1-Pyrroline has a highly characteristic odor, which is employed by living organisms for chemical signaling and other purposes, but the mechanism whereby this odor is formed remains poorly understood. Here we used a combination of ambient mass spectrometry (AMS) and nuclear magnetic resonance (NMR) spectroscopy to experimentally address the mechanistic aspects of 1-pyrroline volatility and other controversies regarding the chemistry of this compound. Our results indicate that in solution the volatility of the monomer species is significantly higher than that of the trimer species, and 1-pyrroline is evaporated mainly in its monomer state. Neat 1-pyrroline is essentially the pure trimer and displays ca. 100-fold lower evaporation rate than the monomer state in solution. In the gas-phase the trimer species is irreversibly decomposed into monomer species. Under equilibrium conditions the vapor of 1-pyrroline entirely consists of monomer species. The evaporation rate of 1-pyrroline in water has a step-wise dependence on the solution pH, the abrupt increase in volatility (>1,000-fold) occurring around the pKa value of 1-pyrroline (6.8). The pronounced step-wise dependence of 1-pyrroline volatility around neutral pH may also be an important evolutionary factor allowing living systems to regulate the odor strength from very weak to very strong with minimal efforts.
Bo Yin,Rui Rui Liu,Ya Jie Meng,Hong Lin Zhai,Sha Sha Li,Jules Muhire
Found in various natural food products, many in vitro evidence indicated that resveratrol (RES) has been linked to neuroprotective and cardioprotective effects and prevent cancer development. However, human clinical trials have been conducted with varying results, making the usage of RES controversial. In this paper, we demonstrated that the drug RES could be conjugated with the high levels of endogenous GSin cancer cells. 5,5-Dimethyl-1-Pyrroline-N-Oxide (DMPO) was employed to capture the GS•. The molecular mechanism of the reaction between RES and GSwas further studied by UV-Vis spectrometry, mass spectrometry and Density Functional Theory (DFT) calculations. Besides, the formation of the adduct GS-RES in cancer cell was obtained when RES was added during incubation. Further study indicated that over 77.6% of the RES was consumed in cancer cells. This study suggested that endogenous GSmay be one of the important factors to cause the depletion of anti-tumour drugs during chemotherapy, which should be paid special attention in clinical therapeutics and drug development.
Chlorobenzene (CB) is an important organic chemical material that is volatile and difficult to degrade, and has received much attention because of its strong ozone generation potential. An electrochemical-sodium peroxydisulfate (PDS) system was constructed and the oxidation reaction path of chlorobenzene in this system was analyzed. The effects of current density, PDS concentration, initial pH, CB blow-off gas ratio and temperature on the oxidation and mineralization rate of chlorobenzene in the system were investigated respectively. At a current density of 168 A/m 2 , a PDS concentration of 0.5 mol/L, an initial pH of 10, a CB blow-off gas ratio of 20% and a reaction temperature of 60 °C, the CB conversion and mineralization rates were able to reach more than 90%. The results of electron paramagnetic resonance (EPR) experiments using 5,5-dimethyl-1-pyrroline N-oxide (DMPO) and 2,2,6,6-tetramethyl-4-piperidone hydrochloride (TEMP) as spin trapping agents indicate the presence of ⦁OH, · S O 4 − and 1 O 2 in the system. The signal of · O 2 − was also captured after the quenching of ⦁OH, which further indicates the presence of 1 O 2 . And the results of active substance quenching experiments showed that the active species that mainly contributed to the oxidation of chlorobenzene included ⦁OH, · S O 4 − and 1 O 2 , and their contributions to the oxidation of chlorobenzene were 25.0%, 31.7% and 22.2%, respectively. The Liquid Chromatograph Mass Spectrometer (LC-MS) characterization results showed that the formation of chlorophenol and hydroquinone and their ring-opening reactions were the most critical processes in the oxidative decomposition of chlorobenzene, and the reaction pathways for the oxidation of chlorobenzene by ⦁OH, · S O 4 − and 1 O 2 were proposed by these characterization results.
危险品化学品经营许可证（带存储）