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941.
The mass spectrometric behavior of eleven 1-(N-benzyloxycarbonyl(Cbz)amino)alkylphosphonate diesters was studied under positive ion electrospray ionization (ESI) conditions. Their fragmentation pathways are depicted and supported by tandem mass spectrometry. Besides the common eliminations of ether, benzyl alcohol, phosphite and an ether plus benzyl alcohol from molecular ions, the title compounds show a tendency to undergo an interesting intramolecular benzyl rearrangement to yield benzylphosphonate ions. The fragmentation patterns do not depend on the substituent attached to the alpha-carbon atom. 相似文献
942.
The extended Koopmans’ theorem is related to Fukui function, which measures the change in electron density that accompanies
electron attachment and removal. Two approaches are used, one based on the extended Koopmans’ theorem differential equation
and the other based directly on the expression of the ionized wave function from the extended Koopmans’ theorem. It is observed
that the Fukui function for electron removal can be modeled as the square of the first Dyson orbital, plus corrections. The
possibility of useful generalizations to the extended Koopmans’ theorem is considered; some of these extensions give approximations,
or even exact expressions, for the Fukui function for electron attachment. 相似文献
943.
Shigeru Arimoto 《Journal of mathematical chemistry》2007,41(3):231-269
The present article is the first part of a series devoted to extending the Repeat Space Theory (RST) to apply to carbon nanotubes
and related molecular networks. Four key problems are formulated whose affirmative solutions imply the formation of the initial
investigative bridge between the research field of nanotubes and that of the additivity and other network problems studied
and solved by using the RST. All of these four problems are solved affirmatively by using tools from the RST. The Piecewise
Monotone Lemmas (PMLs) are cornerstones of the proof of the Fukui conjecture concerning the additivity problems of hydrocarbons.
The solution of the fourth problem gives a generalized analytical formula of the pi-electron energy band curves of nanotube
(a, b), with two new complex parameters c and d. These two parameters bring forth a broad class of analytic curves to which the PMLs and associated theoretical devices apply.
Based on the above affirmative solutions of the problems, a central theorem in the RST, called the asymptotic linearity theorem
(ALT) has been applied to nanotubes and monocyclic polyenes. Analytical formulae derived in this application of the ALT illuminate
in a new global context (i) the conductivity of nanotubes and (ii) the aromaticity of monocyclic polyenes; moreover an analytical
formula obtained by using the ALT provides a fresh insight into Hückel’s (4n+2) rule. The present article forms a foundation of the forthcoming articles in this series.
The present series of articles is closely associated with the series of articles entitled ‘Proof of the Fukui conjecture via
resolution of singularities and related methods’ published in the JOMC. 相似文献
944.
Highly concentrated, well-stable gold colloids can be prepared directly from an amine-bearing polyelectrolyte-HAuCl4 aqueous solution at room temperature. It is found that increasing molar ratio of polyelectrolyte to gold leads to increasing particle size. UV-vis spectra, transmission electron microscopy (TEM), and X-ray photoelectron spectra (XPS) were used to characterize the products thus formed. 相似文献
945.
A simple and very sensitive spectrophotometric method for the direct determination of copper ions 总被引:1,自引:0,他引:1
A sensitive spectrophotometric method for the direct determination of copper in aqueous samples without a preconcentration step has been developed. It is based on the formation of a yellow complex with the chromogenic reagent di-2-pyridyl ketone benzoylhydrazone (dPKBH) in an alkaline medium. The complex stoichiometry was 1:2 (Cu:dPKBH) and presents maximum absorbance at 370 nm. The influence of chemical variables affecting the behaviour of the system such as pH, concentration of dPKBH, buffer solution and ethanol, order of addition of the reagents and stability of the complex, were evaluated. The molar absorptivity (epsilon) was 3.92x10(4) L mol(-1) cm(-1), and Beer's law was obeyed up to 3 mg L(-1) of copper. The relative standard deviation was 0.46% (n=11) for a sample containing 1 mg L(-1) Cu(II). The limit of detection was 2.5 micro g L(-1) and was therefore more sensitive than the direct methods reported previously. Finally, the method was successfully validated by analysing several real samples with different matrices, such as tap water, natural water or copper alloys, with an average relative error of 2.46%. 相似文献
947.
Yi-Lu Sun Ren-Jang Wu Yu-Ching Huang Pi-Guey Su Murthy Chavali Yi-Zhen Chen Chu-Chieh Lin 《Talanta》2007,73(5):857-861
In situ preparation of polypyrrole (Ppy) by photo-polymerization coated on a quartz crystal microbalance (QCM) as a low humidity sensor was reported. Different concentrations of Ppy films say 0 wt.% (as blank), 0.1, 1, and 10 wt.% were investigated to measure humidity concentrations between 14.7 and 5412.5 ppmv. The adsorption/desorption behavior was also examined at humidity concentration 510.2 ppmv. The sensitivities of 0, 0.1 and 1 wt.% Ppy films at 51.5 ppmv were 0.143, 0.219 and 0.427, respectively. For 1 wt.% Ppy, the highest sensitivity was obtained. The slope and correlation coefficients (R2) for 1 wt.% Ppy at the ranges of 14.7–898.6 ppmv were 0.0646 and 0.9909, respectively. A series of molecular simulations have been carried out to calculate bond energy for the water molecule interaction with Ppy, which was found to be 3 kcal/mol indicating the existence of hydrogen bonding during the sorption process. Based on Langmuir isotherm adsorption assumption, for 0.1 and 1 wt.% Ppy films, the association constants were 2606.30 and 5792.98, respectively. This larger association constant for 1 wt.% Ppy film explains higher sensitivity. 相似文献
948.
N. A. Mohamed Farook 《Journal of solution chemistry》2007,36(3):345-356
The oxidation kinetics of substituted and unsubstituted 4-oxoacids (S) by N-chlorosaccharin (NCSA) have been studied in aqueous acetic acid media. The reaction follows first-order kinetics in each
of the 4-oxoacids, NCSA and H+. The effect of changes in the electronic nature of the substrate reveals that positive charge develops in the transition
state. Based on the kinetic results and product analysis, a suitable mechanism has been proposed for the reaction of NCSA
with 4-oxoacids. 相似文献
949.
煤的孔结构特征对水煤浆性质的影响 总被引:7,自引:3,他引:7
本文选用17种不同变质程度的中国煤,详细研究了煤孔结构特征对煤浆性质的影响。发现煤孔体积通过影响煤在分散体系中的吸水性,从而影响煤之成浆性。但由于不同变质程度煤表面亲水性的显著差异,煤孔体积在影响煤成浆性的能力方面差别很大,这使得煤吸水性和浆体最高煤浓度与煤孔体积并不存在直接的相关性,而是取决于煤孔体积V和以煤-水接触角(θ)的余弦值表示的煤表面亲水性因子的乘积,即煤之有效孔体积:V×cos(θ/ 相似文献
950.
Gamil A. Al-Hazmi Mohammed S. El-Shahawi Ahmed A. El-Asmy 《Transition Metal Chemistry》2005,30(4):464-470
The redox properties of the title mono- and binuclear copper(II) chelates have been investigated by cyclic voltammetry in DMF at a working platinum electrode. The cathodic reduction and anodic oxidation of the investigated chelates produced the corresponding electrochemical CuI and CuIIIspecies stable only in the voltammetric time scale, The effects of substituents on E1/2, redox properties and stability towards oxidation of the complexes were related to the electron-withdrawing or releasing ability of the substituents on the C=N1[H, CH3 or C6H5] and/or N4H [H, C2H5, C6H5 or pClC6H4] groups, The electron attracting substituents stabilize the Cu(II) complexes while electron-donating groups favor oxidation to Cu(III). Changes in the E1/2 for the complexes due to remote substituent effects could be related to changes in basicity of N4H.Thus, variation in N41-J has more influence on E1/2 than changes in C=N1. The correlation between E1/2 of the complexes and pKa of the ligands has been attributed to the spherical potential generated by the electron density of the donor atoms at the antibonding d orbitals. 相似文献