13C analysis

Methods for pretreatment of samples for 13C analysis had been described in Chen et al. (2002a). After pretreatment, soil samples and plant debris were sent to the State Key Laboratory of Loess and Quaternary Geology, Chinese Academy of Sciences (CAS), for 13C analyses. The 13C analyses were conducted using a Finnigan MAT-251 mass spectrometer manufactured by Finnigan-Mat Company, with a precision of 0.2%o. Results are reported as 513C, in parts per thousand of the 13C/12C ratio from that of the International Pee Dee belemnite (PDB) standard, where ... 

N.m.r. spectroscopy T.l.c.-m.s. analysis of oligosaccharides coupled to a lipid amine (neoglycolipids) H n.m.r. spectrum in D20 after exchange of free protons with deuterium Experiments conducted at 295 K, with acetone as the internal standard (set at 2.225 p.p.m. from 4,4-dimethyl-4-silapentane-1-sulfonate) Results compared, to within 0.005 p.p.m. (laboratory-to-la-boratory variation) of data in the literature Conformational studies by n.O.e. experiments Natural-abundance-13C analysis Chemical-shift assignment by 2D H- H and H-13C n.m.r. spectroscopy... 

A study was made of the effects of derivatization on the 13C analysis of amino acid enantiomers. Conventional isotope ratio MS and GC-isotope ratio MS were used. The latter method requires volatilization of the analytes, which was accomplished by introducing O-isopropyl and A-trifluoroacetyl groups, causing a change in the 13C analysis of the original analytes. It was proposed to use a set of known standards for such analyses, which are applied in geological studies68. 

Stable carbon isotope ratios have also been used to determine the sources of lake DOC. Baron et al. (1991) used 13C analysis to show that autochthonous sources dominated the DOC of an alpine lake during most periods while allochthonous sources dominated the DOC in a subalpine lake. The high DOC concentrations observed during spring snowmelt and early summer in both lakes, however, were mostly derived from allochthonous sources. As with streams and rivers, synoptic regional studies of 13C and 14C would provide important new information on broad spatial patterns and controls on the sources of DOC in lakes. 

The H and 13CNMR spectra of various cyclopentazepines have been recorded (Tables 1 and 2), as has the HNMR spectrum of 7V,7V-dimethylcyclopent[e]azepin-l-amine.68 A detailed analysis of geminal and long-range 13C-H coupling constants for cyclopent[c]azepine is also available.87 The HNMR spectra of 9//-pyrrolo[l,2-a]azepin-9-one (8b) and its fully delocalized cation have been recorded in various solvents.7... 

Another example is dimethyl 3,6-dichloro-l-tosyl-l//-azepine-4,5-dicarboxylate which, on the basis of ]H and 13C NMR spectral studies, is a 9 1 equilibrium mixture of azepine and benzene imine tautomers at —70 C(AG = 50.16 kJ mol-1) 22 however. X-ray analysis indicates that the mixture crystallizes as the 1//-azepine isomer. 

Most recent work is in accord with mechanism (b). In an effort to distinguish these mechanisms studies on model propagating species have been carried out.IS6 liW For S-MMA polymerization initiated by AIBMe- -13C (Scheme 8.13) it has been established by end group analysis that extremely small amounts of ethyl aluminum sesquichloride (<10 3M with 1.75 M monomers) are sufficient to cause a substantial enhancement in specificity for adding S in the initiation step. This result suggests that complexation of the propagating radical may be sufficient to induce alternating copolymerization but does not rule out other hypotheses. 

The 13C-NMR spectra of 4-7, 9-11 show a close similarity to the spectral data of analogous carbene complexes. The shift differences between the metal carbonyls of the silylene complexes and the related carbon compounds are only small. These results underline the close analogy between the silicon compounds 4-7, 9-11 and Fischer carbene complexes. This view is also supported by the IR spectral data. On the basis of an analysis of the force constants of the vco stretching vibration,... 

As a consequence of restricted internal mobility in molecules in the crystalline state, nuclei in different conformation environments, but identical in other respects, can produce different signals in 13C cross polarization, magic angle spinning (CPMAS) solid-state NMR. This analysis is not necessarily limited to crystalline regions, since signals of different conformations are resolved if the exchange is slow with respect to the time scale of the NMR experiment. 

The novel highly substituted spiro[4.4]nonatrienes 98 and 99 are produced by a [3+2+2+2] cocyclization with participation of three alkyne molecules and the (2 -dimethylamino-2 -trimethylsilyl)ethenylcarbene complex 96 (Scheme 20). This transformation is the first one ever observed involving threefold insertion of an alkyne and was first reported in 1999 by de Meijere et al. [81]. The structure of the product was eventually determined by X-ray crystal structure analysis of the quaternary ammonium iodide prepared from the regioisomer 98 (Ar=Ph) with methyl iodide. Interestingly, these formal [3+2+2+2] cycloaddition products are formed only from terminal arylacetylenes. In a control experiment with the complex 96 13C-labeled at the carbene carbon, the 13C label was found only at the spiro carbon atom of the products 98 and 99 [42]. 

A number of analytical techniques such as FTIR spectroscopy,65-66 13C NMR,67,68 solid-state 13 C NMR,69 GPC or size exclusion chromatography (SEC),67-72 HPLC,73 mass spectrometric analysis,74 differential scanning calorimetry (DSC),67 75 76 and dynamic mechanical analysis (DMA)77 78 have been utilized to characterize resole syntheses and crosslinking reactions. Packed-column supercritical fluid chromatography with a negative-ion atmospheric pressure chemical ionization mass spectrometric detector has also been used to separate and characterize resoles resins.79 This section provides some examples of how these techniques are used in practical applications. 

ADMET polymers are easily characterized using common analysis techniques, including nuclear magnetic resonance ( H and 13C NMR), infrared (IR) spectra, elemental analysis, gel permeation chromatography (GPC), vapor pressure osmometry (VPO), membrane osmometry (MO), thermal gravimetric analysis (TGA), and differential scanning calorimetry (DSC). The preparation of poly(l-octenylene) (10) via the metathesis of 1,9-decadiene (9) is an excellent model polymerization to study ADMET, since the monomer is readily available and the polymer is well known.21 The NMR characterization data (Fig. 8.9) for the hydrogenated versions of poly(l-octenylene) illustrate the clean and selective nature of ADMET. 

ADMET reaction. The 13C NMR spectrum also allows the scientist to distinguish between cis and trans internal sp2 carbons as well as the allylic carbons, which are adjacent to the internal vinyl position. Using quantitative 13C NMR analysis, the integration of the peak intensities between die allylic carbon resonances and diose of the internal vinyl carbons gives die percentage of trans/cis stereochemistry diat is present for the polymer.22 Empirically, the ratio of trans to cis linkages in ADMET polymers has typically been found to be 80 20. Elemental analysis results of polymers produced via ADMET demonstrate excellent agreement between experimental and theoretical values. 

Subsequent tables cover important titration methods (Table 17), useful 13C-NMR data for the analysis of LAB/LAS (Table 18), molecular fragments of alkylbenzenes (Table 19), and characteristic infrared absorption bands of an LAB/LAS molecule (Table 20). 

Nuclear magnetic resonance (NMR) spectrometry has seldom been used as a quantitative analytical method but can have some practical importance in the characterization of surfactants [296-298]. 13C-NMR spectrometry has been used for the qualitative and also quantitative analysis of dodecyl, tetradecyl, and cetyl sulfates [299]. H- and, 3C-NMR spectra of sodium dodecyl sulfate are given by Mazumdar [300]. 

The formation of alkyl shifted products H and 14 can be explained in terms of the formation of endo-intermediate 21 formed by endo attack of bromine to 2 (Scheme 4). The determined endo-configuration of the bromine atom at the bridge carbon is also in agreement with endo-attack. Endo-Intermediate 21 is probably also responsible for the formation of cyclopropane products 12 and 15. The existence of cyclopropane ring in 12 and 15 has been determined by and 13c NMR chemical shifts and especially by analysis of cyclopropane J cH coupling constants (168 and 181 Hz). On the basis of the symmetry in the molecule 12 we have distinguished easily between isomers 12 and 15. Aryl and alkyl shift products IQ, H, and 14 contain benzylic and allylic bromine atoms which can be hydrolized easily on column material. 

Azides 2a-g were characterized by their elemental analysis, IR, IR and 13c NMR spectra (including INAPT measurements to support the assignations of 13c NMR spectra) and MS data. 

From the analysis described above, we now know that a very important molecule that may be adsorbed together with water is OH. Also, this system has been studied quite extensively within surface science [Thiel and Madey, 1987 Bedurftig et al., 1999 Clay et al., 2004 Karlberg and Wahnstrom, 2005]. It appears that a mixed water—OH system forms a hexagonal structure much like the water stmcture discussed above (see Fig. 3.13c, d). Both from DFT calculations and UHV experiments, the most stable stmcture appears to be that where every other molecule is water and every other OH. This is interesting, since it coincides with the electrochemical observation, discussed above, where the maximum OH coverage was measured to be about one-third of a monolayer [Stamenkovic et al., 2007a]. 

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