Woess Claudia, Unterberger Seraphin Hubert, Roider Clemens, Ritsch-Marte Monika, Pemberger Nadin, Cemper-Kiesslich Jan, Hatzer-Grubwieser Petra, Parson Walther, Pallua Johannes Dominikus
Institute of Legal Medicine, Medical University of Innsbruck, Innsbruck, Austria.
Material-Technology, Leopold-Franzens University Innsbruck, Innsbruck, Austria.
PLoS One. 2017 Mar 23;12(3):e0174552. doi: 10.1371/journal.pone.0174552. eCollection 2017.
Due to the influence of many environmental processes, a precise determination of the post-mortem interval (PMI) of skeletal remains is known to be very complicated. Although methods for the investigation of the PMI exist, there still remains much room for improvement. In this study the applicability of infrared (IR) microscopic imaging techniques such as reflection-, ATR- and Raman- microscopic imaging for the estimation of the PMI of human skeletal remains was tested. PMI specific features were identified and visualized by overlaying IR imaging data with morphological tissue structures obtained using light microscopy to differentiate between forensic and archaeological bone samples. ATR and reflection spectra revealed that a more prominent peak at 1042 cm-1 (an indicator for bone mineralization) was observable in archeological bone material when compared with forensic samples. Moreover, in the case of the archaeological bone material, a reduction in the levels of phospholipids, proteins, nucleic acid sugars, complex carbohydrates as well as amorphous or fully hydrated sugars was detectable at (reciprocal wavelengths/energies) between 3000 cm-1 to 2800 cm-1. Raman spectra illustrated a similar picture with less ν2PO43-at 450 cm-1 and ν4PO43- from 590 cm-1 to 584 cm-1, amide III at 1272 cm-1 and protein CH2 deformation at 1446 cm-1 in archeological bone material/samples/sources. A semi-quantitative determination of various distributions of biomolecules by chemi-maps of reflection- and ATR- methods revealed that there were less carbohydrates and complex carbohydrates as well as amorphous or fully hydrated sugars in archaeological samples compared with forensic bone samples. Raman- microscopic imaging data showed a reduction in B-type carbonate and protein α-helices after a PMI of 3 years. The calculated mineral content ratio and the organic to mineral ratio displayed that the mineral content ratio increases, while the organic to mineral ratio decreases with time. Cluster-analyses of data from Raman microscopic imaging reconstructed histo-anatomical features in comparison to the light microscopic image and finally, by application of principal component analyses (PCA), it was possible to see a clear distinction between forensic and archaeological bone samples. Hence, the spectral characterization of inorganic and organic compounds by the afore mentioned techniques, followed by analyses such as multivariate imaging analysis (MIAs) and principal component analyses (PCA), appear to be suitable for the post mortem interval (PMI) estimation of human skeletal remains.
由于受到多种环境过程的影响,已知精确测定骨骼遗骸的死后间隔时间(PMI)非常复杂。尽管存在用于调查PMI的方法,但仍有很大的改进空间。在本研究中,测试了红外(IR)显微成像技术(如反射显微镜成像、衰减全反射(ATR)显微镜成像和拉曼显微镜成像)在估计人类骨骼遗骸PMI方面的适用性。通过将红外成像数据与使用光学显微镜获得的形态组织结构叠加,以区分法医和考古骨骼样本,从而识别并可视化PMI的特定特征。ATR光谱和反射光谱显示,与法医样本相比,考古骨骼材料在1042 cm-1处有一个更突出的峰(骨矿化的指标)。此外,对于考古骨骼材料,在3000 cm-1至2800 cm-1(倒数波长/能量)之间可检测到磷脂、蛋白质、核酸糖、复合碳水化合物以及无定形或完全水合糖的水平降低。拉曼光谱呈现出类似的情况,在考古骨骼材料/样本/来源中,450 cm-1处的ν2PO43-和590 cm-1至584 cm-1处的ν4PO43-较少,1272 cm-1处的酰胺III和1446 cm-1处的蛋白质CH2变形较少。通过反射法和ATR法的化学图谱对各种生物分子分布进行半定量测定,结果表明,与法医骨骼样本相比,考古样本中的碳水化合物、复合碳水化合物以及无定形或完全水合糖较少。拉曼显微镜成像数据显示,在PMI为3年后,B型碳酸盐和蛋白质α-螺旋减少。计算得出的矿物质含量比和有机与矿物质比表明,矿物质含量比随时间增加,而有机与矿物质比随时间降低。与光学显微镜图像相比,拉曼显微镜成像数据的聚类分析重建了组织解剖特征,最后,通过应用主成分分析(PCA),可以清楚地区分法医和考古骨骼样本。因此,通过上述技术对无机和有机化合物进行光谱表征,随后进行多变量成像分析(MIA)和主成分分析(PCA)等分析,似乎适用于人类骨骼遗骸的死后间隔时间(PMI)估计。