Applied Spectroscopy

This paper presents the results of study of titanium–magnesium catalysts often used in polymerization processes, by photoluminescence spectroscopy (PL) in combination with diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The interaction of dibutyl phthalate (DBP) with MgCl₂ was studied at DBP_added/Mg = 0–1 (mol/mol). The luminescence spectra with excitation at 278 nm and the excitation spectra for main emission bands were recorded. It was shown that DBP adsorbed on magnesium chloride, both in the form of donor–acceptor complexes (D⁺A^–) and in the form of molecular complexes. At DBP_added/Mg <0.15, the formation of D⁺A^– complexes occur predominantly; with an increase in DBP_added/Mg, the fraction of molecular complexes increases. Molecular complexes are destroyed during the treatment of the support by TiCl₄. In this case, the structure of magnesium chloride is disordered and new coordination–unsaturated sites are formed. This work is a first attempt to apply PL spectroscopy in combination with DRIFTS spectroscopy to study titanium–magnesium Ziegler–Natta catalysts. The application of PL spectroscopy to such systems made it possible to detect interactions within and between donor molecules, which would be particularly challenging to achieve using other spectroscopic methods. Both spectroscopic methods provided crucial information about the existence of two types of complexes on the sample surface which is important for tuning the synthesis procedure of the titanium–magnesium catalysts for olefin polymerization.

A nondispersive infrared gas analyzer was demonstrated for investigating metal alkylamide precursor delivery for microelectronics vapor deposition processes. The nondispersive infrared analyzer was designed to simultaneously measure the partial pressure of pentakis(dimethylamido) tantalum, a metal precursor employed in high volume manufacturing vapor deposition processes to deposit tantalum nitride, and dimethylamine, the primary decomposition product of pentakis(dimethylamido) tantalum at typical delivery conditions for these applications. This sensor was based on direct absorption of pentakis(dimethylamido) tantalum and dimethylamine in the fingerprint spectral region. The nondispersive infrared analyzer optical response was calibrated by measuring absorbance as a function of dimethylamine and pentakis(dimethylamido) tantalum density. The difference between the mass of material removed from the ampoule during flow tests as measured gravimetrically and as determined optically, by calculating flow rates from the nondispersive infrared analyzer measurements, was only ≈2 %. The minimum detectable molecular densities for pentakis(dimethylamido) tantalum and dimethylamine were ≈2 × 10¹³ cm⁻³ and ≈5 × 10¹⁴ cm⁻³, respectively (with no signal averaging and for a sampling rate of 200 Hz), and the corresponding partial pressures were ≈0.1 Pa and ≈2 Pa for pentakis(dimethylamido) tantalum and dimethylamine, respectively (for an optical flow cell temperature of 93 ℃). Pentakis(dimethylamido) tantalum could be detected at all conditions of this investigation and likely the majority of conditions relevant to high volume manufacturing tantalum nitride deposition. Dimethylamine was not detected at all conditions in this study, because of a lower nondispersive infrared analyzer sensitivity to dimethylamine compared to pentakis(dimethylamido) tantalum and because conditions of this study were selected to minimize DMA production. While this nondispersive infrared gas analyzer was specifically developed for pentakis(dimethylamido) tantalum and dimethylamine, it is suitable for characterizing the vapor delivery of other metal alkylamide precursors and the corresponding amine decomposition products, although in the case of some metal alkylamides a different bandpass filter would be required.

The confocal Raman microscope (CRM) is a powerful tool in analytical science. Image quality is the most important performance indicator of CRM systems. The point spread function (PSF) is one of the most useful tools to evaluate the image quality of microscopic systems. A method based on a point-like object is proposed to measure the PSF of CRM, and the size effect of spherical objects is discussed. A series of phantoms are fabricated by embedding different sizes of polystyrene microspheres into polydimethylsiloxane matrix. The diameters of microspheres are from 0.2 µm to 5 µm. The phantoms are tested by measuring the PSF of a commercial CRM whose nominal lateral resolution is about 1 µm. Results of the PSF are obtained and the accuracy of resolution is used to evaluate the size effect of the microspheres. Experimental results are well consistent with theoretical analysis. The error of the PSF can be decreased by reducing the diameter of the microsphere but meanwhile the signal-to-noise ratio (S/N) will be lowered as well. The proper diameter of microspheres is proposed in consideration of the trade-off between the S/N and the measurement error of the PSF. Results indicate that the method provides a useful approach to measurement of the PSF and the resolution of the CRM.

Establishing the precise timeline of a crime can be challenging as current analytical techniques used suffer from many limitations and are destructive to the body fluids encountered at crime scenes. Raman spectroscopy has demonstrated excellent potential in forensic science as it provides direct information about the structural and molecular changes without the need for processing or extracting samples. However, its current applicability is limited to pure body fluids, as signals from the substrate underlying these fluids greatly influence the current models used for age estimation. In this study, we utilized Raman spectroscopy to identify selective spectral markers that delineate the bloodstain age in the presence of interfering signals from the substrate. The pure bloodstains and the bloodstains on the substrate were aged for two weeks at 21 ± 2 ℃ in the dark. Least absolute shrinkage and selection operator (LASSO) regression was employed to guide the feature selection in the presence of interference from substrates to accurately predict the bloodstain age. Substrate-specific regression models guided by an automated feature selection algorithm yielded low values of predictive root mean square error (0.207, 0.204, 0.222 h in logarithmic scale) and high R² (0.924, 0.926, 0.913) on test data consisting of blood spectra on floor tile, facial tissue, and linoleum-polymer substrates, respectively. This framework for an automated feature selection algorithm relies entirely on pure bloodstain spectra to train substrate-specific models for estimating the age of composite (blood on substrate) spectra. The model can thus be easily applied to any new composite spectra and is highly scalable to new environments. This study demonstrates that Raman spectroscopy coupled with LASSO could serve as a reliable and nondestructive technique to determine the age of bloodstains on any surface while aiding forensic investigations in real-world scenarios.

Chemical processing of highly radioactive materials commonly takes place in heavily shielded hot cells. The remote, real-time monitoring of chemical processing streams via optical spectroscopic techniques in hot cells may be particularly useful. Here, we describe the implementation of Raman spectroscopy and chemometric analysis to monitor the dissolution of aluminum-clad targets containing irradiated aluminum–neptunium oxide cermet pellets in caustic solutions in a hot cell environment. Partial least squares regression analysis was used to generate calibration models to quantify the concentration of dissolved aluminum, nitrate, and hydroxide in solutions within the radiochemical hot cell. This work explored a systematic approach to optimize a matrix of calibration standards using a D-optimal experimental design. The Design of Experiments-based regression model, in comparison to more traditional analytical approaches, was found to be the more practical method for building calibration models, with fewer samples, to obtain informative analytical data from Raman spectra.

In critically ill patients, direct knowledge of intracellular pO₂ would allow for identification of cellular hypoxia, which when prolonged leads to organ failure. We have developed a visible–near-infrared optical system that noninvasively measures myoglobin saturation, which is directly related to intracellular pO₂, from the surface of the skin. We used an animal model of graded hypoxia from low levels of inspired oxygen (n = 5) and verified that low intracellular pO₂ is correlated with high steady-state serum lactate values. In addition, the pO₂ gradient between arterial blood and inside muscle cells was 83 mm Hg at 21% O₂, but fell to 24 mm Hg at 8% O₂. Continuous myoglobin saturation measurement in skeletal muscle displayed the same trends as cerebral oxygenation with no lag in changes over time, demonstrating its relevance as a measure of systemic oxygenation.

Laser-induced wavefront distortion is detectable by several techniques based on the photothermal effect. The effect is probed by monitoring the phase shift caused by the bulging of the heated area, the photoelastic effects, and the spatial distribution of the refractive index within the sample and in the fluid surrounding it. A simple analytical solution for the wavefront distortion was only possible for low absorbing materials, with the assumption that the stresses obey either the thin-disk or the long-rod type distributions. Recently, a unified theoretical description for the laser-induced optical path change was proposed to overcome part of this limitation for weakly absorbing materials, regardless of its thickness. In this work, we perform an experimental investigation taking the sample–fluid heat coupling effect into account using the thermal lens technique. The experimental investigation presented here validates the unified model. In addition, we show that the heat-coupling model provides an alternative method to obtain physical properties of non-absorbing fluid by using a reference solid sample.

The present work reports the results of structural and optical investigations in samples of natural dolomite, subjected to thermal treatment at different temperatures (500 ℃ to 700 ℃) and times (one up to three hours). The motivation is the evaluation of the changes that may occur in carbonaceous asteroids and meteorites, respectively, subjected to the action of the solar radiation and heated during the fall in the atmosphere. We carried out scanning electron microscopy, electron dispersive spectroscopy, X-ray diffraction, optical reflectance and photoluminescence measurements

Based on Beer's law, it is assumed that the absorbance of a mixture is that of the neat materials weighted by their relative amounts (linear mixing rule). In this contribution, we show that this is an assumption that holds only under various approximations for which no change of the chemical interactions is just one among several. To understand these approximations, which lead incrementally to different well known mixing rules, we finally derive the linear mixing rule from the Lorentz–Lorenz relation, with the first approximation that the local electric field is correctly described in this relation. Further levels of approximation are that the local field equals the applied field (Newton–Laplace mixing rule) and that the change of the index of refraction and, equivalently, absorption is weak (Gladstone–Dale/Arago–Biot mixing rule). Even then the linear mixing rule is only strictly valid if the indices of refraction in the transparency region at higher frequency than the absorption have the same value and the mixing is homogeneous relative to the resolving power of the light (“micro-homogeneous”). Under these preconditions, linear mixing of the individual absorbances is established. We illustrate the spectral differences between the different mixing rules, all of which are based on volume and not on mass fractions, with examples. For micro-heterogeneous samples, a different linear mixing rule governs the optical properties, which refers to the experimental quantities, reflectance, and transmittance. As a result, for such samples, mixtures of already comparably high content give only weak signals due to band flattening, which are hard to distinguish from baseline effects.

Presented here is a facile and practical method for calibrating anti-Stokes–Stokes intensity ratios in low-frequency Raman spectra that is devised specifically for temperature measurements inside cells. The proposed method uses as an intensity standard the low-frequency Raman spectrum of liquid water, a major molecular component of cells, whose temperature is independently measured with a thermocouple. Rather than calibrating pixel intensities themselves, we obtain a correction factor at each Raman shift in the 20–200 cm⁻¹ region by dividing the anti-Stokes–Stokes intensity ratio calculated theoretically from the Boltzmann factor at the known temperature by that obtained experimentally. The validity of the correction curve so obtained is confirmed by measuring water at other temperatures. The anti-Stokes–Stokes intensity ratios that have been subjected to our calibration are well fitted with the Boltzmann factor within ∼1% errors and yield water temperatures in fairly good agreement with the thermocouple temperature (an average difference ∼1 ℃). The present method requires only 15 min of spectral acquisition time for calibration, which is 50 times shorter than that in a recently reported calibration method using the pure rotational Raman spectrum of N₂. We envision that it will be an effective asset in Raman thermometry and its applications to cellular thermogenesis and thermoregulation.