臺灣博碩士論文加值系統

針對核磁共振及磁共振影像技術上，相較於其它光譜分析方法上，低靈敏度及低解析度一直是該技術先天上受到的限制。就目前為止，藉由超極化 (hyperpolarization) 技術、高磁場條件、低溫實驗 (<25K) 和各式脈衝序列技術來改善。相較於上述的技術，本實驗室的研究方向是藉由微型線圈以無線傳輸的方式，在應用上具有高便利性和低成本上的優勢，也可以達到提高偵測線圈的靈敏度及解析度。利用該技術在核磁共振及磁共振成像，可以使靈敏度和解析度得到進一步的改善。本工作在200 MHz和500 MHz兩個場下，對不同核種（1H, 31P, 23Na, 79Br）使用的微線圈之管徑、匝數、匝間距離等參數進行優化，以獲取最佳靈敏度。此外，我們發現當待測樣品塗布在管壁外圍且與偵測線圈緊密接觸下，相較於將待測樣品填充在裝置的管柱內，可以得到更好偵測訊號，我們稱此技術為表面微線圈魔角旋轉(Micro Surface Coil Magic Angle Spinning，MISCMAS)。這個技術對於微量樣品之NMR檢測能夠進一步降低偵測極限。

The most critical problem of NMR spectroscopy and magnetic resonance imaging (MRI) is the relatively low sensitivity compared to other forms of spectroscopy, limiting the applicability of these techniques. Most of the existing research focused on trying to alleviate these problems through hyperpolarization techniques, strong magnetic fields, low temperature experiments (<25K), and pulse sequence development. Going beyond the previously stated methods, researchers found that the implementation of smaller resonant coils is a more convenient and effective way to alleviate the problem of low sensitivity in NMR spectroscopy and magnetic resonance imaging. In this work, a systematic optimization of the parameters for micro-coil probes and magic-angle coil spinning (MACS) probes was carried out with various common NMR nuclear species such as 1H, 31P, 23Na, 79Br on two NMR spectrometers (200 MHz and 500 MHz). The optimized wire diameter, coil diameter, number of turns, the inner and outer diameters of the capillary, the matching capacitors etc have been obtained and demonstrated with a real biological system. In addition, we found that the conventional placement of the sample within the glass tube wrapped by a coil yields a lower signal and sensitivity when compared to coating the sample onto the coil prior to wrapping around the capillary. A new method of performing MACS experiment with micro-coil technology, therefore, was subsequently proposed, namely, micro surface coil magic angle spinning (MISCMAS). The optimized experimental conditions were then determined with both liquid and solid state samples.

第壹章 緒論
1-1前言 1
1-2靈敏度 2
1-3微線圈技術 4
第貳章 文獻探討 5
第參章 螺旋管微線圈偵測裝置
3-1研究動機 11
3-1-1螺旋管型微線圈分析 13
3-1-2 RLC電路與元件 14
3-1-3電感及電容元件 15
3-2 MACS (magic-angle coil spinning) 16
第肆章 結果與討論
4.1實驗儀器與裝置 18
4.2微線圈 21
4-2-1微線圈諧振條件 21
4-2-2微線圈條件下各種探針訊號比較 48
4-2-3當激發射頻功率增強待測樣品pw的變化 54
4-3微線圈應用示例 56
4-3-1利用微線圈測量微量成份 56
4-3-2發現微線圈的一個特殊現象及MISCMAS (Micro Surface Coil Magic Angle Spinning)的提出 58
4-4微線圈於500 NMR下不同探針參數比較 68
4-4-1氫探針於NMR 500場下，改變纏繞漆包線線徑 68
4-4-2磷探針於NMR 500場下，改變纏繞漆包線線徑 71
4-4-3鈉探針於NMR 500場下，改變纏繞漆包線線徑及毛細管管徑 74
4-4-4溴探針於NMR 500場下，改變纏繞漆包線線徑 82
4-4-5各核種於NMR 500場下，改變纏繞漆包線線徑所必須搭配條件 85
4-4-6比較不同玻璃管徑下訊號差異 86
4-4-7比較不同漆包線線徑下訊號差異 86
4-5比較不同漆包線線徑在四種樣品塗布方式下訊號之差異 92
第伍章 結論 100
參考文獻 102

(1) Sakellariou, D.; Goff, G. L.; Jacquinot, J. F. Nature 2007, 447, 694.
(2) Lacey, M. E.; Subramanian, R.; Olson, D. L.; Webb, A. G.; Sweelder, J. V. Chem. Rev. 1999, 99, 3133.
(3) Olson, D. L.; Peck, T. L.; Webb, A. G.; Magin, R. L.; Sweedler, J. V. Science 1995, 270, 1967.
(4) Ardenkjae, J.H. Proc. Natl Acad. Sci. USA 100, 2003, 10158.
(5) Grey, C. P.; Tycko, R. Phys.Toda 2009, 62, 44.
(6) Brown, S. P. Prog. NMR Spectrosc. 2007, 50, 199.
(7) Brown, S. P. Macromol. Rapid Commun. 2009, 30, 688.
(8) Minard, K. R.; Guo, X.; Wind, R. A. J. Magn. Reson. 1998, 133, 368.
(9) Shoeniger, J. S.; Aiken, N.; Hsu, E.; Blackband, S. J. J. Magn. Reson. 1994, 103, 261.
(10) Bowtell, R. W.; Peters, A.; Sharp, J. C.; Mansfield, P.; Hsu, E. W.; Aiken, N.; Horsman, A.; Blackband, S. J. Magn. Reson. Med. 1995, 33, 790.
(11) Brandl, M.; Tonn, J. C.; Kotitschke, K.; Goldbrunner, R.; Kerkau, S.; Haase, A. Magn. Reson. Med. 1995, 34, 596.
(12) Shoeniger, S. J.; Blackband, S. J. J. Magn. Reson. 1994, 104, 127.
(13) Hoult, D. I.; Lauterbur, P. C. J. Magn. Reson. 1979, 34, 425.
(14) Gadian, D. G.; Robinson, F. N. H. J. Magn. Reson. 1979, 34, 449.
(15) Odeblad, E. Nordisk Forening for Obsterik och Gynekologi, Lund, Sweden, 1966.
(16) Timothy, L. P.; Richard, L. M.; Lauterbur, P. C. J. Magn. Reson. Series B. 1995, 108, 114.
(17) Webb, A. G. Prog. Nucl. Magn. Reson. Spectrosc. 1997, 31, 1.
(18) Wu, N.; Peck, T. L.; Webb, A. G.; Magin, R. L.; Sweedler, J. V. Anal. Chem. 1994, 66, 3849.
(19) Behnia, B.; Webb, A. G. Anal. Chem. 1998, 70, 5326.
(20) Seeber, D. A.; Cooper, R. L.; Ciobanu, L.; Pennington, C. H. Rev. Sci. Instrum. 2001, 72, 4.
(21) Seeber, D. A.; Hoftiezer, J. H.; Daniel, W. B.; Rutgers, M. A.; Pennington, C. H. Rev. Sci. Instrum. 2000, 71, 4263.
(22) Rogers, J. A.; Jackman, R. J.; Whitesidesa, G. M.; Olson, D. L.; Sweedler, J. V. Appl. Phys. Lett. 1997, 70, 18.
(23) Ciobanu, L.; Seeber, D.A.; Pennington, C. H. J. Magn. Reson. 2002, 158, 178.
(24) Yamauchi, K; Asakura, T. Chem. Lett. 2006, 35, 426.
(25) Janssen, J. W. G.; Brinkmann, A.; vanEck, E. R. H.; vanBentum, P. J. M.; Kentgens, A. P. M. J. Am. Chem. Soc. 2006, 128, 8722.
(26) Inukai, M.; Takeda, K. Concepts Magn. Reson. 2008, B33, 115.
(27) Inukai, M.; Takeda, K. J. Magn. Reson. 2010, 202, 274.
(28) Shoolery, J. N. Varian Instrum. Appl. 1976, 10, 18.
(29) Shoolery, J. N.; Wehrli, F.; Wirthlin, T. Chem. Technol. 1977, 6, 55.
(30) Lacey, M. E.; Subramanian, R.; Olson, D. L.; Webb, A. G.; Sweelder, J. V. Chem. Rev. 1999, 99, 3133.
(31) Hoult, D. I.; Richards, R. E. J. Magn. Reson. 1976, 24, 71.