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Aims: Afforestation causes important alterations in SOM content and composition that affect the soil functions and C balance. The aim of this study was to identify the mechanisms that determine the changes in SOM composition following afforestation of grasslands. Methods: The study included 4 chronosequences and 5 paired plots comprising pastures and land afforested with Pinus radiata. The SOM was characterized by C CP-MAS NMR spectroscopy and differential scanning calorimetry. Results: During the first 10-20 year after afforestation, the changes in SOM content varied from slight gains to large losses (>40 %). The analyses revealed that even SOM compounds considered resistant to decomposition were degraded during this time. The SOM gains, observed 20 year after stand establishment, were favoured by the higher recalcitrance of pine litter and possibly by soil acidification. The concentrations of most SOM compounds, particularly the stable compounds, were higher at the end of the rotation. The low degree of protection, along with the favourable climatic conditions, may also explain the rapid decomposition of SOM, including resistant compounds, in these soils. DSC analysis complemented the information about SOM composition provided by other techniques. Conclusions: The accumulation of stable SOM compounds at the end of the rotation suggests a longer soil C turnover in these afforested soils, which may alleviate the gradual loss of SOC in intensively managed forest soils. [ABSTRACT FROM AUTHOR]

A 2D-HSQC-carbon selective/proton selective-constant time COSY, 2D-HSQC-(sel C, sel H)-CT COSY experiment, which is applicable to uniformly 13C isotopically enriched samples (U-13C) of oligosaccharides or oligonucleotides is proposed for the measurement of proton–proton RDC in crowded regions of 2D-spectra. In addition, a heteronuclear constant time-COSY experiment, 13C-13C CT-COSY, is proposed for the measurement of one bond carbon–carbon RDC in these molecules. These two methods provide an extension, to U-13C molecules, of the original homonuclear constant time-COSY experiment proposed by Tian et al. (1999) for saccharides. The combination of a number of these RDC with NOE data may provide the method of choice to study oligosaccharide conformation in the free and receptor-bound state. [ABSTRACT FROM AUTHOR]

The heptasaccharide isolated from the cell wall polysaccharide of Streptococcus mitis J22 serves as an important model for the dynamics and conformation of complex polysaccharides, illustrating the nature of flexibility with rigid epitopes joined by flexible hinges. One-bond C-H residual dipolar couplings (1DCH) and long-range H-H residual dipolar couplings (nDHH) were measured for the heptasaccharide in a cetylpyridinium chloride/hexanol/brine lamellar liquid crystal medium. A method is proposed to determine the nDHH in natural abundance based on a 13C resolved 1H TOCSY pulse sequence previously published to determine the homonuclear scalar couplings. Different methods for interpretation of the 1DCH and the nDHH residual dipolar coupling data obtained were compared and combined with the NOE and long-range H,C and C,C scalar couplings available for this heptasaccharide. A flexible model of the heptasaccharide was determined in which two structurally well-defined regions involving four and two sugar residues, respectively are joined by a flexible hinge which involves two 1→6 glycosidic linkages. [ABSTRACT FROM AUTHOR]

The conformational and dynamical features of a branched mannan isolated from a fungal cell wall have been analysed by homo and heteronuclear NMR methods, employing different magnetic fields. 1HNMR cross relaxation times have been obtained for this polysaccharide and have been interpreted qualitatively using different motional models. 13C NMR relaxation parameters (T1, T2, NOE) have also been measured and interpreted using different approximations based on the Lipari and Szabo model free approach. The analysis of the data indicate the existence of important flexibility for the different linkages of the polysaccharide. Motions in the range of 4–6 ns contribute to the relaxation of the macromolecule, although faster internal motions in the 500 ps and 100 ps timescales are also present. These time scales indicate that segmental motions as well as internal motions around the glycosidic linkages are the major sources of relaxation for this molecule at 318 K. Molecular dynamics simulations have also been performed. The obtained results also indicate that the polysaccharide possess a substantial amount of conformational freedom. [ABSTRACT FROM AUTHOR]