Surmik Dawid, Boczarowski Andrzej, Balin Katarzyna, Dulski Mateusz, Szade Jacek, Kremer Barbara, Pawlicki Roman
Faculty of Earth Science, University of Silesia, Będzińska 60, 41-200, Sosnowiec, Poland.
Park of Science & Human Evolution, 1 Maja 10, 46-040, Krasiejów, Poland.
PLoS One. 2016 Mar 15;11(3):e0151143. doi: 10.1371/journal.pone.0151143. eCollection 2016.
Fossil biomolecules from an endogenous source were previously identified in Cretaceous to Pleistocene fossilized bones, the evidence coming from molecular analyses. These findings, however, were called into question and an alternative hypothesis of the invasion of the bone by bacterial biofilm was proposed. Herewith we report a new finding of morphologically preserved blood-vessel-like structures enclosing organic molecules preserved in iron-oxide-mineralized vessel walls from the cortical region of nothosaurid and tanystropheid (aquatic and terrestrial diapsid reptiles) bones. These findings are from the Early/Middle Triassic boundary (Upper Roetian/Lowermost Muschelkalk) strata of Upper Silesia, Poland. Multiple spectroscopic analyses (FTIR, ToF-SIMS, and XPS) of the extracted "blood vessels" showed the presence of organic compounds, including fragments of various amino acids such as hydroxyproline and hydroxylysine as well as amides, that may suggest the presence of collagen protein residues. Because these amino acids are absent from most proteins other than collagen, we infer that the proteinaceous molecules may originate from endogenous collagen. The preservation of molecular signals of proteins within the "blood vessels" was most likely made possible through the process of early diagenetic iron oxide mineralization. This discovery provides the oldest evidence of in situ preservation of complex organic molecules in vertebrate remains in a marine environment.
此前通过分子分析在白垩纪至更新世的化石骨骼中鉴定出了内源性来源的化石生物分子。然而,这些发现受到了质疑,并有人提出了细菌生物膜侵入骨骼的另一种假说。在此,我们报告一项新发现,在幻龙类和长颈龙类(水生和陆生双孔亚纲爬行动物)骨骼皮质区域的氧化铁矿化血管壁中,发现了形态保存完好的类似血管的结构,其中包裹着有机分子。这些发现来自波兰上西里西亚的早/中三叠世边界(上罗特阶/下木舍尔阶)地层。对提取的“血管”进行的多种光谱分析(傅里叶变换红外光谱、飞行时间二次离子质谱和X射线光电子能谱)显示存在有机化合物,包括各种氨基酸的片段,如羟脯氨酸和羟赖氨酸以及酰胺,这可能表明存在胶原蛋白残基。由于除胶原蛋白外的大多数蛋白质中都不存在这些氨基酸,我们推断这些蛋白质分子可能源自内源性胶原蛋白。“血管”内蛋白质分子信号的保存很可能是通过早期成岩氧化铁矿化过程实现的。这一发现为海洋环境中脊椎动物遗骸原位保存复杂有机分子提供了最古老的证据。