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排序方式: 共有180条查询结果,搜索用时 15 毫秒
1.
Bo Olsson György Marko-Varga Lo Gorton Roger Appelqvist Gillis Johansson 《Analytica chimica acta》1988
A selective and sensitive flow-injection system for the determination of myo-inositol (hexahydroxycyclohexane) is described. Inositol dehydrogenase, IDH, lactate dehydrogenase, LDH, and lactate oxidase, LOD, are co-immobilized on porous glass and used in a packed-bed enzyme reactor. myo-Inositol reacts to produce an equivalent amount of hydrogen peroxide, which oxidizes hexacyanoferrate(II) to hexacyanoferrate(III) in a second reactor containing immobilized peroxidase. The hexacyanoferrate(III) is then detected amperometrically at 0 mV vs. SCE in a flow-through detector. The system responds linearly to injected samples of myo-inositol (25 μl) in the concentration range 1–300 μM. The maximum throughput was 90 samples per hour. The IDH/LDH/LOD reactor was stable for at least 5 weeks. 相似文献
2.
The chemistry of several of the Diels-Alder adducts formed by the reaction of 4,4-diethylpyrazoline-3,5-dione ( 1 ) with conjugated dienes was studied with respect to reduction (hydride and catalytic) and reaction with base. Reaction of the 2,3-dimethyl-1,3-butadiene adduct with lithium aluminum hydride followed by hydrogenation gave 1,3,5,6,7,8-hexahydro-cis-endo-6,7-dimethyl-2,2-diethylpyrazolo[1,2-a]pyridazine ( 11 ). Attempted conversion of this compound to 3,3-diethyl-cis-7,8-dimethyl-1,5-diazacyclononane ( 12 ) gave instead a compound which has been tentatively identified as N-(2,3-dimethyl-4-aminobutyl)-2-ethyl-2-methylbutanaldimine ( 14 ). Lithium aluminum hydride reduction of 4,4-diethylpyrazolidine-3,5-dione ( 22 ) or the adducts formed from 1 and cyclopentadiene or 1,3-cyclohexadiene gave good yields of 4,4-diethylpyrazolidine ( 21 ). This later reduction gave a new and efficient synthetic route to the pyrazolidine ring system. Lithium aluminum hydride reduction of 5,6,7,8-tetrahydro-5,8-ethano-2,2-diethylpyrazolo[1,2-a]pyridazine-1,3(2H)dione ( 26 ) followed by hydrogenolysis led to a high yield of 4,4-diethyl-2,6-diazabicyclo[5.2.2]undecane ( 28 ) which is the first reported example of this ring system. Reaction of several of the adducts with ethanolic potassium hydroxide resulted in the opening of the five-membered ring. 相似文献
3.
A flow system for substrate recycling of NAD+/NADH was set up with an enzyme reactor containing coimmobilized glycerol dehydrogenase (GDH) and diaphorase. The product from the diaphorase catalysis, hexacyanoferrate(II), aws detected amperometrically at a glassy carbon electrode. The amplification factor was 150 for a reactor volume of 100 μ l at a flow-rate of 0.5 ml/min. With a stopped flow of four minutes, the signal increased another 88 times, resulting in a signal amplification of 13 300 times. Equations are derived for the amplification factor and used for a discussion of the optimization of amplification systems. The Km for GDH with glycerol as a substrate was found to be 5 × 10−3 M at pH 8.0. GDH from Cellulomonas sp. was purified on a gel filtration column and the purified enzyme showed a specificity toward NAD+, compared to NADP+, that was higher than 99.9%. Due to the NAD+ specificity of the purified GDH, the enzyme amplification system reported here could be used in detection systems for enzyme immunoassays when using alkaline phosphatase as a label and NADP+ as a substrate. The stability of immobilized GDH and diaphorase is several orders of magnitude better than that of alcohol dehydrogenase, which is the enzyme commonly used for NAD+-specific detection in these applications. 相似文献
4.
A flow-through voltammetric cell with a hanging mercury drop electrode has been developed to fit the static mercury drop electrode (PAR 303). The design has resulted in a linear increase of sensitivity with flow rate and an enhancement of sensitivity by the wall-jet effect. The cell is used in a flow injection system in which samples are introduced with a R??i?ka—Hansen injector. The mercury drop is held at plating potentials while the sample peak passes through the cell. Stripping is done under stopped flow conditions, to reduce noise, after the sample has been washed completely from the cell. The stripping thus takes place into the carrier electrolyte which always has a constant composition independent of sample constituents. Film-forming interfering species will, however, remain on the surface of the mercury drop. The effect of medium exchange on films produced by l-cysteine is reported. The flow-through medium exchange simplifies deaeration, speeds up analysis and reduces contamination. 相似文献
5.
DETECTION OF DNA-PSORALEN PHOTOADDUCTS in situ 总被引:1,自引:0,他引:1
ZOFIA ZAREBSKA† MARIA JARZABEK-CHORZELSKA ‡ GENOWEFA RZSA WIESLAW GLISKI MARIA PAWIKA TADEUSZ CHORZELSKI STEFANIA JABLOKA 《Photochemistry and photobiology》1984,39(3):307-312
Abstract— An immunological method, with the use of specific immune serum, has been developed for detection of 8-methoxypsoralen (8-MOP) photoadducts to DNA, formed in situ in cell nuclei, after combined treatment with 8MOP and UV-A irradiation (Zarçbska et al. , 1978). Lymphocytes fixed on slides or in suspension, and cryostat sections of different mammalian tissues, served as antigenic substrate, after treatment with 8-MOP and UV-A in vitro. Specific fluorescence in these substrates was detected in the nuclei after treatment with 30 ˜ 140 kJ/m2 UV-A in the presence of 0.1-0.3 μg/cm2 8-MOP. PHA-stimulated-lymphocytes appeared to be the most sensitive substrate.
However, hairless mice treated with high doses of UV-A in vivo , 70 ˜ 360 kJ/m2 did not reveal a specific fluorescence of epidermal nuclei, unless a high local concentration of 8-MOP was attained.
The apparent discrepancy in the level of photoadduct detection between the in vitro and in vivo treated specimens was explained by the low number of DNA-8-MOP-photoadducts formed in vivo under these experimental conditions. The relevance of these findings to the role of DNA-8-MOP-photoadducts formed during PUVA photochemotherapy is discussed. 相似文献
However, hairless mice treated with high doses of UV-A in vivo , 70 ˜ 360 kJ/m
The apparent discrepancy in the level of photoadduct detection between the in vitro and in vivo treated specimens was explained by the low number of DNA-8-MOP-photoadducts formed in vivo under these experimental conditions. The relevance of these findings to the role of DNA-8-MOP-photoadducts formed during PUVA photochemotherapy is discussed. 相似文献
6.
Carrier solutions for stripping voltammetry in flow systems are deoxygenated by reaction with glucose added to the carrier. The reaction was catalyzed by glocuse oxidase and catalase co-immobilized in an enzyme reactor which was inserted before the injector. The oxygenated was removed at least as efficiently as with nitrogen purging and the voltametric behaviour of cadmium(II), lead(II) and zinc(II) was unaffected by the glucose/gluconic acid system. A particular advantage is the rapid start-up compared to the lengthy purging of carrier solution when nitrogen degassing is used. The enzyme reactor made from porous glass was effective for several months. 相似文献
7.
Diels-Alder adducts were formed in the lead tetraacetate oxidations of substituted cyclic hydrazides of furan, pyridazine and pyrrole dicarboxylic acids in the presence of 1,3-cyclo-hexadiene or 1,3-cyclopentadiene. The products resulting were furo[3,4-g]pyridazino[1,2-a]-pyridazine-6,10-diones, pyridazino[4,5-g]pyridazino[1,2-a]pyridazine-6,11-diones, and pyrrolo-[3,4-g]pyridazino[1,2-a]pyridazine-6,10-diones, respectively. Some hydrogenations and ring opening reactions were studied. 相似文献
8.
Lo Gorton Arne Torstensson Hans Jaegfeldt Gillis Johansson 《Journal of Electroanalytical Chemistry》1984,161(1):103-120
Meldola Blue (7-dimethylamino-1,2-benzophenoxazine) can be adsorbed on graphite to give chemically modified electrodes. The electrochemical redox reactions of the phenoxazine are fairly reversible at low coverages with an E′o of ?175 mV vs. SCE at pH 7.0. The electrode was most stable in acid solutions, at pH 6.0 its electrochemical activity decreased by 15% during 2h. The adsorbed compound mediated electron transfer in the electrocatalytic oxidation of the nicotinamide coenzymes (NADH and NADPH). The formation of a charge transfer complex between Meldola Blue and the coenzyme is demonstrated by experiments with a rotating disk electrode. The complex decomposes in a rate limiting step (k+2=30 s?1) to the oxidized coenzyme and the reduced Meldola Blue. The latter can be reoxidized in a fast electrochemical step. The overall result is an electrocatalytic oxidation at a voltage which is about 500 mV lower than at an unmodified electrode. 相似文献
9.
Characterization of multiple fragmentation pathways initiated by collision‐induced dissociation of multifunctional anions formed by deprotonation of 2‐nitrobenzenesulfonylglycine 下载免费PDF全文
Tara E. Tovstiga Elizabeth A. L. Gillis J. Stuart Grossert Robert L. White 《Journal of mass spectrometry : JMS》2014,49(2):168-177
The correlation of anion structure with the fragmentation behavior of deprotonated nitrobenzenesulfonylamino acids was investigated using tandem mass spectrometry, isotopic labeling and computational methods. Four distinct fragmentation pathways resulting from the collision‐induced dissociation (CID) of deprotonated 2‐nitrobenzenesulfonylglycine (NsGly) were characterized. The unusual loss of the aryl nitro substituent as HONO was the lowest energy process. Subsequent successive losses of CO, HCN and SO2 indicated that an ortho cyclization reaction had accompanied loss of HONO. Other pathways involving rearrangement of the ionized sulfonamide group, dual bond cleavage and intramolecular nucleophilic displacement were proposed to account for the formation of phenoxide, arylsulfinate and arylsulfonamide product ions at higher collision energies. The four distinct fragmentation pathways were consistent with precursor–product relationships established by CID experiments, isotopic labeling results and the formation of analogous product ions from 2,4‐dinitrobenzenesulfonylglycine and the Ns derivatives of alanine and 2‐aminoisobutyric acid. The computations confirmed a low barrier for ortho cyclization with loss of HONO and feasible energetics for each reaction step in the four pathways. Computations also indicated that three of the fragmentation pathways started from NsGly ionized at the carboxyl group. Overall, the pathways identified for the fragmentation of the NsGly anion differed from processes reported for anions containing a single functional group, demonstrating the importance of functional group interactions in the fragmentation pathways of multifunctional anions. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
10.
The nonnegative rank of a nonnegative matrix is the minimum number of nonnegative rank-one factors needed to reconstruct it exactly. The problem of determining this rank and computing the corresponding nonnegative factors is difficult; however it has many potential applications, e.g., in data mining and graph theory. In particular, it can be used to characterize the minimal size of any extended reformulation of a given polytope. In this paper, we introduce and study a related quantity, called the restricted nonnegative rank. We show that computing this quantity is equivalent to a problem in computational geometry, and fully characterize its computational complexity. This in turn sheds new light on the nonnegative rank problem, and in particular allows us to provide new improved lower bounds based on its geometric interpretation. We apply these results to slack matrices and linear Euclidean distance matrices and obtain counter-examples to two conjectures of Beasley and Laffey, namely we show that the nonnegative rank of linear Euclidean distance matrices is not necessarily equal to their dimension, and that the rank of a matrix is not always greater than the nonnegative rank of its square. 相似文献