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991.
Yinghong Sheng Jerzy Leszczynski Thuc-Quyen Nguyen Anu Bamgbelu 《Structural chemistry》2007,18(6):827-832
A theoretical study using density functional theory was performed to understand the structure/property relationship of the
cationic conjugated polyelectrolytes, poly[9,9-bis-(6′-N,N,N-trimethylammonium) hexyl] fluorene-alt-4,7-(2,1,3-benzothiadiazole)] (PFBT-X, where X = Br). The torsion angle between the fluorene and benzothiadiazole units in the PFBT monomer was found to substantially affect
the structural and electronic properties of the cationic PFBT monomer. The changes of geometrical parameter, HOMO and LUMO energy levels, and band gap, as well as the absorption maximum
are discussed in terms of the torsion in the PFBT monomer structure. For comparison, its neutral analogue, the monomer of
poly(9,9-di-n-octylfluorene-alt-benzothiadiazole) (F8BT) was also studied. The length of conjugation backbone was also examined. 相似文献
992.
Electrodeposition of nanocrystalline zinc from acidic sulfate solutions containing thiourea and benzalacetone as additives 总被引:1,自引:0,他引:1
Mou Cheng Li Li Li Jiang Wen Qi Zhang Yu Hai Qian Su Zhen Luo Jia Nian Shen 《Journal of Solid State Electrochemistry》2007,11(4):549-553
Nanocrystalline zinc coatings were produced by pulse electrodeposition in acid sulfate bath containing thiourea and benzalacetone
additives and characterized by X-ray diffraction and scanning electron microscopy techniques. The influence of benzalacetone
concentration and pulse peak current density on the grain size and crystallographic orientation of zinc deposits was investigated.
Zinc electrodeposited from additive-free solutions or with one of the two additives is not composed of nanosized crystals.
The mixture additives of thiourea and benzalacetone give rise to the formation of particle-like nanocrystalline zinc with
a (10ī1) random orientation. A change in peak current density from 2 to 1 A/cm2 only increases the grain size from 60 to 62 nm. 相似文献
993.
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
994.
An easy method for the determination of the enantiomeric excess (ee) of mixtures of alpha-amino acids, and also for the elucidation of the absolute configuration of each component of the mixture, is reported. The method is based on the formation of diastereoisomers by reaction of the enantiomerically pure acetylacetonate derivative [Pd(acac-O,O')(P(2)-dach)]ClO(4) (4) [P(2)-dach = (1R,2R)-C(6)H(10)(NHPPh(2))(2)] with d,l-mixtures of alpha-amino acids AaH (Pd:AaH = 1:1 molar ratio, refluxing MeOH). The reaction occurs with protonation of the acac ligand and N,O-coordination of the amino acidate group, giving the corresponding [Pd(Aa-N,O)(P(2)-dach)]ClO(4) complexes l-5 and d-6. The composition of these mixtures of amino acidate complexes was analyzed by integration of the corresponding peaks (four doublets, two for each diastereomer) in their (31)P((1)H) NMR spectra. A series of 14 alpha-amino acids was studied (a, alanine; b, 2-aminobutyric acid; c, valine; d, phenylalanine; e, proline; f, leucine; g, isoleucine; h, norleucine; i, serine; j, threonine; k, methionine; l, aspartic acid; m, glutamine; n, cysteine), and excellent agreement between the expected values of ee and those obtained from integration of the (31)P((1)H) NMR spectra was obtained. Moreover, the position of the signals of each isomer is diagnostic, in such a way that the outer doublets are always due to the l-derivatives 5a-l, while the inner ones are due to the d-derivatives 6a-l, allowing the assignation of absolute configurations to each isomer in the mixture. 相似文献
995.
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
996.
Csar Ricardo Teixeira Tarley Srgio Luis Costa Ferreira Marco Aurlio Zezzi Arruda 《Microchemical Journal》2004,77(2):163-175
The use of rice husks as an alternative adsorbent in an on-line preconcentration system for Cd (II) and Pb (II) determination by flame atomic absorption spectrometry (FAAS) is described. The potential of rice husks as a natural adsorbent was evaluated as a material modified with 0.75 mol l−1 NaOH solution and in the unmodified form. For this task, several techniques such as spectroscopy and thermogravimetry were used for elucidation of possible functional groups responsible for the uptake of Cd (II) and Pb (II). Furthermore, based on adsorption studies and adsorption isotherms applied to the Langmüir model, it was possible to verify that modified rice husks present a higher adsorption capacity for both metals. After establishing this material as a promising natural adsorbent, it was used for on-line preconcentration of Cd (II) and Pb (II) metals. The multivariate optimisation of chemical and flow variables was performed by using a full factorial design (24) including the following factors: preconcentration time, preconcentration flow rate, concentration and volume of eluent. The optimum pH values used for on-line preconcentration were taken from prior univariate experiments. Under optimised conditions for Cd (II) determination (4 min of preconcentration at a 6 ml min−1 preconcentration flow rate, in which comprises 24 ml of preconcentration volume, 200 μl elution volume and 1.0 mol l−1 HNO3 solution as eluent), the system achieved a detection limit of 1.14 μg l−1 and an enrichment factor of 72.4. Similar conditions were used for Pb (II) determination (4 min of preconcentration, 6 ml min−1 preconcentration flow rate, 300 μl elution volume and 1.0 mol l−1 HNO3 solution as eluent) from which a detection limit of 14.1 μg l−1 and enrichment factor of 46.0 were achieved. Also, rice husks have been shown to be a homogeneous and stable adsorbent in which more than 100 preconcentration/elution cycles provide a relative standard deviation (RSD) of less than 6.0% on the analytical signal. The satisfactory accuracy of the method developed was obtained by using spiked water samples (mineral water and lake water) and spiked red wine samples. These values were confirmed by electrothermal atomic absorption spectrometry (ETAAS). The certified reference material [pig kidney (CRM 186)] and the reference material [beech leaves (CRM 100)] were also used. 相似文献
997.
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
998.
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
999.
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
1000.
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