Heat treatment at relatively high temperatures (from 150 to 260 degrees C is an effective method to improve the durability of wood. This study investigates the reasons for the decay resistance of heat-treated and nontreated wood with respect to the polymeric structural constituents by solid-state cross-polarization/magic-angle spinning (CP-MAS) C-13-NMR analysis before and after exposure to brown rot and white rot fungi. An industrial two-stage heat-treatment method under relatively mild conditions (< 200 degrees C) has been used to treat the samples. Brown rot fungi attack polymeric carbohydrates of nontreated Scots pine sapwood at C4, resulting in cleavage and eventually depolymerization of cellulose and hemicelluloses. The attack at the carbohydrate C6, which has never been observed before, is remarkable because the C6-CH2OH group has no covalent structural function but acts in fixing the three-dimensional carbohydrate configuration just by secondary forces. The -CH,OH group carries -OH, which forms some of the strongest hydrogen bonds in the structure of the crystalline native cellulose. It is suggested that the fungus tries to cleave this group to open the cellulose crystalline structure into an amorphous structure to decrease its water repellency to facilitate enzymatic cellulose degradation. Considerable degradation of the hemicelluloses occurs during brown rot fungal exposure, whereas in general the attack on lignin is rather limited, being mainly demethoxylation. However, Gloeophyllum trabeum is an active brown rot fungus in the (partial) degradation of lignin because there is some indication of ring opening of the aromatic ring of lignin during fungal exposure. Aromatic ring opening has also been observed after exposure to Coriolus versicolor, a white rot fungus. The demethoxylation of lignin and some attack on wood carbohydrates are also characteristic of the attack of this white rot fungus. The CP-MAS C-13-NMR spectra of heat-treated Norway spruce reveal similarities but also clear differences after fungal exposure in comparison with non-treated Scots pine sapwood. Brown rot fungi seem to have a preference to attack the carbohydrates of heat-treated wood at C4 and especially C1, cleaving the skeleton of cellulose and glucomannans. In untreated Scots pine sapwood, this attack mainly occurs at C4, the nonreducing end of the glucose unit. An attack on the out-of-the-ring alcoholic group -CH2,OH of the carbohydrates of heat-treated Norway spruce is less obvious than that in untreated Scots pine. The attack on C3/C5 of the carbohydrates is remarkable, indicating ring opening of the glucose units, which has not been observed in nontreated Scots pine sapwood. Lignin degradation is limited to demethoxylation, and low or no aromatic ring opening is observed, even after C. versicolor exposure. (c) 2006 Wiley Periodicals, Inc.