Modeling, measuring, and minimizing the instrument response function of a tunable diode laser spectrometer

The instrument response function (IRF) of a spectrometer limits the accuracy of measured spectroscopic parameters by broadening recorded spectral lines/features. We describe methods to model the effects of the IRF on spectral data, to minimize the IRF widths, and to measure the resulting width of the spectrometer IRF. We have modeled the IRF of our Tunable Diode Laser Spectrometer as a Voigt function. A real-time method of eliminating the effects of low-frequency spectrometer drift has been implemented and has resulted in a substantial reduction in the width of the IRF, its residual Gaussian component reduced from about to about . An accurate measurement of the IRF Gaussian width utilizes a computationally simple method making use of the spectral dependence of the RMS noise of each signal-averaged data point. Various noise sources affecting the spectrometer (preamp/detector noise, laser AM noise, and laser FM noise) are identified and separately quantified by use of the same method. The IRF Gaussian-width measurement can be automatically applied to each measured spectrum of an experimental data set. A related method is discussed which allows accurate determination of the spectral dependence of statistical noise appropriate for use in quantitative Chi-square fitting of absorption spectra. We explore simple, efficient numerical processes which can dramatically enhance the quality and usefulness of acquired spectral data, improving the ability to apply TDL spectroscopy to high-precision, quantitative measurements and the determination of detailed spectroscopic lineshape parameters. This paper provides a guide for interested readers to implement these developments in their own spectrometers.     

Unitary Correlations and the Fejér Kernel

Let M be a unitary matrix with eigenvalues t _j , and let f be a function on the unit circle. Define X _f (M)=f(t _j ). We derive exact and asymptotic formulae for the covariance of X _f and X _g with respect to the measures |(M)|²dM where dM is Haar measure and an irreducible character. The asymptotic results include an analysis of the Fejér kernel which may be of independent interest.     

Economy of effort in different speaking conditions. I. A preliminary study of intersubject differences and modeling issues

This study explores the hypothesis that clear speech is produced with greater "articulatory effort" than normal speech. Kinematic and acoustic data were gathered from seven subjects as they pronounced multiple repetitions of utterances in different speaking conditions, including normal, fast, clear, and slow. Data were analyzed within a framework based on a dynamical model of single-axis frictionless movements, in which peak movement speed is used as a relative measure of articulatory effort (Nelson, 1983). There were differences in peak movement speed, distance and duration among the conditions and among the speakers. Three speakers produced the "clear" condition utterances with movements that had larger distances and durations than those for "normal" utterances. Analyses of the data within a peak speed, distance, duration "performance space" indicated increased effort (reflected in greater peak speed) in the clear condition for the three speakers, in support of the hypothesis. The remaining four speakers used other combinations of parameters to produce the clear condition. The validity of the simple dynamical model for analyzing these complex movements was considered by examining several additional parameters. Some movement characteristics differed from those required for the model-based analysis, presumably because the articulators are complicated structurally and interact with one another mechanically. More refined tests of control strategies for different speaking styles will depend on future analyses of more complicated movements with more realistic models.     

Brake squeal: a literature review

Brake squeal, which usually falls in the frequency range between 1 and 16 kHz, has been one of the most difficult concerns associated with automotive brake systems since their inception. It causes customer dissatisfaction and increases warranty costs. Although substantial research has been conducted into predicting and eliminating brake squeal since the 1930s, it is still rather difficult to predict its occurrence. In this paper, the characteristics and current difficulties encountered in tackling brake squeal are first described. A review of the analytical, experimental and numerical methods used for the investigation of brake squeal is then given. Some of the challenges facing brake squeal research are outlined.     

Power limitations in fiber-optic frequency-division multiplexed systems

Launch power is limited to the milliwatt level by stimulated Brillouin scattering (SBS) in a single-channel, coherent fiber-optic network. Increasing the number of frequency-division multiplexed channels causes the power limit to decrease quickly to submilliwatt levels due to three-wave intermodulation to keep the signal-to-noise ratio from deteriorating significantly. As the number of channels increases, stimulated Raman scattering (SRS) begins to dominate. If a maximum of 0.5-dB depletion in the highest-frequency channel is allowed, SRS dominates when the number of multiplexed channels reaches about 300. Generally, the launch-power-limiting phenomenon is dependent on the number of channels being multiplexed.     

Flexural rigidity of a liquid surface

The energy of a mass of liquid is evaluated asymptotically in powers of the range of the intermolecular potential divided by a typical dimension of the liquid. The leading term is the internal energy, proportional to the liquid volume. The second term is the energy of surface tension, proportional to the area of the liquid surface. The third term is proportional to an integral over this surface of the square of the mean curvature of the surface minus one-third of its Gaussian curvature. This new term has exactly the form of the bending energy of a thin elastic plate. Comparing it with the bending energy yields expressions for the flexural rigidity and the Poisson ratio of the liquid surface. This flexural rigidity of the surface leads to new terms in the equation of equilibrium of the liquid surface, in addition to the usual surface tension terms.     

Synthesis and Spectral Study of Several Solid M3[Eu(2,6-Pyridinedicarboxylate)3] Salts (M=Li+, Na+, K+, Rb+, Cs+, NH4 +, and Pyridinium+)

Abstract

Salts of the [Eu(2,6-pyridinedicarboxylate)₃]^3- complex anion and various monovalent inorganic and organic counterions (Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, NH₄ ⁺, and pyridinium⁺) have been synthesized and studied by emission spectroscopy. The Eu³⁺ ion emission spectra exhibited by these salts have been observed with high resolution (less than 1.0 cm^?1) and at low temperature (77 K). The emission spectra of these compounds indicate that changing the attached counterion does not affect the site symmetry observed by the europium ion beyond slight distortions indicated by small shifts in the energies of the Eu³⁺ electronic levels.     

Fundamental relationships between deformation-induced surface roughness,critical strain localisation and failure in AA5754-O

This research employs two approaches to characterise the apparent structure observed in localised strain maps constructed from surface topography data acquired from AA5754-O sheet stock that was deformed in three in-plane stretching modes. The first uses a conventional two-point autocorrelation function (ACF), while the second uses the combination of the eigenvalue spectrum associated with each map and information theory. The results from the ACF analysis are inconclusive, implying that this technique lacks the sensitivity necessary to quantify the relationships between multi-point clustering and strain localisation. The information theory-based approach reveals that the relative spectral entropy increases monotonically, attains a maximum and then decreases sharply to the failure strain. This behaviour occurs in all three strain modes and results from two competing processes: one where the formation of structure is favourable and one where it is not. The crossover point is a clear indicator of the onset of critical strain localisation and, therefore, can be regarded as a precursor to failure because once the dominant process shifts, additional strain results in the precipitate formation of a critical strain localisation event.     

Mass Spectrometry,Review of the Basics: Electrospray,MALDI, and Commonly Used Mass Analyzers

Abstract

Mass spectrometry (MS) has progressed to become a powerful analytical tool for both quantitative and qualitative applications. The first mass spectrometer was constructed in 1912 and since then it has developed from only analyzing small inorganic molecules to biological macromolecules, practically with no mass limitations. Proteomics research, in particular, increasingly depends on MS technologies. The ability of mass spectrometry analyzing proteins and other biological extracts is due to the advances gained through the development of soft ionization techniques such as electrospray ionization (ESI) and matrix-assisted laser desorption ionization (MALDI) that can transform biomolecules into ions. ESI can efficiently be interfaced with separation techniques enhancing its role in the life and health sciences. MALDI, however, has the advantage of producing singly charges ions of peptides and proteins, minimizing spectral complexity. Regardless of the ionization source, the sensitivity of a mass spectrometer is related to the mass analyzer where ion separation occurs. Both quadrupole and time of flight (ToF) mass analyzers are commonly used and they can be configured together as QToF tandem mass spectrometric instruments. Tandem mass spectrometry (MS/MS), as the name indicates, is the result of performing two or more sequential separations of ions usually coupling two or more mass analyzers. Coupling a quadrupole and time of flight resulted in the production of high-resolution mass spectrometers (i.e., Q-ToF). This article will historically introduce mass spectrometry and summarizes the advantages and disadvantages of ESI and MALDI along with quadrupole and ToF mass analyzers, including the technical marriage between the two analyzers. This article is educational in nature and intended for graduate students and senior biochemistry students as well as chemists and biochemists who are not familiar with mass spectrometry and would like to learn the basics; it is not intended for mass spectrometry experts.     

Use of Crustacean Shells for Uptake and Removal of Metal Ions in Solution

Abstract

The use of crustacean shells, in particular crab shells, for the removal of metal ions in solution is described. Research studies found in the literature on the ability of the shells, effect of particle size, pH, competitive studies in mixtures of metals, application to real samples such as acid mine drainage, and use of the shells in a column are presented. The major component of the shells that allows uptake to occur is chitin. Several mechanisms are proposed for uptake. There are conflicting accounts in the literature on such areas as the effect of pH, flow rate, and particle size.