The destruction-free analysis of polymers by fourier transform infrared photoacoustic and fourier transform Raman spectroscopy: A comparison

With the introduction of rapid–scanning Fourier transform infrared (FTIR) and recently Raman (FT–Raman) spectroscopy, vibrational spectroscopy has been launched into a new era of applications in polymer chemistry and physics. Thus, the increase in sensitivity provided by multiple scanning has led to the breakthrough of new, destruction–free sampling techniques, such as photoacoustic and Raman spectroscopy. This paper provides a comparison between data produced by FTIR photoacoustic and FT–Raman analysis of a range of polymers, and structural information available from both techniques is discussed.     

In-situ measurement of photochemical changes of solid samples by fourier transform infrared photoacoustic spectroscopy

Infrared spectral changes of lithographic printing plates were measuredin-situ by PAS and RAS. The advantages of PAS over RAS were discussed for the spectral measurements of organic coatings on roughened metal surface.     

Ultrahigh‐resolution mass spectrometry of simulated runoff from treated oil sands mature fine tailings

There is interest in using mature fine tailings (MFT) in reclamation strategies of oil sands mining operations. However, simulated runoff from different dried MFT treatments is known to have elevated levels of salts, toxic ions, and naphthenic acids, and alkaline pH and it is phytotoxic to the emergent macrophyte, common reed (Phragmites australis). Fourier transform ion cyclotron resonance mass spectrometry (FT‐ICR MS) of the acidic species in the runoff confirmed that the distribution of oil sands naphthenic acids and associated oil sand acids was dependent on the MFT treatment. Furthermore, FT‐ICR MS studies of the acidic species in hydroponic systems revealed that there was no plant‐mediated change in the electrospray ionization mass spectra of the runoff. O_o‐containing species were prevalent (>90%), O_oS_s were predominant (<10% relative abundance), and O_oN_n were least abundant in all runoff water samples. O_oS_s species were predominant in all the samples investigated. The heteroatomic classes present in runoff water at greater than 1% relative abundance include: O₂N₁, O₃N₁, O₂, O₂S₁ O₃, O₃S₁, O₄, O₄S₁, O₅, O₅S₁, O₆, O₆S₁, O₇, O₇S₁, O₈ and O₈S₁. Assuming the same response factor for all O_o species, the O₄ class, presumably dicarboxylic acids, was generally more prevalent than the O₂ class in all samples. The O₂ class is indicative of classical naphthenic acids. However, dicarboxylic acids will form negative ions more readily than the monocarboxylic acids as there are two acidic hydrogens available for formation of these species. Copyright © 2010 John Wiley & Sons, Ltd.     

The silver-oxygen system in catalysis: new insights by near ambient pressure X-ray photoelectron spectroscopy

We addressed the interaction of oxygen with silver by synchrotron based near ambient pressure X-ray photoelectron spectroscopy at temperatures relevant for industrial oxidation reactions performed with silver catalysts. For silver single crystals, polycrystalline foils and powders in equilibrium with gas phase O(2), we observed the dynamics of the formation of five different atomic oxygen species with relative abundances depending on the temperature and time. Correlation of their formation kinetics with spectroscopic features and thermal stability indicates that these are distinct species with different electronic structures, which might relate to the different roles of silver in oxidation reactions.     

Biological applications of fourier transform infrared spectroscopy: a study of phase transitions in biomembranes

The thermal response of aqueous lipid membranes has been investigated by Fourier transform infrared spectroscopy. Changes in infrared spectral parameters are applied to the analysis of the strutural changes which occur within the lipid bilayer as the temperature is varied. Such studies provide the basis for the interpretation of phase transitions in complex biomembranes.     

FT-Raman and photoacoustic infrared spectroscopy of Syncrude heavy gas oil distillation fractions

FT-Raman and photoacoustic (PA) infrared spectra of six distillation fractions derived from Syncrude heavy gas oil (HGO), which has a boiling range from 343 to 524 degrees C, were analyzed in detail in this study. Most of the information on the fingerprint region (200-1,800 cm(-1)) is provided by the FT-Raman spectra, which display approximately 30 bands that are assignable to functional groups in alkanes or aromatics. Monocyclic, bicyclic and tricyclic aromatics in the six fractions were also monitored using bands in this region. The C-H stretching region in both the FT-Raman and PA infrared spectra of the HGO distillation fractions was analyzed according to a curve-fitting algorithm used in previous investigations of samples with lower boiling points. The PA spectra of the HGO fractions were also analyzed by integration. The curve-fitting results show that the frequencies of the 11 Raman and 8 infrared bands used to model the aliphatic (approximately 2,775-3,000 cm(-1)) parts of the respective spectra are approximately constant across the entire HGO boiling range. These band positions are consistent with the results obtained in earlier studies of other distillation fractions obtained from Syncrude sweet blend. Both curve-fitting and integration show that the respective proportions of CH(2) and CH(3) groups do not vary significantly within the HGO region.     

FT-Raman and photoacoustic infrared spectroscopy of syncrude light gas oil distillation fractions

FT-Raman and photoacoustic (PA) infrared spectra of 12 distillation fractions derived from Syncrude light gas oil (LGO), which has a boiling range from 195 to 343 degrees C, were analyzed in detail in this study. In the fingerprint region (200-1800 cm(-1)) most of the information is obtained from the FT-Raman spectra, which display 36 bands that are assignable to various alkyl or aryl functional groups. Monocyclic, bicyclic and tricyclic aromatics in the 12 fractions were also characterized using Raman bands in this region. The corresponding section of the infrared spectra is much simpler, displaying a relatively small number of bands due to either aromatic or aliphatic CH(n) (n=1, 2 or 3) groups. The Cz.sbnd;H stretching region in both FT-Raman and PA infrared spectra of the LGO distillation fractions was curve-fitted according to procedures established in previous investigations of Syncrude samples with various boiling ranges. The PA spectra of the LGO fractions were also analyzed using an accepted integration strategy that requires no a priori assumptions with regard to the number of constituent bands or their shapes. The curve-fitting results show that the frequencies of the 11 Raman and eight infrared bands used to model the aliphatic ( approximately 2775-3000 cm(-1)) parts of the respective spectra decrease systematically as the median boiling points of the LGO fractions increase. These band positions are consistent with those determined in earlier studies of other distillation fractions. Both curve fitting and integration show that the abundance of CH(2) groups increases at the expense of CH(3) groups as the boiling points of the fractions increase within the LGO region.     

Characterization by fourier transform infrared spectroscopy (FT-IR) and 2D IR correlation spectroscopy of PAMAM dendrimer

FT-IR and 2D correlation spectroscopy were employed to study the microstructural changes occurring during phase transitions of a liquid crystal poly(amidoamine) codendrimer (PAMAM (L1)16(L2)16) generation 3, functionalized on the terminal groups by one-chain promesogenic calamitic units (4-(4'-decyloxybenzoyloxy)salicylaldehyde (L1)) and two-chain promesogenic calamitic units (4-(3',4'-didecyloxybenzoyloxy)salicylaldehyde (L2)). Spectral modifications associated with molecular conformation rearrangements allowing for molecular shape change on going from a liquid-crystalline organization to another were found. The transition temperatures were calculated, and they are in good agreement with the DSC data. Spectral analysis gives evidence of the LC phase transitions and to an additional transition associated with the existence of conformers. Various types of hydrogen bonding have been established.     

Phosphorus-containing podands. 8. A study of metal-ligand interaction by fourier transform infrared spectroscopy in anhydrous acetonitrile

The interaction of phosphorus-containing monopodands with Li⁺, Na⁺, and K⁺ cations in anhydrous CH₃CN has been studied by FTIR spectroscopy. It has been shown that phosphoryl groups of the ligands take part in the formation of complexes with the alkali metal cation. The IR results obtained do not permit a clear conclusion as to whether or not the ether oxygen atoms of the ligand polyether chain participate in the complexation. It is suggested that in CH ₃ CN the formation of 1:1 complexes is not accompanied by conformational reorganization of the monopodand.Institute of Physiologically Active Substances, Russian Academy of Sciences, Chernogolovka 142432. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 4, pp. 884–889, April, 1992.     

Reflective interferometric fourier transform spectroscopy: a self-compensating label-free immunosensor using double-layers of porous SiO2

An interferometric biosensor comprised of two layers of porous Si, stacked one on top of the other, is described. A fast Fourier transform (FFT) of the reflectivity spectrum reveals three peaks that correspond to the optical thickness of the top layer, the bottom layer, and both layers together. Binding of immunoglobulin G to a protein A capture probe adsorbed to the surface of the top layer induces changes in reflectivity at the top layer/solution interface. The FFT method allows discrimination of target analyte binding from matrix effects due to nonspecific changes in the analyte solution. The sensor response is shown to be insensitive to the addition of 4000-fold excess sucrose or 80-fold excess bovine serum albumin interferents.     

Chemical insights from high-resolution X-ray photoelectron spectroscopy and ab initio theory: propyne, trifluoropropyne, and ethynylsulfur pentafluoride.

High-resolution carbon 1s photoelectron spectroscopy of propyne (HC triple bond CCH3) shows a spectrum in which the contributions from the three chemically inequivalent carbons are clearly resolved and marked by distinct vibrational structure. This structure is well accounted for by ab initio theory. For 3,3,3-trifluoropropyne (HC triple bond CCF3) and ethynylsulfur pentafluoride (HC triple bond CSF5), the ethynyl carbons show only a broad structure and have energies that differ only slightly from one another. The core-ionization energies can be qualitatively understood in terms of conventional resonance structures; the vibrational broadening for the fluorinated compounds can be understood in terms of the effects of the electronegative fluorines on the charge distribution. Combining the experimental results with gas-phase acidities and with ab initio calculations provides insights into the effects of initial-state charge distribution and final-state charge redistribution on ionization energies and acidities. In particular, these considerations make it possible to understand the apparent paradox that SF5 and CF3 have much larger electronegativity effects on acidity than they have on carbon 1s ionization energies.     

Catalytic isomerization of quadricyclane using fourier transform near-infrared absorption spectroscopy: diffusion, conversion, and temperature effect

By using Fourier transform near-infrared (NIR) absorption spectroscopy, the kinetic behaviors of quadricyclane isomerization, as catalyzed by anhydrous CuSO(4) in chloroform mixture with and without agitation, are presented. Given the acquired NIR spectra, the concentration decay of quadricyclane with the reaction time is determined with the aid of partial least-squares analysis. When the mixture is not agitated, the diffusion coefficients in chloroform are evaluated to be (3.8 +/- 0.1) x 10(-5) cm(2) s(-1) at 27 degrees C and (4.4 +/- 0.1) x 10(-5) cm(2) s(-1) at 39 degrees C. In the size-dependent experiments of the catalyst, the one-site and two-site coordinated conversion rate constants are further determined to be (8.5 +/- 5.9) x 10(-6) s(-1) A(-1) and (2.2 +/- 0.8) x 10(-8) s(-1) A(-2), respectively, at 27 degrees C and (1.3 +/- 0.8) x 10(-5) s(-1) A(-1) and (1.92 +/- 0.01) x 10(-6) s(-1) A(-2), respectively, at 39 degrees C. A denotes the total catalyst surface area per unit effective volume of solvent. Accordingly, the activation energies for one-site and two-site coordination are evaluated to be 24.8 and 286.2 kJ mol(-1), respectively. The reaction is dominated by one-site coordination (1:1 complex) between the reactant and the catalyst. Unless temperature increases, the two-site coordinated reaction may be ignored. In contrast, when analogous experiments are performed in the stirred solution, the diffusion factor is ignored but the conversion rate constants rise due to the increase of collision frequency. For instance, the one-site and two-site coordinated rate constants are increased to (1.7 +/- 1.4) x 10(-5) s(-1) A(-1) and (1.27 +/- 0.06) x 10(-5) s(-1) A(-2) at 39 degrees C. The two-site coordinated reaction rate is enhanced by a factor of 10. Thus, isomerization may proceed via both 1:1 and 1:2 coordination between the reactant and the catalyst. The Arrhenius plot yields the corresponding activation energies to be 24 +/- 3 and 275 +/- 3 kJ mol(-1). The activation energies remain constant, no matter whether the solution is agitated or not.     

Depth-profiling of polymer laminates using fourier transform infrared (ATR) spectroscopy: The barrier film technique

We report FTIR-ATR spectra of a polymer laminate (PMMA/PVOH) at different base layer thicknesses and different angles of incidence on a ZnSe substrate. By varying this ‘barrier’ layer (of PMMA) we have demonstrated that different effective penetration depths into the PVOH are achieved, in very good agreement with the calculated electric fields as a function of distance away from the substrate surface. Such work forms the basis for depth profiling measurements in order to detect interfacial interactions between the polymer molecules. © 1994 John Wiley & Sons, Inc.     

Fiber-optic evanescent wave fourier transform infrared (FEW-FTIR) spectroscopy of polymer surfaces and living tissue

The new method of fiber-optic evanescent wave Fourier transform infrared (FEW-FTIR) spectroscopy has been applied to studies of polymer surfaces and the diagnostics of normal, precancerous and cancerous tissue. This technique using optical fibers and fiber-optic sensors operating in the attenuated total reflection (ATR) mode in the mid-infrared (IR) region of the spectrum (850 – 1850 cm⁻¹) has found recently application in the area of tissue diagnostics. The method is suitable for noninvasive and rapid (seconds) direct measurements of the spectra of normal and pathological tissues in vitro, ex vivo, and in vivo. The FEW-FTIR technique is an ideal diagnostic tool for different types of soft, porous, foam, and rough polymer surfaces. Inhomogeneous coatings and defects on polymer surfaces as well as layer structures have also been detected by this method. It is convenient to apply this method to analyze large pieces of soft plastics and/or surfaces covered by plastics, since these types of surfaces are comparatively hard to analyze by traditional absorption spectroscopy. The FEW-FTIR technique is non-destructive, fast (15 seconds), and remote (up to a fiber length of 3m). In addition, it is sensitive enough to detect any changes in the vibrational spectra of a polymer surface, without heating and damaging it. The surfaces of polyethylene crumpled bags and rumpled films have been investigated in the range of 2000 – 1000 cm⁻¹. The distinct spectra of these surfaces as well as spectra of polytetrafluoroethylene have been recorded. The spectra of white and colored foams and different plastics have also been studied. Weak but distinct spectra have been recorded for carbon fibers (black, narrow fibers with a diameter of about 10 μm). Using the FEW-FTIR technique, measurements can be taken without preparing the sample. High quality spectra have also been obtained for the bulk and surfaces of apple, banana, grapefruit, and other food products. The method is expected to be further developed for geological and microelectronic applications.     

Characterization of modified silica powders by fourier transform infrared spectroscopy and cross-polarization magic angle spinning NMR

Silica gel and Cab-O-Sil were chemically modified (silylated) with 3-aminopropyltriethoxysilane and 3-methacryloxypropyltrimethoxysilane under carefully controlled conditions. Subsequently the products were investigated by elemental analysis, Fourier transform IR spectroscopy, and ¹³C and ²⁹Si cross-polarization magic angle spinning NMR (CP-MAS NMR). The influence of the reaction conditions of the silylation and the effect of subsequent heat treatment and water addition were studied. The resulting differences shed new light on the combined effects of reaction conditions and silica surface structures on the course of the reactions. Some assignments of ²⁹Si NMR signals to specific structures were confirmed, while in one case a reassignment was proposed.     

Application of fourier transform infrared spectroscopy to the study of semicrystalline polymers: Poly(ethylene terephthalate)

An infrared absorbance subtraction technique has been used to “isolate” bands in the composite spectrum of semicrystalline polymers according to their crystalline or amorphous character. Amorphous and crystalline spectra for annealed, melt-quenched, and solution-cast poly(ethylene terephthalate) have been separated. The spectra of the amorphous component show an increased intensity of bands associated with the trans configuration of oxygen about the C? C bond when the polymer is annealed. This increased “trans” band intensity reflects the increased proportion of trans structures as a result of annealing. The amorphous trans bands are shifted approximately 1–3 cm^?1 from their positions in the crystalline “trans” spectrum. The frequency shift of these bands can be attributed to the differences in chain interactions that exist in the amorphous phase and the crystalline lattice. We have also found that under identical anealing conditions the amorphous phase of the melt-quenched polymer contains an increased intensity of conformational trans bands compared to the sample cast from solution.     

Characterization of nano FeIII-tannic acid modified polyacrylate in controlled-release coated urea by Fourier transform infrared photoacoustic spectroscopy and laser-induced breakdown spectroscopy

Polyacrylate polymer (PA) has been widely applied in coating products for decades. Recently, it has been used in controlled-release fertilizers. Nano Fe^III-tannic acid modified PA (PA-Fe) provides a better nutrient controlled release performance than conventional PA. In this work, a preliminary database of molecular and elemental information about the polymer was obtained using FTIR-PAS (Fourier transform infrared photoacoustic spectroscopy) and LIBS (laser-induced breakdown spectroscopy), respectively. The PA-Fe polymer contained more hydrophobic groups (–CH₃) and fewer hydrophilic groups (–COOR, –COOH) than PA. More elements were detected for PA-Fe than PA. LIBS was useful to identify and classify PA and PA-Fe samples using principal component analysis. The combination of spectroscopic results and a film formation process model explained the lower nutrient release rate of PA-Fe. These results showed the strong analytical capabilities of FTIR-PAS combined with LIBS for identifying and characterizing modified PA.     

Two-dimensional fourier transform spectroscopy of adenine and uracil using shaped ultrafast laser pulses in the deep UV

We compare two-dimensional (2D) ultrafast Fourier transform spectroscopy measurements in the deep UV (262 nm) for adenine and uracil in solution. Both molecules show excited-state absorption on short time scales and ground-state bleaching extending for over 1 ps. While the 2D spectrum for uracil shows changes in the center of gravity during the first few hundred femtoseconds, the center of gravity of the 2D spectrum for adenine does not show similar changes. We discuss our results in light of ab initio electronic structure calculations.