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11.
Ursula E. Spichiger Rudolf Eugster E. Haase G. Rumpf Peter Gehrig Angela Schmid Bruno Rusterholz Wilhelm Simon 《Fresenius' Journal of Analytical Chemistry》1991,341(12):727-731
Summary The selectivity of a new magnesium ionophore (ETH 7025) induced in membranes of different compositions is experimentally studied in view of the ion activities in human serum. The required selectivity coefficient against calcium for the application of an ion-selective magnesium electrode to human serum is calculated for the worst case. Other critical parameters for the application of a liquid PVC-based ion-selective membrane to undiluted human serum discussed are: the sensor lifetime which is related to the lipophilicity of the carrier as well as the ruggedness of the membrane against interactions with components of the relatively lipophilic sample. 相似文献
12.
Ursula Ehrmann Lante Carbognani Claudio Ceccarelli 《Journal of separation science》1992,15(7):467-471
Two methods have been developed for the determination of trace levels of acetonitrile and propionitrile in light naphthas. One involves clean-up and preconcentration by medium pressure liquid chromatography (MPLC) in which nitriles are concentrated ten-fold while the complex hydrocarbon matris is removed. The concentrated solution is then analyzed by high resolution GC with flame ionization detection. The second method involves direct injection of samples into a capillary GC equipped with chemiluminescence nitrogen detection. The results and repeatability obtained from both methods are comparable. Preconcentration enables identification by GC-MS and simultaneous analysis of other polar species, with no need for selective detectors. Direct analysis is, on the other hand, much less time-consuming and requires less sample. 相似文献
13.
Enhancing the enzymatic hydrolysis of cellulosic materials using simultaneous ball milling 总被引:1,自引:0,他引:1
Mais Ursula Esteghlalian Ali R. Saddler John N. Mansfield Shawn D. 《Applied biochemistry and biotechnology》2002,98(1-9):815-832
One of the limiting factors restricting the effective and efficient bioconversion of softwood-derived lignocellulosic residues
is the recalcitrance of the substrate following pretreatment. Consequently, the ensuing enzymatic process requires relatively
high enzyme loadings to produce monomeric carbohydrates that are readily fermentable by ethanologenic microorganisms. In an
attempt to circumvent the need for larger enzyme loadings, a simultaneous physical and enzymatic hydrolysis treatment was
evaluated. A ball-mill reactor was used as the digestion vessel, and the extent and rate of hydrolysis were monitored. Concurrently,
enzyme adsorption profiles and the rate of conversion during the course of hydrolysis were monitored. α-Cellulose, employed
as a model substrate, and SO2-impregnated steam-exploded Douglas-fir wood chips were assessed as the cellulosic substrates. The softwood-derived substrate
was further posttreated with water and hot alkaline hydrogen peroxide to remove >90% of the original lignin. Experiments at
different reaction conditions were evaluated, including substrate concentration, enzyme loading, reaction volumes, and number
of ball beads employed during mechanical milling. It was apparent that the best conditions for the enzymatic hydrolysis of
α-cellulose were attained using a higher number of beads, while the presence of air-liquid interface did not seem to affect
the rate of saccharification. Similarly, when employing the lignocellulosic substrate, up to 100% hydrolysis could be achieved
with a minimum enzyme loading (10 filter paper units/g of cellulose), at lower substrate concentrations and with a greater
number of reaction beads during milling. It was apparent that the combined strategy of simultaneous ball milling and enzymatic
hydrolysis could improve the rate of saccharification and/or reduce the enzyme loading required to attain total hydrolysis
of the carbohydrate moieties. 相似文献
14.
4-(N,N-dioctylamino)-4-trifluoroacetyl-azobenzene (ETHT 4001), together with the catalyst tridodecylmethylammonium chloride, is dissolved in the hydrophilic polymer polyurethane Tecoflex. The resulting membrane layers show high sensitivity toward water vapour and allow the application of the membranes for humidity measurements. Upon exposure to humid air, the membrane exhibits a decrease in absorbance at a wavelength around 490 nm and an increase at around 430 nm. This signal change is caused by the conversion of the trifluoroacetyl group of the reactand into a diol, thus changing the electron delocalisation of the reactand. The sensor layer exhibits a dynamic range from 1% to 100% RH with highest sensitivity in the 5%–40% RH range. The limit of detection is 0.5% RH. The amount of added catalyst enables the sensitive range to be tailored. The selectivity over ethanol and carbonate is sufficient for the membrane to be used for long-term measurements of air. The change in colour of the humidity-sensitive membrane from red to yellow also means it can be used as an optical test strip. 相似文献
15.
Different methods for representing the upper orbitals in Rydberg transitions are tested by means of a series of ab initio SCF and CI calculations for ethylene and various properties for such diffuse united-atom species are reported. Calculated transition energies indicates the maximum separation between individual components of the (π,3d) Rydberg species to be in the 0.1-0.2 range, with similarly small energy separations being obtained for the corresponding (π, 3p) states 相似文献
16.
17.
Ursula Baumann 《Fresenius' Journal of Analytical Chemistry》1963,193(6):456
Ohne Zusammenfassung
Folin, O.: Hoppe-Seylers Z. physiol. Chem. 41, 223 (1904); vgl. diese Z. 44, 459 (1905). 相似文献
18.
Ursula Schmid Paul Gilgen Heinz Heimgartner Hans-Jürgen Hansen Hans Schmid 《Helvetica chimica acta》1974,57(5):1393-1403
Irradiation of 2, 3-diphenyl-2H-azirine ( 1a ) and 1-azido-1-phenyl-propene, the precursor of 2-methyl-3-phenyl-2H-azirine ( 1b ), in benzene, with a high pressure mercury lamp (pyrex filter) in the presence of acid chlorides yields the oxazoles 5a–d (Scheme 2). Photolysis of 2, 2-dimethyl-3-phenyl-2H-azirine ( 1c ) under the same conditions gives after methanolysis the 5-methoxy-2, 2-dimethyl-4-phenyl-3-oxazolines 7a, b, d , while hydrolysis of the reaction mixture leads to the formation of the 1, 2-diketones 8a, c, d (Scheme 4). The suggested reaction path for all these reactions is a 1, 3-dipolar cycloaddition of the photochemically generated benzonitrilemethylides 2 to the carbonyl double bond of the acid chlorides to give the intermediates 4 , followed by either elimination of hydrogen chloride or solvolysis (Schemes 2 and 4). Irradiation of 1c in the presence of acetic acid anhydride leads via the intermediate 9 to the 5-hydroxy-3-oxazoline 10 and the 5-methylidene-3-oxazoline 11 (Scheme 5). 相似文献
19.
Hartmut Schmidt‡ Ahmed Al-Ibrahim Ursula Dietzel Ludwig Bieker 《Photochemistry and photobiology》1981,33(1):127-130
Abstract— The quantum yield of the photodynamic inactivation of lysozyme increases in the sequence acridine orange, methylene blue, proflavine and acriflavine (1:5:6:12). At least up to protein concentrations of 0.1 m M , singlet oxygen is exclusively responsible for the inactivation of the enzyme. For methylene blue, acriflavine and proflavine the quantum yields decrease considerably with increasing dye concentrations. From measurements in H2 O and D2 O buffer solutions it was concluded that in the case of methylene blue the effect is mainly caused by the quenching of singlet oxygen [rate constant (3–4) × 108 M −1 s−1 ]. For the acridine sensitizers both singlet oxygen and dye triplet quenching processes have to be taken into consideration. It has been found that all sensitizers act as competitive inhibitors of the enzymatic reaction of lysozyme. However, the dye-protein interaction near the active center cannot be responsible for the observed dye self-quenching effect. 相似文献
20.
Cascella M Micheletti C Rothlisberger U Carloni P 《Journal of the American Chemical Society》2005,127(11):3734-3742
The biological function of the aspartic protease from HIV-1 has recently been related to the conformational flexibility of its structural scaffold. Here, we use a multistep strategy to investigate whether the same mechanism affects the functionality in the pepsin-like fold. (i) We identify the set of conserved residues by using sequence-alignment techniques. These residues cluster in three distinct regions: near the cleavage-site cavity, in the four beta-sheets cross-linking the two lobes, and in a solvent-exposed region below the long beta-hairpin in the N-terminal lobe. (ii) We elucidate the role played by the conserved residues for the enzymatic functionality of one representative member of the fold family, the human beta-secretase, by means of classical molecular dynamics (MD). The conserved regions exhibit little overall mobility and yet are involved into the most important modes of structural fluctuations. These modes influence the substrate-catalytic aspartates distance through a relative rotation of the N- and C-terminal lobes. (iii) We investigate the effects of this modulation by estimating the reaction free energy at different representative substrate/enzyme conformations. The activation free energy is strongly affected by large-scale protein motions, similarly to what has been observed in the HIV-1 enzyme. (iv) We extend our findings to all other members of the two eukaryotic and retroviral fold families by recurring to a simple, topology-based, energy functional. This analysis reveals a sophisticated mechanism of enzymatic activity modulation common to all aspartic proteases. We suggest that aspartic proteases have been evolutionarily selected to possess similar functional motions despite the observed fold variations. 相似文献