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1.
2.
Atomic populations and localization [lambda(A)] and delocalization [delta(A,B)] indices (LIs and DIs) are calculated for a large set of molecules at the Hartree-Fock (HF), MP2, MP4(SDQ), CISD, and QCISD levels with the 6-311++G(2d,2p) basis set. The HF method and the conventional correlation methods [MP2, MP4(SDQ), CISD, and QCISD] yield distinct sets of LIs and DIs. Yet, within the four conventional correlation methods the differences in atomic populations and LIs and DIs are small. Relative to HF, the conventional correlation methods [MP2, MP4(SDQ), CISD, QCISD] yield virtually the same LIs and DIs for molecules with large charge separations while LIs and DIs that differ significantly from the HF values--the LIs are increased and DIs decreased--are obtained for bonds with no or small charge separations. Such is the case in the archetypal homopolar molecules HC(triple bond)CH, H2C=CH2, CH3-CH3, and "protonated cyclopropane" C(3)H(7) (+), in which case the bonding may be atypical. Relative to HF, the typical effect of the conventional correlation methods is to decrease the DI between atoms. 相似文献
3.
4.
Poly(ethylene glycol)-modified glucose oxidase was immobilized in a poly(vinyl alcohol) cryogel membrane, obtained by a freezing-thawing cyclic process, to obtain a suitable amperometric glucose sensor. The covalent linkage between PEG and GOD molecule improved the physical immobilization of enzyme in the polymeric matrix, by decreasing its loss in time. Sensor behaviour was evaluated electrochemically with a hydrogen peroxide electrode. The glucose content in standard solutions was determined and linear calibration curves in the 5x10(-5)-5x10(-3) mol l(-1) range were obtained. The kinetic parameters in the immobilized system were evaluated and analytical characteristics of sensor, including stability and influence of pH and temperature, were determined. 相似文献
5.
Gino Bontempelli Franco Magno Benedetto Corain Gilberto Schiavon 《Transition Metal Chemistry》1985,10(1):8-11
Summary The reduction of nickel perchlorate in the presence of carbon monoxide and substituted phosphines or diphosphines has been studied in acetonitrile by cyclic voltammetry. The results show that only mono- and bis-carbonylphosphinenickel(O) complexes are formed, while no evidence for the formation of carbonyl-nickel(I) and -nickel(II) species was obtained. Although the oxidation processes are not reversible, a good correlation between the anodic peak potentials relative to nickel(O) complexes and the -donor--acceptor abilities of the phosphines employed was observed. 相似文献
6.
Rosanna Toniolo Alan Valentino G. Bontempelli Gilberto Schiavon 《Fresenius' Journal of Analytical Chemistry》1998,360(2):260-262
A simple method for the analysis of nanoliter droplets is proposed, which is profitable when larger samples cannot be collected
as, for instance, in the case of several biological fluids and particularly in clinical chemistry. A glass capillary associated
to a micromanipulator is used to collect submicroliter volumes which are partially transferred into transparent polymeric
tubings with known internal diameters (120–178 μm), where the volumes sampled are measured by meniscus collimations with a
collimator microscope at suitable magnification. Both ends of these tubings are preliminarily equipped with ferrules and fittings,
so as to make them suitable for connection as the loop to a conventional high-pressure injection valve. The reliability of
this procedure has been tested for the analysis of Na+, K+ and Ca2+ present in minute synthetic standard samples (10–200 nL) by a conventional ion-chromatographic instrumentation. Relative
standard deviations in peak area measurements (5–6%) are discussed in terms of the whole approximation affecting volume measurements,
which depends on both the inconstancy of the inner diameter of the polymeric tubings employed and the uncertainty characterizing
meniscus collimations. The proposed procedure can be easily extended to the determination of any organic or inorganic species
present in very small samples, provided that their detection can be achieved by any chromatographic approach or, more generally,
by flow injection analysis.
Received: 16 June 1997 / Revised: 12 August 1997 / Accepted: 14 August 1997 相似文献
7.
The development of a very sensitive, direct injection high-performance liquid chromatographic method, using a post-column reactor with immobilized alcohol oxidase, was undertaken with the aim of determining methanol and ethanol levels in microlitre volumes of biological samples. After reversed-phase chromatography to separate methanol and ethanol, the analytes were enzymically converted into the respective aldehydes with formation of stoichiometric amounts of hydrogen peroxide, which could be measured via electrochemical oxidation at a platinum electrode. Some problems were encountered in the development of solid-phase enzymic reactors, using a delicate enzyme, that is prone to lose activity, such as alcohol oxidase. Owing to the slightly alkaline pH required for the optimum activity of alcohol oxidase, polymeric columns seemed to be preferable for the chromatography. HEMA copolymer was chosen as the stationary phase, but the methanol and ethanol peaks eluted close together and posed severe problems of limiting post-column band spreading. Reactors based on coarse supports for enzyme immobilization gave unacceptable band spreading, causing the methanol and ethanol peaks to overlap. On the other hand high-performance liquid chromatographic packings maintained the efficiency of the chromatographic separation, quite independently of the reactor volume. Polymeric supports proved superior to silicas in maintaining the enzyme activity. However, relevant changes in the enzyme substrate specificity were observed after immobilization. 相似文献
9.
We use molecular dynamics simulations to investigate the structure of the hydrated Na-Nafion membranes. The membrane is "prepared" by starting with the Nafion chains placed on a cylinder having the water inside it. Minimizing the energy of the system leads to a filamentary hydrophilic domain whose structure depends on the degree of hydration. At 5 wt % water the system does not have enough water molecules to solvate all the ions that could be formed by the dissociation of the -SO3Na groups. As a result, the -SO3Na groups aggregate with the water to form very small droplets that do not join into a continuous phase. The size of the droplets is between 5 and 8 A. As the amount of water present in the membrane is increased, the membrane swells, and SO3Na has an increasing tendency to dissociate into ions. Furthermore, a transition to a percolating hydrophilic network is observed. In the percolating structure, the water forms irregular curvilinear channels branching in all directions. The typical dimension of the cross section of these channels is about 10-20 A. Calculated neutron scattering from the simulated system is in qualitative agreement with experiment. In all simulations, the pendant sulfonated perfluorovinyl side chains of the Nafion hug the walls of the hydrophilic channel, while the sulfonate groups point toward the center of the hydrophilic phase. The expulsion of the side chains from the hydrophilic domain is favored because it allows better interaction between the water molecules. We have also examined the probability of finding water molecules around the Na+ and the -SO3(-) ions as well as the probability of finding other water molecules next to a given water molecule. These probabilities are much broader than those found in bulk water or for one ion in bulk water (calculated with the potentials used in the present simulation). This is due to the highly inhomogeneous nature of the material contained in the small hydrophilic pores. 相似文献
10.
Nick Herbert 《Foundations of Physics》1982,12(12):1171-1179
The FLASH communicator consists of an apparatus which can distinguish between plane unpolarized (PUP) and circularly unpolarized (CUP) light plus a simple EPR arrangement. FLASH exploits the peculiar properties of measurements of the Third Kind. One purpose of this article is to focus attention on the operation of idealized laser gain tubes at the one-photon limit.FLASH: acronym for First Laser-Amplified Superluminal Hookup. 相似文献