title: Tailoring noise frequency spectrum between two consecutive second derivative filtering procedures to improve liquid chromatography-mass spectrometry determinations.
abstract: This paper reports a simple chemometric technique to alter the noise spectrum of a liquid chromatography-mass spectrometry (LC-MS) chromatogram between two consecutive second-derivative filter procedures to improve the peak signal-to-noise (S/N) ratio enhancement. This technique is to multiply one second-derivative filtered LC-MS chromatogram with another artificial chromatogram added with thermal noises prior to the other second-derivative filter. Because the second-derivative filter cannot eliminate frequency components within its own filter bandwidth, more efficient peak S/N ratio improvement cannot be accomplished using consecutive second-derivative filter procedures to process LC-MS chromatograms. In contrast, when the second-derivative filtered LC-MS chromatogram is conditioned with the multiplication alteration prior to the other second-derivative filter, much better ratio improvement is achieved. The noise frequency spectrum of the second-derivative filtered chromatogram, which originally contains frequency components within the filter bandwidth, is altered to span a broader range with multiplication operation. When the frequency range of this modified noise spectrum shifts toward the other regimes, the other second-derivative filter, working as a band-pass filter, is able to provide better filtering efficiency to obtain higher peak S/N ratios. Real LC-MS chromatograms, of which 5-fold peak S/N ratio improvement achieved with two consecutive second-derivative filters remains the same S/N ratio improvement using a one-step second-derivative filter, are improved to accomplish much better ratio enhancement, approximately 25-fold or higher when the noise frequency spectrum is modified between two matched filters. The linear standard curve using the filtered LC-MS signals is validated. The filtered LC-MS signals are also more reproducible. The more accurate determinations of very low-concentration samples (S/N ratio about 5-7) are obtained via standard addition procedures using the filtered signals rather than the determinations using the original signals.
authors.affiliation: Department of Chemistry and Biochemistry, National Chung Cheng University, 168 University Road, Min-Hsiung, Chia-Yi 621, Taiwan. chescw@ccu.edu.tw
authors.forename: Shau-Chun
authors.initials: SC
authors.lastname: Wang
authors.forename: Chiao-Juan
authors.initials: CJ
authors.lastname: Lin
authors.forename: Shu-Min
authors.initials: SM
authors.lastname: Chiang
authors.forename: Sung-Nien
authors.initials: SN
authors.lastname: Yu
mesh_terms: D002853:Chromatography, Liquid / Q000379:methods*; D013058:Mass Spectrometry / Q000379:methods*; D015203:Reproducibility of Results