Phase-shifting birefringent scatterplate interferometer

We realized what we believe is a new phase-shifting scatterplate interferometer by exploiting the polarization characteristics of a birefringent scatterplate. The common-path design of the interferometer reduces its sensitivity to environmental effects, and phase shifting allows quick and accurate quantitative measurements of the test surface. A major feature of the birefringent scatterplate approach for phase shifting is that no high-quality optical components are required in the test setup. The theory of the interferometer is presented, the procedure for the fabrication of the birefringent scatterplate is described, and experimental results are shown.     

SPIFI: a direct-detection imaging spectrometer for submillimeter wavelengths

The South Pole Imaging Fabry-Perot Interferometer (SPIFI) is the first instrument of its kind-a direct-detection imaging spectrometer for astronomy in the submillimeter band. SPIFI's focal plane is a square array of 25 silicon bolometers cooled to 60 mK; the spectrometer consists of two cryogenic scanning Fabry-Perot interferometers in series with a 60-mK bandpass filter. The instrument operates in the short submillimeter windows (350 and 450 microm) available from the ground, with spectral resolving power selectable between 500 and 10,000. At present, SPIFI's sensitivity is within a factor of 1.5-3 of the photon background limit, comparable with the best heterodyne spectrometers. The instrument's large bandwidth and mapping capability provide substantial advantages for specific astrophysical projects, including deep extragalactic observations. We present the motivation for and design of SPIFI and its operational characteristics on the telescope.     

Oligonucleotide mixture analysis via electrospray and ion/ion reactions in a quadrupole ion trap

Electrospray ionization combined with ion/ion reactions in a quadrupole ion trap can be used for the direct analysis of oligonucleotide mixtures. Elements to the success of this approach include factors related to ionization, ion/ion reactions, and mass analysis. This paper deals with issues regarding the ion polarity combination, viz., positive oligonucleotides/negative charge-transfer agent versus negative oligonucleotides/positive charge-transfer agent. Anions derived from perfluorocarbons appear to be directly applicable to mixtures of positive ions derived from electrospray of oligonucleotides, in direct analogy with positive protein ions. Conditions for forming positive oligonucleotide ions devoid of adducts were more difficult to establish than for forming relatively clean negative oligonucleotide ions. A new approach for manipulating negative ion charge states in the ion trap is described and is based on use of the electric field of the positive charge-transfer agent for storage of high-mass negative ions formed during the ion/ion reaction period. Oxygen cations are shown to be acceptable for charge-state manipulation of mixed-base oligomers but induce fragmentation in polyadenylate homopolymers. Protonated isobutylene (C4H9+), on the other hand, is shown to induce significantly less fragmentation of polyadenylate homopolymers.     

Electrokinetic stacking injection of neutral analytes under continuous conductivity conditions

In capillary electrokinetic chromatography, neutral analytes can be injected by electroosmotic flow directly from a sample matrix into a separation buffer containing an electrokinetic vector with an opposite mobility. Analytes are injected at the velocity of electroosmotic flow but are retained at the interface of the sample matrix co-ion and separation buffer micelle zones as analyte/micelle complexes. A simple electrokinetic chromatography system containing sodium dodecyl sulfate as the micellar agent with borate as the buffering electrolyte included in the separation buffer and in the sample matrix to provide continuous conductivity was investigated. Concentrations of the micelle, methanol, and borate in the separation buffer were explored to increase maximum injection length of neutral analytes. Reducing the analyte velocity in the separation buffer without substantially decreasing the velocity of the analyte during injection from the sample vial allowed greatly extended sample plug injection lengths. It is presently possible to inject sample solvent volumes equivalent to approximately 7 effective capillary lengths (180 cm) with a 50-microm-i.d. capillary (24.5 cm effective capillary length), total volume of sample injection approximately 3.5 microL Equations describing the injection process and maximum injection lengths for this mode of stacking in electrokinetic capillary chromatography are introduced. The result of this work leads to a postulated generalization of electrokinetic stacking injection maximums for electrophoretic processes, and the concept of orthogonal analyte stacking/injection systems is discussed.     

Optimizing the multielement analysis capabilities of an ICP quadrupole mass spectrometer using electrothermal vaporization sample introduction

A mathematical solution and an experimental procedure are described for calculating the maximum number of transient signals, such as those obtained using ETV sample introduction into an ICPMS, that can be monitored by a scanning spectrometer, such as a quadrupole mass analyzer. The total number of masses that can be monitored per ETV firing is shown to be dependent on the values chosen for data collection (i.e., scan time and dwell time) and the necessary limits of detection required by the method. The theory shows the effect that statistical noise, peak shapes, and inconsistent peak appearance times have on the overall variance calculated for the sample concentration based on total counts or "peak area". Also included in the variance calculation is the contribution made by the autosampler as an example of one type of error that is not associated with the data collection parameters. The theory is validated by two experiments where 21 and 68 transient signals are monitored per ETV firing; and as predicted, a 10 ppb sample is accurately quantified with precision better than 9% in both cases.     

Wavelength interval selection in multicomponent spectral analysis by moving window partial least-squares regression with applications to mid-infrared and near-infrared spectroscopic data

A new wavelength interval selection procedure, moving window partial least-squares regression (MWPLSR), is proposed for multicomponent spectral analysis. This procedure builds a series of PLS models in a window that moves over the whole spectral region and then locates useful spectral intervals in terms of the least complexity of PLS models reaching a desired error level. Based on a proposed theory demonstrating the necessity of wavelength selection, it is shown that MWPLSR provides a viable approach to eliminate the extra variability generated by non-composition-related factors such as the perturbations in experimental conditions and physical properties of samples. A salient advantage of MWPLSR is that the calibration model is very stable against the interference from non-composition-related factors. Moreover, the selection of spectral intervals in terms of the least model complexity enables the reduction of the size of a calibration sample set in calibration modeling. Two strategies are suggested for coupling the MWPLSR procedure with PLS for multicomponent spectral analysis: One is the inclusion of all selected intervals to develop a PLS calibration model, and the other is the combination of the PLS models built separately in each interval. The combination of multiple PLS models offers a novel potential tool for improving the performance of individual models. The proposed procedures are evaluated using two open-path Fourier transform infrared data sets and one near-infrared data set, each having different noise characteristics. The results reveal that the proposed procedures are very promising for vibrational spectroscopy-based multicomponent analyses and give much better prediction than the full-spectrum PLS modeling.     

Comparison of exact pupil astigmatism conditions with Seidel approximations

The aberrations of axisymmetric imaging systems can be calculated to third order by use of the Seidel formula. The Coddington equations give aberrations that have quadratic dependence on the pupil, for all field points. The pupil astigmatism conditions were recently developed to predict and control aberrations that have quadratic field dependence and arbitrary pupil dependence. We investigate the relationship between the exact pupil astigmatism conditions and the classical Seidel treatment of pupil aberration.     

Three-dimensional imaging laser radar with a photon-counting avalanche photodiode array and microchip laser

We have developed a threedimensional imaging laser radar featuring 3-cm range resolution and single-photon sensitivity. This prototype direct-detection laser radar employs compact, all-solid-state technology for the laser and detector array. The source is a Nd:YAG microchip laser that is diode pumped, passively Q-switched, and frequency doubled. The detector is a gated, passively quenched, two-dimensional array of silicon avalanche photodiodes operating in Geigermode. After describing the system in detail, we present a three-dimensional image, derive performance characteristics, and discuss our plans for future imaging three-dimensional laser radars.     

Effects of characteristics of image quality in an immersive environment

Image quality issues such as field of view (FOV) and resolution are important for evaluating "presence" and simulator sickness (SS) in virtual environments (VEs). This research examined effects on postural stability of varying FOV, image resolution, and scene content in an immersive visual display. Two different scenes (a photograph of a fountain and a simple radial pattern) at two different resolutions were tested using six FOVs (30, 60, 90, 120, 150, and 180 deg.). Both postural stability, recorded by force plates, and subjective difficulty ratings varied as a function of FOV, scene content, and image resolution. Subjects exhibited more balance disturbance and reported more difficulty in maintaining posture in the wide-FOV, high-resolution, and natural scene conditions.     

Studies of the antenna effect in polymer molecules. 29. Synthesis and properties of poly[sodium styrene sulfonate-co-(4-acryolyloxyphenyl)-10,15,20-tritolylporphyrin] in aqueous solution

The novel water soluble antenna polyelectrolyte: poly[sodium styrene sulfonate-co-(4-acryolyloxyphenyl)-10,15,20-tritolylporphyrin] (PSSS-Po) was synthesised, and its photophysical and photochemical properties were studied. Solubilisation of the various molecular probes such as pyrene or perylene in aqueous solution of the PSSS-Po proved that the polymer chain adopts the compact conformation. The interior of the polymer pseudomicelle is significantly less polar than water. The effective quenching of polymeric porphyrin fluorescence by sulfopropyl viologen (SPV) can be explained considering the possibility of electron transfer from the singlet-excited state of Po to SPV. This has been supported by measuring an absorption spectrum for PSSS-Po/SPV system after selective irradiation of Po chromophores. The formation of the new absorption bands characteristic for SPV⁻ radical anion indicated that the charge separation was achieved in that system.