本研究利用阿達瑪轉換-氣相層析質譜 (Hadamard transform-gas chromatography/mass spectrometry, HT-GC/MS)，成功偵測到人體呼出氣體中微量的丙酮。實驗用氣體樣品分別採自於數名糖尿病患及正常志願者。每次採集測試者100 mL的吐氣。採樣袋的氣體不需要任何前處理步驟，即可直接測量。依據Hadamard code由電腦控制的電磁閥，依序注射到氣相層析質譜儀中。每次氣體樣品的注射量為11 µL。在最佳化的條件下，當測試樣品以阿達瑪矩陣255、511、2047次的編碼分別進行實驗時，訊號雜訊比可以得到6.4、11.3、20.9倍的改良效果。這樣的增加倍率與理論值 (8.0、11.3、22.6) 相當吻合。就單一樣品的測量，在3.5分鐘內即可完成。本研究同時以傳統的頂空固相微萃取法進行比較。實驗結果發現，使用SU-57310U型號的固相微萃取針進行頂空萃取時，在4分鐘內可完成一次測量。在實際測量8位非糖尿病患志願者的呼出氣體，合計30袋的氣體，每袋重複實驗5次，得到的平均值為0.1 ~ 1 ppmv。在此情況下，無論使用阿達瑪轉換法或使用成本較高的固相微萃取法，對於提高偵測靈敏度都十分有效。阿達瑪轉換法適用於各類氣體，而固相微萃取法則須視偵測氣體的種類，選用適合的微萃取管，才能達到預期的效果。此外，本研究發現糖尿病患呼出氣體中的丙酮濃度很高，不須經由阿達瑪轉換或固相微萃取法亦可偵測得到。經實際測量4位糖尿病患 (含 type I及 type II糖尿病患) 的呼出氣體，合計30袋的氣體，每袋重複實驗20次，得到的平均值為1 ~ 10 ppmv。

關鍵字：阿達瑪、丙酮、氣相層析質譜術

In this study, the Hadamard transform-gas chromatography/mass spectrometry (HT-GC/MS) technique was successfully employed for detecting of a trace of acetone from human exhaled breath. Experimental gas samples were collected from several diabetic patients and normal volunteers. A 100mL exhaled breath was collected from each subject, and the collected gases in gas sampling bags did not require any extraction procedure before measurement. Based on the Hadamard code’s electromagnetic valve controlled by the computer, the gas samples were sequentially injected into the GC/MS with the volume of 11 μL each. Under the optimized conditions, when the Hadamard matrices of 255, 511 and 2047 were used, the S/N ratios were substantially improved to 6.4-, 11.3-, and 20.9-fold, respectively, matched with those expected from theoretical values (8.0-, 11.3-, 22.6-fold). The measurement of a single sample could be completed within 3.5 minutes. This study also employed traditional headspace solid-phase microextraction (HS-SPME) for comparison. The result showed that when the extraction needle, model SU-57310U, was used, a single measurement could be completed within 4 minutes. According to medical reports, the acetone concentration in normal people’s exhaled breath is very low. This view was confirmed by the actual measurement of eight non-diabetic volunteers’ exhaled breath, 30 bags of gases in total, each of which was measured five times repeatedly, obtaining an average value of 0.1 to 1 ppmv. In this case, both HT and higher-cost SPME are effective in improving detection sensitivity. HT is suitable for various types of gas while SPME should choose the proper microextraction syringe depending on the detected gas type in order to achieve desired results. Besides, due to the higher concentration of acetone in the exhaled breath from diabetic patients used in this experiment, it could also be detected without employing HT or SPME. The actual measurement on the exhaled breath from four diabetic patients (including type I and type II), 30 bags of gases in total, each of which was measured 20 times repeatedly, obtained an average value of 1 to 10 ppmv.

Keywords: Hadamard, acetone, gas chromatography/mass spectrometry

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