Synthesis of the indenotryptoline bisindole alkaloid, BE-54017, was accomplished using osmium-promoted cis-dihydroxylation of maleimide as a key step. After optical resolution, the absolute configuration of this molecule was determined by comparing its optical rotation and HPLC profile to those obtained for BE-54017 derived from enantiopure cladoniamide A, whose stereochemistry has been reported previously. BE-54017 with the correct absolute stereochemistry induced apoptosis of epidermal growth factor (EGF)-stimulated EGF receptor overexpressing A431 cells and inhibited vacuolar-type H(+)-ATPase (V-ATPase). 相似文献
Living anionic polymerization of tert‐butyl acrylate initiated by 1,1‐diphenylhexyllithium is conducted in a flow microreactor system in the presence of lithium chloride. A high degree of control over the molecular weight distribution is achieved under easily accessible conditions, for example at ?20 °C. The subsequent reaction of a reactive polymer chain end with an alkyl methacrylate in an integrated flow micoreactor system leads to the formation of a block copolymer with a narrow molecular weight distribution.
We develop novel calculation and analysis methods for the dynamic first hyperpolarizabilities β [the second-order nonlinear optical (NLO) properties at the molecular level] in the second-harmonic generation based on the quantum master equation method combined with the ab initio molecular orbital (MO) configuration interaction method. As examples, we have evaluated off-resonant dynamic β values of donor (NH(2))- and/or acceptor (NO(2))-substituted benzenes using these methods, which are shown to reproduce those by the conventional summation-over-states method well. The spatial contributions of electrons to the dynamic β of these systems are also analyzed using the dynamic β density and its partition into the MO contributions. The present results demonstrate the advantage of these methods in unraveling the mechanism of dynamic NLO properties and in building the structure-dynamic NLO property relationships of real molecules. 相似文献
To investigate the molecular interaction between guest species inside of the small and large cages of methane + propane mixed gas hydrates, thermal stabilities of the methyl radical (possibly induced in small cages) and the normal propyl and isopropyl radicals (induced in large cages) were investigated by means of electron spin resonance measurements. The increase of the total amount of the normal propyl and isopropyl radicals reveals that the methyl radical in the small cage withdraws one hydrogen atom from the propane molecule enclathrated in the adjacent large cage of the structure-II hydrate. A guest species in a hydrate cage has the ability to interact closely with the other one in the adjacent cages. The clathrate hydrate may be utilized as a possible nanoscale reaction field. 相似文献
Photocatalytic mineralization of aqueous formic acid and phenol on pure TiO(2) under sunlight irradiation was substantially accelerated to give a reliable photocatalytic efficiency by conducting the reactions in the presence of a CO(2) sorbent, amine-containing SBA-15, placed in the gas phase of the reactor. 相似文献
We report synthesis of hollow calcium phosphate (CaP) nanospheres with high surface area by using block copolymer micelles as templates. The obtained CaP nanospheres exhibit very high biocompatibility, showing great promise for intracellular bio-applications in future. 相似文献
This report describes the electrochemical detection of a redox component in droplets using a local redox cycling-based electrochemical (LRC-EC) chip device consisting of 256 sensors. The time-course analyses showed that the redox compound in the droplet was dynamically changed during droplet evaporation or mass transfer through a water/oil interface. 相似文献
Vertically aligned fluorescent polymer arrays with poly(9,9-di-n-octylfluorenyl-2,7-diyl) (PFO) are prepared by simple drop-casting onto mesoporous alumina film. The obtained PFO arrays exhibit anisotropic photoluminescence (PL) along the orientation of the main chains. 相似文献
Polar states are realized in pseudocubic manganite films fabricated on high-index substrates, in which a Jahn-Teller (JT) distortion remains an active variable. Several types of orbital orders (OOs) were found to develop large optical second harmonics, signaling broken-inversion symmetry distinct from their bulk forms and films on (100) substrates. The observed symmetry lifting and first-principles calculation both indicate that the modified JT q2 mode drives Mn-site off centering, which can be controlled by a magnetic-field-induced phase transition via a coupling of OO and spin orders. 相似文献
Three (1)H-(1)H homonuclear dipolar decoupling schemes for (1)H indirect detection measurements at very fast MAS are compared. The sequences require the following conditions: (i) being operable at very fast MAS, (ii) a long T(2)(') value, (iii) a large scaling factor, (iv) a small number of adjustable parameters, (v) an acquisition window, (vi) a low rf-power requirement, and (vii) a z-rotation feature. To satisfy these conditions a modified sequence named TIlted Magic-Echo Sandwich with zero degree sandwich pulse (TIMES(0)) is introduced. The basic elements of TIMES(0) consist of one sampling window and two phase-ramped irradiations, which realize alternating positive and negative 360° rotations of (1)H magnetization around an effective field tilted with an angle θ from the B(0) axis. The TIMES(0) sequence benefits from very large chemical shift scaling factors at ultra-fast MAS that reach κ(cs)=0.90 for θ=25° at ν(r)=80kHz MAS and only four adjustable parameters, resulting in easy setup. Long κ(cs)T(2)(') values, where T(2)(') is a irreversible proton transverse relaxation time, greatly enhance the sensitivity in (1)H-{(13)C} through-bond J-HMQC (Heteronuclear Multiple-Quantum Coherence) measurements with (1)H-(1)H decoupling during magnetization transfer periods. Although similar sensitivity can be obtained with through-space D-HMQC sequences, in which (13)C-(1)H dipolar interactions are recoupled, J-HMQC experiments incorporating (1)H-(1)H decoupling benefit from lower t(1)-noise, more uniform excitation of both CH, CH(2) and CH(3) moieties, and easier identification of through-bond connectivities. 相似文献