on a new type magneto-optical disk for blue lasers

The conventional TbFeCo magneto-optical (MO) medium has a relatively smaller Kerr rotation angle in the blue region than in the red. With the recording wavelength gradually moving to the short wavelength, if TbFeCo is still used as recording medium, the conventional MO disk structure must be optimized to get a larger carrier to noise ratio (CNR). Sabi et al. have found that adding a metal layer attached to the TbFeCo film as thermal control layer is a useful way to get a high CNR. In this paper, we proved this through calculation, and carried out optimization of the new type of disk. Calculation results showed that the new structure is useful in preventing an excessive temperature increase, and has a better thermal response. (c) 2005 Elsevier B.V. All rights reserved.

Contributions to learning Bayesian network models from weakly supervised data: Application to Assisted Reproductive Technologies and Software Defect Classification

162 p.

Thermal and thermal-optical effects in high-power photonic crystal fiber lasers

A series-parallel model is introduced to calculate the effective thermal conductivities of hollow claddings of photonic crystal fibers ( PCFs ). The temperature distribution and thermal-optical properties of PCF lasers are studied by solving the heat transfer equations. The average power scaling of the PCF lasers in respect of the thermal effects is also discussed. (c) 2006 Society of Photo-Optical Instrumentation Engineers.

Mass spectrometry coupled to imaging techniques: The better the view the greater the challenge

These are definitively exciting times for membrane lipid researchers. Once considered just as the cell membrane building blocks, the important role these lipids play is steadily being acknowledged. The improvement occurred in mass spectrometry techniques (MS) allows the establishment of the precise lipid composition of biological extracts. However, to fully understand the biological function of each individual lipid species, we need to know its spatial distribution and dynamics. In the past 10 years, the field has experienced a profound revolution thanks to the development of MS-based techniques allowing lipid imaging (MSI). Images reveal and verify what many lipid researchers had already shown by different means, but none as convincing as an image: each cell type presents a specific lipid composition, which is highly sensitive to its physiological and pathological state. While these techniques will help to place membrane lipids in the position they deserve, they also open the black box containing all the unknown regulatory mechanisms accounting for such tailored lipid composition. Thus, these results urges to different disciplines to redefine their paradigm of study by including the complexity revealed by the MSI techniques.

Output beam quality of edge pumped planar waveguide lasers with confocal unstable resonators

Output beam quality of edge pumped planar waveguide lasers with confocal unstable resonators is investigated by diffraction methods, taking into account gain saturation, asymmetric pumping, and beam interaction. The influences of pumping uniformity, doping concentration, cavity length and effective Fresnel number are analyzed with respect to output beam quality and pumping efficiency. It is found that good beam quality and high efficiency can be obtained with asymmetric pumping and optimized negative branch confocal unstable resonators. (c) 2005 The Optical Society of Japan.

High power coherent beam combination from two fiber lasers

Phase locking of two fiber lasers is demonstrated experimentally by the use of a self-imaging resonator with a spatial filter. The high-contrast interference strips of the coherent beam profile are observed. The coherent output power of the fiber array exceeds 12W and the efficiency of coherent power combination is 88% with pump power of 60W. The whole system operates quite stably and, for the spatial filter, no thermal effects have been observed, which means that we can increase the coherent output power further by this method. (c) 2006 Optical Society of America

Nd-glass belt lasers with improved beam quality

Nd-doped phosphate glass belt lasers pumped by laser diodes are demonstrated. The Nd-glass belt with a large cross-section and a small Fresnel number is air-cooled to provide around 18-W continuous wave (CW) output power with a beam quality factor of My2