Determination of pyrolysis temperature for charring materials

An energy and mass balanced method of determining the pyrolysis temperature is proposed. The concept is to find the pyrolysis temperature that consumes the same amount of energy to produce the same amount of mass when using the pyrolysis front model as when using finite rate kinetics models for the entire charring process. The resulting pyrolysis temperature has the form of pyrolysis rate weighted average temperature. Comparisons between finite rate kinetics and pyrolysis front models for various boundary conditions, geometries, heats of decomposition, kinetic parameters and assumptions used in the literature were made to assess the proposed method. Models using energy and mass balanced pyrolysis temperature show good agreement with finite rate models and the experiments. Extensive numerical studies on various factors influencing the charring material pyrolysis show that heat flux, sample size, heat of decomposition and kinetic parameters are the most important factors for determining an appropriate pyrolysis temperature. Thermal conductivity, specific heat and density have a lesser effect on the pyrolysis temperature. For practical application, a non-dimensional correlation is developed to determine the appropriate pyrolysis temperature without solving the problem by using finite rate models. With this correlation the energy and mass balanced pyrolysis temperature can be determined with a standard deviation of 7.6 K. These predictions are validated by comparison with measurements of wood cylinder pyrolysis. A good agreement suggests that simpler pyrolysis front models yield practically useful and accurate results given an appropriate pyrolysis temperature.     

Avoiding temporal distortions in tilted pulses

Tilted femtosecond laser pulses, having an intensity front with an angle to the propagation direction, can be generated by a dispersive element and a lens or mirror for imaging. Here we show that conventional geometries, for example with a grating at Littrow's condition, produce significant temporal distortions over the beam profile. The aberrations are the result of a mismatch between the grating's surface and the object plane of the imaging system. This changes the chirp of the pulses over the beam profile and lengthens the pulses to picoseconds for millimeter-sized beams. The distortions can be avoided by choosing a geometry in which the propagation direction of the tilted pulses is perpendicular to the grating's surface.     

A practical synthesis of 2-((1H-pyrrolo[2,3-b]pyridine-4-yl)methylamino)-5- fluoronicotinic acid

A practical synthesis of a key pharmaceutical intermediate, 2-[(1H-pyrrolo[2,3-b]pyridine-4-yl)methylamino]-5-fluoronicotinic acid (1), is described. To introduce the aminomethyl moiety of 2 via a palladium-catalyzed cyanation/reduction sequence, a regioselective chlorination of 7-azaindole via the N-oxide was developed. A highly selective monodechlorination of 2,6-dichloro-5-fluoronicotinic acid was discovered to afford the nicotinic acid 3. The two building blocks 2 and 3 were then coupled to complete the preparation of 1.     

Development of capillary electrophoresis methods for quantitative determination of taurine in vehicle system and biological media

CE methods have been developed for the determination of taurine in pharmaceutical formulation (microemulsion) and in biological media such as sweat. The CE system with end-column pulsed amperometric detection has been found to be an interesting method in comparison with UV and fluorescence detection for its simplicity and rapidity. A gold-disk electrode of 100 mm diameter was used as the working electrode. The effects of a field decoupler at the end of the capillary, separation voltage, injection and pressure times were investigated. A detection limit of 4 x 10(-5) mol/L was reached using integrated pulsed amperometric detection, a method successfully applied to taurine analysis of the biological samples such as sweat. For taurine analysis of oil-in-water microemulsion, fluorescence detector was the favored method, the detection limit of which was 4 x 10(-11) mol/L.     

Isotope shift and hyperfine structure measurements at the242f Am fission isomer

Istope shift and hyperfine structure measurements have been performed for the^242fAm fission isomer with target production rates of only a few per second. The method is based on resonance ionization spectroscopy (RIS) in a buffer gas cell with radioactive decay detection of the ionization process (RADRIS). A relative isotope shift ratioX _exp=IS^242f,241/ IS^243,241=41.7±0.9 has been measured for the 500.02 nm transition corresponding to a nuclear parameter ^242f,241=5.4±0.3 fm². The analysis of the quadrupole moment based on the deformed Fermi-model of the nuclear charge distribution including second order corrections results inQ ₂₀=38.2 ±1.4( _–0.8 ^+0.4 )_model eb. The measurement of the hyperfine structure splitting of the transition at 466.28 nm yields a negativeg-factor and a nuclear spin ofI=2 orI=3.Work supported by the Bundesministerium für Bildung und Forschung under contract 06 MZ 5661.     

Tunable sub-10-fs ultraviolet pulses generated by achromatic frequency doubling

Tunable UV pulses shorter than 10 fs are generated by achromatic frequency doubling of a noncollinear optical parametric amplifier. With a suitable two-prism sequence we achieve first- and second-order achromatic phase matching and increase the natural bandwidth of the nonlinear crystal by a factor of 80. Extremely broad UV spectra with a Fourier limit of 2.9 fs are generated in a 360-microm-thick beta-barium borate crystal at a conversion efficiency of 20%. We compensate for the angular dispersion and the first-order chirp of the highly stable UV pulses with a second prism sequence and fully characterize the temporal pulse shape with zero-additional-phase spectral phase interferometry for direct electric-field reconstruction (ZAP-SPIDER). Pulses as short as 7 fs are generated by controlling the higher-order chirp with a deformable mirror.     

12-fs pulses from a continuous-wave-pumped 200-nJ Ti:sapphire amplifier at a variable repetition rate as high as 4 MHz

We demonstrate a novel compact femtosecond Ti:sapphire laser system operating at repetition rates from 10 kHz to 4 MHz. The scheme is based on the combination of a broadband cavity-dumped oscillator and a double-pass Ti:sapphire amplifier pumped by a low-noise cw solid-state laser. Amplified pulses with an extremely smooth spectrum, a duration of only 12 fs, and less than 0.25% rms fluctuation are generated in a beam with M2 < 1.2. A maximum pulse energy of 210 nJ and an average output power of as much as 720 mW are achieved. This output energy is sufficient to generate a stable continuum in a sapphire disk.