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841.
Su-Hong Ge Xin-Lu Cheng Xin-Xing Wang Guang-xing Dong Gui-hua Sun 《Structural chemistry》2007,18(6):985-991
Some explosives are stable molecules with large energy barriers to chemical reaction, and in shock or impact initiation, a
sizable amount of phonon energy must be converted to the molecular internal higher vibrations by multiphonon up pumping. To
investigate the relationship between impact sensitivities and energy transfer rates, the number of doorway modes of explosive
molecules is estimated by a simple theory in which the rate is proportional to the number of normal mode vibrations. We evaluated
frequencies of normal mode vibrations of 13 explosive molecules which are CHNO nitramine-contained and have not been analyzed
previously. The number of doorway modes in the regions of 200–700 cm−1 was evaluated by the direct counting method. For more clear investigation of the relationship we have classified these 13
nitramine explosive molecules, by the number of nitramine group they contained, into two groups. There are eight molecules
that contained one nitramine group and five molecules that contained poly-nitramine groups. It is found that the number of
doorway modes shows a linearly correlation to the impact sensitivities derived from drop hammer tests. This result is in agreement
with that of several previous works. Besides, it is also noted in our study that in those nitramine explosives molecules with
similar molecular structure (similar number nitramine group they contained) and similar molecular weight, the correlation
between the sensitivity and the number of doorway modes is higher. We found that the vibrational frequency of ω corresponds
to nitro group motions of every molecule is contributed to the number of doorway modes in the regions of 200–700 cm−1. 相似文献
842.
Neira-Carrillo A Yazdani-Pedram M Retuert J Diaz-Dosque M Gallois S Arias JL 《Journal of colloid and interface science》2005,286(1):134-141
The biopolymer chitosan was chemically modified by grafting polyacrylamide or polyacrylic acid in a homogeneous aqueous phase using potassium persulfate (KPS) as redox initiator system in the presence of N,N-methylene-bis-acrylamide as a crosslinking agent. The influence of the grafted chitosan on calcium salts crystallization in vitro was studied using the sitting-drop method. By using polyacrylamide grafted chitosan as substrate, rosette-like CaSO4 crystals were observed. This was originated by the presence of sulfate coming from the initiator KPS. By comparing crystallization on pure chitosan and on grafted chitosan, a dramatic influence of the grafted polymer on the crystalline habit of both salts was observed. Substrates prepared by combining sulfate with chitosan or sulfate with polyacrylamide did not produce similar CaSO4 morphologies. Moreover, small spheres or donut-shaped CaCO3 crystals on polyacrylic acid grafted chitosan were generated. The particular morphology of CaCO3 crystals depends also on other synthetic parameters such as the molecular weight of the chitosan sample and the KPS concentration. 相似文献
843.
The Diels-Alder reaction of protonated N-benzyl imine of methyl glyoxylate with cyclopentadiene in different solvents gave mixtures of exo/endo adducts. The exo/endo selectivity of the reaction was elucidated by NMR experiments. Theoretical calculations by means of density functional theory (DFT) at the B3LYP/6-31G(d) level have also been performed to elucidate the molecular mechanism of this reaction. The DFT results suggest a highly asynchronous concerted mechanism, which in turn can explain the preferred exo stereoselectivity of the reaction. Inclusion of solvent effects enhances the exo selectivity, and this effect increases with the polarity of the solvent, in good agreement with the experimental findings. 相似文献
844.
The inducing method for preparing Ag-micelle solution with the use of mixed solvent/nonsolvent, and the morphological characterization of the generated metal–micelles were investigated and reported in this paper. In this method, an Ag containing metal chelate polymer (MCP) raw solution was preprepared by dissolving poly(vinyl acetate) (PVAc)–silver nitrate (AgNO3) MCP in conc. formic acid, and a mixed solvent of HCOOH/H2O with specific water composition was then added to induce the micellization of the MCP chain. The critical water concentration (CWC) that was needed for inducing the formation of the Ag-micelles, and the water concentration at which the flocculation of the Ag-micelles occurred in micellar solution, were studied by measuring the transmittance of the dilute MCP solution; the results showed that a long-lasting MCP solution with stable micelles might be prepared by using a H2O/HCOOH solvent of specific weight ratio 1:1.2. The effect of the AgNO3 concentration on the morphology of the Ag-micelles was also investigated by transmission electron microscopy (TEM). At AgNO3 concentration below 0.5 wt%, the Ag-micelles displayed a variety of core-shell structure; but as the AgNO3 concentration was increased to 1.0–2.0 wt%, micelles that had Ag-solid embedded in the micellar core were observed. 相似文献
845.
Binary excess molar volumes, V
m
E, have been evaluated from density measurements, using a vibrating tube densimeter over the entire composition range for binary
liquid mixtures of ionic liquids 1-ethyl-3-methyl-imidazolium diethyleneglycol monomethylethersulphate [EMIM]+[CH3(OCH2CH2)2OSO3]− or 1-butyl-3-methyl-imidazolium diethyleneglycol monomethylethersulphate [BMIM]+[CH3(OCH2CH2)2OSO3]− or 1-methyl-3-octyl-imidazolium diethyleneglycol monomethylethersulphate [MOIM]+[CH3(OCH2CH2)2OSO3]−+methanol and [EMIM]+[CH3(OCH2CH2)2OSO3]−+water at 298.15, 303.15 and 313.15 K. The V
m
E values were found to be negative for all systems studied. The V
m
E results are explained in terms of intermolecular interactions and packing effects. The experimental data were fitted by the
Redlich-Kister polynomial. 相似文献
846.
Coordination reactions of copper(II) ions and their effect on non-covalent interactions in uridine (Urd) or uridine 5′-monophosphate (UMP) systems with nucleosides (Ado, Cyd, Thd) and nucleotides (AMP and CMP) in aqueous solutions have been studied. At high pH the effective coordination centers are deprotonated N(3) atoms from Urd and Thd, whereas at low pH, the N(3) atoms of pyrimidine nucleosides are blocked for coordination and the metallation sites are endocyclic
nitrogen atoms from Ado, Cyd, AMP and CMP. Moreover, at low pH, the main reaction center in nucleotide solutions is the phosphate group. The NMR study has proven the
occurrence of non-covalent ion-dipole interactions and stacking interactions in the systems considered. Introduction of a
copper ion in the majority of systems causes the disappearance of weak interactions between ligands. The structures of the
complexes in solution have been inferred from the equilibrium study: an analysis of the pH range of their occurrence with
respect to the pH range of deprotonation of particular groups in the compounds studied, using Vis, EPR and 13C as well as 31P NMR spectral analysis. 相似文献
847.
We present a method for computing classical Newtonian trajectories that minimize the path length or transit time from reactant
to product. Our approach is based on a generalization of the fast-marching method, which allows us to construct the solution
of the Hamilton-Jacobi equation for the action that optimizes the desired quantity. The resulting “reactive paths” can be
interpreted as reaction coordinates but, unlike more conventional choices, they contain dynamical information about the chemical
system of interest. 相似文献
848.
Jeong Hwan Kim Ji Hoon Ko Byeong-Soo Bae 《Journal of Sol-Gel Science and Technology》2007,41(3):249-255
Multi-scale hybrid nanocomposites containing both ∼15 nm silica colloids and ∼2 nm oligosiloxanes in a methacryl polymer matrix
were newly designed and fabricated. Colloidal silica sols were dispersed in methacryl oligosiloxanes nano-hybrid resins synthesized
by sol-gel reaction of methacryloxypropylmethoxysilane and diphenylsilanediol. On the basis of TEM and SANS analyses, it was
confirmed that the silica colloids were compatibly dispersed and different sizes of colloidal silica and oligosiloxanes co-exist
in the solutions. Multi-scale hybrid nanocomposites fabricated by UV and thermal curing with incorporation of silica colloids
in the nano-hybrid materials show enhanced mechanical and thermal characteristics. 相似文献
849.
The geometry of the 4′-cyano-(4′-CNPTB) and the 4′-methoxy-(4′-MePTB) phenylthiolbenzoates were obtained by ab initio calculations
employing 6–31G basis set at Hartee-Fock level of theory. The results predict an extended form of the molecules and torsional
angle between the phenyl rings at 90.85(6)0 and 90.87(3)0, respectively. On the basis of vibrational analysis the frequency assignment was carried out. The calculated frequencies
were compared with the experimental IR spectral data in carbon tetrachloride, carbon disulfide solutions and in solid state. 相似文献
850.
František Kvasnička Rudolf Ševčík Michal Voldřich Jana Krátká 《Central European Journal of Chemistry》2004,2(3):417-424
A simple and rapid capillary zone electrophoresis (CZE) method for the determination of aristolochic acid (AA) in dietary
supplements and selected herbs is described. A clear separation of AA from other sample constituents was achieved within 5
minutes without any sample clean up. A mixture of 20 mM-morpholinethanesulphonic acid+10 mM-BisTrisPropane+0.2% hydroxyethylcelullose
in 10% methanol serves as a background electrolyte. The linearity, accuracy, intra-assay and detection limit of the developed
method are 200–6000 ng/mL, 95–103%, 3.5%, and 50 ng/ml, respectively. Ease of use, sufficient sensitivity and low running
cost are the most important attributes of the CZE method. The proposed CZE method was compared with HPLC. 相似文献