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Selective excitation with recoupling pulse schemes uncover properties of disordered mineral phases in bone-like apatite grown with bone proteins
Solid State Nuclear Magnetic Resonance ( IF 1.8 ) Pub Date : 2023-02-23 , DOI: 10.1016/j.ssnmr.2023.101860
Irina Matlahov 1 , Alexey Kulpanovich 1 , Taly Iline-Vul 1 , Merav Nadav-Tsubery 1 , Gil Goobes 1
Affiliation  

Bone construction has been under intensive scrutiny for many years using numerous techniques. Solid-state NMR spectroscopy helped unravel key characteristics of the mineral structure in bone owing to its capability of analyzing crystalline and disordered phases at high-resolution. This has invoked new questions regarding the roles of persistent disordered phases in structural integrity and mechanical function of mature bone as well as regarding regulation of early events in formation of apatite by bone proteins which interact intimately with the different mineral phases to exert biological control.

Here, spectral editing tethered to standard NMR techniques is employed to analyze bone-like apatite minerals prepared synthetically in the presence and absence of two non-collagenous bone proteins, osteocalcin and osteonectin. A 1H spectral editing block allows excitation of species from the crystalline and disordered phases selectively, facilitating analysis of phosphate or carbon species in each phase by magnetization transfer via cross polarization. Further characterization of phosphate proximities using SEDRA dipolar recoupling, cross-phase magnetization transfer using DARR and T1/T2 relaxation times demonstrate that the mineral phases formed in the presence of bone proteins are more complex than bimodal. They reveal disparities in the physical properties of the mineral layers, indicate the layers in which the proteins reside and highlight the effect that each protein imparts across the mineral layers.



中文翻译:

具有再耦合脉冲方案的选择性激发揭示了用骨蛋白生长的骨样磷灰石中无序矿物相的特性

多年来,使用多种技术对骨骼构造进行了深入研究。固态核磁共振光谱有助于揭示骨骼矿物结构的关键特征,因为它能够以高分辨率分析结晶和无序相。这引发了关于持续无序相在成熟骨结构完整性和机械功能中的作用以及关于通过骨蛋白调节磷灰石形成的早期事件的新问题,这些骨蛋白与不同的矿物相密切相互作用以发挥生物控制作用。

在这里,使用与标准 NMR 技术相结合的光谱编辑来分析在存在和不存在两种非胶原骨蛋白、骨钙素和骨连接蛋白的情况下合成制备的类骨磷灰石矿物质。1 H 光谱编辑块允许选择性地从结晶相和无序相中激发物质,从而通过交叉极化的磁化转移促进分析每个相中的磷酸盐或碳物质使用 SEDRA 偶极耦合进一步表征磷酸盐邻近,使用 DARR 和 T 1 /T 2的交叉相磁化转移弛豫时间证明在存在骨蛋白的情况下形成的矿物相比双峰态更复杂。它们揭示了矿物层物理特性的差异,指出了蛋白质所在的层,并突出了每种蛋白质对矿物层的影响。

更新日期:2023-02-23
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