Gao Xx

Investigation on the relationship between solubility of artemisinin and polyvinylpyrroli done addition by using DAOSD approach

In this work, we investigated the influence of polyvinylpyrrolidone (PVP) on the solubility of artemisinin in aqueous solution by using quantitative 1H NMR. Experimental results demonstrate that about 4 times of incremental increase occurs on the solubility of artemisinin upon introducing PVP. In addition, dipole-dipole interaction between the ester group of artemisinin and the amide group of N-methylpyrrolidone (NMP), a model compound of PVP, is characterized by two-dimensional (2D) correlation FTIR spectroscopy with the DAOSD (Double Asynchronous Orthogonal Sample Design) approach developed in our previous work. The observation of cross peaks in a pair of 2D asynchronous spectra suggests that dipole-dipole interaction indeed occurs between the ester group of artemisinin and amide group of NMP. Moreover, the pattern of cross peaks indicates that the carbonyl band of artemisinin undergoes blue-shift while the bandwidth and absorptivity increases via interaction with NMP, and the amide band of NMP undergoes blue-shift while the absorptivity increases via interaction with artemisinin. Dipole-dipole interaction, as one of the strongest intermolecular interaction between artemisinin and excipient, may play an important role in the enhancement of the solubility of artemisinin in aqueous solution.

Investigation on the trioctylphosphine oxide-based super-concentrated HCl system

We report a new super-concentrated HCl system prepared by using trioctylphosphine oxide (TOPO)-based reverse micelles. The observed molar ratio between acid and water (nHCl/nH2O) in the super-concentrated HCl are much higher than that in the saturated aqueous HCl solution (0.28). Moreover, FT-IR spectroscopic results reveal that a significant amount of HCl remains in the molecular form rather than being ionized into H(+) and Cl(-). As a result, two H-Cl stretching bands can be observed in the FT-IR spectrum. The super-concentrated HCl provides a unique chemical environment in which many chemical substances occur in unusual states. For example, the color of super-concentrated HCl solution containing copper ion was found to be reddish brown rather than green as in conventional state. UV-Vis-NIR spectral results indicate that both d-d transition band of Cu(2+) and charge transfer band of Cl-Cu in super-concentrated HCl underwent significant variation. Additionally, copper ions bring about remarkable variation on the hydrogen bond network among HCl in the super-concentrated HCl solution as demonstrated by FT-IR spectra. According to the EXAFS results, we suggest that copper ion may occur as HCuCl3 in the super-concentrated HCl.

Superconcentrated hydrochloric acid.

We report the discovery of a potentially useful superconcentrated HCl at ambient temperature and pressure by using a simple surfactant-based reversed micelle system. Surprisingly, the molar ratios of H(+) to H(2)O (denoted as n(H+)/n(H2O)) in superconcentrated HCl can be larger than 5, while the maximum achievable n(H+)/n(H2O) value for conventional saturated HCl aqueous solution (37 wt %) is only about 0.28. Furthermore, both NMR and FT-IR results indicate that a significant amount of HCl remains in the molecular form rather than being ionized into H(+) and Cl(-). The superconcentrated HCl may promote some organic reactions that are not feasible by using conventional 37 wt % HCl solution. For example, addition reaction between C═C and HCl occurs in superconcentrated HCl solution without using catalysts.