Analysis of bufadienolides in the Chinese drug ChanSu by high-performance liquid chromatography with atmospheric pressure chemical ionization tandem mass spectrometry

The qualitative analysis of bufadienolides in the Chinese drug ChanSu was performed using high-performance liquid chromatography with atmospheric pressure chemical ionization tandem mass spectrometry (APCI-MS/MS). Bufadienolides are the major bioactive constituents of ChanSu, which is used to treat heart failure and cancer in traditional Chinese medicine. The APCI-MS fragmentation behavior of bufadienolides was studied. For bufadienolides with only hydroxyl substituents, the fragmentation was characterized by successive eliminations of H(2)O and CO molecules, and the profile of MS/MS product ions was correlated with the number of hydroxyl groups. If a C-16 acetoxyl group was present, the fragmentation of [M+H](+) ions was triggered by initial loss of 60 Da (HOAc). The elimination of CO was significant for bufadienolides with a 19-formyl group, and the 19-hydroxyl group could be characterized by the loss of 30 Da (HCHO). These fragmentation rules were applied to the identification of bufadienolides in a methanolic extract of ChanSu, which was separated on a C(18) column with gradient elution. A total of 35 bufadienolides were identified, including four new constituents. The method established here facilitated the convenient and rapid quality control of ChanSu crude drug and its pharmaceutical preparations.     

Toward a total synthesis of peloruside A: enantioselective preparation of the C8-C19 region

An efficient synthetic sequence toward the C8-C19 region of peloruside A has been developed. The route is highlighted by a selective electrophilic cyclization reaction, a single-step epoxide ring-opening/methylation sequence, and a stereoselective Mukaiyama aldol reaction. [reaction: see text]     

Observation of isomeric states in197Bi

The high spin states of¹¹⁹Te, populated in¹¹⁰Pd(¹³C,4n) and¹¹⁰Pd(¹²C,3n) reactions, have been studied through -ray spectroscopy. The level scheme has been established upto a spin of 55/2. Three-quasiparticle states, based on g² _7/2h_11/2 and g_7/2d_5/2h_11/2 configurations, have been identified. The 35/2 and 39/2 states are suggested to be the fully aligned states constituted by five valence h_11/2 ³, g_7/2, d_5/2 quasiparticles.     

A solvothermal synthesis and the structure of K4Ag2Sn3S9 x 2KOH

A novel layered K(4)Ag(2)Sn(3)S(9) x 2KOH was synthesized solvothermally. A mixture of ethanol and HSCH(2)CH(SH)CH(2)OH was used for the synthesis. The HSCH(2)CH(SH)CH(2)OH plays an important role and appears to serve as a mineralizer for the solvothermal reaction. A layer comprises Sn(3)S(9)(6)(-) clusters linked by Ag(+) ions and possesses two types of 1D channels in which potassium ions are located. The compound crystallizes in the monoclinic P2(1)/m space group [a = 7.8071(2) A, b = 27.3508(1) A, c = 10.5008(2) A, alpha = 90 degrees, beta = 103.874(1) degrees, gamma = 90 degrees, Z = 4]. Its crystal structure, composition analysis, and IR are presented.     

Enantioselective total synthesis of (+)-gigantecin: exploiting the asymmetric glycolate aldol reaction

The enantioselective synthesis of the potent, selective, cytotoxic, annonaceous acetogenin, (+)-gigantecin, has been completed. An asymmetric glycolate aldol serves to establish the stereocenters at C13,14 and at C21,22. A Carreira asymmetric acetylide addition is used to establish the C17 stereocenter.