Migration of 99Tc in a Weak Loess Aquifer: A Field Column Experiment

The migration of ⁹⁹Tc in a weak loess aquifer was investigated in-situ with undisturbed aquifer medium columns. The columns were obtained horizontally at a depth of 3236 m in an Underground Research Facility (URF). Quartz containing ³H (HTO) and ⁹⁹Tc (in the form of ⁹⁹TcO₄ ^-) was introduced into one end of the columns and the columns were covered tightly. Aquifer water was introduced into the columns directly from an experimental shaft in the UFR. Effluents from the columns were collected and the activity of ³H and ⁹⁹Tc were determined with a liquid scintillation analyzer. The breakthrough curves of ³H and ⁹⁹Tc indicate that ⁹⁹Tc migrates a little faster than that ³H does in the aquifer.     

Anomalies in the asymmetric hydroboration of olefins with the 11 adduct of (+)-α-pinene and BH3 · THF

The hydroboration of cis-2-butene and cis-3-hexene with pure diisopinocampheylborane (IPC₂BH) and monoisopinocampheylborane (IPCBH₂), both prepared from (+)-α-pinene, were studied. In contrast to IPC₂BH, which yielded R-(?)-2-butanol and R-(?)-3-hexanol in 98.4 and 94.5% optical purities, IPCBH₂ yielded S-(+)-2-butanol and S-(+)-3-hexanol in 23.6 and 19.7% optical purifies respectively. PMR examination of the methanolyzed products were utilized to establish the species present in the freshly prepared and aged $\text{1}\text{1}$ adduct from (+)-α-pinene and BH₃ · THF. The results confirm the interpretation previously advanced for the major differences realized in asymmetric hydroboration with the fresh and aged $\text{1}\text{1}$ adducts.     

Molecular structure and pseudopolymorphism of squamtin A from Annona squamosa

The cyclopeptide, squamtin A (1, formula: C₃₉H₆₀O₁₁N₈S), was found to crystallized in two pseudopolymorphisms, i.e. 1·(H₂O)_3.5 and 1·(H₂O)_3.9. The composition of the amino acids and their linkage sequences are the same. The main differences between the two kinds of crystals lie in the positions and occupancies of the water molecules, the positions of the sulfur atoms and the conformation of the side chains. The absolute configuration of 1 is established by X-ray analysis in combination with the Marfey's analysis of its hydrolysates.     

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.     

Re(CO)5Br-catalyzed addition of carboxylic acids to terminal alkynes: a high anti-Markovnikov and recoverable homogeneous catalyst

The addition of carboxylic acids to terminal alkynes is efficiently catalyzed by the early transition-metal complex Re(CO)5Br in toluene or n-heptane at 110 degrees C in an air atmosphere, affording the anti-Markovnikov adducts in good yields with high selectivity. In most cases, the reactions afford unusual Z-adduct predominantly. When n-heptane was used as solvent, Re(CO)5Br can be partly recovered from the reaction mixture.     

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.     

UV-blocking property of dumbbell-shaped ZnO crystallites on cotton fabrics

A facile process to prepare uniform dumbbell-shaped ZnO crystallites was presented. The evidence in this Article discovered a unique morphological effect on the UV-blocking property. The as-prepared ZnO crystallites were characterized by XRD, HRTEM, FESEM, UV-blocking, and Raman scattering spectra. Our tentative investigation created a breakthrough to both the ultrahigh "Ultraviolet protection factor" (UPF) and the overall-range of complete UV-radiation blocking. Therefore, the as-prepared structural material demonstrated a significant advance in protective functional treatment and provided a potential commercialization.     

Acidities in cyclohexanediols enhanced by intramolecular hydrogen bonds

Equilibrium gas-phase acidities of the six isomeric cyclohexanediols were measured in a Fourier transform ion cyclotron resonance mass spectrometer. Although all six cyclohexanediols have the same functional groups and similar structures, the acidities vary over 11 kcal/mol. This large difference is due mostly to the balance between hydrogen bonding and geometric strain. To understand the origins of the acidity differences in more detail, the conformations and energetics of the cyclohexanediols were studied using density functional theory, which gave good agreement with the experimental acidities. Finally, methanol-methoxide and methanol-methanol interactions were used as a model for the hydrogen bonding.     

Calculations on the octupolar molecules with enhanced two-photon absorption cross sections based on the Zn (II) and Cu (I) as centers

The equilibrium geometries, electronic structures, as well as one- and two-photon absorption cross sections of a series of octupolar chromophores with Zn(2+) or Cu(+) as coordinate centers and 4,4'-bis(dibutylaminostyryl)-[2,2']-bis(bipyridyl) as ligands have been determined by using B3LYP/6-31G and ZINDO methods. These molecules are designed by controlled combination of two or three bipyridyl ligands with the metal centers. The results show that Zn(2+) is an effective template for the design of octupolar structures which enable it to form tetrahedral and octahedral coordinated complexes; while Cu(+) only exists in a tetrahedral coordinated complex, comparing the tetrahedral complex with Zn(2+) as the center with that of Cu(+) as the center, it is found that the complex with the Cu(+) center is a better two-photon absorption material than the former as far as the transparency/nonlinearity is concerned. Furthermore, for the same metal center of Zn(2+), both one- and two-photon absorptions of the tetrahedral complex are redshifted relative to those of the octahedral complex, is attributed to the spiroconjugation effect in the tetrahedral complex. Our theoretical findings are consistent with recent experimental observations and provide an important foundation for the design of improved transparency-nonlinearity two-photon absorption materials.