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991.
Remedios González-Luque Manuela Merchán Piotr Borowski Björn O. Roos 《Theoretical chemistry accounts》1993,86(6):467-476
Summary Multiconfigurational electron correlation methods have been analyzed in order to theoretically compute the electron affinity (EA) of ozone. The near-degeneracy correlation effects, which are so important in O3 and O
3
–
, have been described using complete active space (CAS) SCF wave functions. Remaining dynamic correlation effects are computed using second-order perturbation theory (the CASPT2 method). The best calculated adiabatic value (including zero-point energy corrections), 2.19 eV, is about 0.09 eV larger than the experimental value. Comparative studies using size-consistent coupled pair functional approaches (CPF and ACPF) have also been performed. The harmonic frequencies in O
3
–
have been determined to be: 1=992, 2=572, and 3=879 cm–1, which gives a zero-point energy of 0.151 eV. 相似文献
992.
Mid infrared spectroscopy is a non-destructive technique that can provide detailed information on important, molecule-specific features such as the conformation and functional groups of a large range of compounds. Infrared spectroscopy is now an established and frequently used technique for qualitative analysis, i.e. the identification of chemical constituents in a sample. In addition, its use for quantitative purposes has grown dramatically in recent years. It is important to realise that the analytical problem defines the mode of operation and implementation of the FTIR technique. This Highlight article focuses on the advantages and scope of on-line FTIR detection strategies. However, in common with all techniques, on-line FTIR detection has a number of potential shortcomings, which are also discussed. 相似文献
993.
J. Krägel J. B. Li R. Miller M. Bree G. Kretzschmar H. Möhwald 《Colloid and polymer science》1996,274(12):1183-1187
The surface viscoelastic properties of monolayers of two phospholipids DPPC (L--dipalmitoylphosphatidylcholine) and DMPE (L--dimyristoylphosphatidyl-ethanolamin), at the air-water interface have been investigated. Two techniques were used for the investigation. One involved use of an interfacial shear rheometer (torsion pendulum apparatus ISR1), to provide measurements of the shear viscosity s as a function of surface pressure, and the second, a modified LB trough with an oscillating barrier to generate periodie dilation and compression so as to measure the dilational elastic modulusE as a function of surface area.Results indicate a strong dependence of s andE upon monolayer phases. This suggests that the viscoelastic relaxation of monolayers can be understood as molecular rearrangements, domain exchange and molecular reorientations between different monolayer states. 相似文献
994.
The enzyme catalyzed conversion of R/S-(±)-2-octanol with hexanoic acid to R/S-(±)-2-octyl hexanoate has been studied in
different microenvironments and in the presence of the competing substrate ethanol. The reactions were performed in various
gels made from aqueous gelatin solutions and liposome dispersions or isotropic liquid solutions, with or without oil and ethanol.
The lipase Candida sp. (SP 525) was dissolved in the dispersions or solutions stabilized by the naturally occurring zwitterionic surfactant
soybean lecithin. The sectioned porous gel was immersed in hexane containing 0.33 mol dm-3 of racemic 2-octanol and hexanoic acid. Since ethanol acts both as a substrate and as a part of the gel it is of fundamental
interest to know the phase behaviour of the used systems. Partial phase diagrams for the systems ethanol–water–soybean lecithin
and ethanol/water (7:3)–oil–soybean lecithin were determined at 298.2 K. The oil was either castor oil or hexadecane. The
conversion of R-2-octyl hexanoate was about 0.45 when no or small amounts of ethanol was present, but decreased considerably
with high amounts of ethanol present and ethyl hexanoate became the main product. Hydrolysis of R-2-octyl hexanoate was favoured
in the latter systems and hexanoic acid formed was immediately esterified to ethyl hexanoate. The conversion of R-2-octyl
hexanoate and ethyl hexanoate depends only on the ethanol content present in the systems and is thus independent of the environment
of the enzyme. However, the chiral esters synthesized from racemic 2-octanol and hexanoic acid showed high optical purities
regardless of the ethanol content.
Received: 1 July 1996 Accepted: 30 August 1996 相似文献
995.
The measurement is carried out of aqueous solutions. The burner is supplied with a mixture of acetylene and nitrous oxide. Interfering influences by acid and iron concentrations of the sample solution as well as by organic solvents are shown. The standard deviation is ± 0.001%. The agreement with conventional analysis methods is very good. By this procedure a rapid and safe determination of aluminium will be possible. 相似文献
996.
Eberling J Braun P Kowalczyk D Schultz M Kunz H 《The Journal of organic chemistry》1996,61(8):2638-2646
The selective C-terminal deprotection of O-glycopeptide (methoxyethoxy)ethyl esters is achieved under mild conditions (pH 6.6, 37 degrees C) by enzymatic hydrolysis using papain or lipase M from Mucor javanicus to give building blocks useful for chain-extending glycopeptide synthesis. On the other hand, the selective removal of acetyl protecting groups from the saccharide portion of glycopeptides is accomplished by alternative enzymatic hydrolysis with lipase WG from wheat germ to furnish model substrates for enzymatic glycosyl transfer reactions in order to extend the carbohydrate side chain of these conjugates. 相似文献
997.
James O'Donnell Bruno Rusterholz Barbara Aebersold Denise Rüegg Wilhelm Simon Ernö Pretsch 《Mikrochimica acta》1994,113(1-2):45-52
In an investigation of octamethylene bis(malonic acid diamides) and their selectivities for magnesium, it was found that presence of secondary amides within the particular ionophore played a considerable role in the enhancement of magnesium selectivity. Similar effects in other ionophores, i.e. tris(malonic acid diamides), were thus systematically looked at with the help of selectivity measurements with the hope of optimizing the number of secondary and tertiary amides so as to improve the magnesium selectivity. The syntheses of several investigated tris(malonic acid diamide) isologues are equally reported.Deceased in November 1992 相似文献
998.
A. Oumghar J. C. Legrand A. M. Diamy N. Turillon R. I. Ben-Aïm 《Plasma Chemistry and Plasma Processing》1994,14(3):229-249
Conversion of CH4 with a N2 microwave plasma (2.45 GHz) is studied. The experiments cover the absorbed microwave power range 300–700 W with 17–62% of methane in the gas mixture, with pressures of 10–40 mbar and flow rates of 140–650 ml· min–1. The yields of C2 hydrocarbons and dihydrogen are analyzed by gas chromatography. The distance of methane addition downstream of the plasma plays an important role on the composition and the concentration of the products obtained. This distance mainly determines the energy concentrated in the active species of the plasma when they react with methane. Different behaviors for acetylene formation, on the one hand, and for ethane and ethene formation, on the other hand, have been observed, and this finding allows us to propose a kinetic mechanism for the decay of methane and for the formation of C2 hydrocarbons. 相似文献
999.
The amphiphilic shape-persistent macrocycle 1 containing four phenol-OH groups as polar side groups and four hexyloxy groups as nonpolar side groups in an adaptable arrangement was recrystallized from solvents of different polarity. X-ray crystallography reveals that the conformation of the macrocycle is solvent dependent such that in the pyridine solvate only two of the nonpolar side groups point outward while in the THF solvate all four of them point outward. Moreover, in the latter case the three-dimensional packing leads to the formation of a supramolecular channel structure with a large pore size. 相似文献
1000.
- The concentration dependence of theF/A-isotherms (premixed spreading, separate spreading) and the equilibrium spreading pressuresF e of the system dipalmitoylcephaline/dimyristoyl-cephaline were studied atT=298 K. The results were analysed and compared by means of thermodynamics with respect to miscibility of the components.
- The spreading technique (pre-mixed spreading, separate spreading (with and without barrier), does not essentially influence the run of theF/A-isotherm. Alone, the collaps pressuresF K differ.
- The concentration dependence of theF/A-isotherms of premixed spread monolayers is analysed in terms of theA-x σ-diagram. The additivity of molecular areas at all surface pressures are assumed to indicate complete miscibility of the cephalins.
- The phase rule according to Crisp was applied to analyse the spreading diagram in connection with the phase diagram of the mixtures in bulk. The results show that the cephalins are completely miscible in the monolayer.
- The experimental collaps pressuresF K of pre-mixed spread monolayers are very much larger than the equilibrium collapse presuresF K calculated according to Garrett. The difference indicate the strong supercompression of mixed film during the compression.