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Abstract: Pyrolysis of carboxylic acid group at C-4 of 2, an oxidation product from the C19-diterpenoid alkaloid lycoctonine 1, generated an unexpected but novel rearranged product 13 (37%). The structure of 13 was confirmed by its 2D NMR data and its single crystal X-ray crystallographic analysis. In addition, hydrogenolysis of 13 in the presence of acetic acid yielded the N–C6 bond fission products 16 and 17, which represents the first hydrogenolysis involving the breakage of the N–C6 bond of the diterpenoid alkaloids. Some new observations on the oxidation of lycoctonine 1 were described as well. [ABSTRACT FROM AUTHOR]

Abstract: We have corrected (Tetrahedron 2013, 69, 5859–5866) the structures of diterpenoid alkaloids reported in the Journal of Natural Products 2012, 75, 1145–1159. Our follow-up experiments compel us to present further revisions and clarifications on the diterpenoid alkaloids: (1) The naturally occurring forms of carmichaelines B, C, and D in Shi's paper (Journal of Natural Products 2012, 75, 1145–1159) are neither quaternary ammonium hydroxides 2–4 nor the initially revised trifluoroacetates. They are indeed the vakognavine-type C20-diterpenoid alkaloids 11–13. (2) The samples' concentration is the critical factor to the signals' intensity for F3CCOO− in the alkaloid trifluoroacetates. Incorporation of TFA into the corresponding salts resulted in signals' enhancement due to the closeness of δ values (∼116 ppm, ∼159 ppm) of free TFA and those of F3CCOO−. After removal of free TFA, the carbon signals of CF3COO− could become weaker, but their chemical shifts remained almost unchanged. The possible reason might be the ionization of TFA in acetone. (3) The NMR data cannot distinguish TFA from trifluoroacetates (e.g., F3CCOONa and C19-diterpenoid alkaloid trifluoroacetates), indicating that the signal at around δ −76 cannot be used to exclude the existence of trifluoroacetates. In addition to the NMR and CSI-MS data, 1H–15N HMBC technique was also used to distinguish the free alkaloids from their trifluoroacetates. (4) The X-ray crystallographic analysis of compound 20 confirmed that the ‘new alkaloid’ (-b) in the Shi's paper is indeed the known compound aconifine trifluoroacetate. (5) Collectively, Shi's paper mixed-up the free alkaloids with their salts and the concepts of structure and conformation. Naming different structures with A-b and A-c is also confusing. [Copyright &y& Elsevier]

Abstract: A theoretical study of the structural, elastic and electronic properties of spinel LiTi2O4 anode has been performed by density functional theory (DFT) plane-wave pseudopotential method. The independent elastic constants, shear modulus (G), bulk modulus (B), and Young''s modulus (E) are evaluated, respectively. The results suggest that cubic LiTi2O4 is mechanically stable. The G/B ratio of 0.584 indicates the ductility of LiTi2O4 is good. The electron density difference of LiTi2O4 shows that the O2p orbits overlap effectively with Ti3d ones, confirming the formations of strong covalent bonds between them, while Li is fully ionized in the lattice. The formation enthalpy for LiTi2O4 is calculated to be −2070.723±1.6kJmol−1. The strong covalent bonds between O and Ti atoms are not only responsible for the excellent mechanical stabilities but also very crucial for the thermodynamic stability of LiTi2O4 compound. Furthermore, in Li2Ti2O4 compound, the full occupation of 16(c) sites by Li+ not only leads to a smaller C 12 value but also leads to a much larger C 44 one. Therefore, the plasticity and ductility of the Li2Ti2O4 become poor in comparison to LiTi2O4, while the thermodynamic stability of Li2Ti2O4 can be further improved after the Li+ intercalation of LiTi2O4. [Copyright &y& Elsevier]

Abstract: Optical properties and structural aspects of As x S100-x glasses from visible to terahertz wavelengths were explored. A series of annealed, bulk As x S100-x glasses (x =30 to 42) were made and their refractive indices determined at terahertz, infrared, and visible frequencies using a quasi-optical backwards wave oscillator spectrometer for terahertz measurements combined with a prism coupler for visible and infrared measurements. It was found that the refractive index at all frequencies increases with arsenic composition up to 40at.% arsenic and then decreases with additional arsenic. The structure in X-ray diffraction patterns supports the notion of a minimum volume at 40at.%, while the average covalent coordination number indicates that the rigidity percolation threshold is reached there. At arsenic concentrations >40at.%, the network becomes over-constrained, and the molar volume increases. [Copyright &y& Elsevier]