Biological and Biomimetic Materials Laboratory, Center for Sustainable Materials (SusMat), School of Materials Science and Engineering, Nanyang Technological University (NTU), 50 Nanyang Avenue, 639798, Singapore.
Center for Integrated Materials Research, Department of Chemistry and iNANO, Aarhus University, Gustav Wieds Vej 14, 8000 Aarhus, Denmark; Sino-Danish Center for Education and Research, University of Chinese Academy of Sciences.
Acta Biomater. 2023 Oct 15;170:479-495. doi: 10.1016/j.actbio.2023.08.054. Epub 2023 Sep 1.
The stomatopod Odontodactylus scyllarus uses weaponized club-like appendages to attack its prey. These clubs are made of apatite, chitin, amorphous calcium carbonate, and amorphous calcium phosphate organized in a highly hierarchical structure with multiple regions and layers. We follow the development of the biomineralized club as a function of time using clubs harvested at specific times since molting. The clubs are investigated using a broad suite of techniques to unravel the biomineralization history of the clubs. Nano focus synchrotron x-ray diffraction and x-ray fluorescence experiments reveal that the club structure is more organized with more sub-regions than previously thought. The recently discovered impact surface has crystallites in a different size and orientation than those in the impact region. The crystal unit cell parameters vary to a large degree across individual samples, which indicates a spatial variation in the degree of chemical substitution. Energy dispersive spectroscopy and Raman spectroscopy show that this variation cannot be explained by carbonation and fluoridation of the lattice alone. X-ray fluorescence and mass spectroscopy show that the impact surface is coated with a thin membrane rich in bromine that forms at very initial stages of club formation. Proteomic studies show that a fraction of the club mineralization protein-1 has brominated tyrosine suggesting that bromination of club proteins at the club surface is an integral component of the club design. Taken together, the data unravel the spatio-temporal changes in biomineral structure during club formation. STATEMENT OF SIGNIFICANCE: Mantis shrimp hunt using club-like appendages that contain apatite, chitin, amorphous calcium carbonate, and amorphous calcium phosphate ordered in a highly hierarchical structure. To understand the formation process of the club we analyze clubs harvested at specific times since molting thereby constructing a club formation map. By combining several methods ranging from position resolved synchrotron X-ray diffraction to proteomics, we reveal that clubs form from an organic membrane with brominated protein and that crystalline apatite phases are present from the very onset of club formation and grow in relative importance over time. This reveals a complex biomineralization process leading to these fascinating biomineralized tools.
十足目口虾蛄 Odontodactylus scyllarus 使用武器化的棍棒状附肢来攻击猎物。这些棍棒由磷灰石、几丁质、无定形碳酸钙和无定形磷酸钙组成，具有高度分层的结构，具有多个区域和层。我们通过在蜕皮后特定时间收获的棍棒来研究生物矿化棍棒的发育过程。我们使用广泛的技术套件来研究棍棒，以揭示棍棒的生物矿化历史。纳米焦点同步加速器 X 射线衍射和 X 射线荧光实验表明，与之前的想法相比，棍棒结构更加有序，具有更多的亚区。最近发现的撞击面的晶体具有与撞击区不同的尺寸和取向。晶体的晶胞参数在单个样本之间有很大的变化，这表明化学取代程度存在空间变化。能量色散光谱和拉曼光谱表明，这种变化不能仅用晶格的碳化和氟化来解释。X 射线荧光和质谱表明，撞击面覆盖着一层富含溴的薄膜，该薄膜在棍棒形成的最初阶段形成。蛋白质组学研究表明，部分棍棒矿化蛋白-1 具有溴化酪氨酸，这表明在棍棒表面的棍棒蛋白的溴化是棍棒设计的一个组成部分。综上所述，这些数据揭示了在棍棒形成过程中生物矿化结构的时空变化。意义声明：螳螂虾使用包含磷灰石、几丁质、无定形碳酸钙和无定形磷酸钙的棍棒状附肢进行狩猎，这些物质按高度分层的结构有序排列。为了了解棍棒的形成过程，我们分析了自蜕皮以来特定时间收获的棍棒，从而构建了一个棍棒形成图。通过结合从位置分辨同步加速器 X 射线衍射到蛋白质组学的几种方法，我们揭示了棍棒是从带有溴化蛋白的有机膜形成的，并且结晶磷灰石相从棍棒形成的初始阶段就存在，并且随着时间的推移其重要性逐渐增加。这揭示了一个复杂的生物矿化过程，导致了这些迷人的生物矿化工具的形成。
