Development of 14N high-resolution solid-state NMR and its application

14N高分辨率固态核磁共振的研制及其应用

• 批准号: 14340181
• 负责人: TAKEGOSHI Kiyonori
• 金额: $ 8.26万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-14340181/
• 关键词: Nitorogen-14; Quadrupole interaction; Overtone NMR

The aim of this work is to build a new NMR system for a ^<14>N high-resolution NMR method developed recently by us, and further apply to structural studies of biomolecules such as peptides. In the two years, we did(1) Construction of a new NMRE systemTo realize the best experimental condition for ^<14>N observation, a triple-resonance MAS probe was purchased and tuned for our current NMR system. Further, a stabilizer for the MAS speed was developed.(2) Theoretical calculation of indirectly observed ^<14>N lineshapeFor small molecules with known ^<14>N quadrupole coupling constants, we applied ab-initio molecular orbital calculation (GAUSSIAN98) to evaluate quadrupole coupling constants.(3) Determination of α helix and β sheetTheoretical calculation was done for model molecules having α helix or β sheet structures to simulate ^<14>N lineshapes. It was found that these two secondary structures can be distinguished by the present ^<14>N observation. Hence, we prepared 7 peptides, whose secondary structures were known to be either α helix or β sheet. While observed ^<14>N lineshapes indicate it is possible to discriminate the secondary structures, the tendency is opposite to that predicted by ab initio calculation. Presently, we re-examine ab initio calculation.

这项工作的目的是为我们最近开发的高分辨率核磁共振方法建立一个新的核磁共振系统，并进一步应用于多肽等生物分子的结构研究。在这两年中，我们进行了以下工作：(1)建立了一个新的NMRE系统，为实现观测的最佳实验条件，为我们现有的核磁共振系统购买并调谐了一个三共振MAS探头。(2)间接观测线型的理论计算对于已知四极耦合常数的小分子，我们应用从头算分子轨道计算(GAUSSIAN98)来计算四极耦合常数。(3)α螺旋和β层的确定对具有α螺旋或β片状结构的模型分子进行了理论计算，模拟了^&lt；14&gt；N线型。结果表明，这两种二级结构可以通过现在的观测来区分。因此，我们制备了7个多肽，它们的二级结构被认为是α螺旋或β折叠。虽然观察到的线形表明有可能区分二级结构，但这种趋势与从头计算预测的相反。目前，我们重新检查从头计算。

项目成果

T.Miyoshi: "Effects of Xe Gas on Segmental Motion in a Polymer Blend As Studied by ^<13>C and ^<129>Xe High-Pressure MAS NMR"Macromolecules. 35(1). 151-154 (2002)

T.Miyoshi：“通过 13 C 和 129 Xe 高压 MAS NMR 研究 Xe 气体对聚合物共混物中链段运动的影响”大分子。

Y.Nishiyama: "Chemical-shift γ-encoding nuclear magnetic resonance for uniaxially oriented matter under sample spinning"J.Chem.Phys.. 119(16). 3297-3308 (2003)

Y. Nishiyama：“样品旋转下单轴取向物质的化学位移 γ 编码核磁共振”J.Chem.Phys.. 119(16) (2003)。

Y.Nishiyama: "^<13>C NMR spectral assignments for nematic liquid crystals by 2D chemical shift γ-encoding NMR"J.Magn.Reson.. 158(1/2). 60-64 (2002)

Y.Nishiyama：“通过2D化学位移γ-编码NMR对向列液晶的^ 13 C NMR光谱分配”J.Magn.Reson..158(1/2)(2002)。

F.Amita: "Development of a high-temperature and high-pressure nuclear magnetic resonance probe for studies of chemical reactions in supercritical water"Rev.Sci.Instrum. 75(2). 467-471 (2004)

F.Amita：“开发用于研究超临界水化学反应的高温高压核磁共振探针”Rev.Sci.Instrum。

K.Takegoshi, N.Nakamura, T.Terao: "^<13>C-^1H dipolar-driven ^<13>C-^<13>C recoupling without ^<13>C rf irradiation in nuclear magnetic resonance of rotating solids"J.Chem.Phys.. 118(5). 2325-234 (2003)

K.Takegoshi、N.Nakamura、T.Terao：“旋转核磁共振中 ^<13>C-^1H 偶极驱动 ^<13>C-^<13>C 重耦合，无需 ^<13>C 射频辐射