Abstract. We report a reaction apparatus developed to monitor singlet oxygen ( 1 O 2 ) reactions in solution using on-line ESI mass spectrometry and spectroscopy measurements.
1O 2 was generated in the gas phase by the reaction of H 2 O 2 with Cl 2 , detected by its emission at 1270 nm, and bubbled into aqueous solution continuously. O 2 oxidation were monitored by UV-Vis absorption and positive/negative ESI mass spectra, and product structures were elucidated using collision-induced dissociation-tandem mass spectrometry. To suppress electrical discharge in negative ESI of aqueous solution, methanol was added to electrospray via in-spray solution mixing using theta-glass ESI emitters. Capitalizing on this apparatus, the reaction of 1 O 2 with methionine was investigated. We have identified methionine oxidation intermediates and products at different pH, and measured reaction rate constants.1 O 2 oxidation of methionine is mediated by persulfoxide in both acidic and basic solutions. Persulfoxide continues to react with another methionine, yielding methionine sulfoxide as end-product albeit with a much lower reaction rate in basic solution. Density functional theory was used to explore reaction potential energy surfaces and establish kinetic models, with solvation effects simulated using the polarized continuum model. Combined with our previous study of gas-phase methionine ions with 1 O 2 , evolution of methionine oxidation pathways at different ionization states and in different media is described.
The vibration disturbance caused by incipient faults is an important factor affecting the measurement accuracy of the cam-driven absolute gravimeter. Based on the characteristics of the cam-driven absolute gravimeter, such as the small amplitude of the incipient faults, the inadequate representation of features for the faults, and hard-to-find in the noise, a novel method for incipient fault diagnosis of the cam-driven absolute gravimeter is put forward in this paper, which integrates the parameter-optimized Variational Mode Decomposition (VMD) with Light Gradient Boosting Machine (LightGBM). The sparrow search algorithm is used to optimize the VMD parameters. The parameter-optimized VMD algorithm is used to adaptively decompose the vibration signals of the gravimeter under different cases, and then an effective intrinsic mode function (IMF) is selected based on the Pearson correlation coefficient. Some high-frequency IMFs are subjected to adaptive noise reduction combined with low-frequency IMF reconstruction, and then the multi-scale permutation entropy with sensitive characteristics under different time scales is extracted as the fault feature vectors. The extracted multi-dimensional vector matrix is entered into the LightGBM classifier to realize the accurate diagnosis of the incipient faults for the cam-driven absolute gravimeter. The test results show that this method can effectively detect various incipient failures of the cam-driven absolute gravimeter, with an identification accuracy of 98.41%. With this method, the problem of low measurement accuracy for the cam-driven absolute gravimeter caused by the incipient faults is solved, and the rapid tracing and accurate positioning of these faults for the gravimeter are realized, promising a good prospect for engineering application.
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