Cogulet Antoine, Blanchet Pierre, Landry Véronic
Département des sciences et de la forêt, Pavillon Gene H. Kruger, 2425, rue de la terrasse, université Laval, Québec, G1V 0A6, Québec, Canada.
Département des sciences et de la forêt, Pavillon Gene H. Kruger, 2425, rue de la terrasse, université Laval, Québec, G1V 0A6, Québec, Canada.
J Photochem Photobiol B. 2016 May;158:184-91. doi: 10.1016/j.jphotobiol.2016.02.030. Epub 2016 Mar 6.
The photodegradation of white spruce by artificial ageing was studied by several techniques: colourimetry, FTIR-ATR and FT-Raman spectroscopy. Samples were exposed at a xenon lamp for 2000h. Two distinct colour changes were found by colourimetric analysis, yellowing and silvering. These colour modifications indicate the formation of chromophoric structures which supports previous FTIR-ATR experiments. The degradation of lignin to generate the first chromophoric group for yellowing and then the appearance of surface layer cellulose. New carbonyl compounds conjugated with double bond at 1615cm(-1) are probably the second chromophoric group. The crystallinity index was also calculated and showed an increase of cellulose crystallinity by prior degradation of amorphous cellulose. The FT-Raman analysis confirms the wood sensitivity to photodegradation but the most remarkable results is the increase of fluorescence as a function of time. In softwood lignin, the compound able to produce fluorescence is a free rotating 5-5' linkage of one biphenyl structure. At native state these linkages are not free rotating, this phenomenon means the release of 5-5' linkage of lignin structure by cleavage of both α carbon linkages (Norrish type I reaction). These data confirm also the photosensitivity of α and β carbon in lignin and the resistance of 5-5' linkages.
通过比色法、傅里叶变换红外衰减全反射光谱法(FTIR-ATR)和傅里叶变换拉曼光谱法等几种技术研究了人工老化对白云杉的光降解作用。样品在氙灯下暴露2000小时。比色分析发现了两种明显的颜色变化,即变黄和变银。这些颜色变化表明形成了发色结构,这支持了先前的FTIR-ATR实验。木质素降解产生第一个用于变黄的发色基团,随后表面层纤维素出现。在1615cm(-1)处与双键共轭的新羰基化合物可能是第二个发色基团。还计算了结晶度指数,结果表明无定形纤维素的预先降解使纤维素结晶度增加。傅里叶变换拉曼分析证实了木材对光降解的敏感性,但最显著的结果是荧光随时间增加。在软木木质素中,能够产生荧光的化合物是一种联苯结构的自由旋转5-5'键。在天然状态下,这些键不是自由旋转的,这种现象意味着通过α碳键的断裂(Norrish I型反应)释放木质素结构的5-5'键。这些数据也证实了木质素中α和β碳的光敏感性以及5-5'键的抗性。