臺灣博碩士論文加值系統

　　在連續兩個做為低通濾波器的小波轉換程序中間利用內積修飾雜訊的譜圖來改善液相串聯式質譜儀訊號的訊雜比。
　　用一個簡單的化學計量方法來處理經過一次小波轉換的LC-MS/MS層析圖，在要經第二次小波轉換之前，先與一個加有熱雜訊的人造方波進行內積的計算。只利用兩個連續的小波轉換中間沒經內積計算來處理LC-MS/MS層析圖，與只用一次小波轉換來處理的圖譜比較，無法更有效地改善訊號的雜訊比；經第一次小波轉換後只剩較低頻的訊號及雜訊，因為第二次小波轉換也為一個低通濾波器，直接再經第二次小波轉換仍無法消除低頻的雜訊。內積是為了修飾經第一次小波轉換後層析圖上的雜訊，因內積後含有高頻率的組成雜訊，當雜訊圖移到高頻區，再經第二次小波轉換來處理LC-MS/MS層析圖可以更有效的提升雜訊比。
　　利用小波轉換來處理消除之前使用匹配濾波器（亦為低通濾波器的一種）造成訊號變寬的缺點，處理後圖譜檢量線的回歸係數仍都在0.999以上，且處理完回推濃度的誤差也較原始的小，又因S/N的改善可降低偵測極限及定量極限。在一組QC sample數據裡，處理完回推濃度的誤差及標準差也都比原始的小，藉此來改善精確度及準確度。

A simple chemometric technique alter the noise spectrum of liquid chromatography – mass spectrometry (LC-MS/MS) chromatogram between two consecutive wavelet-based low-pass filtering procedures to improve the peak signal-to-noise (S/N) ratio enhancement. When only the components of appromiximation coefficients are recovered to construc the waveform, the wavelet transform works as a low-pass filter. This technique is to multiply one wavelet transform filtered LC-MS/MS chromatogram with another artificial chromatogram added with thermal noises prior to the other wavelet transform filter. Because wavelet transform cannot eliminate lower frequency components, more efficient peak S/N ratio improvement cannot be accomplished using consecutive wavelet transform filter procedures to process LC-MS/MS chromatograms. In contrast, when the wavelet transform filtered LC-MS/MS chromatogram is conditioned with the multiplication alteration prior to the other wavelet transform filter, much better ratio improvement is achieved. The noise frequency spectrum of wavelet transform filtered chromatogram, which originally contains lower frequency components, is altered to span a higher range with multiplication operation. When the frequency range of this modified noise spectrum shifts toward the other regimes, the other s wavelet transform filter, working as a low-pass filter, is able to provide better filtering efficiency to obtain higher peak S/N ratios.
In contrast to the procedures of using noise-modification between two matched filters, these new procedures do not result in broaden peaks. In addition, tedious tuning of wavelet coefficients is not required either.

摘要 I
總目錄 II
表目錄 IV
圖目錄 VI
第一章　緒論 1
1-1　前言 1
1-2　液相層析質譜儀的介紹 3
1-2-1　層析技術發展簡介 3
1-2-2　質譜儀簡介及其基本原理 4
1-2-3　離子源-電噴灑游離法簡介及其基本原理 7
1-2-4　四極柱質譜儀原理 12
1-3　層析法與質譜儀結合介紹 15
1-3-1　高效能液相層析與質譜儀的結合 15
1-3-2　液相層析串聯式質譜儀原理與應用 17
1-4　藥品簡介 21
1-4-1　山梔子（Fructus Gardeniae）簡介 21
1-4-2　Dopamine簡介 23
1-4-3　Lidocaine簡介 24
1-5　以軟體的方法減少雜訊 25
1-5-1　數位訊號處理與雜訊的簡介 25
1-5-2　軟體介紹-Matlab 30
1-5-3　小波轉換介紹 32
1-5-3-1　連續小波轉換 33
1-5-3-2　離散小波轉換 34
1-5-3-3　多重解析度分析 34
1-5-3-4　以小波轉換作為低通濾波器之方法 36
1-5-4　乘積運算方法 37
第二章　實驗部份 40
2-1　溶劑及藥品 40
2-1-1　溶劑 40
2-1-2　藥品 40
2-2　實驗器材、儀器裝置及軟體 41
2-3　藥品與溶液之配製 42
2-3-1　動相溶液之配製 42
2-3-2　藥品之配製 43
2-4　儀器參數設定 45
2-4-1　液相層析儀相關設定 45
2-4-2　質譜儀相關條件設定 45
2-5　訊號處理流程 47
2-6　校正曲線的建立 49
2-7　訊雜比計算方式 50
第三章　實驗結果與討論 51
3-1　三種藥物的初始質譜條件 51
3-1-1　dopamine的初始質譜條件 51
3-1-2　Lidocaine的初始質譜條件 52
3-1-3　Geniposide的初始質譜條件 54
3-2　將小波轉換當為低通濾波器 55
3-3　以含隨機雜訊的人造方波當參考波形做乘積 57
3-4　分析方法之可行性評估 60
3-4-1　原始層析圖校正曲線的建立 60
3-4-2　經WT-M-WT後層析圖校正曲線的建立 62
3-5　訊號處理前後三種藥品校正曲線的比較 63
3-5-1　訊號處理前後dopamine校正曲線的比較 63
3-5-2　訊號處理前後lidocaine校正曲線的比較 64
3-5-3　訊號處理前後geniposide校正曲線的比較 66
3-6　訊號處理前後品管樣品的比較 67
3-7　WT-WT與WT -M-WT兩個方法之差異 70
3-8　乘積運算之頻譜分析 72
第四章　結論 74
第五章　參考文獻 76

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