The availability of deuterium-labeled nicotinic acid makes stable isotope dilution mass spectromerty (MS) coupled with liquid chromatography (LC) an attractive option for the determination of the water-soluble B-vitamin niacin in food samples. A method was developed based on acid digestion, solid-phase extraction with a strong cation exchange column, and reversed-phase chromatography with a C18 column. Detection is by positive ion electrospray MS. Analysis in selected ion recording mode is subject to interference problems similar to those found with other LC determinations of niacin, but the additional selectivity of multiple reaction monitoring mode largely eliminates interference problems. The method was applied to 6 different food matrixes and to appropriate reference materials, including milk samples with niacin levels near 1 ppm. The method exhibited good accuracy, based on levels obtained for the reference materials, and relative standard deviations in the range of 0.5-5%. 相似文献
The complete basis set method CBS-QB3 has been used to study the thermochemistry and kinetics of the esters ethyl propanoate (EP) and methyl butanoate (MB) to evaluate initiation reactions and intermediate products from unimolecular decomposition reactions. Using isodesmic and isogeitonic equations and atomization energies, we have estimated chemically accurate enthalpies of formation and bond dissociation energies for the esters and species derived from them. In addition it is shown that controversial literature values may be resolved by adopting, for the acetate radical, CH3C(O)O(.-), DeltaH(o)(f)298.15K) = -197.8 kJ mol(-1) and for the trans-hydrocarboxyl radical, C(.-)(O)OH, -181.6 +/- 2.9 kJ mol(-1). For EP, the lowest energy decomposition path encounters an energy barrier of approximately 210 kJ mol(-1) (approximately 50 kcal mol(-1)), which proceeds through a six-membered ring transition state (retro-ene reaction) via transfer of the primary methyl H atom from the ethyl group to the carbonyl oxygen, while cleaving the carbon-ether oxygen to form ethene and propanoic acid. On the other hand, the lowest energy path for MB has a barrier of approximately 285 kJ mol(-1), producing ethene. Other routes leading to the formation of aldehydes, alcohols, ketene, and propene are also discussed. Most of these intramolecular hydrogen transfers have energy barriers lower than that needed for homolytic bond fission (the lowest of which is 353 kJ mol(-1) for the C(alpha)-C(beta) bond in MB). Propene formation is a much higher energy demanding process, 402 kJ mol(-1), and it should be competitive with some C-C, C-O, and C-H bond cleavage processes. 相似文献
By adjusting to the steric and electronic requirements of differing metal centers, the new multidentate monoanionic ligand [N(2)P(2)] has demonstrated a unique ability to stabilize a range of transition metal-dinitrogen complexes in a variety of oxidation states and coordination geometries. 相似文献
Submicron silver tubes have been synthesized by a polymer-based template approach. Two different approaches to metallization, electroless deposition and exchange plating, were evaluated within the template approach. Silver films with average thickness approximately 50-100 nm were deposited on polycarbonate fibers approximately 400 nm in diameter by each technique, resulting in tubes with a diameter between 450 and 500 nm after thermal degradation of core fibers. These nanomaterials were characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and scanning thermal microscopy. The thermal conductivity of the silver submicron tubes was found to differ depending on the method of preparation, with tubes from electroless plating possessing relative thermal conductivity values that were 1 order of magnitude higher than that from exchange plating, 3000 W/m x K and 660 W/m x K, respectively. Interestingly, these results indicate that silver submicron tubes possess higher thermal conductivity than the bulk metal. This observation is discussed in the context of the continuous conduction path of the tubes and their high surface area-to-volume ratio. 相似文献
We describe a new algorithm for finding integer solutions to for specific values of . We use this to find representations for values of for which no solution was previously known, including and .
We study the dynamics of a finite chain of diffusively coupled Lorenz oscillators with periodic boundary conditions. Such rings possess infinitely many fixed states, some of which are observed to be stable. It is shown that there exists a stable fixed state in arbitrarily large rings for a fixed coupling strength. This suggests that coherent behavior in networks of diffusively coupled systems may appear at a coupling strength that is independent of the size of the network. 相似文献
The static and dynamic properties of an amorphous polymer nanofiber are investigated via Monte Carlo simulation. Each nanofiber is composed of rings represented by 50 beads. The results are compared with recent simulation, by a similar method, of a nanofiber composed of linear chains with the same number of beads. The coarse‐grained model is one that permits reverse‐mapping of the macromolecules to C100H202 or C100H200. The radial density profiles can be fitted to a hyperbolic tangent function. The orientation of the chains is similar in the two fibers. The cyclic chains move slower than the linear chains, both on the scale of individual beads and on the scale of entire molecules. Both fibers experience an increase in mobility in the surface region, with this increase being larger in the fibers composed of linear chains. 相似文献
A novel, pyrene‐functionalised copolymer has been synthesised in a single step via imidisation of poly(maleic anhydride‐alt‐1‐octadecene) with 1‐pyrenemethylamine, and its potential for the detection of volatile nitro aromatic compounds (NACs) evaluated. The new copolymer forms complexes in solution with NACs such as 2,5‐dinitrobenzonitrile, as shown by 1H NMR, UV‐vis and fluorescence spectroscopy. Moreover, thin films of this copolymer, cast from THF solution, undergo almost instantaneous fluorescence quenching when exposed to the vapour of 2,5‐dinitrobenzonitrile (a model for TNT) at ambient temperatures and pressures.