Anomalous solvent shift effect and observation of phosphorescence in bilirubin

Bilirubin IX-α has a large extinction coefficient but shows a weak blue-shift in solvents of increasing dielectric constant. A blue-shift is typical of an n → π^* transition, and is here interpreted in terms of the amide group present in the terminal pyrrole rings. Compounds undergoing n → π^* transitions usually form triplet states. With bilirubin, an emission is observed at 77 K; evidence is presented that this may be phosphorescence from an excited triplet state. The energy of this triplet level is 230 kJ mole^?1, thus bilirubin should be capable of sensitizing the formation of ¹Δ_g O₂.     

The scanning acoustic microprobe: II. Application to the measurement and characterization of a piston reflector

In a pulsed ultrasound beam, echoes detected from a flat, circular piston of arbitrary size depend on the time-space characteristics of the entire pulse-echo measurement system, being a function of as many parameters as it takes to accurately define the system. In the limiting case of a target that is small relative to the spatial extent of an interrogating plane wave, an echo pattern is known to be a relatively simple function of the dimensionless product k0b, where k0 is the wave number and b is the radius of the target. In a companion paper preceding this one [F. E. Barber, J. Acoust. Soc. Am. 90, 8-17 (1991)], the author has described the scanning acoustic microprobe, a pulse-echo system in which the time-space properties of the interrogating waves are specified completely by k0 and a single additional parameter s0, which is the characteristic radius of a spherically symmetric, Gaussian-distributed scattering volume. In this system, the reflection pattern of a flat, circular piston of any arbitrary size is thus a function of two dimensionless parameters, namely k0b and b/s0. In this paper, this functional relationship is derived, a physical system is described, and analytical and experimental results are reported. It is shown that the diameter, orientation, and impedance mismatch properties of this simple target can be measured unambiguously over a range of target sizes from about a wavelength (2 pi/k0) to a beam diameter (about 3s0). For a typical ultrasound system, this is about a 5-1 range; i.e., a range extending to target sizes about five times smaller than can be detected in a simple B-mode imaging system.(ABSTRACT TRUNCATED AT 250 WORDS)     

Submm heterodyne mixing using NbCN/Nb sis tunnel junctions

We describe heterodyne mixing experiments with NbCN/Nb quasi-particle tunnel junctions at submillimeter wavelengths. In this wavelength range junctions with niobium nitride as superconducting material are promising because of the high gap voltage, about 5.7 mV, as compared to 3 mV for the more commonly used niobium. As a first step towards all-NbN junctions we investigate the development of junctions with a NbN base electrode and a Nb upper electrode. We present results from samples with two different insulating barriers: aluminum oxide and magnesium oxide. Measured noise temperatures range from 500 K at 345 GHz and 1600 K at 482 GHz to 8500 K at 644 GHz. These results are about one order of magnitude worse than the best results obtained with all-Nb junctions. The difference can be attributed partly to the relatively high radio-frequency (rf) losses in NbN films as compared to Nb. Also sensitivity is reduced because of the relatively high leakage current in the sub-gap region of the I-V curve of the junction.     

Surface characteristics and electrochemical behaviour of sputter-deposited NiTi thin film

Thin nanocrystalline amorphous NiTi film was deposited on Si substrate using DC magnetron sputtering. The as-deposited NiTi thin film was crystallized by heat treatment at 500 °C for 1 h. The crystal structure, surface morphology, microstructure and surface chemistry of the deposited films were studied using X-ray diffraction, atomic force microscopy, scanning electron microscopy and X-ray photoelectron spectroscopy (XPS), respectively. Corrosion behaviour was assessed in Ringer’s solution at 37 °C by open circuit potential (OCP), potentiodynamic polarization and electrochemical impedance spectroscopy as a function of exposure time. OCP values indicate that the tendency for the formation of a spontaneous oxide film is greater for the NiTi thin films than the bulk NiTi. Long time exposure to Ringer’s solution was found to have a great effect on the corrosion behaviour of the samples. Significantly low corrosion current density was obtained for the annealed NiTi film from the potentiodynamic polarization curves indicating a typical passive behaviour, but as-deposited film and bulk NiTi alloy exhibited breakdown of passivity at potentials approximately +1.4 V (vs. SCE). XPS showed that the oxide film formed on the annealed NiTi thin film mainly composed of Ti oxides, and no evidence of Ni was found up to 8.2 nm beneath the top surface, suggesting the excellent corrosion resistance of this sample in Ringer’s solution.     

Characterization of an actively linearized ultrabroadband chirped laser with a fiber-laser optical frequency comb

The optical frequency sweep of an actively linearized, ultrabroadband, chirped laser source is characterized through optical heterodyne detection against a fiber-laser frequency comb. Frequency sweeps were measured over approximately 5 THz bandwidths from 1530 nm to 1570 nm. The dominant deviation from linearity resulted from the nonzero dispersion of the fiber delay used as a reference for the sweep linearization. Removing the low-order dispersion effects, the residual sweep nonlinearity was less than 60 kHz rms, corresponding to a constant chirp with less than 15 ppb deviation across the 5 THz sweep.     

Analysis of some combination-overtone infrared bands of SO3

Several new infrared absorption bands for ³²S¹⁶O₃ have been measured and analyzed. The principal bands observed were ν₁+ν₂ (at 1561 cm⁻¹), ν₁+ν₄ (at 1594 cm⁻¹), ν₃+ν₄ (at 1918 cm⁻¹), and 3ν₃ (at 4136 cm⁻¹). Except for 3ν₃, these bands are very complicated because of (a) the Coriolis coupling between ν₂ and ν₄, (b) the Fermi resonance between ν₁ and 2ν₄, (c) the Fermi resonance between ν₁ and 2ν₂, (d) ordinary l-type resonance that couples levels that differ by 2 in both the k and l quantum numbers, and (e) the vibrational l-type resonance between the A₁^′ and A₂^′ levels of ν₃+ν₄. The unraveling of the complex pattern of these bands was facilitated by a systematic approach to the understanding of the various interactions. Fortunately, previous work on the fundamentals permitted good estimates of many constants necessary to begin the assignments and the fit of the measurements. In addition, the use of hot band transitions accompanying the ν₃ band was an essential aid in fitting the ν₃+ν₄ transitions since these could be directly observed for only one of four interacting states. From the hot band analysis we find that the A₁^′ vibrational level is 3.50 cm⁻¹ above the A₂^′ level, i.e., r₃₄=1.75236(7) cm⁻¹. In the case of the 3ν₃ band, the spectral analysis is straightforward and a weak Δk=±2, Δl₃=±2 interaction between the l₃=1 and l₃=3 substates locates the latter A₁^′ and A₂^′ “ghost” states 22.55(4) cm⁻¹ higher than the infrared accessible l₃=1 E^′ state.     

High-Resolution Infrared Spectra of the ν2, ν3, ν4, and 2ν3 Bands of SO3

New measurements are reported for the infrared spectrum of sulfur trioxide, ³²S¹⁶O₃, with resolutions ranging from 0.0015 cm⁻¹ to 0.0025 cm⁻¹. Rovibrational constants have been measured for the fundamentals ν₂, ν₃, and ν₄ and the overtone band 2ν₃. Comparisons are made with the earlier high-resolution measurements on SO₃, and the high correlation among some of the constants related to the Coriolis coupling of the ν₂ and ν₄ levels is discussed in order to understand the areas of disagreement with the earlier work. Splittings of some of the levels are observed and the splitting constant for K=3 of the ground state is determined for the first time. Other observed splittings include the K=1 levels of 2ν₃ (l=2), the K=2 levels of ν₃ and ν₄, and the K=3 levels of ν₂. The analysis shows that there are level crossings between the l=0 and l=2 states of 2ν₃ that allow one to determine the separation of the subband centers for these two states even though access to the l=0 state from the ground state is electric-dipole forbidden. This is a generalized phenomenon that should be found for many other molecules with the same symmetry. The l-type resonance constant, q₃, that causes the splitting of the l₃=±1, k=±1 levels of ν₃ also couples the l₃=0 and 2 states of 2ν₃.     

The proposed Penning trap mass spectrometer facility at TASCC

The proposed Penning trap mass spectrometer, to be located at the TASCC facility of the Chalk River Laboratories, is described. The facility will be used for precise atomic mass determinations among both stable and unstable nuclides. The unstable nuclides would be produced in heavy ion reactions using the TASCC facility. The products from these reactions would be collected using an He-jet transport system loaded with NaCl aerosols. After transport to a background free area, the nuclides of interest would be laser desorbed and resonantly ionized. Subsequently, these ions would be accumulated in a Paul trap, cooled and injected into a precision Penning trap mass spectrometer for mass analysis.