Department of Wood Science and Thermal Techniques, Faculty of Forestry and Wood Technology, Poznan University of Life Sciences, ul. Wojska Polskiego 38/42, 60-637 Poznan, Poland.
Forest Biopolymers Science and Engineering, Forest Products Laboratory, USDA Forest Service, One Gifford Pinchot Drive, Madison, WI 53726, USA.
Molecules. 2022 May 25;27(11):3407. doi: 10.3390/molecules27113407.
Some organosilicon compounds, including alkoxysilanes and siloxanes, proved effective in stabilizing the dimensions of waterlogged archaeological wood during drying, which is essential in the conservation process of ancient artifacts. However, it was difficult to determine a strong correlation between the wood stabilizing effect and the properties of organosilicon compounds, such as molecular weight and size, weight percent gain, and the presence of other potentially reactive groups. Therefore, to better understand the mechanism behind the stabilization effectiveness, the reactivity of organosilicons with wood polymers was studied using a 2D H-C solution-state NMR technique. The results showed an extensive modification of lignin through its demethoxylation and decarbonylation and also the absence of the native cellulose anomeric peak in siloxane-treated wood. The most substantial reactivity between wood polymers and organosilicon was observed with the (3-mercaptopropyl)trimethoxysilane treatment, showing complete removal of lignin side chains, the lowest syringyl/guaiacyl ratio, depolymerization of cellulose and xylan, and reactivity with the C6 primary hydroxyls in cellulose. This may explain the outstanding stabilizing effectiveness of this silane and supports the conclusion that extensive chemical interactions are essential in this process. It also indicates the vital role of a mercapto group in wood stabilization by organosilicons. This 2D NMR technique sheds new light on the chemical mechanisms involved in organosilicon consolidation of wood and reveals what chemical characteristics are essential in developing future conservation treatments.
一些有机硅化合物,包括烷氧基硅烷和硅氧烷,已被证明在干燥过程中稳定饱水考古木材尺寸方面非常有效,这对于古代文物的保护过程至关重要。然而,很难确定木材稳定效果与有机硅化合物的性质(如分子量和大小、重量百分比增益以及其他潜在反应性基团的存在)之间存在很强的相关性。因此,为了更好地理解稳定效果的机制,使用二维 H-C 溶液态 NMR 技术研究了有机硅与木材聚合物的反应性。结果表明,木质素通过脱甲氧基和脱羰基得到了广泛的修饰,并且在硅氧烷处理的木材中不存在天然纤维素的端基峰。在与木材聚合物反应性最强的是(3-巯丙基)三甲氧基硅烷处理,其显示出木质素侧链的完全去除、最低的愈创木基/松柏基比率、纤维素和木聚糖的解聚以及与纤维素 C6 伯羟基的反应。这可能解释了这种硅烷出色的稳定效果,并支持了这样的结论,即该过程中需要广泛的化学相互作用。它还表明巯基在有机硅稳定木材中的重要作用。这项二维 NMR 技术为有机硅稳定木材的化学机制提供了新的见解,并揭示了在开发未来保护处理中哪些化学特性是必不可少的。