## 2 Results and Discussion
### Analysis of the Unmodified Lignin
From our previous work on birch lignin we detected evidence of significant 6-C condensation of the aromatic ring, this was detected as the chemical shift of the 5-OMe in the syringylic unit was shifted in a similar manor as the 4-OMe in the 5-condensed methylated guaiacyl unit. We did not see any such shift in the softwoods due to the fact that a condensation on the 6-position in guaiacyl units would not yield an OMe-group which has two neighboring substituents, which leads to the increase in the chemical shift. The broadening and slight shift of the HSQC correlation peaks of C\({}_{2}\)-H \(\delta_{\rm C}/\delta_{\rm H}\) (110.3/6.94) to (112.0/6.79) ppm and C\({}_{6}\)-H \(\delta_{\rm C}/\delta_{\rm H}\) (118.9/6.83) to (120.3/6.66) ppm compared to that of the MWL is caused by, among other things, the 5-condensation of the guaiacyl units [33]. The integrals of the aromatic C\({}_{2}\)-H, C\({}_{5}\)-H and C\({}_{6}\)-H from the HSQC correlation peaks gave us an indication of the condensation pattern and showed the least \begin{table}
\begin{tabular}{c c c} \hline \hline
**Label** & **\(\delta_{\rm C}\)/\(\delta_{\rm H}\) (ppm)** & **Assignment (C-H Correlation)** \\ \hline H\(\gamma\) & 21.0/1.48 & \(\gamma\) in G-hydroxyethyl ketone \\ F\({}_{\alpha}\) & 31.2/2.51 & \(\alpha\) in G-propanol \\ D\({}_{\alpha}\) & 33.9/2.53 & \(\alpha\) in secoisolariresinol \\ F\({}_{\beta}\) & 34.4/1.70 & \(\beta\) in G-propanol \\ D\({}_{\beta}\) & 42.5/1.89 & \(\beta\) in secoisolariresinol \\ C\({}_{\beta}\) & 53.1/3.47 & \(\beta\) in phenylcolumnaran \\ B\({}_{\beta}\) & 53.5/3.06 & \(\beta\) in resinol (\(\beta\)-\(\beta\)) \\ OMe & 55.5/3.76 & Methoxy peaks \\ A\({}_{\gamma}\) & 59.9/3.61 & \(\gamma\) in \(\beta\)-O-4 \\ Ey & 61.5/4.10 & \(\gamma\) in cinnamyl alcohol \\ Cy & 62.8/3.73 & \(\gamma\) in phenylcoumaran \\ J\({}_{\gamma}\) & 62.8/3.47 & \(\gamma\) in arylglycerol \\ B\({}_{\gamma}\) & 70.8/4.16 and 3.73 & \(\gamma\) in resinol \\ A\({}_{\alpha}\) & 71.06/4.76 & \(\alpha\) in \(\beta\)-O-4 \\ J\({}_{\alpha}\) & 73.5/4.45 & \(\alpha\) in arylglycerol \\ J\({}_{\beta}\) & 75.4/3.56 & \(\beta\) in arylglycerol \\ K\({}_{\alpha}\) & 83.2/4.84 & \(\alpha\) in dibenzodioxocin \\ A\({}_{\beta}\) & 84.0/4.30 & \(\beta\) in \(\beta\)-O-4 \\ B\({}_{\alpha}\) & 84.9/4.64 & \(\alpha\) in resinol (\(\beta\)-\(\beta\)) \\ K\({}_{\beta}\) & 85.4/3.89 & \(\beta\) in dibenzodioxocin \\ C\({}_{\alpha}\) & 87.0/5.47 & \(\alpha\) in phenylcoumaran \\ L\({}_{\alpha}\) & 108.9/5.56 & aryl end ether \\ G\({}_{2}\) & 110.3/6.94 & 2 in the guaiacyl unit \\ L\({}_{\beta}\) & 112.1/6.17 & Aryl end ether \\ G\({}_{5}\) & 115.2/6.85 & 5 in the guaiacyl unit \\ G\({}_{6}\) & 118.9/6.83 & 6 in the guaiacyl unit \\ I\({}_{6}\) & 123.2/7.22 & 6 in cinnamyl aldehyde \\ I\({}_{\beta}\) & 126.3/6.77 & \(\beta\) in cinnamyl aldehyde \\ M & 128.3/7.12 & Stilbene \\ E\({}_{\alpha}\) & 128.4/6.24 & \(\alpha\) in cinnamyl alcohol \\ E\({}_{\beta}\) & 128.5/6.46 & \(\beta\) in cinnamyl alcohol \\ L\({}_{\alpha^{\prime}}\) & 139.8/6.71 & Aryl end ether \\ L\({}_{\beta^{\prime}}\) & 143.0/7.31 & Aryl end ether \\ I\({}_{\alpha}\) & 153.7/7.61 & \(\alpha\) in cinnamyl aldehyde \\ N\({}_{\alpha}\) & 190.8/9.80 & Benzylic aldehyde \\ I\({}_{\gamma}\) & 193.8/9.60 & \(\gamma\) in cinnamyl aldehyde \\ \hline \hline \end{tabular}
\end{table} 
Table 1: Assignment of the identified \({}^{13}\)C-\({}^{1}\)H cross-signals.