We report the first vibrational circular dichroism (VCD) spectra with continuous coverage from 800 cm(-1) in the mid-infrared (MIR) region to 10 000 cm(-1) in the near-infrared (NIR) region. This coverage is illustrated with MIR and NIR absorbance and VCD spectra of 2,2-dimethyl-dioxolane-4-methanol (DDM), alpha-pinene, and camphor that serve as calibration samples over this entire region. Commercially available, dual-source Fourier transform (FT) MIR and NIR VCD spectrometers were equipped with appropriate light sources, optics, and detectors, and were modified for dual-polarization-modulation (DPM) operation. The combination of liquid-nitrogen- and thermoelectric-cooled HgCdTe (MCT) detectors, as well as InGaAs and Germanium (Ge) detectors operating at room temperature, permitted collection of the desired absorbance and VCD spectra across the range of vibrational fundamental, combination band, and overtone frequencies. The spectra of DDM and alpha-pinene were measured as neat liquids and recorded for both enantiomers in the various spectral regions. Spectra for camphor were all measured in CCl(4) solution at a concentration of 0.6 M, except for the carbonyl-stretching region, where a more dilute concentration was used. The typical anisotropy ratios (g) of the three molecules were estimated with respect to their strongest VCD bands in each spectral region. It was found that for all three molecules in the spectral regions above 2000 cm(-1), anisotropy ratios are approximately the same order (10(-5)) of magnitude. However, in the MIR region, the typical anisotropy ratios are significantly different for the three molecules. This study demonstrates that with modern FT-VCD spectrometers modified for DPM operation, VCD spectra can be measured continuously across a wide spectral range from the MIR to nearly the visible region with an unsurpassed combination of signal-to-noise ratio and spectral resolution.
We used Fourier transform infrared (FT-IR) spectroscopy to characterize silicon dioxide (SiO(2)) films on a 4H-SiC(0001) Si face. We found that the peak frequency of the transverse optical (TO) phonon in SiO(2) films grown on a 4H-SiC substrate agrees well with that in SiO(2) films grown on a Si substrate, whereas the peak frequency of the longitudinal optical (LO) phonon in SiO(2) films on a 4H-SiC substrate is red-shifted by approximately 50 cm(-1) relative to that in SiO(2) films on a Si substrate. We concluded that this red-shift of the LO phonon is mainly caused by a change in inhomogeneity due to a decrease in density in the SiO(2) films. Furthermore, cathodoluminescence (CL) spectroscopy results indicated that the channel mobility of the SiC metal-oxide-semiconductor field-effect transistor (MOSFET) decreases roughly in proportion to the increase in the intensity of the CL peak at 460 and 490 nm, which is attributed to the increase in the number of oxygen vacancy centers (OVCs). FT-IR and CL spectroscopies provide us with a large amount of data on OVCs in the SiO(2) films on a 4H-SiC substrate.
In order to evaluate the suitability of a polymer as a sealing material for certain working fluids used in process plants, information about the fluid diffusivity into the polymer or the polymer permeability
to the fluid is a prerequisite. The fluid of interest in the present work is 1,1,1,2-tetrafluorethane, CH2FCF3, a partly fluorinated hydrocarbon (HFC) commonly known as refrigerant
R134a. HFCs are increasingly used in refrigeration, air conditioning, and heat pump applications as substitutes for the chlorofluorocarbons (CFCs) or hydrochlorofluorocarbons (HCFCs) that are believed to
be responsible for ozone depletion in the stratosphere. The polymers studied were FPM, a perfluoroelastomer, and EPDM, an ethylene-propylene-diene rubber. The study was carried out using magnetic resonance
imaging (MRI). The contact time dependence of diffusion of the fluid into the polymer, as well as the spatial distributions of spin-lattice, T1, and spin-spin, T2, relaxation times,
were used as indicators of the influence of the EPDM matrix on the mobility of R134a molecules.
A perfluorinated ketone, 2-trifluoromethyl-1,1,1,2,4,4,5,5,5-nonafluoro-3-pentanone, has been investigated to determine several physical and spectroscopic properties. It was found to exhibit fluorescence similar to that of acetone, emitting over the 360-550 nm range with a peak near 420 nm when excited at 355 nm. This compound's emission is nearly unaffected over a wide range of temperature and pressure in an argon bath gas. Its fluorescence efficiency was found to be three times higher than that of acetone. Combined with low reactivity and thermal stability up to 500 degrees C, this makes the material an excellent tracer for spectroscopic measurement techniques.
There has been rapid growth in the application of in situ optical spectroscopy techniques for reaction and process monitoring recently in both academia and industry. Vibrational spectroscopies such as mid-infrared, near-infrared spectroscopy, and Raman spectroscopy have proven to be versatile and informative. Accurate determination of concentrations, based on highly overlapped spectra, remains a challenge. As an example, 1,2-butylene oxide (BO) polymerization, an important industrial reaction, initiated by propylene glycol (PG) and catalyzed by KOH, is studied in this work in a semi-batch fashion by using in situ attenuated total reflectance Fourier transform infrared spectroscopy (ATR FT-IR) monitoring. The weak BO absorbance, the constantly changing interference from the product oligomers throughout the course of the reaction, and the change in BO spectral features with system polarity posed challenges for quantitative spectral analysis based on conventional methods. An iterative concentration-guided classical least-squares (ICG-CLS) method was developed to overcome these challenges. Taking advantage of the concentration-domain information, ICG-CLS enabled the estimation of the pure oligomer product spectra at different stages of the semi-batch process, which in turn was used to construct valid CLS models. The ICG-CLS algorithm provides an in situ calibration method that can be broadly applied to reactions of known order. Caveats in its applications are also discussed.
Many molecules or transient radicals have well-documented absorption cross-sections in the ultraviolet (UV) region, but their absorption cross-sections in the near-infrared (NIR) region are much less often known and are difficult to measure. We propose a method to determine the unknown NIR absorption cross-sections using the known absorption cross-sections in the UV region, in which single-path UV absorption spectroscopy and NIR continuous wave cavity ringdown spectroscopy (cw-CRDS) are employed in a cross-arm reaction chamber for simultaneous measurements. Without knowing the actual sample partial pressures (or concentrations), the NIR absorption cross-sections can be accurately determined through the two sets of measurements. The method is demonstrated by measuring the NIR absorption cross-section of the first overtone of the asymmetric C-H stretch of 2-methyl-1,3-butadiene (isoprene) (3.24 (+/-0.16) x 10(-22) cm(2) molecule(-1)) at 1651.52 nm using the known value of the absorption cross-section at 220 nm. The diode laser wavelength was calibrated by atmospheric cavity ringdown spectra of CH(4), CO(2), and H(2)O. By comparison with sample pressure measurements, this method can also be used as a pressure calibration means for the reaction chamber, and this has been demonstrated with two additional measurements of the absorption cross-sections of 1,3-butadiene and 2,3-dimethyl-1,3-butadiene (2.50 (+/- 0.08) x 10(-22) and 2.82 (+/-0.16) x 10(-22) cm(2) molecule(-1), respectively) at 1651.52 nm. The applicability of the method to determining absorption cross-sections using the simultaneous measurements of cw-CRDS and single-path absorption spectroscopy is discussed.
This work describes the behavior of 1,6-diphenyl-1,3,5-hexatriene (DPH) in ethanol/water mixtures. The dependence of DPH photophysical properties (absorption and fluorescence emission) on the water percentage in ethanol indicates that DPH undergoes self-aggregation processes in solvent conditions above a critical water content. Evidence such as an additional absorption band, Beer's law deviation, kinetic behavior, and other experimental results obtained from temperature variation and surfactant addition demonstrated the presence of several types of DPH aggregates. Resonance light scattering measurements proved that the aggregate grew in water-rich media by a self-catalyzed process.
The United States Army and the first responder community are evaluating optical detection systems for the trace detection of hazardous energetic materials. Fielded detection systems must be evaluated with the appropriate material concentrations to accurately identify the residue in theater. Trace levels of energetic materials have been observed in mutable polymorphic phases and, therefore, the systems being evaluated must be able to detect and accurately identify variant sample phases observed in spectral data. In this work, we report on the novel application of drop-on-demand technology for the fabrication of standardized trace 1,3,5-trinitro-1,3,5-triazine (RDX) samples. The drop-on-demand sample fabrication technique is compared both visually and spectrally to the more commonly used drop-and-dry technique. As the drop-on-demand technique allows for the fabrication of trace level hazard materials, concerted efforts focused on characterization of the polymorphic phase changes observed with low concentrations of RDX commonly used in drop-on-demand processing. This information is important when evaluating optical detection technologies using samples prepared with a drop-on-demand inkjet system, as the technology may be "trained" to detect the common bulk α phase of the explosive based on its spectral features but fall short in positively detecting a trace quantity of RDX (β-phase). We report the polymorphic shifts observed between α- and β-phases of this energetic material and discuss the conditions leading to the favoring of one phase over the other.
1,6-Diphenyl-1,3,5-hexatriene (DPH) is the most widely proposed molecular probe for the post-column fluorescence derivatization of lipids after liquid chromatography separation. This kind of detection consists of a supramolecular combination of DPH and eluted lipids. The detection is optimally performed in a mainly aqueous environment (over 80% v/v) because the weak fluorescence of DPH in water is drastically enhanced upon formation of supramolecular assemblies with lipids. In the present study, and in order to obtain better spectroscopic insights into the nature of these supramolecular assemblies, two different lipids were tested, 1,2,3-tridodecanoylglycerol (LLL) as a model triglyceride (nonpolar lipid) and dimyristoylphosphatidylcholine (DMPC) as a model phosphatidylcholine (charged amphiphilic lipid). Stoichiometry and association constants were determined on the basis of the variation of fluorescence intensity in the presence of various concentrations of lipids. LLL(60)-DPH(2) and DMPC(200)-DPH(2) complexes were identified with association constants as high as K(2) = (5.8 +/- 0.5) x 10(13) M(-2) and (17.3 +/- 2.0) x 10(13) M(-2) for LLL and DMPC, respectively. The fluorescence intensity of DPH in the presence of LLL is greater than in the presence of DMPC. An attempt to characterize the insertion mode of DPH in the lipidic supramolecular assemblies is also made.
We measured the 229 nm deep-ultraviolet resonance Raman (DUVRR) spectra of solution and solid-state hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). We also examined the photochemistry of RDX both in solution and solid states. RDX quickly photodegrades with a solution quantum yield of
φ ~ 0.35 as measured by high-performance liquid chromatography (HPLC). New spectral features form over time during the photolysis of RDX, indicating photoproduct formation. The photoproduct(s) show stable DUVRR spectra at later irradiation times that allow standoff detection. In the solution-state
photolysis, nitrate is a photoproduct that can be used as a signature for detection of RDX even after photolysis. We used high-performance liquid chromatography‐high-resolution mass spectrometry (HPLC-HRMS) and gas chromatography mass spectrometry (GCMS) to determine some of the major
solution-state photoproducts. X-ray photoelectron spectroscopy (XPS) was also used to determine photoproducts formed during solid-state RDX photolysis.
The vibrational spectra and surface-enhanced Raman scattering (SERS) of 1,6-diphenyl-1,3,5-hexatriene (DPH) are discussed. The fundamental vibrational frequencies, overtones, and combinations observed in the infrared and Raman spectra of DPH are reported. The interpretation of the observed vibrational spectra was supported by a complete geometry optimization, followed by vibrational frequency and intensity computations for the cis- and trans- isomers of the DPH using density functional theory at the B3LYP/6-31G(d,p) level of theory. Because the molecule is photo-chemically active on Ag metal surfaces, the best SERS results for silver islands were obtained at low temperature and low energy density of the exciting laser line. DPH SERS on Au films was obtained at room temperature.
J. Cabalo and R. Sausa, "Detection of Hexahydro-1,3,5-trinitro1,3,5-triazine (RDX) by Laser Surface Photofragmentation–Fragment Detection Spectroscopy," Appl. Spectrosc. 57, 1196-1199 (2003)
The photochemical reaction and molecular reorientation of a novel photosensitive polyester, poly[oxy(4-n-butyl-3,5-benzoate)oxy-1,4-phenylenediacryloyl] (PPDA-C4BZ), which contains n-butyl side groups and 1,4-phenylenediacryloyl units (PDA chromophores) in the main chain, are reported in detail. We applied two-dimensional (2D) correlation analysis for the infrared (IR) and ultraviolet (UV) absorption spectra of nanoscaled films of PPDA-C4BZ to establish the sequence of the photo-induced segmental reorientations that result from UV irradiation. The photochemical reaction was found to have a greater effect on the polymer's main chains than on its side groups and to induce the reorientation of the polymer molecules. In particular, a cycloaddition process occurs first in the PDA chromophore units and then the local reorientation of the polymer molecules is induced. Namely, such photodimerization of the PDA chromophores induces the molecular reorientations of the PDA chromophores and the benzoate units in the main chain. The photo-induced molecular reorientations occur in the following sequence: photodimerization --> benzoate units --> PDA chromophores --> n-butyl side groups. In addition, a two-dimensional map of the first derivatives of the UV absorption spectra with respect to the exposure energy provided evidence of the formation of head-to-head aggregates (i.e., H-aggregates) of PPDA-C4BZ molecules.
Hindered Diels-Alder adducts have been prepared from 3,6-dibromophencyclone, 2, with cis-1,4-diacetoxy-2-butene, 3; cis-2-butene-1,4-diol, 4; and N-benzylmaleimide, 5. The adduct from the parent phencyclone, 1, with N-benzylmaleimide was prepared for comparison. One- and two-dimensional (1D and 2D) proton and carbon-13 NMR studies (at 7.05 tesla, ambient temperatures), including high-resolution COSY45 and HETCOR (XHCORR) chemical shift correlation spectra, were performed, allowing extensive rigorous assignments for protons and protonated carbons. Substantial anisotropic shielding was seen for the ortho protons of the N-benzyl group in the adducts of 5 with 1 or 2, with these aryl protons resonating at 6.25 ppm (CDCl3) for each adduct. The unsubstituted bridgehead phenyls of all four adducts showed slow exchange limit (SEL) 1H and 13C spectra. Greater shift dispersions for the bridge-head phenyl protons in the adducts from 5 relative to those from 3 or 4 suggested the role of the imide carbonyls for anisotropic contributions or for influences on adduct geometry. Ab initio geometry optimizations were performed at the Hartree-Fock level with the 6-31G* basis set (or the LACVP* basis set for the bromine-containing compounds) for each of the adducts. For the two adducts from benzylmaleimide, separate minima were located corresponding to conformers in which the benzyl group was directed into the adduct cavity (syn) or out of the adduct cavity (anti). Calculated energies and geometric parameters for the adducts are presented, and these suggested a significantly different structure for the dibromo diacetate adduct, in terms of general symmetry and bridgehead phenyl geometries, compared to the other adducts.
A novel 4-(tetrahydro-2-furanmethoxy)-N-octadecyl-1,8-naphthalimide (TNN) was synthesized as a spectrofluorimetric probe for the determination of proteins. The effect of different solvents on the spectral characteristics of TNN was investigated. The results showed that TNN displayed dependent solvent polarity properties due to the effect of internal charge transfer. The interactions between TNN and human serum albumin (HSA) were studied by fluorescence and absorption spectroscopy. Fluorescence data revealed that the fluorescence quenching of HSA by TNN was the result of the formation of TNN-HSA complex. The binding parameters of interactions between TNN and HSA at different temperatures were obtained according to the Stern-Volmer equation. The thermodynamic parameters, enthalpy change (ΔH) and entropy change (ΔS), for the interactions were calculated to be -7.31 kJ mol(-1) and 72.75 J mol(-1) K(-1) according to the van't Hoff equation, indicating that the hydrogen bonds and hydrophobic interactions were the dominant intermolecular force in stabilizing the complex. The effect of TNN on the conformation of HSA was analyzed by circular dichroism and synchronous fluorescence spectroscopy. Furthermore, the results of displacement experiments using warfarin indicated that TNN could bind to site I of HSA. The fluorescence of TNN could be largely quenched by HSA, based on which a new fluorometric method for detecting HSA in the HCl-Tris buffer solution (pH = 7.4) was developed. The linear ranges of the calibration curves were 0.1~14.2 μM for HSA, 0.1~13.0 μM for bovine serum albumin (BSA), 0.2~9.7 μM for γ-globulin, and 0.3~11.3 μM for hemoglobin (Hb), with detection limits (3σ) of 1.37 × 10(-10) M for HSA, 1.84 × 10(-10) M for BSA, 3.14 × 10(-10) M for γ-globulin, and 6.86 × 10(-10) M for Hb. The effect of metal cations on the fluorescence spectra of TNN in ethanol was also investigated. The method has been applied to the determination of total proteins in human serum samples collected from the hospital and the results were in good agreement with those reported by the hospital.
We describe the performance of a high-sensitivity wavelength modulated cavity enhanced infrared tunable diode laser absorption spectrometer for the detection of water vapor in the 1.37 mum region. The spectrometer can measure a fractional absorption of approximately 10(-5) for an absorption path length of a few kilometers. The instrument's sensitivity is more than sufficient to detect water isotopomers (H(2)(16)O, H(2)(18)O, HDO) at Martian atmospheric concentrations. The instrument is amenable to miniaturization, so a future compact, multiple-species version of the spectrometer will be highly suitable for in situ planetary exploration.
Photoacoustic spectroscopy, based on an external cavity diode laser operating at 1431 nm, was used for measuring CO2 concentration as a minority component in a gas mixture. By using N2 as a buffer gas, a molecular relaxation effect was observed, which influenced both the amplitude and the phase of the measured photoacoustic signal and consequently reduced the sensitivity of the PA system. This molecular relaxation effect could be suppressed by adding water vapor of a constant and relatively high (approximately 4%) concentration to the gas sample. In parallel with this, the arising spectral interference between H2O and CO2 necessitated the development of a simple yet efficient signal analysis method, which increased the sensitivity of the system by more than one order of magnitude and accordingly reduced the minimum detectable CO2 concentration down to approximately 1000 ppm.
Theoretical and empirical detection limits have been estimated for aripiprazole (analyte) in alpha lactose monohydrate (matrix model pharmaceutical formulation) using a micro-attenuated total reflection Fourier transform infrared (ATR FT-IR) spectroscopic imaging instrument equipped
with a linear array detector and a 1.5 mm germanium hemisphere internal reflection element (IRE). The instrument yielded a theoretical detection limit of 0.0035% (35 parts per million (ppm)) when operating under diffraction-limited conditions, which was 49 times lower than what was achieved
with a traditional macro-ATR instrument operating under practical conditions (0.17%, 1700 ppm). However, these results may not be achievable for most analyses because the detection limits will be particle size limited, rather than diffraction limited, for mixtures with average particle diameters
greater than 8.3 μm (most pharmaceutical samples). For example, a theoretical detection limit of 0.028% (280 ppm) was calculated for an experiment operating under particle size-limited conditions where the average particle size was 23.4 μm. These conditions yielded a detection limit
of 0.022% (220 ppm) when measured empirically, which was close to the theoretical value and only eight times lower than that of a faster, more simplistic macro-ATR instrument. Considering the longer data acquisition and processing times characteristic of the micro-ATR imaging approach (minutes
or even hours versus seconds), the cost‐benefit ratio may not often be favorable for the analysis of analytes in matrices that exhibit only a few overlapping absorptions (low-interfering matrices such as alpha lactose monohydrate) using this technique compared to what can be achieved
using macro-ATR. However, the advantage was significant for detecting analytes in more complex matrices (those that exhibited several overlapping absorptions with the analyte) because the detection limit of the macro-ATR approach was highly formulation dependent while that of the micro-ATR
imaging technique was not. As a result, the micro-ATR imaging technique is expected to be more valuable than macro-ATR for detecting analytes in high-interfering matrices and in products with unknown ingredients (e.g., illicit tablets, counterfeit tablets, and unknown powders).
A sensor using a single distributed-feedback (DFB) diode laser at 1.57 μm for the simultaneous measurement of CO(2) and CO concentration at elevated temperatures is developed. A proper line pair near 6361.250 and 6361.344 cm(-1) is chosen based on absorption strength, separation of the two lines, and isolation from interference of neighboring transitions of the major combustion gases. The concentrations of CO(2) and CO are inferred from their wavelength modulation spectroscopy (WMS) 1ƒ-normalized absorption-based WMS-2ƒ signal peak heights. The CO(2) and CO concentration measurements are within 3.3% and 5% of the expected values over the full temperature range.
The operating characteristics of a pulsed (10 ns) tunable near-infrared (NIR) laser source are described for temperature-jump (T-jump) applications. A Q-switched Nd:YLF laser (approximately 10 ns pulses) with a 1 kHz repetition rate is used to pump a potassium titanyl arsenate (KTA) crystal-based optical parametric oscillator (OPO), producing approximately 1 mJ NIR pulses that are tunable (1.80-2.05 microm) across the 1.9 microm vibrational overtone band of water. This T-jump source has been coupled to a deep ultraviolet (UV) probe laser for Raman studies of protein dynamics. T-jumps of up to 30 degrees C, as measured via the O-H stretching Raman band of water, are readily achieved. Application to cytochrome c unfolding is demonstrated.
Vacuum ultraviolet single-photon ionization time-of-flight mass spectrometry (VUV-SPI-TOFMS) has been applied to the detection of volatile organic compounds (VOCs), including aromatic, chlorinated, and oxygenated compounds. Photoionization mass spectra of 23 VOCs were measured using SPI-TOFMS at 10.5 eV (118 nm). The limits of detection of VOCs using SPI-TOFMS at 10.5 eV were estimated to be a few ppbv. The mass spectra of 20 VOCs exhibit only the parent ion and its isotopes' signals. The ionization processes of the VOCs were discussed on the basis of the reaction enthalpies predicted by the quantum chemical calculations. Absolute photoionization cross-sections for 23 VOCs, including 12 newly measured VOCs, at 10.5 eV were determined in comparison to the reported absolute photoionization cross-section of NO.
We report on the local microenvironment surrounding three small fluorescent probe molecules (pyrene, [6-propionyl-2-(N,N-dimethylamino) naphthalene] (PRODAN), and [4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran] (DCM)) when they are sequestered at low concentration within thin biodegradable films formed from poly( L-lactic acid) (PLLA) and Pluronic P104 blends. Despite each probe molecule being neutral, they sense and report from much different microenvironments in comparison to each other. Specifically, the non-polar pyrene probe senses a slightly more polar microenvironment as the PLLA content in the polymer blend increases. In contrast, the polar PRODAN and DCM probes sense less polar microenvironments as the PLLA content within the polymer blend increases. Time-resolved fluorescence intensity decay experiments on pure PLLA films reveal that each probe molecule encounters significant heterogeneity. Pyrene emits simultaneously from three discrete microenvironments. This is consistent with pyrene molecules reporting from crystalline, amorphous-crystalline intermediate, and amorphous regions. PRODAN and DCM appear to emit from a continuum of microenvironments. These results have ramifications on the performance of biodegradable drug delivery platforms loaded with small drug molecules.
In the early sixties, coating with molten beeswax was considered a valuable method for preventing the erosive action of weather and/or salinity on the surface of granite sculptures and monuments. This technique had been traditionally employed by the Galician stoneworkers for partial repair of historical monuments. For this purpose, beeswax was applied to the Renaissance Frieze in the Cloister of the Cathedral of Santiago de Compostela in Galicia (Northwest Spain). The beeswax treatment was counterproductive. An intense grain disaggregation of the granite can be observed in the Frieze, owing to the crystallization of salts. As a consequence, the restoration of the Cloister presents many problems. This fact imposes the need for an exhaustive study of the wax-stone system and the demand for a nondestructive method to measure the beeswax thickness at the stone surface. The aim of this contribution is the evaluation of a laser-based method, namely Fourier transform Raman spectroscopy, for analyzing the wax presence in specific rocky material of the Frieze to be restored. To obtain a reliable quantitative calibration, we prepared beeswax films of five different thicknesses on aluminum plates (26.6-97.2 microm). Nylon was selected as external reference to obtain the Raman emission independently from the laser beam power. The ratios of the relative intensities of the Raman bands corresponding to beeswax and nylon were used for the construction of a calibration curve used for the quantitative analysis. The intensities at 2879 cm(-1), I(c2879), and 2880 cm(-1), I(n2880), for beeswax and nylon, respectively, in the Raman spectra of each material were used. A linear dependence was found for the ratio I(c2879)/I(n2880) with the beeswax thickness. The validation of this calibration curve was tested with a second validation set of samples that spans beeswax film thicknesses both inside and outside the calibration range (12.1 to 180 mum), in order to evaluate in addition the accuracy of the model at extrapolation. Without complex sample preparation, near-infrared Raman spectroscopy resulted in an effective technique for localizing the wax with lateral resolution of tens of micrometers, and for determining wax layer thickness in the stone with an uncertainty of a few micrometers.
Anti-Stokes Raman spectra of 28 explosive materials were obtained with 1064-nm excitation using fiber-optic sampling and a dispersive spectrograph equipped with a charge-coupled device (CCD) array detector. By using a silicon CCD detector, anti-Stokes features could clearly be observed for the majority of samples from -250 to -1650 cm(-1). Using the fiber-optic probe, spectra were routinely obtained from samples positioned up to twelve meters from the spectrograph within 240 s. The utility of an anti-Stokes correction routine is demonstrated, which routine allowed anti-Stokes spectra measured with 1064-nm excitation to be successfully searched and identified against libraries of Stokes spectra obtained using a Fourier transform (FT) Raman system equipped with a 1064-nm Nd:YAG laser.
We have constructed a 1064 nm deep near-infrared (NIR) excited multichannel Raman microspectrometer using an InP/InGaAsP multichannel detector. This microspectrometer achieves high sensitivity suitable for in vivo measurements of single living cells with lateral resolution of 0.7 μm and depth resolution of 3.1 μm. It has been applied to the structural analysis of living cyanobacterial cells, well-known model organisms for photosynthesis research, which are too photolabile to be measured with visible laser excitation. High signal-to-noise ratio (S/N) Raman spectra have been obtained from carotenoid, chlorophyll α, and phycocyanin in a single living cyanobacterial cell with no appreciable interference from autofluorescence or photodamage. Sub-micrometer mapping of Raman intensities provides clear distribution images of the three pigments inside the cell.
Biomass representing different classes of bioenergy feedstocks, including woody and herbaceous species, was measured with 1064 nm Raman spectroscopy. Pine, oak, poplar, kenaf, miscanthus, pampas grass, switchgrass, alfalfa, orchard grass, and red clover were included in this study. Spectral differences have been identified with an emphasis on lignin guaiacyl and syringyl monomer content and carotenoid compounds. The interpretation of the Raman spectra was correlated with (13)C-nuclear magnetic resonance cross-polarization/magic-angle spinning spectra of select biomass samples. Thioacidolysis quantification of guaiacyl and syringyl monomer composition and the library of Raman spectra were used as a training set to develop a principal component analysis model for classifying plant samples and a principal component regression model for quantifying lignin guaiacyl and syringyl composition. Raman spectroscopy with 1064 nm excitation offers advantages over alternative techniques for biomass characterization, including low spectral backgrounds, higher spectral resolution, short analysis times, and nondestructive analyses.
A surface plasmon resonance spectroscopy study showed that citrate-reduced gold nanoparticles ( approximately 15 nm diameter, approximately 9 x 10(-9) M concentration, approximately 2 x 10(-2) M ionic strength) were found to be utilized as a colorimetric sensor by exhibiting a distinct color change at a highly alkaline pH > 11.5. Surface-enhanced Raman scattering (SERS) of 4-ethynylpyridine (4-EP) on gold nanoparticle surfaces indicated that the multiple peaks in the v(C identical withC) stretching bands should vary significantly in the highly alkaline region from pH 12 to 14. As the pH value increased, the v(C identical withC) stretching band intensity at approximately 2080 cm(-1) became stronger than that at approximately 2010 cm(-1). The pK(1/2) value was determined to be around 13 by the SERS titration of taking intensity ratios of I(2080) with respect to I(2010). Using SERS enhancements and conspicuous spectral changes, self-assembled monolayers (SAMs) of 4-EP on Au nanoparticles holds potential as a pH sensor for sensitive detection of the hydroxide OH(-) concentration at around pH 13 in an aqueous solution. The pH calibration from SERS titration of 4-EP is expected to have advantages in terms of higher alkaline detection limit and more precise measurements, if compared with the indigo carmine, the pK(1/2) value of which is 12.2.
Time-resolved Fourier transform near-infrared (FT-NIR) spectroscopic imaging was applied to the diffusion process of butanol(OD) into polyamide 11 (PA11) with a novel sheet-structured variable-temperature-controlled sample holder in order to demonstrate the significant differences of diffusion rate below and above the glass transition temperature of PA11. The diffusant butanol(OD) was chosen for two reasons: (1) it allows the diffusion front to be monitored by the intensity decrease of a NH-specific absorption band of PA11 due to the NH/ND isotope exchange and (2) under the measurement conditions the diffusion of butanol(OD) into PA11 takes place in an experimentally manageable time frame. Apart from the in situ visualization of the diffusion front in the time-resolved FT-NIR images, the type of diffusion and the diffusion coefficient of butanol(OD) into PA11 have been determined.
This paper describes the development of practical Fourier transform infrared (FT-IR) methods for the determination of acid number (AN) and base number (BN) in lubricants through the combined use of signal transduction via stoichiometric reactions and differential spectroscopy to circumvent matrix effects. Trifluoroacetic acid and potassium phthalimide were used as stoichiometric reactants to provide infrared (IR) signals proportional to the basic and acidic constituents present in oils. Samples were initially diluted with 1-propanol, then split, with one half treated with the stoichiometric reactant and the other half with a blank reagent, their spectra collected, and a differential spectrum obtained to ratio out the invariant spectral contributions from the sample. Quantitation for AN and BN was based on measurement of the peak height of the v(C = O) or v(COO) absorptions, respectively, of the products of the corresponding stoichiometric reactions, yielding a standard error of calibration of < 0.1 mg KOH/g oil. The AN/BN FT-IR methods were validated by the analysis of a wide range of new and used oils supplied by third parties, which had been analyzed by ASTM methods. Good correlations were obtained between the chemical and FT-IR methods, indicating that the measures are on the whole comparable. From a practical perspective, these new FT-IR methods have significant advantages over ASTM titrimetric methods in terms of environmental considerations, sample size, and speed of analysis, as well as the variety of oil types that can be handled. FT-IR analysis combining stoichiometric signal transduction with differential spectroscopy may be of wider utility as an alternative to titration in the determination of acid or basic constituents in complex nonaqueous systems.
Fourier transform infrared (FT-IR) spectroscopic imaging with focal plane array detectors has proved a powerful technique for rapid chemical visualization of samples, with a lateral resolution up to 10-15 microm in the transmission micro mode. In the present communication the application of this technique is described for the study of the diffusion of D2O into a polyamide 11 (PA11) film. Apart from the in situ visualization of the diffusion front propagation in the time-resolved FT-IR images, the type of diffusion and the diffusion coefficient of D2O in the investigated polyamide have been determined.
The fourth-order coherent Raman response of a TiO2 (110) surface covered by HCl aqueous solution, neat octanol, acetic acid, or carbon tetrachloride layers is acquired. Four fourth-order optical responses were identified at 837-826, 452-448, 371-362, and 184-183 cm(-1) and assigned to near-surface phonons of TiO2. A third-order response produced in the bulk liquid layer was superimposed on the fourth-order response, when coherent vibrations are efficiently excited in the layer.
This work represents a characterization study of silicon oxide on Si(111) and Si(100) surfaces intended for use as substrates in organic light-emitting diodes (OLEDs) on chip devices. Samples have been prepared using either native oxide formation or thermal oxidation, and they have also been treated for activation of hydroxyl groups on their surface. Both Fourier transform infrared (FT-IR) and X-ray photoelectron spectroscopy (XPS) have been used in order to understand the molecular orientation as well as the chemical composition of the various oxide types formed during these different oxidation processes. These spectroscopic studies reveal the formation of two different types of oxides on these substrates. The first type is a thin oxide layer on the surface, whereas the second type, called interstitial, is found deeper in the substrate. Specifically, it was found that the Si(100) substrate forms a randomly oriented interstitial oxide, whereas the presence of a lower quantity but more oriented interstitial oxide was found for the Si(111) substrate. In addition, we report for the first time the position of the impurity oxygen for Si(111) substrates at 1122 cm(-1). Finally, in both Si(100) and Si(111) substrates, the thin (<15 A) silicon oxide layers are oriented and appear to contain silicon atoms of similar oxidation states. In contrast, both the thicker surface film (100 A) as well as the interstitial oxide produced by the thermal oxidation procedure show random orientation and relative uniformity. Overall these orientation studies clearly show that the formation process of surface oxides in different substrates clearly creates species that are oriented differently with respect to the surface.
The capability to analyze and detect the composition of distant samples (minerals, organics, and chemicals) in real time is of interest for various fields including detecting explosives, geological surveying, and pollution mapping. For the past 10 years, the University of Hawaii has been developing standoff Raman systems suitable for measuring Raman spectra of various chemicals in daytime or nighttime. In this article we present standoff Raman spectra of various minerals and chemicals obtained from a distance of 120 m using single laser pulse excitation during daytime. The standoff Raman system utilizes an 8-inch Meade telescope as collection optics and a frequency-doubled 532 nm Nd : YAG laser with pulse energy of 100 mJ/pulse and pulse width of 10 ns. A gated intensified charge-coupled device (ICCD) detector is used to measure time-resolved Raman spectra in daytime with detection time of 100 ns. A gate delay of 800 ns (equivalent to target placed at 120 m distance) was used to minimize interference from the atmospheric gases along the laser beam path and near-field scattering. Reproducible, good quality single-shot Raman spectra of various inorganic and organic chemicals and minerals such as ammonium nitrate, potassium perchlorate, sulfur, gypsum, calcite, benzene, nitrobenzene, etc., were obtained through sealed glass vials during daytime. The data indicate that various chemicals could easily be identified from their Raman fingerprint spectra from a far standoff distance in real time using single-shot laser excitation.
A rapid, practical, and accurate Fourier transform infrared (FT-IR) method for the determination of moisture content in edible oils has been developed based on the extraction of water from oil samples into dry acetonitrile. A calibration curve covering a moisture content range of 0-2000 ppm was developed by recording the mid-infrared (MIR) spectra of moisture standards, prepared by gravimetric addition of water to acetonitrile that had been dried over molecular sieves, in a 500 microm ZnSe transmission flow cell and ratioing these spectra against that of the dry acetonitrile. Water was measured in the resulting differential spectra using either the OH stretching (3629 cm(-1) or bending (1631 cm(-1)) bands to produce linear standard curves having standard deviations (SDs) of approximately +/-20 ppm. For moisture analysis in oils, the oil sample was mixed with dry acetonitrile in a 1:1 w/v ratio, and after centrifugation to separate the phases, the spectrum of the upper acetonitrile layer was collected and ratioed against the spectrum of the dry acetonitrile used for extraction. The method was validated by standard addition experiments with samples of various oil types, as well as with oil samples deliberately contaminated with alcohols, hydroperoxides, and free fatty acids to investigate possible interferences from minor constituents that may be present in oils and are potentially extractable into acetonitrile. The results of these experiments confirmed that the moisture content of edible oils can be assessed with high accuracy (on the order of +/-10 ppm) by this method, thus providing an alternative to the conventional, but problematic, Karl Fischer method and facilitating the routine analysis of edible oils for moisture content.
Phencyclone, 1, a potent Diels-Alder diene, reacts with a series of N-alkylmaleimides, 2, to form hindered adducts, 3. The 300 MHz 1H and 75 MHz 13C NMR studies of these adducts at ambient temperatures have demonstrated slow rotations on the nuclear magnetic resonance (NMR) timescales for the unsubstituted bridgehead phenyl groups, and have revealed substantial magnetic anisotropic shielding effects in the 1H spectra of the N-alkyl groups of the adducts. The selected N-alkyl groups for the target compounds emphasized smaller branched alkyls, including C3 (isopropyl, a); C4 (isobutyl, b; and t-butyl, c); C5 (n-pentyl, d; isopentyl [isoamyl], e; 1-ethylpropyl, f; t-amyl, g;) and a related C8 isomer (1,1,3,3-tetramethylbutyl ["t-octyl"], h). The straight-chain n-pentyl analog was included as a reference. This present work on the branched N-alkylmaleimide adducts appreciably extends our earlier compilation on the N-n-alkylmaleimide adducts. Key methods for proton assignments included "high-resolution" 1H-1H chemical shift correlation spectroscopy, COSY45. 13C NMR of the adducts, 3, verified the expected number of aryl carbons for slow exchange limit (SEL) spectra of the bridgehead phenyl groups. The synthetic routes involved reaction of the corresponding amines, 4, with maleic anhydride to give the N-alkylmaleamic acids, 5, which underwent cyclodehydration to form the maleimides, 2. Magnetic anisotropic shielding magnitudes for alkyl group protons in the adducts were calculated relative to corresponding proton chemical shifts in the maleimides. Geometry optimizations for the above adducts (and for the N-n-butylmaleimide adduct) were performed at the Hartree-Fock level with the 6-31G* basis set. The existence of different contributing conformers for the adducts is discussed with respect to their calculated energies and implications regarding experimentally observed anisotropic shielding magnitudes.
X-ray diffraction, scanning electron microscopy (SEM), and solid-state cross-polarization magic-angle-spinning (CP/MAS) (13)C-NMR spectroscopy were applied to determine changes over time in the morphology and crystallinity of lime wood (Tilia cordata Miller) generated by the soft-rot fungi. Wood samples were inoculated with Trichoderma viride Pers for various durations up to 84 days. Structural and morphological modifications were assessed by comparing the structural features of decayed lime wood samples with references. Significant morphology changes such as defibration or small cavities were clearly observed on the SEM micrographs of lime wood samples exposed to fungi. Following the deconvolution process of the diffraction patterns, the degree of crystallinity, apparent lateral crystallite size, the proportion of crystallite interior chains, and the cellulose fraction have been determined. It was found that all crystallographic data vary with the duration of exposure to fungi. The degree of crystallinity and cellulose fraction tend to decrease, whereas the apparent lateral crystallite size and the proportion of crystallite interior chains increase with prolonged biodegradation processes. The most relevant signals in CP/MAS (13)C-NMR spectra were assigned according to literature data. The differences observed were discussed in terms of lignin and cellulose composition: by fixing the lignin reference signal intensity, the cellulose and hemicelluloses moieties showed a relative decrease compared to the lignin signals in decayed wood.
The chemical interactions between maleic anhydride grafted polypropylene (MAPP) and wood were studied with solid-state carbon-13 cross-polarization magic-angle-spinning nuclear magnetic resonance ((13)C CPMAS NMR) spectroscopy. MAPP was synthesized with 100% (13)C enrichment at the C(1) and C(4) carbons to allow detection of the [1,4-(13)C(2)]MAPP functional groups and was melt blended with cellulose, lignin, and maple wood. In the cellulose/MAPP blend, changes in (13)C CPMAS NMR corrected signal intensities for the anhydride and dicarboxylic maleic acid functionalities suggested that esterification may have occurred predominantly from the more numerous diacid carbons. A single proton longitudinal relaxation in the rotating frame, (H)T(1rho), for the MAPP and the cellulose carbons in the blend suggested that they were spin coupled, i.e., homogeneous on a 10-200 Angstrom scale. Esterification was also suggested in the lignin/MAPP blend. Furthermore, the more significant changes in the intensities of the carbonyl signals and (H)T(1rho) values suggested that lignin may be more reactive to MAPP than cellulose. Finally, when maple was melt blended with MAPP, the same trends in the (13)C CP-MAS NMR spectra and (H)T(1rho) behavior were observed as when MAPP was blended with cellulose or lignin. This study therefore clarifies that during melt compounding of wood with MAPP, esterification occurs with wood polymers, preferentially with lignin. Understanding the interactions of MAPP with wood is of significance for the development of natural-fiber-reinforced thermoplastic composites.
3,6-Dibromophencyclone, 2, reacted with N-ethylmaleimide, 3a; N-n-propylmaleimide, 3b; and N-n-butylmaleimide, 3c; to form the corresponding Diels-Alder adducts, 4a, 4b, and 4c. The nuclear magnetic resonance (NMR) spectra of the adducts were studied at ambient temperatures at 300 MHz for proton and 75 MHz for carbon-13. Full proton assignments were achieved by high-resolution COSY45 spectra for the aryl proton regions. Rigorous assignments for protonated carbons were obtained with the heteronuclear chemical shift correlation spectra (HETCOR). Slow exchange limit (SEL) spectra were observed for both proton and carbon-13 NMR for each adduct, with slow rotation on the NMR timescales for the unsubstituted bridgehead phenyl groups. Endo Diels-Alder adduct stereochemistry was supported by substantial magnetic anisotropic shielding effects in the 1H NMR spectra of the alkyl groups. Proton NMR shifts are compared with those previously reported for the corresponding adducts, 5b and 5c, obtained from 3b and 3c, respectively, with the parent compound, phencyclone, 1. Results of ab initio molecular modeling calculations at the Hartree-Fock level using the LACVP* basis set for conformers of the dibrominated adducts, 4a-4c, are presented, together with HF/6-31G* results for the non-brominated adducts, 5a, 5b, and 5c. Novel aspects of this present work include: (a) attempts to quantitatively evaluate alkyl proton NMR shielding magnitudes in the adducts, relative to maleimide precursors, and (b) use of ab initio Hartree-Fock level calculations to try to reconcile adduct geometries with the observed shielding magnitudes. Our results here complement and extend studies of: (a) adducts of the parent phencyclone with straight-chain N-n-alkylmaleimides, and (b) adducts of 3,6-dibromophencyclone with other symmetrical dienophiles.
Solid-state nuclear magnetic resonance (NMR) spectroscopic studies are reported for the interactions of probe molecules with respirable silicon-containing dusts as experimental evidence complementing computational studies reported by Snyder and Madura recently in J. Phys. Chem. B 112, 7095 (2008). The selected probe molecules represent the individual functional groups of a model lung surfactant dipalmitoylphosphatidyl choline (DPPC) deposited on a respirable silica and kaolin from water solution. (13)C and (31)P solid-state NMR spectroscopies were employed to detect chemical shift, line width, and chemical shift anisotropy, providing experimental evidence of mobility and relaxation changes describing the site and orientation of surface-associated species. NMR results confirm that only the phosphate and adjacent carbons are immobilized by surface hydroxyls on kaolin, while these and the carbons of the cationic head group are likewise immobilized by surface silanols on Miu-U-Sil 5. The phosphates in phosphoryl- and phosphatidyl-cholines were the primary interaction sites, with additional weak coordination with the trimethylammonium cation species. Covalent Al-O-P formation is not likely a factor in in vivo or in vitro toxicity mechanisms of respirable silicon-containing materials, but is rather the result of dehydration or demethoxylation reactions occurring over time or during heating or reduced pressure used in preparing materials for NMR spectroscopic study. Hydration is a critical factor in the formation and preparation for spectroscopic observation of coated dusts. Care must be taken to ensure that products formed and studied correspond to species formed in vivo under suitable concentration and hydration conditions.
The physical and chemical properties of crude oil depend on the type and relative amount of hydrocarbons present. When it is not possible to elucidate the exact composition of the oil, "average structural information" may be a meaningful description of the bulk properties of the oil. In this paper, the application of NMR for this purpose has been extended by the use of two-dimensional (2D) 13C-1H J-resolved spectroscopy (HET-JRES) to obtain the average structural information of a set of crude oils. This makes it possible to estimate the molar concentration of the different CHn (n = 0, 1, 2, 3) spin systems in the sample. It is demonstrated here that structural information, derived from HET-JRES, correlates with the density and viscosity of the crude oils. Hence this new approach, which is rapid, may represent a useful method for crude oil characterization.
In this paper, a ternary aqueous mixture of sucrose and two metal ions (Mg(2+) and K(+)) has been examined by mid-infrared spectroscopy coupled with principal component analysis (PCA) and the partial least-squares regression method (PLS). PCA was first used for the description of Fourier transform mid-infrared (mid-FTIR) spectral data of the complex samples. The resulting factorial map, set up with the two most influential component axes, features distinct concentration distribution specific to each component. Prediction equations that linked sucrose, magnesium, and potassium concentrations to the spectral data were established by the partial least-squares regression method. A quite good correlation was obtained between the first 5 axes and the concentration variables, with coefficient values ranging from 0.984 to 0.997. It was thus possible to predict specifically both metal ion concentrations in the ternary mixture with relatively good accuracy. The ternary mixtures of sucrose, Mg(2+), and K(+) were also subjected to (13)C NMR (nuclear magnetic resonance) analysis. From the relative displacements of chemical shifts of the carbon atoms of sucrose, it was possible to determine the influence of each metal ion present in the mixture.
Ergosta-4,6,8(14),22-tetraen-3-one (ergone) isolated from Polyporus umbellatus possesses a variety of pharmacological activities in vivo and in vitro, including cytotoxic, diuretic, and immunosuppressive effect. The interaction of cerium ions (Ce(3+)) with ergone was studied by fluorescence and absorption spectroscopy. Spectra data revealed that Ce(3+) ions exhibited emission maxima around 350 nm when the excitation wavelength was fixed at 255 or 290 nm, and the fluorescence of Ce(3+) ions was quenched by the addition of ergone, indicating that a Ce(3+)-ergone complex was formed. According to the modified Benesi-Hildebrand equation, the binding constant of interaction of Ce(3+) ions with ergone was obtained at room temperature. Based on this, a sensitive spectrofluorometric method using Ce(3+) ions as a probe was applied for the identification and quantification of ergone in rat plasma, feces, and urine. The linear ranges of the calibration curves were 1.31 to 4.50 μM for plasma, 1.12-9.87 μM for feces, and 1.28-3.42 μM for urine, and the ergone recoveries were found to be 97.1 ± 0.9%, 98.2 ± 0.7% and 96.5 ± 1.4% for plasma, feces, and urine, respectively. The intraday and inter-day relative standard deviations were less than 9.7%. The proposed spectrofluorometric method is simple and rapid for the quantitative determination of ergone in rat plasma, feces, and urine, and it is affordable for most laboratories because it has few requirements and uses low cost, easy to operate equipment.
Laser-induced breakdown spectroscopy (LIBS) measurements are typically carried out using pulses (<20 ns, >50 mJ) from a flashlamp-pumped electro-optically Q-switched Nd:YAG laser (EO-laser) or excimer laser. Here we report LIBS analyses of solids using an acousto-optically Q-switched Nd:YAG laser (AO-laser) producing 150 ns pulses of lower energy (10 mJ) at repetition rates up to 6 kHz. The high repetition rate allows increased spatial or depth sampling over a given time period compared to the EO-laser. Results of AO-laser based LIBS analysis of (1) steels, (2) soils, and (3) surface stains and dusts are described. Detection limits for Cr, Cu, Mn, Ni, and Si in steel ranged from 0.11 to 0.24% using a commercial polychromator-based detection system with limits 4--30 times lower achieved using a laboratory-based detection system. The minimum detectable masses of Ba, Cr, Mn, and Sr on a metal surface were estimated with 1.2 pg/shot achieved for Sr. Detection limits for Ba and Sr in soil were 296 and 52 ppm, respectively. The temperatures, spectra, and emission decay curves from plasmas generated by the AO- and EO-lasers are compared and some characteristics of particles ablated by the AO-laser are described.
During the past decade, the use of portable Raman analyzers for field measurements has grown dramatically. However, most analyzers use 785 nm excitation lasers that can cause permanent eye damage. To overcome this safety concern, we have built a portable Fourier transform (FT) Raman analyzer using a 1550 nm retina-safe excitation laser and have compared its performance to our 1064 nm FT-Raman analyzer, which uses the same optical design. Raman theory predicts approximately five times lower peak intensities at 1550 nm. Although we found that intensities were as much as 20 times less intense, the analyzer is still capable of measuring spectra of sufficient quality to identify and differentiate chemicals.
The surface-enhanced coherent anti-Stokes Raman scattering (SECARS) from a self-assembled monolayer (SAM) of benzenethiol on a silver-coated surface-enhanced Raman scattering (SERS) substrate has been measured for the 1574 cm(-1) SERS mode. A value of 9.6 ± 1.7×10(-14) W was determined for the resonant component of the SECARS signal using 17.8 mW of 784.9 nm pump laser power and 7.1 mW of 895.5 nm Stokes laser power; the pump and Stokes lasers were polarized parallel to each other but perpendicular to the grooves of the diffraction grating in the spectrometer. The measured value of resonant component of the SECARS signal is in agreement with the calculated value of 9.3×10(-14) W using the measured value of 8.7 ± 0.5 cm(-1) for the SERS linewidth Γ (full width at half-maximum) and the value of 5.7 ± 1.4×10(-7) for the product of the Raman cross section σSERS and the surface concentration Ns of the benzenethiol SAM. The xxxx component of the resonant part of the third-order nonlinear optical susceptibility |3 χxxxx((3)R)| for the 1574 cm(-1) SERS mode has been determined to be 4.3 ± 1.1×10(-5) cm(.)g(-1.)s(2). The SERS enhancement factor for the 1574 cm(-1) mode was determined to be 3.6 ± 0.9×10(7) using the value of 1.8×10(15) molecules/cm(2) for Ns.
Nitrification and mineralization of organic nitrogen (N) are important N transformation processes in soil, and mass spectrometry is a suitable technique for tracing changes of (15)N isotopic species of mineral N and estimating the rates of these processes. However, mass spectrometric methods for tracing N dynamics are costly, time consuming, and require long and laborious preparation procedures. This study investigates mid-infrared attenuated total reflection (ATR) spectroscopy as an alternative method for detecting changes in (14)NO(3)-N and (15)NO(3)-N concentrations. There is a significant shift of the nu(3) absorption band of nitrate according to N species, namely from the 1275 to 1460 cm(-1) region for (14)NO(3)(-) to the 1240-1425 cm(-1) region for (15)NO(3). This shift makes it possible to quantify the N isotopes using multivariate calibration methods. Partial least squares regression (PLSR) models with five factors yielded a determination error of 6.7-9.2 mg N L(-1) for aqueous solutions and 5.9-7.8 mg N kg(-1) (dry soil) for pastes of a Terra rossa soil. These PLSR models were used to monitor the changes of (15)NO(3)-N and (14)NO(3)-N content in the same Terra rossa soil during an incubation experiment in which [(15)NH(4)](2)SO(4) was applied to the soil, allowing the estimation of the contributions of applied N and mineralized N to the net nitrification rate, the potential losses of the applied (15)NH(4)-N, and the net mineralization of soil organic N.
Samples of blue wall paint layers from selected 15th to 18th century religious mural paintings from southern Portugal (Alentejo) have been analyzed using a multi-analytical methodology involving the combination of in situ visible spectro-colorimetry with microanalytical techniques such as optical and scanning electron microscopy and Raman spectroscopy. In situ analyses and micro-sampling were carried out in nine different churches, many in an advanced state of deterioration. The objectives of this study were: (a) to identify and compare the pigments that were used in the blue paint layers across the Alentejo region and through time by analysis of the elemental and mineralogical composition and pictorial techniques, and (b) to correlate the data between the actual color of the paint layer and the state of conservation of the pigments. For the paintings dated from the 16th century forward, the results show a generalized use of smalt blue. To a lesser extent, natural azurite was used despite the geological richness of the region in copper and pyrite ores. In only one painting was an optical blue made of carbon black and lime found. The pigments, pure or mixed with red and yellow ochres, were coarsely ground and used in different concentrations to create three-dimensional effects. These parameters as well as the presence of iron oxides in underlayer paints influence the colorimetric coordinates in the more transparent smalt blue paint layers. The state of conservation of the pigments plays an important role in the alteration of the paint color. A clear example of this is the fading of the smalt blue in several paintings due to lixiviation processes.
This paper describes the development of a practical Fourier transform infrared (FT-IR) method for the determination of moisture in lubricants through the combined use of signal transduction and differential spectroscopy to circumvent matrix effects. The acid-catalyzed stoichiometric reaction of 2,2-dimethoxypropane (DMP) with moisture to produce acetone was used to provide IR signals proportional to the amount of moisture present in oils. Calibration standards were prepared by spiking polyalphaolefin (PAO) gravimetrically with water using dioxane as a carrier. For FT-IR analysis, standards and samples were diluted with acidified isooctane and then split, with one aliquot treated with DMP and the other with a blank reagent. The spectra of the two aliquots were collected, and a differential spectrum was obtained so as to ratio out the invariant spectral contributions from the sample. Quantitation for moisture was based on measurement of the peak height of the nu(C=O) absorption of acetone at 1717 cm(-1), yielding a standard error of calibration of approximately 40 ppm H2O. The method was validated by standard addition of water in dioxane to PAO containing added base as well as to new and used oils. In all cases the method responded quantitatively to standard addition, the average standard error of prediction being approximately 80 ppm, with the results showing only a minor dependence on the oil formulation. From an analytical perspective, the FT-IR method is both more reproducible and more accurate than Karl Fischer methods and has advantages in terms of environmental considerations, sample size, and speed of analysis as well as the variety of oil types that can be handled. Signal transduction/differential spectroscopy may have broader utility as an alternative means for the determination of low levels of moisture in complex matrices.