FT–IR spectroscopic study on the thermal and thermal oxidative degradation of nylons

The effects of heat and oxygen on nylon films were studied by FT–IR spectroscopy. Nylons 6, 66 and nylons containing carbonyl groups in either the diamine or the diacid moiety were prepared. Nylon films cast on aluminum were studied in an environmental chamber under controlled conditions. The progress of chemical and physical changes was monitored by FT–IR spectroscopy. Thermal energy caused largely an increase in crystallinity due to annealing and also an increase of nonhydrogen-bonded amide groups, which seemed to entail mainly amide groups from the amorphous region. The intensities of IR absorption bands related to the folded structure reduced as soon as heating began. The IR spectra of the carbonyl groups formed by thermal oxidation showed band shapes that indicated that the formed carbonyl groups were of many different origins. The presence of keto groups purposely inserted into the backbone chains increased the rate of oxidation. Pyrolysis of the nylons was also studied to supplement data obtained at lower temperatures.     

Hydrogen bonds in silk fibroin-poly(acrylonitrile-co-methyl acrylate) blends: FT–IR study

FT–IR spectroscopy was used to study the specific interactions in polyacrylonitrile-silk fibroin (PAN–SF) and poly(acrylonitrile-co-methyl acrylate)-silk fibroin (PANMA–SF) blends. No specific interaction was found in PAN–SF blends. In PANMA–SF blends, however, a new 1703 cm⁻¹ band, assigned to be hydrogen-bonded carbonyl groups of PANMA, appears, and its intensity depends on the compositions of the blends and the MA contents in PANMA. Furthermore, when the sample was heated, considerable changes in position and intensities of the hydrogen-bonded bands, in both stretching regions of the carbonyl group of PANMA and the hydroxl group of SF, were found, and these changes were irreversible on cooling. Finally, we suggested that the bands of hydrogen bonds in PANMA–SF blends may be the average result of several kinds of possible hydrogen bondings. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 1405–1414, 1997     

FT–IR microspectroscopy study of blends of ester functionalized ethylene–propylene copolymer with (vinylidene fluoride-hexafluoropropene) elastomer

An ethylene—propylene (EPR) copolymer functionalized with (1,2-dicarboethoxy)ethyl groups has been blended with a vinylidene fluoride—hexafluropropene elastomer (NML). The existence of intermolecular interactions involving mainly the carbonyl groups of the side chains of the functionalized copolymer and the methylene hydrogens of the fluoroelastomer through hydrogen bonding was shown by means of FT—IR spectroscopy. The structure and composition of some microdomains in the mixture was examined by means of FT—IR microspectroscopy.     

Synthesis,spectroscopic (FT–IR and UV–Vis), crystallographic and theoretical studies,and a molecular docking simulation of an imatinib‐like template

The aim of the present study was to report the crystal structure and spectroscopic, electronic, supramolecular and electrostatic properties of a new polymorph of 4‐(pyridin‐2‐yl)pyrimidin‐2‐amine (C₉H₈N₄). The compound was synthesized under microwave irradiation. The single‐crystal X‐ray structure analysis revealed an angle of 13.36 (8)° between the planes of the rings, as well as molecules linked by Nsp²—H…N hydrogen bonds forming dimers along the crystal. The material was analyzed by FT–IR vibrational spectroscopy, while a computational approach was used to elucidate the vibrational frequency couplings. The existence of Nsp²—H…N hydrogen bonds in the crystal was confirmed spectroscopically by the IR peaks from the N—H stretching vibration shifting to lower wavenumbers in the solid state relative to those in the gas phase. The supramolecular studies confirmed the formation of centrosymmetric R₂²(8) rings, which correspond to the formation of dimers that stack parallel to the b direction. Other weak C—H…π interactions, essential for crystal growth, were found. The UV–Vis spectroscopic analysis showed a donor–acceptor process, where the amino group acts as a donor and the pyridine and pyrimidine rings act as acceptors. The reactive sites of the molecule were identified and their quantitative values were defined using the electrostatic potential model proposed in the multifunctional wave function analyzer multiwfn. The calculated interaction energies between pairs of molecules were used to visualize the electrostatic terms as the leading factors against the dispersion factors in the crystal‐growth process. The docking results showed that the amino group of the pyrimidine moiety was simultaneously anchored by hydrogen‐bonding interactions with the Asp427 and His407 protein residues. This compound could be key for the realization of a series of syntheses of molecules that could be used as possible inhibitors of chronic myelogenous leukemia.     

FT‐IR Study of Some Carotenoids

Some natural and semisynthetic carotenoids were examined by means of FT‐IR spectroscopy. The IR bands of the characteristic functional groups (CH₃, CH₂, CC, CO, OH, etc.) were assigned when possible. Some special functional groups – without H‐atoms – such as CCC, ‘cross epoxides', etc., which cannot be easily identified by ¹H‐NMR methods, were also detected in the FT‐IR spectra.     

FT–IR spectroscopic and thermal studies of poly(styrene-co-1-vinyl naphthalene) and poly(vinyl methyl ether) blends

The FT–IR spectroscopic analysis and the thermal behavior of the blends of styrene-1-vinyl naphthalene copolymers [P(S-co-1VN)] and poly(vinyl methyl ether) (PVME) were investigated in this work. The copolymers containing 23, 50, and 80% by weight of styrene were synthesized by radical polymerization. The blend films of the P(S-co-1VN) and PVME were cast from the mixed solvent of benzene/trimethylbenzene [50/50 (v/v)]. It was found from the optical clarity and the glass transition temperature behavior that the blends of PVME with P(S-co-1VN) of 80 wt % styrene and 20 wt % 1-vinylnaphthalene (1VN) show miscibility below 50 wt % of the copolymer concentration and the concentration range to show miscibility becomes wider as the composition of 1VN decreases in the copolymers. From the FT–IR results, the relative peak intensity of the 1100 cm^?1 region due to COCH₃ bond of PVME and the peak position of 774 cm^?1 region due to the naphthyl ring of 1VN were sensitive to the miscibility of the P(S-co-1VN)/PVME blends. The frequency differences of the phenyl ring and the naphthyl ring in the P(S-co-1VN) from each frequency in the P(S-co-1VN)/PVME blends increase with increasing composition of styrene in the copolymers and with increasing concentration of PVME in the blends. A threshold energy exists to induce molecular interaction between the naphthyl ring of 1VN and the COCH₃ of PVME and to result in the miscible blends, regardless of the copolymer composition as well as the blend concentration. The threshold energy was estimated as about 3.689 × 10^?21 cal (779 cm^?1) for the P(S-co-1VN)/PVME blend system. It can be concluded that the miscibility in P(S-co-1VN)/PVME blends is largely affected by the composition of the copolymers, and the blends become more miscible as the composition of styrene in the copolymers increases.     

FT‐IR kinetic and product study of the OH radical and Cl‐atom–initiated oxidation of dibasic esters

Using a relative kinetic technique, rate coefficients have been measured, at 296 ± 2 K and 740 Torr total pressure of synthetic air, for the gas‐phase reaction of OH radicals with the dibasic esters dimethyl succinate [CH₃OC(O)CH₂CH₂C(O)OCH₃], dimethyl glutarate [CH₃OC(O)CH₂CH₂CH₂C(O)OCH₃], and dimethyl adipate [CH₃OC(O)CH₂CH₂CH₂CH₂C(O)OCH₃]. The rate coefficients obtained were (in units of cm³ molecule^?1 s^?1): dimethyl succinate (1.89 ± 0.26) × 10^?12; dimethyl glutarate (2.13 ± 0.28) × 10^?12; and dimethyl adipate (3.64 ± 0.66) × 10^?12. Rate coefficients have been also measured for the reaction of chlorine atoms with the three dibasic esters; the rate coefficients obtained were (in units of cm³ molecule^?1 s^?1): dimethyl succinate (6.79 ± 0.93) × 10^?12; dimethyl glutarate (1.90 ± 0.33) × 10^?11; and dimethyl adipate (6.08 ± 0.86) × 10^?11. Dibasic esters are industrial solvents, and their increased use will lead to their possible release into the atmosphere, where they may contribute to the formation of photochemical air pollution in urban and regional areas. Consequently, the products formed from the oxidation of dimethyl succinate have been investigated in a 405‐L Pyrex glass reactor using Cl‐atom–initiated oxidation as a surrogate for the OH radical. The products observed using in situ Fourier transform infrared (FT‐IR) absorption spectroscopy and their fractional molar yields were: succinic formic anhydride (0.341 ± 0.068), monomethyl succinate (0.447 ± 0.111), carbon monoxide (0.307 ± 0.061), dimethyl oxaloacetate (0.176 ± 0.044), and methoxy formylperoxynitrate (0.032–0.084). These products account for 82.4 ± 16.4% C of the total reaction products. Although there are large uncertainties in the quantification of monomethyl succinate and dimethyl oxaloacetate, the product study allows the elucidation of an oxidation mechanism for dimethyl succinate. © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 33: 431–439, 2001     

FT‐IR kinetic and product study of the Br‐initiated oxidation of dimethyl sulfide

An FT‐IR kinetic and product study of the Br‐atom‐initiated oxidation of dimethyl sulfide (DMS) has been performed in a large‐volume reaction chamber at 298 K and 1000‐mbar total pressure as a function of the bath gas composition (N₂ + O₂). In the kinetic investigations using the relative kinetic method, considerable scatter was observed between individual determinations of the rate coefficient, suggesting the possibility of interference from secondary chemistry in the reaction system involving dimethyl sulfoxide (DMSO) formation. Despite the experimental difficulties, an overall bimolecular rate coefficient for the reaction of Br atoms with DMS under atmospheric conditions at 298 K of ≤1 × 10⁻¹³ cm³ molecule⁻¹ s⁻¹ can be deduced. The major sulfur products observed included SO₂, CH₃SBr, and DMSO. The kinetic observations in combination with the product studies under the conditions employed are consistent with rapid addition of Br atoms to DMS forming an adduct that mainly re‐forms reactants but can also decompose unimolecularly to form CH₃SBr and CH₃ radicals. The observed formation of DMSO is attributed to reactions of BrO radicals with DMS rather than reaction of the Br–DMS adduct with O₂ as has been previously speculated and is thought to be responsible for the variability of the measured rate coefficient. The reaction CH₃O₂ + Br → BrO + CH₃O is postulated as the source of BrO radicals. © 1999 John Wiley & Sons, Inc. Int J Chem Kinet 31: 883–893, 1999     

Direct IR spectroscopic study of the cyclopentadienyl radical

The products of vacuum pyrolysis of bis(cyclopentadienyl)nickel have been studied by matrix isolation infrared spetroscopy. Three IR bands at 3079, 1383 and 661 cm^–1 corresponding to the cyclopentadienyl radical have been observed. A comparison of the IR spectrum of the radical C₅H₅ with those of the ligand -C₅H₅ and free anion^–C₅H₅ has been performed.These results were presented for the first time in O. M. Nefedov's plenary lecture at X IUPAC Conference on Physical Organic Chemistry (Haifa, Israel, August 1990) (see ref. 1 and literature cited therein).Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1497–1499, August, 1993.     

Lanthanide-nitrate interaction in anhydrous acetonitrile and coordination numbers of the lanthanide ions: FT‒IR study

The interaction between lanthanide ions Ln^III (Ln = La, Nd, Sm–Dy, Er, Yb) and nitrate ions is investigated by FT-IR spectroscopy in dilute anhydrous MeCN solution. The work is performed for ratios R = [NO]_t/[Ln^III]_t ranging from 0 to 8 and for solutions generally 0.05M in Ln^III, prepared from anhydrous lanthanide perchlorates Ln(ClO₄)₃. When nitrate is progressively added to the Ln(ClO₄)₃ solutions, the formation of [Ln(NO₃)_n]^(3?n)+ species is clearly evidenced by the FT-IR spectra. All the NO₃^? ions are coordinated and bidentate. A quantitative study was performed using the v₁ and v₆ vibrational modes for coordinated NO ions. The average coordination numbers estimated for Nd, Eu, Tb, and Er in solutions of trinitrates are 9.0, 9.1, 8.3 and 8.2, respectively (±0.3 unit). In presence of an excess NO, these numbers become 9.8, 10.2, 10.0, 9.8, 9.9, and 9.9 (±0.3 unit) for La, Nd, Eu, Tb, Er, and Yb, respectively. No hexanitrato species forms under the experimental conditions used (R up to 8). The structural aspect of the various nitrato species is also investigated. In the pentanitrato species, all the ligands appear to be equivalent, while large inequivalences are observed for Ln(NO₃)₃ solutions. Since for the latter most of the absorption bands assigned to nitrate vibrations contain several components, a curve-fitting procedure has been used for decomposing the v₂, v₄ and v₆ vibrations. There is a considerable difference between Ln^III ions, the nitrate inequivalences being larger in the middle of the series.     

Generation and IR spectroscopic study of benzyl radical

The benzyl radical C₆H₅CH₂ has been obtained by gas phase pyrolysis of two different precursors, benzyl bromide and dibenzyl, and studied in an argon matrix at 12 K by IR spectroscopy. Similarly, the deuterosubstituted benzyl radicals, C₆H₅CD₂ and C₆D₅CH₂, have been investigated. The assignment of the IR bands of the benzyl radical and its deuteroanalogs to fundamental modes and a calculation of the valence force field have been performed. The obtained data give evidence of sp² hybridization of the methylene carbon atom and delocalization of the electron density between the ring and the CH₂ group, and are in good agreement with the planar structure of the radical.These results were presented for the first time in O. M. Nefedov's plenary lecture at X IUPAC Conference on Physical Organic Chemistry (Haifa, Israel, August 1990).Deceased July, 1986.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1499–1502, August, 1993.     

FT‐IR and Isotherm Study on Anion Adsorption onto Novel Chelating Fibers

A new chelating fiber, poly(acrylo‐amidino diethylenediamine), was synthesized based on polyacrylonitrile fibers in diethylenetriamine with the aid of AlCl₃. Complex formation with CrO₄^2– was strongly pH‐dependent, as complexes formed only in the presence of NH₃⁺ and NH₂⁺. In the medium pH region, both ionic and hydrogen bonds were formed between poly(acrylo‐amidino diethylenediamine) and the chromate ion, as was confirmed by means of FT‐IR spectroscopy.     

IR spectroscopic study of filled polymeric films

Distribution of scattering centers (filler particles and pores) in films of an ultra-high-molecular-weight polyethylene xerogel was studied by IR spectroscopy and optical microscopy.     

Study on the intermediate of photooxidative degradation of phenylenevinylene oligomers

The results of the investigation on photooxidative degradation of five phenylenevinylene oligomers are as follows. The sequence of the photodegradation rate in self-sensitized reaction is the same as that in the biacetyl-sensitized reaction and the rate of photooxidative degradation increases upon the incorporation of electron-donating groups and decreases upon the incorporation of electron-accepting groups on the oligomers. The self-sensitized reaction rate of oligomers increases as the solvent changing from benzene to deuterated benzene and decreases with the addition of the singlet oxygen (¹O₂) scavenger. ¹O₂ is shown to be the main reactive intermediate in self-sensitized photolysis of phenylenevinylene oligomers, which was directly confirmed by ESR spin trapping experiments.     

An IR spectroscopic study of amorphous silicas

The IR absorption spectra of various amorphous silicas were studied. Depending on the conditions of the preparation of amorphous SiO₂, Si-O bonds with various strengths were formed in siloxane groups.     

Combined Raman and IR spectroscopic study on the radical-based modifications of methionine

Among damages reported to occur on proteins, radical-based changes of methionine (Met) residues are one of the most important convalent post-translational modifications. The combined application of Raman and infrared (IR) spectroscopies for the characterisation of the radical-induced modifications of Met is described here. Gamma-irradiation was used to simulate the endogenous formation of reactive species such as hydrogen atoms (^•H), hydroxyl radicals (^•OH) and hydrogen peroxide (H₂O₂). These spectroscopic techniques coupled to mass experiments are suitable tools in detecting almost all the main radical-induced degradation products of Met that depend on the nature of the reactive species. In particular, Raman spectroscopy is useful in revealing the radical-induced modifications in the sulphur-containing moiety, whereas the IR spectra allow decarboxylation and deamination processes to be detected, as well as the formation of other degradation products. Thus, some band patterns useful for building a library of spectra–structure correlation for radical-based degradation of Met were identified. In particular, the bands due to the formation of methionine sulfoxide, the main oxidation product of Met, have been identified. All together, these results combine to produce a set of spectroscopic markers of the main processes occurring as a consequence of radical stress exposure, which can be used in a spectroscopic protocol for providing a first assessment of Met modifications in more complex systems such as peptides and proteins, and monitoring their impact on protein structure.