Chemical activation of carbon nanofibers and nanotubes

Method of thermodynamic simulation was used to calculate the equilibrium parameters of reactions of graphite with anhydrous LiOH, NaOH, and KOH and with the alkalis in the presence of water vapor. The change in the specific surface area and mass loss were used to analyze the interaction of carbon nanofibers and multilayer carbon nanotubes produced by catalytic pyrolysis of CH₄ with the alkalis.     

Tasumatrols P – T,Five New Taxoids from Taxus sumatrana

The phytochemical investigation of the more polar fractions from the leaves and twigs of Taxus sumatrana (Taxaceae) afforded five new taxane diterpene esters, tasumatrols P–T ( 1 – 5 ) possessing an 11(15→1),11(10→9)‐diabeotaxane skeleton. Compounds 1, 4 , and 5 contain an α‐hydroxy group at C(14), while 3 has no OH group at either C(13) or C(14). Compound 2 is a natural 4,5‐acetonide derivative, while 4 has an unusual spiro‐connected 2‐hydroxy‐2‐phenyl‐1,3‐dioxolane ring. Ten known taxoids, were also isolated in the course of the chromatographic fractionation. Five additional new O‐acetyl derivatives 3a, 4a, 4b, 5a , and 5b were prepared from the taxanes 3 – 5 . The structures of all new compounds were established on the basis of their spectroscopic analyses. Compound 1 showed mild cytotoxic activity against human Hela and Daoy tumor cells.     

Synthesis of 5‐Radioiodoarabinosyl Uridine Analog for Probing the HSV‐1 Thymidine Kinase Gene

Tumor cells transduced with herpes simplex virus thymidine kinase gene have been intensively applied to the field of positron emission tomography via imaging of its substrate. As a pilot synthesis approach, a facile preparation of 5‐[¹²⁵I] iodoarabinosyl uridine starting from commercially available uridine is reported herein.     

Semiempirical Molecular Orbital Studies of the Acylation Step in the Lipase‐Catalyzed Ester Hydrolysis

In this study, we present the results from the semiempirical molecular orbital calculations for the acylation step in the lipase‐catalyzed ester hydrolysis. The results reveal that the lowest energy path for the formation of the tetrahedral intermediate is for the serine residue of the catalytic triad to attack the substrate, followed by coupling heavy atom movement and proton transfer. The calculations of four active site models show that the cooperation of the aspartate group and the oxyanion hole is capable of lowering the activation energy by about 16 kcalmol^?1. Our results further suggest that the lipase‐catalyzed ester hydrolysis adopts the single proton transfer mechanism.     

Hydrothermal Synthesis and X‐Ray Structural Characterization of Manganese,Nickel, and Cadmium Coordination Polymers Containing 2,3‐Pyridinedicarboxylate as Multidentate Ligands

Three divalent transiton‐metal complexes of 2,3‐pyridinedicarboxylate (2,3‐pda²), [Mn(2,3‐pda)‐(H₂O)3]_∞ ( 7 ), [Ni(2,3‐pda)(H₂O)3]_∞ ( 8 ), and [Cd2(2,3‐pda)₂(H₂O)]_∞ ( 9 ) have been hydrothermally synthesized and structurally characterized. X‐ray diffraction analyses reveal that compounds 7 and 8 are zigzag‐ and linear‐type one‐dimension (1D) coordination polymers, respectively, whereas compound 9 is a three‐dimension (3D) coordination polymer. A simple comparison of the coordination geometries with the available neutral analogues {M_x(2,3‐pda)_x(H₂O)_y}_∞ containing one or two divalent transition‐metal atoms and equal ligands in the presence or absence of coordinated water molecules is also presented.     

Resonant Raman spectra and first molecular hyperpolarizabilities of strongly charge-transfer molecules

The effect of vibrational structure on the frequency dependence of the first molecular hyperpolarizability of two thiophene-based charge-transfer chromophores is investigated. A time domain formulation is used to express the polarizability. The new expression includes the solvent-induced inhomogeneous distribution of electronic transition frequencies as well as the effect of the motion of solvent molecules that modulates the vibrational and electronic transition frequencies of the nonlinear optical molecule on which the first molecular hyperpolarizability depends. Resonance Raman scattering and one-photon absorption spectra of the chromophores are measured. By simultaneously fitting the experimental one-photon absorption spectrum and Raman cross sections of vibrational lines derived from resonance Raman scattering to a theoretical model, important parameters needed for the calculation of the first molecular hyperpolarizability are obtained. The first molecular hyperpolarizability is calculated as a function of frequency covering both nonresonance and two-photon resonance regions. The calculated result is compared with the measured hyperpolarizability as a function of frequency of the excitation laser. The resonance Raman-based analysis is shown to account reasonably well for the dispersion of the hyperpolarizability of the two charge transfer chromophores.