Assessment of historic Tilia codrata wood by solid-state C CPMAS NMR spectroscopy

Historic lime (Tilia cordata Mill.) wood samples, differing by their provenance, conservation status and period have been investigated by solid-state carbon-13 cross polarization magic angle sample spinning nuclear magnetic resonance (¹³C CPMAS NMR) spectroscopy. Structural and chemical modifications were assessed by comparing the historic samples with a reference wood sample. The conventional NMR measurements followed by the ¹³C resonance integral intensities of the wood samples have been carried out in order to acquire information of the chemical changes due to the natural ageing process taking place over the years. The main results concern the decrease of the carbohydrates moiety, especially the decrease of the hemicelluloses and amorphous cellulose signals, while the signals for aliphatic and methoxyl carbons from lignin present and increase of the intensity up to 120 years then start to decrease. At the same time a slight widening of the amorphous carbohydrate signals was observed, which may evidence the occurring of some chemical rearrangements, with the formation of new chemical species. These lead in the ¹³C NMR spectra to the line broadening of the signals induced by their chemical shifts dispersion.     

Characterization of cyclotriveratrylene inclusion compounds by means of solid state13C NMR

Solid inclusion compounds of cyclotriveratrylene (CTV) with benzene, toluene, acetone, tetrahydrofuran, acetic acid and chloroform, as well as two hydrated forms, were prepared and characterized by solid state¹³C NMR. The inclusion process for CTV appears to be quite selective, and in some instance depends critically on the presence or absence of water. A number of different structural types are indicated by the solid state¹³C NMR splitting paterns. For the guests listed above,¹H NMR in solution indicated a guest to host ratio close to 0.5, except for chloroform, for which the ratio is closer to 2.     

Oxidation of C-labeled ethyl linoleate monitored and quantitatively analyzed by C NMR

The oxidation of ¹³C-labeled ethyl linoleate (¹³C-EL), a model compound for alkyd resins, was investigated by ¹³C NMR in the presence of Co(II)-2-ethylhexanoate (Co-EH), Mn(acac)₃ (acac = acetylacetonate), and Mn(acac)₃ in combination with 2,2′-bipyridine (bpy), respectively. The use of ¹³C-EL allows us, in an unprecedented way, to reveal the individual evolution of hydroperoxides (ROOH) and peroxy (ROOR) links by ¹³C NMR and to quantify the oxidation intermediates during the oxidation. Mn(acac)₃ appeared to be less effective in decomposing ROOH than Co-EH and the Mn(acac)₃/bpy combination. Quantitative analyses were attempted for a few major ¹³C peaks.     

Secondary structure of peptides 16th. Characterization of proteins by means of13C NMR CP/MAS spectroscopy

50.3 or 75.4 MHz¹³C NMR cross-polarization/magic angle spinning spectra of human hair, horse hair, horse hoof, parrot feather, sperm whale myoglobin, and horse heart cytochrome C were measured. The spectra of human hair and horse hair indicate nearly equal mole fractions of-sheets and-helices and a low percentage of amorphous regions, whereas horse hoof contains a higher fraction of amorphous proteins. The parrot feathers contain a small-helix fraction (ca. 10±5 %) in additon to a large-sheet fraction whereas cytochrome C contains 70–90%-helices. The spectrum of myoglobin could not interpreted in terms of defined secondary structures. The usefulness of the¹³C NMR CP/MAS spectroscopy for the characterization of proteins is compared with that of IR spectroscopy and X-ray diffraction.     

Solid state13C NMR spectra of metal carbonyl clusters

The solid state¹³C NMR spectra of four¹³CO enriched carbonyl clusters having a tri-iron metallic core have been analyzed to provide structural and dynamic information. In Fe₃(CO)₁₂ (1), the high temperature spectra suggest the occurrence of large amplitude motions of the CO groups around their position at the vertexes of the coordination polyhedron in addition to the motion involving the Fe₃-triangle previously detected in the VT-¹³C MAS spectra.¹³C and³¹P NMR data of Fe₃(CO)₁₁PPh₃ (2) indicates the presence of one molecule in the asymmetric unit in apparent disagreement with the previously reported X-ray data. Furthermore, we show that structural information can be obtained from the chemical shift tensor components readily available from the analysis of the spinning sideband manifold.     

Characterization of milled wood lignin and ethanol organosolv lignin from miscanthus

Ethanol organosolv lignin extracted from Miscanthus × giganteus (using the following conditions: T = 190 °C, t = 60 min, sulfuric acid = 1.2% w/w, EtOH/H₂O = 0.65) and milled wood lignin from Miscanthus × giganteus were subjected to a comprehensive structural characterization by ¹³C, ³¹P NMR, FTIR, UV spectroscopies and size exclusion chromatography. The results showed that Miscanthus lignin is an H/G/S type (4%, 52%, 44% respectively) with ∼0.41 β-O-4 linkage per aromatic ring and contains coumarylate linkages (0.1/Ar). It was shown that during organosolv treatment, cleavage of β-O-4 linkages and of ester bond (acetyl and coumaryl residues) was the major mechanisms of lignin breakdown but the process did not significantly change the core of the lignin structure.     

13C NMR spectra and the structure of dithizone

The structural characteristics of dithizone in the solid state and in solution were studied by a high-resolution¹³C NMR method. A highly symmetrical structure of dithizone was established in the crystalline state, and it was suggested that it exhibits dual behavior in complexation reactions with metal ions.V. I. Vernadskii Institute of Geochemistry and Analytical Chemistry, Russian Academy of Sciences, 117975 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 113–117, January, 1992.     

13C NMR spectroscopy of tautomeric conversions in imidazole compounds

A study has been made of¹³C NMR spectra of several series of imidazoles and their salts in solution and in the solid state. It has been shown that in compounds containing a pyridine ring, prototropic tautomerism on the NMR time scale may be retarded. The possible mechanism of these processes is discussed.V. I. Vernadskii Institute of Geochemistry and Analytical Chemistry, Russian Academy of Sciences, 11795 Moscow. Torino University, Italy. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 2, pp. 299–308, February, 1992.     

Characterization of n-butyl acrylate centered triads in poly(n-butyl acrylate-co-carbon monoxide-co-ethylene) by isotopic labeling and two dimensional NMR

Poly(n-butylacrylate-co-carbon monoxide-co-ethylene) (polyEBC) samples prepared from 13C-labeled monomer, n-butyl acrylate, were characterized using two dimensional (2D) pulsed field gradient (PFG) 750 MHz NMR spectroscopy. To elucidate the complex structure of the terpolymer, 2D-1H/13C-heteronuclear single quantum coherence (HSQC) and heteronuclear multiple bond correlation (HMBC) experiments were conducted by selectively exciting the enhanced resonances in the spectra of two polymer samples, one polymer resulting from synthesis with 1-13C-n-butylacrylate monomer and a second polymer obtained from a synthesis with 2-13C-n-butylacrylate monomer. High-resolution 2D-NMR combined with 13C-labeling of the polymer greatly simplifies the 2D-NMR spectra, selectively enhances the weak peaks from low occurrence B-centered triad structures, and aids in their resonance assignments. In all experiments, the sample temperature was 120 degrees C, to ensure a homogeneous solution and sufficient molecular mobility. Electronic Supplementary Material: Supplementary material (1D 13C NMR spectra of the 13C-labeled and unlabeled polymers) is available in the online version of this article at http://dx.doi.org/100.1007/s00216-003-2402-3.     

Solid-state C NMR and molecular modeling studies of acetyl aleuritolic acid obtained from Croton cajucara Benth

Solid-state ¹³C nuclear magnetic resonance (¹³C NMR) with magic-angle spinning (MAS) and with cross-polarization and magic-angle spinning (CP/MAS) spectra, and differential scanning calorimetry (DSC) techniques were used to obtain structural data from a sample of acetyl aleuritolic acid (AAA) extracted from the stem bark of Croton cajucara Benth. (Euphorbiaceae) and recrystallized from acetone. Since solid-state ¹³C NMR results suggested the presence of more than one molecule in the unitary cell for the AAA, DSC analysis and molecular modeling calculations were used to access this possibility. The absence of phase transition peaks in the DSC spectra and the dimeric models of AAA simulated using the semi-empirical PM3 method are in agreement with that proposal.     

Characterization of chemically bonded phases on precoated thin-layer plates by29Si and13C cross-polarization and magig-angle spinning NMR

Summary The paper reports results for commercial precoated plates and home-made bonded phases for TLC examined by²⁹Si and¹³C NMR of solid samples. The NMR spectra readily reveal differences in degree of silylation, details pertaining to the type of reactive silanes used, and differences in the methods of synthesis. They can also be used to explain the cause of the wettability problems encountered with some types of (precoated) TLC plates.     

13C NMR spectra of azolopyridines and their quaternary salts

¹³ C NMR spectra of some azole series have been investigated: 2-pyridylbenzimidazoles, 2-pyridylimidazo [4,5-b]-pyridines, 2-pyridylimidazo[4,5-c]-pyridines, analogous oxazole compounds, as well as their mono- and bisquaternary salts. Some problems, related to the structure of these compounds in solution, have been discussed.V. I. Vernadskii Institute of Geochemistry and Analytical Chemistry, Russian Academy of Sciences, Moscow 117975. Torino University, Italy. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 4, pp. 866–872, April, 1992.     

N-Oxides of polychloropyridines.13C NMR study

The effect ofN-oxidation of a series of polychloropyridines on¹³C NMR parameters has been studied. It has been established that inN-oxides of polychloropyridines an electric field through-space effect of theN-oxide group predominates in the shielding of the -carbon atom compared to the other carbon atoms. A linear correlation between¹³C NMR chemical shifts and total charge densities calculated by the MNDO method for the carbon atoms ofN-oxides of polychloropyridines has been found.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2425–2428, December, 1995.The authors are grateful to V. V. Kolchanov for help in the synthesis of compounds under study.     

A 13C, 15N and 77Se NMR Study of Some Diseleno Sulfonamides

¹³C, ¹⁵N and ⁷⁷Se NMR data are reported for ten title compounds. Some linear correlations of selenium, nitrogen and carbon chemical shifts values are described. A number of one- and two- bond ⁷⁷Se-¹³C coupling constants values are also given.     

Iminopropadienones R–NCCCO and carbon suboxide, C3O2. Theoretical and experimental C NMR spectra

The ¹³C NMR data of five iminopropadienones R–NCCCO as well as carbon suboxide, C₃O₂, have been examined theoretically and experimentally. The best theoretical results were obtained using the GIAO/B3LYP/6-31+G**//MP2/6-31G* level of theory, which reproduces the chemical shifts of the iminopropadienone substituents extremely well while underestimating those of the cumulenic carbons by 5–10 ppm. The computationally faster GIAO/HF/6-31+G**//B3LYP/6-31G* level is also adequate.     

13C NMR Spectra of 6-Hydroximinosteroids of the Stigmastane Series

¹³ C NMR spectra were studied and signals of C atoms were assigned for 6-keto- and 6-hydroximinosteroids 1-10.     

Variable temperature CP/MAS13C NMR study of cyclodextrin complexes of benzaldehyde

Fully hydrated as well as dried benzaldehyde complexes of - and -cyclodextrins were studied by using CP/MAS¹³C NMR techniques. Variable temperature studies have shown that below 200 K the guest is rigidly held in the complex, whereas at 328 K, only the aromatic ring performs rapid two-fold flips about the C₁–C₄ axis. In the -Cd complex the benzaldehyde performs more general reorientation. Removal of water causes marked changes in both guest and host spectra, generally consistent with a loss of short-range order and increase in guest motional rate.NRCC No. 27826.     

Structure Elucidation and NMR Characterization of Two New Cyclophane Derivatives

In the course of our on-going investigation to develop synthetic methods for helical cyclophanes using Diels–Alder methodology, a great variety of polycyclic aromatic compounds have been formed. In some cases, the cycloaddition reactions, in addition to the target compounds, gave rise to unexpected products, which were identified by spectroscopic methods. The structure determination based on NMR measurements and semiempirical calculations of two such new compounds are presented in this paper.     

H and C NMR spectroscopy of 9-acridinones

The ¹H and ¹³C NMR spectra of 9-acridinone and its five derivatives dissolved in CDCl₃, CD₃CN and DMSO-d₆ were measured in order to reveal the influence of the constitution of the compounds and features of the solvents on chemical shifts and ¹H-¹H coupling constants. Experimental data were compared with theoretically predicted chemical shifts, on the GIAO/DFT level of theory, for DFT (B3LYP)/6-31G^∗∗ optimized geometries of molecules—also for four other 9-acridinones. This comparison helped to ascribe resonance signals in the spectra to relevant atoms and enabled revelation of relations between chemical shifts and physicochemical features of the compounds. It was found that experimentally or theoretically determined ¹H and ¹³C chemical shifts of selected atoms correlate with theoretically predicted values of dipole moments of the molecules, as well as bond lengths, atomic partial charges and energies of HOMO.     

Precise and accurate quantitative C NMR with reduced experimental time

In order to detect small variations in ¹³C isotopomers concentrations, high sensitivity, accuracy and precision have to be achieved. To assess such criteria, when using ¹³C NMR, ¹³C bi-labelled ethanol has been proposed as a molecular probe. Advantage has been taken of the pre-established structural relationship between the peak areas of the ¹³C NMR spectrum of this molecule, i.e. the ratio of signal areas is set to a fixed value. It is shown that the quality performance, required by quantitative ¹³C NMR spectroscopy, is not affected by a large reduction of the repetition delay using relaxation reagents.