Shifu Weng

A spectroscopic study of pigment gallstones in China

Spectroscopic studies of various types of gallstones carried out in China are reviewed. Three basic classes of gallstones are surveyed: cholesterol stones, brown pigment stones, and black pigment stones. The emphasis of this review is on brown gallstones. The primary spectroscopic methods used in the studies surveyed are Fourier transform infrared absorption and Fourier transform Raman scattering. Chemical components studied in gallstones include cholesterol, bile pigments, glycoproteins, proteins, bilirubin metal complexes, and salts of calcium and other metals. Further studies are needed characterize the relationship of these components to more complex features of gallstones.

The interaction of Co2+ ions and sodium deoxycholate micelles

Abstract To mimic the interaction between divalent metal ions and bile slats in vivo, two groups of coordination complex compounds, crystalline and gel-like, were synthesized in vitro by mixing the aqueous solutions of CoCl 2 with sodium deoxycholate (NaDC) at various concentrations. Structures and compositions of the compounds were investigated using FT-IR, EXAFS, XRD as well as elemental and ICP analysis, respectively. Then the interaction of Co 2+ with deoxycholate in solution was observed by laser light scattering (LLS), Transmission electronic microscope techniques and ICP analysis. Conclusions are (1) the crystalline complexes, Co (DC) 2 ·3H 2 O were obtained by reaction of Co 2+ with mono-molecules of NaDC, and the gel-like complexes, Na n Co m (DC) n +2 m formed by reaction of Co 2+ with NaDC micelles. The gel-like complexes exhibit the non-stoichiometric character; (2) the coordination structures of carboxyl groups with Co 2+ were different between the crystalline and gel-like complexes. In Co(DC) 2 ·3H 2 O complex, the carboxyl groups of deoxycholate coordinated with Co 2+ in chelating and pseudo-chelating modes, but that in bridge mode in the case of Na n Co m (DC) n +2 m complexes. The non-stoichiometric complexes of Na n Co m (DC) n +2 m are formed with a macromolecular structure through the Co 2+ bridges; (3) NaDC can increase the solubility of Co(DC) 2 ·3H 2 O in aqueous solution, and larger micelles (30–80 nm diameter) formed in the supernate. It is a mixed micelle formed by Co 2+ ions bridges connecting with NaDC simple micelles. So these micelles are a new kind of micelle containing two kinds of metal ions; (4) these results are in agreement with those formed under physiological conditions in that the different states such as gel, precipitate, micelles of various structures are present in bile of gallbladder. An ideal model of the interaction between Co 2+ and bile salts in vivo has been proposed.

FT-IR study of rare earth 4-aminobenzenesulfonate complexes

Abstract The crystal structure of lanthanum 4-amino-benzenesulfonate complex has been determined by X-ray diffraction. The crystal data indicate that lanthanum and neodymium 4-amino-benzenesulfonates are isomorphous. The FT-IR spectroscopic study of rare earth 4-amino-benzenesulfonate complexes showed that the spectra of light rare earth (La, Nd, Sm, Eu) complexes are similar and so are the spectra of heavy rare earth (Dy, Er, Y) complexes. There are remarkable differences between the spectra of light rare earth and heavy rare earth complexes. Based on above results, we infer that light rare earth (La, Nd, Sm, Eu) complexes are isomorphous and three heavy rare earth (Dy, Er, Y) complexes are of a different structure but also isomorphous.

The interaction of Cu2 + ions and NaDC micelles.

By mixing an aqueous solution of CuCl2 with an NaDC aqueous solution of various concentration and initial molar ratio, seven coordinated samples with distinct appearances and characters were obtained. Their structures and components were investigated by FT-IR spectroscopy, EXAFS (the extended X-ray absorption fine structure), thermal analysis, X-ray diffraction, laser light scattering, TEM (transmission electron micrograph), element analysis and ICP (inductively coupled plasma) analysis. The following conclusions were given: (1) The complexes of Cu2+-NaDC with distinct appearances and properties were synthesized. (2) After Cu(DC)2 dissolved in NaDC aqueous solution, larger micelles (30-90 nm diameter) formed in the supernate, it is a mixed micelle with Cu(DC)2 and NaDC. So these micelles are a new kind of micelle containing two kinds of metal ions. This is a new result using metal ions as bridges to form micelle. (3) According to the different concentration of Cu2+ to NaDC, the complexes formed as gel or poly-crystals. Both the composition of gel complexes and the coordination structure of carboxyl groups with metal ions varied with the initial molar ratio of Cu2+ to Na+. The gel complexes exhibits the non-stoichiometric character. (4) These results are in agreement with physiological condition. All the different states such as gel, precipitate, micelles of various structures are present in bile of gallbladder. We can suggest an ideal model of the interaction between Cu2+ and bile salts in vivo.

Development of narrow-band TLC plates for TLC/FTIR analysis

The present paper focuses on the development of narrow-band thin-layer chromatography (TLC) coupled with Fourier transform Infrared spectroscopy (FTIR) technique. We adopted a new method to prepare a narrow-band TLC plate by using silver iodide as stationary phase. The narrow-band TLC plate exhibits a variety of advantages: the preparation time is about 20 minutes, while 3–7 days are needed to prepare a common TLC plate suitable for TLC/FTIR analysis by using “settlement volatilization method”. Furthermore, the usage of stationary phase in narrow-band TLC plates decreases by about one order of magnitude in comparison with that of common TLC plates. This is very important for an expensive stationary phase such as silver iodide. In addition, experimental results of TLC/FTIR analysis on mixed samples containing rhodamine B and bromocresol green demonstrate the detection limit significantly improves by using the narrow-band TLC technique.

The interaction between amino acids and metal ions (I). The FT-IR spectroscopic study of the binding between d,l-homocysteic acid and alkali metal ions

D,L-Homocysteic acid (DLH), an amino acid in the mammalian central nervous system, can excite the cerebral activities and has been proposed as an agonist of endogenous glutamate receptor. It contains -NH(3)(+), -COOH and -SO(3)(-) groups, therefore, the interactions between DLH and metal ions may be expected. In the present investigation, the complexes of DLH with NH4(+), Li+, Na+ and K+ at different pH conditions were synthesized and characterized by Fourier transform infrared (FT-IR) spectroscopy. It was concluded that the structures of the complexes prepared at pH 2.6 and 4.0 are similar to each other and the C=O groups are mono-dentate coordination for these complexes. However, the structures of the complexes synthesized at pH 13.0 change considerably from the complexes at pH 2.6 and 4.0, which show that dissociation has occurred in aqueous solution. The four cations coordinate to DLH, which result in the rearrangement of the hydrogen bond network and the skeletal structure change of the ligand.

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.

Using Lanthanum Fluoride Fine Particles as Stationary Phase for Thin-Layer Chromatography/Fourier Transform Infrared Spectroscopy Analysis

While in situ TLC/FTIR technique has tremendous potential in the analysis of complex mixtures, the conventional stationary phase, such as silica gel, used for TLC/FTIR analysis, has strong absorption in IR region and thus brings about severe interference in the obtained FTIR spectra of the separated samples. In this work, we propose to use lanthanum fluoride fine particles as a new stationary phase of a TLC plate. The average size of LaF3 particles is around 100 nm. FTIR spectrum of the LaF3 particles has no interfering absorption. Preliminary TLC experiments show that mixtures of rhodamine B and methylene blue mixture can be successfully separated by this new TLC plate using LaF3 fine particles as a stationary phase. Methylene blue and rhodamine B from separated spot can be clearly detected by using in situ FTIR spectra.

Analysis of an Alanine/Arginine Mixture by Using TLC/FTIR Technique

We applied TLC/FTIR coupled with mapping technique to analyze an alanine/arginine mixture. Narrow band TLC plates prepared by using AgI as a stationary phase were used to separate alanine and arginine. The distribution of alanine and arginine spots was manifested by a 3D chromatogram. Alanine and arginine can be successfully separated by the narrow band TLC plate. In addition, the FTIR spectra of the separated alanine and arginine spots on the narrow band TLC plate are roughly the same as the corresponding reference IR spectra.

Analysis of a Benzamide/Cholesterol Mixture by Using TLC/FTIR Technique

We applied TLC/FTIR coupled with a mapping technique to analyze a cholesterol/benzamide mixture. Narrow-band TLC plates by using AgI as a stationary phase were used to separate benzamide and cholesterol. The distribution of cholesterol and benzamide spots was manifested by 3D chromatogram. Benzamide and cholesterol can be successfully separated by the narrow-band TLC plate. Moreover, characteristic bands of benzamide and cholesterol can be identified from their FTIR spectra. In addition, the FTIR spectra of the separated benzamide and cholesterol spots on the narrow band TLC plate are roughly the same as the corresponding reference IR spectra.