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排序方式: 共有127条查询结果,搜索用时 31 毫秒
1.
Dr. Andrea Marraffa Dr. Piero Presenti Prof. Beatrice Macchi Dr. Francesca Marino-Merlo Prof. Mariella Mella Prof. Paolo Quadrelli 《ChemistryOpen》2020,9(5):528-537
Two new families of N,O-nucleoside analogues containing the anthracene moiety introduced through the nitrosocarbonyl ene reaction with allylic alcohols were prepared. The core structure is an isoxazolidine heterocycle that introduces either atom either a phenyl ring or dimethyl moiety at the C3 carbon. Different heterobases were inserted at the position 5 of the heterocyclic ring. One of the synthesized compounds demonstrated a good capacity to induce cell death and an appreciable nuclear fragmentation was evidenced in treated cells. 相似文献
2.
The study of the reaction with MeONa/MeOH of chlorinated γ-lactams, prepared from the atom transfer radical cyclization of N-allyl-α-perchloroamides, has been extended to the case of substrates carrying an exo halogen atom on a branched carbon. Only with secondary exo C-Cl groups, that are not located on a fused ring, does the functional rearrangement follow the typical transformation route, which with trichloro-lactams can proceed further to give 4-alkylidene derivatives. From a practical point of view, the outcome of the reaction with di- or trichloro N-cinnamylamides is synthetically valuable, affording the 5-methoxy-1H-pyrrol-2(5H)-one or 3-benzylidenepyrrolidine-2,5-dione, respectively, in good to excellent yield. 相似文献
3.
We report a theoretical investigation of the solution properties of Cu and Ag atoms dissolved in He clusters. Employing our recent ab initio ground state pair potential for Me-He (Me = Ag, Cu), we simulated the species Me@He (n) (n = 2-100) by means of diffusion Monte Carlo (DMC) obtaining exact information on their energetics and the structural properties. In particular, we investigated the sensitivity of structural details on the well depth of the two interaction potentials. Whereas Ag structures the first He solvation layer similarly, to some extent, to a positive ion such as Na(+), Cu appears to require the onset of a second solvation shell for a similar dense structure to be formed despite an interaction well of 28.4 μhartree. An additional signature of the different solution behavior between Ag and Cu appears also in the dependence of the energy required to evaporate a single He atom on the size of the MeHe(n) clusters. The absorption spectrum for the (2)P ← (2)S excitation of the metals was also simulated employing the semi-classical Lax approximation to further characterize Me@He(n) (n = 2-100) using novel accurate interaction potentials between He and the lowest (2)P state of Ag and Cu in conjunction with the Diatomic-in-Molecules approach. The results indicated that Ag exciplexes should not form via a direct vertical excitation into an attractive region of the excited manifolds and that there is an interesting dependence of the shape of the Cu excitation bands on the local structure of the first solvation shell. 相似文献
4.
The characteristic properties of the principal solution for half-linear differential equation
(a(t)Φ(x′))′+b(t)Φ(x)=0, 相似文献
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8.
Rodríguez-Castrillón JA Moldovan M García Alonso JI Lucena JJ García-Tomé ML Hernández-Apaolaza L 《Analytical and bioanalytical chemistry》2008,390(2):579-590
Isotope pattern deconvolution is a mathematical technique for isolating distinct isotope signatures from mixtures of natural
abundance and enriched tracers. In iron metabolism studies measurement of all four isotopes of the element by high-resolution
multicollector or collision cell ICP–MS allows the determination of the tracer/tracee ratio with simultaneous internal mass
bias correction and lower uncertainties. This technique was applied here for the first time to study iron uptake by cucumber
plants using 57Fe-enriched iron chelates of the o,o and o,p isomers of ethylenediaminedi(o-hydroxyphenylacetic) acid (EDDHA) and ethylenediamine tetraacetic acid (EDTA). Samples of root, stem, leaves, and xylem sap,
after exposure of the cucumber plants to the mentioned 57Fe chelates, were collected, dried, and digested using nitric acid. The isotopic composition of iron in the samples was measured
by ICP–MS using a high-resolution multicollector instrument. Mass bias correction was computed using both a natural abundance
iron standard and by internal correction using isotope pattern deconvolution. It was observed that, for plants with low 57Fe enrichment, isotope pattern deconvolution provided lower tracer/tracee ratio uncertainties than the traditional method
applying external mass bias correction. The total amount of the element in the plants was determined by isotope dilution analysis,
using a collision cell quadrupole ICP–MS instrument, after addition of 57Fe or natural abundance Fe in a known amount which depended on the isotopic composition of the sample. 相似文献
9.
The photochemistry of some Hantzsch 4-phenyl-1,4-dihydropyridines bearing a substituent on the phenyl ring (the three isomeric chloro derivatives and the 4′-nitro derivative) has been studied. All of these compounds underwent inefficient aromatization to the corresponding pyridines (quantum yield <10−4 at 366 nm, <10−2 at 254 nm). This process is scarcely affected by molecular oxygen and is initiated by proton transfer (from C4-H), probably to the solvent, from the excited singlet. In turn, the thus formed pyridines were photoreactive with comparable or higher efficiency. Thus, the 4-(3′-chlorophenyl) and 4-(4′-chlorophenyl) Hantzsch pyridines underwent positional rearrangement to form two isomers each. The reaction occurs via Dewar benzene--prismane path. In the case of the minor isomer a further 1,3-shift take place at the Dewar benzene level. The 4-(2′-chlorophenyl) derivative underwent C-Cl bond homolysis, which led to cyclization of the phenyl group onto one of the ester groups forming a pyrane ring. 相似文献
10.
Mella M 《The Journal of chemical physics》2007,126(20):204305
The dynamics of the isotopic scrambling in the energized and metastable complex D2O-H3O+ has been studied using classical molecular dynamics (MD) trajectories starting from regions of phase space corresponding to an already formed collisional complex. The simulations cover the range of internal energies spanned by gas phase collision experiments. Rate constants for the isotopic exchange and the complex dissociation have been computed; the isotopic branching ratio R=[HD2O+]/[H2DO+] has also been obtained from MD simulations and found to deviate substantially from an equivalent prediction based on a previously proposed kinetic scheme. This finding suggests the possibility that details of the reaction dynamics play a role in defining the isotopic branching ratio. The analysis of trajectory results indicated a relatively long lifetime for the collisional complex and the presence of multiple time scales for the exchange process, with a large fraction of the exchange events being separated only by a single oxygen-oxygen vibration or half of it. The occurrence of these fast consecutive jumps and their different probabilities as a function of the relative direction between first and second jumps suggest the presence of ballistic motion in the complex following each reactive event. This can be explained on the basis of overlapping regions in phase space and it is used to provide an explanation of the difference between kinetic and MD branching ratios. 相似文献