Applied Spectroscopy

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Equidistant combination multiple linear regression (EC-MLR) for the quasi-continuous wavelength selection of spectroscopic analysis was proposed and successfully applied to the reagent-free determination of soil organic matter with near-infrared spectroscopy. For comparison, the continuous-mode moving window partial least squares (MWPLS) and the discrete-mode successive projections algorithm (SPA) were improved by considering the stability and applied to the same analysis object as well. All methods exhibited good effect, but the modeling accuracy, stability, and validation effect of EC-MLR were better than that of the other two methods. Compared with MWPLS, the optimal EC-MLR model contained only 16 wavelengths, and method complexity was substantially reduced. Compared with SPA-MLR, the optimal EC-MLR model could easily undergo spectral preprocessing to improve predictive capability. Moreover, appropriate equidistant discrete wavelength combination with EC-MLR corresponded to the spectral absorption band with proper resolution and can effectively overcome co-linearity interruption for the MLR model. Thus, the EC-MLR method has great potential in practical application and instrument design.

Atomization of cadmium compounds (acetate, chloride, nitrate, perchlorate, sulfate, formate, propionate) was studied using flame atomic absorption spectrometry. Our goal was to study processes influencing atomization separately, the focus was on the contribution of thermal properties of substances to atomization. For this purpose new techniques and equipment have been developed, such as a special separated three-slot burner, quartz flame furnace, and an electrically heated thermospectrometer. According to quartz flame furnace and thermospectrometric measurements, cadmium salts do not atomize below 600 °C in an inert atmosphere. We found that in the thermospectrometer the atomization of cadmium compounds follows at least two different reaction courses. At lower temperatures (650–700 °C) a slower mechanism is dominant at higher regions of the furnace, while at 800 °C a faster mechanism demanding less residence time in the furnace becomes dominant. Under inert atmosphere the degree of atomization strongly depends on the thermal properties of substances.

Soap formation in traditional oil paintings occurs when heavy-metal-containing pigments, such as lead white, 2PbCO₃·Pb(OH)₂, and lead tin yellow type I, Pb₂SnO₄, react with fatty acids in the binding medium. These soaps may form aggregates that can be 100–200 μm in diameter, which swell and protrude through the paint surface, resulting in the degradation of the paint film and damage to the integrity of the artwork. The factors that trigger soap formation and the mechanism(s) of the process are not yet well understood. To elucidate these issues, chemical and structural information is necessary, which can be obtained using solid-state ²⁰⁷Pb and ¹³C nuclear magnetic resonance (NMR). In this article, we report ²⁰⁷Pb and ¹³C solid-state NMR spectra and ²⁰⁷Pb chemical-shift tensors of lead carboxylates implicated in soap formation: lead stearate, lead palmitate, and lead azelate, in addition to lead oleate and lead heptanoate for comparison. The ¹³C cross polarization with magic-angle spinning (MAS) spectra of these lead carboxylates show resonance doubling for the carbons closest to the lead, indicating two different conformations of the fatty acid chains in the asymmetric unit. The ²⁰⁷Pb NMR spectra, from which tensors were determined, were obtained with direct excitation and spin-temperature alternation, with and without MAS, and with the wide band uniform rate smooth truncation Carr-Purcell-Meiboom-Gill pulse sequence. The results of these experiments show that the local coordination environment of lead azelate is different from lead palmitate and lead stearate and could thus be distinguished from these in a paint film displaying soap formation. In addition, comparing the ²⁰⁷Pb NMR chemical-shift tensors of the lead carboxylates studied shows that crystal packing of the acyl chains may be a factor in determining the coordination environment around the lead.

The United States Army and the first responder community are increasingly focusing efforts on energetic materials detection and identification. Main hazards encountered in theater include homemade explosives and improvised explosive devices, in part fabricated from simple components like ammonium nitrate (AN). In order to accurately detect and identify these unknowns (energetic or benign), fielded detection systems must be accurately trained using well-understood universal testing substrates. These training substrates must contain target species at known concentrations and recognized polymorphic phases. Ammonium nitrate is an explosive precursor material that demonstrates several different polymorphic phases dependent upon how the material is deposited onto testing substrates. In this paper, known concentrations of AN were uniformly deposited onto commercially available surface-enhanced Raman scattering (SERS) substrates using a drop-on-demand inkjet printing system. The phase changes observed after the deposition of AN under several solvent conditions are investigated. Characteristics of the collected SERS spectra of AN are discussed, and it is demonstrated that an understanding of the exact nature of the AN samples deposited will result in an increased ability to accurately and reliably “train” hazard detection systems.

A highly sensitive method for the detection and quantitative evaluation of antimony(III) using the surface-enhanced Raman scattering (SERS) technique is demonstrated. The method is based on the analysis of SERS spectra intensity of antimony bound to phenylfluorone (Sb-PhF). Phenylfluorone is widely used as an organic reagent for the spectrophotometric determination of some heavy metals. For the SERS experiment a Sb-PhF complex was adsorbed onto the silvered porous silicon substrate. The significant degradation of the SERS signal was observed during measurements in the air. The time evolution of SERS spectra at ambient and degassed conditions was investigated to find an optimal regime for SERS measurements. The limit of Sb detection in degassed samples was determined to be near 1 ng/mL, which is one order of magnitude less than that attainable by the photometric approach. The linear range of the method to Sb(III) was found to a mass concentration range of 1–10 ng/mL. This approach permits an absolute quantity of Sb(III) to be detected at the picogram level (∼50 pg). It is remarkable that a very small sample volume (50 μL) is required for SERS analysis. Moreover this technique offers high selectivity owing to the distinctive vibrational features for the metallorganic complex and to the resonance character of Raman spectra. The proposed SERS-based detection of Sb is a fast and highly sensitive method for use in environmental and industrial waste monitoring as well as for forensic science to determine gunshot residue. We expect that the approach reported herein can be further extended to develop new detection techniques for other heavy metals.

Surface-enhanced Raman scattering (SERS) of an antifungal reagent, myclobutanil (MCB), was performed on Au and Ag nanoparticles (NPs) to estimate the drug-release behaviors in fungal cells. A density functional theory (DFT) calculation was introduced to predict a favorable binding site of MCB to either the Ag or Au atom. Myclobutanil was presumed to bind more strongly to Au than to Ag in their most stable, optimized geometries of the N4 atom in its 1,2,4-triazole unit binding to the metal atom. Strong intensities were observed in the Ag SERS spectra only at acidic pH values, whereas the most prominent peaks in the Au SERS spectra of MCB matched quite well with those of 1,2,4-triazole regardless of pH conditions. The Raman spectral intensities of the MCB-assembled Ag and Au NPs decreased after treatment with either potato dextrose agar (PDA) or glutathione (GSH). Darkfield microscopy and confocal SERS were performed to analyze the MCB-assembled metal NPs inside Penicillium digitatum fungal cells. The results suggested that MCB was released from the metal NPs in the intracellular GSH in the fungi because we observed only fungal cell peaks.

Thin-film luminescent sensors were used to measure dissolved oxygen in picoliter volumes for the purpose of monitoring single-cell oxygen consumption rates, and that work served as the motivation for the development of the method described here. A few different platinum porphyrin sensor materials were examined, with all measurements conducted microscopically. By employing convolution theory to understand observed responses, including an unexpected red luminescent emission from an optic, we developed a new, rapid method for the determination of exponential decay lifetime. This new method of long-pulsed luminescence offers substantially improved signal-to-noise ratios for detected signals as long as self-illumination sources are carefully controlled in the experimental set-up.

The design for a new high-pressure–low-temperature infrared (IR) cell for performing experiments using conventional Fourier transform infrared or fast laser-based time-resolved infrared spectroscopy, in a range of solvents, is described. The design builds upon a commercially available compressor and cold end (Polycold PCC® and CryoTiger®), which enables almost vibration-free operation, ideal for use with sensitive instrumentation. The design of our cell and cryostat allows for the study of systems at temperatures from 77 to 310 K and at pressures up to 250 bar. The CaF₂ windows pass light from the mid-IR to the ultraviolet (UV), enabling a number of experiments to be performed, such as Raman, UV-visible absorption spectroscopy, and time-resolved techniques where sample excitation/probing using continuous wave or pulsed lasers is required. We demonstrate the capabilities of this cell by detailing two different applications: (i) the reactivity of a range of Group V–VII organometallic alkane complexes using time-resolved spectroscopy on the millisecond timescale and (ii) the gas-to-liquid phase transition of CO₂ at low temperature, which is applicable to measurements associated with transportation issues related to carbon capture and storage.

Marbling is an important quality attribute of pork. Detection of pork marbling usually involves subjective scoring, which raises the efficiency costs to the processor. In this study, the ability to predict pork marbling using near-infrared (NIR) hyperspectral imaging (900–1700 nm) and the proper image processing techniques were studied. Near-infrared images were collected from pork after marbling evaluation according to current standard chart from the National Pork Producers Council. Image analysis techniques—Gabor filter, wide line detector, and spectral averaging—were applied to extract texture, line, and spectral features, respectively, from NIR images of pork. Samples were grouped into calibration and validation sets. Wavelength selection was performed on calibration set by stepwise regression procedure. Prediction models of pork marbling scores were built using multiple linear regressions based on derivatives of mean spectra and line features at key wavelengths. The results showed that the derivatives of both texture and spectral features produced good results, with correlation coefficients of validation of 0.90 and 0.86, respectively, using wavelengths of 961, 1186, and 1220 nm. The results revealed the great potential of the Gabor filter for analyzing NIR images of pork for the effective and efficient objective evaluation of pork marbling.

The photothermal properties of several near-infrared-absorbing nanoparticles derived from group of uniform materials based on organic salts (GUMBOS) and composed of cationic dyes coupled with biocompatible anions are evaluated. These nanoparticles were synthesized using a reprecipitation method performed at various pH values: 2.0, 5.0, 7.0, 9.0, and 11.0. The cations for the nanoparticles derived from GUMBOS (nanoGUMBOS), [1048] and [1061], have absorbance maxima at wavelengths overlapping with human soft tissue absorbance minima. Near-infrared-absorbing nanoGUMBOS excited with a 1064 nm continuous laser led to heat generation, with an average temperature increase of 20.4 ± 2.7 °C. Although the [1061][Deoxycholate] nanoGUMBOS generated the highest temperature increase (23.7 ± 2.4 °C), it was the least photothermally efficient compound (13.0%) due to its relatively large energy band gap of 0.892 eV. The more photothermally efficient compound [1048][Ascorbate] (64.4%) had a smaller energy band gap of 0.861 eV and provided an average photothermal temperature increase of 21.0 ± 2.1 °C.

The performance of a super-resolution fluorescence depletion microscope system depends crucially on the precise alignment of the pump and erase beams with the axis of the focusing objective. Here, we propose a new design method for a two-color spiral phase plate with a single-layer structure (S2SPP), and we experimentally investigate the image properties given by the phase plate. In spite of its simple structure, the plate can provide a super-resolution image with a spatial resolution better than 70 nm. Beside eliminating alignment problems and yielding a compact setup, the simplicity of fabrication of the S2SPP makes our proposed method very suitable for commercial microscope systems.

The temperature in an aluminized propellant is determined as a function of height and plume depth from diatomic AlO and thermal emission spectra. Higher in the plume, 305 and 508 mm from the burning surface, measured AlO emission spectra show an average temperature with 1σ errors of 2980 ± 80 K. Lower in the plume, 152 mm from the burning surface, an average AlO emission temperature of 2450 ± 100 K is inferred. The thermal emission analysis yields higher temperatures when using constant emissivity. Particle size effects along the plume are investigated using wavelength-dependent emissivity models.

Our measurements of micro-plasma following laser-induced optical breakdown of nitro compound explosive simulants, here 3-nitrobenzoic acid, show well-developed molecular spectra during the first several hundreds of nanoseconds. Analysis of recorded carbon spectra is accomplished using accurate line strengths for the diatomic molecular Swan system. Presence of hydrogen-beta allows us to infer electron density in the plasma evolution. Computational challenges include accounting for background variation and appropriate modeling of hydrogen embedded in molecular spectra. Recorded and computed spectra agree nicely for time delays on the order of 1.6 μs from optical breakdown when using a single temperature for local thermodynamic equilibrium plasma.

The thermal behavior of poly(lactic acid) (PLA) was studied by near-infrared imaging to provide a molecular-level understanding of the physical improvement caused by nanoclay dispersion. A set of PLA samples, each having different nanoclay dispersion, was prepared under varying sonication time. Crystallinity variation of the polymer interacting with the nanoclay particles was analyzed by a roundtrip temperature scan below the melting temperature. Namely, the samples underwent heating and then cooling in the opposite way during the spectral measurement. The discrepancy of the spectral feature between the heating and the cooling indicated the development of the hysteresis associated with the cold crystallization of the PLA lamellae. The generation of the spectral residuals revealed the inner working mechanism of how the polymer structure undergoes variation depending on the presence of the clay particles and their dispersions. The sonication brings substantial dispersion of the nanoclay over the polymer matrix. The nanoclay particles then induce the additional development of the crystalline structure due to the molecular interaction between the PLA and nanoclay arising from the presence of enormous surface area, which in turn induces variation of mechanical strength to the polymer.

Currently, there are no direct and reliable methods to measure the body fat content of women during pregnancy. Estimates of fat accretion can significantly affect calculations of energy requirements. We report here the first direct measurement of determining the body fat content of two women during pregnancy using the Fourier transform near-infrared spectroscopy (FT-NIR) method. Fourier transform near-infrared spectroscopy was shown to provide comparable results to dual-energy X-ray absorptiometry and magnetic resonance imaging. These latter methods, even though very reliable to measure body fat levels, cannot be used to measure the body fat of women during pregnancy because of health concerns, while FT-NIR poses no health risk. The FT-NIR results showed the percent body fat remained relatively constant throughout pregnancy, but fat mass and fat free mass increased. Fat mass followed an S curve with a maximum increase between 15 to 25 weeks of gestation that was only detected by repeated measurements using the FT-NIR technique. These results demonstrate the value of the FT-NIR method to directly measure the fat content of pregnant women in minutes instead of relying on indirect calculations or taking measurements before and after pregnancy to track gestational fat mass accretion.

Transmission near-infrared (NIR) measurements of a 1 mm thick aspirin disk were made at different positions as it was moved through a stack of eight 0.5 mm thick disks of microcrystalline cellulose (Avicel). The magnitude of the first derivative of absorbance for the aspirin interlayer at 8934 cm⁻¹ was lower when the disk was placed at the top or bottom of the stack of Avicel disks, with the largest signal observed when the aspirin was positioned at the central positions. The variation in signal with depth is consistent with that observed previously for transmission Raman spectrometry. In both cases, the trend observed can be attributed to lower photon density at the air-sample interface, relative to the center of the sample, owing to loss of photons to the air. This results in a reduction in the number of photons absorbed or Raman photons generated and subsequently detected when the interlayer occupies a near-surface position.